3,299,016 United States Patent Office Patented Jan. 17, 1967 2 mingling a reducible metal compound, such as Vanadium 3,299,016 tetrachloride or vanadium oxytrichloride, with a reducing POLYMERS OF MONOOLEFNS AND AN compound of a metal, usually aluminum, such as ethyl ALKENYLACETYLENE AND PROCESS FOR aluminum sesquichloride. The novel polymers produced PREPARNG SAME Richard J. Sonnenfeid, Bartlesville, Okla., assignor to 5 by this invention have some degree of unsaturation and Phillips Petroleum Company, a corporation of Dela can range from crystalline or plastic materials to elas Ware tomeric materials, and they can be vulcanized with Sul No Drawing. Fied Sept. 3, 1963, Ser. No. 306,341 fur to produce polymeric products which have useful 6 Claims. (C. 260-80.5) properties that make them widely applicable. 10 The ethynyl ethylenes employed as novel comonomers This invention relates to a process for copolymeriz with 1-monoolefins, according to this invention, can be ing 1-monoolefins with a monomer which imparts un represented by the general formula saturation to the resulting polymer, and to the poly mers so produced. In another aspect, it relates to a R process for copolymerizing ethylene, at least one other 15 HCC-C-CE 1-monoolefin such as propylene, and a monomer which where R is hydrogen or an inert hydrocarbon radi imparts unsaturation to the resulting polymer and ren cal, such as an alkyl, cycloalkyl, or aryl radical (pref ders the same sulfur-Vulcanizable. In another aspect, erably a lower alkyl), or combinations of such radicals, it relates to novel copolymers of 1-monoolefins and mono such as alkaryl, aralkyl, arylcycloalkyl, cycloalkylalkyl, mers which impart unsaturation to the copolymers. 20 alkylcycloalkyl, cycloalkylaryl, and the like, the number Many 1-monoolefins, such as ethylene and propylene, of carbon atoms in R generally being from 1 to 20. are inexpensive polymerizable monomers which are com Representative ethynyl ethylenes which can be used as mercially available in great volumes. Such monomers comonomers in the copolymerization of 1-monoolefins can be polymerized to form polymers ranging from low include: molecular weight oils to high molecular weight solids. 25 1-buten-3-yne (vinylacetylene), The curing or vulcanization of many of these polymers 2-methyl-1-buten-3-yne (isopropenylacetylene), cannot be conveniently carried out in the conventional 2-ethyl-1-buten-3-yne, manner, for example by vulcanization with sulfur as 2-n-propyl-1-buten-3-yne, in the case of butadiene/styrene polymers, because of 2-isobutyl-1-buten-3-yne, the lack of ethylenic unsaturation in the polymer. Vul 30 2-n-amyl-1-buten-3-yne, canization of these polymers, such as an ethylene/pro 2-n-decyl-1-buten-3yne, pylene copolymer, requires the use of expensive high 2-(5-methyldecyl)-1-buten-3-yne, energy radiation or organic peroxides, or requires pre 2-n-pentadecyl-1-buten-3-yne, treatment such as chlorosulfonation or chlorination of 2-(9,10-diethylhexadecyl)-1-buten-3-yne, the polymer in order to render it suitable for curing. 35 2-(4-methyl-9-ethylheptadecyl)-1-buten-3-yne, Such process limitations detract from the gains to be had 2-(n-octadecyl)-1-buten-3-yne, by the unique properties possessed by the polymers, 2-(3,6-dipentyl) decyl-1-buten-3-yne, especially ethylene/propylene copolymers which are high 2-n-eicosyl-1-buten-3-yne, molecular weight rubber-like substances having a high 2-cyclopentyl-1-buten-3-yne, degree of resistance to weathering, sunlight and ozone. 40 2-cyclohexyl-1-buten-3-yne, A number of processes have been proposed for chem 2-(3-ethylcyclopentyl)-1-buten 3-yne, ically modifying polymers of 1-monoolefins, particularly 2-(2-cyclohexylethyl)-1-buten-3-yne, ethylene/propylene copolymers, in order to impart some 2-3 (3-methylcyclohexyl)propyl)-1-buten-3-yne, degree of unsaturation to the copolymers and make it 2-(14-cyclohexyltetradecyl)-1-buten-3-yne, possible to cure them with sulfur. Such modification 45 2-phenyl-1-buten-3-yne, can be achieved by incorporating a different copolymer 2-(4-tolyl)-1-buten-3-yne, izable monomer, such as an open-chain diolefin, but in 