United States Patent I‘O?lice 3,285,893 Patented Nov. 15, 1966 1 . 2 3,285,893 where R is an ethylenically unsaturated radical as de?ned CROSS LINKED ELASTOMERIC FIBERS FROM C0 above and R’ is hydrogen, R, alkyl, cycloalkyl, aryl or POLYMERS 0F EPIHALOHYDRINS AND ETHYL alkaryl or R and R’ together with the two carbons of the ENICALLY UNSATURATED MONO-EPOXIDES epoxy group may form a cycloaliphatic ring, e.g. Edwin J. Vandenberg, Wilmington, Del., assignor to Hercules Incorporated, a corporation of Delaware No Drawing. Filed Sept. 17, 1964, Ser. No. 397,326 HC———CH 9 Claims. (Cl. 260—88.3) R—R’ This application is a continuation-in-part of my appli ‘10 which may itself contain an ethylene double bond or cation U.S. Serial No. 4,594, ?led January 26, 1960‘, now ‘ which may be substituted by an ethylenically unsaturated U.S. 3,158,591, which is in turn a continuation-in-part ‘ hydrocarbon group such as a vinyl group. Exemplary of of my application U.S. Serial No. 738,627, ?led May 29, the'rn’onoepoxides of diene-s and polyenes having the 1958, now abandoned, and of my application U.S. Serial above general formula are‘ butadiene monoxide, c'hloro No. 812,079, ?led May 11, 1959, now U.S. 3,135,705 is 15 prone monoxide, 3,4-epoxy-l-pentene, 4,5-epoxy-2-pen sued June 2, 1964, which is in turn a continuation~in-part tene, 4,5-epoxy-l-hexene, 5,6-epoxy-l-hexene, 5,6-epoxy of my application U.S. Serial No. 738,626, ?led May 29, 2-hexene, 3,4-epoxy-l-vinylcyclohexene, 1,2-epoxy-5~cy 1958, now abandoned. ‘ clooctene, 1,2-epoxy-5,9-cyclododecadiene, divinylben This invention relates to new elastomeric ?bers, and zene monoxide, 5,6‘-epoxy-1,7-octadiene, etc. more particularly to elastomeric ?bers derived from the Another class of the ethylenically unsaturated epoxides vulcanizates of copolymers of epihalohydrins with ethyl that can be copolymerized with epihalohydrins to pro enically unsaturated epoxides. duce the copolymers used in this invention are the glycidyl In accordance with this invention, it has been discov esters of ethylenically unsaturated carboxylic acids which ered that elastomeric ?ibers can be obtained by spinning have the‘ general formula‘ a vulcanizable composition containing a copolymer of 25 an epihalohydrin ‘and an ethylenically‘ unsaturated epox / ll ide and then curing the spun ?ber. The copolymers uti lized are unique in that they :are essentially linear poly: CHACEY-CHfO-C-R Where R is an ethylenically unsaturated radical. Exem ethers, copolymen'zation having taken place through the. plary of such'glycidyl esters are glycidyl acrylate, ‘glycidyl epoxy groups. Hence, they provide two types of loci for 30 cross-linking reactions, the halogen atoms in the epihalo methacrylate, glycidyl ,crotonate, glycidyl 2,4-dimethyl hydrin portions of the polymer and the ethylene double‘ pentenoate, glycidyl 4:,hexenoate', glycidyl 4-heptenoate, bonds in the ethylenically unsaturated epoxide portion of glycidyl 5-methyl-4-heptenoate, glycidyl sorbate, glycidyl the polymer. As a result, it is possible to compound the-m linoleate, glycidyl ,oleate', glycidyl 3-butenoate, glycidyl with standard sulfur recipes to produce compositions 3-pentenoate, glycidyl 4-methyl-3-pentenoate, glycidyl 35 abietate, the glycidyl ester of 3-cyclohexene carboxylic which can be spun and then vulcanized to yield excellent acid, the glycidyl ester of 4-methyl-3-cyclohexene carbox elastomeric ?bers with superior solvent resistance and ylic acid, etc. stability characteristics. Such ?bers can also be prepared in ?ne deniers and are thus more useful than conventional Any epihalohydrin, as for example, epichlorohydrin, cut rubber threads. ' 40 epibromohydrin, ep-i?uorohydrin, or mixtures thereof, The copolymers which are spun and vulcanized into can be copolymerized with the ethylenically unsaturated ?bers in accordance with this invention are those pro epoxides to produce the polymers used in ‘this invention. duced by the copolymerization of an epihalohydrin with In addition, other epoxides can also be incorporated in at least one other epoxide, at least one of which contains, these copolymerizations so that the ?nal copolymer can be a terpolymer, a quaternary