CA1151800A - Emulsion process for preparing elastomeric vinyl acetate-ethylene copolymers - Google Patents

Emulsion process for preparing elastomeric vinyl acetate-ethylene copolymers

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Publication number
CA1151800A
CA1151800A CA 341321 CA341321A CA1151800A CA 1151800 A CA1151800 A CA 1151800A CA 341321 CA341321 CA 341321 CA 341321 A CA341321 A CA 341321A CA 1151800 A CA1151800 A CA 1151800A
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CA
Grant status
Grant
Patent type
Prior art keywords
vinyl acetate
ethylene
weight
process
surface active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA 341321
Other languages
French (fr)
Inventor
Manfred Heimberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equistar Chemicals LP
Original Assignee
Millennium Petrochemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00Copolymers having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02Esters of monocarboxylic acids
    • C08F218/04Vinyl esters
    • C08F218/08Vinyl acetate

Abstract

ABSTRACT OF THE DISCLOSURE

Elastomeric vinyl acetate-ethylene copolymers having high Mooney viscosity and low gel content are prepared by the process which comprises:
a) copolymerization from about 40% to about 70% by weight of vinyl acetate monomer with from about 60% to about 30% by weight of ethylene monomer in an aqueous emulsion reaction medium to provide a latex, the reaction medium for vinyl acetate-ethylene elastomer containing:
(i) at least one surface active agent in an amount above about 2.2% by weight of the total monomer.
(ii) a polymerization catalyst, and (iii) at least one protective colloid in an amount of less than about one part for each part by weight of total surface active agent, with the total weight of the surface active agent and vinyl acetate being present in the reaction medium at the commencement of copolymerization: and, b) recovering the vinyl acetate-ethylene elastomer from the latex.

Description

-l- A-2544 EMULSION PROCESS FOR PREPARING ELASTOMERIC
VI~Y. ~0~1~5~ ~r~Y~a~ coP LYMERS _ Vinyl acetate-ethylene (VAE) copolymers constitute a well known class of synthetic resins demonstrating a broad range of properties d.epending upon the relative quantities 5 of copolymerized ethylene and vinyl acetate (and other ethylenic monomers which may be present~ in the copolymer chain. Elastomeric amorphous VAE gum stocks contain from about 40~ to about 70% vinyl acetate by weight randomly distributed throughout the copolymer chain and, when cross-1~ linked, for example, by a peroxide crosslinking agent, -: possess properties which make them especially useful as elastomers for rubber compounding, as base copolymers for adhesive formulations and as impact modifiers for polyvinyl chloride (PVC). Among the physical and chemical.properties 15 which make the rubbery VAE copolymers attractive or such applications are the ollowing: heat aging resistance; oil and solvent resistance; low compression set, good low temperature performance; excellent weatherability and ozone resistance; resistance to natural light; transparent or : 20 white-to-black vulcanizates; high loadability; -receptance to dielectric heating; and high dampening characteristics.
Thus, the elastomeric VAE copolymers are excellent candidates for such automotive applications as gaskets, seals and O-rings, wire insulation, radiator tubing and : ~5 hose, bumper strips and auto body filler panels and are ideal for other demanding applications as well such as - machinery mounts, weather stripping, washing machine hose, refrigeratox gaskets, and the like.

,: 30 ..;

: .~

1 In accordance with the present invention, VA~
elastomers are obtained in the ~orrn of latices employing an improved emulsion copolymerization process and the elastomers are recovered therefrom employiny such con~
5 ventional techni~ues as coagulation. In general, a VAE
copolymer latex is prepared by first charging an aqueous phase containing water, surfactant, buffer, catalyst or catalyst system of the free radical type, and usually a protective colloid such as polyvinyl alcohol (PVA), to a 10 reactor as, for example, described in U. S. Patent No.
3,708,38a. In some procedures, an initial charge of vinyl acetate monomer, and in others, the entire amount of vinyl acetate monomer, is also charged to the reactor.
The reactor is flushed with nitrogen, sealed,and stirring 15 is commenced. Ethylene is then pumped to the reactor until the desired pressure is attained. The reactor can be repressurized one or more times if the batch is carried out under variable ethylene pressure, or a con-stant pressure can be maintained automatically employing 20 techniques which are well known in the art. After reactor pressure has stabilized, the contents thereof are heated to the polymerization temperature, usually by circulating hot water or steam through a jacket ~urrounding the reactor.
When the desired polymerization temperature (commonly ~rom 25 about 120 to about 165E'.) is reached, temperature is maintained at this level by automated controls. Thereafter, a co-catalyst such as sodium hydrogen sulfite ~NaH~O3) can .L.~'33L~

1 be added t~ the reactor (if a catalyst system employing a reducing agent to generate free radicals by a redox reaction is used) followed by any remaining vinyl acetate monomer. The completion of polymerization is 5 indicated by cessation of ethylene demand and stabilization of the reactant coolant temperature at about 6 - 8F.
above the reactor tempera~ure~ Upon completion of polymerization, the reactor contents are cooled and discharged through a pressure l~t-down valve to areceiving tank at atmospheric pressure from which unreacted ethylene is vented. The finished VAE copolymer latex is passed through a screen of desired mesh to complete the manu-facturing process.
Various manipulations of both the amount and nature of the components of a ~AE copolymerization medium and the copolymerization process variables have heretofore been attempted in order to optimize one or a few properties of the resulting latex. U. S. Patent No. 3,6~4,262 describes a copolymerization which by regulating the addition of vinyl acetate to an aqueous emulsifying composition containing a free-radical initiator at a rate which will maintain the concentration of unpolymerized vinyl acetate at a level not exceeding about 3.5% by weight of emulsifying composition and, optionally by delaying the addition of surface active agent, permits the introduction of substantially more ethylene into the copolymer for a given pressure and temperature than would ,1 ~"~ 7~

be o-therwise attainable. The resulting high ethylene content VAE copolymer latices are said to be better adapted to their end uses than the latices of relatively low ethylene content. A different approach to improved VAE copolymer latices is described in U.S. Patent NoO
3,423,352 in which high solids content VAE copolymer latices of reduced viscosity and improved freeze-thaw stability are obtained by controlling the addition of monomer, catalyst and surfactant. According to this patent, relatively large amounts of surfactant, i.e., from about 3% to about 10% by weight, and catalyst are added to a conventionally pr~pared polyvinyl acetate latex, having a solids content of up to about 52% and con-taining relatively large amounts of vinyl acetate, at specified times once polymerization has proceeded to a certain extent. This is said to resul-t in a marked reduction in the viscosity of the emulsion. Frequently, these and other prior art techniques for preparing VAE
copolymer latices achieve an improvement in one or two performance characteristics but at the expense of one or more other vital performance characteristics.
In accordance with an emulsion copolymerization process, VAE copolymer latices are prepared by copolymer-izing from about 40% to about 70% by weight of vinyl acetate with from about 60% to about 30% by weight of ethylene in an ~ r~

