CN1278286A - Modified condensation polymer - Google Patents

Abstract

The invention pertains to methods for preparing modified condensation polymers wherein the steps include: (a) preparing a polymer colloid system comprising a first polymer dispersed in a liquid continuous phase; (b)introducing the polymer colloid system into a condensation reaction medium prior to or during the condensation reaction, wherein the condensation reaction medium comprises (1) a diacid, di-isocyanate, dialkyl carbonate, diaryl carbonate, dihalo carbonate or a mixture thereof, wherein the condensation reaction medium optionally comprises a diol component; and polymerizing the diol component and component (1), thereby forming a modified condensation polymer.

Description

Modified polycondensate

Related applications

This application claims the benefit of U.S. Provisional Application Serial No. 60/057,714 filed on 1997-08-28 and U.S. Provisional Application Serial No. 60/058,008 filed on 1997-08-28, 2 of 60/057,714 and 60/058,008 The entire contents of this application are incorporated herein by reference.

Field of Invention

This invention relates to diol latex compositions and methods of making such diol latex compositions. The diol latex composition is preferably prepared with diol as the main component of the continuous phase.

The invention also relates to polycondensates and processes for their preparation. The polycondensate is prepared using a polymer colloid system which preferably comprises a diol component. In a preferred embodiment, the polymer colloid system is the diol latex composition. The polycondensates prepared according to the process of the invention are heterogeneous materials.

Background of the Invention

Referring to the first major embodiment of the present invention, latex polymers are used in a wide variety of products due to the unique characteristics of their feed systems. Latex polymers, by their very nature, have a lower viscosity than their solution counterparts. This lower viscosity allows it to be dosed at higher polymer concentrations in use without encountering one or another of the problems associated with high viscosity fluids. The unique viscosity behavior of latex polymers arises from the heterogeneity of the system. The fact that the latex polymer is dispersed rather than dissolved in the low viscosity continuous medium reduces the effect of the latex polymer on the viscosity of the medium. Therefore, the continuous phase or solvent of the latex is the main component affecting the viscosity of the system.

Typically, the continuous phase of most commercial latexes is water. The advantage of this is that the water is less toxic and non-flammable. Water is a good choice when using the continuous phase as the polymer feed system. In some cases, however, water may be detrimental to the substrate or necessarily alter the drying characteristics of the latex.

Solvents other than water may be used in the continuous phase. For example, it is known to add small amounts of diol solvents. JP 04335002 discloses the addition of alcohol as antifreeze to produce low temperature vinyl ester emulsions. The amount of diol solvent disclosed is less than 50% by weight. JP 63186703 discloses the addition of up to 10% by weight of solid components of film formers and plasticizers to influence the film forming properties of the finished emulsion. JP 06184217 discloses adding polyhydric alcohols and water-soluble inorganic salts in vinyl chloride suspension polymerization to produce vinyl chloride polymers with excellent powder fluidity. EP 255137 discloses the use of water-soluble alcohols with a water/alcohol content ratio of 100/0 to 50/50 to produce highly polymerized polyvinyl esters.

US 3,779,969 describes the use of propylene glycol or diethylene glycol at 10-50% by weight of the emulsion. The purpose of adding ethylene glycol is to improve the wettability of the emulsion.

US 4,458,050 describes a method of making polymer dispersions in diol chain extenders. This patent concerns the production of low viscosity polymers for the preparation of polyurethanes. The '050 patent does not disclose achieving a stable composition of the latex in the diol solvent. The patent also discloses the use of large amounts of polymer stabilizers to prepare the dispersed polymer.

JP 60040182 and JP 64001786 disclose compositions for the treatment of water-oil repellent fabrics. This composition is intended for the preparation of fluoropolymer emulsions in glycol solvent mixtures. Such fluoropolymers are not the object of the present invention.

US 4,810,763 discloses suspension polymerization in an organic medium to prepare pressure sensitive adhesives. The compositions described in the '763 patent are specifically aimed at producing large particle dispersions. This patent does not disclose compositions capable of producing particle size latexes with particle sizes below 1000 nm. This patent also does not disclose emulsion polymerization.

US 4,885,350 and US 5,061,766 disclose dispersion polymerization of vinyl monomers in hydrophilic organic liquids. For the production of dispersion polymers it is recommended to use large amounts of polymer dispersion stabilizers.

Prior to the present invention, no one was known to have used 40%, more preferably 60% by weight or more of a diol in the continuous phase of a latex polymer. Such levels of diol use can impart certain advantages to the latex composition, such as improved compatibility with certain substrates, improved drying characteristics of the latex, or can be used in the second main embodiment of the present invention (condensate/second 1 Preparation of polymer matrix).

With regard to the second main embodiment of the invention, it is known that the modification of the polycondensate can be achieved by blending the polycondensate with another polymer in an extruder. For example, to improve the impact properties of polyesters, low glass transition temperature (Tg) elastomers are often added to polyesters in a twin-screw extruder. Japan Kokai JP 02155944 describes a compounding compound for moldings, comprising a physical blend of saturated polyester and styrene polymer containing 1 to 100 phr (parts per hundred resin) methyl Glycidylamido-grafted olefin polymers of glycidyl acrylate grafted olefin polymers. Japanese Kokai JP02016145, JP 02024346, JP 01123854, JP 01153249 and JP 01163254 all disclose the blending of aromatic polyesters with resins prepared by graft emulsion copolymerization. The size of the dispersed phase is critical to obtain good properties. This is an energy-intensive process that sometimes results in a decrease in the physical properties of the polymer, especially molecular weight, and it also requires a blending step that uses more resources and time.

US Patents 5,652,306, 4,180,494 and 5,409,967 disclose compositions for improving the impact resistance of aromatic polyesters involving the blending of acrylic or polybutadiene/acrylic rubber powders with polyethylene terephthalate (PET) . Acrylic rubber particles are produced by typical core/shell emulsion polymerization followed by spray drying of the latex for recovery. A procedure for recovering this latex is outlined in US Patent 3,895,703.

Extrusion blending of elastomers and plastics is labor intensive and time consuming. Generally, polybutadiene or poly(butyl acrylate) is used as a low glass transition temperature polymer to achieve impact resistance modification of polyester. This type of low Tg elastomer is difficult to handle, so it requires the use of a second monomer, typically poly(methyl methacrylate) as a "shell" to wrap the "core" of the low Tg polymer in order to make the low Tg polymer able to operate. The core-shell polymer is isolated, dried and then added to the polyester in an extruder.

There is a need for a method of producing polymer blends in an economical manner. It would also be desirable to be able to produce polymer blends using either or both core-shell and non-core-shell polymers in the same process. This need has been addressed by the present invention, which makes it possible to obtain such blends using a polymerization reactor in which the physical properties of the polycondensate are maintained or improved.

Invention Summary

The first main aspect of the present invention relates to a diol latex composition comprising:

(a) latex polymer particles comprising residues of ethylenically unsaturated monomers, wherein the latex polymer particles have a particle size of less than 1000 nm;

(b) surfactants; and

(c) A continuous liquid phase comprising a diol component, wherein the diol component accounts for 60 to 100 wt% of the continuous phase.

A second main aspect of the present invention relates to a method of preparing a polycondensate/first polymer matrix comprising the following steps;

(a) preparing a polymer colloid system comprising a first polymer dispersed in a continuous liquid phase; and

(b) introducing the polymer colloid system into the condensation reaction medium, which can be carried out before or during the condensation reaction, wherein the condensation reaction medium comprises (1) diacid, diisocyanate, dialkyl carbonate, diaryl carbonate, Dihalo carbonate or mixtures of the above;

Where the continuous liquid phase, the condensation reaction medium, or both contain the diol component, a "condensate/first polymer matrix" is formed.

                    Invention Details

The present invention will be better understood by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.

Before disclosing and describing the compositions of matter and methods of this invention, it is to be noted that this invention is not limited to these specific synthetic methods or specific formulations, as these may, of course, vary. It should also be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

A number of terms will be used herein and in the claims that follow, and as defined they shall have the following meanings:

The singular forms "a" and "an" and "the" include plural references unless the context clearly dictates otherwise.

"Optional" or "optionally" means that the event or situation described later may or may not occur, and means that the described content includes instances where the event or situation occurs and instances where it does not occur .

"Latex" is defined herein as a dispersion of polymer particles, preferably having a particle size in the range of 10 to 1000 nm, in a continuous phase. The polymer particles are prepared by emulsion polymerization. "Latex particles" are defined herein as such polymer particles dispersed in a continuous phase.

"Diol" is a synonym for diol or dihydric alcohol. "Polyol" is a polyhydric alcohol containing 3 or more hydroxyl groups.

Throughout this application, whenever a publication is referred to, the entire disclosure of that publication is hereby incorporated by reference in order to more fully describe the current state of the art to which this invention pertains.

The first main aspect of the present invention relates to a diol latex composition comprising:

(a) latex polymer particles incorporating residues of ethylenically unsaturated monomers, wherein the latex polymer particles have a particle size of less than 1000 nm;

(b) surfactants; and

(c) A continuous liquid phase comprising a diol component, wherein the diol component accounts for 60 to 100 wt% of the continuous phase.

A second main aspect of the present invention relates to a method of preparing a polycondensate/first polymer matrix comprising the steps of:

(a) preparing a polymer colloid system comprising a first polymer dispersed in a continuous liquid phase; and

(b) introducing the polymer colloid system into the condensation reaction medium, which can be carried out before or during the condensation reaction, wherein the condensation reaction medium comprises (1) diacid, diisocyanate, dialkyl carbonate, diaryl carbonate, Dihalocarbonates or mixtures of the above;

Where the continuous liquid phase, the condensation reaction medium, or both contain the diol component, a polycondensate/first polymer matrix is formed.

The first main aspect of the present invention relates to a diol latex composition and a method for preparing such a diol latex composition, wherein the diol latex composition comprises an ethylenically unsaturated monomer in a free radical initiator, a suitable surface active A latex polymer derived by polymerization in the presence of an agent and a diol continuous phase that does not dissolve the polymer. The diol latex compositions are prepared by emulsion polymerization, wherein the continuous phase of the emulsion comprises a diol component or a combination of 1 or more diols with other (co)solvents.

A second main aspect of the invention concerns the introduction of a polymer colloid system in the polycondensation reaction, which system preferably comprises a diol component as coreactant. The diol component can be used as a co-reactant in polycondensation reactions to make polyesters, polycarbonates, polyurethanes, or in any other polycondensation reaction using diols.

More specifically, the second main aspect of the present invention comprises methods and compositions for entrapping polymer particles during a polycondensation reaction involving diols by introducing a polymer colloid system into the polycondensation reaction. In one embodiment of the invention, the polymer colloid system is the diol latex composition of the first aspect of the invention, wherein the continuous phase containing the diol component is the source of diol for the polycondensation reaction. In another embodiment, the polymer colloid system comprises an aqueous based continuous phase. The water-based continuous phase may or may not contain a diol component. In another embodiment, the polymer colloid system comprises a continuous phase that is primarily diol. If the polymer colloid system is properly stabilized, the polymer colloid system will retain its integrity and maintain a dispersed phase in the resulting condensation polymer matrix. Depending on the nature of the polymer particles, the physical properties of the polycondensate can be improved. The present invention includes compositions and methods for the production of polymers in which a first polymer, ie, the polymer comprising the polymer colloid system, is incorporated during the polymerization of a second polymer, ie, a polycondensate.

The polycondensate obtained then comprises polymer particles constituting the polymer colloid system, wherein the polymer particles in turn are preferably dispersed in the solid polycondensate continuous phase. This provides a polymer blend with improved physical properties. For example, if the glycol latex polymer is a low Tg rubber and the polycondensate is a polyester such as poly(ethylene terephthalate) (PET), the resulting polycondensate blend can have improved impact resistance . Also, doing so avoids the need to use a core-shell system to obtain low Tg rubbers as in the prior art. I. Diol Latex Composition

As already mentioned above, the first main aspect of the present invention relates to the preparation of diol latex compositions by emulsion polymerization, wherein the continuous phase comprises the diol component. The diol latex compositions are useful for a variety of purposes including, but not limited to, ink compositions, pigment masterbatches, coatings, and as reactants in polycondensation reactions. The diol latex composition comprises a latex polymer and a continuous phase comprising a diol component.

The diol component useful in the continuous phase of the diol latex composition includes, but is not limited to, any aliphatic or cycloaliphatic diol containing from about 2 to about 10 carbon atoms, and mixtures thereof. Preferred diols include ethylene glycol, 1,3-trimethylene glycol, 1,2-propanediol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, cis- or trans-cyclohexanedimethanol, cis- or trans-2,2 , 4,4-tetramethyl-1,3-cyclobutanediol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol , 2-methyl-1,3-pentanediol or mixtures thereof; more preferred diols include ethylene glycol, 1,2-propanediol, tripropylene glycol, 1,4-butanediol, diethylene glycol, neopentyl Diols, cis- and trans-cyclohexanedimethanol and mixtures thereof; further preferred diols include neopentyl glycol, ethylene glycol, cis- or trans-cyclohexanedimethanol, 1,4-butanediol or a mixture thereof.

In addition to the diol component, the continuous phase may also contain 1 or more polyol components. Typical polyol components that can be used in the continuous phase include, but are not limited to, glycerol, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis(hydroxy Methyl)cyclohexane, tris(2-hydroxyethyl)isocyanurate, dipentaerythritol and mixtures thereof. In addition to low-molecular-weight polyols, higher-molecular-weight polyols (MW 400-3000) can also be used, preferably composed of alkylene oxides containing 2-3 carbon atoms such as ethylene oxide or propylene oxide and 3-3 carbon atoms. 6 carbon atom polyol initiators such as condensation derived triols such as glycerol.

The continuous phase may also contain co-solvents. Such co-solvents include, but are not limited to, water, methanol, ethanol, propanol, n-butanol, and mixtures thereof. The amount of co-solvent used is less than 60 wt%, more preferably less than 40 wt%, based on the total weight of the continuous phase.

As used throughout, "total continuous phase weight" includes the weight of the diol component, polyol component, and co-solvent. The weight of any surfactant is not included in the total weight of the continuous phase.

