JPS60186516A - Manufacture ofchemical-bonded,phase-separated and natural-cured hydrophilic thermoplastic graft copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a chemically bonded, phase separated, naturally cured (5el)
f-cured: relates to self-hardening hydrophilic @i■plastic grade 7toko, fe IJ machine and its manufacturing method. This hydrophilic copolymer has excellent wet strength and has wide utility in a variety of applications, particularly in the field of biomedics such as contact lenses and prosthetics.

A considerable amount of research and development has been undertaken to obtain all hydrophilic polymers with sufficient wet strength to be considered substantially water-insoluble. For example, hydrophilic polymers of the type with improved wet strength are available from Otto Wic.
U.S. Patent No. 277I, 3;
Sharnal Op Applied Polymer Scissors such as Refojo (M, F, Refojo) etc.
Our own of Applied Polyme
r 5science No. 7, 24', 2j-, 2≠3
These polymers are disclosed on page J (2013).
) is polymerized with at least 7 hydrophilic groups, such as hydroxyl groups, of acrylic acid or methacrylic acid, and at the same time polymerizes the monomers with polyunsaturated crosslinking, such as non-glycol dimethacrylate. It is produced by cross-linking with agents. The cross-linking agent usually has a molecular weight of about 1 molar or less than its mononisdel. It's common these days
c It is carried out in the presence of a redox initiator.

It can be obtained by copolymerizing a water-soluble vinyl monomer containing at least 7 nitrogen atoms with a minimum of 7 nitrogen atoms. 3? Hydrophilic yl with adverb strength derived from Lima Jt?
IJ is also disclosed. These polymers have a close relationship with body tissue and/or mucosa.
It has been suggested that it is useful in a variety of biomedical applications because of its properties. Some of these polymers are described in Maurice Seiderman, US Pat.
It is disclosed in the issue number sub.

A key factor in the preparation of these prior art hydrophilic polymers with improved adverbial strength is the use of less polyunsaturated cross-linking agents. The amount of cross-linking agent used is generally so small that it can be varied only slightly. Therefore, the final properties of the hydrophilic zymer cannot be effectively adjusted by varying the amount of cross-linking agent. Various attempts to avoid this problem have been made by Seidaman US Pat.
aul Stamberger) U.S. Patent No. 37!
; glA4t1.

Pending U.S. Pat. No. 212, dated Aug. 2, 1972.
No. 097, the description of which is incorporated herein by reference, discloses the outstanding pioneering discovery of the production of chemically bonded phase separated thermoloe plastic graft copolymers. These copolymers are essentially physically cross-linked (as opposed to chemically cross-linked) polymers and have been referred to as 'naturally cured 1 or 1 naturally reinforced thermo-OT plastic graft copolymers. . This phenomenon is a single-phase (domain)
The large molecular weight side 11i1't of the domain ) ) is observed during controlled dispersion into the main chain polymer phase (matrix Cmatrix )). All large molecular weight monomer side chains 1 and 9 main (integral part: integra
l part ), so (that is, the main S d? I
Inserted between J-ma's big mouth and toe! If there is a large difference in the Tg or Tm of the main chain and side chain segments, the resulting graft polymer will have all the properties of a cross-linked polymer. This JJf is actually true until the temperature required to break the thermodynamic cross-links of the dispersed phase is reached. In order to impart a desired cross-linking or spontaneous hardening effect to the domains of the dispersed phase of the IJ polymer, large molecular weight monomers (macromolecules) constituting the domains of this dispersed phase are added.
It is important that the regular monomers have substantially the same molecular composition, ie, that the macromolecules should have a ratio of W/W of substantially no greater than about. This also has a wider molecular weight distribution, approximately /,j
Alternatively, large molecular weight monomers with a ratio of 2 or more are usually very low molecular weight polymerizable reactive species (polymeric 5pe
ies) has f, which is extremely high, making it the main source of g!
Boria has 1 combination of 1 effect and 4, this detective! ? A bipartite phase, or domain gold, of different size than the polymer subdivision phase will form.

The end result is an opaque polymer of inferior quality with respect to the desired physical properties of the principally pure polymer.

The present invention relates to a process for producing chemically bonded, phase separated and self-curing hydrophilic thermoplastic graft copolymers that are water-insoluble and water-swellable. This novel copolymer comprises at least a hydrophilic (water-soluble) ethylenically unsaturated monomer or a mixture thereof (or a hydrophilized compound) and a copolymerizable hydrophobic monomer having at least seven copolymerizable end groups. Sexy large molecules European stuff! Tonoko, j? This copolymerizable hydrophobic large molecular weight monomer can be copolymerized with the above-mentioned hydrophilic monomer based on the relative reactivity ratio of each copolymerizable moiety, and its characteristic is that the load W/excitation n have a substantially uniform molecular weight distribution such that the ratio is substantially no greater than about /, /, and further have a molecular weight of at least about 1 ooo.

The egg copolymer according to the present invention is water-resistant and water-swelling!
Various products such as hydrodals for biomedical applications such as contact lenses, prosthetics, etc., industrial thickeners, ion exchange resins, and drilling muds. It finds use in applications. This new copolymer provides hygroscopic and water permeable properties for various products (useful for dialysis tube manufacturing).
JJ and belt gun prevention (anti-5taticpr
oper ties) f('j etsuru.

Furthermore, in the case M11, the present invention is a chemically bonded, phase-separated, and naturally hardened parent / consisting of (1) at least a tolerant and usually hydrophobic large molecular weight monomer with a substantially rostral-1 molecular weight distribution; 7 types of hydrophilic (water-soluble) polymers for each base such that all the chains are formed, and in this case, the above-mentioned copolymerizable, usually hydrophobic, large molecular weight monomers form all the linear polymer side chains of the graft copolymer 1. A copolymerizable comonomer or a hydrophilized compound, provided that a) the main chain of the polymer consists of the polymer units of the copolymerizable common 1 above, and the copolymerizable comonomer is hydrophilic or water-soluble; consisting of at least /
b) the linear polymer side chains of the graft copolymer consist mainly of polymerized hydrophobic large molecular weight monomers, and the hydrophobic monomers are at least It has a molecular weight of about 20θO,
consisting of a linear polymer or copolymer having a substantially uniform molecular weight distribution such that its Mw/Mn ratio is substantially less than or equal to about C) The copolymerizable moiety is less than or equal to 1, and the copolymerization occurs between the copolymerizable end groups of the hydrophobic large molecular weight monomer and the copolymerizable hydrophilic comonomer; The linear polymer side chains of the graft copolymer copolymerized into the hydrophilic polymer backbone contain at least 20 consecutive monomeric repeats 11 of the hydrophilic polymer backbone. , in the main chain of the
The distribution of the III chain and the copolymerization are controlled by the ratio of the reaction 1·L of the hydrophobic V1-7jf-total-7-7 and the co-merging group of the co-merging hydrophilic comonomer. The tocopoly 1 has a 1-type structure when its only side chain is co-combined into the aqueous cobo-lima main 4. However, hydrophilic backbone 4? When 7 or more types of +tlll songs are copolymerized in Lima, the graft copolymer 4 Hirima has a comb-shaped structure C-C-C-
b-C-C-C-b-C-C-CH-Fist 1 1 1 B a (wherein 1a'' is such that the physical property of at least one substantially linear hydrophobic poIJ-r appears) Represents a usually hydrophobic polymer or polymer with a substantially linear molecular weight of molecular weight, "bl is the co-J column after the reaction is chemically bonded to its side chain 1a" At the same time as representing the base end group, it also indicates that it is completely copolymerized into the main chain polymer.
c, 'hThe physical properties of the hydrophilic polymer appear.
Th41'4 has a 7KM segment/(represents a hydrophilic main chain y1?IJ with .).

The backbone of the graft copolymer according to the invention preferably contains at least about 20, more preferably at least about 30 consecutive monomeric repeat units in each segment. However, it has been found that particularly favorable physical properties are obtained when there are at least about 100 consecutive monomeric repeat units in each segment. This condition was found to give a graft copolymer with hydrophilic, /IJ polymer properties in the main chain. In other words, at least about 2
The presence of segments containing 0 consecutive monomeric repeating units provides a graft copolymer with physical properties ascribed to the polymer backbone, such as water affinity and water swelling +M a .

The backbone polymer segments of the chemically bonded, self-cured, hydrothermizable polymers of the present invention are derived from copolymerizable comonomers, preferably low molecular weight comonomers. These copolymerizable comonomers include d-licargenic acid, its anhydrides and amides, polyinyanates, organic epoxides (L urea-formaldehyde, including thioethoxides, siloxanes and ethylenically unsaturated monomers.Copolymerizable copolymers A particularly preferred group of ethylenically unsaturated monomers include monomeric vinyliso/type compounds, i.e. at least one vinyl 11,--CH2=
Monomers containing CH groups are included. General formula cH2=C)
+ (provided that hydrogen is 1 of the free valence of the vinyl IJ dene group)
It is intended that the vinyl-type compounds of the formula (bonded to) fall within the general scope of the vinyl-type compounds described above.

Copolymerizable comonomers useful in the practice of this invention are not limited to the exemplified compounds set forth above. Few restrictions on the specific comonomers used are free radical, ionic/condensate, condensation or coordination polymerization (Zigura or Zigra-Nata catalysts) side chains under reaction! It is the ability to copolymerize with the end groups of the repolymer. Another constraint on low molecular weight comonos 1 is that they have a functional moiety that makes them hydrophilic or that can be rendered hydrophilic by subsequent reactions.

Particularly preferred examples of this latter group of compounds consist of vinyl esters such as vinyl acetate.

This vinyl ester is copolymerized with a copolymerizable hydrophobic large molecular weight monomer having a copolymerizable double bond at the position of its molecular chain, and following the copolymerization, the obtained graft copolymer gold cake is
to make the polymer main chain hydrophilic. In other words, that/
The IJ main chain consists of 7 ribinyl alcohols.

As is clear from the description of copolymerizable large molecule quantum polymers below, the selection of copolymerizable end groups includes all commercially available copolymerizable comonomers. Therefore, the selection of the respective copolymerizable end groups for the large molecular weight monomer and the copolymerizable comonomer is selected based on the ratio of relative reactivities under the respective copolymerization reaction conditions suitable for copolymerization. That is, a simple examination of the reactivity of various comonomer pairs in the literature can provide the appropriate end groups for large molecule substrates and copolymerizable comonomers. Preferably, as is well known to those skilled in the art of copolymerization, the r value of each copolymerizable moiety is as close to/as possible. For example, acrylate or methacrylate-terminated large monomers copolymerize with acrylate and methacrylate under free-lasocal conditions in a manner governed by the ratio of the respective reactivities of the comonomers.

The advantageous combination of beneficial properties of the graft copolymers of the present invention, as explained below, is the large segments of the hydrophilic backbone of the continuous copolymer, and the fully copolymerized polymers with controlled molecular weights and narrow molecular weight distributions. linear hydrophobicity,
39 Lima side chain.

The term I-linear 1 above is used in its conventional sense and refers to a polygonal backbone with no cross-linking.

The term 1 hydrophilic 1 above is used in its conventional sense to denote a polymeric or monomeric material or thread that absorbs or adsorbs water.

The term 1hydrophobic 1 above is used in its conventional sense and refers to Ilima materials that repel water.

The average molecular weight +ll] chain polymers consist of substantially linear hydrophobic polymers and copolymers produced by anionic polymerization of any anionically polymerizable monomer or mixture thereof to produce a hydrophobic polymer. This side chain polymer will clearly be different from the hydrophilic main chain polymer.