2-10(3-n-butylphenyl) decyl)-1-buten-3-yne, general Such modifications have not produced the poly 2-benzyl-1-buten-3-yne, mer in good yields and have, for example, in the case 2-(4,6-diphenyl)octyl-1-buten-3-yne, of a dicyclopentadiene, required large amounts of the 50 2-(4-n-amylbenzyl)-1-buten-3-yne, additional monomer to impart sufficient unsaturation and 2-(4-cyclopentylphenyl)-1-buten-3-yne, require long periods for the polymer to cure. 2-3 (3-methylcyclohexylphenyl) hexyl)-1-buten-3-yne, Accordingly, an object of this invention is to provide an improved process for the copolymerization of 1-mono and the like, including mixtures thereof. olefins. Another object is to provide improved poly 55 The 1-monoolefins which are copolymerized with ethyl mers of 1-monoolefins, which polymers can be cured ene and any one of the above-mentioned ethynyl ethylenes with sulfur. Another object is to provide an improved can be represented by the general formula CH2=CHR, process for chemically modifying an ethylene/propylene where R is an alkyl radical having 1 to 6 carbon atoms. copolymer so as to impart some degree of unsaturation Representative 1-monoolefins which can be used as thereto and make it amenable to vulcanization with sul 60 comonomers with any one of the above-mentioned ethynyl fur. Further objects and advantages of this invention ethylenes include propylene, 1-butene, 1-pentene, 1-hex will become apparent to those skilled in the art from ene, 1-octene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 the following description and accompanying claims. methyl-1-hexene, 4-ethyl-1-hexene, 4,4-dimethyl-1-pen Briefly, the improved process of this invention com tene, 3,3-dimethyl-1-butene, 5-methyl-1-hexene, 4-methyl 65 1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 6 prises copolymerizing ethylene, or ethylene and at least methyl-1-heptene, 3,4,4-trimethyl-1-pentene, and the like, one other 1-monoolefin such as propylene, with an including mixtures of two, three or more thereof. ethynyl ethylene, and recovering the resulting novel poly The relative percentages of the polymers of this inven mer from the polymerization reaction mixture. Such tion attributable to each of the monomers employed can polymerization can be carried out with any polymeriza 70 vary widely, with the minimum amount of the ethynyl tion coordination catalyst known in the art, which cat ethylene comonomer being that sufficient to impart sulfur alyst generally comprises that obtained upon com curability to the polymer. Generally, the ethynyl ethyl 3,299,016 3 4. ene comonomer will make up from 0.5 to 20 weight per oxydichloride, tetraisopropyl titanate, titanium trichloride, cent, preferably from 1 to 10 weight percent, of the co tetra-n-butyl titanate, tetra-2-ethylbutyl titanate, vanadium polymer. Where ethylene is the sole 1-monoolefinem trichloride, vanadium tetrachloride, vanadium oxytrichlo ployed with an ethynyl ethylene, the former will usually ride, vanadium acetylacetonate, vanadyl acetylacetonate, make up 80 to 99.5 weight percent of the copolymer. In 5 tetra-n-butyl vanadate, tetraethyl vanadate, trimethyl the case where an ethynyl ethylene and ethylene are co orthovanadate, vanadium oxydichloride, vanadium dichlo polymerized with one or more additional 1-monoolefins as ride, 2-ethylhexylvanadate, vanadium dibromide, vanadi comonomers, the copolymer comprises 20-75 weight per um pentoxide, chromyl chloride, chromium acetylace cent ethylene, 20-75 weight percent of the additional 1 tonate, chromyl acetylacetonate, chromium chloride, co monoolefins, and 0.5-20 weight percent of an ethynyl 10 baltous chloride, manganese bromide, cuprous chloride, ethylene, and preferably with the total weight percent of ferric bromide, molybdenum chloride, nickel chloride, and the additional 1-monoolefins being at least 20 weight per the like, including mixtures thereof. cent of the copolymer and not exceeding 15 Weight per Representative reducing compounds which can be com cent of the ethynyl ethylene in the copolymer. For most mingled with any one of the above-named transition metal purposes of polymer utility it is preferred that the