polymer, etc. Thus, the in addition to the oxirane ring, an ethylenically unsatu 45 ra-ted group. Exemplary of the ethylenically unsaturated copolymers can include, in addition to the epihalohydrin epoxides that can be copolymerized with the epihalohy monomer units and the ethylenically unsaturated epoxide drins to produce the copolymers used in this invention are ' monomer units, other epoxide monomer units, such as unsaturated glycidyl ethers, monoepoxides of dienes or those of ethylene oxide, propylene oxide, butene-l oxide, butene-Z oxides, dodecene-l oxide, octadecene-l oxide, polyenes, glycidyl esters,‘etc. The unsaturated glycidyl 50 ethers that can be copolymerized with the epihalohydrins cyclohexene oxides, styrene oxide, alkyl glycidyl ethers have the general formula. . such as methyl glycidyl ether, phenyl glycidyl ethers, etc. The copolymers utilized in this invention will then con tain at. least the following two repeating units 55 where R is an ethylenically unsaturated radical, as for -—O-—CH2—CH and -£O—C—Cl example, ethylenically unsaturated aliphatic radicals such as vinyl, isopropenyl, allyl, methallyl, butenyl, oleyl, etc., L taxi L l Z'J and cycloalkyl or aryl radicals containing an ethylenically where X is halogen and Y is H, alkyl, aryl or cycloalkyl unsaturated sulbstituent and cycloalkyl radicals containing when Z is —R, —CH2—O—~R, or an ethylenic double bond in the ring, ‘as for example, 60 4—vinylcyclohexyl, a-terpinyl, 'y-terpinyl, abietyl, cyclo hexenylmethyl, o-allylphenyl, p-vinylbenzyl, etc. Exem plary of these ethers are vinyl glycidyl ether, allyl glycidyl ether, vinylcyclohexyl glycidyl ether, o-allylphenyl gly or Y and Z may both be R, or Y and Ztogether with the cidyl ether, etc. 65 carbons to which they are attached may be a cycloaliphatic The monoepoxides of dienes and polyenes that can be . nucleus which itself contains an ethylene double bond or copolymerized with epihalohydrins to produce the copoly is in turn substituted with a group R, e.g. mers used in this invention have the general formula 70 L as 3,285,893 3 4 where R in each case is an ethylenically unsaturated this invention. In some cases, the ?ber will have better radical such as vinyl, isopropenyl, allyl, methallyl, bu strength characteristics if the copolymer exhibits some tenyl, oleyl, vinylcyclohexyl, a-terpinyl, abietyl, vinyl degree of crystallinity, particularly on stretching, and phenyl, vinylbenzyl, alkylphenyl, etc. Will then be preferred, provided that the elastomeric prop— These copolymers will contain from about 99.5% to erties and recovery characteristics are not adversely in about 20% of epihalohydrin and at least about 0.5% of ?uenced. The amount of crystallinity that generally the ethylenically unsaturated epoxide monomer and pref can be tolerated, without serious interference with rub erably will contain from about 98% to about 30% of bery properties, is an amount less than about 25%, as the epihalohydrin and at least about 2% of the ethylen measured by X-ray diffraction methods, in the unstretched ically unsaturated epoxide. Where one or more other 10 state and preferably will be below about 15%. Higher epoxide monomers are present, these copolymers will con crystallinity may, of course, appear on stretching and this tain at least about 20% and preferably about 30% of is desirable. epihalohydrin and at least about 0.5% and preferably The elastomeric ?bers are prepared by compounding about 2% of the ethylenically unsaturated epoxide, so that the copolymer of epihalohydrin and ethylenically un in such terpolymers (or tetrapolymers, etc.) the unique 15 saturated epoxide with a suitable vulcanization system, properties of vulcanizability, etc., due to the presence of spinning a ?ber from the composition, and then curing these monomers will not be lost. The amount will, of (vulcanizing) the ?ber. Since the copolymer is a poly course, depend somewhat upon the additional epoxide ether having repeating units that contain ethylenic un monomers incorporated. Thus, when ethylene oxide or saturation, it can be vulcanized by any conventional sulfur methyl glycidyl ether is copolymerized with the epihalo 20 curing system, that is, sulfur