Gra7toco according to the present invention, j? It is preferred that at least seven segments of the side chain 4 lj polymers have sufficient molecular weight to exhibit the beneficial properties of each polymer. In other words, side chain physical properties such as glass transition temperature (Tg) should be expressed. The molecular weight of the polymer side chain is generally at least about 2000, and preferably its molecular weight of 4177 is in the range of about jOQθ to about 5oooθ. Particularly favorable results were observed when the molecular weight of the polymer side chain was between about 10,000 and about 33,000. More preferably about 1000
0 to approximately 25,000.

In view of the unusually improved physical properties of the thermoplastic graft copolymers of the present invention, polymer side chains bonded by a single functional group of substantially uniform molecular weight are precipitated and dispersed in the matrix of the polymer backbone. It is believed to be what is known as a 6-domain 1 droplet. This domain, or droplet, is microscopic in size and contains a main chain polyester in the shell. The wavelength of light is F. The completed graft, J'' IJ, is clear -7'-4, which is 1 Hideaki. The hydrophobic Δ? polymer side chain is completed to give a natural hardening or reinforcement effect to the hydrophilic polymer main chain. improves the wet strength of the material.

Copolymerizable water-based Oita E amount monomer The above chemically bonded, phase-separated, and naturally hardened hydrophilic graft copolymer, l? Hydrophobicity of Lima, J? The +7mer side chain is preferably produced by anionic polymerization of a polymerizable monomer or combination of monomers. In many cases, this monomavinyl-containing compound is an olefinic compound such as 7Mk. This olefinic group-containing monomer can also be used in combination with an epoxy or theoepoxy-7-containing compound.

Co@combinant hydrophobic person-1! - Is the first step in making Numotsuma living room d? (living polymer)
) to make k. The living polymer is conveniently prepared by contacting the alkali metal hydrocarbon or alkoxide salt with the sucrose in the presence of an inert organic diluent that does not precipitate or inhibit the polymerization reaction.

These monomers that are susceptible to anionic polymerization are well known and the present invention encompasses the use of all anionically polymerizable monomers that yield substantially hydrophobic polymers of molecular weight of at least about 20θQ. Non-limiting exemplary reactants include vinyl aromatic compounds such as styrene, alpha methyl styrene, vinyl toluene and its isomers; acenaphthalene; acrylonitrile and methacrylonitrile; lower alkyl, phenyl, lower alkylphenyl and Organic incyanates, including halophenyl incyanates, lower alkylenes, phenylenes and tolylene diinsyanates; lower alkyl and allyl acrylates and methacrylates (including methyl, t-butyl acrylates and methacrylates); ethylene, f-ropylene, Lower olefins such as butylene, imbutylene, (ndene, hexane, etc.); aliphatic carbines such as vinyl acetate, vinyl fLX bionate, vinyl octoate, vinyl oleate, vinyl stearate, vinyl benzoate, vinyl lower alkyl ether Acid vinyl ester: Isogrene J5
This includes conjugated dienes such as butatsuene and kanakura. 'Low grade 1
The term is used to refer to all organic groups containing up to F carbon atoms.

Suitable olefin group-containing monomers useful for producing this hydrophobic large molecule quantum molecule are ≠~/, ]li! (7) Conjugated dienes containing carbon atoms and vinyl substituted aromatic hydrocarbons containing up to about 7.2 carbon atoms.

% K Suitable monomers include styrene, alpha methylstyrene, butatsuene and isogrene.

A number of monomers suitable for the production of side chains by anionic polymerization are listed in Macromolecule Reviews.
ecular Reviews) Volume 2, No. 74L~3, In4science... Seven Britsn Yaz Co., Ltd. (Int.
erscience Publishers, Inc.
) Published in 1967 by IT? Nomer's iIe Remerized Pie Anionic Initiator (Mon
ownersPolymerized by Anio
nic Inltia Lors), the description of which is cited throughout this specification.

These anionic polymerization initiators are all alkali metal hydrocarbons and alkoxide salts that yield monofunctional living polymers (ie, only one end of 4117 contains a reactive anion). Suitable catalysts have the general formula RMe, where Me is an alkali metal such as sodium, lithium and potassium, and R is a hydrocarbon radical, such as up to about -0 or more, preferably up to about g carbons. Aryl radical, aryl radical, alkaryl radical or aralkyl 2 containing atoms
・Contains lithium, sodium or potassium hydrocarbons 11e with zocal (all shown). Exemplary alkali metal hydrocarbons include ethyl sodium, rhoglovir sodium, n-butyl potassium, n-octyl potassium,
Includes phenylsodium, ethyllithium, 5ec-glylithium, t-butyllium and σ, 2-x tylhexyllithium. se,c-butyllithium is a preferred UM sl agent because of its rapid start-up properties, which is important for the production of narrow molecular weight distribution polymers. When the polymerizable monomer has a nitrile or carbonyl functional group, m3 such as potassium
The use of alkali metal salts of 'rkkol is preferred.

Both the alkali metal hydrocarbon and the gamma loxylate are either commercially available or prepared by known methods such as halohydrocarbons, halobenzenes or alcohols and n2
J rfE is produced and used by reaction with an alkali metal.

Generally, an inert solvent is used to facilitate heat transfer and proper mixing of the initiator and monomer.

Hydrocarbons and ethers are preferred solvents. Solvents useful in anionic polymerization processes include aromatic hydrocarbons such as benzene, toluene, gy/lene, ethylbenzene, t-glybenzene, and the like.

Saturated aliphatic and cycloaliphatic hydrocarbons such as n-hexane, n-hebutane, n-octane, cyclohexane and the like are also suitable. Furthermore, for example ° dimethyl ether,
diethyl ether, butyl ether, tetrahydro 7
Lan, dioxane, anisole, tetrahydro7,
Diglyme, Glyme
) using aliphatic and cyclic ether solvents.

The rate of polymerization is faster in ether solvents than in hydrocarbon solvents, and the addition of small amounts of ether to hydrocarbon solvents increases the rate of polymerization.

The amount of initiator used is an important factor in anionic polymerization because it determines the molecular weight of the living polymer.

When a small amount of initiator is used relative to the amount of monomer, the molecular weight of the living polymer is higher than when a large amount of initiator is used. It is generally desirable to add the initiator dropwise to the monomer (if that is the selected order of addition) until the characteristic color of the organic anion persists, adding the calculated amount of initiator for the desired molecular weight. Pre-dropwise addition helps to destroy contaminants and thus allows better control of the polymerization.

To produce polymers with narrow molecular weight distributions, it is generally advantageous to introduce all reactants into the system simultaneously.

By this method, polymer growth by sequential addition of O and monomer occurs at the same rapid IFL with active end groups without chain transfer or termination reactions. Once this is done, the molecular weight of the polymer is controlled by the monomer/initiator ratio as stated by the following equation: As is clear from the above equation, a high concentration of initiator will produce a low molecular weight polymer; Low concentrations of initiator destroy the entire polymerized polymer.

The mlK of monomer added to the reaction vessel varies widely, but
The viscosity of the living polymer obtained by avoiding the loss of polymerization heat
However, it is limited to the ability of the reactor to mix all suitable crucian carp.

Use 50% by weight or more of high-a-grade sagebrush based on the weight of the reaction mixture. However, the preferred monomer a degree is from about j to about 2j% to provide proper incorporation.

As is clear from the above formula and the above limitations on monomer concentration, the initiator concentration is critical and can be varied depending on the desired molecular weight of the living polymer and the relative concentration of the monomers. Generally, the initiator concentration is about o, ooi per mole of monomer.
~about 0. / mole of active alkali gold M or more.

Preferably, the initiator concentration will be from about 0.0/ to about 0.00≠ mole active alkali metal per mole of monomer.

Polymerization temperature depends on the monomer. Generally this reaction is about -7
It can be carried out at a temperature of 0.00 to about 700°C.

The preferred temperature range for r+1 aliphatic and hydrocarbon solvents is from about -70 to about 700C. Using ether as the solvent, the preferred temperature range is from about -700 to about 700C. Polymerization of styrene is generally carried out slightly above room temperature. The polymerization of alpha methylstyrene is preferably carried out at low temperatures, for example -,! Performed at 1″θ°C.

Living polymers are produced by adding a solution of an alkali metal hydrocarbon initiator in an inert organic solvent to a mixture of monomers and diluent at a desired polymerization temperature, and leaving the mixture with stirring or without stirring until polymerization is complete. The vine is done. In another method, monomers are added to a diluent solution of catalyst at the desired polymerization temperature at Mti equal to the polymerization rate. In either method, the monomer is quantitatively converted to living polymer as long as the thread does not contain impurities that would inactivate the anionic reactant. However, as previously indicated, it is important to add all reaction components together quickly to ensure formation of a polymer with uniform molecular weight distribution.

Anionic polymerizations must be carried out under carefully controlled conditions to exclude substances that would destroy the catalytic effect of the catalyst or initiator. For example, impurities such as water, oxygen, carbon oxide, and carbon dioxide. That is, the polymerization is generally carried out in a drying apparatus using anhydrous reactants under an atmosphere of an inert gas such as nitrogen, helium, albo/methane, and the like.

The living polymers described above are susceptible to subsequent reactions, including subsequent polymerization. That is, when an additional monomer, such as styrene, is added to this living polymer, the polymerization is reformed and the chains grow until no more styrene monomer is present.

or by adding a different anionically polymerizable monomer (such as butadiene or ethylene oxide) to the pond.
The double glue/glue polymer initiates the polymerization of butadiene or ethylene oxide and the final living number obtained? Lima H,t = consisting of a restyrene segment and a polybutadiene or polyoxyethylene segment.

dibtock hydrophobic copolymers combine a first living polymer, such as living polystyrene or a living polymer of a vinyl aromatic compound, such as H I7 bing poly(alpha-methylstyrene), with another anionically polymerizable monomer, such as butadiene. or produced by contacting with a conjugated diene such as Inglene.

Thus, according to the method of carrying out the present invention, the reaction is completed and a living diblock, je lima, is obtained. Using this method, the following general living diblock polymer can be obtained (A is a polymer block of a vinyl aromatic compound, and A is a polymer block of conjugated tzene). 6) Copolymerization with a diblock structure A monomer with a large molecular weight is disclosed in the pending U.S. Patent Application No. 3≠7//O, the description of which is cited throughout the present specification.

As mentioned above, the living polymer used in the present invention is characterized by a relatively uniform molecular weight. That is, the molecular weight distribution of the living polymer mixture is extremely narrow.

This is in sharp contrast to typical po-17-r, which has a very broad molecular weight distribution. The difference in distribution is due to commercially available polystyrene (Dak CDow) manufactured by free radical polymerization.
6b b u') and polystyrene produced by the anionic throat method used according to the invention. That is, a characteristic of the V/G polymers produced in accordance with the teachings of the present invention is that they have a Mw/Mn ratio that does not exceed the actual T(T).

Here, Mw is the weight average molecular weight of the living polymer, and Mn is its number average molecular weight, which can be determined by a conventional analytical method such as permeation chromatography (GPC).

This living polymer is terminated by reaction with a halodane-containing compound that also contains polymerizable moieties such as olefinic groups or epoxy or thioepoxy groups. Suitable -rodane-containing terminators include vinylyl groups containing up to 6 carbon atoms such as methyl, ethyl, globyl, butyl, imbutyl, 5ee-butyl, amyl or hexyl; Vinyl esters of loalkanoic acids; vinylnonoids, allylnolides, methallyl halides, where the acid contains 6 or fewer carbon atoms, such as acetic acid, globionic acid, acetic acid, pycnic acid, or hexypic acid. , 6-nohero/-olefin/2-ide with up to 6 carbon atoms, such as hexenato;
non-lomethyl-/, 3-butadiene, epihalohydrin, acrylyl and methacrylyl ha/F()', haloalkylmaleic anhydride, die/halide such as loalkylmaleic ester; vinylhaloalkylsilane; vinyltroaryl; vinyl Pen silk 0I
J) Vinylno-10 alkaryl such as '(VBG);
Included are bromomethylnorzenene, gamnol, and epoxy compounds such as ethylene or gouvile/oxide. The base of this compound is fluorine, fluorine, fluorine, or iodine, but is preferably fluorine.

