3,629,215 United States Patent Office Patented Dec. 21, 1971 2 3,629,215 wherein R and R2 are respectively hydrogen atom, halo 1:1. ALTERNATING COPOLYMERS OF SUBST gen atoms, hydrocarbon radicals having 1 to 20 carbon TUTED CONUGATED WNY COMPOUNDS atoms, halogen-containing hydrocarbon radicals having AND OLEFNC COMPOUNDS AND PROCESS 1 to 20 carbon atoms, or substituted radicals thereof, FOR PRODUCING THE SAME and B) a substituted conjugated compound having the Kohei Nakaguchi, Osaka, Shohachi Kawasumi, Kobe, formula: Masaaki Hirooka, Ibaraki-shi, Hiroshi Yabuuchi, Takat suki-shi, and Hiroyoshi Takao, Ashiya-shi, Japan, as RIE ises to Sumitomo Chemical Company, Ltd., Osaka, RICH-C-Q apan No Drawing. Continuation of application Ser. No. 10 wherein R and R are respectively hydrogen or halogen 567,353, July 25, 1966. This application Oct. 31, atoms or hydrocarbon radicals having 1 to 20 carbon 1969, Ser. No. 871,781 atoms, halogen-containing hydrocarbon radicals having Claims priority, application Japan, July 30, 1965, 1 to 20 carbon atoms, substituted hydrocarbon radicals 40/46,495 thereof, either of RI and RI is hydrogen atom but both Int. C. C08f3/40, 3/62, 3/74 5 of them are not hydrogen at the same time; and Q is a U.S. C. 260-85.5 HC 41 Claims nitrile or

ABSTRACT OF THE DISCLOSURE An alternating copolymer consists of AJ a terminally 20 group, wherein Y is Z2H, Z2R, Z2Me, MR'R'', R, halo unsaturated olefinic compound, for example, an ox-olefin, gen atoms or hydrogen atom; in which Z and Z are an isoolefin, or a halogenated olefinic compound (vinyl respectively an oxygen or sulfur atom; R is an organic chloride, vinylidene chloride, allyl chloride or the like) radical having 1 to 20 carbon atoms; R and R'' are and BJ a substituted conjugated vinyl compound, such respectively hydrogen atom or organic radicals having as a substituted acrylonitrile or a substituted acrylic acid 25 1 to 20 carbon atoms, including the case where R and derivative (esters, amides, acids, acid halides, ketones, R'' are mutually bonded at other portion than nitrogen; acrolein and the like) which has a substituent, such as and Me represents a monovalent portion of an element of a hydrocarbon, halogenated hydrocarbon or halogen Groups I to III of the Mendeleev's Periodic Table or substituent on the cy- or 3-position. Said alternating co an ammonium group. polymer can be prepared by subjecting said monomers 30 Further, the present invention provides a process for to copolymerization with an organoaluminum halide or producing copolymers, which comprises contacting said an organoboron halide or a product of reaction between olefinc compound and substituted conjugated vinyl com an organic compound of a metal of Groups IIb, IIIb and pound with (1) an organo-metal halide having the IVb of the Periodic Table and a halide of a metal of formula: Groups IIIb and IVb of the Periodic Table in the presence 35 of at least said substituted conjugated vinyl compound, wherein M is aluminum or boron; R' is an organic at least one of said organic compound and halide being radical; X is a halogen atom; and n is an arbitrary num aluminum or boron-containing compound. ber from 1 to 2, or a mixture of at least two compounds -autaumam 40 having the following formulas: This application is a continuation of application Ser. (A) MR'X (B) MRV and (C) M'X's No. 567,353, filed July 25, 1966, and now abandoned. wherein M, M' and M' are aluminum or boron; R'' and This invention relates to copolymers of substituted RIV are organic radicals; X and X’ are halogen atoms; conjugated vinyl compounds and olefinic compounds, and n is an arbitrary number from 1 to 2, or with (2) and a proces for producing the same. More particularly, 45 catalyst components (a) an organo-compound of a metal the invention provides alternating copolymers of o- or of Group IIb, IIIb or IVb of the Mendeleev's Periodic B-substituted conjugated vinyl compounds and olefinic Table and catalyst components (b) a halogeno-compound unsaturated compounds, and a method for the production of a metal of Group IIIb or IVb of the Mendeleev's of said copolymers. 