plus an accelerator such as hydrin and the ethylenically unsaturated epoxide, in an a thiazole, thiuram, sulfenamide, dithiocarbamate, etc. amount up to about 50% of the total monomers, the There are many advantages in using a sulfur-curing sys co-polymer will be essentially water insoluble, and little tem in the preparation of these elastomeric ?bers. Sul swollen by water, whereas in an amount above about fur-curing systems have curing rates that can be widely 50%, the copolymer will, before vulcanization, be either 25 varied and controlled to suit operating conditions, they at least partially Water soluble or swollen by water. For are well recognized as being non-toxic and free of derma example, with an ethylene oxide or methyl glycidyl ether titis problems and they do not liberate corrosive hydrogen content of 60-80%, the terpolymer, after vulcanization, halides as a by-product. However, small amounts of exhibits some swelling in water, which is desirable in some other curatives which react with the halogen content of ?ber applications Where moisture vapor transmission is 30 these copolymers, as for example, diamines such as eth desired, as in various articles of Wearing apparel, and for ylene diamine, hexamethylene diamine, hexamethylene this reason ?bers prepared from these terpolymers are of diamine carbamate, etc., ethylene thiourea, urea, ammoni outstanding Value. um salts such as ammonium benzoate, etc., can also be The polymeric epoxides or polyethers containing both used to obtain a faster initial cure or other desirable effects. halogen and ethylenic unsaturation used in this invention 35 A particularly effective and rapid curing system is zinc can be prepared by contacting a mixture of an epihalo oxide, thiourea, tetramethyl thiuram disul?de, mercapto hydrin and epoxide-containing ethylenic unsaturation with benzothiazole and sulfur. Other well ‘known accelerators an organoaluminum compound. Organoaluminum com can be substituted in this formula and the sulfur can be pounds that may be used to catalyze the polymerization replaced with thiuram tetrasul?de such as bis pentameth are trialkyl-aluminum compounds, dia-lkylaluminum ha ylene thiuram tetrasul?de. lides, monoalkylaluminum dihalides, dialkylaluminum hy To obtain the highest tensile strengths in the ?nal ?ber, drides, dialkylaluminum monoalkoxides and the corre it is generally desirable to include a reinforcing ?ller in sponding cycloalkyl and aryl compounds. These organo the elastomeric ?ber formulation. Preferably, a rein aluminum compounds may |be reacted with a chelating forcing mineral ?ller such as silica is used, but any of the agent such as acetylacetone, trifluoroacetylacetone, etc., if 45 other well known reinforcing ?llers can be used, as for desired. An effective catalyst may also be produced by example, aluminas, aluminum silicates, clays, titanium di reacting these organoaluminum compounds, including the oxide, carbon black, etc. Such ?llers will generally be chelated complexes, with from about 0.1 to about 1.5 used in the amount of from about 5 to about 50 parts moles of water and preferably 0.5 to 1 mole of water per per ‘hundred parts of copolymer, and preferably will be mole of the organoaluminum compound. 50 8 to 30 parts per 100 parts of copolymer. The reinforc~ The polymerization reaction is generally carried out in ing ?ller can, of course, be omitted or used in smaller the presence of an inert, liquid, organic diluent but may amounts when the copolymer has adequate tensile strength be carried out in an essentially bulk polymerization proc due to crystallization on stretching. ess. Suitable diluents that may be used for the polym Other additives can be incorporated in the elastomer erization are the ethers such as diethyl ether, dipropyl 55 ?ber formulation, either before or after compounding and ether, dibutyl ether, etc., halogenated hydrocarbons such before the ?ber is spun, as for example, antioxidants, as chrolobenzene, methylene chloride, etc., or a hydro dyes, pigments, etc. The copolymer is preferably sta carbon diluent such as n-heptane, cyclohexane, benzene, bilized before the compounding step by adding an anti toluene, etc. The