WO1994010242A1 - Systeme de nucleation pour des polyesters et articles formes a partir de ces derniers - Google Patents

Systeme de nucleation pour des polyesters et articles formes a partir de ces derniers Download PDF

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Publication number
WO1994010242A1
WO1994010242A1 PCT/US1993/010252 US9310252W WO9410242A1 WO 1994010242 A1 WO1994010242 A1 WO 1994010242A1 US 9310252 W US9310252 W US 9310252W WO 9410242 A1 WO9410242 A1 WO 9410242A1
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Prior art keywords
polyester
polyesters
poly
polymer
groups
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Shaul M. Aharoni
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Honeywell International Inc
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AlliedSignal Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6926—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals

Definitions

  • This invention relates to novel nucleating agents for polyesters and to polymer based compositions containing the nucleating agents as well as the articles of manufacture formed totally or in part from the polymer based composition of this invention.
  • the invention also relates to a process for preparing the nucleated polymer materials.
  • the crystalline units are arranged in polycrystalline aggregates known as spherulites. These spherulites may be detected by microscopic examination under polarized light. They are characterized by a more or less symmetrical growth in all directions from a nucleus and are composite structures made up of crystalline and amorphous
  • the number and size of the spherulites determines the texture or graininess in the bulk of the material and influences optical as well as physical properties. Physical properties improve with
  • increased crystallinity and improved morphological structure are abrasion resistance, heat distortion temperature, inherent stability or resistance to deformation, resistance to hot water, coefficient of expansion, hardness, tensile yield strength and surface hardness.
  • Other working nucleating agents for polyolefin are described by J.P. Mercier, Polymer Engineering and Science, 30, 270 (1990), Wijga, P. W. O. US pat. 3,207,735; -6;
  • nucleating agents when cooling semi-crystalline polymers from the molten state into the solid form is to increase the number of nuclei formed in a given time interval at a predetermined temperature.
  • the final and overall crystallinity depends not only on the number of nuclei that are formed but also on the spherulitic growth rate from such nuclei.
  • spherulites develop with respect to a center, or nucleus, of growth. Addition of the nucleating agents thus provides a large number of sites for growth upon cooling from a melt. In order to be of practical use, such nucleating agents not only must produce a fine spherulitic structure but also must do this under conditions of rapid cooling to a
  • induction time Subsequent growth from the spherulitic center depends on the polymer chain mobility. Thus, a factor in the spherulitic growth rate is the macroscopic viscosity of the polymer and its temperature dependence. All segmental motion is “frozen in” at the glass transition temperature (Tg) and no additional crystallization occurs even when nuclei are present.
  • Tg glass transition temperature
  • nucleating agents for polyester contain sodium or potassium ions in a form that makes them mobile in the molten polyester.
  • the nucleation mechanism is still in dispute, but with no exception, nucleation of polyesters by these ions is always associated with substantial chain cleavage, as
  • the nucleating agents of this invention contain none of the above ions and the nucleation process is not accompanied by chain cleavage. On the contrary, often in our case, molecular weight increases are combined with relatively large increases in T cc , a combination dramtically different from existing
  • crystallization temperature (T cc ) of polyesters can be increased by the addition of one or more effective nucleating agents having a particle size which is about equal to or more than the lamellar thickness of the desired polyester.
  • the crystallization temperature upon cooling reflects the overall crystallization rate due to the combined effects of nucleation and growth of crystallites/spherulites.
  • a non-nucleated polymer would have a lower T cc than a nucleated material, and a polymer crystallizing at a lower rate would have a lower T cc than a faster crystallizing polymer. It is believed that an increase in T cc and the corresponding increase in the crystallization rate cause an
  • composition of this invention comprises (a) at least one polyester and (b) one or more nucleating agents having an effective particle size.
  • Yet another aspect of this invention relates to a novel process for enhancing the rate of crystallization of a polyester from the melt, which comprises adding to said polymer a nucleating agent of this invention.
  • FIG. 1 is a graph of the heat of formation of selected oxides of table II as a function of the group of the Periodic Table to which the element forming the oxide belongs.
  • the composition of this invention comprises one or more polyesters.
  • polyester chosen for use can be homo-polyester, or a random or block copolyester or terpolymer, or mixtures thereof as desired.