toluene 15 compounds to prepare the coordination catalyst used in insoluble content of the polymer, if any, be below 50 this invention include: ethylaluminum Sesquichloride, weight percent, more preferably below 25 weight percent, ethylaluminum sesquiiodide, n-butylaluminum Sesqui of the polymer. bromide, isopropylaluminum sesquichloride, n-hexylalumi Any of the polymerization coordination catalysts known num sesquichloride, n-decylaluminum sesquiiodide, tri in the prior art can be employed in the polymerization 20 hexylaluminum, triethylaluminum, diethylaluminum chlo process of this invention, such catalysts comprising (1) at ride, ethylaluminum dichloride, diisobutylaluminum bu least one compound of a reducible polyvalent transition toxide, triisobutylaluminum, aluminum hydride, isobutyl metal of Groups IV-A, V-A, VI-A, VII-A, VIII of the aluminum dichloride, isobutylaluminum dibutoxide, n Periodic Table (e.g., titanium, vanadium, chromium, butylaluminum dichloride, n-butyllithium, sodium naph manganese, iron, cobalt, and nickel), said reducible com- 25 thalene, diisobutylzinc, lithium aluminum tetra-n-decyl, pound being a halide, oxyhalide, alcoholate, or acetylace lithium aluminum tetra-n-octyl, amylpotassium, tetraphen tonate, and (2) at least one reducing compound of a metal yltin, diethyltin diiodide, n-butylmagnesium bromide, di of Groups I, II, III, IV-B, and V-B of the Periodic Table phenylcalcium, di-tert-butylzinc, diethylmercury, and the (e.g., lithium, sodium, potassium, rubidium, cesium, beryl like, including mixtures thereof. lium, magnesium, calcium, strontium, barium, copper, 30 Representative of the coordination catalysts which can zinc, cadmium, mercury, aluminum, tin, and antimony), be used in this invention are those obtained upon com which is preferably above hydrogen in the electromotive mingling vanadium tetrachloride and ethylaluminum ses series, said reducing compound being an organometal quichloride, vanadium trichloride and ethylaluminum ses compound, a metal hydride, an organometal hydride or an quibromide, vanadium oxytrichloride and n-butylalumi organometal halogen compound. (The Periodic Table 35 num sesquibromide, vanadium oxydichloride and isopro referred to herein and in the claims is shown on pages pylaluminum sesquichloride, vanadium acetylacetonate 448-449 of the Handbook of Chemistry & Physics, 34th and n-hexylaluminum sesquichloride, vanadium oxydichlo Edition, published by Chemical Rubber Publishing Co., ride and diisobutylaluminum butoxide, vanadium oxytri Cleveland, Ohio.) Preferably, the metal of the reducible chloride and triisobutylaluminum, vanadium oxytrichlo compound is vanadium, titanium or chromium, with 40 ride and aluminum hydride, vanadium dichloride and tri vanadium trichloride, vanadium tetrachloride, vanadium isobutylaluminum, vanadium trichloride and isobutylalu oxytrichloride, vanadium oxydichloride, vanadium acetyl minum dichloride, vanadium tetrachloride and isobutyl acetonate, vanadyl acetylacetonate, titanium tetrachloride, aluminum dibutoxide, vanadium tetrachloride and triiso tetrabutyl titanate, tetraisopropyl titanate, chromic chlo butylaluminum, vanadium tetrachloride and aluminum hy ride, chromium acetylacetonate, and chromyl acetylace-45 dride, 2-ethylhexyl vanadate and triisobutylaluminum, tonate being examples of preferred reducible components titanyl dichloride and isobutylaluminum dichloride, tita of the coordination catalyst. Preferably, the reducing nium tetrachloride and isobutylaluminum dichloride, tita compound has the general formula RMX, where R is a nium tetrachloride and lithium aluminum hydride or di saturated aliphatic, cycloaliphatic, or aromatic hydrocar dodecyldichloride, titanium tetrachloride and n-decyl bon radical having from 1 to 20 carbon atoms, M is a 50 aluminum sesquiiodide, titanium tetrachloride and so metal selected from the group consisting of lithium, sodi dium naphthalene, tetraisopropyl titanate and triisobutyl um, potassium, magnesium, calcium, zinc, mercury, alumi aluminum, tetraisopropyl titanate and sodium naph num, and tin, X is a halogen selected from the group con thalene, cobaltous