CA1063750A - Interpolymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polymeric compositions, comprises interpolymers of: (A) about 50 mol percent of one or more acyclic or alicyclic esters of acrylic acid wherein the ester radical moiety is free of olefinic unsaturation or readily replaceable halogen; (B) one or more of acyclic or alicyclic Type I or Type III mono-olefins; and (C) 0.3 to 30 mol percent of one or more halomethylated aromatic vinyl compounds, the sum of the (B) and (C) components totaling about 50 mol percent of the interpolymer. The interpolymers cross-link readily with nucleophilic reagents at moderate vulcanization temperatures to yield elastomerspossessing good tensile strength, elongation and modulus which have utility as general purpose or especially as oil and heat resistant elastomers.

Description

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This invention relates to cFoss-linlcable interpolymers comprising a major proportion of one or more oleElns and one or more esters of acrylic acid and a minor proportion of a vinyl aromatic compound having a halo-methyl group substituted for one of the aromatic ring hydrogens.
More particularly, this invention relates to interpolymers, having elastomeric properties when cross-linked by means of nucleophilic reagents, said interpolymers prepared with the aid of a catalyst system comprising a Lewis acid and a free-radical generator from monomers comprising one or more acrylic or alicyclic olefins; one or moreacycllcor alicyclic esters of acrylic acid wherein the acyclic or alicyclic radical moiety is free of olefinic unsaturation or readily replaceable halogen; and from 0.3 to 30 mol percent of the total monomers present in said interpolymer of a halo-methylated aromatic vinyl compound.
Most particularly, this invention relates to interpolymers, having elastomeric properties when cross-linked by means of one or more nucleo-philic reagents, prepared with the aid of a catalyst system comprising a Le~is acid and a free-radical generator such as an organic peroxide com-prising (A) about 50 mol percent of one or more Cl to C20 acylic or alicyclic esters of acrylic acid in which the Cl to C20 acyclic or alicyclic ester ~ 20 radical moiety is free of olefinic unsaturation or readily replaceable hal-: ogen; and a total of about 50 mol percent of the sum of: (B) one or more C2 to C20 acyclic or alicyclic Type I (R-CH=CH2) or Type III (R(R')C=CH2) mono-olefins wherein R and R' are independently selected from the group consisting of hydrogen, and Cl to C18 straight and branched chain alkyl radicals, aryl, alkylaryl, arylalkyl and cy ~ alkyl radicals; and (C) 0.3 to 30 mol percent, preferably not more than 10 mol percent (in the : , . . . , , ~ ~
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total interpolymer) of one or more halomethylated aromatic vinyl compounds.
While the preferred method for the preparation of the interpolymers of this invention is from the said monomers, an alternative method comprises polymerizing ~A) one or more Cl to C20 acyclic or alicyclic esters of acrylic acid in which the Cl to C20 ester radical moiety is free of olefinic unsaturation or readily replaceable halogen; (B) one or more C2 to C20 acyclic or alicyclic Type I or Type III monoolefins; 0.3 to 30 mol percent of an aromatic vinyl compound, followed by halomethylation of the aromatic ring in the interpolymer.
The interpolymers of this invention may be blended, prior to cross-linking, with halogenated polymers such as halogenated polyolefins;
halogenated butyl rubber; halogenated terpolymers such as the brominated EPDM described in U.S. Patent 3,524,826 issued October 18, 1970 to Esso Research and Engineering; sulfochlorinated polyolefin elastomers such as ~ ~;
Hypalon*; polychloroprenes such as neoprene; polyvinyl chloride; epichloro~
hydrin rubbers. Such blends may also include process oils, plasticizers, ~-resins, fillers and reinforcing agents. The cross-linked elastomers of this invention possess a high tensile strength, elongation and modulus and are ; ~ -useful as general or special purpose elastomers.
The highly reactive nature of the halogen in a halomethyl group attached to an aromatic ring not only facilitates cross-linking at moderate vulcanization temperatures but provides a means for conversion of the halomethyl moiety to a variety of derivatives having increased utility.
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For example, reaction of the interpolymers of this invention with reagents well known to those having ordinary skill in the chemical arts permits -conversion of the halomethyl group . .; .
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to a cyanomethyl group; hydroxymethyl group; carboxymethyl group; aldehyde group; thiomethyl group; aminomethyl group; alkoxy methyl group; methylene ester of a carboxylic acid; quaternary nitrogen halides and the like. These may be further reacted with for example difunctional reagents to give cross-linked networks. Non-limiting examples include reaction of the hydroxymethyl and aminomethyl derivatives with a dibasic acid or anhydride, or reaction of the carboxylic acid derivative with a glycol.
Copolymers of alkyl acrylates with chlorine containing monomers are old in the art. For example, copolymers of ethyl acrylate with from