  • Many polyesters are generally prepared by the condensation of an organic dicarboxylic acid and an organic diol, and, therefore, illustrative examples of useful polyesters will be described
  • Polyesters which are suitable for use in this invention are those which are derived from the
  • aromatic diols condensation of aromatic, cycloaliphatic, and aliphatic diols with aliphatic, aromatic and cycloaliphatic dicarboxylic acids.
  • useful aromatic diols are those having from about 6 to about 24 carbon atoms.
  • aromatic diols include bis-(p-hydroxyphenyl)ether; bis-(p-hydroxyphenyl)thioether; bis-(p-hydroxyphenyl)-sulphone; bis(p-hydroxyphenyl)-methane; 1,2-(bis-(p-hydroxyphenyl)-ethane); 1-phenyl-bis-(p-hydroxy-phenyl)-methane; diphenyl-(bis-(p-hydroxyphenyl)-methane); 2,2-bis(4-hydroxydimethylphenyl) propane); 1,1- or 2,2-(bis(p-hydroxypheny1)-butane); 1,1-dichloro-or 1,1,1-trichloro-2,2-(bis-(p-hydroxyphenyl)-ethane); 1,1-(bis- (p-hydroxyphenyl)-cyclopentane); 2,2-(bis-(p-hydroxyphenyl)-propane (Bisphenol A); 1,1-(bis-(p-hydroxyphenyl)-cyclo
  • Suitable cycloaliphatic diols include those having from about 5 to about 24 carbon atoms.
  • Exemplary of such useful cycloaliphatic diols are 1, 4-dihydroxy cyclohexane, 1, 4-dihydroxy methylcyclohexane, 1,3- dihydroxy- cyclopentane, 1,5-dihydroxycycloheptane, 1,5- dihydroxycyclooctane, 1,4-cyclo-hexane dimethanol, 2,2- bis(4-hydroxycyclohexane)propane and the like.
  • Useful and aliphatic diols include those having from about 2 to about 12 carbon atoms, with those having from about 2 to about 6 carbon atoms being particularly preferred.
  • Illustrative of such preferred diol precursors are 1,2-ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,8-octanediol, 1,6- nonanediol, neopentyl glycol, pentyl glycol, 1,6- hexanediol, 1,4-butanediol, and the like.
  • Cycloaliphatic diols and aliphatic diols are preferred for use.
  • Propylene glycol, ethylene glycol, neopentyl diol, 1,4-dihydroxy methylcyclohexane, 1,4- butanediol and 2,2-bis(4-hydroxy cyclohexyl) propane are particularly preferred as diol precursors of polyesters for use in the conduct of this invention.
  • Suitable dicarboxylic acids for use as precursors in the preparation of useful polyesters are linear and branched chain saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic
  • polyesters containing up to about 80% repeat units of monomer containing both hydroxyl and carboxyl groups, such as hydroxybenzoic acid, vanillic acid, syringic acid and the like, may also be used in the practice of this invention.
  • Illustrative of aliphatic dicarboxylic acids which can be used in this invention are those having from about 2 to about 50 carbons atoms, as for example, malonic acid,
  • dimethylmalonic acid succinic acid, itanoic acid, octadecylsuccinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, suberic acid, azelaic acid and dimer acids (dimerisation products of unsaturated aliphatic carboxylic acids such as oleic acid) and alkylated malonic and succinic acids, such as octadecylsuccinic acid, and the like.
  • dicarboxylic acids are those having from about 6 to about 15 carbon atoms.
  • Such useful cycloaliphatic dicarboxylic acids include 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3- and 1,4- cyclohexanedicarboxylic acid, 1,3- and 1,4- dicarboxymethylcyclohexane and 4,4- dicyclohexyldicarboxylic acid, and the like.
  • Polyester compounds prepared from the condensation of a diol and an aromatic dicarboxylic acid are
  • aromatic carboxylic acids are terephthalic acid and isophthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-diphenylsulphone-dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)-indane,
  • aforementioned aromatic dicarboxylic acids based on a benzene ring such as terephthalic acid and isophthalic acid are preferred for use and amongst these preferred acid precursors terephthalic acid is particularly preferred.
  • Copolymers and terpolymers prepared from mixtures of the above aromatic diacids are especially preferred.
  • poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate) as well as copolymers and terpolymers thereof such as
  • poly(tetramethylene/terephthalate/2,6-naphthalene dicarboxylate) are the polyesters of choice.
  • polyesters of choice poly(ethylene
  • the molecular weight of the polyester may vary widely, for example, the polyester may be a wax having relatively low molecular weight, i.e. about 1000 to 5000 or more.