Anhydrous compounds containing olefinic groups or 49-oxy or thioepoxy groups, such as anhydrous acids, acrylic or methacrylic acids (hydrogens may also be used).

Termination of the living/tumor reaction is accomplished by simply adding a terminating agent to the living polymer solution at the time the living polymer is being produced. The reaction is instantaneous and the yield agrees with the theoretical value/). Does the reaction proceed in a mole-mole relationship? However, a slight molar excess of terminator is used relative to the amount of anionic initiator, ttC.

This termination reaction can be carried out in any suitable inert solvent. It is generally recommended to use the same solvent yarn used for living polyph production. In a preferred embodiment of the present invention, the termination reaction is carried out in a hydrocarbon solvent rather than in a polar ether type solvent such as tetrahydrocarbon. Tae. It has been found that hydrocarbon solvents such as aromatic hydrocarbons, saturated aliphatic and cycloaliphatic hydrocarbons produce some differences in reaction conditions and products obtained. For example, termination reactions occur at higher temperatures in hydrocarbon solvents as opposed to ether solvents.

Depending on the nature of the living polymer and the monomers from which it is made, or the nature of the terminating agent, certain harmful side reactions may occur resulting in impure products. For example, some living 4-lima carbanions tend to react with the functional groups of the terminator or with any active hydrogens. (
-Thus, for example, acrylyl chloride or methallyl halide has a chlorine atom in its structure, so it acts as a terminator, and at the same time it has a carmenyl group in the terminating chain, and this carmenyl group is The living polymer, which has a high degree of reactivity, becomes the center of attack.

The resulting polymer has twice the expected molecular weight or contains some chlorine, with some glue/glymer combined with the λth living 4 lima or one activated hydrocarbon of acrylyl chloride or methallyl halide. It has been found that one means of overcoming the above-mentioned problem of termination by the reaction of the terminating agent is to make the reactive carbanion less susceptible to reaction with the functional group of the terminating agent or with any active hydrogen. 7Lfco
! A preferred method of propagating I-Vi/G polymers with adverse reactions is to W-cap the highly reactive living polymer with a less reactive reactant. Some favorable f! , 'capping
Examples of 'agent)' include lower alkylene oxide,
i.e., those having f or more carbon atoms, such as ethylene and globylene oxide: nophenylethylene, etc. This one-cap one reaction still yields a product that is a living polymer, but subsequent reaction with a terminator containing a functional group or active hydrogen does not yield an even purer product.

It has been found that sophenyl ethylene chloride is an excellent single cap agent 1 when using a terminating agent such as phenyl chloralkanoate.

Particularly preferred compounds are ester silyl oxides such as ethylene oxide. This is so funny oxy2ffl'
r is destroyed and reacts with the living polymer. The following is a representative example of a single cap reaction, which shows the reaction between a living/IJ polymer prepared by the polymerization of ethylene oxide as a cap agent and a styrene initiator 5ee-butyllithium: The cap reaction, like the termination reaction, is carried out very simply by adding the cap reactant to the living polymer at the polymerization temperature. This reaction, as in the case of immediate termination reactions, employs a slight molar excess of cap reactant compared to the amount of initiator. This reaction occurs on a mole-mole basis.

It will be appreciated that reacting a large molar excess of 1-rukylene oxide with the living 4e lima yields a two polymer block fc motripy/g polymer. A representative example with the polystyrene segment J1 hyliooxoalkylene segment is illustrated below: (where X is an integer).

Any of the above-mentioned ethylene oxide monomers and (?+) polymers can be conveniently terminated by a compound having a moiety that reacts with the anion of the d-cap polymer and a polymerizable tidal group. Typical examples of this compound include: racrylyl chloride, methacrylyl chloride, vinyl-2-aryl ethyl ether, vinyl chlorahitate, chloromethylmaleic anhydride and its esters, anhydrous Maleic acid (7'a)ylation of water followed by -
Allyl chloride and hymetalyl chloride and vinylpe/sol chloride.

. The reaction of the above l crown r41 living polymer with l crylyl or methacrylyl chloride can be represented by the following reaction: where n is a positive integer of at least about jO, X is 0 or a positive integer, R4 is hydrogen or methyl.

) When lohydrin is used as a terminator, the resulting polymer contains terminal epoxy groups. This terminal epoxy can be used as the polymerizable group itself, as in the preparation of polyglobylene oxide/de backbone graft copolymers, or
Any one of several known reactions can be used to convert a variety of molecules into useful polymerizable end groups.

In one embodiment of the invention, a terminated living polymer containing epoxy or thioepoxy end groups is reacted with a polymerizable carmenic acid...ride, such as an acrylic, methacrylic or maleic acid halide, to form a polymerizable polymer of substantially uniform molecular weight. The end moieties are used to produce beta-human 90-quine alkyl acrylate, methacrylate or maleate esters. These same polymerizable esters are prepared from this terminated epoxy polymer by first converting the epoxy groups to the corresponding glybules by heating the N177 with an aqueous solution of gadolinium hydroxide, and then converting the glycol end groups to the appropriate glycol end groups. Polymerization 1 Raw Cal J? +, fl 'f tobacco i
It is produced by esterification using a single-use method using a dredger.

The glycol obtained by aqueous hydrolysis of the epoxy group of the base (f:
It can be converted into a copolymer by reacting excess molar amount of talic anhydride, maleic anhydride, succinic anhydride, etc. with high molecular weight phosphoric acid 1 prepared by Tokura. These reactions'fc, 10 restyrene blocks and +1? Liamid block (nylon) and change to get money. This glycol-terminated polymer is reacted with a diisocyanate,
You can also make Nohiri urethane. This diiso'/ft may be, for example, 5 C of the reaction product iJQ of l+e IJ ethylene glycol with an excess molar excess of phenylene noisocyanate with an average content of J-S0≠00.

In another aspect of the present invention, Tateki epoxide is epoxy i1' or toni, 1? Coconut end, end containing group at rt,
I? Let's get together with IJ Ma. The graft copolymer has characteristics of at least about 20, preferably at least about 30
If of organic epoxide! It is a main chain with continuous segments/trs. Suitable organic epoxides include ethylene oxide,
Included are cyclohexene epoxide and styrene oxide, ie, those having g or more F carbon atoms. This backbone polymer is made hydrophilic by simple hydrolysis.

If the large molecular weight monomer is to be separated from the solvent in which it was produced and further purified, any known technique used by those skilled in the art for recovery of the de 177 material may be used. These techniques include (1) solvent-nonsolvent precipitation; (2) evaporation of the solvent in an aqueous medium; (3) evaporation of the solvent by methods such as vacuum roll drying, spray drying, and freeze drying; (4) Includes steam jet coagulation.

Separation and recovery of large molecular weight monomers is not a limiting aspect of the invention. There is no sense of security in actually recovering large molecular weight monomers. In other words, the large molecular weight monomer produced is placed into the yarn from which the large molecular weight monomer was made along with the appropriate monomer and polymerization catalyst and copolymerized as shown in Figure 1. Tsuba 1 in this large molecular weight seven-piece production reactor
Insect vectors, poisonous insects, and granoids have no adverse effect on the copolymerization process). What is the wise folding resistance of the solvent and the material used in the grafting process of the present invention? This results in significant savings in Lima 111 construction.

As mentioned above, the large molecular weight monomers that are completely polymerized into the backbone polymer and ultimately become the side chains of the graft copolymer must have a narrow -F lj,1 distribution.

71 like this large molecule/pickled mushroom? l) Methods for determining the molecular weight distribution of polymers are known in the art. Using these known methods, i, 9 quantity ゛ weight average molecular weight (young W) and number ゛ (le average weight - r - 1 □ ('i □ n) are confirmed, and the dog molecule hanging sheep's weight is determined. Molecule - Determine the best distribution (iw/kan) (~Tsuru・Kono Oita 1-11 Seven Tsumas have the highest degree of ) Cloth UJ
min-f-1it f, 4:I-) IJ)t fc
h Real gL upper 111, minute M property (rnonodispe
rse ). j-nawara cargo w/M
The n ratio is substantially no more than about /, /. Preferably Konoya [
The Mw/Mn ratio of regular large molecular weight monomers is about /, / or less. The large molecular weight monomers according to the invention have the narrow molecular weight and purity described above by the above-described production method. Therefore, Oita-
It is important that the order of the fi monomer manufacturing steps be followed to best impart beneficial properties to this graft copolymer.

As is clear from the above description, the hydrophobic copolymerizable large molecular weight monomers contemplated in the present invention are generally represented by the following structural formula: where 1 represents a single monofunctional monomer initiator. residue, P
At least 7 anionically polymerized monomers Py
, ”), P p l'i at least 7 anionic polymers (can be the same as or different from P□; R is hydrogen or lower alkyl, R' is hydrogen or 1-C-OX ( where X is hydrogen, lower alkyl or /lli metal); ni"J is a positive integer of at least about 20, m is the genus of θ or +1, and n+m is a large molecular weight monomer. The number of molecules of is at least about,! ooo, preferably a value of 5000 to about 5oooo, and 0\
qsr and S are θ or /, p is 0 or (l-
is an integer of 1F within the range of t/ to about , and 0 and p are /
then q is 0, r is 0 or /, s is 0 or /, t
is /, and if 0 is 0, p is an integer of 1) q, ,
rsss and t can be θ or / and \0\Q%
If r-= S and t are θ, then p is an integer and 5 can be 0 or /: IJ B and V are 0 or /, and if U is /, then V is 0, and if ■ is /, then baU is 0
It is. And this large molecular weight monomer is the sleeve w/Mn
It means to have a substantially uniform distribution of molecules such that the ratio is substantially equal to or less than A/A. Ta! W is the weight of the monomer, P is the average molecular weight, and Mn is the average molecular weight of the monomer.

As mentioned above, P and P2 are preferably vinyl aromatics and conjugated dienes. It's Lima.

Copolymerizable Hydrophilic (Water-Soluble) Compounds The copolymerizable comonomers suitable for obtaining the hydrophilic polymer backbone of the graft copolymers according to the invention are those which are water-soluble or which are not made water-soluble after copolymerization. Must not be.

These compounds must be copolymerized to form water-soluble substances or water-solubilized substances. The term water-soluble 1 is used herein to include compositions that are homogeneously miscible in water at room temperature at least about 10% by weight, preferably at least 30% by weight. Suitable copolymerizable monomers contemplated for use in preparing the hydrophilic polymer chains of the graft copolymers according to the invention include: acrylic and methacrylic acids; A diester whose nistermoieties contain at least seven hydrophilic groups such as hydroxyl groups. That is, typical human mixy lower alkyl acrylates or methacrylates are as follows: λ-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, no-hydroxygumivir acrylate, 2,L-hydroxyethyl methacrylate, 3-hydroxyfOvir acrylate, 3-
Hydroxyethyl methacrylate, noethylene glycol monomethacrylate 1, ethylene glycol monoacrylate, nonoropyre/glyl monomethacrylate, oyohidideropyre/glycol monoacrylate 1 root.