2.5 to 5 percent of 2-chloroethyl acrylate or 2-chloroethyl vinyl ether have been available commercially as Lactoprene* EV since 1944.
Similar copolymers including alkyl acrylates or substituted alkyl acrylates are disclosed in U.S. Patents Wos. 3,201,373 issued August 17, 1975 to American Cyanamid; 3,578,636 issued May 11, 1971 to Sumitomo;

3,629,215 issued December 21, 1971 to Sumitomo; and 3,63S,924 issued January 18, 1972 to Sumitomo, and Belgian Patent No. 763,733 published September 3, 1971 to Sumitomo.
In distinction to the products and processes of the prior art, it has now been found that interpolymers which have elastomeric properties when cross-linked by means of nucleophilic reagents may be prepared from monc~mers which comprise tA) one or more Cl to C20 acyclic or alicyclic esters of acrylic acid wherein the es*er radical moiety is free of olefinic unsaturation or halogen which will react with nucleophilic reagents under the conditions normally used for the vulcanization of elastomeric compositions -referred herein as "readily replaceable halogen"; (B) one or more C2 to C20 acyclic or alicyclic Type I or Type III monoolefins; and (C) one or more halomethylated aromatic vinyl compounds by means of a catalyst system comprising a Lewis acid and a free-radical generator.

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t~5~ ., The interpolymer contains about 50 mol percent o~ the acrylic ester and a totaL o~ about 50 mol percent of the oleEin and chloromethylated aromatic ~finyl compound Witll the llmitat:ion that the halomethylated aromatic vinyl compouncl does not exceed more than 30 mol percent, preferably not more than 10 mol percent, of the monomers present in the interpolymers.
The properties of the interpolymer suggest a micro-structure for the polymer chain in which acrylate ester monomer units a]ternate with either an olefin monomer unit or a randomly distributed halomethylated aromatic vinyl monomer unit. According to this structure a segment of the interpolymers of this invention may be illustrated as follows:
~ --(B-A) ~^~ C)~ (A~B)n----------wherein m and n are integers which cannot be determined with any major degree of accuracy with the analytical methods available at the present time, but for any particular macromolecule of the instant invention~may be in the range of 1 to about 500. ,~
For the specific case where the acrylate ester (A) is ethyl acrylate; the olefin (B) is isobutylene; and the halomethylated aromatic vinyl compound (C) is 4-chloromethyl styrene, a segment of the interpolymer macromolecule of this invention may be iilustrated as follows: -20 /~ R H H~ H H ~H H H R~
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OR' - OR' where R is a methyl radical, R' is an ethyl radical and m and n are as indicated above.

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lL~ 5 . onomers crylic_L~.~ters Cl to C20 acyclic or alicylic esters oE acrylic acid in which the ester radical moiety is free of olefinic unsaturation or readily replaceable halogen may be illustrated by the general for~ula CH2=CH-COOR wherein R is selected from the group consisting of straight or branched chain primary alkyl radicals, arylalkyl radicals, cycloalkylalkylene radicals, and per-fluoroalkyl radicals. Non-limiting examples are: methyl; ethyl; n-propyl;
n-butyl; isobutyl; n-amyl; n-hexyl; 2-ethyl-hexyli n-octyl; isooctyl, derived by the oxonation of mixed heptenes followed by hydrogenation; isodecyl;
3,5,5-trimethylhexyl; n-dodecyl; tridecyl; tetradecyl; heptadecyl; octa-decyl; benzyl; hexahydrobenzyl; and perfluoro butyl radicals.
B. Olefins Mon-olefins suitable for the practice of this invention include C2 to C20 hydrocarbons which may be Type I olefins having the general formula R-CH=CH2 and Type III olefins having the general formula R'(R')C=CH2 ~herein R and R' are independently selected from the group consisting of hydrogen; straight and branched-chain alkyl radicals; aryl; alkylaryl;
arylalkyl and cycloalkyl radicals having from 1 to 18 carbon atoms. ~`
Non-limiting examples of suitable Type I olefins include: ethylene, , propylene; l-butene; l-pentene; l-hexene; 4-methyl-1-pentene; 1 heptene;