  • the polyester may also be a melt- spinnable and of a fiber-forming molecular weight.
  • the polyester has film-forming molecular weight.
  • the film-forming polyester has a molecular weight of at least about 10000.
  • the molecular weight of the polyester is from about 1000 to about 200,000 and in particularly preferred embodiments is from about 25,000 to about 150,000. Amongst the particular preferred embodiments, the most preferred are those in which the molecular weight of the
  • polyester is from about 35,000 to about 140,000.
  • a second essential component of the composition of this invention will include at least one effective nucleating agent.
  • an effective nucleating agent has a particle size which is about equal to or more than the lamellar thickness of the polymer (i.e. effective particle size).
  • the lamellar thickness is the average thickness of the flat polymer crystals plus half of the thickness of the amorphous layers separating such crystals.
  • a common lamellar thickness is about 50 ⁇ to 150 ⁇ .
  • the nucleating agents possess a compound or material having a particle size of about 500 ⁇ or less.
  • the nucleating agents is at least about 50 ⁇ , and more preferably, the particle size of the nucleating agent is about 100 ⁇ to about 300 ⁇ .
  • the particle size is from about 100 ⁇ to about 200 ⁇ with from about 100 ⁇ to 150 ⁇ being the size of choice.
  • nucleating agents are guided by those materials which satisfy the above particle size requirements, processing conditions and end-use properties.
  • the nucleating agent is selected from one or more of the elements of groups VA and VIA of the periodic table.
  • an "effective amount” is an amount which is sufficient to improve the homogeneity and/or fineness of spherulitic structures in the polyester to any extent.
  • the amount of nucleating agent used is sufficient to increase the T cc of the nucleated polymer at least 10oC over that of other polyesters prepared without the nucleating agents of this invention.
  • the enhanced crystallization characteristics can be measured by comparing the crystallization temperature upon cooling (T cc ).
  • the amount nucleating agent may correspond to amounts of conventional nucleating agents. However, it is noted that lesser amounts of the nucleating agents may be used since the use nucleating sites tends to be
  • the amount of nucleating agent employed is in the range of from about 0.001 to about 5 weight percent based on the total weight of polyester and agent, and in the more
  • preferred embodiments of the invention is from about 0.01 to about 3 weight percent on the aforementioned basis.
  • the amount of nucleating agent employed is from about 0.01 to about 2.0 weight percent based on the total weight of agent and polyester.
  • the amount of nucleating agent is from about 0.01 to about 1.0%.
  • the nucleating agent is uniformly dispersed in the polyester.
  • a preferred process for forming the nucleated polyester compositions of this invention is a process by which not only crystallization properties are enhanced but also the molecular weight of the polyester can be increased.
  • the process for enhancing the crystallization and melt viscosity properties of a polyester by forming an extended chain polyesters and block or graft polyesters or copolyesters comprising the steps of (a) forming an intimate mixture of one or more polyesters, one or more effective nucleating agents and at least one effective chain extension reagent compound; (b) heating said mixture for a time and at a temperature sufficient to form said extended chain, or graft or block copolyester or polyester.
  • the polymer chain extended or coupled as often referred to in the art.
  • Chain extension or coupling as discussed herein shall both apply coupling polyesters and preparing graft and/or block polyesters and copolyesters.
  • polyesters such as
  • PET poly (ethyleneterephthalate) (PET), with a phosphorus (III) chain extension reagent, such as
  • TPP triphenylphosphite
  • polyesters by reaction with one or more phosphorus (III)-containing chain extension reagents, such as aryl phosphites, in the presence of one or more substances which contain at least one element belonging to groups VA and VIA of the periodic table, will produce polyesters having enhanced T cc values.
  • the polyester composition which is melt processed in accordance with this invention, generates a polyester material having not only improved T cc values but also the molecular weight of the polymer, as measured by the I.V., is reduced to a much lesser extent, if it is not maintained or increased when compared with materials prepared in the absence of the chain extension agent and selected nucleating agent.
  • the substances which contain an element belonging to groups VA and VIA of the periodic table can be of many forms, for example inorganic or organic compounds, complexes or salts containing of substances which comprise elements of group VA or VIA. It is noted for example that in the presence of substances like oxides or organic salts or organic coordination compounds of antimony, arsenic, bismuth, tellurium and selenium, or in the presence of residues from polymerization
  • a catalyst employed for the original polymerization of the polyester is selected from those inorganic and organic catalysts that contain substances which reduce to elemental form by the reaction with the chain extension reagent (e.g. aryl phosphite) at elevated temperatures of the chain extension process.