temperature of the polymerization proc ’ oxidant. Any of the well known “hindered phenolic anti ess may be varied over a wide range, generally from about 60 oxidants can be used. Amine antioxidants, while —‘80° C. to about 250° C., and while atmospheric or operable, are generally not preferred because of discolora~ autogenous pressure is usually used, the pressure may be tion on aging. Peroxide decomposers, such as sul?des, varied from subatmospheric up to several atmospheres, if disul?des, etc., as for example laury-l thiodipropionate, desired. distearyll disul?de, polymeric sul?des and disul?des, etc., The new elastomeric ?bers of this invention are pre 65 can also be incorporated. Frequently it is desirable to pared from the above-described copolymers of epihalo add an acid acceptor such as mono-, di- and polyepoxides hydrins and ethylenically unsaturated epoxides which are as for example, phenyl glycidyl ether, the diglycidyl ether largely amorphous in character and which have a reduced of Bisphenol A, etc., oxides of calcium, magnesium, zinc, speci?c viscosity of at least about 0.5 and preferably at lead, etc., carbonates of calcium, magnesium, lead, etc., least about 1.0 as measured on a 0.1% solution in oc-ChlO 70 ronaphthalene at 100° C. or of at least about 0.7 and and stearates, phthalates, etc., of calcium, magnesium, preferably at least about 1.4 when measured on a 0.1% zinc, cadmium, lea-d, etc. solution in cyclohexanone at 50° C. In general, the The ‘step of mixing, or compounding, the ?lter, vull solid, essentially wholly amorphous copolymers are pre canizing ingredients, and other additives with the copoly ferred for the preparation of the elastomeric ?bers of 75 mer should be ‘carried out under conditions such that 3,285,895 6 good dispersion of all of the ingredients is obtained. The 0.1% solution of the polymer‘in a-chlo‘ron-aphthalene exact means for carrying out the dispersion of the ingre containing 0.1 g. of the polymer per 100 ml. of solution, dients in the polymer will depend on the type of spin at 100° C. In cases where the catalyst has not been ning process to be used, but in general, two-roll mills, removed or only partially removed, the RSV can be kneader~type mixers, high shear ‘agitators and the like measured by adding 3% of acetylacetone to the a-c-hloro are used. The dispersion process can-‘also be utilized as naphthalene and obtain essentially the same value as if a means of degrading very high molecular weight copoly~ no catalyst residue were present. mers ‘to a narrower molecular weight distribution copoly mer, which then yields a ?ber of improved strength prop Example 1 erties. Obviously, such degradation should be carried 10 A stainless steel, stirred reactor was charged under a out only on copolymers that have a higher initial molecu nitrogenatmosp'here with 2900 parts of dry toluene, 100 lar Weight than is ?nally needed. Other means of ob .parts of-epich-lorohydrin, 17 parts of n-heptane, 6.3. parts taining narrow molecular‘ weight distribution are, of of ethylene oxide-and 8.2_parts. oflallylglycidyl ether. course, appropriate control of the polymerization process The temperature was increased to 130° C. and then, while or, alternatively, if the molecular weight is too ‘high, by 15 stirring, 13.5 parts of the catalyst solution was added to mechanical (shear) of chemical degradation, or by ther start the polymerization. ‘The ‘catalyst solution used was‘ mal cracking of the base polymer. , that prepared by adding to a 0.5 M' solution of t-r‘iethyl- ‘ " The elastomeric ?ber is then produ'ced‘by spinning the aluminum in 70:30 n~heptane~diethyl ether 0.5 mole of copolymer that has been compounded as described above. waterper mole of triethylaluminum at 0“ C. during 15 Preferably the ?ber is wet‘ spun into water from a solu-, 20. minutes,_,;stirring, the mixture at 0° C. for 1 hour, then tion of the compounded polymer in a water-miscible sol ‘adding ‘0.5 mole of acetylacetone per mole of aluminum vent such as acetone, dioxane, dimethyl formamide, di and after stirringfor 15 ‘minutes at 0° C., stirring the methyl sulfoxide, etc. The wet ?ber is dried and partially, mixture at room temperaturefor ,20 hours. After