1 emulsion reaction meclium containing a su~face active a~ent in an amount of not less than abou~ 1.0'~ by weight, and no-t more than ahout 2.0~ by weiyht, of the total monomer, a catalyst and a protective colloid, the total 5 weight of the surface active agent and vinyl acetate being introduced into the reaction medium in delayed increments prior to and after the commencement of copolymerization.
The resulting VAE copolymer latices, which are employed as such as bases for paints and other surface coatings, 10 as adhesives, textile treatiny agents, and the like, possess high inherent viscosity, i.e., not less than about 1.90, and demonstrate superior performance in the Time of Set Test and Vinyl Wetting Test.
Such properties are especially desirable attribute.s 15 of a VAE polymer latex. ~owever, where as here VAE elastomers are concerned, other physical properties, significantly, Mooney viscosity and gel content, are dominant considerations in the acceptability of the resins for rubbery articles such as enumerated above.

The emulsion copolymerization process of this invention provides a relatively simple procedure for obtaining VAE elastomers having high Mooney viscosity and low gel content which are ideally suited materials for 25 fabrication into rubber-like articles meeting fairly demanding performance criteria. The expressions"hiyh Mooney viscosity" and "low gel content" contemplate VAE

' -6~

1 e]astomers havi.ng a Mooney vi.scosi.ty at 212F. o from about 30 MI. (1 ~ to about ~0 ML (1 -I 4) and preferably from about 30 ML (1 -~ 4) to about 70 ML (1 -~ 4), and a gel content as measured by insolubility in xylene at 80C.
5 of not more than about 2 %, preferably not more than 1 % by weight insolubles.
Broadly stated, the process herein comprises:
a) copolymerizing from about 40~ to about 70~ by weight of vinyl acetate monomer with from about 60% to about30% by weight of ethylene monomer in an aqueous emulsion reaction mediu~ to provide a latex, the reaction medium for VAE elastomer containing:
(i) at least one surface active agent in an amount above about 2.0% by weight of the total monomer, (ii) a polymerization catalyst, and (iii) at least one protective colloid in an amount of less than about one part for each part by weight of total surface active agent, with the total weight of the surface active agent and vinyl acetate being present in the reaction medium at the commencement of copolymerization; and b) recovering the ~'AE elastomer from the latex.
Recovery of the VAE elastomer from the latex can be readily accomplished employing well known methods such 1 as coa~ulatlnc3 the ela.stomer by freezlncJ the latex or by adding a coagulatiny amount of a salt such as sodiurn chlorlde to the latex and thereafter filteriny the coagulum. The VAE elastomer can then be subiec-ted to 5 further processlng, e.g., crosslinking, compounding with antioxidants, stàbili~ers, fillers, other modifying polymers, etc.

The amount of vinyl acetate monomer copolymerized ~ with ethylene monomer will vary from about 40% up to about 70~ by weight of the total comonomer charge, the balance of said charge being made up of ethylene, and if desired, small quantities, i.e., up to about 15%, of one or more other ethylenically unsaturated comonomers not exceeding 5 the weight ~uantity of ethylene. Included among such additional comonomers are monoethylenically unsaturated aliphatic hydrocarbons such as propylene and isobutylene;
monoethylenically unsaturated substituted aliphatic hydro-carbons such as vinyl fluoride, vinyl chloride, vinyl 20 bromide, vinylidene fluoride, l-chloro-l-fluoroethylene, chlorotrifluoroethylene and tetrafluoroethylene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid, as well as polymerizable derivatives thereof, e.g. alkyl acrylates and methacrylates such as methyl acrylates, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl-methacrylate, 5~

1 1,6-hexanediol diacrylate and isobutyl methacrylate, - acxylonitrile, methacrylonitrile, acrylamide, meth-acrylamide, N-methylolacrylamide, alkylated N-methylol-acrylamides such as N-methoxymethylacrylamide and 5 N-butoxymethylacrylamide~ and acrolein; aliphatic vinyl esters such as vinyl formate, vinyl propionate and vinyl butyrate; aliphatic vinyl e-thers such as methyl vinyl ether, ethyl vinyl ether and n-butyl vinyl ether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone . ,.
~0 and isobutyl vinyl ketone; allyl esters of saturated monocarboxylic acids, e.g. allyl acetate~ allyl propionate and allyl lactate; and, alkyl esters o~ monoethylenically unsaturated dicarboxylic acids, e.g., diethyl maleate, dibutyl maleate, dioctyl maleate, dipropyl fumaxate, 15 dibutyl fumarate, dioctyl ~umarate, dodecyl ~umarate, dibutyl itaconate and dioctyl itaconate.
The surface active agents contemplated by this invention include any of the known and conventional surfac-tants and emulsifying agents, principally the nonlonic 20 and anionic materials, and mixtures thereof heretofore employed in the emulsion copolymerization of vinyl acetate and ethylene. One group of nonionic surface active agents which can be employed has a water-insoluble polyoxyalkylene glycol (other than ethylene glycol) nucleus with a molecular 25 weight of more than 900 which has been extended with water-soluble polyoxyethylene groups at each end. The water-soluble portion of the molecule should constitute at least 3~