  • the catalysts employed should also not attack the polymers after their formation.
  • the catalyst is selected from catalysts which contain substances belonging to groups VA and VIA. Catalysts from these groups are used to catalyze the initial polymeric condensation for forming polyesters with the added advantage of effecting enhanced crystallization characteristics in the polyester after the chain extension reaction. More preferably, the catalyst is selected from catalysts which contain one or more elements selected from antimony, arsenic, bismuth, tellurium or selenium Illustrative of useful
  • catalysts are antimony triacetate, arsenic triacetate, bismuth triacetate, tellurium oxide, selenium oxide, antimony (III) oxide, arsenic (III) oxide and bismuth (III) oxide. Many of these catalysts are commercially available.
  • polyester such as poly(ethylene
  • the first step of the process consists of forming an intimate mixture of one or more appropriate polyesters, one or more chain extension reagent compounds and one or more substances as described above which contain at least one element from group VA or VIA.
  • the intimate mixture is heated at a temperature and for a time sufficient to mix the ingredients thoroughly and form the desired extended chain polyester, or block or graft copolyester or polyester, as indicated by an increase in the viscosity of the polymer mixture.
  • an intimate mixture in the first process step is a molten mixture.
  • molten mixture is an intimate mixture which has been heated to a temperature which is equal to or greater than the melting point of at least one of the polymer components of the mixture.
  • the manner in which the molten mixture is formed is not critical and conventional methods can be employed.
  • the molten mixture can be formed by
  • the polymeric components are heated to a temperature equal to or greater than the melting point of at least one of the polymers, and below the degradation temperature of each of the polymers.
  • the polymers are heated above the melting point of each of the polymers in the mixture.
  • An effective amount of one or more chain extension reagent compounds in a liquid or powdered form is added to the melted polymers while at the same time vigorously stirring the melt, or added prior to melting and mixing. Heating is continued until the desired extended chain, or block and/or graft polyester or copolyester is formed as indicated by an increase in the melt viscosity.
  • the components of the intimate mixture can be granulated, and the
  • a suitable mixer as for example, a tumbler or a Banbury Mixer, or the like, as uniformly as possible. Thereafter, the composition is heated in an extruder until the polymer components are melted. As described above, the mixture is heated until the desired extended chain, or block and/or graft copolyester or polyester is formed as indicated by an increase in the melt viscosity. Thereafter the mixture is ejected with cooling.
  • a suitable mixer as for example, a tumbler or a Banbury Mixer, or the like
  • one or more effective chain extension reagents are injected directly into the molten stream of polymer formed from the polycondensation reaction wherein the polymer and phosphites are thoroughly mixed prior to subsequent processing.
  • the order of mixing of the various components of the intimate mixture is not critical. Accordingly, the order of addition of the polymers and chain extension reagent compounds and other optional components to be described in more detail hereinbelow, to form the intimate mixture, can be varied as desired.
  • the process can be carried out in a batchwise or discontinuous fashion, as for example, carrying out the process in a sealed container. Alternatively, the process can be carried out in a continuous fashion in a single processing zone, as for example, by use of an extruder as described hereinabove, or in a plurality of such reaction zones, in series or parallel.
  • Reaction temperature can be varied over a wide range. However, it should be appreciated that the process temperature employed in any specific instance will depend on the particular polyesters employed and, in the preferred embodiments should be at least as high as the melting point of semi-crystalline polyesters, and below the degradation temperature of such
  • the process temperature is such that the polyesters will remain in the molten state at the extended chain polyester, or block or graft polyester or copolyesters are formed. Normally this can be accomplished in one of two ways. Either the process can be carried out at a temperature which is equal to or greater than the melting point of the desired product; or process temperatures can be increased periodically over the course of the conduct of the process so as to maintain the mixture in the molten state.
  • An optimal process temperature is the highest temperature which is below the degradation temperature of the polyester or polyesters.
  • the process temperature is at least about 200oC. Amongst these particularly preferred embodiments, most
  • preferred process temperatures are in the range of from about 225oC to about 325oC.
  • reaction times can be varied over a wide range. Usually, reaction times will depend on a variety of factors such as the polymeric components, reaction temperatures, chain extension reagent compound and its concentration, and other factors known to those of skill in the art to affect reaction times. In most instances, the reaction time can vary from a few seconds to 24 hours or more. In the preferred embodiments of this invention,
  • reaction times will vary from about 1 min. to about 2 hours and in the particularly preferred embodiments from about 2 min. to about 30 to 60 min.