the cross-‘linked by passing it through a ‘heating zone, pref polymerization ‘reaction had proceeded for 5 minutes, a erably through a hot gas such as air, nitrogen, or‘steam, .25 monomer mixture prepared from 123 parts of epichloro or by passing'it through a hot nonsolyent liquid, or by hydrin‘, 56 parts of ethylene oxide" and‘ 20 parts of allyl other appropriate means, and then winding it up on a glycidyl ether was fed into‘ the reactor at such a rate bob'bin. Cross4linkin~g is then completed ‘by further heat that'the initial ‘concentration of all monomers was main ing in an oven for an appropriate time 'andlatan appro tained, as determined ‘by ‘periodic. gas chromatography priate temperature. ' The time and temperature will’, of 30 analyses of“ the reaction mixture (using‘the ' n1~heptane as' course, depend upon the curing systemused, but generally an internal standard). »At the same (time, additional cataé will. be ‘from fractions of a minute up to several hours lystywas also‘pumpedfini periodically to maintain a uni at temperatures within the range of about 70‘0 to 200° C. form polymerization rate.~ Duringthe nine-hour reaction and preferably 90° to 160° C. Other spinning processes. period'at'13.0°’C.; there’ was added1115 vparts of catalyst can also be used, as for example dry spinning. 'In the 35 solution and 106 parts or the'monomer mixture. The latter. case, the lower boiling 'solvent-s‘usedfor wet spin polymeriiz-ation was stopped by adding anhydrous eth ning can be used, or water-immiscible solvents such as M1011.alldtherolymerwas stabilized. by adding to the aromatic hydrocarbons, as for example benzene, toluene, reaction mixture about 1% each of the condensation xylene, etc., or chlorinated solvents, as for example meth product of'crotonaldehyde with about 3 moles of 3-meth ylene chloride, ethylene dichloride, etc., can be used. In yl-6-tert-butylphenol and of lauryl thiodipropionate, fact, the copo'lymerization process can be carried out in ‘based on the polymer formed. The polymer was then a suitable solvent, such as dioxane, toluene, methylene recovered by allowing the solvent to evaporate off at room chloride, etc., and the additives dispersed therein, and temperature, followed 'by further drying at 80° C. under the spinning operation then carried out without the inter vacuum. Analysis showed the'copolymer to contain 54% mediate step of isolating the copolymer. The ?bers can 45 epichlorohydrin, 37% ethylene oxide and 9% allyl glyc also be prepared by melt extrusion in the absence of idyl ether. It had a Mooney viscosity (ML-4, 212° F.) added solvent. Another spinning process that can be of 35 and‘ an RSV of 1.7 as measured on a 0.1% solution used is that of preparing a latex of the polymer and other in ot-chloron-aphthalene containing 3%. acetylacetone . at. ingredients and spinning the ?ber into a coagulating aque-, 100° C. . ous medium, such as is used for spinning conventional 50 Example 2’ rubbers. The copolymers used in the preparation of the elas Example 1 was repeated except that the polymeriza~ tomeric ?bers of this invention have quite low solution tion was run for 10.6 hours and 159 parts of the mono viscosities for a given molecular weight which permits mer mixture was added during the run. The polymeriza the use of spinning solutions of much higher solids con 55 tion reaction was short-stopped by adding a solution con tents and thus more economic operation than in the case taining 39 parts of toluene, 36 parts of anhydrous ethanol of solvent spinning many polymers. -It is frequently de and 2.9 parts each of the two stabilizers used in that sirable to add to the spinning solution a chela-tin'g agent example. In this example, the polymer was isolated by such as acetylacetone so as to solubilize any catalyst resi precipitation from the reaction mixture by the addition due that may be present in the copolymer. This can, 60. of 1100 parts of commercial heptane containing 0.44 part of course, be omitted if the catalyst is completely removed. and 1.3 parts, respectively, of the two stabilizers. The prior to the compounding step or if it is properly deacti insoluble polymer was separated, washed twice with the