chloride and triisobutylaluminum, co sisting of chlorine, bromine, and iodine, n is a number balt bromide or chloride and triisobutylaluminum, man from 1 to 4, m is a number from 0 to 2, and n--m is equal 55 ganese bromide and triisobutylaluminum, manganese bro to the valence of metal M. The mole ratio of the reduc mide and diisobutylzinc, chromium chloride and triiso ing compound to the reducible compound in the catalyst butylaluminum, chromium acetylacetonate and n-heptyl system can vary widely, and generally this ratio will be in aluminum sesquichloride, cuprous chloride and triisobutyl the range of 1/1 to 20/1. The total catalyst level in the aluminum, ferric bromide and triisobutylaluminum, reaction system can also vary widely, and generally will be 60 molybdenum chloride and triisobutylaluminum, nickel 0.001 to 10 percent by weight of the total monomers, or as chloride and triisobutylaluminum, vanadium oxytrichlo expressed in terms of the amount of reducible compound, ride and diethylaluminum chloride, vanadium tetrachlo the catalyst level can be in the range of 0.25 to 40 milli ride and ethylaluminum dichloride, vanadium oxydiacetyl moles (mmoles) per 100 grams of the total monoolefin acetonate and triethylaluminum, trimethyl orthovanadate charged to the reaction system. The catalyst can be pre- 65 and trihexylaluminum, vanadium tetrachloride and tri mixed, i.e., the catalyst components can be admixed prior heXylaluminum, vanadium oxytrichloride and butyl to charging to the reaction system, or the catalyst can be lithium, vanadium triacetylacetonate and diethylaluminum prepared in situ in the reaction system. These components chloride, titanium tetrachloride and trihexylaluminum, or the premixed catalyst can be charged to the reaction vanadium trichloride and trihexylaluminum, titanium tri system as solutions in solvents like those employed as reac- 70 chloride and trihexylaluminum, titanium dichloride and tion diluents for the monomers and polymer. trihexylaluminum, vanadium trichloride and n-butyl Representative reducible transition metal compounds lithium, vanadium tetrachloride and amylpotassium, vana which can be used in making up the coordination catalysts dium oxytrichloride and sodium naphthalene, vanadium used in preparing the polymers of this invention include: Oxydichloride and diethylmagnesium, vanadium acetyl titanium tetrachloride, titanium tetrabromide, titanium 75 acetonate and butylmagnesium bromide, vanadyl acetyl 3,299,016 5 6 acetonate and diphenylcalcium, chromic chloride and di The objects and advantages of this invention are illus tert-butylzinc, chromium acetylacetonate and diethylmer trated in the following examples, but it should be under cury, chromyl acetylacetonate and tetraphenyltin, titanium stood that the various materials used in these examples, tetrachloride and diethyltin diiodide, tetra-n-butyl titanate the conditions of operation, and other details, should not and diethylmagnesium, and the like. be construed to unduly limit this invention. The polymerization reaction of this invention is carried Example I out in the absence of oxygen, carbon dioxide and Water and in a liquid phase system using a solvent, which will Copolymers of ethylene, propylene and isopropenyl usually be a hydrocarbon or a halogenated hydrocarbon, acetylene were prepared in a series of runs employing such as propane, butane, pentane, hexane, benzene, tol O toluene or cyclohexane as a reaction diluent and using as uene, xylene, tetrachloroethylene, cyclohexane, methyl a polymerization coordination catalyst ethylaluminum cyclohexane, chlorobenzene, o-dichlorobenzene, dichloro sesquichloride commingled with either vanadium tetra methane, 1,1,2,2-tetrachloroethane, and the like. The chloride or vanadium oxytrichloride. In preparation of polymer will be soluble in the solvent and usually will be said polymers, a 3/1 volume mixture of propylene and present in a concentration of 1 to 15 weight percent. The 5 ethylene was made up by charging propylene to an polymerization conditions can vary widely, but generally evacuated bomb until the pressure reached 30 p.s.i.g., and the polymerization