  • the process of this invention employs one or more chain extension reagents.
  • the reagents are referred to as chain extension reagents since they will extend polymeric chains by coupling the polymeric chains together at reactive sites on the polymer reactants.
  • the reaction of chain extension is the coupling
  • An effective chain extension reagent is a compound containing a trivalent phosphorus atom (phosphorus III) to which is attached at least one effective leaving group, but not more than three leaving groups.
  • the effective leaving group contains a hetero atom bonded to the phosphorus atom, and the hetero atom is bonded to a carbon which is double bonded to an atom other than the hetero atom.
  • the hetero atom is nitrogen or oxygen.
  • the hetero atom either forms a conjugated system with the double bonded carbon or the hetero atom is bonded to a carbon of a conjugated system. It is believed that the conjugated system of the leaving group provides the leaving group with the ability to delocalize negative charge and therein the leaving group is a "stable" moiety.
  • the phenomenon of stability as used herein relates to the ability of the leaving group to
  • An effective leaving group can be a cyclic aromatic or cyclic non-aromatic. It is noted that cyclic includes monocyclic and polycyclic moieties.
  • the leaving group is a cyclic structure; that is the hetero atom of the leaving group is part of a cyclic ring or the carbon to which the hetero atom is bonded is part of a cyclic ring. It is proposed that the cyclic structures can more efficiently delocalize negative charge than a linear leaving group.
  • the hetero atom is part of the cyclic ring it is preferred that the hetero atom is nitrogen. Chain extension reagents having such nitrogen bonded to the phosphorus atom are referred to herein as phosphinamines.
  • phosphinamines Illustrative of such phosphinamines are the phosphorus trislactams disclosed in U.S. Patent No.
  • phosphinamines are efficient chain extension reagents and may be used instead of or in combination with any other effective chain extension reagents.
  • phosphinamines include phosphorus triscaprolactam, phosphorus tris (2-pyrrolidone),phosphorus
  • phosphorus (III) chain extension reagent need only have one lactam as a leaving group.
  • the remaining moieties attached to the phosphorus atom may be identical or similar lactam leaving groups or other varied leaving groups which are discussed infra.
  • the phosphinamines chain extension reagents are compounds having at least one bond of a trivalent phosphorus atom bonded to the nitrogen of an imide.
  • the leaving group is an imide such as succinimide, phthalimide and maleimide as shown below.
  • the chain extension reagent has (a) one or more aryl containing leaving groups wherein the hetero atom of the chain extension reagent is bound to a carbon atom of the aryl group and/or (b) one or more leaving groups wherein the hetero atom is actually part of a heteroaromatic ring (although the hetero atom is bound to the other ring atoms through single bonds only).
  • aryl containing leaving groups wherein the hetero atom of the chain extension reagent is bound to a carbon atom of the aryl group
  • one or more leaving groups wherein the hetero atom is actually part of a heteroaromatic ring (although the hetero atom is bound to the other ring atoms through single bonds only.
  • heteroaromatic leaving groups are pyrrolyl, indolyl, carbazolyl, imidazolyl and benzimidazolyl.
  • aryl containing chain extension reagents which are phosphites, i.e. a phosphorus atom single bonded directly to three oxygen atoms.
  • phosphites i.e. a phosphorus atom single bonded directly to three oxygen atoms.
  • effective phosphite chain extension reagents are phosphites having one or more aryloxy groups bound directly through the oxygen of the aryloxy group to the phosphorus atom of the phosphite.
  • an effective phosphite is a compound which is commonly referred to as a phosphite ester or
  • polyphosphite ester More specifically, an aryloxy containing phosphite as described above is referred to as an aryl phosphite ester.
  • the aryloxy moiety of the phosphite can be derived from any aromatic alcohol which contains a hydroxylated aryl group; wherein the aryl group is substituted or unsubstituted yet the aryl ring itself is hydroxylated.
  • Useful aromatic compounds employed in forming the aryloxy groups are mono-, di- and other polycyclic aromatics, which include but are not limited to substituted and unsubstituted benzenes, naphthalenes, anthracenes, biphenyl or polyphenyl compounds, methylene bridged aromatic compounds and the like.
  • the aromatic group which forms the arlyoxy is selected such that the aryloxy group is a least hazardous, volatile or toxic material.
  • Useful phosphite esters, and polyphosphite esters are known compounds.