In one embodiment, the diol component is present in an amount of 60 to 100% by weight based on the total weight of the continuous phase, preferably 65 to 100% by weight of the total weight of the continuous phase, more preferably 75% by weight of the total weight of the continuous phase. ~100% by weight, still more preferably 90-100% by weight of the total weight of the continuous phase, even more preferably 100% by weight of the total weight of the continuous phase. In another embodiment, the diol-containing phase consists essentially of the diol component.

In an alternative embodiment, the diol component is present in an amount of 40-100 wt % based on the total weight of the continuous phase, preferably 50-100 wt % of the total weight of the continuous phase, more preferably the total weight of the continuous phase 65-100wt% of the total weight of the continuous phase, more preferably 90-100wt% of the total weight of the continuous phase. In another embodiment, the continuous phase consists essentially of the diol component. The total weight of the continuous phase includes the weight of the diol component, polyol component and co-solvent. The weight of any surfactant is not included in the total weight of the continuous phase. In this embodiment, the diol component consists essentially of tripropylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, or mixtures thereof.

The diol latex compositions of the present invention are prepared by emulsion polymerization. The solids content in the reaction is preferably 5 to 60 wt%, but more preferably 20 to 50 wt%. The particle size of the latex polymer particles of the diol latex composition is preferably less than 1000 nm; more preferably in the range of 20-700 nm, further preferably 60-250 nm. The reaction temperature is preferably in the range of 0 to 190°C, more preferably in the range of 60 to 90°C.

Surfactants are preferably used in the preparation of the diol latex composition. The type and amount of surfactant used in emulsion polymerization depends on the combination of monomers and polymerization conditions. Typical surfactants used in emulsion polymerization are anionic, cationic or nonionic surfactants. Anionic surfactants useful herein include surfactants such as alkali metal or ammonium alkyl, aryl or alkaryl sulfonic, sulfate or phosphoric acid salts and mixtures thereof. Suitable nonionic surfactants include, but are not limited to, alkyl and alkaryl polyglycol ethers, such as ethoxylated products of lauryl alcohol, oleyl alcohol, and stearyl alcohol; alkylphenol glycol ethers, including but It is not limited to ethoxylated products of octyl or nonylphenol. Suitable surfactants can be found in McCutheon, Volume I: Emulsifiers and Detergents, 1996, North American Edition, MC Publishing Company, Glen Rock, NJ, 1996. Surfactants may or may not be reactive in polymerization. In one embodiment, useful surfactants are the sulfate/sulfonate salts of nonylphenol and alkanol ethoxylates. Preferred surfactants include, but are not limited to, polymerizable or non-polymerizable alkyl ethoxylated sulfates, alkylphenol ethoxylated sulfates, alkyl ethoxylates, alkylphenol ethoxylates or its mixture.

The latex polymers of the diol latex compositions can be prepared by any conventional method known in the art. Monomers useful in preparing latex polymers can be broadly characterized as ethylenically unsaturated monomers. These include, but are not limited to, non-acid vinyl monomers, acid vinyl monomers, and/or mixtures thereof. The latex polymers of the present invention may be copolymers of non-acid vinyl monomers and acid monomers, mixtures thereof or derivatives thereof. The latex polymers of the present invention may also be homopolymers of ethylenically unsaturated monomers.

Non-acid vinyl monomers suitable for use in preparing latex polymers include, but are not limited to, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, methyl acrylate, methyl methacrylate, acrylic acid Ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-acrylate Ethylhexyl ester, isoprene, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, trimethylolpropane triacrylate, styrene, alpha-methylbenzene Ethylene, glycidyl methacrylate, methacryloyl carbodiimide, C ₁ -C ₁₈ alkyl crotonic acid ester, di-n-butyl maleate, α- or β-vinyl naphthalene, maleic acid Dioctyl methacrylate, allyl methacrylate, diallyl maleate, diallyl malonate, methoxybutenyl methacrylate, isobornyl methacrylate, methyl Hydroxybutyl acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl 1,2-ethylene Carbonate, epoxybutene, 3,4-dihydroxybutene, hydroxyethyl (meth)acrylate, methacrylamide, acrylamide, butylacrylamide, ethacrylamide, butadiene, Vinyl ester monomer, vinyl (meth)acrylate, isopropenyl (meth)acrylate, cycloaliphatic epoxy (meth)acrylate, ethyl formamide, 4-vinyl-1,3- Dioxolan-2-one, 2,2-dimethyl-4-vinyl-1,3-dioxolane and 3,4-diacetoxy-1-butene or mixtures thereof. Suitable monomers are described in "The Brandon Associates" 2nd Edition, 1992 Merrimack, New Hampshire, and in the Catalog of Polymers and Monomers, 1996-1997, Polyscience Corporation, Warrington, Pennsylvania, USA.

Acid vinyl monomers useful in preparing latex polymers include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and monovinyl adipate.

Preferred monomers for use in preparing latex polymers/(co)polymers are ethylenically unsaturated monomers including, but not limited to, acrylates, methacrylates, vinyl esters, styrene, styrene derivatives, chlorine Ethylene, vinylidene chloride, acrylonitrile, isoprene and butadiene. In a more preferred embodiment, the latex polymer comprises (co)polymers of the following monomers: 2-ethylhexyl acrylate, styrene, butyl acrylate, butyl methacrylate, ethyl acrylate, methacrylic acid Methyl esters, butadiene and isoprene.

In a preferred embodiment, the latex polymer has a weight average molecular weight (Mw) of 1,000 to 1,000,000 as measured by gel permeation chromatography (GPC), more preferably 5,000 to 250,000. In one embodiment, the latex polymer has a glass transition temperature (Tg) equal to about 170°C.

The diol latex compositions of the present invention can be characterized as a latex stabilized in a continuous phase containing the diol component. A stable latex is defined for the purposes of the present invention as a latex containing particles that are colloidally stable, i.e. latex particles that remain dispersed in the in the continuous phase.

The latex polymer particles are generally spherical in shape. The latex polymer can be a core-shell polymer or a non-core-shell polymer. Core/shell polymers can be prepared by adding monomers in stages. For example, the composition of the polymerized monomer feed can change in an abrupt manner throughout the reaction, resulting in distinct core and shell polymer fractions. Core/shell polymer particles can also be made into leafy, peanut shell, acorn, raspberry shapes. In such particles, the core portion may comprise from about 20 to about 80% by weight of the total weight of the particle, and the shell portion may comprise from about 80 to about 20% by weight of the total weight of the particle.

In one embodiment, chain transfer agents are used in emulsion polymerization. Typical chain transfer agents are those known in the art. Chain transfer agents useful in emulsion polymerization to prepare diol latex compositions include, but are not limited to, butanethiol, dodecanethiol, mercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, 3- n-butyl mercaptopropionate, octyl mercaptan, isodecyl mercaptan, stearyl mercaptan, mercaptoacetate, allyl mercaptopropionate, allyl mercaptopropionate, crotyl mercaptopropionate, thioglycolic acid Crotyl esters, and those reactive chain transfer agents disclosed and described in US Pat. No. 5,247,040, which is hereby incorporated by reference. Preferably, the chain transfer agent is selected from mercaptans and various alkyl halides, including but not limited to, carbon tetrachloride; a more preferred chain transfer agent is 2-ethylhexyl 3-mercaptopropionate. The chain transfer agent is added in an amount of 0 to 2 parts per hundred monomer (phm), more preferably 0 to 0.5 phm.

The latex polymers of the present invention may be uncrosslinked or crosslinked. When crosslinking, suitable crosslinking agents include polyfunctional unsaturated compounds including, but not limited to, divinylbenzene, allyl methacrylate, allyl acrylate, polyfunctional acrylates, and mixtures thereof. Suitable multifunctional acrylates include, but are not limited to, dimethacrylate of ethylene glycol, diacrylate of ethylene glycol, triacrylate of trimethylolpropane, trimethacrylate of trimethylolpropane , tetraacrylates of pentaerythritol, and mixtures thereof. The amount of crosslinking monomer used in the emulsion polymerization can be controlled to vary the gel fraction of the latex in the range of 20-100%. "Gel fraction" is the amount insoluble in a good solvent.

Latex particles can be rendered functional by incorporating monomers with pendant functional groups. Functional groups that can be incorporated into latex particles include, but are not limited to, epoxy groups, acetoacetoxy groups, carbonate groups, hydroxyl groups, amine groups, isocyanate groups, amide groups, and mixtures thereof. These functional groups can be derived from a variety of different monomers including, but not limited to, glycidyl methacrylate, acetoacetoxyethyl methacrylate, vinyl ethylene carbonate, hydroxyethyl methacrylate ester, tert-butylaminoethyl methacrylate, methacryloyldimethylamine, m-isopropenyl-α,α-dimethylbenzyl isocyanate, acrylamide and N-methylolacrylamide. The addition of functional groups enables the polymer to be further reacted after latex synthesis. This functionality can be used to provide latent crosslinking capability or to utilize it to react with condensation polymers, as discussed in Section II below.

Initiators may be used in the emulsion polymerization to produce diol latex compositions including, but not limited to, persulfates, water- or diol-soluble organic peroxides, and azo-type initiators. Preferred initiators include, but are not limited to, hydrogen peroxide, potassium or ammonium peroxodisulfate, dibenzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, 2,2'-azobis Isobutyronitrile, tert-butyl hydroperoxide, benzoyl peroxide and mixtures thereof. Redox initiating systems such as the iron catalyzed reaction of t-butyl hydroperoxide with erythorbic acid are also useful. Preferably, no initiators are used which generate strong acid by-products. This avoids possible side reactions between the diol component of the solvent and the acid. The amount of the initiator added can be 0.1-2 phm, more preferably 0.3-0.8 phm.

Reducing agents can also be used in the emulsion polymerization. Suitable reducing agents are those which accelerate the polymerization reaction and include, for example, sodium dithionite, sodium bisulfite, sodium formaldehyde sulfoxylate, ascorbic acid, erythorbic acid, and mixtures thereof. If the reducing agent is introduced in the emulsion polymerization, its preferred addition amount is 0.1-2 phm, more preferably 0.3-0.8 phm. The reducing agent is preferably added to the reactor over a period of time.

Buffering agents may also be used in glycol-containing emulsion polymerizations to control the pH of the reaction. Suitable buffers include, but are not limited to, carbonate- and ammonium or sodium bicarbonate. Buffering is preferably added in the case of acid-generating initiators including, but not limited to, persulfates.

Polymerization catalysts can also be used in emulsion polymerization. Polymerization catalysts are those compounds that can accelerate the polymerization reaction and can cooperate with the above-mentioned reducing agent to promote the decomposition of the polymerization initiator under the reaction conditions. Suitable catalysts include, but are not limited to, transition metal compounds such as ferrous sulfate heptahydrate, ferrous chloride, copper sulfate, copper chloride, cobalt acetate, cobalt sulfate, and mixtures thereof.

The preparation of the diol latex composition involves first formulating an emulsion or solution comprising monomer, initiator, surfactant and continuous phase. In one embodiment, the continuous phase comprises 60 to 100 wt% diol component. Subsequently, the mixture is heated to polymerize the monomers and form a latex polymer. Typically, monomer is fed to the reactor over a period of time, and a separate initiator charge is also fed to the reactor over a period of time.

The diol latex composition may contain a stabilizer, but the presence of a stabilizer is not required. Stabilizers suitable for use in the diol latex composition include, but are not limited to, anionic stabilizers, nonionic suspension stabilizers, amphoteric suspension stabilizers, or mixtures thereof. Suspension stabilizers must be soluble in the continuous phase but substantially insoluble in the monomer. Suspension stabilizers, if present, are present in an amount of 3 to 15% by weight of the monomers; preferably 7 to 8% by weight of the monomers.

As the concentration of diol in the continuous phase approaches 100%, the wettability of the diol latex composition to the hydrophobic surface will gradually improve, and at this time the volatility of the diol latex composition becomes smaller. The reduced volatility of the diol latex composition, as disclosed in Section II below, is especially advantageous when the diol latex composition is used in a condensation reaction.

The polymer prepared by the invention can be used for thermoplastic engineering resin, elastomer, film, sheet and container plastic. The diol latex compositions of the present invention are useful in a wide variety of coating compositions such as architectural coatings, maintenance coatings, industrial coatings, automotive coatings, textile coatings, inks, adhesives, and coatings for paper, wood, and plastics. Accordingly, the present invention also relates to such coating compositions comprising the diol latex compositions of the present invention. The diol latex compositions of the present invention may be incorporated into these coating compositions in the same manner as known polymer latexes and may be used with conventional ingredients and/or additives of such compositions. These coatings can be clear or pigmented.

Once formulated, coating compositions containing the diol latex compositions of the present invention can then be applied to a wide variety of surfaces, substrates, or articles, such as paper, plastic, steel, aluminum, wood, gypsum board, or galvanized ( primed or not primed). The type of surface, substrate or article to be coated generally determines the type of coating composition that should be used. The coating composition can be applied in a manner known in the art. For example, the coating composition can be applied to the substrate by spraying or by conventional coating methods. Typically, the coating can be dried by applying heat, but it is preferred to allow it to air dry.

The coating composition comprises the diol latex composition of the present invention and may also contain water, solvents, pigments (organic or inorganic), and/or other art-known additives or fillers. Such additives or fillers include, but are not limited to, leveling, rheology, and flow control agents such as silicones, fluorocarbons, urethanes, or celluloses, bulking agents, reactive coalescing aids as described in U.S. Patent No. 5,349,026 Those described, matting agents, pigment wetting and dispersing agents, as well as surfactants, UV absorbers, UV stabilizers, coloring pigments, extenders, defoamers and suppressors, anti-settling agents, anti-sagging And thickeners, anti-skinning agents, anti-floating and anti-blooming agents, fungicides and anti-mold agents, corrosion inhibitors, thickeners, plasticizers, active plasticizers, curing agents or coalescing agents. Specific examples of such additives can be found in the Raw Materials Index, published by the National Paint and Coatings Association, 1500 Rhode Island Avenue, NW, Washington, DC 20005, USA.