4,4-dimethyl-1-pentene; l-octene; l-nonene; l-decene; 3,7-dimethyl-1-octene;
l-dodecene; l-tridecene; l-tetradecene; l-octadecene; styrene; 4-methyl-styrene; vinyl cyclopentane; vinyl cyclohexane; 2-vinyl norbornane;C~-vinyl naphthalene; 5,5,7,7-tetramethyl-1-octene; and 3,6,10-trimethyl-1-hendecene.

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Non-limitillg examples o~ suitn~le Type III olefins include:
isobutylene; 2,3-dimethyl-l-butene; 2,4,4-trimethyl-1-pentene; 2,6-dimethyl-l-octene; 4-isopropellyl toluene; isopropenyl cyclopentarle; ~-methyl styrene, l-isopropenyl naphthalene; 2,5,9-trimethy:l-1-decene; 2,6,10-~rimethyl-1-hendecene; and 2,7,11-tr:imethyl-1-dodecene.
The general formulae used to illustrate the types of olefins suitable for the practice of this invention are based on the Boord Class-ification described by Schmidt and Boord in ~.A.C.S. 54, 751 ~1932).
C. Halomethyl Aromatic Vinyl Compounds Cg to Cl8 halomethyl aromatic vinyl compounds useful in the practice of this invention may be illustrated by the general formula CH23CH-R-CH2X wherein R is an arylene radical having from 1 to 3 rings and X is a halogen independently selected from the group consisting of chlorine, bromine and iodine. Non-limiting examples include: 3-chloro-methyl styrene; 4-chloromethyl styrene; 1-vinyl-4-chloromethyl naphthalene;
4-chloromethyl-2,3,5,6-tetramethyl styrene; 4-bromomethyl styrene; 3-chloromethyl-4-methyl styrene; 3-methoxy-4-chloromethyl styrene. Of particular utility lS a commercially available chloromethylated styrene herein referred to as VBC (vinyl benzyl chloride) which is a mixture of approximately 60 wt. percent of the meta isomer and 40 wt. percent of the para isomer.
II Catalysts Catalyst compositions suitable for the practice of this invention ~-comprise, in combination, a Lewis acid and a source of free-radicals. Pre-ferred Lewis acids are metal halides and alkyl aluminum halides and pre-ferred sources of free-radicals are organic peroxy compounds and azo com-pounds. In addition to the Lewis acid reagent and peroxy compound, ~ , -:: : -: : . : , , : :.