temperature will be in the range of then charging ethylene until the total pressure was 45 -80 to 150° C. and the reaction pressure will be that Suf p.s.i.g. The procedure used in each of the continuous ficient to maintain the reaction mixture in the liquid phase polymerization runs was to charge the diluent (100 ml.) and can be up to 500 or more atmospheres. Polymeriza 20 to the polymerization reactor first and then purge the tion can be carried out in a batch manner or a continuous reactor with nitrogen. Isopropenylacetylene was then fashion, much like the polymerization processes of the added to the reactor, followed by the ethylaluminum prior art. Following polymerization, the polymer product sesquichloride. The ethylene/propylene mixture was can be conventionally recovered from the effluent by then introduced from the bomb reservoir, raising the pres coagulation with a non-solvent such as an alcohol like 25 Sure in the polymerization reactor to about 45 p.s.i.g. isopropyl alcohol or n-butyl alcohol, acetone, or the poly Charging of the reactor was done at room temperature. mer can be recovered by stripping the solvent with heat The polymerization reaction mixture was agitated for 5 or steam. An antioxidant can be incorporated in the min., after which polymerization was initiated by in polymer during the recovery procedure, such as phenyl troducing the vanadium component of the catalyst. Then beta-naphthylamine, di-tert-butylhydroquinone, triphenyl 30 additional ethylene/propylene mixture was passed to the phosphite, heptylated diphenylamine, 2,2'-methylene-bis reactor from its reservoir to maintain a constant pressure (4-methyl - 6 - tert-butylphenol), and 2,2,4-trimethyl-6- as polymerization continued. The temperature of po phenyl-1,2-dihydroquinoline. lymerization increased due to the exothermic reaction. The vulcanization or curing of the novel polymers of Table I sets forth charged materials used in the runs. this invention can be carried out using conventional Sul 35 fur vulcanization procedures (e.g., 250-400' F., for 5 TABLE I 120 minutes), the amount of sulfur employed generally Ethyl- Wanadium Wanadium isopro being from 0.1 to 5 parts per 100 parts of polymer (phr.) aluminum tetra. oxytri- penyl and usually about 0.5 to 3 phr. The polymers can also Run Diluent sequi- chloride, chloride, acetylene, be cured with compounds which can decompose to form chloride, immoles Immoles immoles free radicals such as peroxide (e.g., 0.1 to 10 phr.) like immoles diisopropyl peroxide, di-tert-butyl peroxide, dibenzoyl 1----- Toluene.------0.25 0. 0. 2.5 peroxide, tert-butyl perbenzoate, etc. The polymers can 2------do------0.25 0.1 O 5.0 3. Cyclohexane- 0.25 0.1 O 2.5 also be cured with combinations of peroxide and sulfur, 4------do------0.25 0. 0. 2.5 e.g., with peroxide/sulfur weight ratio of 0.1/1 to 4/1. 45 5----- Toluene.------0.25 () 0. 2.5 Vulcanization accelerators, accelerator activators, rein forcing agents, extenders, plasticizers, antioxidants and fillers, like those agents used in compounding natural and After a 30-min. polymerization period, the reaction of synthetic rubber, can also be employed. Fillers and rein each run was terminated (shortstopped) with an isopropyl 50 alcohol solution of 2,2'-methylene-bis(4-methyl-6-tert forcing agents such as carbon black, clay, calcium silicate, butylphenol) antioxidant, the amount of antioxidant used talc, silica, whiting, and titanium dioxide, and plasticizers being one phr. The ethylene/propylene/isopropenyl such as naphthenic and paraffinic oils, can be used in com acetylene polymer was coagulated in isopropyl alcohol, pounding the polymers of this invention. Such polymers Separated and dried. Certain properties of the polymers will have molecular weights in the range of about 5000 55 from the runs were determined and these are set forth in to 1,000,000, and can be used in fabricating such rubber Table II, the number of the "polymer sample’ in the goods and plastic products as coatings for electrical cables, latter table corresponding to the number of the “run” of window-seals, garden hose, soles and heels, belts, coated Table I.