  • the polyphosphite esters which may be symmetrical or asymmetrical, have more than one aryl phosphite ester. Such compounds can be
  • triphenyl phosphite can be prepared by reacting three moles of phenol with one mole of phosphorus trichloride
  • trisnonylphenol phosphite can be prepared by reacting three moles of nonylphenol with one mole of phosphorus trichloride.
  • Mixed phosphites such as diphenyl
  • isodecyl phosphite diphenyl isooctyl phosphite and phenyl diisodecyl phosphite, can be prepared by
  • useful phosphites containing more than one phosphite ester moiety can be prepared by reacting aromatic and aliphatic alcohols at least one of which is polyhydric with phosphorus trichloride.
  • Illustrative of useful phosphite esters and polyphosphite esters are compounds of the formula I;
  • R 1 , R 2 and R 3 are the same or different and are hydrogen, metal cations, ammonium radicals, or
  • n is 0 or a positive whole number and R 4 , R 5 and R 6 are the same or different and are R 1 , R 2 and R 3 , R 7 can be a single bond between the two oxygens, or a divalent aromatic or aliphatic group, R 8 can be R 4 , R 3 , or R 6 ; and R 5 , R 7 and R 8 together can be polyalkoxy group derived from an aromatic or aliphatic polyalcohol; with the proviso that each phosphite moiety includes a substituted or unsubstituted aryl group.
  • Permissible R 1 , R 2 and R 3 groups include aliphatic groups such as t-butyl, n-butyl, isopropyl, hexyl, pentyl, 2-chloroethyl, neophentyl, decyl, dodecyl, isodecyl, butoxyethyl, 3-chlorobutyl and the like;
  • aromatic groups such as 2, 4-di-tert-butyl-phenyl, 4- tert-butylphenyl, 3-isopropylphenyl, 2,4- dimethylphenyl, 4-nonyl-phenyl, octylphenyl, 4- chlorophenyl, 2,4-dibromophenyl, 4-fluorophenyl, 3,5- dichlorophenyl, 4-cyanophenyl, 2-nitrophenyl, bisphenol methyl and the like; metal cations such as sodium, potassium, zinc, lithium, calcium, aluminum, and the like and groups containing one or more phosphite moieties, as for example, ethylene diphenyl phosphite, or a poly- (dipropylene glycol) phenyl phosphite moiety bonded to the oxygen atom via the dipropylene glycol moiety.
  • R 1 , R 2 and R 3 are the same or different and are a alkyl, aryl or aryl substituted with one or more alkyl groups, with the proviso that at least one of R 1 , R 2 , and R 3 is aryl or substituted aryl. More preferred for use are such esters in which at least two of R 1; R 2 , R 3 are aryl or alkyl substituted aryl, and most preferred for use are those esters in which R 1 , R 2 , and R 3 are the same or different and are aryl or alkyl substituted aryl, such as nonyl phenyl or 2,4-di-tert butyl phenyl.
  • R 1 , R 3 , and R 3 are selected from phenyl groups, bisphenyls and
  • R 7 is an alkoxy or polyalkoxy derived from a divalent aromatic alcohol such as bisphenol A or a biphenol.
  • R 5 , R 7 and R 8 together are a divalent aromatic alcohol such as bisphenol A or a biphenol.
  • the polyalcohols may be a pentaerythritol, pyrogallol, tetrahydroxybenzophenone, and saccharides, such as galactose, or polyalcohols such as phenol-aldehyde or resorcinol-formaldehyde oligomers and the like.
  • phosphites having biphenyls and polyphenyls in the arlyoxy group are disclosed by Beck et al. and are shown the formula below.
  • X is sulfur or lower alkylene (e.g. methylene); R is hydrogen or an alkyl radical and R 1 is an alkyl radical.
  • one or more, preferably three of the oxygens of the phosphite ester are bonded to the same compound, which may be a dimer, oligomer or polymer of a repeating unit as shown below:
  • n 0 to about 6.
  • an effective amount of one or more effective chain extension reagents is employed in forming the intimate mixture.
  • an effective amount is an amount of the chain extension reagents which when added to the polymeric component in accordance with this invention forms a mixture which when heated forms the desired graft copolymer. The formation of the graft copolymer will be accompanied by an increase in the melt viscosity of the mixture.
  • viscosity denotes the internal friction, i.e.