Water-soluble vinyl monomers having at least 7 nitrogen atoms in the molecule, examples of which are: niacrylamide, methacrylamide, methyl acrylamide, methyl acrylamide, diacetone acrylamide, N-methyl Acrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, N,N-disubstituted acrylamide (even GzN,N-,zomethylacrylamide; N,N-ethylacrylamide;
-ethyl-methylacrylamide; N,N-dimethylol-acrylamide and N,N-dihydroxyethylacrylamide), heterocyclic nitrogen-containing compounds (eg. Aku IJ Royle pylori r
y, N-acryloylbivorysine and N-acryloylmorphole/), and also monomeric gold with cationic functionality (e.g., vinylpylidene 77monium salt, and trimethylaminoethyl methacrylate 77monium salt). High grade ammonium salt and trade name Sipomer
A compound known as Q-/).

A particularly preferred group of compositions includes those that can be rendered hydrophilic in a post-bolification reaction. For example, vinyl formate, vinyl acetate, vinyl monochloroacetate, and vinyl butyrate are copolymerized with the copolymerizable large molecular weight monomers described above, and following the copolymerization reaction, vinyl chloride Estelle's Nanatsume Link I
<B The main chain of HD 177, including the tit position, is hydrolyzed to make it hydrophilic as polyvinyl alcohol. In other words, the polymer backbone of the polymer is Iridonyl alcohol.

The above-mentioned hydrophilic monomers are made hydrophilic by a subsequent reaction and are used either in moromi or in combination, or in copolymers with copolymerizable comonomers (interpol).
ymer) as 11j! can be used. The copolymerizable monomer used in admixture or combination with the woody monomer or hydrophilized vine may be any ethylenically unsaturated monomer, including the free-flowing or hydrophobic monomer,
'A combination with a hydrophobic copolymerizable large molecular weight monof1 is included. Suitable hydrophobic copolymerizable monomers to be interpolymerized with the hydrophobic copolymerizable large molecular weight monomer 1 described above and the hydrophilic comonomer 1 described above include alkyl acrylates and methacrylates such as methyl acrylate or methacrylate. , ethyl acrylate or methacrylate, globyl acrylate or methacrylate, butyl acrylate or methacrylate, with butyl acrylate being preferred.

Suitable hydrophobic comonomers for use include vinyl chloride, pinylene chloride, acriminitrile, methacrylate tolyl, vinylidene/anide, vinyl acetate, vinyl gropionate, and vinyl aromatics (e.g., styrene and alpha methylstyrene, and anhydrous male 47m).

Suitable groups of comonomers useful in preparing the water-soluble polymer backbone of the graft copolymers according to the present invention include acrylics and (-
monoesters of methacrylic acid and polyhydric alcohols (e.g. -human acrylate and methacrylate); and vinyl monocargenates such as vinyl gamma sedate, which are saponified with an alkali during the copolymerization reaction.

Flooded pj-copolymer ÷ chain-forming coffi-forming comonomer and the above-mentioned co-ii-forming hydrophobic Oita-r which is co-IJ-combined
The amount of Motsuma 1 is in the range of about 733% to about 733% of the copolymerizable comonomer forming the hydrophilic polymer. Stated another way, a bonded, phase-separated thermoplastic granoid copolymer with a hydrophilic polymer backbone has (1) a narrow fraction I-B of about 7 to about 5 wt.
Copolymerization with liquid distribution 115 Hydrophobic large molecule attached monot and (
2) Hydrophilicity of about 77 to about 5 layers; 1? It consists of a copolymerizable comonomer that forms the entire main chain of Lima. Preferably polymer 1
& To achieve final mechanical strength, this graft copolymer, 7p lima, has a strength of up to about 6θM vertical %, more preferably from about 2 to about 1 It.
% by weight of the hydrophobic large molecule monomers described above.

A copolymerizable comonomer (and possibly a small amount of IE modified by a person skilled in the art) to form the IJ polymer backbone
mower -7 (modifier mono+ner
) with a suitable small amount of comonomer) 1
It is carried out by l-volume liquid polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and non-aqueous suspension polymerization.

Generally, it is preferable to remove all the copolymerization 1 hydrophobic macromolecular monomers remaining unreacted in the polymer thread after the copolymerization reaction is completed. Removal of monomer at one end of this large molecule 1&:
This can be accomplished using any suitable IE means, such as solvent extraction.

Depending on the situation, especially when the nails are put together, the joints are molded like a contact lens! The test was carried out in the LJ type.

In this case, in order to further improve the wet strength of the kraft copolymer, a cross-linking agent is fully added to the copolymerization reaction.

Suitable cross-linking agents for this purpose include ethylene glycol no methacrylate, noetele/glycol no methacrylate, novinylbenzene and N,N-methylene-bis-methacrylamide. Generally depends on the desired cross-linking adhesive.The appropriate amount of cross-linking agent is from about 0.0% to about 0.0%, Zti&%, or generally less than about 1 mol. lsuuru.

When using a polymerization reaction catalyst for a copolymerization reaction, a suitable polymerization reaction environment should be used for the catalyst. IC
For example, oil or solvent-soluble acid, such as benzoyl, is a copolymerizable and water-dispersible monomer with a large molecular weight and an ethylenically unsaturated fumonomer in bulk. Generally effective for copolymerization in solutions or aqueous solutions in solvents such as toehabenzene, toluene, toluene, chloride/V7, etc.1. and ammonium salts are useful in aqueous suspension and emulsion threads. In the copolymerization reaction of many copolymerizable and hydrophobic monomers of large molecular weight, such as monomers with ethylenically unsaturated end groups and polystyrene/polyingrene or polygetadiene, emulsifiers or dispersants are used. It can be used in aqueous suspension.

Particular advantages can be achieved in these yarns by dissolving the water-insoluble, high molecular weight monomers in small amounts of suitable solvents, such as hydrocarbons, at medium pressure. This novel technique copolymerizes monomers in a solvent with polymerizable large molecular weight monomers in an aqueous system surrounding the solvent-polymer yarn. Of course, the polymerization reaction catalyst is selected to be soluble in the organic system of the polymerization reaction yarn.

The polymerization reaction catalyst used can be any suitable catalyst for polymerizing compounds having ethylenically unsaturated bonds (but meeting the above criteria), but is preferably a 7-radical catalyst. Catalysts of particular interest are, for example, azobisin butyronide substitutes and arm oxide catalysts. Suitable mother-oxide ll1ll! Some examples of media include hydrogen peroxide, benzoyl, IF-oxide, t-butyl! -Octoate, 7-tarinoku-hei-oxide, zakushininoku-! -Oxide, benzoylacetic/mono-oxide, coconut oil oxide, laurinoc/mother-
oxide, stearic acid, male ink/
Included are arm oxide, t-butylhydro-oxide, not-t-butyl g-oxide and the like.

Suitable catalysts are suitable at moderately low temperatures such as about 4/-, t-a',
It is effective at t°C.

In addition to free radical polymerization reaction catalysts, catalysts include materials that polymerize primarily by cleavage of epoxide groups, such as copolymerizable hydrophobic monomers having epoxy-terminated groups. Such catalysts include p-toluenesulfonic acid,
Included are sulfuric acid, phosphoric acid, aluminum chloride, stannic chloride, ferric chloride, boron trifluoride, boron trifluoride-ethyl ether complex, and iodine. It may be desirable to use multiple polymerization methods.

The amount of catalyst used depends on the type of catalyst yarn used.
Generally, about θ per 100 parts by weight of the comonomer mixture
, / to about /θ heavy seams, preferably from about 0.7 to about / parts by weight per 100 parts of the comonomer mixture.

The copolymerization reaction is generally conducted at a temperature of about room temperature to about tAs<0>C. Generally, however, the polymerization reaction is initiated at a relatively low temperature, e.g., from about 4LO to about 60SC, and then the temperature is maintained at a temperature of from about 70 to about 6S as long as the reaction continues, preferably after most of the reaction is complete. : It is preferable to raise it to . The optimum polymerization reaction initiation temperature range is between about ≠j and 70°C. This polymerization reaction is usually carried out under autogenous pressure in a closed reactor. However, any suitable means may be used to prevent significant evaporation of any of the monomers.

The copolymerization reaction is generally completed in about ≠ to about lI-g hours, but preferably in about 6 to about 2≠ hours.

Of course, time and temperature are in an inversely proportional relationship. That is, temperatures used at the upper end of the temperature range provide a polymerization process that can be completed in times near the lower end of the time range.

(2) +: After the polymerization reaction, if desired, the graft copolymer can be post-cured by any suitable means. However, the graft copolymer according to the present invention has a natural f
Since it exhibits strong ylf action and natural hardening action, such post-curing is generally not necessary, but is an exception for applications where significant C-sparing is desired. If post-curing is desired, the general or diagonal shape of the desired product and (
or) including post-curing which may be carried out in a mold or cast to size;
jo 1) After Ma is completed, a solid, hard, and transparent coy + = IJ Ma? be moved. The manufactured product is then immersed in a simple liquid until reaching V-equilibrium or resulting in a hydrogel containing the desired amount of liquid, e.g. an aqueous liquid.
or can be moistened. In addition, it should be noted that for human locales it is also possible to obtain the polymers according to the invention by swelling them with water-soluble swelling agents instead of aqueous liquids. Water-soluble swelling agents include ethylene dalicol,
Liquid Polyé f-Rengelicol! Includes glycol chloride, formamide, dimethylformamide, dimethyl sulfoxide and the like.

In addition to being molded as is, the copolymers according to the invention can be processed by compression molding, extrusion or injection molding.

It is also within the scope of this invention that the copolymer be coated onto the pond substrate material. In this example, Dashi 7 Toko J 171 according to the invention is particularly useful as it has both hydrophilic and hydrophobic groups. Either or both of these groups may be compatible with the coated substrate.

Copolymerization with a hydrophobic large molecular weight monomer that is copolymerizable with a second monomer as indicated in pending U.S. Patent Application No. 1077, the disclosure of which is herein incorporated by reference. The reactive or reactive end groups are specifically selected based on the relative reactivity ratio of the second comonomer chosen to form the hydrophilic polymer backbone. That is, the present invention provides a means for controlling the backbone of a graft copolymer.

In further detail, control of the tocopolymer backbone can be achieved by any one or all of the following means.

(1) During the co-111 polymerization reaction, the reactivity ratio of the hydrophobic large molecular weight monomer 3L and the second 7 monomer fiil
('C means homo, +?Polymer means l)
An undyed pure graft copolymer can be produced = (2) coi1j synthesis hydrophobic large molecular weight (·) - during the coiJj synthesis reaction of the second copolymer By increasing the addition rate k r+, 1 Jta1, l?
! The distance between side chains in the J-ma structure can be controlled: j-3
and (3) the size of the grafted chains can be controlled in the negative polymerization reaction step for producing co-jU-combinable hydrophobic macromolecules.

Phase separation is controlled by appropriately removing the reaction stop. In the production of lima r
It will be apparent to those skilled in the art that any copolymerization reaction mechanism may be used.

Is it +I to be heavily armored? The positioning of the side chains in the main chain of U is due to the large molecular weight Nanatsuma and the second copolymerizable j-T-
The fact is that it is based on the terminal group of Tuma.

That is, the main chain; 'side Hd along the lima? The distribution of Lima is controlled by the reactivity ratio of each Gomonomer.

As shown in the above text, the i (polymerizable hydrophobic monomer of the present invention has a reactivity ratio of 1, i, and λ (C, therefore, UtaI>1)) The U!I is copolymerized with monomers that form the entire main chain of the IJ polymer.