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co-catalysts p~rticularly vanadi~lm compouncls may optionally be used to enhance and direct the activity o~ the catalyst system. In no case should thP Le~is acid be pre-reacted with the halomethyl aromatic vinyl compound since doing so inter~eres with the proper lncorporation of the monomer in the interpolymer chain.
Non-limiting examples of Lewis acids which are suitable for the practice of this invention include: Aluminum trichloride, aluminum tribromide, aluminum triiodide, hydrofluoric acid, boron trichloride, boron tri1uoride, ferric chloride, stannic chloride, zinc chloride, zirconium tetrachloride, and organoaluminum halides having the general formula AlR X wherein R is a monovalent hydrocarbon radical selected from the group consisting of Cl to C12 alkyl, aryl, alkylaryl, arylalkyl and cycloalkyl radicals, m is a number from 1 to 3, X is a halogen selected from chlorine, bromine and iodine, and the sum of m and n is 3. Preferred are ethyl aluminum sesquichloride, Etl 5AlC11 5 and ethyl aluminum dichloride, EtAlC12.
Useful co-catalyst vanadium compounds have the general formula VO Xt wherein z has a value of O or 1, t has a value of two to four, and X is independently selected from the group consisting of chlorine, bromine, iodine, acetylacetonates, haloacetylacetonates, alkoxides and haloalkoxides.
Non-limiting examples include VC14, VOC13, VO(OEt)3, VOC12(0Bu), V(AcAc)3, VO~AcAc)2, and VOC12(AcAc) where ~AcAc) is an acetylacetonate.
While free-radical generators such as ultraviolet light and high-energy radiation may be used as the source of free-radicals in the catalyst system of this invention, preferred are organic peroxides, hydro-peroxides, peracids, peroxyesters and azo compounds. Non-limiting examples - . -- , :: . : : : :: :
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include benzoyl peroxide: acetyl peroxkle, Lauroyl peroxide; t-butyl peroxide; t-butyl peracetate; t-butyl peroxypivalate; cumene hydroperoxide;
2-methyl pentanoyl peroxide, dic~lmy:Lperoxide and 2,2'-azo b:is(lsobutyroni-trile).
r~e concentration of the individual catalyst components may be varied over a wide range depending on the reactivity of the individual monomers. Suitable mol ratios of acrylate ester to organoaluminum halide, for example, may range from l to 2000 mols of acrylate ester per mol of organoaluminum halide, or higher. Preferred is a ratio of 5 to 1500 mols of acrylate ester per mol of organoaluminum halide. Most preferred is a rat~io of from about 10 to 1000 mols of acrylate ester per mol of organo-aluminum halide. , The peroxide component is similarly variable over a wide range ofmol ratios. Suitable ra~ios range from 10 to 2000 mols of acrylate ester per mol of peroxide or azo compound. Preferred is a ratio of from about -20 to 1000. Most preferred is a ratio of from 30 to about 500 mols of acrylate ester per mol of the free radical generator. `-~
As indicated above, a vanadium co-catalyst may optionally be used to enhance the activity and selectivity of the prlncipal catalyst system. When used, the vanadium compound may be added to the catalyst system in the range of from 1 to about 100 mols of organoaluminum halide per mol of vanadium compound. Preferred is a range of from 2 to 50. Most preferred is a molar ratio of from about 3 to 30 mols or organoaluminum halide per mol of vanadium compound.
- III Solvents Suitable media for dissolving or dispersing the monomers, catalyst components and polymeric reaction products include the general group of ali-- phatic and aromatlc petroleum hydrocarbons and halogenated hydrocarbons.

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~cyclic or alicyclic C~ or lower ~traigh~ or brallcl~ed chaLtl saturated hydro-carbons ~nd sromatic hydrocarbolls are preferred. Cl to C8 halogenated hydro-carbons are also userul solvents. Choice oE a particular solvent or mlxture of solvents will depend on the process conditlons, e.g. whether a homo-geneous solution process, suspension or slurry process, or cement suspension process is used.
In a homogeneous solution process for the production of high-molecular weight polymers, the concentration of polymer in the cement is usually limited to the range of 5 to 10 weight percent, since higher con-centration require excessive power input to insure good mixing, efficientheat-exchange is difficult to achieve and the high viscosity of the solution at the temperatures which are usually employed during the polymerization reaction causes sticking and fouling of the reactor with the reaction products.
In a slurry process in which the monomers and catalyst components are soluble in the solvent, but in which the po~ymer is not, higher con-centrations of dispersed polymer in the range of 10 to 20 wt. percent may be attained. Similar concentrations may be handled in reactors e~uipped with conventional mixers in a cement-suspension process in which a single or mixture of solvents is chosen which yields two phases; a dispersed cement phase of polymer swollen with monomers and solvent and a continuous phase consisting essentially of the pure solvent containing a small amount of monomers. Any of the above solvent systems may be used in batch, semi-continuous or fully continuous processes.
Non-limiting examples of suitable solvents which may be used alone or in admixture include: butane; pentane; cyclopentane; hexane; heptane;
isooctane; benzene; cyclohexane; toluene; methyl cyclohexane; mixed xylenes;