_9_ 1 50~ by weight of the total. The polyoxyalkylene glycol can be aliphatic, aromatic or alicyclic in nature, can be saturated or unsaturated, and can be represented by the formula:
HO~C2H4O)y(cm~lno)x(c2 4 )y wherein x, y, m and n are integers. When (CmHnO)x is saturated aliphatic, n-2m.
Compounds in this class are described in U. S.
10 Patent Nos. 2,674,619 and 2,677,700.
The polyoxyalkylene compounds of U. S. Patent No. 2,674,619 which can be used herein are defined by the formula:
Y[(C3H6O)n E H]x 15 wherein Y is the residue of an organic compound containing therein x active hydrogen atoms, n is an integer, and x is an integer greater than 1.
The values of n and x are such that the molecular weight of the compound, exclusive of E, is at least ~00 as determined by hydroxyl number; E is a polyoxyalkylene chain wherein the oxygen/carbon atom ratio i.9 at least 0.5, and E constitutes at least 50% by weight of the compound.
The polyoxyalkylene compounds of U. S. Patent No. 2,677,700 , which are useful herein, are defined by the formula:

ll l2 Y(f I--) n R
3~ 3 4 S6~0 ~10-1 wherein Y is the residue of an orc3anic compound con-taining therein a single hydrogen atom capabl~ of reacting with a 1,3-alkylene oxide; Rl, R2, R3 and R4 are selected from the group consistiny of H, aliphatic radieals and aromatic radicals, at least one sueh substituent bein~ a radical other than hydrogen; n is greater than 6.4 as determined by hydroxyl number and X is a water-solubilizing group which is nonionie and eonstitutes at least 50% by wei~ht of the total compound.
The eompounds of U. S. Patent No. 2,674,619 are sold commercially under the trademark "Pluronic" (BASF
Wyandotte Corp.)~ The following are examples of eompounds eorresponding to the above formula:

Name Moleeular Ethylene oxide Moleeular weight, poly eontent in final weight of oxypropylene produet, weight final base percent produet Pluronie F68 1,700 80 8,750 Pluronie P75 2,050 50 4,100 Pluronie F-98 2,700 80 13,500 Pluronie F-108 13,400 80 12,000-22,000 Another group of surface active agents which ean be employed has a water-insoluble nueleus with a moleeular weight of at least 900 containing an organie eompound having a plurality of reaetive hydrogen atoms eondensed with an alkylene oxide other than ethylene oxide and having water-soluble polyoxyethylene groups attaehed to eaeh end. The weight pereent of the hydrophilic portion of the moleeule -:L1-1 should be at least 50. These e~hylene oxide adducts of an aliphatic diamlne such as ethylene diamine extended with propylene oxide have the fo]lowing formula:

~(C~ O)~(C3~I60)x\ (C3f~6o)y~(c2H4o)yH
/ N -C~ CH2 -N ~
Il(C2~40)y~c3H60)x (C3Hoo)x(c2H4o)yH

Compounds in this class are described in U. S.
Patent Nos. 2,674,619 and 3,250,719 and are sold commercially under the trademark "Tetronic" (BASF Wyandotte Corp.~. The following are examples of compounds corresponding-to the above formula:

Name Molecular weight for Ethylene oxide Molecular ethylene di content in final weight of amine-propylene product, weight final oxide base percent product Tetronic 707 3,000 75 12,000 Tetronic 908 4,050 85 27,000 Another useful group of nonionics are the "Igepals"*
(GAF Corp. Chemical Products), a homologous series of alkylphenoxypoly (ethyleneoxy) ethanols which can be represented by the general formula:
~3-- ~CH2~20~C~2C~

* Trade Mark ~12--1 wherein R represents an alkyl radical and n represents the number of mols of ethylene oxide employed, among which are alkylphenoxypoly (ethyleneoxy) ethanols having alkyl groups containing frorn about 7 to about 18 carbon atoms, inclusive, and having from about 4 to about 100 ethyleneoxy units, such as the heptylphenoxypoly (ethyleneoxy) ethanols; nonylphenoxypoly~ethyleneoxy) ethanols and dodecylphenoxypoly-(ethyleneoxy) ethanols; the sodium or ammonium salts of the sulfate esters of these alkylphenoxypoly (ethyleneoxy) ethanols; alkylpoly(ethyleneoxy) ethanols;
alkylpoly(propyleneoxy)-ethanols; octylphenoxyethoxyethyl-dimethylbenzylammonium chloride; and polyethylene glycol t-dodecylthioether.
Other compounds in this class include ethylene oxide adducts of polyhydroxy alcohols extended with alkylene oxide, e.g., the "Tweens"*~ICI United States Inc.), ethylene oxide adducts of polyoxyalkylene esters of polybasic acids, ethylene oxide adducts of polyoxy-alkylene extended amides of polybasic acids, ethylene oxide adducts of polyoxyalkylene extended alkyl, alkenyl and alkynyl aminoalkanols, of which the hydrophobic nucleus should have a molecular weight of at least 900 and the hydrophilic part of the molecule should be at least 50%
by weight of the total. It is to be understood that the above-mentioned organic compounds having a plurality of active hydrogen atoms as well as the polyoxyalkylene glycols can be aliphatic, aromatic or alicyclic in nature and can contain unsaturation.

* Trade Mark ~1 .