The diol latex compositions of the present invention can be used alone or in combination with other conventional polymers. Such polymers include, but are not limited to, polyesters such as terephthalate-based polymers, polyester amides, cellulose esters, alkyds, polyurethanes, polycarbonates, epoxies, polyamides, Acrylics, vinyl polymers, styrene-butadiene polymers, vinyl acetate-ethylene copolymers and mixtures thereof.

The diol latex compositions of the present invention are also useful as reactants in polycondensation reactions. As reactants in polycondensation reactions, the diol latex compositions of the present invention can be used to react the latex diols with diacids, diisocyanates and dialkyl-, diaryl- or dihalo-carbonates to Modification of thermoplastic condensation polymers. In Section II below, as one of its examples, such use of the diol latex composition as a reactant in a polycondensation reaction is described. In addition, the present invention also serves as a convenient dosing method for adding latex polymers to thermoplastic condensation polymers. II. Modified polycondensate matrix

A second main aspect of the present invention relates to the introduction of a polymer colloid system into the reaction for the preparation of polycondensates, resulting in a product comprising polymer particles entrapped in the polycondensate matrix. The polymer colloid system introduced into the polymerization reaction is defined herein as polymer particles dispersed in the continuous phase, the particles preferably have a particle size in the range of 0.020 μm to 1000 μm. The continuous phase may contain small amounts of unreacted monomers, surfactants and the like. Polymer particles suitable for use in such polymer colloid systems, referred to herein as the first polymer, comprise the same ethylenically unsaturated monomers described in Section I above in connection with the diol latex composition and can be functionalized or crosslinked in the same manner as disclosed for the latex polymer of Section I. Where functionalization is performed, it is preferred that the functional groups include groups reactive with diacid, diisocyanate, diaryl carbonate, dialkyl carbonate, dihalocarbonate, or diol components. These functional groups include, but are not limited to, epoxy, acid, hydroxyl, isocyanate, amine, amide, and carbonate groups or mixtures thereof. Additionally, the first polymer may be a core-shell or non-core-shell polymer.

The polymer colloid system can be prepared by a variety of methods including, but not limited to, emulsion, suspension or dispersion polymerization, and mechanical emulsification. Generally, dispersion and suspension polymerization produce larger particle sizes, typically in the range of 1 to 500 μm; while emulsion polymerization produces smaller particle sizes, typically in the range of 10 to 1000 nm.

In a preferred embodiment, the first polymer is a non-core-shell polymer, and the first polymer of the polymer colloid system comprises 50-100%, preferably 70-100%, more preferably 80-100% of the following monomers Residues of one of: 2-ethylhexyl acrylate, butyl acrylate, isoprene, styrene, butadiene or acrylonitrile.

Emulsion, suspension, dispersion and mechanical emulsion polymerization are known techniques for preparing polymer colloid systems. If dispersion polymerization is selected to prepare the polymer colloid system introduced into the polycondensation reaction, methods similar to those described in US Pat. If mechanical emulsification is used, methods similar to those described in US Patent 4,177,177, US Patent 5,358,981 and US Patent 5,612,407 can be used.

Whether emulsion, suspension, dispersion or mechanical emulsification polymerized polymer colloid system prepared as a precursor to be introduced into the condensation reaction, the solvent or continuous phase can be based on water or glycol. Preferably, however, the continuous phase is diol-based, so that the diol in the continuous phase of the polymer colloid system can participate in the polycondensation reaction. In a particularly preferred embodiment, the polymer colloid system is the diol latex composition described in Section I above. Furthermore, the continuous phase of each polymer colloid system may consist essentially of or consist of water or diol; or contain both in any proportion.

In polymer colloid systems comprising a diol-based continuous phase, the diol in the continuous phase is capable of reacting with the diacid, diisocyanate, dialkyl- or diaryl- or Halo-carbonates or mixtures thereof "co-react". In this embodiment, the diol component preferably accounts for 25 to 100 wt% of the continuous phase; preferably accounts for 50 to 100 wt% of the continuous phase; more preferably accounts for 70 to 100 wt% of the continuous phase; further preferably accounts for 90 to 100 wt% of the continuous phase 100% by weight. In a preferred embodiment, the continuous phase consists essentially of the diol component. Suitable diol components for the ethylene glycol-based continuous phase of the polymer colloid system include, but are not limited to, the diol components described in Section I.

The diol component can be present in the continuous phase, in the condensation reaction medium, or both. Adjustment of the diol concentration present in the original reaction medium should be considered together with the diol concentration in the polymer colloid system. The polymer colloid system can be introduced into the polycondensation reaction at various stages of the polymerization reaction. For example, in poly(ethylene terephthalate) (PET) polymerization, dimethyl terephthalate (DMT), ethylene glycol (EG), and a catalyst metal are charged into a flask and polymerized. Latex can be added 1) "pre-", i.e., initially added together with other materials, 2) after other materials have melted and formed a homogeneous solution, 3) after the first stage of DMT and EG has occurred After reaction and evolution of methanol, 4) immediately after the nitrogen is turned off and vacuum is applied, 5) sometimes at the final "polycondensation stage" or at any point in between, ie during transesterification. The final blend is influenced by the time at which the latex is added to the polycondensate. While not wishing to be bound by any mechanism, the author believes that the particle size and shape of the emulsion polymer in the condensation polymer matrix can be affected by this addition time. Likewise, the specific chemical interactions between the emulsion polymer and the polycondensate are also affected by the time of addition, and they thus also affect the final blend properties.

The method of the present invention does not require the isolation of the polymer in the polymer colloid system. Thus, the present invention avoids the need to prepare core-shell polymers or to isolate the polymers from the emulsion. Furthermore, since the blending occurs during the preparation of the polycondensate, there is no need for polymer/polymer post-blending, an energy intensive, costly and often resulting reduction in the molecular weight of the polycondensate.

In a preferred embodiment, the reaction medium incorporating the polymer colloid system of the present invention forms a polyester. The term "polyester" refers herein to any polyester unit type that falls within the polyester portion of the blend, including, but not limited to, homopolyesters and copolyesters (two or more monomers residues of monoacids and/or diols). The polyesters of the present invention comprise acid residues and diol residues. The acid residues of the polyesters of the invention total 100 mol %, and the diol residues of the polyesters of the invention total 100 mol %. It is to be understood that the use of the corresponding derivatives of these acids, especially anhydrides, esters and acid chlorides, is encompassed throughout the application by the term "acid residue". In addition to acid residues and diol residues, the polyesters may also contain other modifying residues. These modifying residues include, but are not limited to, diamines, in which case polyesters/amides will be formed.

The polyester preferably comprises dicarboxylic acid or ester residues, including but not limited to, aromatic dicarboxylic acid or ester residues, preferably having 8 to 14 carbon atoms; aliphatic dicarboxylic acid or ester residues, preferably having 4 to 12 carbon atoms; or a cycloaliphatic dicarboxylic acid or ester residue, preferably having 8 to 12 carbon atoms. The acid or ester residues that make up the acid portion of the polyester include the residues of: phthalic acid; terephthalic acid; naphthalene dicarboxylic acid; isophthalic acid; cyclohexanediacetic acid; diphenyl-4 , 4'-dicarboxylic acid; succinic acid; glutaric acid; adipic acid; fumaric acid; azelaic acid; resorcinol diacetic acid (resorcinoldicetic acid); didiolic acid (dihydroxy acid); 4,4' -Oxybis(benzoic acid); Diphenyldicarboxylic acid; 1,12-dodecanedicarboxylic acid; 4,4'-sulfonyldibenzoic acid; 4,4'-methyldibenzoic acid; 4,4'-stilbene dicarboxylic acid; 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acids; and mixtures thereof. The polyester can be prepared from one or more of the above dicarboxylic acids.

Examples of preferred dicarboxylic acids or derivatives thereof for the preparation of the polyesters are terephthalic acid or esters thereof and 2,6-naphthalene dicarboxylic acid or esters thereof, succinic acid, isophthalic acid, glutaric acid, Adipic acid or their esters. Other naphthalene dicarboxylic acids or esters thereof may also be used. This includes 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,4-, 2,5 -, 2,6-, 2,7- and 2,8-naphthalene dicarboxylic acids and mixtures thereof. More preferably, 2,6-naphthalene dicarboxylic acid is used as the modifying acid.

The diol component of the polyester comprises residues preferably selected from the following diols: cycloaliphatic diols, preferably having 6 to 20 carbon atoms; or aliphatic diols, preferably having 2 to 20 carbon atoms. Examples of such diols include ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-propanediol, 1,10-decanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3-methyl-2,4-pentanediol, 2- Methyl-1,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1-1,3-hexanediol, 2,2-diethyl -1,3-propanediol, 1,3-hexanediol, 1,4-bis(hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy- 1,1,3,3-tetramethylcyclobutane, 2,2-bis(3-hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxypropoxyphenyl)propane and their mixture. The diol component is more preferably selected from ethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, diethylene glycol and mixtures thereof. These diols can be modified with up to about 50 mole percent, more preferably up to about 20 mole percent, of any of the other diols disclosed herein.

Preferably, the polyesters of the present invention are substantially linear. The polyester can be modified with a small amount of one or more branching agents. Branching agents are defined herein as molecules with at least 3 functional groups capable of participating in polyester formation reactions, such as hydroxyl, carboxylic acid, carboxylate, phosphorus-based ester (potentially trifunctional), and anhydride (difunctional). function).

Branching agents that can be used in the preparation of the polyester of the present invention include, but are not limited to, glycerin, pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric acid and mixtures thereof. If a branching agent is used in the condensation reaction, the preferred amount of branching agent is in the range of 0.1 to 2.0 wt%, more preferably about 0.2 to 1.0 wt%, based on the total weight of the polyester.

The addition of a small amount of branching agent will not significantly impair the physical properties of the polyester, but it can provide additional melt strength, which is very useful for film extrusion operations. Adding too much branching agent to the copolyester will deteriorate the physical properties of the resulting copolymer, such as reducing its elongation.

Chemical agents comprising one or more ionic monomers may be added to increase the melt viscosity of the polyester. Ion-containing monomers useful in the present invention include, but are not limited to, alkaline earth metal salts of sulfisophthalic acid or derivatives thereof. The preferred weight percent of ion-containing monomers is about 0.3 to 5.0 mole percent, preferably about 0.3 to 3.0 mole percent. Ionic containing monomers also increase the melt viscosity of the polyester without significantly reducing film elongation.

The homo- or copolyesters of the present invention are preferably prepared by reaction of diols with diacids (or diesters or anhydrides) at temperatures from about 150°C to about 300°C in the presence of polycondensation catalysts including, but not limited to, Titanium tetrachloride, titanium tetraisopropoxide, manganese diacetate, antimony oxide, antimony triacetate, dibutyltin diacetate, zinc chloride or mixtures thereof. Typical amounts of catalyst used are between 10 and 1000 ppm based on the total weight of reactants. The final stage of the reaction is usually carried out under high vacuum (<10 mmHg) in order to produce high molecular weight polyesters.

The present invention also relates to the modification of high molecular weight homo- or co-polyesters, as described herein, prepared by a process comprising the following steps.

(I) mixing the diols and diacids described herein with the catalyst system,

(II) in stage 1, heating the reaction mixture at 190°C to 220°C at or slightly above atmospheric pressure, and

(III) In the second stage, a phosphorus-based additive is added, and the reaction mixture is heated at a temperature of 220° C. to 290° C. under a reduced pressure of 0.05 to 2.00 mmHg.

These polyesters are preferably prepared using one of the catalyst systems described above in the presence of phosphorus-based additives. The preferred concentration of catalyst in the reaction is from about 5 to about 220 ppm, and the most preferred concentration is from about 20 to about 200 ppm. The reaction is preferably carried out in 2 stages as described above.

In another embodiment of the invention, the polycarbonate can be modified by introducing a polymer colloid system into the reaction medium. Modifiable polycarbonates include, but are not limited to, homopolymers, copolymers, and mixtures thereof prepared by the reaction between dihydric phenols and carbonate precursors. Dihydric phenols that can be used to produce carbonates include, but are not limited to, bisphenol A, (2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxyphenyl)methane, 2,2-bis(4 -Hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3',5'-tetrachloro-4,4'- Dihydroxydiphenyl) propane, 2,2-(3,5,3′,5′-tetrabromo-4,4′-dihydroxydiphenyl)propane, (3,3′-dichloro-4, 4'-dihydroxydiphenyl)methane, and mixtures thereof. Branching agents useful in preparing the polycarbonates of the present invention include, but are not limited to, glycerin, pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric acid, and mixtures thereof. If a branching agent is used in the condensation reaction, the preferred amount of branching agent is in the range of 0.1 to 2.0 wt%, more preferably about 0.2 to 1.0 wt%, based on the total weight of the polyester.

In another embodiment of the present invention, the thermoplastic condensation polymer modified by incorporation into the polymer colloid system may include polyurethane. The modifiable polyurethanes comprise one or more diol residues and one or more di-isocyanante or di-isocyanates residues. The diol residues of polyurethanes are derived from diols including but not limited to: 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1, 3-cyclohexanediol, 1,4-cyclohexanediol, 2-cyclohexane-1,4-diol, 2-methyl-1,4-cyclohexanediol, 2-ethyl-1, 4-cyclohexanediol, 1,3-cycloheptanediol, 1,4-cycloheptanediol, 2-methyl-1,4-cycloheptanediol, 4-methyl-1,3-cycloheptanediol Diol, 1,3-Cyclooctanediol, 1,4-Cyclooctanediol, 1,5-Cyclooctanediol, 5-Methyl-1,4-Cyclooctanediol, 5-Ethyl-1 , 4-Cyclooctanediol, 5-Propyl-1,4-Cyclooctanediol, 5-Butyl-1,4-Cyclooctanediol, 5-Hexyl-1,4-Cyclooctanediol, 5 -Heptyl-1,4-cyclooctanediol, 5-octyl-1,4-cyclooctanediol, 4,4'-methylenebis(cyclohexanol), 4,4'-methylene Bis(2-methylcyclohexanol), 3,3'-methylenebis(cyclohexanol), 4,4'-ethylenebis(cyclohexanol), 4,4'-propylenebis (cyclohexanol), 4,4'-butylenebis(cyclohexanol), 4,4'-isopropylidenebis(cyclohexanol), 4,4'-isobutylenebis(cyclohexanol) , 4,4'-dihydroxydicyclohexyl, 4,4'-carbonylbis(cyclohexanol), 3,3'-carbonylbis(cyclohexanol), 4,4'-sulfonylbis(cyclohexanol) ), 4,4'-oxybis(cyclohexanol), and mixtures thereof.