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c~lmene; methyL chlorlde; methylene chlori(le; dlchloroethane; orthodlcloro-bellzene ancl fluorinated or chloroÇluor:Lnatecl C2 to C4 acyclic hydrocarbons.
Solvents which are known to form stnble complexes or coordination compounds ~ith any of the catalyst components, particularly the Lewis acid, or vanadium compound iE used as a co-catalyst, are undesirable and should be avoided.
IV Process Conditlons The interpolymers oE this invention may be prepared in batch, semi-continuous or fully continuous processes in which homogeneous solution, slurry or cement-suspension solvent systems are utilized. In a typical batch process, a reactor fitted with efficient agitation means, and means for cooling the reaction mixture and withdrawing the heat of reaction is purged of air by displacement with oxygen-free nitrogen, argon or low-boiling olefin-free hydrocarbon vapors such as methane, ethane or propane ;
and charged with dry solvent or mixture or solvents.
Monomers and catalyst components in all processes, pre-diluted with solvent if desired may than be introduced into the stirred reactor, either simultaneously or sequentially, at a rate consistent with the means - used for heat-exchange to maintain the desired temperature range. Pressure on the reactor is maintained at a leveI sufficient to keep the reactants in the liquid phase. The catalyst components may be mixed in line in the absence of monomers before they are added to the reactor, or they may be added directly to the reactor in the presence of the monomers.
Temperatures at which polymerization may be conducted may range from -100C to 100C. Preferred are temperatures ln the range of -80C
to 50C. Most preferred are temperatures in the range of -40C. to 40C.