-~3-1 Amon~ the many anionic s~lrface active agents which can be used herein are 'rriton*~-200 (~ohm & ~laas Co.), a sodium salt of an alkylaryl polyether sulfonate;Triton X~301 (Rohm ~ Haas Co.), a sodium salt of alkylaryl polyether 5 sulfate; Triton QS-9 (Rohm & ~aas Co.), a phosphate ester;
Alipal*CO 433 ~GAF), a sodium salt of sulfated nonylphenol (ethyleneoxy) ethanol; Dupanol*ME Dry (DuPont), a sodium lauryl sulfonate; Ultrawet*(Atlantic Refining Co.), an alkyl aryl sulfonate; Sipon ESY*(Alcolac, Inc.), a sodium lauryl ~o ethoxylate sulfate; and the like. Sipon ESY , 25.5 percent in aqueous solution, has been found to provide especially good results.
In accordance with this invention, a protective colloid is incorporated in the aqueous emulsionsO Such 15 known and conventional protective colloids as: the partially and fully hydrolyzed polyvinyl alcohols; cellulose ethers, e.g., hydroxymethyl cellulose, hydroxyethyl cellulose, ethyl hydroxylethyl cellulose and ethoxylated starch derivatives;
the natural and synthetic gums, e.g., gum tragacanth and gum 20 arabic; polyacrylic acid, poly(methyl vinyl ether/maleic anhydride), are well suited for use herein. The partially hydrolyzed polyvinyl alcohols such as Gelvatol*20-30 (Monsanto) are especially advantageous for use in this invention.
The catalysts used in the copolymerization reaction 25 are any of the known and conventional free radical polymeriza-tion catalysts heretofore used for the preparation of VAE
copolymer latices and include inorganic peroxides such as hydrogen peroxide, sodiurrl perchlorate and sodium per~orate, inorganic persulfates such as sodium persulfate, potassium 30 persulfate and ammonium persulfate and reducing agents such as sodium hydrogen sulfite. Catalyst (including co-catalyst reducing agent, if employed) is generally utilized at a * Trade Marks 3~
~ I ~
1 level oE from about O.l~ to about l'~ by weight of total comonom~rs.
An alkaline buffering agent such as sodium bicar-bonate, ammonium bicarbonate sodium acetate, and the like, 5 may be added to the aqueous system to maintain the p~l at the desired value. The amount of buffer is generally about O.Ol to 0.5% by weight, based on the monomers.
In order to obtain the hiyh Mooney viscosity, low gel content VAE elastomers herein, it has been found 10 necessary to employ an amount of surface active agent which is at least above about 2.0~ by weight of the total monomer and can range as high as about 5.0% by weight of the total monomer although amounts in excess of this are also operable.
Similarly, high levels of Mooney viscosity and low gel content 15 require that there be less than about a l.5:l weight ratio of protective colloid to total surface active agent, and preferably less than a ratio of about l~ ll of the surface active agent and vinyl acetate monomer may be present in the polymerization medium from the outset as distinguis~ed from ~0 other processes in which one or both of these ingredients are added incrementally to the raction medium during polymerization.
The temperature and pressure of the copolymerization reaction hcrein can be selected at levels which have heretofore been employed in VA~ emulsion copolymerization. Accordingly,

2~ temperatures of from about 70F. to about l~OF. and pressures of lOOO to 5000 p.s.i. can be used with good results. It is, of course, recognized by those skilled in the art that at the lower end of the temperature rancJe, it may be necessary to employ a reducing agent ko generate the free radical required 30 for initiating copol~merization.

B~

1 The VAE elastomer which is recovered fro~ the latex produced in accordance with this invention, preferably af~er being treated for the removal of residual surface active agent, protective colloid and other extraneous 5 substances, can thereafter be cured with a crosslinking (vulcanizing) agent while compounding with such optional ingredients as fillers; antioxidants; modifying resins (at from about 10% to about 40% by weight of VAE copolymer), e.g., polyvinyl chloride, ethylene propylene rubber (EPR), 10 polychloroprene, polyacrylate rubber, polyurethane, chlorinated polyethylene, polyester, ethylene-propylene diene monomer (EPDM) terpolymer, ethylene-methyl acrylate elastomer, ethylene butyl acrylate elastomer, and acrylonitrile elastomer; and other known elastomer 15 additives. The foregoing can be combined with the VAE
elastomer in conventional mixing equipment, typified by a two-roll rubber mill, a mixing extruder or preferably a high shear internal mixer such as a ~anbury mixer, until a homogeneous blend is obtained. Upon completion 20 of the mixing stage, the xesin blend is processed lnto any of several forms convenient for subsequent manufacturing operations, for example, pellets formed by an underwater pelletizer, strand cut, etc.
The crosslinking agents which can be used herein include such peroxides as: t-butyl perbenzoate, dicumyl peroxide; 2,5-dimethyl 2,5-di(t-butyl peroxy) hexane;
2,5-dimethyl-2,5-di(t-butyl peroxy) hexyne-3; 1,3,5-tris[alpha, alpha-dimethyl-alpha-(t-butyl peroxy)]-methyl 1 benzene; alpha, alpha-bis~-t-butyl peroxy) diisopropyl benzene; and, n-butyl-4,4-bis(t-butyl peroxy) valerate.
These crosslinking agents can be used alone or in com-bination with any of several polyfunctional auxiliary 5 crosslinking agents such as triallyl phosphate; trimethylol propane triacrylate; diallyl fumarate; triallyl cyanurate;
triallyl isocyanurate; pentaerythritol tetraacrylate;
trimethylol propane trimethacrylate; 1,3-butylene glycol dimethacrylate; allyl methacrylate; ethylene glycol 10 dimethacrylate; and, 1,3-butylene glycol diacrylate.
A preferred curing agent for use herein is Vul-Cup*40 KE
(~0% dicumyl peroxide on calcium carbonate) from Hercules Inc. The amount of peroxide crosslinking agent can range from about 1.0 to about 10.0 parts, and preferably\
15 from about 2.0 parts to about 5.0 parts per hundred parts of EVA copolymer. The polyfunctional auxiliary cross-linking agents are useful within the range of from about 0.1 to about 3.0 parts per hundred parts o EVA gum stock.
Examples of fillers which can advantageously be `
employed herein are: Hydral*710, an alumina trihydrate obtained from Alcoa; Hi-Sil*EP and Hi-Sil 233, amorphous precipitated hydrated silicas obtained from PPG Industries, Inc.; Cab-0-Sil* a fumed silica obtained from Cabot 25 Corporation; Mistron*Monomix,*a talc (magnesium silicate) from Cyprus Industrial Minerals Company; Burgess KE,* a surface treated (silane) calcined kaolin clay (anhyclrous * ~rade Marks 1 alumlnum slllcat~) obtalned from the sur~ess Piyment Company; and, antimony oxide. As is appreciated by those skilled in the art, the amounts of filler incorpoxated into a polymer blend of this invention will depend on the 5 nature of the filler and the properties desired of the final product. Non-reinforcing fillers such as alumina trihydrate can be used in amounts ranging from about 5.0 parts to about 400.0 parts and preferably from about 100.0 parts to about 150.0 parts, per hundred parts of 10 polymer blend. Reinforcing fillers such as hydrated silica, carbon black and sintered colloidal silica are useful in the range of from about S parts to about 100 parts per hundred parts of polymer blend but the useful upper xange is limited by the high viscosity imparted 15 by fillers of this type. The preferred amounts of these reinforcing fillers range from about 20 parts to about 80 parts per hundred parts of polymer blend for hydrated silica and carbon black and from about 10 parts to about 50 parts per hundred parts of polymer blend for sintered 20 colloidal silica.