vated or :solu'bi‘lized at the end of the polymerization precipitant solution and then was dried for 16 hours at process. room temperature under vacuum. There was obtained The ‘following examples illustrate the preparation of 65 74.5 parts of the copolymer, which on analysis was shown to contain 57% epiehlorohydri'n, 34% ethylene oxide, the epiha'lohydrin copolymers and the preparation of elas and 9% allyl glycidyl ether. It had a Mooney viscosity tomeric ?bers therefrom in accordance wit-h this inven of 62 and an RSV of 2.2 as measured on a 0.1% solution tion. All parts and percentages 'are ‘by weight unless in a-chloronaphthalene containing. 3% of acetylacetone otherwise indicated. The molecular weight of the poly at 100° C. mers is shown 'by their Reduced Speci?c Viscosity (RSV). 70. Example 3 By the term “Reduced Speci?c Viscosity” is meant the asp/C. determined on a 0.1% solution of the polymer; The procedure of Example 1 was repeated except that in cyclohexanone containing 0.1 g. of the polymer per the initial- monomer charged to‘ the reactor was 282 parts of. epichlorohydrin,f6.3 parts of ethylene oxide, 100 ml.‘ of solution, at 50°_C._or ‘as determined ona 75. and 18.2 parts of allyl glycidyl. ether. .The monomer 3,285,893 7 8 mixture added during the polymerization was made up This copolymer was compounded as described in Ex of 176.5 parts epichlorohydrin, 28 parts of ethylene oxide amples 1~3 using the formulation and 22.7 parts of allyl glycidyl ether, 180 parts of this Parts mixture being added during the 11 hours of polymeriza Copolymer ______100 tion. The copolymer was isolated as described in Ex Reinforcing grade of fumed silica ______10 ample 2. It had a Mooney viscosity of 47 and an RSV Zinc stearate ______1.5 of 3.4 as measured on a 0.1% solution in a-chloro Rutile grade 'TiOZ ______3 naphthalene containing 3%‘ acetylacetone at 100° C. and Zinc oxide ______5 analysis showed it to contain 72% epichlorohydrin, 19% Bis pentamethylene thiuram disul?de ______5 ethylene oxide, and 9% allyl glycidyl ether. ' 10 Z-mercaptobenzothiazole ______1.0 The terpolymers produced in Examples 1-3 were com Thiourea ______1 pounded by mixing the following formulation on a two The compounded copolymer was dissolved and spun as roll mill for 12 minutes with the rolls at 100-125° F.: described above except that after removing from the Parts water bath, they were passed through a hot air zone at 15 160° C. for 2 minutes to give some prevulcanization and Terpolymer ______‘ ______,__'______-_.. 100 then were collected on a bobbin and cured for 30 minutes Reinforcing grade of fumed silica _____' ______20 at 150° C. The ?ber so obtained was strong and rubbery, Zinc stearate ______i_____ 1.5 with excellent recovery characteristics.v Rutile grade TiO2~ ___>. ______'___. 3 Zinc oxide ______'______.__ 5 20 Example 5 Tetramethyl thiuram disul?d __; ______1.5 .A polymerization vessel in which the air had been re Z-mercaptobenzothiazole ______.._ 0.75 placed with nitrogen was charged with 40 parts of tolu Thiourea __'______- ______1 ene, 7 parts of epichlorohydrin, 1 part of ethylene oxide Sulfur ______1.5 and 2 parts of butadiene monoxide. After equilibrating 25 at 30° C., a solution of the catalyst was injected. The During the milling, the compound was cross-cut and catalyst solution was prepared by reacting a 0.5 M solu end-rolled six times each. The compounded mixture was tion of triethylaluminum in 70:30 n-heptanezdiethyl sheeted .out, cooled and then dissolved in a solvent made ether with 0.5 mole of acetylacetone per mole of alumi up of 97.5% acetone and 2.5% acetylacetone. The solu num and then with 0.5 mole of water per mole of alumi tions were spun through a 0.0135 inch diameter spinneret 30 num compound. An amount of this catalyst solution into a water coagulation bath and the resulting ?bers equivalent to 0.23 part of the triethylaluminum was then were passed through hot air at 160° C. and collected on injected in the polymerization mixture. After 27 hours a bobbin. Curing was completed by heating the bobbins at 30° C., the polymerization was stopped. The ether in a forced air oven at 140° C. T abulated‘below are the insoluble copolymer