The polyurethanes of the present invention can be prepared by bringing together polyisocyanate, chain extender and optionally high molecular weight polyol by any known method in the presence or absence of a solvent. This includes manual or mechanical mixing measures, including casting, reaction extrusion, reaction injection molding and related methods. Typical preparation methods useful in the present invention are disclosed in US Pat. Nos. 4,376,834 and 4,567,236, which are incorporated herein by reference, the disclosures of the various ingredients and preparation procedures for producing polyurethane plastics.

The mixing of the reactants can be carried out at room temperature, that is, at a temperature of 20°C to 25°C. The obtained mixture is preferably heated to a temperature of 40°C to 130°C, more preferably 50°C to 100°C; preferably, one or more of the reactants are heated to the above temperature range before being blended.

A catalyst may optionally be included in the reaction mixture used to prepare the polyurethane. Any catalyst conventional in the art for catalyzing the reaction between isocyanates and active hydrogen-containing compounds can be used for this purpose. Suitable catalysts are disclosed in US Patent 4,202,957, column 5, lines 45-67, which is hereby incorporated by reference. The catalyst is preferably used in an amount of about 0.02-2.0 wt% based on the total weight of the reactants. In a particular embodiment of the one-step process, the reaction is carried out in a continuous manner using equipment and procedures such as those disclosed in US Patent No. 3,642,964.

The polyurethanes of the present invention include both thermoplastic injection moldable and thermosetting resins. Thermoplastic resins are prepared using essentially difunctional polyisocyanates with difunctional chain extenders and polyols with a functionality preferably not exceeding 4, although higher functionality polyols can be used at low weight ratios . Those skilled in the art understand that this range will vary with the nature of the polyol, the molecular weight of the polyol and the amount of polyol used. Generally, the higher the molecular weight of the polyol, the higher the functionality allowed without loss of thermoplasticity of the polyurethane product.

The diisocyanate residue may be derived from groups including but not limited to diisocyanates derived from: methylene bis(phenylisocyanate), including 4,4'-isomer, 2,4'-isomer and Mixtures thereof, m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, α,α-xylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and the latter two isomers Mixtures, benzylidine diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate and the like, cycloaliphatic diisocyanates such as methylene bis(cyclohexyl isocyanate), Including 4,4'-isomers, 2,4'-isomers and their mixtures and all their geometric isomers, including trans/trans, cis/trans, cis/cis and their mixtures, cyclohexylene di Isocyanate (1,2-, 1,3- or 1,4-), 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2,4-cyclohexylene diisocyanate, 1- Methyl-2,6-cyclohexyl diisocyanate, 4,4'-isopropylidene bis(cyclohexyl isocyanate), 4,4'-diisocyanatodicyclohexyl and all geometric isomers and mixtures thereof . Various modifications of methylene bis(phenylisocyanate) are also included. The latter refers to those modified forms of methylene bis(phenylisocyanate) that have been treated so as to remain stable liquids at room temperature. Such products include those obtained by reaction with small amounts (up to about 0.2 equivalents per equivalent of polyisocyanate) of aliphatic diols or mixtures of aliphatic diols, such as those described in U.S. Patent Nos. Modified methylene bis(phenyl isocyanate) in.

Modified methylene bis(phenylisocyanates) also include those that have been treated to convert a small proportion of the diisocyanate to the corresponding carboimide, which then interacts with additional diisocyanate to form aerated-imide. The amine groups thereby render the product a stable liquid at room temperature, as described, for example, in US Patent 3,384,653. Mixtures of any of the above polyisocyanates, if desired, may also be used. Furthermore, in the case of the preparation of thermosetting polyurethanes according to the invention, it is possible to introduce small amounts (up to 30% by weight) of polymethylene polyphenyl polyisocyanates into the polyisocyanate component used in the reaction. The latter is a mixture comprising about 20 to 90% by weight of methylene bis(phenylisocyanate), while the remainder of the mixture is polymethylene polyphenyl polyisocyanate having a functionality greater than 2.0. Such polyisocyanates and methods for their preparation are well known in the art; see, for example, US Patents 2,683,730, 2,950,263, 3,012,008, and 3,097,191. Branching agents useful in preparing the polyurethanes of the present invention include, but are not limited to, glycerin, pentaerythritol, trimellitic anhydride, pyromellitic dianhydride, tartaric acid, and mixtures thereof. If a branching agent is used in the condensation reaction, it is preferred that the branching agent be used in an amount ranging from 0.1 to 2.0 wt%, more preferably from about 0.2 to 1.0 wt%, based on the total weight of the polyester.

Other ingredients may also optionally be added to the compositions of the present invention to enhance the properties of the polycondensate/latex polymer matrix. For example, surface lubricants, anti-cashing agents, stabilizers, antioxidants, UV absorbers, mold release agents, metal deactivators, colorants such as black iron oxide and carbon black, nucleating agents, phosphate ester stabilizers, Zeolites, fillers, mixtures thereof, and the like can be included. All these additives and their use are well known in the art. Any of these compounds can be used as long as they do not impair the present invention to achieve its purpose.

End uses of the polycondensate compositions prepared according to the present invention include impact-modified polymers, elastomers, high-barrier films and coatings, polymers with improved barrier properties, and polymers with improved mechanical properties, such as improved tensile strength, fracture Improved elongation, improved weathering resistance and improved flexural strength. Other end uses include engineering resins, coatings, containers for barriers, and molded plastics. In addition, powder coatings can also be prepared from the modified polycondensates produced according to the invention. The polymers produced according to the invention can be used in thermoplastic engineering resins, elastomers, films, sheets and container plastics.

In a preferred embodiment, an impact modified polyester is prepared comprising a non-core-shell first polymer derived from a polymer colloid system. In another preferred embodiment, a hydroxy-functional polyester coating is prepared comprising a non-core-shell first polymer derived from a polymer colloid system.

In one embodiment of the present invention, modified polycondensates include, but are not limited to, impact-modified plastics prepared from a polymer colloid system comprising a non-core-shell polymer first polymer and polycondensates. The polymer colloids in this embodiment have a Tg of less than 40°C, while the condensation polymers have a Tg of greater than 40°C. The impact-modified plastic is preferably prepared from a polymer colloid system comprising a first polymer comprising residues of the following compounds: 2-ethylhexyl acrylate, butyl acrylate, isoprene, butadiene , lauryl acrylate, acrylonitrile, vinylidene chloride or mixtures thereof.

In another embodiment of the present invention, modified condensation polymers, including but not limited to thermoplastic elastomers, are prepared from a polymer colloid system comprising a non-core-shell polymer first polymer. The polymer colloids in this embodiment have a Tg greater than 40°C; whereas the condensation polymer has a Tg less than 40°C, and is preferably substantially non-crystalline. The thermoplastic elastomer is preferably prepared from a polymer colloid system comprising a first polymer comprising residues of the following compounds: vinyl chloride, styrene, alpha-methylstyrene, methyl methacrylate, vinyl naphthalene , isobornyl methacrylate or mixtures thereof.

Elastomers are gaining increasing use, especially the thermoplastic elastomers (TPE types) described below, which are elastomers at service temperatures but can be processed as plastics at appropriate temperatures (e.g., injection molding, extrusion molding) . Elastomers can be prepared by the method of the present invention. For example, amorphous and low Tg polycondensates can be viscous fluids and cannot be used as plastics or elastomers. The low Tg viscous polymers can however be used to make elastomers by adding a second polymer in the form of a polymer colloid system which acts as a physical crosslinker and serves as a bonding agent for the viscous polymer chains. point. A phase separated polymer blend with elastomeric properties will then result.

Example

The examples given below are intended to provide those skilled in the art with a comprehensive disclosure and description of how to prepare and evaluate the material composition and method required by the application, and are not intended to limit the scope of the invention identified by the inventor. Every effort has been made to be precise about various numbers (such as quantity, temperature, etc.), but some errors and deviations are still inevitable. Unless indicated otherwise, parts are by weight; temperature is in °C; otherwise, is at room temperature; pressure is at or near atmospheric.

The materials and test procedures used in the results given in this paper are as follows:

Intrinsic viscosity (Ih.V.) is measured at 25°C using a solution of 0.50 g of sample in 100 mL of 60/40 (by weight) phenol/tetrachloroethane.

The molecular weight distribution was determined by gel permeation chromatography (GPC). A solution was prepared by dissolving 4 mg of polymer in 30/70 (by weight) hexafluoroisopropanol/dichloromethane containing 10% by volume toluene as a flow rate marker. The system was calibrated using a series of narrow molecular weight distribution polystyrene standards. Molecular weights are given as absolute molecular weight values determined using a set of Mark-Houwink constants related to PET versus polystyrene.

Thermal transitions were determined using differential scanning calorimetry (DSC) on a DuPont Instruments 2200 DSC. The percent crystallinity was also determined by DSC. DSC was performed at a scan rate of 20°C/min after the sample was heated above its melting temperature and rapidly quenched below its glass transition temperature.

Films are prepared from dried polymers by compression molding. Drying was accomplished overnight in a vacuum oven at 120°C (20 mmHg). The dry polymer was compression molded as follows: On a Pasadena Hydraulics press, between 2 metal plates with a 15 mil backing and Tm + 30-50°C, into a 6" x 6" film . Gradually increase the pressure to a final pressure of 15,000 plunger force pounds within 2 minutes and maintain it for 1 minute. After compression molding, the films were quickly quenched by immersion in an ice bath. Instrumented film impact tests were performed in accordance with ASTM method D3763 "Determination of High Speed Puncture Properties of Plastics Using Load and Displacement Transducers". The test was carried out at 23°C on a CeastFractovic testing machine. The film thickness ranges from 0.33 to 0.38mm. The film was placed over a hole with an inner diameter of 76 mm, and at the same time, the film was impacted by a weight 0.5 inch in diameter moving at a speed of 11.1 ft/s. If the film shattered or broke into pieces, it was rated as brittle failure, whereas if a hole was created in the film, it was recorded as ductile failure.

Transmission Electron Microscopy (TEM). Cross-sectional thin sections were prepared on a Cryo-Ultramicrotome operated at -105°C. Thin sections were observed under a Philips CM12 TEM operating at 80 kV. The control was neutral, unstrained.

Light Microscopy. Thin sections were prepared at -60°C and observed with a Zeiss optical microscope. Example 1

Add 300 g of ethylene glycol and 2.33 g of Hitenol A-10, a polymerizable, polyoxyethylene alkylphenyl ether ammonium sulfate, to a 1 L jacketed reactor equipped with a condenser, nitrogen purge, and stirrer. Manufactured by DKS International. The contents of the reactor were heated to 80°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 118.75 g 2-ethylhexyl acrylate, 6.25 g trimethylolpropane triacrylate, and 3.60 g Hitenol A-10 was prepared. 12.85 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 3.0 g sodium persulfate in 15 g water was added to the reactor. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The rest of the monomer mixture was fed to the reactor over 39 min. Simultaneously with the addition of the monomers to the reactor, a solution of 1.50 g of sodium persulfate in 50 g of water was added to the reactor. After all monomer addition was complete, the reaction was held at 80°C for an additional 1 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. After drying, 0.815 g of grounds were collected on the screen. The solids content of the latex was determined using a CEM microwave dryer and was found to contain 28.1% solids. The effective diameter measured by dynamic light scattering was 181 nm. Example 2

Add 300 g of ethylene glycol and 2.3 g of Hitenol A-10 to a 1 L jacketed reactor equipped with a condenser, nitrogen purging and a stirrer. The contents of the reactor were heated to 70°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 118.75 g 2-ethylhexyl acrylate, 6.25 g trimethylolpropane triacrylate, and 3.60 g Hitenol A-10 was prepared. 12.85 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a suspension of 3.0 g of azobisisovalerate in 15 g of ethylene glycol was added to the reactor. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 58 min. After all monomer addition was complete, the reaction was held at 70°C for an additional 1.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. After drying, 0.741 g of crushed residue was collected on the screen. The solids content of the latex was determined using a CEM microwave dryer and found to contain 27.6% solids. The effective diameter measured by dynamic light scattering was 122 nm. Example 3

Add 272g of ethylene glycol, 0.839g of sodium formaldehyde sulfoxylate and 5.04g of Hitenol A-10 into a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer/surfactant consisting of 132.81 g 2-ethylhexyl acrylate, 6.99 g trimethylolpropane triacrylate, 35.66 g ethylene glycol, and 2.88 g Hitenol A-10 agent mixture. 17.8 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.777 g of 90 wt % tert-butyl hydroperoxide in 15 g of ethylene glycol was added to the reactor. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 58 min. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. After drying, 0.837 g of grounds were collected on the screen. The solids content of the latex was determined using a CEM microwave dryer and was found to contain 25.2% solids. The effective diameter determined by dynamic light scattering was 126 nm. Example 4

To a 1 L jacketed reactor equipped with a condenser, nitrogen purge and stirrer was added 379.25 g of ethylene glycol and 24.65 g of Disponil FES 77, which is an alkyl ethoxylated sodium sulfate, (30% active aqueous solution), manufactured by Henkel. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer/surfactant consisting of 191.55 g 2-ethylhexyl acrylate, 22.54 g styrene, 11.27 g allyl methacrylate, 47.89 g ethylene glycol, and 14.09 g DisponilFES77 agent mixture. 28.7 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.751 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.255 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.901 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.501 g of 90 wt% tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.5% solids and had a particle size of 184 nm as determined by dynamic light scattering. Example 5