Any of several known and conventional antioxidants can be incorporated into the polymer blends herein at from about 0.1 parts to about ~.0 parts, and preferably at about 1.0 part, per hundred parts of resin. Agerite*MA
25 ~R. T. Vanderbilt Company, Inc.), a polymerized trimethyl dihydroquinoline antioxidant, has been used with good results.

* Trade Mark ~0 1 of the ~ollowing examples in which all percentages are by weight, Examples l and 2 demonstra-te by way of comparison with the remaining examples which are illustra-tive of the invention herein, -the critical importance of 5 the presence of both the protective colloid and the surface active agent in the polymerization medium.

L~

am~le 1 This example demonstrates that the use of a protective colloid alone yields a polymer with high Mooney viscosity (more than a value of 30) but high 5 gel content. The following solution was prepared:

Deionized Water 850 gm Gelvatol 20-30 45.7 gm Sodium Bicarbonate l.13 gm (Gelvatol 20-30 is a Monsanto Company polyvinyl alcohol, ~7~89% hydrolyzed and of 4.7 - 5.4 cp viscosity for a 4 10 solution.) The polyvinyl alcohol and the bicarbonate were suspended in the water and the mixture was stirred until complete dissolution was achieved. The solution was sparged with nitrogen-for 30 minutes and then 0.04 gm (4 cc of a l~ solution) of ferrous sulfate heptahydrate 15 was added~ The solution and:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50 cc water were charged to a one-gallon, stainless steel pressure reactor equipped with external electric heating strips, 20 internal cooling coil and agitator. The reactor was then purged with nitrogen to remove all oxygen. The charge was heated to 120F. During the heat-up period the reactor was stirred at 670 rpm and ethylene was added to a pressure of 2500 psig. When the reaction conditions of pressure 25 and temperature were reached, the polymerization was started by adding 2 gm of sodium bisulfite dissolved in 65 cc of water. The reactor temperature and pressure ~l~lB~30 ,, o 1 were kept constant during the run~ The polymerization was considered completed 7-1/2 hours after the bisulfite addition, when the demand of ethylene ceased. The emulsion was cooled to room temperature and then the 5 polymer was coagulated from the emulsion by freezing the latex. The coagulated pol~ner was then dried in an air oven at 120F.
A vinyl acetate/ethylene copo].~ner was obtained with the following properties:

Vinyl acetate content 59.5%
Mooney viscosity, ML(1~4) at 212F. 70~5 Gel content 42~ (xylene 80C.) 1 Example 2 This example demonstrates that the use of surface active agent(s) as the sole dispersant yields a polymer with low Mooney viscosity (less than a value of 30) and low gel content. The following solution, after being sparged with nitrogen, was charged to the reactor described in Example 1:

Deionized Water 850 gm Pluronic F~68 51.2 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm Ferrous Sulfate Heptahydrate 0.04 gm Along with this solution, the following were charged to the reactor:

Vinyl Acetate 800 gm Ammonium Persulfate 3.3 gm dissolved in 50 cc ~2 ~5 The polym~rization was carried out in the same way as described in Example 1.
The polymer was coagulated from the emulsion by adding with stirring a hot saturated solution of so.dium chloride. The coagulated polymer was washed four times with water and then dried in an air oven at 120F. The vinyl acetate/ethylene copolymer obtained had the following properties:

Vinyl acetate content 55.9%
Mooney viscosity, ML(1+4) at 212F. 25 Gel content 0.32% (xylene 80C) ~3 This exa~ple demonstrates that the use of a combination of protective colloid and surface active agents as dispersants yield a polymex with high Mooney 5 viscosity and low gel content. The following solution, after being sparged with nitrogen, was charged to the reactor described in Example 1:

Deionized Water 850 gm Gelvatol 20-30 11.6 gm Pluronic F-68 38.4 gm Sipon ES~ 14 gm 10 Sodium Acetate 3.2 gm Ferxous Sulfate Heptahydrate 0.04 gm ~long with this solution the following were charged to the reactor:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50 cc Water The polymerization was started with 1.08 gm of sodium bisulfite dissolved in 35 cc of waterO The remainder of the run was carried out as described in Example 1-. The polymer was recovered from the emulsion by coagulating 20 the latex with sodium chloride as described in Example 2.
The vinyl acetate/ethylene copolymer obtained had the following properties:

Vinyl acetate content 57.8 Mooney viscosity, ML~1~4) at 212F. 38.5 Gel content 0.16% (xylene 80C) Although the combination of polyvinyl alcohol and surface active agents as practiced in this example would be expected on the basis of prior expexience to result in .

3~

1 high or low values of both Mooney viscosiky and gel, or at best some average values of these in the copolymer product, surprisingly,Mooney viscosity was maintained at a desirable level while gel content was actually reduced. In sub-5 sequent examples (e.g., Examples 4 and 5), it is demonstratedthat gel can be vir-tually eliminated while attractive Mooney viscosity is achieved by proper protective colloid to surface active agent ratios.

~2~-1 Example 4 This example demonstrates that the ratio of concentration of protective colloid to that of surface active a~ent(s) used as dispersants for Example 3 may 5 be varied within certain limits without affecting sub-stantially desirable polymeric properties of hiyh Mooney viscosity and low gel content. I'he following solution, after being sparged with nitrogen, was charged to the reactor described in Example l:

Deionized Water 850 ~m Gelva~ol 20-30 24.4 gm Pluronic F-68 20.5 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm Ferrous Sulfate ~eptahydrate 0.04 gm Along with this solution the following were charged 15 to the reactor:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50 cc Water The polymerization was started with 25 cc of a 3~ sodium bisul~ite solution. Then,every hour an additional lO cc of this solution was pumped to the reactor, for~a total of six additions. The remainder of the run was carried out as described in Example l. The polymer was recovered from the latex as described in Example 2.
The vinyl acetate/ethylene copolymer obtained had the following properties:

Vinyl acetate content 61.7 Mooney viscosity, ML(1~4) at 212F. 47 Gel content -- All dissolved except for trace of slimy material (not measurable) (xylene ~0C.) ~3 1 Example 5 In this example, a different ratio of protective colloid/surface active agent (5) iS employed. The following solution after being sparged with nitrogen was charged to the reactor described in Example 1:

Deionized Water 850 gm Gelvatol 20-3~ 30.9 gm Pluronic F-68 17.9 gm Sipon ESY 14 gm Sodium ~cetate 3.2 gm Ferrous Sulfate Heptahydrate 0.04 gm Along with this solution the following were charged to the reactor: --Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50 cc Water The run was carried out following the procedure described15 in Example 1, using 2 gm of sodium bisulflte dissolved in 65 cc of water to start thè polymerization. The polymer was recovered from the latex following the procedure described in Example 2.
The vinyl acetate/ethylene copolymer obtained had the following properties:.