TABLE II

Amt. of Total unsatura- Amt. of Toluene Polymer polymer, tion, a mmoles propylene Inherent insolubles, Sample gll. IClgm. in polymer,b viscosity wt. percent polymer wt. percent

2.3 0.30 4. 27 Trace. 1, 4 0.36 34 1.14 3. 1.5 0.27 38 1.36 9 ... 8 0.20 ------1.16 32 2.0 0.29 37 1.13 20 it Determined by iodine chloride titration. b Petermined by infrared analysis. Portion insoluble in toluene after 24 hrs. at room temperature. fabrics, tires, films, coatings, containers (bottles), pipes, Infrared analysis indicated the presence of isopropenyl fibers, etc. 75 groups along the polymer chain. Based on the data of 3,299,016 7 8 Table II, the compositions of the polymers from runs 1 Resilience, percent ------65.3 to 3 and 5 were calculated and these are set forth in Shore A hardness ------58.0 Table III. In calculating the wt. percent of isopropenyl Gehrman freeze point, C. ------56 acetylene, it was assumed that each molecule incorporated Example III into the polymer chain furnished two double bonds. In this example, a copolymer of ethylene/propylene/ TABLE III vinylacetylene was prepared according to this invention by a continuous process. In this process, two makeup Amt. Of Amt. of Amt. ofisopro Polymer Sample propylene, ethylene, penylacetylene, tanks or reservoirs were used and their contents were wt. percent wt. percent wt. percent O introduced simultaneously into a 1-liter autoclave at rates

such that completion of addition of materials from both 4.0 58.0 O 340 64.8 1.2 makeup tanks occurred at the same time. One of the 38.0 61. 0.9 composite streams ("makeup tank No. 1') consisted of 37.0 62.1 0.9 toluene, ethylene, and vanadium tetrachloride and the other stream ("makeup tank No. 2') consisted of toluene, 5 propylene, vinylacetylene and ethylaluminum sesquichlo Example II ride. Compositions of the makeup tanks from which A blend of ethylene/propylene/isopropenylacetylene these streams were withdrawn are set forth in Table VII. copolymers prepared in two runs according to this inven TABLE VII tion was compounded, cured, and the physical properties 20 of the cured polymer product determined. In preparing Makeup Makeup the polymer of each run, 600 ml. of toluene was first Tank No. 1 Tank No. 2 charged to a polymerization reactor, followed by 50gm. of propylene and 1.5 mmoles of ethylaluminum sesqui Toluene, ml------1,600 1,600 Ethylene, gn- 80 O chloride. The reactor was pressured to 40 p.s.i.g. with 25 Propylene, gill------O 200 ethylene, agitated for 10 min, and charged with iso Vinylacetylene, mimole O 60 Vanadium tetrachloride, mimoies------4. 0. propenylacetylene and one mmole of vanadium tetra Ethylaluminum sesquichloride, minoles... O O chloride. The reactor pressure was maintained at 40 p.s.i.g. throughout the run, which was carried out for 1 At the beginning of the run, 500 ml. of toluene was hr. at 80° F. The amount of isopropenylacetylene used 30 charged to the polymerization reactor, which had pre in preparing "polymer sample No. 1' was 22.5 mmoles, viously been filled with nitrogen. The reactor was then and the amount used in preparing "polymer sample No. pressured with nitrogen to 180 p.s.i.g. The two streams 2' was 2.5 mmoles. Each of the polymerization reac were pumped into the reactor at the same time and the tions was shortstopped, and the polymer was recovered, entire contents from the two makeup tanks were added to and evaluated. These polymer properties are set forth 35 the reactor. Throughout the run, 500 ml. of material in Table IV. was maintained in the reactor by regulating the rate of TABLE IV withdrawal of effluent. The time required to pump out the contents of the makeup tank was 47 min, and the Polymer Polymer total reaction time was 52 min. Unreacted ethylene and sample Sample 40 propylene were flashed from the reactor effluent, after No. 1 No. 2 which 2 wt. percent of 2,2'-methylene-bis(4-methyl-6- Amt. of propylene in polymer, wt. percent---- 44 44 tert-butylphenol) antioxidant was added. The rubbery Inlherent viscosity------1.50 1.59 polymer was then coagulated with isopropyl alcohol, sepa Amt. toluencilsolubles, wt. percent------O 3 rated and dried; the polymer recovered weighed 58 gm. Total unsaturation, minoles ICl(gm. polymer- 0.21 0.22 45 The properties of the polymer are set forth in Table VIII. TABLE WII The polymer products from the two runs were then combined and blended, and the blended material (having Amt. of propylene, Wt. percent ------33 a Mooney viscosity ML-4 of 82 at 212 F.) was com Total unsaturation, mmoles ICl/gm. polymer ----- 0.33 50 Inherent viscosity ------1.04 pounder using the compounding recipe of Table V. Toluene insolubles, wt. percent ------47 TABLE W Parts by The ethylene/propylene/vinylacetylene copolymer ob weight tained from the continuous run was then compounded Polymer blend ------100 using the recipe of Table V, except that only 20 parts by High