It can be shown that the copolymer equation according to the present invention: is easily transformed into the approximate formula: (2) % formula % when the molecular concentration of M is extremely low. That is, the co-reaction reaction of a large molecular weight monomer (M) with a pond monomer (M2) is described solely by the r2 value and the monomer feed composition. If we rearrange equation (2) completely, we get q-.

The reactivity ratio r2 can be estimated from a relatively low conversion sample of a single copolymerization reaction experiment. This concept of predictable and controllable reactivity of copolymerizable hydrophobic large molecular weight monomers can thereby be established. It has been shown that the reactivity between commercially available monomers and the copolymerizable hydrophobic large molecular weight monomer according to the present invention having various terminal groups is related to the manually determined literature value for the reactivity ratio of r2.

Unique properties according to the method outlined above
Graft Co., Ltd., which has a combination of 15 lima, is produced. These unique combinations of properties are made possible by the novel methods described herein that enhance the overall miscibility of immiscible segments in the case of II. These immiscible pigments separate into phases of their own kind. In other words, hydrophilic zl? ! Jp main chain and hydrophobicity, Jp lima +
In the case of the graft copolymers according to the invention with III chains, separate phases of the respective polymers are formed. The structure of this product consists of hydrophobic regions dispersed within a hydrophilic polymer matrix. The hydrophobic regions are interconnected by water-soluble linking segments. The hydrophobic regions act as cross-links and provide wet strength to the water-swollen polymer backbone. The degree of swelling in water can be controlled by the amount and molecular weight of the copolymerized hydrophobic large molecular weight monomer and by the organization of the water-soluble or hydrophilic polymer backbone. Examples of one type include acrylic acid/ethyl acrylate with a hydrophilic backbone of about j~1oo10 and about /θ,000~
of molecular weight and total product in the range of about 35,0θθ, 20
- Compositions comprised of methacrylate-terminated polystyrene having a weight range of 0%. This product is swollen with water to provide a useful hydrodal.

Since the graft copolymers consist of hydrophilic and hydrophobic segments, they are pigment 1. T? It is particularly useful as a protective colloid or suspension stabilizer for lJ mass suspensions, emulsions, etc. They also address the rheology of paints.
It is useful in the production of four-layer formulations in which the protective coating and coating or hydrophobic polymer Illm which can control the ogy) serve as stabilizers and adhesion promoters.

The novel graft copolymers according to the invention are also particularly hydrophilic 4? It is useful as a flocculant when the Lima backbone harbors some monomers. Polymeric materials with these types of backbones can also be used as wet end additives.
dditives).

These copolymers can also be used as thickening agents or defoamers. The dual nature of the novel copolymers according to the invention also makes them useful as wetting and coupling agents for hydrophilic surfaces in applications as adhesives and binders.
) is useful as

The high wet ff4 strength of the novel copolymers of the present invention makes the Ilima compositions of the invention useful as water permeable membranes, membranes, hydrogels, ion exchange resins, conductive, ff1J polymers. Water-permeable and water-absorbent compositions can also be produced by incorporating copolymers according to the invention into films and the like. When copolymerizable hydrophobic large molecular weight monomers are used at low concentrations, the product has antistatic properties, especially when cationic functional moieties are included in the hydrophilic Ft polymer backbone. The copolymers according to the invention are also useful for their antistatic properties when deposited on packaging films λ and for providing atomization-free surfaces.

Gelabto polymers, which contain a combination of hydrophilic and hydrophobic polymer chains in a single molecule, have enhanced thickening properties over conventional industrial thickening agents.

The solubility of Gra7tco, L177 according to the present invention is that of random copolymer (R).
It is different from.

Even if the solubility of the random copolymer allows it to be treated as if it were a new polymer composed of a single heptad unit, the graft copolymer according to the invention contains elements that constitute homopolymer chains. Immiscibility and phase separation usually occur as soon as the interaction of two different polymer chains becomes significant.

For example, a compound consisting of water-soluble and water-insoluble components
When Toco I Lima is added to a compounded latex, interactions between the polymer thickener and the latex particles, or pigments, and clay occur and the molecules of the polymer thickener disintegrate.
Since the two homopolymer chains are incompatible, the hydrophobic chains combine to form microparticles of gold. 1 (6 is ta immediately)
The microglue particles of the hydrophobic part of the thickening agent molecules act as cross-linking points, forming a network where all the particles are bound together by the latex thickening agent molecules to form large aggregates. is formed. When using polymers as industrial viscosity agents, flocculants, etc., the most effective structure is two incompatible Pomopa structures. Lima chain, one of which is hydrophilic and the other is hydrophobic.
block copo+)-r or graft core f containing
? It is 177. The hydrophilic portion of the molecule makes the hydrophobic portion soluble, making the entire molecule water (or alkali) #1.

When a thickening agent is added to a compounded latex, an interaction between the thickening agent and the latex particles, clay, and pigment occurs, reducing its water solubility.

The hydrophobic part of the molecule becomes insoluble in water and is incompatible with the rest of the molecule, so it aggregates into microdals.

- The novel graft copolymers according to the invention can also be used for pharmaceutically active substances and for natural and synthetic flavorings,
Essence, flavoring, sugar, food layer coloring, sweetener,
Adapted as a carrier for dyes and their analogs.

That is, various additives are described by Thomas Hsieh, Tho
mas Fl, 5heppard) '5, the disclosure of which is incorporated herein by reference.
520 R≠T Specification +1 may be incorporated into the graft copolymers according to the invention in the disclosed embodiments.

The invention is further illustrated by the following examples, which are not intended to limit the invention in any respect. Care should be taken to keep all materials pure and the reacted mixture dry and free of contaminants in each case.

All parts and parts unless otherwise specified are by weight.

Example / Production of polystyrene terminated by allyl chloride In a stainless steel reactor
0, LU calcium hydride was charged with pre-dried A, C, S, grade benzene (9 yb, 5'b part containing no thiophene. Reaction profit ≠ θ Heat it to 0°C and inject it into the skin IK'
0.015 part of nophenyl ethyl alcohol was added. I dissolved 5eC-butyllithium gold in hesan! ,
2. /To solution gold added little by little to the reactor and permanent orange 6
I had to hold the second color gold, and at this point I was in the 5th place in history.
, g and 5 parts (/6 o7r:/shi) of 5ec-butyllithium bath solution were added to the solution, and the temperature was increased to 2.2.741X (2/g mole) for t≠ minutes. The reactor temperature was maintained at 36-IL°C. Tie 1 during polymerization
The -)C reaction was quenched by adding 1 styrene/70,/, 27 parts of -Rilku01J to the reaction mixture. In order to precipitate the resulting polymer, α-olefins are added to the end and -f l, +5 styrene-benzene in gold methanol, and in this way the 1? Rimmer was precipitated.

This alpha olefin-terminated polyester V7 was dried in an air-circulating hot air dryer at ≠0 to ≠jC, and then traces of methanol were removed in a fluidized bed. The concentration of methanol juice after purification was /Q ppm. The molecular weight of 4f 177 is /611 when measured by a membrane phase osmometer.
tOθ (theory: /30θ0), and the molecular weight distribution was extremely narrow, that is, MW/M n was 7.05 or less. The Oita hand-stitched monomer had the following structural formula: (where n has a value such that the molecular length of the polymer/f′ θθ).

Example Production volume of poly(α-methylstyrene) terminated with corelyl chloride 4L7 in 2300 tnl of tetrahydro7 run
jg (lAθ mole) of α-methylstyrene-<g but this solution contains /! of n-butyllithium. Treated by dropping thihexane solution to maintain pale red grapes/2. Sui
ni [n −-f-/-Rurichiu! -304(0)
, 3 to 3) gave a bright red color when gold was added.

Next, 5'g (0.06 mol) of allyl chloride was added to the IA:i of this mixture to θC. (The red color disappeared almost instantaneously, indicating the termination of Libi/G.1? Lima) 11 (The colored solution was poured into ethanol and terminated by an α-olefin. Tapoly(α-
According to vapor phase osmotic pressure measurements, this material was precipitated in methyl styrene). //θ00 (theoretical 2/230θ)
It is shown that the enemy distribution is extremely narrow, that is, MVV/Mn is /
, 6/ζ from 0j to F. Obtained 1st. The large molecular weight monomer had the following structure (where n is a value such that the molecular weight of the polymer is /100θ).

Example 3 Preparation of polystyrene terminated with vinyl chloroacetate 1 drop of diphenylethylene was dissolved in 2300 ml of cyclohexane and 4 parts of this solution was treated dropwise at 0°C with a 12% solution of 5ec-butyllithium in cyclohexane. Add /r-(060241 mol) of the 5ec-butyllithium solution to maintain a pale red color and then 3/2I
C3.0 mol) of styrene was added. After maintaining the temperature of the polymerization reaction mixture at tl-≠θ℃ for 3θ minutes, ftnt(0,
The living polyIJ styrene was capped by treatment with diphenylethylene (OIAθ mol) and end-terminated by treatment with l, w (0, OJ′ mol) of vinyl chloroacetate. This cyclohexane solution was added to methanol to precipitate the resulting polymer, which was then filtered to separate the polymer. Its average molecular weight as measured by vapor phase osmotic pressure is /, 2θ
0θ (theory: /3.2b!;), and the molecule-leaf distribution was extremely narrow, i.e., iW/sen n was /,06 or less. The produced large molecular weight monomer had the following structural formula: (where n is an angle 1 such that the molecular weight of the polymer is /, 2000) Example ≠ Vinyl chloroacetate is terminated by Tahori (α
-Methylstyrene) production volume, 357 in 2 j 00- of tetrahydrofuran
．． 9 (3.0 mol) of α-methylstyrene was dissolved, and a 72% solution of t-butyllithium in pentane was added dropwise to 7 fL of this solution to maintain a pale red color. Then further/Left 0. When 0.03 mol of the t-butyllithium solution was added, a bright red color was generated.

Next, the temperature of this mixture is reduced to -g0°C and the temperature is increased to 30°C.
After 1 pml of nophenylethylene was added. The resulting mixture was poured into 0-(0,0≠7k)(D vinyl chloride-r acetate) and the thus terminated poly(α-methylstyrene) was precipitated with methanol and separated by filtration. When measured by vapor phase osmotic pressure, the average molecular weight was t41-, uro, c theoretical value: /20 5), and the molecular weight distribution was extremely narrow.

The produced large molecular weight monomer had the following structural formula: (where n is yt? The molecule of IJ polymer has a value such that /≠, 2IO).

Example 5 Vinyl! -Chlorethyl ether VC, J: -')
T-terminated. Preparation of 4M Listyrene A solution of 7 drops of diphenylethylene was dissolved in l/t- at -0°C.
Butyllithium /,, 2%-2% solution k (+N
The light red color lasted for 17 years, making it the 30th in history.
．． ntcθ, 04A mol) of t-butyllithium ml
was added and then 3/2 &<3.0 mol) of styrene was added. The temperature of the polymerization reaction product was kept at ≠θ℃ for 30 minutes, and the end was treated with 1 (o, og mole) novinyl-nochloroethyl ether. I tried to stop. The polymer obtained was precipitated by adding the 727ml solution to methanol, and the polymer was purified by filtration. Vapor phase f, 3! i
When measured by rj pressure, its average molecular area is 7.00 (
Theory: 'll! i'70), and the molecular weight distribution was extremely narrow, with a Mw/Mn of /, 0 and -F. The large molecule monomer produced had the following structural formula: (where n has a value such that the molecular weight of the polymer is 7xoo).

EXAMPLE O Jf Polystyrene Terminated with Epichlorohydrin Preparation A Pe/Zene solution of living polystyrene was prepared by the method described in Example J and end-terminated by treatment with Og (0,/0 mol) of epichlorohydrin. The resulting terminated polystyrene was precipitated with methanol and filtered for 4 tons.