Vinyl acetate content 62.9%
Mooney viscosity, ML(1+4) at 212F. 37.5 Gel content less than 0.05%

.. ~0 1 Example 6 This example demonstrates that the incorporation of t-butyl alcohol in the polymerization reaction medium has no substatial effect on -the polymer properties. The 5 following solution, after being sparged with nitrogen, was charged to the reactor described in Example 1:

Deionized Water 760 gm t-butyl alcohol 90 gm Gelvatol 20-30 11.6 gm Pluronic F-68 38.4 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm 10 Ferrous Sulfate Heptahydrate 0.04 gm Along with this solution the following were charged to the reactor:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50 cc Water 15 Following the procedure described in Example l, the polymerization was started with 2 gm of sodium bisulfite dissolved in 65 cc of water. Then,every two hours an additional 20 cc of this solution were pumped to the reactor for a total of three additions.
The polymer was recovered from the latex following the procedure described in Example 2.
The following vinyl acetate/ethylene copolymer was obtained:

Vinyl acetate content 58.6% -Mooney viscosity, ML(1+4) at 120F. 40 5 Gel content Polymer completely soluble in xylene at 80C.

1 F~arnple 7 his example demonstrates the use of a higher total concentration of surface active agent. The following solution, after being sparged with nitrogen, was charged 5 to the reactor described in E~ample l:

Deionized Water 850 gm Gelvatol 20~30 22.9 gm Pluxonic F-68 38.4 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm Ferrous Sulfate Heptahydrate 0.04 gm lO Along with this solution the following were charged to the reactor:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolved in 50-cc Water The polymerization was started ~ith 25 cc of a 3% sodium 15 bisulfite solution. Then, every hour an additional lO cc of this solution was pumped to the reactor for a total of six additions. The remainder of the run was carried out as described in Example l. The polymer was recovered from the latex as described in Example 2. The vinyl acetate/
20 ethylene copolymer obtained had the following properties:

Vinyl acetate content 56.8%
Mooney ViSCGSity~ ML(1~4) at 212F. 50 ~0 1 E~ le 8 This example demonstrates the further processing of the elastomers of this invention and the resulting products.
The VAE copolymers produced in Examples 3, 4, 6 and 7 were subjected to evaluation as elastomeric products. A cor~mercial high pressure process VAE copolymer elastomer (VYNATHENE*
EY-907, a U. S. Industrial Chemicals Co. product having about 60 percent vinyl acetate content) was used as a standard. To carry out this evaluation the elastomers 10 were compounded according to the following formulation:

Elastomer 100 phr HiSil 233 55 phr Silane A-172* 1 phr Agerite MA 1 phr VulCup 40 KE 3 phr * Vinyl tris (betamethoxyethoxy) silane coupling agent (Union Carbide) The compounding was done on a 6"x12" two-roll rubber mill.
The compounds were then press cured into 6"x6"x0.075"
plaques in an ASTM mold. The plaques were pressed with 2000 psig pressure at 396F. for five minutes. The results of the evaluation are indicated in Table l.

TABLE I

(1) (1) Tensile % Swell %
Strength psi Elong. Ratio Extract Example No. 3 2250 370 5.12 8.20 25 Example No. 4 2520 420 5.28 7.~30 Example No. 6 2320 440 5.63 7.84 Example No. 7 2270 360 5.54 7.34 Vynathene EY-907 3000 280 3.62 5.46 (1) In xylene at 80C.

30 `
* Trade Mark ~xamPle 9 This example demonstrates that the VAE elastomers of this invention can provide cured resins having properties such as elongation and low temperature brittleness (Compound III) which are superior to those commercially available.
Using the reaction medium and polymerization conditions described in Example 7, several batches of elastomer were made. The elastomers obtained were blended and subsequently cured using different levels of curing agent and using 10 a coagent in the compounding formulation. The blend had the following properties:

Vinyl acetate content 62.5%
Mooney viscosity, ML(H4) at 212F. 37.5 Vynathene EY-907 was used as the standard.
The experimental resin and the commercial elastomer were compounded as indicated in Table II as follows:

TABLE II

Compound Compound Compound I II III
Elastomer lO0 100 100 HiSil 233 55 55 55 Silane A-172 Agerite MA
VulCup 40 KE 3.75 4.5 3 TAIC (Triallyl isocyanurate) The amounts are given in parts/100 parts of resin.

The products were compounded and cured as indicated previously.
The results of the evaluation are indicated in Table III
below.

.

~s~

o ~ cO
E~ ~ ~ r~ r~ r~7 r~ r~

~r~ o d o o t~
~ s~ co r~ ~ co X OJ u~

_ r~ ~~ ~ ~ ~~ r~ I
~ Ocn r~ rn o 3 ~~ r~~ rf~ r~

1 0 r~
~ O
rl rdo r~ ~ cn , r~ ~I~ ~D D In, ~D Ln 0 3 cn H
H
h ~ ¦ o r > o O
rt~

a) ~ ,_ ~ s~ O O
b~l ~1 ~ h o ~a O O O O O O O :~ o r.~ Iq ~ cn ~1 ~ ~ o ~ o s~ ~ ~ ~ D ~ ~D O O
Cl ~ Q U Q, rt~ n~
~ U ~ u~ ~
, ~ ~ rd S~
~ ~ ~ ,1 rC ; ~C lq o s~
~J) ~ r-l ~> '>1~ .4 ~r-l ~ Lf~ cn1~ o r~ ~ ~
u~ ~~Y tO ~ ~
r~c~l r~ rl ~ o E S ~q R , r~ r-l ~
rd ,Q ~~ ~ ~1 U ~P ~/

(~ rcJ r~ I r-l 3 E~ ~ E.~ ~ (d q ~1 1~1 f~ d~
,, ~,) C~ C.) 1.
.