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rhc tem~craturc m.~y ~c varied d-lrLn~l the tLme required for optlmum yleld and polyner properties, wLth Eor example a low temperature durlng the i~itial phase of the reaction and a higher temperature during the flnal phase.
Reaction time may vary widely, depending on the reactivity of the particular monomers, catalyst concentrat:Lon and temperature of the reaction. Generally, reaction times are shorter at higher monomer, organo-aluminum and peroxide concentrations and at higher polymeriæation temper-atures. Accordingly, polymerization times may vary from as little as two minutes to Z00 hours. Preferred are reaction times in the range of from 10 minutes to 24 hours. Most preferred are reaction times in the range of 15 minutes to 10 hours.
Isolation of the interpolymer at the completion of the reaction may be accomplished in a variety of ways. In a preferred embodiment, the homogeneous polymer cement solution, or polymer suspension, or polymer - cement suspensions is fed from the reactor in the case of a batch pro-cess, or final reactor or holdi~ng drum in the case of a semi-continuous or fully continuous process to a mixing drum where the reaction mixture has been mixed either in line or is mixed in the drum with a quantity of a lower alcohol such as methanol, ethanol or isopropanol in order to inactivate : -:
_ the catalyst mixture. The alcohol may optionally contain a sequestering reagent such as ethylene diamine tetra-acetic acid or its disodium salt or acetylacetone. While inactivation of the catalyst in the manner indicated is preferred it is not essential and may be omitted if desired.
The polymer solution or suspension, with or without catalyst inactivation is fed to an agitated wash drum where it is mixed with water or a dilute aqueous solution of an acid such as hydrochloric or sulfuric - 1:;~ -~.
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acid in order to deash the polymer. Acid treatment ~ollowed by thorough water washing under efficlent agitation is repeated if necessary so as to obtain a polymer with a minimal ash cont:ent.
Final isolation of the polymer in crumb form is accomplished by feeding the polymer solution suspension to a slurry flash drum where it is treated with steam and hot water to prec:ipitate the polymer and vaporize the solvent. Typically, antioxidants, stabilizers and slurry aids are added to the polymer solution or suspension before slurrying and removal oE solvent. The water slurry of polymer is finally fed to dewatering and --drying extruders before packaging in bale or crumb form. Solvents and un~
reacted monomers, vaporized in ~he slurry flash drums are purified and recycled ~o the polymerization reactors.
V Cross-Linking Reagents Generally, the same nucleophilic reagents which are used for cross-linking and vulcanizing halogenated hydrocarbon elastomers, such as chlorinated butyl rubber, in which the halogen is an allylic relation-ship to a double bond may be used for cross-linking the interpolymers of this invention. Preferred are nucleophilic compounds containing nitrogen or sulfur or both, a comprehensive list of which may be found in "Materials and Compounding Ingredients For Rubber and Plastics", published annually by Rubber World, New York, N. Y.
Non-limiting examples include: diamines, diamine carbamates, ethylene imine derived polyamines; alkylated thioureas particularly the N,N'-dialkylthioureas, 2-mercaptoimidazoline, catechol salts, for examplè, dicatechol borates and polymethylolphenol resins and their halogenated derivatives.
The following examples illustrate the invention.
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E~ IPLE 1 - Pr~paratlon o~ an interpolyn~er of ethyl acrylate _ _ _ l~obutylene iInd Chloromethyl Styrene __ _ _ __ _ The polymerization was carried out in a pressure vessel fabri-cated frorn a solid cylinder oE polypropylene which had been bored to create a cylindrical cavity o~ 800 ml. ~le vessel was sealed.
The polymeri~ation vessel, contained in a dry-box from which air and moisture were excluded by means of a positlve internal pressure of oxygen-free and moisture-free nitrogen, was charged with 200 ml. of toluene which had been purified by percolation through a column oE Linde* 3A mole-cular sieves, 50 grams (0.5 mol) of a commercial grade of ethyl acrylatecontaining 15 ppm of 4-methoxyphenol as an antioxidant and 15.3 (0.1 mol~
grams of a commercial grade of chloromethyl styrene having an isomer distribution of about 60 percent of the meta isomer and about 40 percent of the para isomer, hereinafter designated VBC (commercially designated as vinyl ben~yl chloride).
The pressure vessel was then immersed in a Freon 11 (trichloro-fluoromethane) bath maintained at -20C., located in the dry box and the vessel and contents cooled to -15C. There was then added to the vessel in succession 7.5 ml. of a 1~0 molar solution of ethyl aluminum ~0 sesquichloride (Etl 5~1C11 5) in purified n-heptane, 56 grams (1.0 mol) of liquefied isobutylene and 1 millimol of lauroyl peroxide dissolved in 20 ml. of purified toluene. The reaction vessel was seal-ed, removed from the freon bath and allowed to come to room temperature which required - about 1 hour.
The rcaction vessel was then placed in a tumbling water bath maintained at 32C. and tumbled for a period of 40 hours. The pressure vessel contents were then transferred to a flask and the reaction terminated by tlle addition of 15 ml. of isopropyl alcohol and 10 ml. of methanol.

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~-- The elastomeric product was isolated by addition oE the solution to a boiling water bath whereby the product precipitated as a slurry. The product was filtered from the water and dried in a vacuum oven for 4 hours at 60C. at a pressure of 20 torr. The yield of polymer was 20.4 grams.
It had an inherent viscosity of 0.52 in benzene solution at 0.1 g/dl at 25C.
A sample of the polymeric product dissolved in CC14 was examined by NMR at 60 MHz. The structure of the interpolymer was determined by using the chemical shifts at 7.0 ppm as a measure of aromatic protons, the chemical shift at 4.5 ppm for the -CH2Cl group and the -OCH2-signal at 3.95 ppm for the ester. From the above the structure of the interpolymer was determined as containing the following monomer residues: 52 mol percent of ethyl acrylate; 23 mol percent of isobutylene and 25 mol percent of chloromethyl styrene. The polymer was analyzed for C, H and Cl. Calculated 0-23; tAcry'0.52; VBCo 25; C=67.2, H=8.1~ Cl=8.6 Found:
C,66.6;H, 7.7; Cl, 9Ø
In the following two examples, experiments were carried out - to determine whether prereacting the alkylaluminum halide with the chloro-methyl aromatic vinyl compound was desirable.