Add 396.01g ethylene glycol and 7/89g Hitenol HS-20 polymerizable polyoxyethylene alkylphenyl ether ammonium sulfate to a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator, supplied by DKS Manufactured by international companies. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 112.68 g 2-ethylhexyl acrylate, 112.68 g vinyl acetate, 57.46 g ethylene glycol, and 4.51 g Hitenol HS-20 was prepared. 28.7 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor to re-equilibrate, a solution of 0.751 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.255 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.901 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.501 g of 90 wt% tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 23.18% solids and had a particle size of 114 nm as determined by dynamic light scattering. Example 6

Add 396.01g of ethylene glycol and 7.89g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 169.01 g n-butyl acrylate, 4.507 g Hitenol HS-20 was prepared. 28.7 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.751 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.255 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.901 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.501 g of 90 wt% tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.5% solids and had a particle size of 102 nm as determined by dynamic light scattering. Example 7

Add 396.01g of ethylene glycol and 7.89g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500-mL flask, prepare a mixture consisting of 169.01 g of 2-ethylhexyl acrylate, 45.07 g of methyl methacrylate, 11.27 g of allyl methacrylate, 57.46 g of ethylene glycol, and 4.51 g of Hitenol HS-20. Monomer/Surfactant Mixture. 28.7 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.71 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.255 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.901 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.501 g of 90 wt% tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.0% solids and had a particle size of 140 nm as determined by dynamic light scattering. Example 8

Add 267.5g of ethylene glycol and 1.74g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. A monomer/ Surfactant mixture. 44.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 1.16 g of 90 wt % t-butyl hydroperoxide (t-BHP) in 9 g of ethylene glycol was added to the reactor, followed by 0.348 g of sodium formaldehyde sulfoxylate (SFS ) in 9 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The rest of the monomer mixture was fed into the reactor over 220 min. At the same time, a solution of 1.391 g of SFS in 22 g of distilled water was added to the reactor. A solution of 0.773 g of 90 wt % tert-butyl hydroperoxide in 44 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The resulting emulsion contained 41.78% solids and had a particle size of 337 nm as determined by dynamic light scattering. Example 9

Add 267.5g ethylene glycol and 7.85g Hitenol HS-20, 0.0898g 1wt% ferric ammonium sulfate aqueous solution and 0.449g 1% ethylenediamine to a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator Aqueous solution of tetraacetic acid. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer consisting of 190.82 g 2-ethylhexyl acrylate, 22.45 g styrene, 11.2 g allyl methacrylate, 57.25 g ethylene glycol, and 4.49 g Hitenol HS-20 /surfactant mixture. 28.8 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 1.25 g of 90 wt % tert-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.449 g of d-isoascorbic acid in 11 g of ethylene glycol solution in. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 1.247 g of d-isoascorbic acid in 22 g of ethylene glycol was added to the reactor. A solution of 0.773 g of 90 wt % tert-butyl hydroperoxide in 44 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The resulting emulsion contained 27% solids and had a particle size of 127 nm as determined by dynamic light scattering. Example 10

Add 424.7g 75wt% propylene glycol aqueous solution and 7.78g Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a single mixture consisting of 188.9 g of 2-ethylhexyl acrylate, 22.22 g of styrene, 11.11 g of allyl methacrylate, 56.67 g of 75 wt% aqueous propylene glycol, and 4.44 g of Hitenol HS-20 was prepared. body/surfactant mixture. 28.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 1.73 g of 90 wt % tert-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.95 g of SFS in 22 g of distilled water was added to the reactor. A solution of 0.741 g of 90 wt% tert-butyl hydroperoxide in 44 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.1% solids and had a particle size of 196 nm as determined by dynamic light scattering. Example 11

Add 424.7g 50:50 (weight ratio) propylene glycol:ethylene glycol mixture and 7.78g Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a mixture of 188.9 g 2-ethylhexyl acrylate, 22.22 g styrene, 11.11 g allyl methacrylate, 56.67 g 50:50 (by weight) propylene glycol:ethylene glycol mixture, and Monomer/surfactant mixture consisting of 4.44 g Hitenol HS-20. 28.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 1.73 g of tert-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS) in 11 g of solution in distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.95 g of SFS in 22 g of distilled water was added to the reactor. A solution of 0.741 g of 90 wt% tert-butyl hydroperoxide in 44 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.6% solids and had a particle size of 332 nm as determined by dynamic light scattering. Example 12

Add 394.05g of 75wt% diethylene glycol aqueous solution and 1.15g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a mixture consisting of 195.22 g of 2-ethylhexyl acrylate, 22.97 g of styrene, 11.48 g of allyl methacrylate, 58.56 g of 75 wt% diethylene glycol in water, and 4.59 g of Hitenol HS-20 monomer/surfactant mixture. 29.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.984 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of 75 wt% diethylene glycol in water was added to the reactor, followed by 0.689 g of formaldehyde sulfoxylate A solution of sodium (SFS) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 1.605 g of SFS in 28 g of distilled water was added to the reactor. A solution of 2.297 g of 90 wt % tert-butyl hydroperoxide in 56 g of 75 wt % diethylene glycol in water was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 25.6% solids and had a particle size of 302 nm as determined by dynamic light scattering. Example 13

Add 394.05g of a 50:50 weight ratio diethylene glycol: ethylene glycol mixture and 1.15g Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a mixture of 195.22 g of 2-ethylhexyl acrylate, 22.97 g of styrene, 11.48 g of allyl methacrylate, 58.56 g of a 50:50 weight ratio diethylene glycol:ethylene glycol mixture, and Monomer/surfactant mixture consisting of 4.59 g Hitenol HS-20. 29.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.984 g of 70 wt % t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.689 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 1.608 g of SFS in 28 g of distilled water was added to the reactor. A solution of 2.297 g of 70 wt % tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the latex, as determined by dynamic light scattering, was 497 nm. Example 14

Add 75.70g of 50wt% tripropylene glycol aqueous solution and 4.49g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500-mL flask, a mixture consisting of 190.65 g of 2-ethylhexyl acrylate, 22.43 g of styrene, 11.21 g of allyl methacrylate, 376.94 g of 50 wt % aqueous tripropylene glycol, and 6.73 g of Hitenol HS-20 was prepared. Monomer/Surfactant Mixture. 29.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.984 g of t-butyl hydroperoxide (t-BHP) in 11 g of 50 wt % aqueous tripropylene glycol was added to the reactor, followed by 0.689 g of sodium formaldehyde sulfoxylate (SFS ) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 1.608 g of SFS in 28 g of distilled water was added to the reactor. A solution of 2.297 g of 70 wt % tert-butyl hydroperoxide in 56 g of 50 wt % aqueous tripropylene glycol was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the latex, as determined by dynamic light scattering, was 144 nm. Example 15

Add 322.13g of 75wt% ethylene glycol aqueous solution and 26.71g of Disponil FES 77 surfactant to a 1L jacketed reactor equipped with condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer mixture was prepared consisting of 307.69 g 2-ethylhexyl acrylate, 34.19 g styrene. 34.19 g of this monomer mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.76 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 8.8 g of a 75% ethylene glycol/water mixture was added to the reactor, followed by 0.34 g of formaldehyde. A solution of sodium sulfoxylate (SFS) in 11 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 1.03 g of SFS and 22.79 g of Disponil FES77 surfactant in 22 g of distilled water was added to the reactor. A solution of 0.76 g of 90 wt% tert-butyl hydroperoxide in 44 g of 75% ethylene glycol/water solution was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 45% solids and had a particle size of 63 nm as determined by dynamic light scattering. Example 16

Add 395.38g of 50wt% cyclohexanedimethanol (CHDM) aqueous solution and 5.70g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 193.73 g 2-ethylhexyl acrylate, 34.19 g styrene, 58.12 g 50 wt% aqueous CHDM, and 4.56 g Hitenol HS-20 was prepared. 29.1 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of 50 wt% aqueous CHDM was added to the reactor, followed by 0.0.23 g of sodium formaldehyde sulfoxylate (SFS) solution in 11.2 g distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.50 g 90 wt % tert-butyl hydroperoxide in 56 g 50 wt % CHDM aqueous solution was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the latex, as determined by dynamic light scattering, was 225 nm. Example 17

To a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer, 395.38g of a 25wt% solution of cyclohexanedimethanol (CHDM) in ethylene glycol and 5.70g of HitenolHS-20 were added. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 193.73 g 2-ethylhexyl acrylate, 34.19 g styrene, 58.12 g 25 wt% CHDM in EG, and 4.56 g Hitenol HS-20 was prepared. 29.1 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11 g of 25% CHDM in EG was added to the reactor, followed by 0.0.23 g of formaldehyde sulfoxylate A solution of sodium hydrogen (SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90 wt% tert-butyl hydroperoxide in 56 g of 25% CHDM in EG was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 28% solids and had a particle size of 310 nm as determined by dynamic light scattering. Example 18

Add 395.38g 60wt% neopentyl glycol (NPG) aqueous solution and 5.70g Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a mixture of 186.89 g 2-ethylhexyl acrylate, 27.35 g styrene, 6.84 g allyl methacrylate, 6.84 g methacrylic acid, 58.12 g 60 wt% aqueous NPG and 4.56 g Hitenol A monomer/surfactant mixture consisting of HS-20. 29.1 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of t-butyl hydroperoxide (t-BHP) in 11 g of 50 wt% NPG in water was added to the reactor, followed by 0.0.23 g of sodium formaldehyde sulfoxylate (SFS ) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g 90 wt % t-butyl hydroperoxide in 56 g 60 wt % NPG aqueous solution was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the latex, as determined by dynamic light scattering, was 691 nm. Example 19

To a 1 L jacketed reactor equipped with a condenser, nitrogen purge and stirrer, 392.54 g of a 75 wt % aqueous solution of ethylene glycol and 11.29 g of Tergitol 15-S-40, which is an ethoxylate of a secondary alcohol (70 wt% aqueous solution), manufactured by Union Carbide Corporation. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 203.20 g 2-ethylhexyl acrylate, 22.58 g styrene, 58.64 g 75 wt% EG in water, and 6.45 g Tergitol 15-S-40 was prepared. 28.79 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.50 g of 90 wt % t-butyl hydroperoxide (t-BHP) in 11 g of 75 wt % aqueous ethylene glycol was added to the reactor, followed by 0.23 g of formaldehyde sulfoxylate A solution of sodium (SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.50 g of 90 wt % tert-butyl hydroperoxide in 56 g of 75 wt % aqueous ethylene glycol was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the latex, as determined by dynamic light scattering, was 118 nm. Example 20

Add 229.91g of ethylene glycol and 3.62g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator, and then add 0.72g of 1% ferrous ammonium sulfate aqueous solution. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 65.02 g isoprene, 62.48 g styrene, and 2.60 g methacrylic acid was prepared. 14.17 g of styrene and 0.29 g of methacrylic acid were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.21 g of 70 wt% t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.14 g of sodium formaldehyde sulfoxylate (SFS ) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. After waiting 30 min for the styrene/methacrylic acid reaction, the monomer mixture was fed into the reactor within 150 min. At the same time, a solution of 0.72 g of SFS in 52.50 g of distilled water was added to the reactor. A solution of 1.02 g of 70 wt% tert-butyl hydroperoxide in 52.5 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 18% solids and had a particle size of 109 nm as determined by dynamic light scattering. Example 21

Add 338.66g of 1,4-butanediol (1,4-BD), 127.56g of aqueous solution and 7.90g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 191.91 g 2-ethylhexyl acrylate, 22.58 g styrene, 11.29 g allyl methacrylate, and 4.52 g Hitenol HS-20 was prepared. 23.03 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.65 g of tert-butyl hydroperoxide (t-BHP) in 9.03 g of 1,4-BD was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate ( SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.65 g of 90 wt % tert-butyl hydroperoxide in 45.16 g of 1,4-BD was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 28% solids and had a particle size of 174.9 nm as determined by dynamic light scattering.

Table I example continuous phase monomer Surfactant Initiator reducing agent 1 EG 2-EHA, TMPTA Hitenol A-10 NaPS - 2 EG 2-EHA, TMPTA Hitenol A-10 ABVA - 3 EG 2-EHA, TMPTA Hitenol A-10 t-BHP SFS 4 EG 2-EHA, styrene, ALMA FES 77 t-BHP SFS 5 EG 2-EHA, Vac Hitenol HS-20 t-BHP SFS 6 EG Styrene, BA, ALMA Hitenol HS-20 t-BHP SFS 7 EG MAA, 2-EHA, ALMA Hitenol HS-20 t-BHP SFS 8 EG 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 9 EG 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP IAA 10 PG/H ₂ O 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 11 PG/EG 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 12 DEG/H ₂ O 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 13 DEG/EG 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 14 TPG/H ₂ O 2-EHA, styrene, ALMA Hitenol HS-20 t-BHP SFS 15 EG/H ₂ O 2-EHA, styrene FES 77 t-BHP SFS 16 CHDM/H ₂ O 2-EHA, styrene Hitenol HS-20 t-BHP SFS 17 CHDM/EG 2-EHA, styrene Hitenol HS-20 t-BHP SFS 18 NPG/H ₂ O 2-EHA, styrene, MAA Hitenol HS-20 t-BHP SFS 19 EG/H ₂ O 2-EHA, styrene Tergitol 15-S-40 t-BHP SFS 20 EG Styrene, Isoprene, MAA Hitenol HS-20 t-BHP SFS twenty one 1, 4BD/H ₂ O 2-EHA, styrene, MAA Hitenol HS-20 t-BHP SFS

Modified Polycondensate Example 22 (Comparative Example)

PET homopolymer was prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97 g), ethylene glycol (1.0 mol, 62 g) and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere nitrogen atmosphere. The mixture was heated with stirring at 200 °C for 1 h, then at 210 °C for 3 h. The temperature was increased to 280°C, the nitrogen flow was stopped, and a vacuum was applied. The polymer was stirred under vacuum (0.2-0.3 Torr) for 1 h. The polymer is cooled and ground. After grinding, a part of the polymer was melted and compression molded into a polymer film that can be used for physical property determination. Characteristic data are presented in Table 2. Example 23

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97 g), ethylene glycol (10 mol, 62 g) and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere. The mixture was heated with stirring at 200 °C for 1 h, then at 210 °C for 3 h. The temperature was raised to 275°C and held for 30 minutes. The nitrogen flow was stopped, followed by vacuum (5 torr) for 5 min. Thereafter, the polymerization temperature was lowered to 240°C and the pressure was raised to 300 Torr. 1 mL of the emulsion of Example 1 was syringed into the polymerization flask, which was then dispersed into the polymer melt. The temperature was raised to 275°C while the pressure was reduced to 10 Torr. After 5 min, the pressure was raised to 300 Torr and an additional 2 mL of the Example 1 emulsion was added. The vacuum was raised to 0.2-0.3 Torr within 45 minutes, and the stirring speed was reduced from 200 to 50 rpm. The melt appeared to be homogeneous but somewhat opaque. The heat and agitation were removed and the blend crystallized within 15 min as a white opaque solid. Allow the polymer to cool and grind. After grinding, a part of the polymer is melted and compression molded into a polymer film that can be used for physical property tests. Characteristic data are presented in Table 1. Transmission electron microscopy observations of melt compression molded films showed rubber particles dispersed in the polyester matrix. The particle size is in the range of 50-300nm. Example 24

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97 g), ethylene glycol (1.0 mol, 52 g), and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere. The mixture was heated with stirring at 200 °C for 1 h, then at 210 °C for 3 h. The temperature was raised to 280°C and held for 20 minutes. The nitrogen flow was stopped, followed by vacuum (5 torr) for 5 min. The pressure was raised to 300 Torr. 10 ml of the emulsion of Example 1 was syringed into the polymerization flask, which was then dispersed into the polymer melt. The vacuum was raised to 0.2-0.3 Torr within 60 minutes, and the stirring speed was reduced from 200 to 50 rpm. The melt appeared to be homogeneous but somewhat opaque. The heat and stirring were removed and the blend crystallized into a white opaque solid within 30 min. Allow the polymer to cool and grind. After grinding, a portion of the polymer was melted and compression molded into a polymer film that could be used for testing. Characteristic data are presented in Table 2. Transmission electron microscopy observations of melt compression molded films showed rubber particles dispersed in the polyester matrix. The particle size is in the range of 100-400nm.