Its molecular weight indicated by vapor phase penetration is ♂ Otsu 60
(Theory: 7.737), and the distribution of the average molecule -μ was extremely narrow. The produced large molecular weight monomer has the following structural formula: (where n has a value such that the molecular weight of the polymer becomes g and 60).

Example 7 Preparation of polystyrene terminated with methacrylic chloride Dissolve 0.2 ml of diphenylethylene in a volume of 2.500 ml of methacrylic chloride and add n-butyllithium to this solution.
, 4.phosphorus solution was added to 2% gold to maintain a light reddish-brown color. 24' ml of the n-butyllithium solution
(0,031 mol) of the entire mixture, and then ≠/6 μ (≠ θ mol) of styrene was added, producing an orange color. ≠θ℃ by controlling the external cooling temperature and the addition of nitrogen by 1 degree.
The temperature was maintained throughout.

After all the styrene was added, the temperature was maintained for 30 minutes, then the temperature was lowered to 20°C, then ll-,≠9(0,1
mol) of ethylene oxide was added and the solution became colorless. living, 2 +) ′v i /θmt (0,
1 mol) of methacrylic chloride. The average molecular weight of the obtained polymer was 10θ00 according to vapor phase osmotic pressure.

This high molecular weight monomer had the following structural formula: where n has a value such that the molecular weight of the polymer is 10,000.

Example ♂ Production of polystyrene terminated with methacrylic chloride pre-dried with ringer molecular sieves and lime scale in a stainless steel reactor.
/, /2AC3,2Ga ay) of ACS grade benzene (Thiophene Kanakuramanai) was charged.

The reaction mixture was heated to a temperature between ~'AO° C. and added to the reactor by hypodermic syringe at 10 fn/diphenylethylene. 5eC-Butyllithium//, ≠ Thihequinane fR solution was dropped into the reactor to maintain a permanent orange-yellow color.
kg (3, lI-≠, I?nd) of the 5ec-guterlithium be/zene solution was added to the reactor and then 3 Zl/L,
! , fKg (f2.s pounds) of purified styrene was added once per 10 minutes/hour. Reactor tank Kk31
It was maintained at ~≠θ℃. SuV:! /gpolystyrene 0. /
The reaction solution turned from red-orange to yellow when capped with the addition of ethylene oxide (27/, 2 kg cO, 2 g lb). Obtained capped libi/gboristele/
Next, when it was reacted with 260-methacrylic chloride, the solution turned very pale yellow. The polymer precipitated out of solution by adding the inzene solution of the polymer to methacrylate-terminated 4Hylys tyrene. Polymer gold air circulation in hot air dryer ≠θ~≠j℃
After drying, all traces of methanol were removed on a fluidized bed. It was measured by agricultural phase osmolarity. The molecular weight of IF +7 was /31Il-θO, and the molecular weight distribution was extremely narrow, that is, Mw/Mn was less than AOj.

・Example: By maleic anhydride? Trimmed yl? Production of surilene: AC3 grade benzene (thiophene-free) pre-dried with Ringer's molecular sieves and scaled calcium in a stainless steel reactor.
I prepared t. Reaction gain ≠ 0℃ heating 1 - subcutaneous injection < 4
by 0. ,! - of diphenylethylene was added to the reactor. 5eC-butysilium/2. /llJ hexane solution was added to the reactor in portions to maintain a permanent orange-yellow color (0.7fnt), then the 5eC-
2.2.3 of the butyllithium solution was added followed by ≠, 2/7 g of styrene over a period of 76 minutes. The reactor was kept at a temperature of 1°C. 5 minutes after the addition of styrene was completed, ethylene oxide was added to the reactor in a lecture bottle until the solution became colorless and transparent.
ottle) to surface F intermittently. 10, 7 hours after the end of the addition of ethylene oxide! ; j
ml of maleic anhydride in a bottle/bottle solution: (Maleic anhydride solution is made by dissolving ≠ g of maleic anhydride in total 3!; Living room? Added to Lima. Seven hours after the maleic anhydride was added, the contents of the reactor were discharged into methanol and precipitated. The polystyrene-terminated sacetamaleic acid half ester was obtained using Get Permeation Chromatography.
tography) to approximately 1 aoo when measured at L.

Met. This co-11-polymerized Oita-F-monomer has the following structural formula: % Formula % Preparation of polybutadiene terminated by allyl chloride was condensed and collected in a 0.561 ton (T-Zo India) bottle. These bottles are heated in an oven to ≠ hours/J0°C, bubbled with nitrogen during cooling, and capped with a perforated metal crown using a plastic wrapper and a polyethylene film backing. These bottles containing getadiene were stored at 0.71 Kg/c at -lθ°C in a laboratory refrigerator before use.
wT2 (/Opsi) was stored under nitrogen pressure. A hexasolvent was charged into the reactor and heated to 50°C, and then 0.2-diphenylethylene was added using a syringe.

The color of the red sophenylethylene anion is at least 10~
5ec-butyllithium was dripped into the reactor via syringe for a duration of lj minutes. The temperature of the reactor was lowered to 0°C, 31 & θI of butadiene was charged into the polymerization reactor, and then when half of the getatsuene charge was added, lZg-(0,0
A solution of 2117% 5ec-butyllithium in 72 thihexane was added. Butadiene was polymerized for hours at jθ°C in hexa/hexane. After the polymerization reaction, the anionic polygetadiene solution in the reactor was divided into ≠θθ− portions and transferred to a capped bottle under nitrogen pressure. Allyl chloride (
0,≠do-10, θOjr in moles) was injected into each term. The bottles were fixed in a water bath at a temperature of 50-70° C. for up to 2≠ hours. Samples in each section were quickly stopped with methanol and ionol solutions and analyzed by chromatography. Each sample was clear and colorless, and analysis by luminescence chromatography showed that the sample had a narrow longitudinal molecular distribution. Norchlorobutane (0, gu, 00
Termination of several control samples was carried out in sections from the same lot of glue/glyptagene capped with 00376 mol). The no-chlorobutane-terminated polymer was yellow in color and, after being kept at 70 DEG C. for 21 hours, examination by chromatography showed a broad molecular distribution.

It is clear that the reaction and reaction product of nochlorbutadiene with the anionic, J5 liptadiene is different from the reaction and reaction product of 1lyl chloride with the anionic polygtazoene.

Example: / / Chemco (chemC) has a production capacity of 3.71 t (/gal) for methacrylate-terminated polyurethane.
O) glass-bow (I) 2. of purified hegta/, previously poured into the reactor and dried with calcium hydride.
Prepare jt and then use 0.0 as an indicator. ．． 2, one of nt/
Phenylethylene is added and a solution of t-butyllithium (2% in hexane) is added until the characteristic light yellow color persists.
The reaction 'at sterilize (5t
The reactor was heated to 9°C and a 12% solution of t-butyllithium (0.02 J mol) in hexane was injected into it using a hypodermic syringe, and then 337. ≠9 (44,5'A moles) of Ingrain whole eggs were obtained.This mixture was left at ≠θ℃ for 7 hours, and then θ,
73 moles of ethylene oxide was charged into the reactor and living polyethylene was added to the reactor. Capped or bi/g polyinzolene for 4LO minutes at tit-o°C.
After keeping it at 0. Oll-1 mole of methacrylic chloride was charged into the reactor to terminate the capped living polymer. The mixture was kept at ≠θ° C. for 73 minutes and then all of the ˜butane solvent was removed by stripping under vacuum. Based on polystyrene chromatography, the molecular weight of polyethylene terminated with methacrylate 1 is approximately 10.
OOOC theory: /3000). The large molecular weight monomer of methacrylate-terminated polyingrene has the following structural formula: Molecule 2-7-b of Linde and hydrogenated calci, ., J, d::Jjt of hebutane manufactured by 4'lJ, which had been dried by heating, were charged into a reactor in advance, and 0.0. ．． 2 ml of diphenylethylene was added. A solution of t-butyllithium (in Hekylene/-2
%). The reactor was heated to tl-ti-o°C and 1'AO3mt (0,
02'1-26 mol) of t-butyrrhizicum ml&'4
injected by hypodermic syringe and then 313.39C'AI
, 3 mol) of Inno7° Ren was added. 11 for 66 minutes at 50°C
Toko/J-C, 2.0 ml (0, o, se for use in
It was taken out from the IJ Make reactor.

Kono Jl? When analyzed by chromatography, it was found to have a very narrow molecular distribution, with a Mw/iIn of about 0.06 F or less. The theoretical molecular weight of IP 177 is /J
',000, the copolymerizable large molecule tit had the following structural formula: 4.

Example / 3 gear-knobbed with butadiene and terminated with allyl chloride]1? Production volume of large molecular weight monomer of listyrene; 2. ! Charge i l of benzene (without thiophene) into a reactor, heat it to 70°C, add Oo, 2-diphenylethylene as an indicator, and then add 5ec-butyllithium until the orange-red color persists. 7
2- The reactor was sderilized by dropping the solution. Here in history! i' mt (0,021A
(mol) (D 5ec-dec-decyl chloride solution (2/2 mol in hexane) was added and then a full styrene trough of t/Libq<≠θ mol) was added. The temperature of the polymerization reaction mixture was maintained at 4LO°C for 5 minutes. The ribinog polystyrene was then decontaminated by passing butanoene gas into the reactor until the color of the solution changed from dark red to orange. This living polymer is lIL, /fn! (θ, OS self-terminated with allyl chloride. The large molecular weight monomer thus produced was precipitated with methanol and US
It was held for 1 minute at Si2. The il7. The uniformly divided thousand quantity is 2j000C theory: /do00θ] and -t - f
-'ftk distribution was extremely narrow. Manufactured! +, person, 7th f iti: % Tsuma is the following 1 formula: (Tashi m
had a severe).

Example il7-11? Reacrylic, - hammer mixed t) < 1 cow s5 rima -
1 three injections r5 and +5 listyrene sparsely 1 standard, l? Manufacture of Gukufutco J5 Lima with a polymer millimeter = 1'6 manufactured in Example 5 and approximately 1,000 min Li
A vinyl-, 2-, end-terminated compound with corcot ether has a very -C-interval-f-W+1 distribution such that the ratio of σMw/Mn is about /, θ<F. +?Polystyrene Ogk'lt resin 7 lasco, 2'1-01! acrylic vessel and 5
Dissolved in 0 g of tetrahydrofuran (THF).

Add soog's THF to a 2t 4m tltj flask and add 0. I added y's benzoyl 7-do.

The flask was heated to 65°C and allowed to cool for 2 hours. After the polymerization reaction was completed, 300 g of distilled water was added to the resin flask and the HF gold was distilled off. This aqueous 7-1? An example of using lima thread as a latex thickener: 1? Lima mainly +, ;, and polystyrene hydrophobic polymers +ll! Production of graft copolymer with I chain Triton/(Triton) X-/0
θ's 4 ot g '4t o.

Dissolve all of this in distilled water (wBring).
) A person crashed into Blender. ,
J: In Example 5 of B10 'JJ crush h 3Of of t-butyl polystyrene vinyl ether! 'fc1. θy
A constant dispersion was made by adding this solution to a wall mixer containing a solution of total triton x-10θ dissolved in a high-strength, high-speed drum. This dispersion was placed in a J, T resin flask equipped with a stirrer and a condenser, and the flask was completely flushed with nitrogen for 7 hours. 6t reactor
s L/i llθy of Tacrylic acid was added to the temperature (Pli i, !i'
, neutralized to 0). 7 g of benzoyl 4'-,4-7-dew was added to the resin flask and a polymerization reaction was carried out at 50°C for 3 hours. The polymer was recovered as described in Example/≠ and subjected to evaluation and testing as an industrial latex thickening agent.