  • the quantity of the one or more chain extension reagents employed is at least about 0.05 weight percent, based on the total weight of the mixture. In the particularly preferred embodiments of this invention
  • the weight percent of reagent compounds is in the range of from 0.1 to about 10 weight percent, and amongst these particularly preferred embodiments, those in which the quantity of reagent compounds employed is from about 0.4 to about 4 weight percent based on the total weight of the mixture are most preferred.
  • Polymers which may be employed in the chain extension process of this invention are linear or branched polyesters.
  • the type of polyester is not critical and the particular polyester chosen for use in any particular situation will depend essentially on the physical properties and features, i.e. flexibility, hardness, toughness, desired in the final shaped article of manufacture.
  • a multiplicity of linear thermoplastic polyesters having wide variations in physical properties are suitable for use in the process of this invention.
  • One important feature of the polyesters employed is that they must have terminal reactive groups which allow coupling between two or more polyesters chains via the formation of a linking group.
  • Each polyester should have at least one
  • the polyesters comprise two terminal groups wherein such polyesters may contain the same terminal group or two different terminal groups.
  • one polyester contains two identical terminal groups, it is chain extended with a second polyester having two terminal groups which allow coupling with the two terminal groups of the other polymer.
  • the polyesters are coupled via the formation of an ester as the linking group.
  • useful polyesters are those that are terminated with a hydroxy and/or carboxy group with the proviso that at least one of each of the two terminal groups is present in the polymers selected for chain extension although an individual polymer need not possess both types of terminal groups.
  • the total mole ratio of terminal hydroxy groups to carboxy groups present in all polyesters employed ranges from about 10:1 to about 1:10. More preferably, the total mole ratio of terminal hydroxy groups to carboxy groups present in all polyesters employed ranges from about 4:1 to about 1:4.
  • polyesters employed ranges from about 6:5 to about 5:6.
  • the aforementioned polyesters are generally useful for the chain extension process.
  • compositions of this invention can include various optional components which are additives commonly employed with the polymers and copolymers of this invention.
  • optional components include additional nucleating agents, viscosity enhancers, fillers, plasticizers, impact modifiers, chain extenders, colorants, mold release agents, antioxidants, ultraviolet light stabilizers, lubricants, antistatic agents, fire retardants, and the like.
  • composition of this invention can be prepared by blending or mixing the essential ingredients, and other optional components, as uniformly as possible employing any conventional blending means.
  • Appropriate blending means such as melt extrusion, batch melting and the like, are well known in the art and will not be described here in greater detail.
  • the blending procedure can be carried out at elevated temperatures above the melting point of the polymer and the nucleating agent added either alone or as individual components of the agent separately or as a combination of the components in a suitable form as for example, granules, pellets and preferably powders are added to the melt with vigorous stirring.
  • nucleating agent can be masterbatched or preblended with the polymer in the melt and this premixed or masterbatch added to the polyolefin in the melt in amounts sufficient to provide the desired amount of nucleating agent in the polyolefin product. Stirring is continued until a homogeneous composition is formed.
  • the nucleating agent can also be added to the melt coated on the surface of small particle inert powders which have a high surface to volume ratios.
  • inert powders as for example, fused silica, fused alumina, carbon black and aerogels, and hydrogels of silica or alumina, helps to reduce the amount of nucleating agent required to provide optimum results.
  • Blending pressures, and the order of addition of the various components are not critical and may be varied as desired provided that a substantially
  • the various solid components can be granulated, and the granulated components mixed dry in a suitable blender, or for example, a Banbury mixer, as uniformly as possible, then melted in an extruder and extruded with cooling.
  • composition of this invention can be formulated by dissolving the components in an appropriate inert solvent, after which the solvent is removed by evaporation, or other conventional solvent removing means are employed to provide the composition.
  • the solvent is not critical, the only requirement being that it is inert to the components of the composition, and it is capable of solubilizing the various
  • compositions according to the invention can be partly or highly crystalline, depending on which individual constituents are employed. They are
  • thermoplastic materials from which molded articles of manufacture having valuable properties can be produced by the conventional shaping processes, such as melt spinning, casting, injection molding and extruding.
  • moldings are components for technical equipment, apparatus casting, household equipment, sports equipment, components for the electrical and electronics industries and electrical insulations, car components, circuits, fibers, films, piping, gaskets, tank linings, connectors, valve diaphragms, and
  • the molding compositions according to the invention are outstandingly suitable for specific applications of all types since their spectrum of properties can be modified in the desired direction in many ways.