Table 2: PET properties for impact modification using acrylate emulsions in EG PET 1% acrylate 3.5% acrylate nature polymer film polymer film polymer film Ih V.(dl/g) 0.61 0.58 0.64 0.60 0.73 0.67 Tch ₁ none 142 none 1334 none 135 Tm ₁ 254 ( _Hf = 12.82) 257 ( _Hf = 10.79) 250 ( _Hf = 11.56) 251 (H _f =9.08) 239 (H _f =8.40) 238 (H _f =7.31) _g 81 78 78 77 73 72 Tch ₂ 152 137 161 149 162 150 Tm ₂ 257 (H _f =9.89) 257 ( _Hf = 12.70) 252 ( _Hf = 10.20) 251 ( _Hf = 10.92) 240 (H _f =7.97) 240 (H _f =9.61) Tcc 161 193 158 178 none 154 Film% Xtal NT 7.84 NT 5.6 NT 2.68 M _n 12300 11600 12800 11800 13600 13000 M _w 39900 35900 40300 37500 49200 46400 M _z 67000 59800 64500 60600 81000 76400 Film Impact Resistance (ft-lbs) NT 2.36 NT 2.60 NT 2.74 failure mode - brittleness - toughness - toughness

NT: Not tested instance 25

Add 394.63g of water and 2.31g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 196.15 g butyl acrylate, 23.08 g styrene, 11.54 g allyl methacrylate, 58.85 g water, and 4.62 g Hitenol HS-20 was prepared. 29.4 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.77 g of tert-butyl hydroperoxide (t-BHP) in 11.2 g of distilled water was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS) at 11.2 g. g solution in distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.92 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90 wt % tert-butyl hydroperoxide in 56 g of water was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 28.5% solids and had a particle size of 63 nm as determined by dynamic light scattering. Example 26

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1.0 mol, 62.0 g), 15.0 g of the emulsion of Example 25 and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere middle. The mixture was heated with stirring at 200 °C under a slow nitrogen flow for 1 h, then at 210 °C for 2 h. The temperature was increased to 275°C. The nitrogen flow was stopped, and a vacuum was applied. The polymer was stirred under vacuum (0.1-0.3 Torr) for 60 min, then the stirring was stopped and the heat removed. Allow the polymer to cool and grind. The intrinsic viscosity is 0.50dl/g; Mw is 32,200g/mol; Tg is 86.0°C. Example 27

Add 395.93g of ethylene glycol (EG) and 7.90g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer/surfactant mixture consisting of 182.88 g 2-ethylhexyl acrylate, 31.61 g styrene, 11.29 g allyl methacrylate, 57.57 g EG, and 4.52 g HitenolHS-20 agent mixture. 28.79 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.50 g of 90% tert-butyl hydroperoxide (t-BHP) in 11.2 g of EG was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS) Solution in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.50 g of 90 wt % tert-butyl hydroperoxide in 56 g of EG was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 28.4% solids and had a particle size of 120 nm as determined by dynamic light scattering. Example 28

Blends were prepared according to the following procedure. Diphenyl carbonate (0.30 mol, 64.20 g), bisphenol A (0.30 mol, 68.40 g) and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was stirred and heated at 200°C under a slow nitrogen flow for 0.5h, then at 220°C for 20min, then at 24°C for 30min. 30min at 260°C. The temperature was increased to 280°C. At this point, 13.4 g of the emulsion of Example 27 was added slowly over 2 min through a 125 mL pressure equalizing funnel and heating continued at 280°C under nitrogen atmosphere. The vacuum was started, and the pressure in the flask decreased from 1 atmosphere to 0.35 Torr within 15 minutes. The temperature rises to 290°C within 30 minutes, then to 300°C for 1.5 hours, and then to 320°C for another 20 minutes. The heat and agitation were removed from the viscous melt and the polymer was allowed to cool. Tg is 135°C; intrinsic viscosity is 0.29dl/g. Particles with a particle size of up to 30 μm are dispersed in the polycarbonate matrix (observation by light microscopy). Example 29

Add 395.33g of ethylene glycol (EG) and 5.50g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer/surfactant mixture consisting of 194.84 g 2-ethylhexyl acrylate, 22.92 g styrene, 11.46 g allyl methacrylate, 47.89 g EG, and 3.44 g HitenolHS-20 agent mixture. 29.1 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of 90 wt% t-butyl hydroperoxide (t-BHP) in 11.2 g of EG was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS) Solution in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to a bluish white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90 wt% tert-butyl hydroperoxide in 56 g of EG was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 27.5% solids and had a particle size of 164 nm as determined by dynamic light scattering. Example 30

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), 1,4-cyclohexanedimethanol (0.75 mol, 108 g) and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere nitrogen atmosphere. The mixture was stirred and heated at 310° C. for 10 min under the protection of a slow nitrogen flow, and then the solution became homogeneous. Within 15 minutes, 30 g of the emulsion of Example 29 and 1.5 mL of defoamer DC-7 (Dow Corning) were added, and the reaction was heated for another 45 minutes under a nitrogen atmosphere. At this point, the vacuum was started, so the pressure was reduced to 200 Torr, then (within 1 min) the pressure was reduced to 0.3-0.5 Torr, followed by stirring for 1 h to obtain a viscous polymer solution. The heat was removed and the polymer was allowed to cool before grinding. Intrinsic viscosity was 0.65 dl/g; Tg was 91.4°C (2nd cycle); Tm was 274.4°C (2nd cycle). Example 31

Polymers were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), 1,4-butanediol (0.75 mol, 67.5 g) and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere nitrogen atmosphere. The mixture was stirred and heated at 200°C under the protection of a slow nitrogen flow for 1h, and then the temperature was raised to 255°C for 2h and kept at this temperature for 15min. At this point, the vacuum was started, so the pressure was reduced to 200 Torr, then (within 1 min) the pressure was reduced to 0.3-0.5 Torr, followed by stirring for 1 h to obtain a viscous polymer solution. The heat was removed and the polymer was allowed to cool before grinding. Intrinsic viscosity was 0.94 dl/g; Tg was 45.6°C (2nd cycle); Tm was 224.0°C (2nd cycle). Mn is 13,000; Mw is 35,400. Example 32

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), 1,4-butanediol (0.75 mol, 67.5 g) and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was stirred and heated at 200° C. under a slow nitrogen flow for about 15 min, and then 30 mL of the emulsion of Example 29 was added to the reaction vessel within 2 min. The reaction mixture was heated at 200 °C for an additional 45 min, then at 210 °C for an additional 2 h. The temperature was raised to 255° C., kept for 15 minutes, then vacuumed (200 Torr), and then (within 1 minute) the pressure was reduced to 0.3-0.5 Torr, followed by stirring for 1 hour to obtain a viscous polymer melt. The heat was removed and the polymer was allowed to cool before grinding. Intrinsic viscosity was 0.58 dl/g; Tg was 42.3°C (2nd cycle); Tm was 178.8°C (2nd cycle). Example 33

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1.0 mol, 62.0 g), and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was stirred and heated at 200°C for about 10 min under the protection of slow nitrogen flow until the mixture was homogeneous. 56.5 g of the emulsion of Example 27 were then added over 20 min using a 125 mL pressure equalization funnel. The reaction mixture was heated at 200 °C for an additional 45 min, then at 210 °C for an additional 2 h. The temperature was then raised to 280°C. At this moment, start vacuuming to reduce the pressure from 1 atmosphere to 0.3-0.5 Torr within 35 minutes, and then maintain it at 0.3-0.5 Torr for 45 minutes while stirring the viscous melt. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 200° C. for 15 s yielded a tough (brown) translucent film. Intrinsic viscosity was 0.59 dl/g; Tg was 28°C (2nd cycle). Particles with a particle size of up to 30 μm are dispersed in the polyester matrix (light microscope observation). Example 34

Add 406.17g of ethylene glycol (EG) aqueous solution and 4.58g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 206.11 g styrene, 22.90 g divinylbenzene, 68.70 g EG, and 4.58 g Hitenol HS-20 was prepared. 30.23 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of 90% t-butyl hydroperoxide (t-BHP) in 11.45 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate ( SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.69 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90% tert-butyl hydroperoxide in 34.35 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The emulsion contained 28.0% solids and had a particle size of 174 nm as determined by dynamic light scattering. Example 35

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1.0 mol, 62.0 g), and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was stirred and heated at 200°C under a slow nitrogen flow for 1 h, then at 210°C for 2 h. 56.5 g of the emulsion of Example 34 were then added over 17 min using a 125 mL pressure equalization funnel and the reaction mixture was warmed to 280°C. At this moment, the vacuum is started, and the pressure is reduced from 1 atmosphere to 0.3-0.5 Torr within 11 minutes. The pressure was then maintained at 0.3-0.5 Torr for 1 hour while the viscous melt was stirred. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 280 °C for 15 s to obtain a tough film. The intrinsic viscosity was 0.54 dl/g; Tg was 57°C (2nd cycle); Tm was 200°C (2nd cycle). Optical microscopy observations showed that the particles were agglomerated to a certain extent, with a maximum particle size of about 30 μm. Example 36

Add 406.17g of ethylene glycol (EG) aqueous solution and 4.58g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer consisting of 183.21 g 2-ethylhexyl acrylate, 18.32 g styrene, 27.48 g trimethylolpropane triacrylate, 68.70 g EG, and 4.58 g Hitenol HS-20 /surfactant mixture. 30.23 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of 90% t-butyl hydroperoxide (t-BHP) in 11.45 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate ( SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.69 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90 wt% tert-butyl hydroperoxide in 34.35 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. Example 37

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1.0 mol, 62.0 g), and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was heated with stirring at 200 °C under a slow nitrogen flow for 1 h, then at 210 °C for 2 h. 56.5 g of the emulsion of Example 36 were then added over 21 min using a 125 mL pressure equalization funnel and the reaction mixture was warmed to 280°C. At this moment, start vacuuming to reduce the pressure from 1 atmosphere to 0.3-0.5 Torr within 11 minutes, and then maintain the pressure at 0.3-0.5 Torr for 1 hour while stirring the viscous melt. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 280 °C for 15 s to obtain a tough film. The intrinsic viscosity was 0.66 dl/g; Tg was 51°C (2nd cycle); Tm was 200°C (2nd cycle). Optical microscopy observations showed that the particles were agglomerated to a certain extent, with a maximum particle size of about 30 μm. Example 38

Add 338.86g of 1,4-butanediol (1,4-BD), 127.56g of distilled water and 7.90g of Hitenol HS-20 into a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, a monomer/surfactant mixture consisting of 191.91 g 2-ethylhexyl acrylate, 22.58 g styrene, 11.29 g allyl methacrylate, and 4.52 g Hitenol HS-20 was prepared. 23.03 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.65 g of 70% tert-butyl hydroperoxide (t-BHP) in 9.03 g of 1,4-BD was added to the reactor, followed by 0.23 g of formaldehyde sulfoxylate A solution of sodium (SFS) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.65 g of 70 wt % tert-butyl hydroperoxide in 45.16 g of 1,4-BD was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the obtained latex was determined to be 175 nm by a dynamic light scattering method. Example 39

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.40 mol, 77.6 g), 1,4-butanediol (0.60 mol, 54.0 g) and catalyst metal were placed in a 0.5 L polymerization reactor under a nitrogen atmosphere of 1 atmosphere. The mixture was heated with stirring at 200°C under a slow nitrogen flow for 1 h, then at 210°C for 1 h. 51.8 g of the emulsion of Example 38 were then added over 36 min using a 125 mL pressure equalizing funnel and the reaction mixture was warmed to 255°C. At this point, start vacuuming to reduce the pressure from 1 atmosphere to 0.3-0.5 Torr within 10 minutes, and then maintain the pressure at 0.3-0.5 Torr for 1 hour while stirring the viscous melt. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 260°C for 15s to obtain a very tough film. The intrinsic viscosity was 0.58 dl/g; Tg was 25°C (2nd cycle); Tm was 220°C (2nd cycle). Optical microscopy observations showed that the particles were agglomerated to a certain extent, with a maximum particle size of about 30 μm. Example 40

Add 395.38g 60wt% neopentyl glycol (NPG) aqueous solution and 5.70g Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purging and agitator. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a mixture of 186.89 g 2-ethylhexyl acrylate, 27.35 g styrene, 6.84 g allyl methacrylate, 6.84 g methacrylic acid, 58.12 g 60 wt% aqueous NPG and 4.56 g Hitenol A monomer/surfactant mixture consisting of HS-20. 29.1 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of tert-butyl hydroperoxide (t-BHP) in 11 g of 60% aqueous NPG followed by 0.0.23 g of sodium formaldehyde sulfoxylate (SFS ) in 11.2 g of distilled water. After several minutes, the reactor was observed to change from clear to white with a bluish-white tinge, indicating the formation of small particles. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.51 g of 90 wt % tert-butyl hydroperoxide in 56 g of 60% NPG aqueous solution was added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the obtained latex was determined by the dynamic light scattering method to be a bimodal distribution at 691nm and 211nm respectively. Example 41

Add 496g of neopentyl glycol (NPG), 86g of trimethylolpropane (TMP) and 460g of resorcinol to a 2L reactor equipped with a steam jacketed condenser, a water-cooled condenser and a Dean-Stark trap. Formic acid (IPA). To this was added 250 g of the latex of Example 40 containing NPG. The reaction was heated to 150°C. After reaching 150°C, 1.5g Fastcat 4100 (tin catalyst) was added. After 1 h, the temperature was raised to 220 °C and maintained at this temperature for 3 h. A total of 140 mL of water was collected in the distillate. Subsequently, the reactor was cooled to 120°C, 477g of 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) was added, and the temperature was raised to 230°C. The reaction was maintained at 230 °C for 2.5 h, then cooled. A total of 241 mL of water (88% of theory) was collected over the course of the reaction. Then 325 g of xylene were added to the resin. The resin maintains the hazy nature of its latex. No signs of coagulation of the acrylic rubber were observed.