abrasion furnace black ------50 55 weight of Circosol 2XH was used. The compounded Zinc oxide ------5 polymer was then cured at 320 F., and properties at 30 Stearic acid ------min. and 45 min. cure times are set forth in Table IX. Circosol 2XH' ------30 TABLE IX Sulfur ------1.5 Captax' ------0.5 60 Cure time, min. Monex ------1.5 30 45 iPetroleum hydrocarbon softener, containing hydrocarbons of high molecular weight, in the form of a heavy, Viscous, 300%modulus, p.S.i------1,350 1,580 transparent, pale green, odorless liquid of low, volatility 65 Tensile, p.S.i------2,505 2,850 specific gravity, 0.940; Saybolt Universal viscosity at 100 Elongation, percent. w 535 505 F.,22-mercaptobenzothiazole. about 2000 seconds. Resilience, percent- 62.5 61.8 3 Tetramethylthiuram monosulfide. Shore A hardness--- 86.5 88 The compounded blend was then cured for 45 min. at 320 F., and the properties of the cured product were 70 Example IV then determined, the results being set forth in Table VI. For purposes of comparison, a copolymer of ethylene/ TABLE W. propylene/acetylene was prepared using the continuous 300% modulus, p.S.i. ------360 polymerization process procedure of Example III. The Tensile, psi. ------2020 compositions of the two makeup tanks in this comparison Elongation, percent ------875 75 or control run were the same as that of Table VII except 3,299,016 10 that 24 mmoles of vanadium tetrachloride, 60 mmoles of spectrophotometer. The number of methyl groups (N) ethylaluminum sesquichloride and 120 mmoles of acety was obtained from the formula: lene (instead of vinylacetylene) were used. The total pump time for the comparison run was 45 min., the total (14,000) (A.i.25) (1,000) reaction time was 50 min., and the weight of the polymer N --- (C) (t) (e) (I) obtained was 48.2 gm. The properties of this polymer 14,000-molecular weight of 1,000 methylene groups are set forth in Table X. As=absorbance at the 7.25 micron band TABLE X C=concentration of polymer solution in gram/liter Amt. of propylene, wt. percent ------23 t-cell thickness in centimeters Total unsaturation, mmoles IC/gm. polymer ----- 0.47 O e=specific extinction coefficient Inherent viscosity ------0.22 The specific extinction coefficient (e=28,700) was deter Toluene insolubles, Wt. percent ------43 mined using three samples of an ethylene/propylene co polymer of known propylene content as a reference mate In comparing the preparation of this control polymer rial. The value was obtained by solving the equation with that of Example III, note that the catalyst level 15 used in the comparison run was higher. Such high cata (14,000) (47.25) lyst level was necessary in order to initiate the polymeriza (d) (t) (N) (II) tion reaction, since no ethylene/propylene/acetylene poly d=density of polymer solution in gm./cc. (assumed to mer was obtained at the catalyst levels employed in be 0.9) Example III. Note also that the control polymer had a 20 t=thickness of aborbing layer of polymer in centimeters vary low inherent viscosity as compared to that polymer N = number of methyl branches in control polymer of Example III, indicating that the control polymer Would be unsuitable for many applications, such as in tires. The percent propylene was calculated as follows: Furthermore, when an attempt was made to cure this con trol polymer, using the recipe of Table V (with the omis 25 Percent= (N) (100) sion of the plasticizer, Circosol 2XH), a cure was not 333 (III) obtained, notwithstanding the unsaturation of the control In the Formula III, 333 is the number of methyl branches polymer. per 1,000 methylene groups. Example V The inherent viscosities referred to in the examples 30 were determined by placing one-tenth gram of polymer In this example, a copolymer of ethylene and vinyl in a wire cage made from 80 mesh screen and placing the acteylene was prepared using the recipe of Table XI. wire cage in 100 ml. of toluene contained in a wide mouth, 4-ounce bottle. After standing at room tempera TABLE XI ture (approximately 25 C.) for 24 hours, the cage was 35 removed and the solution was filtered through a sulfur Cyclohexane, ml ------500 absorption tube of grade C porosity to remove any solid Diethylaluminum chloride, mmoles ------5.0 particles present. The resulting solution was run through Vanadium oxytrichloride, mmoles ------1.0 a Medalia-type viscometer supported in a 25 C. bath. Vinylacetylene, mmoles ------45 The viscometer was previously calibrated with toluene. Ethylene, p.s. i.g. Over reactor preSSure ------70 40 The relative viscosity is the ratio of the viscosity of the The reactor used to prepare the ethylene/vinylacetylene polymer solution to that of toluene. The inherent vis copolymer was first purged with hydrogen and 350 ml. of cosity is calculated by dividing the natural logarithm of cyclohexane was then charged. Diethylaluminum chlo the relative viscosity by the weight of the