was precipitated by adding 1—2 vol spinning conditions and physical properties for the ?bers 35 umes of 1% methanolic hydrogen chloride, and was sepa so produced. ' ' rated by ?ltration, washed with methanol until neutral and' then with a 0.2% solution of Santonox, i.e., 4,4’ Ex. 1 Ex. 2 Ex. 3 thiobis (6-tert-butyl-m-cresol), in methanol and ?nally was dried for 16 hours at 50° C. under vacuum. The 40 Terpolymer Composition ECHzEO: ' ether-insoluble polymer so isolated amounted to a 12% AGE ______54:37z9 57:34z9 72:19:9 conversion based on the total monomers charged and had Spinning Conditions: I ' Solution cone, Percent Solids 25 37 24 an RSV of 5.0 in a-chloronaphthalene at 100° C. It was Feed rate, min/cc- _ _ __ _ 10 9. 5 9 amorphous by X-ray and analysis showed it to contain Take-up rate, itJmin - 8 6 6. 5 Cure Time, Hrs ______2 2 1 50% epichlorohydrin, 30% ethylene oxide and 20% bu Phylsjical Properties: 45 tadiene monoxide. enter ______140 121 141 Tensile strength, g./denier____ 0. 13 0. 24 0. 17 A ?ber was prepared from this copolymer by the pro Breaking elongation, percent ._ 900 900 900 cedure described in Examples 1-3. It was a strong, rub bery, solvent resistant ?ber having a tensile strength of 0.2 g. per denier and a breaking elongation of 1000%. Example 4 50 A polymerization vessel with a nitrogen atmosphere Example 6 was charged with ether, 9 parts of epichlorohydrin and A polymerization vessel with a nitrogen atmosphere 1 part of allyl glycidyl ether. After equilibrating at 30° was charged with 318 parts of dry toluene, 4.0 parts of C., a solution of the catalyst was injected. The catalyst the glycidyl ester of tall oil fatty acids (60% linoleic solution was prepared by diluting a solution of triethyl 55 acid,, 31% oleic acid and 9% of saturated C16 to C20 aluminum in n-heptane to 0.5 molar with ether, adding fatty acids), 4.0 pars of ethylene oxide and 32.0 parts of water in an amount of 0.5 mole of water per mole of epichlorohydrin. With the vessel and contents equili aluminum compound and agitating the solution at 30° brated at 30° 0., there was added an amount of a 0.5 C. for 16 hours. An amount of this catalyst solution molar solution of the catalyst described in Example 1 equivalent to 0.45 part of the triethylaluminum was used. 60 equal to 1.80 parts of triethylaluminum. After 19 hours The total diluent amounted to 35 parts and contained at 30° C., the polymerization reaction was shortstopped 95% ether. The reaction mixture was agitated and held by adding 16 parts of anhydrous ethanol containing 0.05 at 30° C. for 3 hours, after which the polymerization was part of a stabilizer which was the condensation product stopped by adding 4 parts of anhydrous ethanol and the of crotonaldehyde with about 3 moles of 3-methyl-6-tert reaction mixture was diluted with 25 parts of ether. It 65 butylphenol. The polymer was precipitated by adding was then washed twice with a 3% aqueous solution of 300 parts of a commercial heptane mixture containing hydrochloric acid, with water until neutral, then with a 0.04% of the same stabilizer used above. The super 2% aqueous sodium bicarbonate solution and ?nally natant was decanted olf; the polymer was agitated with with water. The ether-insoluble polymer was collected, 300 parts more of the precipitant, the supernatant de washed with ether, then with ether containing 0.2% 70 cantedand again repeating this wash procedure. The Santonox and dried. There was obtained a 9.5% con polymer was then separated by ?ltration and dried for version of a snappy rubberlike material having an RSV 16 hours at 80° C. under vacuum. It amounted to 6.1 of 2.8 in cyclohexanone at 50° C. and was shown to be parts (15.2% conversion) and was a rubbery solid having amorphous by X-ray. Based on chlorine analysis it con an RSV of 3.7 as measured on a 0.1% solution in a tained 16.2% allylglycidyl ether. 