Enamels were prepared from latex-containing polyester resins and Resimene 745 (hexamethoxymethylmelamine). The resin/crosslinker weight ratio was 70/30. 0.3% pTSA was used as catalyst; 0.4% FC430 was used as flow aid. Drawdown films were prepared on Bonderite 1000 panels with a wire wound bar coater. The board was baked at 160°C for 30 minutes. The coating had more than 500 methyl ethyl ketone (MEK) double rubs, indicating good cure. Example 42 (prediction example)

Blends were prepared according to the following procedure. Dimethyl glutarate (1 mol), ethylene glycol (1.5 mol), diethylene glycol (0.5 mol), and titanium tetraisopropoxide (100 ppm, based on final polymer weight) were placed under 1 atmosphere of nitrogen 0.5L polymerization reactor. The mixture was stirred and heated at 200°C for about 10 min under the protection of slow nitrogen flow until the mixture became homogeneous. Within 20min, 100g of poly(styrene (95mol%)-co-glycidyl methacrylate (5mol%)) emulsion based on ethylene glycol was added to the reaction, and heated at 200°C for 45min, 210°C Under 2h, then the temperature was raised to 250°C. At this moment, start vacuuming to reduce the pressure from 1 atmosphere to 0.3-0.5 Torr within 35 minutes, and then maintain the pressure at 0.3-0.5 Torr for 45 minutes while stirring the viscous melt. The heat was removed and the polymer was allowed to cool. The elastomeric polymer is isolated.

Above, the present invention has been described in detail in terms of specific preferred embodiments of the present invention, but it should be understood that various changes and modifications can be made within the spirit and scope of the present invention. Example 43

Add in the 1L jacketed reactor that is equipped with condenser, nitrogen purging and stirrer, 341.88g ethylene glycol and 37.99g 15wt% Rhodafac RE-610 (phosphate ester surfactant, Rhone. Planck provides) . The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a monomer/ Surfactant mixture. 30.39 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.51 g of t-butyl hydroperoxide (t-BHP) in 11 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate (SFS) in 11.2 g of solution in distilled water. After several minutes, the reactor was observed to change from off-white to white with a bluish tinge, indicating particle formation. The remainder of the monomer mixture was fed to the reactor over 215 min. At the same time, a solution of 0.68 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.65 g of 70 wt % tert-butyl hydroperoxide in 45.6 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature. The obtained latex was filtered through a 100 mesh screen. Example 44

Urethane/acrylic composites were prepared according to the following procedure. To a 50 mL flask was added 14.61 g of methylenebis(4-cyclohexylisocyanate) and 5.75 g of the latex of Example 43. The catalyst dibutyltin diacetate (0.1 g) was added to the mixture. Within 1 h, the reaction was exothermic and produced a rigid latex-containing polymer foam. Example 45

Add 395.93g of ethylene glycol and 7.90g of Hitenol HS-20 to a 1L jacketed reactor equipped with a condenser, nitrogen purge and stirrer. The contents of the reactor were heated to 65°C. In a separate 500 mL flask, prepare a mixture of 180.62 g of 2-ethylhexyl acrylate, 22.58 g of styrene, 11.29 g of allyl methacrylate, 11.29 g of methacrylic acid, 4.52 g of HitenolHS-20, and 57.57 g of ethylene glycol Monomer/surfactant mixture composed of alcohols. 28.79 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.50 g of 90 wt % tert-butyl hydroperoxide (t-BHP) in 11.2 g of ethylene glycol was added to the reactor, followed by 0.23 g of sodium formaldehyde sulfoxylate ( SFS) in 11.2 g of distilled water. After a few minutes, the reactor was observed to change from a pale off-white to white with a bluish tinge, indicating particle formation. The remainder of the monomer mixture was fed to the reactor over 195 min. At the same time, a solution of 0.65 g of SFS in 28 g of distilled water was added to the reactor. A solution of 0.50 g of 90 wt % tert-butyl hydroperoxide in 56 g of ethylene glycol was then added to the reactor. After all monomer addition was complete, the reaction was held at 65°C for an additional 0.5 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The particle size of the obtained latex was determined to be 100 nm by a dynamic light scattering method. Example 46

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.32 mol, 61.9 g), 56.5 g of the latex of Example 45, and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere of nitrogen. The mixture was heated with stirring at 200 °C under a slow nitrogen flow for 1 h, then at 210 °C for 2 h. At this point, the temperature of the reaction mixture was raised to 280°C, and then a vacuum was started to reduce the pressure from 1 atm to 0.2-0.5 Torr in 11 minutes, and the pressure was then maintained at 0.3-0.5 Torr for 1 hour while the viscous melt was stirred. The heat was removed and the polymer was allowed to cool before grinding. The intrinsic viscosity of the polymer was 0.35 dl/g. Example 47

To a 2L jacketed reactor equipped with a condenser, nitrogen purge, and stirrer, 515.76 g of ethylene glycol, 164.80 g of water, and 12.28 g of 70 wt % Tergitol 15-S-40 (a nonionic product manufactured by Union Carbide) were added. surfactant) solution. The contents of the reactor were heated to 85°C. In a separate 1500-mL flask, a monoalcohol mixture consisting of 325.65 g of 2-ethylhexyl acrylate, 17.19 g of trimethylolpropane triacrylate, 7.37 g of 70% Tergitol 15-S-40, and 103.2 g of ethylene glycol was prepared. body/surfactant mixture. 45.44 g of this monomer/surfactant mixture was added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.69 g of sodium persulfate in 17 g of water was added to the reactor. After several minutes, the reactor was observed to change from clear to a bluish-white tinge, indicating the formation of small particles. The rest of the monomer mixture was fed into the reactor over 90 min. Simultaneously with the addition of the monomers to the reactor, a solution of 1.72 g of sodium persulfate in 34 g of water was added to the reactor. After all the monomer had been added, the reaction was held at 85°C for an additional 1 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The effective diameter measured by dynamic light scattering was 194 nm. Example 48

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1 mol, 62.0 g) and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere nitrogen atmosphere. The mixture was heated with stirring at 200 °C under a slow nitrogen flow for 1 h, then at 210 °C for 2 h. The reaction temperature was raised to 280°C, then the nitrogen was turned off and vacuum started. After evacuation for 10 min (to 0.35 Torr), the vacuum was stopped and nitrogen was blown in to raise the pressure to atmospheric pressure, then 56.5 g of the latex of Example 47 was added over 20 min via a 125 mL pressure equalization funnel. Turn off the nitrogen again and apply vacuum. The pressure is maintained at 0.3-0.5 Torr for 1 hour while stirring the viscous melt. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 240 °C for 15 s to obtain a tough, opaque, white film. The intrinsic viscosity was 0.80 dl/g; Tg was 61.3°C (2nd cycle); Tm was 212.3°C (2nd cycle). TEM (Transmission Electron Microscopy) showed that rubber particles were dispersed in the polyester matrix with a particle size of 0.2-0.9 μm. Example 49

Add 656.7g of ethylene glycol and 26.86g of Disponil FES 77 (anionic surfactant, produced by Henkel) to a 2L jacketed reactor equipped with a condenser, nitrogen purging and agitator. The contents of the reactor were heated to 85°C. In a separate 1500 mL flask, prepare a monomer/surfactant consisting of 326.7 g 2-ethylhexyl acrylate, 17.19 g trimethylolpropane triacrylate, 103.2 g ethylene glycol, and 16.12 g Disponil FES 77 mixture. 46.3 g of this monomer/surfactant mixture were added to the heated reactor. After allowing the reactor contents to re-equilibrate, a solution of 0.69 g sodium persulfate in 16.8 g water was added to the reactor. After several minutes, the reactor was observed to change from clear to a bluish-white tinge, indicating the formation of small particles. The rest of the monomer mixture was fed into the reactor over 90 min. Simultaneously with the addition of the monomers to the reactor, a solution of 1.72 g of sodium persulfate in 33.6 g of water was added to the reactor. After all the monomer had been added, the reaction was held at 85°C for an additional 1 h, at which point the reactor was allowed to cool to room temperature.

The obtained latex was filtered through a 100 mesh screen. The effective diameter measured by dynamic light scattering was 155 nm. Example 50

Blends were prepared according to the following procedure. Dimethyl terephthalate (0.5 mol, 97.0 g), ethylene glycol (1 mol, 62.0 g) and catalyst metal were placed in a 0.5 L polymerization reactor under 1 atmosphere nitrogen atmosphere. The mixture was heated with stirring at 200 °C under a slow nitrogen flow for 1 h, then at 210 °C for 2 h. The reaction temperature was raised to 280°C, then the nitrogen was turned off and vacuum started. After evacuation for 10 min (to 0.35 torr), the vacuum was stopped and nitrogen was blown in to raise the pressure to atmospheric pressure, then 56.6 g of the latex of Example 49 were added over 10 min via a 125 mL pressure equalization funnel. Turn off the nitrogen again and apply vacuum. The pressure is maintained at 0.3-0.5 Torr for 1 hour while stirring the viscous melt. The heat was removed and the polymer was allowed to cool before grinding. Melt compression molding at 240 °C for 15 s to obtain a tough, opaque, white film. The intrinsic viscosity was 0.82 dl/g; Tg was 60.1°C (2nd cycle); Tm was 212.2°C (2nd cycle). TEM showed that the rubber particles were dispersed in the polyester matrix with a particle size of 0.2-0.9 μm.

Claims (120)