  • composition of this invention as compared to other nucleated polyester compositions and un-nucleated compositions as determined by differential scanning colorimetry (DSC) experiments.
  • DuPont 9900 automated system in a nitrogen atmosphere. A sample of 10.0 ⁇ 0.2 mg was crimped in an aluminum cup, heated to 300°C at a program rate of 10°C./min, held there for 5 min. and then cooled at 10°C./min to obtain the Tec (the crystallization temperature).
  • PET obtained in the form of 1" (0.3175 cm) pellets was ground into 12 mesh size particles. After weighing in wide-mouth jars, the PET samples were dried for 16 hours at 100°-110°C in a vacuum oven. This drying step was done prior to blending, and the samples were kept in sealed jars during interim periods to maintain dryness. Weighed amounts of the phosphite additives were added to the polymers and the sealed jars were rotated on a rolling mill for 0.5 hr. This rotation action effectively coated the surface of the pellets with the phosphite additives. B. Melt Processing
  • the torque values of the Haake instrument are a direct indication of the melt viscosity of the polymer during a processing stage.
  • the higher Torque values indicate and increase in the viscosity caused by the chain extension process of this invention (i.e. the chain extension brought about by mixing together the
  • polymeric chain ends with the aryl phosphite ends with the aryl phosphite.
  • Table I demonstrates the increases in T cc for polyesters reacted with aryl phosphite. PET's
  • PET (without nucleating agent) was obtained from Allied-Signal Inc.
  • T m , T cc an d I.V. were examined.
  • the materials were processed in the absence of a chain extension agent.
  • the only increase in T cc is
  • the PET used contains residual amounts (approx 450 ppm) of Sb-containing catalyst.
  • the carboxyl-terminated FP A2105-78B was dissolved in DMAc at over 80oC. To this solution a slight molar excess of KOH in methanol was added, resulting in gradual precipitation. After workup in methanol and acetone, the dried polymer contained over 16.0% by weight potassium. This product was coded A2105-82G.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention se rapporte à une composition comprenant (a) au moins un polyester, et (b) un ou plusieurs agents de nucléation efficaces présentant une dimension de particules plus ou moins égale ou supérieure à l'épaisseur lamellaire du polyester. La dimension des particules est comprise entre environ 100 Å et environ 500 Å.
PCT/US1993/010252 1992-10-26 1993-10-26 Systeme de nucleation pour des polyesters et articles formes a partir de ces derniers Ceased WO1994010242A1 (fr)

Applications Claiming Priority (2)

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US96709592A 1992-10-26 1992-10-26
US967,095 1992-10-26

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WO1994010242A1 true WO1994010242A1 (fr) 1994-05-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0921144A1 (fr) * 1997-12-02 1999-06-09 Mitsubishi Chemical Corporation Polyester, produits moulés par étirage-soufflage à partir de ce polyester et procédé pour la production de ce polyester
WO1999061514A1 (fr) * 1998-05-27 1999-12-02 Eastman Chemical Company Procede de production d'une preforme de polymere thermoplastique et article ainsi produit

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6343921A (ja) * 1986-08-11 1988-02-25 Teijin Ltd ポリエステルの製造方法
EP0429311A2 (fr) * 1989-11-24 1991-05-29 Imperial Chemical Industries Plc Bouteilles de polyester
WO1992000305A1 (fr) * 1990-06-25 1992-01-09 Allied-Signal Inc. Trilactames phosphoreux et procedes de production de ces substances

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6343921A (ja) * 1986-08-11 1988-02-25 Teijin Ltd ポリエステルの製造方法
EP0429311A2 (fr) * 1989-11-24 1991-05-29 Imperial Chemical Industries Plc Bouteilles de polyester
WO1992000305A1 (fr) * 1990-06-25 1992-01-09 Allied-Signal Inc. Trilactames phosphoreux et procedes de production de ces substances

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8814, Derwent World Patents Index; AN 88-094499 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0921144A1 (fr) * 1997-12-02 1999-06-09 Mitsubishi Chemical Corporation Polyester, produits moulés par étirage-soufflage à partir de ce polyester et procédé pour la production de ce polyester
US6200659B1 (en) 1997-12-02 2001-03-13 Mitsubishi Chemical Corporation Polyester, stretch blow molded product formed thereof and method for producing polyester
WO1999061514A1 (fr) * 1998-05-27 1999-12-02 Eastman Chemical Company Procede de production d'une preforme de polymere thermoplastique et article ainsi produit

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