75 chloronaphthalene containing 3% acetylacetone at 100° 3,285,893 10 C. Based on chlorine and bromine-number analysis, the at least about 2% by Weight of repeating units derived copolymer contained 53% epichlorohydrin, 36% ethyl from said ethylenically unsaturated epoxide. ene oxide, and 11% of the glycidyl ester. It was amor phous by X_ray. 3. An elastomeric ?ber in accordance- with claim 1 wherein the ethylenically unsaturated epoxide is a glyc A ?ber was prepared from this terpolyrner by the pro idyl ether having the formula cedure described in Example 4 except that 20 parts of the reinforcing silica was used in the compounding formula tion. The ?ber so produced was a strong, rubbery ?ber. CEQOH~OH2~O~R The foregoing examples have illustrated the prepara Where R is an ethylenically unsaturated group. tion of the elastomeric ?bers of this invention. As will 10 4. An elastomeric ?ber in accordance with claim 1 be readily appreciated, these ?bers have excellent wherein the ethylenically unsaturated epoxide is a mono strength properties. In addition, these ?bers are superior epoxide of a polyene. to the previously known elastomeric ?bers made, for ex 5. An elastomeric ?ber in accordance with claim 1 ample, from natural rubber, neoprene, and nitrile rubbers wherein the ethylenically unsaturated epoxide is a glycidyl in one or more properties as, for example, they have im 15 ester having the formula proved solvent resistance, heat and light stability, and chemical resistance, such as resistance to ozone, bleaching agents, etc. Because of these improved properties, C AGE-CHr-O-OO-R blends can be made of these elastomeric ?bers with con where R is an ethylenically unsaturated hydrocarbon ventional textile ?bers for fabrics which are dry-cleaned 20 group. and which must have long-term stability. Such blends 6. An elastomeric ?ber in accordance with claim 3 make it possible to produce garments which are more wherein the repeating units are derived from epichloro comfortable, require less sizes, are better form-?tting, and hydrin and allyl glycidyl ether. wear longer. 7. An elastomeric ?ber in accordance with claim 3 Another advantage of the elastomeric ?bers of this 25 wherein the repeating units are derived from epichloro invention is that the halogen atoms present in the base hydrin, ethylene oxide and allyl glycidyl ether. polymer are reactive and thus provide a site for cherni~ _8. An elastomeric ?ber in accordance with claim 4 caliy attaching dyes, dyeing sites, surface coatings, anti wherein the repating units are derived from epichloro oxidants, etc. This makes it possible to permanently hydrin, ethylene oxide and butadiene monoxide. attach such agents, as for example, by using dyes or other 30 9. An elastomeric ?ber in accordance with claim 5 additives that contain reactive amine groups, and make wherein the repeating units are derived from epichloro~ them completely resistant to extraction during water hydrin, ethylene oxide and the glycidyl ester of tall oil washing, dry-cleaning, etc. fatty acids. What I claim and desire to protect by Letters Patent is: 1. An elastomeric ?ber comprising a cross-linked co 35 References Cited by the Examiner polymer of an epihalohydrin and at least one other UNITED STATES PATENTS epoxide, at least one of which said other epoxide is ethylenically unsaturated epoxide; said copolymer being 2,476,922 7/1949 Shokal ______.. 260——78.4 a solid, amorphous copolymer having a reduced speci?c 2,995,779 3/ 1959 Winter ______264——21O 3,026,270 3/ 1962 Robinson ______._ 260—-2 viscosity of at least about 0.5 when measured as a 0.1% 40 3,026,305 3/ 1962 Robinson ______260-2 solution in a-chloronaphthalene at 100° C., said copoly 3,030,173 4/1962 Kurzke et a1 ______264—210 mer being esssentially a linear polyether containing at 3,031,439 4/1962 Bailey ______260—88.3 least about 20% by weight of repeating units derived 3,158,591 11/1964 Vandenberg ______._ 260—88.3 from epihalohydrin and at least about 0.5% by weight 45 3,168,488 2/1965 Sommer ______.. 260—18 of repeating units derived from said ethylenically unsatu 3,170,887 2/1965 Ramos ______260——18 rated epoxide, said copolymer having been cross~linked with a sulfur-curing agent in the absence of an amine. FOREIGN PATENTS 2. An elastomeric ?ber in accordance with claim 1 226,554 4/1959 Australia. wherein the copolymer contains at least about 30% by 50 LEON J. BERCOVITZ, Primary Examiner. weight of repeating units derived from epihalohydrin and C, W. IVY, Assistant Examiner.