1. A method for preparing polycondensate/1st polymer matrix, comprising the following steps: (a) preparing a polymer colloid system comprising a first polymer dispersed in a continuous liquid phase; and (b) introducing the polymer colloid system into the condensation reaction medium, which can be carried out before or during the condensation reaction, wherein the condensation reaction medium comprises (1) diacid, diisocyanate, dialkyl carbonate, diaryl carbonate, Dihalocarbonates or mixtures of the above, Where the continuous liquid phase, the condensation reaction medium, or both contain the diol component, a polycondensate/first polymer matrix is formed. 2. The method of claim 1, wherein the continuous liquid phase comprises a diol component. 3. The method of claim 2, wherein the continuous liquid phase is 25 to 100 wt% diol component. 4. The method of claim 2, wherein the continuous liquid phase is 50 to 100 wt% diol component. 5. The method of claim 2, wherein the continuous liquid phase is 75 to 100 wt% diol component. 6. The method of claim 2, wherein the continuous liquid phase is 90 to 100 wt% diol component. 7. The method of claim 2, wherein the continuous liquid phase consists essentially of the diol component. 8. The method of claim 1, wherein the diol component comprises an aliphatic or cycloaliphatic diol or a mixture thereof of 2 to 10 carbon atoms. 9. The method of claim 1, wherein the diol component comprises ethylene glycol, 1,3-trimethylene glycol, 1,3-propanediol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, cis- or trans-cyclohexanedimethanol , cis- or trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, diethylene glycol or mixtures thereof. 10. The method of claim 1, wherein the diol component comprises ethylene glycol, propylene glycol, tripropylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, cis- or trans-cyclohexanedimethanol or a mixture thereof. 11. The method of claim 1, wherein the diol component comprises neopentyl glycol, ethylene glycol, cis- or trans-cyclohexanedimethanol, 1,4-butanediol, or mixtures thereof. 12. The method of claim 1, wherein the diol component is present in a continuous liquid phase, and the continuous liquid phase consists essentially of the diol component. 13. The method of claim 1, wherein the condensation reaction medium comprises a diol component. 14. The method of claim 1, wherein the first polymer comprises residues of ethylenically unsaturated monomers. 15. The method of claim 1, wherein the first polymer comprises non-acid vinyl monomers, acid vinyl monomers, or mixtures thereof. 16. The method of claim 1, wherein the first polymer comprises residues of the following non-acid vinyl monomers: acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, methyl acrylate, methyl Methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethyl methacrylate Hexyl ester, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, trimethylolpropane triacrylate, styrene , α-methylstyrene, glycidyl methacrylate, methacryloylcarbodiimide, C ₁ ~C ₁₈ alkyl crotonic acid, di-n-butyl maleate, α- or β-vinyl Naphthalene, Dioctyl Maleate, Allyl Methacrylate, Diallyl Maleate, Diallyl Malonate, Methoxybutenyl Methacrylate, Isomethacrylate Bornyl ester, hydroxybutenyl methacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl 1, 2-ethylene carbonate, epoxybutene, 3,4-dihydroxybutene, hydroxyethyl (meth)acrylate, methacrylamide, acrylamide, N-butylacrylamide, N-ethyl Acrylamide, butadiene, vinyl (meth)acrylate, isopropenyl (meth)acrylate, cycloaliphatic epoxy (meth)acrylate, ethyl formamide, 4-vinyl-1, 3-dioxolane-2-one, 2,2-dimethyl-4-vinyl-1,3-dioxolane (dioxolate) and 3,4-diacetoxy-1-butene or mixture. 17. The method of claim 1, wherein the first polymer comprises the residues of the following acid vinyl monomers: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, or mixtures thereof. 18. The method of claim 1, wherein the first polymer comprises 50-100% butyl acrylate. 19. The method of claim 1, wherein the first polymer comprises 50-100% isoprene. 20. The method of claim 1, wherein the first polymer comprises 50-100% butadiene. 21. The method of claim 1, wherein the first polymer comprises 50-100% acrylonitrile. 22. The method of claim 1, wherein the first polymer comprises 50-100% styrene. 23. The method of claim 1, wherein the first polymer comprises 50-100% 2-ethylhexyl acrylate. 24. The method of claim 1, wherein the first polymer comprises 80-100% butyl acrylate. 25. The method of claim 1, wherein the first polymer comprises 80-100% isoprene. 26. The method of claim 1, wherein the first polymer comprises 80-100% butadiene. 27. The method of claim 1, wherein the first polymer comprises 80-100% acrylonitrile. 28. The method of claim 1, wherein the first polymer comprises 80-100% styrene. 29. The method of claim 1, wherein the first polymer comprises 80-100% 2-ethylhexyl acrylate. 30. The method of claim 1, wherein the first polymer comprises residues of the following monomers: acrylate, methacrylate, styrene, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, butadiene, Isoprene or mixtures thereof. 31. The method of claim 1, wherein the first polymer comprises residues of 2-ethylhexyl acrylate. 32. The method of claim 1, wherein the first polymer comprises functional groups reactive with diacid, diisocyanate, diaryl carbonate, dialkyl carbonate, dihalocarbonate, or diol components. 33. The method of claim 31, wherein the functional groups comprise epoxy, acid, hydroxyl, isocyanate, amine, amide, carbonate groups or mixtures thereof. 34. The method of claim 1, wherein the polymer colloid system is crosslinked. 35. The method of claim 1, wherein the first polymer is a core-shell polymer. 36. The method of claim 1, wherein the first polymer is a non-core-shell polymer. 37. The method of claim 1, wherein both the continuous phase of the polymer colloid system and the condensation reaction medium comprise a diol component. 38. The method of claim 1, wherein component (b)(1) comprises a diacid, thereby producing a polyester as a polycondensate. 39. The method of claim 38, wherein the polyester comprises acid residues and diol residues. 40. The method of claim 39, wherein the polyester further comprises modifying residues. 41. The method of claim 38, wherein the polymer colloid system is a latex prepared by emulsion polymerization. 42. The method of claim 41, wherein the first polymer comprises a core-shell polymer. 43. The method of claim 41, wherein the first polymer comprises a non-core-shell polymer. 44. The method of claim 41, wherein the continuous phase consists essentially of water. 45. The method of claim 41, wherein the continuous phase consists essentially of diol. 46. The method of claim 41, wherein the latex comprises functional groups reactive with diacid, diisocyanate, diaryl carbonate, dialkyl carbonate, dihalocarbonate, or diol components. 47. The method of claim 46, wherein the functional groups comprise epoxy, acid, hydroxyl, amine, amide, carbonate groups or mixtures thereof. 48. The method of claim 1, wherein the polycondensate has a Tg below 40°C and substantially zero crystallinity. 49. The method of claim 1, wherein the polycondensate has a Tg greater than 40°C. 50. The method of claim 1, wherein the condensation polymer is a thermosetting polymer. 51. The method of claim 1, wherein the polymer colloid system is a latex prepared by emulsion polymerization. 52. The method of claim 51, wherein the continuous phase consists essentially of water. 53. The method of claim 51, wherein the continuous phase consists essentially of diol. 54. The method of claim 1, wherein the polymer colloid system is prepared by dispersion polymerization. 55. The method of claim 54, wherein the continuous phase consists essentially of water. 56. The method of claim 54, wherein the continuous phase consists essentially of diol. 57. The method of claim 1, wherein the polymer colloid system is prepared by suspension polymerization. 58. The method of claim 57, wherein the continuous phase consists essentially of water. 59. The method of claim 57, wherein the continuous phase consists essentially of diol. 60. The method of claim 1, wherein the polymer colloid system is prepared using mechanical emulsification. 61. The method of claim 60, wherein the continuous phase consists essentially of water. 62. The method of claim 60, wherein the continuous phase consists essentially of diol. 63. The method of claim 1, wherein the polymer colloid system is introduced prior to initiation of the condensation reaction. 64. The method of claim 1, wherein the polymer colloid system is introduced during the transesterification stage. 65. The method of claim 1, wherein the polymer colloid system is introduced during the polycondensation stage. 66. A method of preparing a polycondensate/latex matrix comprising the steps of: (1) prepare colloidal diol composition, this composition comprises (a) latex polymer particles comprising residues of ethylenically unsaturated monomers, wherein the latex polymer particles have a particle size of less than 1000 nm; (b) surfactants; and (c) a continuous liquid phase comprising a diol component, wherein the diol component accounts for 60 to 100% by weight of the latex diol composition; and (2) Introducing the diol latex composition into a condensation reaction medium comprising a diacid, a diisocyanate, a dialkyl carbonate, a diaryl carbonate, a dihalocarbonate, or a mixture thereof. 67. The method of claim 66, wherein the diol latex composition contains no polymeric stabilizers. 68. The method of claim 66, wherein the surfactant comprises anionic, cationic, nonionic surfactants or mixtures thereof. 69. The method of claim 66, wherein the surfactant comprises polymerizable or non-polymerizable alkyl ethoxylated sulfate (sulfate), alkylphenol ethoxylated sulfate (sulfate), alkyl ethoxylated , alkylphenol ethoxylates or mixtures thereof. 70. The method of claim 66, wherein the latex particles comprise functional groups reactive with diacids, diisocyanates, diaryl carbonates, dialkyl carbonates, dihalocarbonates, or diol components. 71. The method of claim 70, wherein the functional groups comprise epoxy groups, acetoacetoxy groups, carbonate groups, hydroxyl groups, amine groups, isocyanate groups, amide groups, or mixtures thereof. 72. The method of claim 66, wherein the latex polymer particles are crosslinked. 73. The method of claim 66, wherein the latex polymer is a core-shell polymer. 74. The method of claim 66, wherein the latex polymer is a non-core-shell polymer. 75. The method of claim 66, wherein the latex polymer particles comprise residues of ethylenically unsaturated monomers. 76. The method of claim 66, wherein the latex polymer particles comprise residues of non-acid vinyl monomer-, acid vinyl monomers, or mixtures thereof. 77. The method of claim 66, wherein the latex polymer particles comprise the residues of the following non-acid vinyl monomers: acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, methyl acrylate, methacrylate Methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethyl methacrylate Hexyl ester, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, trimethylolpropane triacrylate, styrene , α-methylstyrene, glycidyl methacrylate, methacryloylcarbodiimide, C ₁ ~C ₁₈ alkyl crotonic acid, di-n-butyl maleate, α- or β-vinyl Naphthalene, Dioctyl Maleate, Allyl Methacrylate, Diallyl Maleate, Diallyl Malonate, Methoxybutenyl Methacrylate, Isomethacrylate Bornyl ester, hydroxybutenyl methacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl 1, 2-ethylene carbonate, epoxybutene, 3,4-dihydroxybutene, hydroxyethyl (meth)acrylate, methacrylamide, acrylamide, N-butylacrylamide, N-ethyl Acrylamide, butadiene, vinyl (meth)acrylate, isopropenyl (meth)acrylate, cycloaliphatic epoxy (meth)acrylate, ethyl formamide, 4-vinyl-1, 3-dioxolane-2-one, 2,2-dimethyl-4-vinyl-1,3-dioxolane (dioxolate) and 3,4-diacetoxy-1-butene or mixture. 78. The method of claim 66, wherein the latex polymer particles comprise 2-ethylhexyl acrylate residues. 79. The method of claim 66, wherein the latex polymer comprises the residues of the following acid vinyl monomers: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, or mixtures thereof. 80. The method of claim 66, wherein the latex polymer particles comprise residues of the following monomers: acrylate, methacrylate, styrene, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, butadiene, Isoprene or mixtures thereof. 81. The method of claim 66, wherein the diol component comprises an aliphatic or cycloaliphatic diol or mixtures thereof of 2 to 10 carbon atoms. 82. The method of claim 66, wherein the diol component comprises ethylene glycol, 1,3-trimethylene glycol, propylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, cis-or trans-cyclohexanedimethanol, cis-or trans-2,2,4,4-Tetramethyl-1,3-cyclobutanediol, diethylene glycol or mixtures thereof. 83. The method of claim 66, wherein the diol component comprises ethylene glycol, propylene glycol, tripropylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, or mixtures thereof. 84. The method of claim 66, wherein the diol component comprises neopentyl glycol, ethylene glycol, 1,4-butanediol, and cis- or trans-cyclohexanedimethanol. 85. The method of claim 66, wherein the diol component is 65 to 100 wt% of the continuous phase. 86. The method of claim 66, wherein the diol component is 75 to 100 wt% of the continuous phase. 87. The method of claim 66, wherein the diol component is 90-100% by weight of the continuous phase. 88. The method of claim 66, wherein the continuous phase consists essentially of the diol component. 89. The method of claim 66, wherein the continuous phase further comprises a co-solvent in an amount less than or equal to 40 wt% of the continuous phase. 90. The method of claim 66, wherein the co-solvent comprises water, methanol, ethanol, propanol, n-butanol, or mixtures thereof. 91. The method of claim 66, wherein the latex polymer particles have a weight average molecular weight, as determined by gel permeation chromatography, of 1,000 to 1,000,000. 92. The method of claim 66, wherein the continuous phase further comprises a polyol. 93. A product prepared by the method of claim 1. 94. A product prepared by the method of claim 66. 95. A polymer blend comprising a first polymer and a condensation polymer, wherein the first polymer is a non-core-shell polymer derived from a polymer colloid system. 96. The polymer blend of claim 95, wherein the first polymer comprises 70-100% 2-ethylhexyl acrylate. 97. The polymer blend of claim 95, wherein the first polymer comprises 70-100% butyl acrylate. 98. The polymer blend of claim 95, wherein the first polymer comprises 70-100% isoprene. 99. The polymer blend of claim 95, wherein the first polymer comprises 70 to 100% butadiene. 100. The polymer blend of claim 95, wherein the first polymer comprises 70 to 100% acrylonitrile. 101. The polymer blend of claim 95, wherein the first polymer comprises 70-100% styrene. 102. The polymer blend of claim 95, wherein the first polymer comprises 70-100% styrene. 103. The polymer blend of claim 95, wherein the first polymer comprises 50 to 100% 2-ethylhexyl acrylate. 104. The polymer blend of claim 95, wherein the first polymer comprises 50-100% butyl acrylate. 105. The polymer blend of claim 95, wherein the first polymer comprises 50 to 100% isoprene. 106. The polymer blend of claim 95, wherein the first polymer comprises 50 to 100% butadiene. 107. The polymer blend of claim 95, wherein the first polymer comprises 50 to 100% acrylonitrile. 108. The polymer blend of claim 95, wherein the first polymer comprises 50 to 100% styrene. 109. The polymer blend of claim 95, wherein the condensation polymer is polyester. 110. The polymer blend of claim 95, wherein the polycondensate has a Tg greater than 40°C. 111. The polymer blend of claim 110, wherein the first polymer comprises residues of the following monomers: 2-ethylhexyl acrylate, butyl acrylate, isoprene, butadiene, lauryl acrylate, Acrylonitrile, vinylidene chloride or mixtures thereof. 112. The polymer blend of claim 95, wherein the polycondensate has a Tg of less than 40°C. 113. The polymer blend of claim 112, wherein the first polymer comprises residues of the following monomers: vinyl chloride, styrene, alpha-methylstyrene, methyl methacrylate, vinylnaphthalene, methyl Isobornyl acrylate or mixtures thereof. 114. The polymer blend of claim 112, wherein the polymer blend is an elastomer. 115. A powder coating comprising the polymer blend of claim 95. 116. A method of preparing a polycondensate/first polymer matrix comprising the steps of: The polymer colloid system is introduced into the condensation reaction medium, which can be carried out before or during the condensation reaction, wherein the condensation reaction medium contains (1) diacid, diisocyanate, dialkyl carbonate, diaryl carbonate, dihalocarbonic acid Esters or mixtures of the above, wherein the polymer colloid system comprises a first polymer dispersed in a continuous liquid phase, Where the continuous phase of the polymer colloid system, the condensation reaction medium, or both contain the diol component, a polycondensate/first polymer matrix is formed. 117. A method of preparing a polycondensate/first polymer matrix comprising the steps of: Before or during the condensation reaction, the diol latex system is introduced into the condensation reaction, wherein the condensation reaction medium comprises (1) Diacids, diisocyanates, dialkyl carbonates, diaryl carbonates, dihalocarbonates or mixtures of the above, wherein the latex diol system comprises: (a) latex polymer particles comprising residues of ethylenically unsaturated monomers, wherein the latex polymer particles have a particle size of less than 1000 nm; (b) surfactants; and (c) a continuous liquid phase comprising a diol component, wherein the diol component comprises 60 to 100% by weight of the latex diol composition; thereby forming a polycondensate/latex matrix. 118. An impact-modified polyester comprising the polymer blend of claim 95. 119. A hydroxy-functional polyester coating resin comprising the polymer blend of claim 95. 120. The method of claim 66, wherein the condensation reaction medium further comprises a diol component.