The preparation and isolation of the interpolymer was the same as was used in Example 1 except that 5.05 grams (0.033 moles) of VBC was used instead of 0.1 mol. The isolated product had an inherent viscosity in benezene at 25C. and a concentration of 0.1 g/dl of 0.76 and on analysis by NMR showed monomer residues of 50 mol percent of ethyl acrylate; 41 mol percent of isobutylene, and 9.0 mol percent of ~BC. Calculated for:
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Isob~l ; Et~cry ; V~C ; C-68.5; Il=9.S, Cl=3.7. Eound: C, 68.1;

~l, 9.~; Cl, 4.2, _.Xf PLL 3 The preparation and isolatlon of the interpolymer was in general the same as Example 2 except that the VBC, dissolved in 100 ~l. of toluene was prereacted at -20C. with the ethylaluminum sesquichloride and then added to the ethylacrylate in toluene. The yield of polymer was 4.:l grams and on elemental analysis contained only 0.16 weight percent of chlorine and when examined by N~ did not show the chemical shift associated with the -CH2Cl group. This result in comparison with that of Example 2 shows that prereacting the alkylaluminum halide with the chloromethyl aromatic compound is to be avoided.
E.YAMPLES 4 to 7 A series of runs were made in the same manner as Example 1, in which the molar proportions of VBC and catalyst were varied. The quantities used and the results obtained are given in Table I.
TABLE I
INTERPOLYMERS OF ETHYL ACRYLATE, ISOBUTYLENE AND VBC( ) Example No. 4 5 6 7 VBC, mmols. 18 18 33 7 Etl 5AlGll 5 mmols 15 15 15 Reaction time, Hrs. ( ) 89 89 89 89 Polymer yield, gms. 74 79 77 77 Inherent Viscosity( ) 0.73 0.90 0.800.86 Notes: (a) All runs were made with 200 ml of toluene, 0.5 mol of ethyl acrylate, 1.0 mol of iso-butylene and 1 mmol of lauroyl peroxide.
(b) All runs made at 32C.
(c) In benzene at a concentration of O.l g/dl :

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Sample 6 was examlnecl by NMR ancl analyzed for C, l~ and Cl.
N~IR an.llysis sllo~ecl monomer residues in the produ~t of 49 mol percent of ethyL acrylate; ~7 mol percent oE isobutylene; and 4 mol percent of the chloromethyl styrene. Calculated for: IsobuO 47; EtAcryO 49; VBCo 04;
C=69.1; ll=9.9; Cl=1.7. Found: C, 68.9; Il, 9.9; Cl, 1.9.
Samples 4, 5 and 7 had on analysis a chlorine content of 1.0, 1.3 and 1.0 weight percent, respectively.
EX~PLE 8 The interpolymer of Example 6 was compared with respect to rate 10 of cure, with a sample of an interpolymer of ethyl acrylate, isobutylene and 2-chloroethyl vinyl ether prepared according to the teachings of the Belgian Patent 763,333 referred to above. Both samples had essentially the same chlorine content and were formulated on a rubber mill with the same recipe. The recipe used was: interpolymer 100, zinc oxide 5, N,N' dibutylthiourea 4. Samples were cured at 320F. for 30 minutes at a pres-sure of 1200 psi and tested on the Instron machine at a strain rate of 20 inches per minute.
The product of Example 6 showed a tensile strength of 2665 psi, an elongation at break of 225% and a modulus at 100% axtension of 950.
; 20 The product made with 2-chloroethyl vinyl ether showed a tensile of only 570 psi and an elongation of 700%.
While the preferred embodiments of this invention are elastomers, it is possible by a suitable selection of components and their ratios to produce thermoplastic and thermoset compositions. Also possible is the production of lower molecular weight materials useful as oil additives.