~t.'~ D~

1 E~ple 10 This example demonstrates that the process of 5 this invention is not limited to the use of a single catalyst system. Thus, the redox catalyst system ammonium persulfate/sodium ~ormaldehyde sulfoxylate reduces polymerization time in comparison to ammonium persulfate/sodium bisulfite, yet produces an entirely 10 acceptable copolymer.
The following solution, after being sparged with nitrogen, was charged to the reactor described in Example 1:

Deionized Water 850 gm Gelvatol 20-30 22.9 gm Pluronic F 68 38.4 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm Ferrous Sulfate Heptahydrate ' 0.04 gm Along wi~h this solution the following was charged to the reactor:

Vinyl acetate 800 gm Ammonium persulfate 3.3 gm dissolYed in 50 cc ~ deionized water A 0.25% aqueous solution o~ sodium formaldehyde sulfoxylate was prepared and charged to the catalyst feed tank. Following the same procedure as described in Example 1, the reactor was heated and pressurized with 25 ethylene. When the reactor conditions of temperature and pressure (120F., 2500 psig) were reached, the polymerization was started by pumping the reducing agent solution to the 1 reactor. The flow was se-t at approximately 40 cc/hour.
The polymerization was considered completed when the ethylene demand ceased, 6 hours after beginniny addition of the reducing agent.
S The polymer was recovered from the emulsion by coagulating the latex with sodium chloride as described in Example 2.
The VAE copol~ner obtained had the following properties:
10 Vinyl acetate content 56.8 Mooney viscosity, ML(1+4) at 212F. 43.5 Gel content All dissolved except for trace slimy material not measurable (xylene 80~.) This e~ample demonstrates the use of the catalyst system ammonium persulfate/sodium hydrosulfite.
The reactor described in Example 1 was charged with 5 the same solution, persulfate and vinyl acetate, as described in Example 10. A 1.5% aqueous solution of sodium hydro-sulfite was prepared and charged to the catalyst feed tank.
The reactor was heated and pressurized as described in Example 1. When the reactor conditions or temperature 10 and pressure (120F.,2sO0 psig) were reached, the polymerization was started by pumping the reducing agent solution to the reactor. The flow was set at approximately 60 cc/hour. The polymerizaton was con-sidered completed when the ethylene demand ceased, 5 5 hours after beginning the addition of the reducing agent.
The polymer was recovered from the emulsion by coagulating the latex with sodium chloride as described in Example 2.

The VAE copolymer that was obtained had the following properties:

Vinyl acetate content 56.7%
Mooney viscosity, ML(1+4) at 212F. 46 Gel content All dissolved except for trace slimy material (not measurable) xylene 80C.

-3~~

Example 12 This example demonstrates the use of acrylic acid as a termonomer, and the attendant production of polymer 5 with increased Mooney viscosity without increased gel.
The reac~or described in Example 1 was charged with the same solution described in Example 10.
Along with this solution the following was charged to the reactor:

Vinyl acetate 800 gm Acrylic acid 18 gm Ammonium persulfate3.3 gm dissolved in 50 cc deionized water A 0.25~ aqueous solution of sodium formaldehyde sulfoxylate was prepared and charged to the catalyst feed tank.
The reactor was heated and pressurized as described in Example 1. When the reaction conditions of temperature and pressure were reached the polymerization was started by pumping the reducing agent solution to the reactor. The flow was set at approximately 45 cc/hour. The polymerization 20 was considered completed 6-1/2 hours a~ter beginning addition of the reducing agent. The polymer was recovered from the emulsion by coagulating the latex with sodium chloride as described in Example 2.
The vinyl acetate/ethylene/acrylic acid terpolymer 25 that was obtained had the following properties:

Vinyl acetate content 58.1%
Mooney viscosity, ML(1~4) at 212F. 5S
Gel content All dissolved except for trace slimy material (not measurable) xylene 80C.

3~

1 Example 13 ~ vinyl acetate/eth~lene/1,6 hexanediol diacr~late terpolymer having unexpec-tedly low gel content and furnishing improved, cured elastomers is preparedO The 5 following solution was prepared:

Deionized Water 850 gm Gelvatol 20~30 22.9 gm Pluronic F-6~ 38.4 gm Sipon ESY 14 gm Sodium Acetate 3.2 gm Ferrous Sulfate Heptahydrate 0.04 gm 10 The polyvinyl alcohol, the Pluronic and the sodium acetate were suspended in the water. The mixture-was - stirred approximately one and one-half hours until complete dissolution of the components. The solution was sparged with nitrogen for 30 minutes and then the 15 Sipon ESY and the ferrous sulfate heptahydrate (1% aqueous solution) were added. The solution plus Vinyl acetate 1,6 hexanediol diacrylate Ammonium persulfate 3.3 gm dissolved in 50 cc Water were charged to a one-gallon stainless steel pressure 20 reactor equipped with external electric heating strips, internal cooling coil and agitator. The reactor was then purged with nitrogen to remove all oxygen ~rom the system.
The charge was heated to 120F. During the heat-up period the reactor was stirred at 670 rpm and the ethylene was 25 added to a pressure of 2500 psig. The polymexization was then started by adding 30 cc of a 3% sodium bisul~ite solution. Then, ever~ hour an additional 10 cc of this -36~

1 solution was pumped to the reactor for a total of six additions. The reaction temperature and pressure were kept constant during the run. The polymerization was considered completed when the ethylene demand ceased, 5 seven and one-halr hours after the first sodium bisulfite addition.
The polymer was coagulaked from the emulsion by adding under stirring a hot saturated sodium chloride solution. The coagulated polymer was then washed four 10 times with warm water and dried in an air oven at 120F.
This procedure was used to make several runs with increasing concentration of 1,6-hexanediol diacrylate.
Table IV below sets forth the amounts of vinyl acetate and 1,6-hexanediol diacrylate used in each run.