1st row / Hydrophilicity of polyacrylic acid +l? Gun 7 toco with IJ chain and the hydrophobic polymer side E'r of polystyrene, I
? Dissolve 1 gg of Lima's Triton X-g05 (or) Otsu I's 7θ solid Triton
The -I was adjusted with ammonium tungsten and the solution was placed in a wall mixer. A solution of 30 g of t-butylnostyrene vinyl ether made as described in Example J in ethyl acrylate in MIW was added to a Walling mixer containing a solution of Triton x-pos in a high shear drum. In addition to the above, a stable dispersion was made.

This dispersion was added to [it was equipped with a stirrer and a cooler].
The mixture was placed in a TD fat flask and flushed with nitrogen for 7 hours.

The reactor was heated to 6t° C. and 0.7 g of ammonium persulfate was added to the reactor. , 200 g of ethyl acrylate and 2-thiopersulfate were added to the polymerization reactor for a total of 3 hours and the polymerization reaction was carried out at 6.5'-67°C. Hydrophilicity was imparted to the polymer main chain by hydrolyzing the acrylic acid groups with alkali under full heating. The resulting hydrophilic and hydrophobic polymers were recovered in the manner described above.

Example / 7 Polyacrylic acid water visibility - polystyrene, -1? Su〒11
latex viscosity of fll m fO% polyacrylic acid polymer backbone prepared as described in the previous example and 20% polymer no. Three graft copolymers consisting of listyrene side chains were tested as all-latex thickeners. ,
+Q l) Styrene +ll! The size of the first term was as follows: 1 The Mn of wipe A (G30) was equal to 1000: The Mn of sample B (G3:l) was equal to l/-000, and the Mn of sample CCG33) was It was equal to θθ0. This one and others' graph toco +1? Lima was tested in the following manner. 3θθy Guikaratex (Wi
caLatex) '7θ35 (3-0% solids), 0.3 g, 0. Otsuy and/, , 29 current water-based planotoko 11? Lima (all solid basis) was added and its viscosity was measured by a Brookfield LVT viscometer (+*3 weights, 7.2 revolutions per minute). The results of this test are shown in Table 1.
30) B (G3..2) CCG33) None /≠
00 /I/L30 /'l-100,3gran
3100 33IO' 33-, foo, ro gr
a rn ≠, 200 ≠ 700 5 Otsu 00/1.2
Tori rans ro soo 7o00 7sO.

As is known from the above data, the graft copolymer according to the invention acts as an excellent thickening agent for Laanoxene due to the presence of both hydrophilic and hydrophobic polymer segments. It was clear that the uniform molecular weight distribution of polymer side chains contributes to the overall ability to form stable radenox. Improvements were also evident. This is because the polymer stage, i.e., the polymer side chains at molecular weights above about 2009, resembles the properties of +f styrene polymers and results in better phase separation when the polymer side chains have a high molecular weight.

Example / f +) Hydrophobicity of styrene, j'i7 Hydrophobicity of polyvinyl alcohol with lima side chains - 45 Preparation of lima backbone graft copolymer manufactured by the method described in example j ffi' with vinyl ether end groups A copolymerizable large-molecular-weight monomer produced by m (in the production of this large-molecular-weight monomer, 5ec-butyl lytecum was used as a single reaction initiator, and +5 leaves had a molecular weight of 2OfO and a Mw/Mn of about 4/or less).
Identical except for the ratio! 601'c in benzene (in which the monomer was prepared) was copolymerized with 1 g θI of bi-ruahitate using be/diyl-oxyto 9 as Mm. Manufactured in this way. I hibinyla heptatate-styrene graphite 1
"Zerima (G)", 5-07j
I-rivinyl alcohol-styrene grafting using sodium methoxide catalyzed in a methanol/benzene mixture, -1? Lima hydrolyzed t, &.

Obtained. ) 5 Lima was washed with methanol, vacuum dried, and then extracted with benzene. Analysis of the extracted copolymer revealed that the copolymer was produced entirely in oil.

The saponified product is formed into a film and commercially available. Its water resistance was confirmed by comparing it with polyvinyl alcohol. The films were each placed on a piece of glass and diluted in water at room temperature F overnight.
C is also according to the present invention, and the water resistance of I5 +77 is that of the control.
I? Much improved water resistance than Rivinyl 7 alcohol.
471. ``It was obvious that C.

Example / 7 Preparation of hydrophilic polymer backbone graft copolymer of polyvinyl alcohol to the hydrophobic iI''!lima side chain of polystyrene to 4g gsy of sodium sulfate (0,≠9).

A latex co-containing reaction is carried out by adding methacrylate-terminated +1 bilisburene prepared in the example of /jp to water with stirring and then adding 30 g of vinyl acetate. It's one.

The polymerization reaction was carried out at 0,/39 (D benzoyl g-oxide whole egg 6 o'clock lid)≠θ~jθ℃.When the polymerization reaction was completed, the copolymer was poured into 100-methanol under stirring. 109 sodium methoxide was added to the solution over a period of 20 minutes. The solution was refluxed for 7 g for 7 g, washed twice with polymer gold and dried under vacuum at 70°C. The copolymer was slightly soluble in DMSO but insoluble in toluene, tetrahydrofuran, benzene and cresol.Films made from this copolymer were transparent with good extensibility and excellent wet strength. l
” Khushita.

Example 20 Preparation of a hydrophilic, 1 mm polymer backbone grafted core) polymer of polyhydroxyethyl methacrylate with hydrophobic polymer side chains of polystyrene A polymer prepared by the method described in Example 7 having a uniform and narrow molecular weight distribution71. 1? Listyrene 7! ;nVk/2! V
The complete initiation of the polymerization reaction was avoided by mixing ia with hydroxyethyl methyl acrylate and using o, Il, t-butyl 9-octoate as a polymerization reaction catalyst. The polymerization reaction of this product ρ was carried out by first heating the mixture at about 50° C. for an hour. The polymerization reaction was then completed by heating to 70° C. for about 7 hours and then heating to /hour i,:zoc. After the polymerization reaction was completed, a transparent, firm and hard copolymer (4) was obtained. The polymer was brought into osmotic equilibrium by contacting with physiological saline lδ solution. The hydrovil film thus produced was transparent, flexible and elastic.

Example 2/ Poly(N,N-dimethylacrylamide) 1#, aqueous 71? Preparation of a Graft Copolymer Having a Lima Backbone and Hydrophobic Polymer Side Chains of Boristyrene/J? Polystyrene /31A
≠θI and OI! of N,N-dimethylacrylamide was dissolved in 130 g of benzene. This mixture was mixed on a shaker to obtain a homogeneous solution. 0. /2
After adding f/(DA IBN(VAZO) polymerization reaction initiator, the contents were transferred to fO,'731(/Fort) polymerization reactor. Inside, the material was injected with nitrogen and then the reactor was sealed. followed by bubbling with nitrogen. The polymerization reactor was placed on a shaker in an OOC water bath for an hour and then brought to 5° C. for 2 hours to terminate the polymerization reaction. The resulting copolymer was clear and highly It was a viscous liquid.Isog of benzene was added to this viscous liquid copolymer to completely reduce its viscosity.The weight velocity of the solvent and copolymer was ≠651, and the
With 0.7% solids (9≠1 solids), the yield of copolymer was more than 1%.

By stretching the be/in copolymer solution onto a glass plate with a drawing rod, Molded lima film. This film was optically clear. The wet films obtained by immersing these coated plates in distilled water were tough and transparent. The swelling ratio of this film is 2.0 for 7 g of copolymer. ．． It was 2g of water. m1
The tensile strength of the first-situ film is b O,9#/crn (g
70 psi) and the stretching ratio was lOθ.

The film was tested for its water vapor permeability (WV T ) using ASTM Test Method -963T (B) and the WVT of the wet film was Otsu 1009/2.
≠ time/d.

R run j-meation chromatography analysis of this copolymer showed the absence of unreacted hydrophobic large molecular weight monomers. The insoluble nature of this copolymer when immersed in water and the high strength of the wet film are due to its hydrophobic nature.
We have shown that the Jl chain acts as a physical cross-linker for normally water-soluble poly(N,N-trimethylacrylamide). The above copolymers were softened in water and tested for their water vapor permeability. The wet copoly 1 film was measured with its WVTK-), and when it was taK 2oooyi
21I 1 hour/d, which indicated its use as a semipermeable membrane.

Example 2.2 7j? Example of Preparation of a Graft Copolymer Having a Hydrophilic Bilimer Backbone of (N,N-dimethylacrylamide) and a Hydrophobic Polymer Side Chain of Polystyrene (methacrylate-terminated polystyrene prepared by the method described The polystyrene terminated with a molecular weight of i, 2io, and a Mw/M (with a ratio of 1) of about /,06 or less as determined by chromatography analysis.
0 parts were added to a mixture of 70 parts of N,N-methacrylamide and 0.0 parts of R-in. The mixture was placed on a shaker until a homogeneous solution was obtained. After that, 0.7 part of AIBNk was added to this solution. fcO,93
;t(/Fort.

Step 1: Charge the mixture into a reactor, pass nitrogen through it, and then seal it tightly. After passing 9uK of nitrogen through this stopper thread, the polymerization reaction mixture was placed on a shaking rack in a water bath at 67°C and the polymerization reaction was continued for 7.2 hours.
Continued for time g. After the polymerization reaction is finished, here is 1? Lima was recovered by precipitating in bequitan, filtering and drying. This copolymer had excellent wet strength properties when immersed in water as a clear, viscous solution.

Example 13 Preparation of a graft copolymer with a tal aqueous polymer backbone of poly(N,N-methylacrylamide) and a hydrophobic polymer of polystyrene L [J Silver methacrylate-terminated polystyrene ( This methacrylate-terminated 21?restyrene has a molecular weight of /2,700 and a Mw/Mn ratio of less than about 405 F, as determined by 5-fi analysis, 70 parts. was dissolved in N,N-trimethylacrylamide for 90 minutes. 5 parts of calcium stearate were dispersed in this comonomer mixture and 100 parts of hegetane and 0.7 parts of AI were added to the comonomer mixture under rapid stirring.
Added BN.

Is this thread O, L? The mixture was charged into a 5 ton (i-fort) polymerization reactor, and after nitrogen was passed through it, the reactor was tightly stoppered. Nitrogen was passed through the sealed thread to completely clean it. This polymerization reactor was placed on a shaker in a water bath at 67°C to conduct the entire polymerization reaction.
It was continued for 12 hours. The copolymer was obtained in the form of a fine powder and was easily cleared and dried. Copolymer recovery is extremely successful due to the use of non-aqueous emulsion polymerization technology?
I was beaten.

Analysis of the product by dermal migration chromatography showed the absence of unreacted methacrylate-terminated polystyrene.

This copolymer had excellent wet strength when immersed in water. This copolymer vi also d? Polyblend with Lipinilk U-Lee (ρolyblend
) was useful when making mini blues. This f7 (3-like l/Lo~Otsu 0 tons, I?Lima and 60-
'-≠0 weight part 9+1? Each ←11 polyblends were prepared by dry blending with lipinyl chloride°. This dry blend is milled under elevated temperature Tht.
A filter with excellent water vapor permeability was obtained when sheared over a filter. To, 1 of N-noargylacrylamide? A detailed description of the formulation with Lima Tobori vinyl chloride resin is contained in co-pending U.S. Patent Application No. 3J, incorporated herein by reference.