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Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE
IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An alternating cross-linkable elastomeric interpolymer which comprises:
A. about 50 mol percent of one or more C1-C20 acyclic or alicyclic esters of acrylic acid wherein the ester radical moiety is free of olefinic unsaturation and is selected from the group consisting of straight and branched-chain alkyl radicals, arylalkyl radicals, cycloalkyl-alkylene radicals and perfluoroalkyl radicals; and a total of about 50 mol percent of:
B. one or more C2-C20 acyclic or alicyclic monoolefins having the general formulae R?CH?CH2 or R(R')C?CH2 wherein R and R' are independently selected from the group consisting of hydrogen, straight and branched-chain alkyl radicals, arylalkyl and cycloalkyl radicals; and C. 0.3 to 30 mol percent of the total monomers present of vinyl benzyl chloride; wherein the microstructure of said cross-linkable elastomeric interpolymers is such that monomer units represented by (A) above alternate with either a monomer unit represented by (B) above or a randomly distributed monomer unit represented by (C) above and can be represented schematically by the formula wherein m and n are integers on the range of 1 to about 500.

2. The cross-linked interpolymer of claim 1 wherein said cross-linking is performed with the aid of a nucleophilic reagent.

3. Composition according to claim 1 wherein said interpolymer chain consists of segments of alternating olefin and acrylic ester monomer units of variable length interconnected by randomly distributed vinyl benzyl chloride monomer units.

4. A method for preparing an alternating cross-linkable elastomeric interpolymer which comprises reacting:
A. about 50 mole percent of one or more acrylic or alicyclic esters of acrylic acid wherein the ester radical moiety is free of olefinic unsaturation and readily replaceable halogen and is selected from the group consisting of straight and branched chain alkyl radicals, aralkyl radicals, cycloalkylalkylene radicals and perfluoro/alkyl radicals;
and a total of about 50 mole percent of:
B. one or more C1-C20 acylic or alicyclic monoolefins having the general formula R?CH?CH2 or R(R')C?CH2, wherein R and R' are independently selected from the group consisting of hydrogen, straight and branched-chain alkyl radicals, aralkyl and cyclo-alkyl radicals; and C. 0.3 to 30 mole percent of the total monomers present of vinyl benzyl chloride; in the presence of an organoaluminum halide having the general formula AlRmXn, wherein R is amonovalent hydrocarbon radical selected from C1 to C12 alkyl, aryl, alkylaryl, arylalkyl and cycloalkyl radicals, m is a number from 1 to 3, X is halogen selected from chlorine, bromine, and iodine and the sum of m and n is 3 and a compound generally employed as an initiator in free radical polymerizations.

5. The method of claim 4 wherein the compound generally employed as an initiator in free radical polymerizations is selected from organic peroxides, hydroperoxides, peracids, peroxy esters and azo compound.

6. A vulcanizable composition comprised of interpolymers of:
(A) one or more monomeric C1 to C20 acyclic and alicyclic radical esters of acrylic acid wherein said radical moiety is free of olefinic unsaturation and readily replaceable halogen and is selected from the group consisting of straight and branched-chain alkyl radicals, arylalkyl radicals and cycloalkyl-alkylene radicals and perfluoralkyl radicals;
(B) one or more monomeric C2 to C20 mono-olefins having the general formulae R-CH=CH2 and R'(R')C=CH2 wherein R and R' are independently selected from the group consisting of hydrogen, straight and branched-chain alkyl radicals, aryl, alkylaryl, arylalkyl and cycloalkyl radicals having from 1 to 18 carbon atoms;
(C) 0.3 to 30 mol percent of the total monomers present in said interpolymer of one or more C9 to C18 halomethyl aromatic vinyl compounds having the general formula CH2=CH-R-CH2X
wherein R is an arylene radical having from 1 to 3 rings and X
is a halogen independently selected from the group consisting of chlorine, bromine and iodine; and wherein said interpolymer is prepared with the aid of a catalyst system comprised of an organoaluminum halide and a free-radical generator, said organoaluminum halide having the general formula A1RmXn wherein R is a monovalent hydrocarbon radical selected from the group consisting of C1 to C12 alkyl, aryl, alkylaryl, arylalkyl and cycloalkyl radicals, m is a number from 1 to 3, X is a halogen selected from the group consisting of chlorine, bromine and iodine and the sum of m and n is 3; and said free-radical generator is selected from the group consisting of organic per-oxides, hydroperoxides, peracids, peroxyesters and azo compounds.

7. The composition of claim 6 which is blended prior to vulcanization with at least one halogenated polymer.