TABLE IV

Gm of 1,6- % of 1,6-Hexanediol Gm of Vinyl Hexanediol Diacrylate Based Run No. Acetate Diacrylate on Vin~ Acetate 1 800 1 0.125

4 800 16 2 7* 670 140 20 * Product coagulated in the reactor.

Table V below summarizes the properties of the polymers made in these runs.

Mooney Viscos- ~ 1,6 Hexanedlol Run Vinyl Acetate ity ML(1~4) at Diacrylate in Gel Con-No~ ~ 212F. ~ ~ tent %

1 60.4 37 --2 59.0 34.5 -- 0 3 60.5 35 -- o 4 60.3 41 1.8 - 2.4 0 60.3 38.53.9 - 4.5 0 6 59.9 35.5 4.2 0 7 56.9 37.5 ~.8 0 The polymers made in these runs were subjected to evaluation l0 as an elastomeric product. A commercial VAE copolymer elastomer (VYNATHENE EY-907, Table III) was used as the standard. To carry ~ut this evaluation, the resins were compounded and cured according to the procedure of Example 8. Results of the evaluation are set forth in Table VI
15 as follows:

TABLE VI

Oil Tensile Tensil Resist., Swell %
Strength Strength % % Swell Ratio Extr.
Run No. psig psig (1) Elong. Ratio(2) (3) (3) 20 EY-907 2740 710 - 280 67 3.82 7.08 1 2230 690 490 89 5.73 6.36 2 2190 690 480 94 5.97 9.12 3 2360 690 490 91 5.72 9.50 4 2370 730 480 75 5.60 8.98 2190 810 370 83 4.58 9.45 6 2380 990 410 81 5.21 8.85 (1) After aging 7 days at 350F.
(2) AST~ #3 oil, 70 hours at 302F.
(3) xylene at 80C.

3~

1It is readily seen that the terpolymer elastomers furnish high elongation with the cured rubbers having improved resistance to loss of tensile strength upon heat aging at 350F. This combination of properties

5 is surprising since the diacrylate monomer, a crosslinking monomer, would be expected to reduce elongation in the compound.

-~0

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for preparing elastomeric ethylene vinyl acetate-ethylene copolymers having a Mooney viscosity value greater than about 30 and low gel content wherein vinyl acetate monomer is copolymerized with ethylene monomer in an aqueous emulsion reaction medium containing surface active agent, polymerization catalyst and pro-tective colloid which comprises:
a) copolymerizing from about 40% to about 70%
by weight of vinyl acetate monomer with from about 60% to about 30% by weight of ethylene monomer in the aqueous emulsion reaction medium to provide a latex, the reaction medium containing:
(i) at least one surface active agent having a hydrophilic lipophilic balance of at least 22 in an amount above about 2.0% by weight of the total monomer, (ii) a polymerization catalyst, and (iii) at least one protective colloid in an amount of less than about one part for each part by weight of total surface active agent, with the total weight of the surface active agent and vinyl acetate being present in the reaction medium at the commencement of copolymerization; and, b) recovering the vinyl acetate-ethylene elastomer from the latex.
2. The process of claim 1 wherein the Mooney viscosity of the copolymer obtained therefrom at 212°F. is from about 30 ML(1+4) to about 80 ML (1+4).
3. The process of claim 2 wherein the Mooney viscosity of the copolymer obtained therefrom at 212°F. is from about 30 ML (1+4) to about 70 ML (1+4).
4. The process of claim 1, wherein the gel content of the copolymer obtained therefrom as measured by insolubility in xylene at 80°C. is not more than about 2%.
5. The process of claim 4, wherein the gel content of the copolymer obtained therefrom as measured by insolubility in xylene at 80°C. is not more than about 1%.
6. The process of claim 1, wherein another ethylen-ically unsaturated monomer up to about 15% by weight of the total monomer charge not exceeding the weight of ethylene is copoly-merized.
7. The process of claim 6, wherein the ethylen-ically unsaturated monomer is 1,6-hexanediol di-acrylate.
8. The process of claim 1, 4 or 6, wherein the surface active agent is a nonionic polyalkyleneoxy surface active agent.
9. The process of claim 1, 4 or 6, wherein the surface active agent is an alkali metal aliphatic ether sulfate.
10. The process of claim 1, 4 or 6, wherein the protective colloid is a partially hydrolyzed polyvinyl alcohol.
11. An elastomeric vinyl acetate-ethylene copolymer having a Mooney viscosity value greater than about 30 ML (1+4) at 212°F. and a low gel content when prepared according to the process of claim 2.
12. A copolymer according to claim 11 having a gel content as measured by insolubility in xylene at 80°C. of not more than about 1%.
13. A crosslinked elastomeric vinyl acetate-ethylene copolymer of Claim 11.
CA 341321 1979-01-22 1979-12-06 Emulsion process for preparing elastomeric vinyl acetate-ethylene copolymers Expired CA1151800A (en)

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BE (1) BE881261A (en)
CA (1) CA1151800A (en)
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US4689370A (en) * 1984-10-29 1987-08-25 National Distillers And Chemical Corporation Halogenated ethylene-vinyl acetate-isobutylene terpolymers
US4594393A (en) * 1984-10-29 1986-06-10 National Distillers And Chemical Corporation Halogenated ethylene/vinyl acetate/isobutylene terpolymers
DE3628315A1 (en) * 1986-08-21 1988-02-25 Bayer Ag Use of specific ethylene-vinyl acetate copolymer for modification of pvc
DE3825450C2 (en) * 1988-07-27 1997-07-10 Bayer Ag A process for the preparation of ethylene / vinyl acetate copolymers having a reduced tendency to stick
US5872181A (en) * 1997-07-09 1999-02-16 Air Products And Chemicals, Inc. Adhesive for difficult to bond surfaces

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FR1348863A (en) * 1962-02-27 1964-01-10 Sicedison Spa A process for obtaining synthetic latex polyvinyl ester particularly suitable for water-based paints
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DE2256154C3 (en) * 1972-11-16 1984-10-04 Basf Ag, 6700 Ludwigshafen, De
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