soluble portion ride was added followed by 50 ml. of cyclohexane, the of the original sample. vinylacetylene, another 50 ml. of cyclohexane, the vana 45 The amount of toluene insolubles referred to in the dium oxytrichloride, and then 50 more ml. of cyclohex examples is that amount of material not dissolved after ane. Ethylene was then added until the pressure reached 0.2 gram sample of the polymer remains in contact with 70 p.s.i.g. over reactor pressure. Polymerization Was 100 milliliters of toluene at room temperature for 24 continued for one hour during which time ethylene was in hours. The value should be below 50 weight percent for troduced to maintain the pressure at 70 p.S.i.g. over re 50 a rubbery polymer. Ordinarily, it is preferred to have actor pressure. Temperature was maintained at 80 F. the value below 25 weight percent, but for some uses throughout the run. The reaction was terminated and (mechanical goods, mats, shoe soles, etc.) it can be the polymer recovered as in the Example I. It had a higher. For uses where high resilience and low heat total unsaturation of 0.14 mmole IC1/gm. polymer. In build-up are important, it is desirable to have the toluene frared examination gave evidence of a conjugated System 55 insolubles low. of double bonds but no -C=C-. Various modifications and alterations of this invention In the foregoing examples, the procedure used to de will become apparent without departing from the scope termine total unsaturation by iodine chloride titration was and Spirit of this invention and it should be understood as follows: A 0.5-gram sample of polymer was dissolved that this invention is not to be limited unduly to that set in a 75/25 volume mixture of carbon disulfide and chloro 60 forth herein for illustrative purposes. form, a chloroform solution of iodine chloride of known I claim: concentration (approximately 0.09-0.10 molar) was 1. An unsaturated rubbery terpolymer consisting essen added, the mixture was placed in a 25 C. bath for one tially of ethylene, at least one other 1-monoolefin, and an hour to allow time for reaction, and the excess of iodine ethynyl ethylene. chloride was titrated with 0.05 N sodium thiosulfate. 65 2. An unsaturated rubbery terpolymer consisting essen The millimoles of iodine chloride that reacted with one tially of 20-75 weight percent ethylene, 20-75 weight gram of sample was then calculated. A blank was run percent propylene and 0.5 to 20 weight percent vinyl using only solvent and iodine chloride and appropriate acetylene. correction was made when calculating unsaturation. 3. An unsaturated rubbery terpolymer consisting essen In the examples, an infrared procedure was used to 70 tially of 20-75 weight percent ethylene, 20-75 weight per determine the wt. percent propylene. A carbon tetra cent propylene and 0.5 to 20 weight percent isopropenyl chloride solution of the polymer containing one gram of acetylene. polymer per 100 milliliters solvent was used. The solu 4. A process comprising contacting ethylene and vinyl tion was placed in a 1500-micron cell and scanned for a acetylene at a temperature ranging from -80 to 150° C. peak at the 7.25 micron band using a commercial infrared 75 and a pressure ranging from 1 to 500 atmospheres in 3,299,016 11. 12 cyclohexane with a coordination catalyst comprising (1) prising (1) vanadium tetrachloride and (2) ethylalumi vanadium oxytrichloride and (2) diethylaluminum chlo num sesquichloride, said vinylacetylene being present in ride, said vinylacetylene being present in an amount rang an amount ranging from 0.5 to 20 weight percent of the ing from 0.5 to 20 weight percent of the resulting co resulting terpolymer, and recovering the resulting ter polymer, and recovering the resulting copolymer from 5 polymer from the reaction mixture. the reaction mixture. 5. A process comprising contacting ethylene, propyl References Cited by the Examiner ene, and isopropenylacetylene in toluene or cyclohexane UNITED STATES PATENTS at a temperature ranging from -80 to 150° C. and a 2,384,731. 9/1945 Denoon ------260-88.2 pressure ranging from 1 to 500 atmospheres with a co O ordination catalyst comprising (1) vanadium tetrachlo 2,781,408 2/1957 Witt et al. ------260-88.2 ride or vanadium oxytrichloride and (2) ethylaluminum 2,898,327 8/1959 McCulloch et al. --- 260-88.2 sesquichloride, said isopropenylacetylene being present in 3,092,613 6/1963 Kennerly et al. ----- 260-88.2 an amount ranging from 0.5 to 20 weight percent of the FOREIGN PATENTS resulting terpolymer, and recovering the resulting ter 5 polymer from the reaction mixture. 224,036 1/1958 Australia. 6. A process comprising contacting ethylene, propyl ene, and vinylacetylene in toluene at a temperature rang JOSEPH L. SCHOFER, Primary Examiner. ing from -80 to 150 C. and at a pressure ranging from W. HOOVER, Assistant Examiner. 1 to 500 atmospheres with a coordination catalyst com