Special examples of polyblends include the above, +5 Lima 3
3.3 parts to 70 parts of polyvinyl chloride [vinyl (V
ygen ) / / 0 ) 13 and 7 parts of dioctyl 7-talate (DOP). Dry blended Oai's proboscis /I1. The sample was placed on a rubber mill for 14 minutes under CC50θ. The blended ingredients melted very easily to form a smooth, transparent film. After blending and placing the mixture in a high shear chamber for 14 minutes,
641! (10 mil) films were tested with TPfilfi L for water vapor permeability and water absorption. This 1?
The reblend had a water vapor permeability of lθθI/nog time/ze and absorbed water at a specific humidity of 5 cm over time. In comparison, a similar blend made from a homopolymer of N,N-methylacrylamide and a polymer of vinyl chloride treated with a plasticizer has a water vapor transmission rate of 7.9/211 h/d. It absorbed 1Aj of water in 7 hours under the ratio of ♂j%. In addition to improved physical properties, hydrophobic polystyrene side chains make polyblends (
It was quite clear that this improved the processability and contributed to the solubility of the polystyrene side chains in dioctyl 7-talate. In other words, the side chains contribute to the melt rheology imparted to poly(N,I'J-methylacrylamide) by these grafts.
fc revised 4.

Example, 2 ≠ Grafted terpolymer a of a hydrophilic polymer backbone of Bori(N,N-methylacrylamide)/butyl acrylate and a hydrophobic polymer side chain of polystyrene. molecular weight monomer (this methacrylate-terminated polystyrene has a molecular weight of 70
A portion was dissolved in 5 g of N,N-methylacrylamide using an air mixer.

Next, add 5 parts of butyl acrylate, 5 parts of calcium stearate, 0.7 parts of AIBN and 100 parts of Hegetan to the total comonomer mixture and stir. ri3;tc/
quart) polymerization reactor. The polymerization reaction mixture was bubbled with nitrogen and capped tightly.

The reactor was placed on a shaker in a hot water bath at 67° C. for 76 hours to carry out the C polymerization reaction. The terpolymer was filtered and dried. The yield of terpolymer was iosg based on 1 solid material added. The yield was 100 cm.

Example 25 Preparation of a Grafted Terpolymer of a Hydrophilic Polymer Backbone of Maleic Acid Half Ester and a Hydrophobic Polymer Side Chain of Polystyrene
wax) 73; 7 by condensing with 0
Methoxypolyethylene oxide ether with a molecular weight of jθ (
Maleic acid diester gold of Cal〆wanox 7 j O) was produced. Part 7 of Calgewanox 7 j O? L/Ionic acid diester and 2! ;08 ino ypy (Nruto CI A = (5oltrol) / Ox
leum) was charged into the reactor. The temperature of the reactor was raised to 73°C, and 735 parts of N,N-trimethylacrylamide and 7.5 parts of a large molecular weight monomer of polymethyl/all-terminated maleic acid half ester (polyester terminated with this maleic acid half ester) were added. is produced by the method described, and this polymer has a molecular weight of 700 θO [L-Mw/Mn ratio of about 405 as measured by chromatography.
04 compound of Komotsmeric (Fr.) was added. J to reaction 4 containing monomers that can be polymerized! ;3/ll
A mixture of -7N,N-methylacrylamide/nouryl methacrylic V-tocopolymer, 20 parts of a 20% inooctane solution and 0.3 parts of AIBN as the polymerization reaction +FJ starting Δ11 was added over a period of 5 hours. Furthermore, inooctane was added. After continuing the polymerization reaction for λ time, 1? The Lima silk dispersion was collected by filtration.

This tarsq IJ had excellent wet resistance when immersed in water.

Example, 2) Hydrophobicity of the W/N polymer main chain of poly(hydroxyethyl methacrylate) and polyisogrene, 1? lima l
Example of structure of grain copolymer of 1ji fn
The --terminated polyisogrene has a molecular weight of 100 and an auxiliary w/Mn ratio of less than /, 5, as determined by chromatography.
0 parts (based on total dry matter of solids) and 700 parts of hydroxyethyl methacrylate were mixed in a 0.7st (ifort) polymerization reactor. Nitrogen was bubbled through the comonomer mixture and 0.2 parts of A I BNM The mixture was copolymerized at 67° C./6 hours by adding a polymerization initiator.

The resulting copolymer was a clear, viscous solution.

This transparent copolymer solution was placed in a mold and irradiated with gamma rays for 20 minutes. The copolymer was then immersed in saline.

The wet n-copolymer has excellent wet strength, which means that the woody backbone is tightly held by the hydrophobic 11111 chains and the side chains are linked to the wood by cross-linking by radiation. This was due to the fact that That is, this coliform was reinforced by a structure of cross-linked hydrophobic regions that were chemically bonded to a hydrophilic host phase.

Hydrophilic-hydrophobic graft copoly-rp according to the invention
If/? properties 'α (for example, tensile strength, tensile strength, 'oE 9p ratio, etc.). Generally water-based, I? (J polymers must be cross-linked by chemical cross-linking agents to improve their physical properties. However, the novel graft copolymers of the present invention uniquely It provides thermally labile physical cross-links that help hold together the elastic modulus of the final product (
modulus) and tensile eaves are completely revised. This graft copolymer f, I? Tg of Lilima 1ftJ m,
When heated to a high grade of 1IJ (71'' Lith fren to λ41. Te&-t: '7'θ = 100℃), the '110 area becomes a moving body and u: Uji below the saw).
move. In other words, they are truly 4′! Luxury (Ichoy, jQ
1"'l: So J5. This graph 7 is a cold MI, and it @ K it that j; To restore the properties of the polymer, the addition of an aqueous liquid merely acts as a plasticizer in the existing aqueous poly and does not change the overall copolymer material.The graft copolymers are It can be rendered human by immersion in an aqueous liquid (such as water or saline).The amount of aqueous liquid varies widely depending on the composition of the graft copolymer, i.e. the amount of polymer side chains in the graft copolymer. Generally the amount of aqueous liquid is from about 70 to about 50% of the graft copolymer, preferably ≠
It is within the range of j to KOchi. Even in the presence of high levels of aqueous liquid in the graft copolymers of the present invention, they retain their shape15, making them useful in making contact lenses, internal implants, and the like. The production of hydrodels by immersion in a copolymer-all-aqueous liquid according to the invention lies in the form of microscopic droplets that completely fill the microscopic pores or voids distributed throughout the entire length of the copolymer and the entire body of the hydrodel. The mechanical retention is enhanced by the covalent forces of the hydrophilic polymer, while the nuclear forces are held in place by the thermally labile cross-links of the hydrophobic, selima side chains on the desired cypolymer material. By applying an FE force to the graph, I? Water is completely removed from the polymer (I
Ru. Even after I: E force is relaxed, air still enters the void, and the total volume of the product is t, which is water or an aqueous H liquid!
It remains small until it is touched by f/2) II
Am) ζ returns to +g +li I, its original size and shape. In such surplus crystals, some f$ of water goes up to the suction force of the hair inside, and some part is retained as a component of the :I l)id threads of hydrovil. In an embodiment as described herein, the hydrodel according to the invention has properties as a +j'&lad agent, which properties can be advantageously applied to a sticky band or layer in, for example, a medicinal wind. . Wooden products are also used as ultra F'n passer J semi-permeable membrane -C 1''J,
Fru. Regarding the latter part, an ejector or a blowing agent can be added to the 7IP compound during the total polymerization reaction, or can be used as an acid treatment to create an aqueous solution. It is desirable to add porosity to 7.

This study has a unique variation that is useful for paper coaching. 7L turbidity - C hydrophilic - icephobic graft co++
? ') It includes making a mat n. These copolymer layers) *+J vinyl acetate++? 177 share polyvinyl aromatic (eg polystyrene) or polyvinyl aromatic/polybutanoene in the main chain.

The reaction formula of F is emulsion graft co, I? The characteristics of the unique method of manufacturing IJ machining are shown.

/' Copolymerizable large molecule -; Tsuji e Nora La) or (b) and Bi; Le r
11. Produced by copolymerizing hydate with 79-radical I dust. Ru. This zt,/1lit body has excellent physical properties that make it suitable for use in paper coaching. For example, it is known that polystyrene-butadiene latex is most widely used as a marine binder in the paper industry. Polyvinyl acetate latex has better disintegration properties, whiteness, and low odor, but its paper pick resistance and
"Poor abrasion resistance limits its application. This is because polyvinyl acetate is a hydrocarbon resin. 1?
Compared to IJ rubber, the solubility of vinyl acetate monomer in water is 2.
ioog water), the rl value for styrene is 0. The r2 value for divinyl acetate at θ/ is jj, and it is impossible to polymerize testylene and vinyl acetate with *-+t. By using the unique copolymerizable large-molecular ambiguous monomer of the present invention, the properties of polyvinyl acedate, polystyrene, and σ polystyrene/butadiene can be combined, and the excellent adhesion and whiteness of polyvinyl acedate and the J+ ”!
+7 Styrene i fc can provide good wet peel resistance and wet friction resistance of 1 sox.

A further unique aspect of the present invention is the wet end additive from the graft copolymer.
e) All manufacturing. For example, if one gram of tocobolima is treated with a cationic reagent, it can be treated with a waste material useful in the paper industry. This method of preparation according to Example 1♂ The graft copolymer described above is unique because the phase separation of the polyvinyl alcohol moiety incorporates the cationic graft copolymer therein to enhance both the wet and dry strength of the paper. It is.

Although this invention has been described with respect to particular embodiments, it will be obvious that it may be further modified and this application is not intended to disclaim in its general principles any modification, use, or adaptation of the invention according to its principles. Even if the present disclosure θ1 et al. contains such deviations, they are known or customary in the art to which the present invention pertains and may be applied to the essential characteristics described herein. and is within the scope of the present invention.

Showa year month day 1, q) Indication of i'1 11t (Wa 59 '11 Fraud application No. 236537: 3. Sode iEi? 4 agents

Claims (1)

[Claims] Chemically bonded, phase separated and naturally hardened hydrophilic heat nff1
In a method for producing a hydrodal-like polymer, the following two steps are carried out: (1) (a) having a molecular weight within the range of about jO00 to about jθooo and having a M w /M n ratio of about A/
a linear polymer or copolymer having a substantially uniform molecular distribution such that the linear polymer or copolymer has no more than 7 polymerizable moieties per chain; of polymerizable hydrophobic large molecular weight monomers that are patented to be at the ends of about l~
and lb) the I lima main mt of the graft copolymer is formed, the copolymerizable hydrophobic large molecular weight monomer forms the linear polymer side of the graft copolymer, and the linear polymer side of the graft copolymer is polymer side chains are copolymerized into the main chain/rift by IK-compatible end groups on the large molecular weight monomers, where the main chain is copolymerized with hydrophilic (water-soluble) ethylenically unsaturated monomers or hydrophilic or water-soluble It has at least one polymer unit of an ethylenically unsaturated monomer that imparts the properties of d? The linear polymer side chains of the graft copolymer copolymerized to the Lima backbone are at least about 2
Separated by 0 consecutive monomeric repeating units, the copolymerization and distribution of side chains along the main m, a lima with the copolymerizable end groups of the hydrophobic large molecular weight monomer and the hydrophilic copolymerizable comonomer. (2) copolymerizing the hydrophilic graft copolymer with from about 5% to about 5% by weight of at least seven hydrophilic copolymerizable comonomers, as controlled by the relative reactivity ratio of the hydrophilic copolymerizable comonomers. approximately 1% based on the weight of the graft copolymer by contacting with an aqueous liquid.
Hydro rA- containing 0 to about Pjii amount of aqueous liquid
The above method, characterized in that it comprises a step of forming gold.