50 Periodic Table, wherein at least one of (a) and (b) The present inventors already found alternating co is a compound of aluminum or boron, and (a) must be polymers of conjugated vinyl compounds having nitrile, contacted with (b) in the presence of at least substituted carbonyl or thiocarbonyl groups at the conjugated posi conjugated vinyl compound of the monomers employed. tions of carbon-carbon double bonds, Such as acrylo Still further the present invention provides a process nitrile acrylic acid derivatives or thioacrylic acid deriva 55 for producing copolymers in which the abovementioned tives, and olefinic unsaturated compounds such as olefins copolymerization reaction is effected in the presence of or halo-olefins, and provided a process for producing oxygen or an organic peroxide, if necessary. copolymers using said monomers. As the result of further The alternating copolymers of the present invention studies, the present inventors have found that this kind are novel copolymers. Many combinations of Al and of complex copolymerization can be extended to substi B group monomers have been known to produce always tuted conjugated vinyl compounds having substituents 60 random copolymers. It is, therefore, quite unexpected in the o- or 6-positions of the above-mentioned vinyl that the combinations of these kinds of monomers give compounds and have discovered a group of novel alternat alternating copolymers. ing copolymers, and have thus attained the present In order to obtain the alternating copolymers in ac invention. cordance with the process of the present invention, the Thus, the present invention provides alternating co 65 nature of catalyst components is important. The process polymers of Al an olefinic compound having the of the present invention requires aluminum or boron as a formula: metal component, and further requires the presence of an R1 organic group and a halogen atom in combination there / 70 with. Other important nature is that the metal component CFI-C is coordinated with the conjugated compound. Particu R2 larly, the coordination to a halogen-containing metal com 3,629,215 3 4. ponent is of significance, and the copolymerization reac wherein, Rand R2 are individually hydrocarbon groups tion proceeds through this kind of coordinated complex. Such as alkyl, aryl, aralkyl, alkylaryl, cycloalkyl and The substituted conjugated vinyl compound is required to bridged ring hydrocarbons; said hydrocarbon groups sub be such that the polar group thereof is in position con stituted with halogens; halogen atoms such as chlorine, jugated with carbon-carbon double bond. This is very im bromine, iodine and fluorine; or hydrogen atom. It is portant in copolymerization to give alternating copoly of importance that the hydrocarbon groups or halogen IeS. substituted hydrocarbon groups do not contain any polym In case of using the catalyst components of (a) an erizable group, i.e. unsaturated group causing polymeriza organo-compound of a metal from Groups IIb, IIIb and tion reaction. Further, said hydrocarbon group may be IVb of the Mendeleev's Periodic Table and (b) a halo O Substituted with other inert substituent. It is, however, geno-compound of a metal from Groups IIIb and IVb of required that said substituent should not be conjugated the table, it is not the case that the catalyst components with the double bond. (a) and (b) are previously mixed and then the mixture is That is, preferable olefinic unsaturated compounds hav employed as the polymerization catalyst. Such mixed ing the general formula: catalyst is not suitable for the production of at least the R1 alternating copolymer. In order to obtain the alternating / copolymer according to the present invention the catalyst CH=C components (a) and (b) must be contacted each other R2 in the presence of at least the conjugated compound. That is, for example, the copolymerization may be effected by 20 are general olefinic compounds such as a-olefins and said contacting catalyst components (b) with conjugated com olefins substituted with halogens or other inert groups. pound previously and then adding catalyst components (a) Examples of these compounds are olefins such as ethylene, thereto. propylene, butene-1, isobutene, pentene-1, hexene-1, In the process of the present invention, the combination heptene-1, octene-1,2-methyl-butene-1,3-methyl-butene-1, of monomers is of importance. No alternating copolymers 2-methyl-pentene-1, 4-methyl-pentene-1, 4-methyl-hex can be obtained unless the olefinic compounds are used in ene-1, decene-1, dodecene-1, octadecene-1, 4-phenyl-bu combination with the substituted conjugated vinyl com tene-1, Styrene, a - methyl- styrene, ox-butyl-styrene, p pounds. The olefinic compounds employed in the present methyl-styrene, m-methyl - styrene, vinyl - cyclobutane, invention must be low in e-value of Q-e reactivity index vinyl-cyclohexane, isopropenyl-benzene, vinyl-naphtha proposed by Price-Alfrey, and those having an e-value be 30 lene, 1-methylene-cyclobutane and allyl-benzene, and hal low 0.5, especially a minus e-value, give favorable results. ogen-containing olefinic unsaturated compounds such as In the process of the present invention, the presence vinyl chloride, vinyl bromide, vinyl iodide, allyl chloride, of polar solvents or polar substances is not desirable, ally bromide, allyl iodide, 4-chloro-butene-1, 4,4,4-tri in general. Particularly, the presence of components form chloro-butene-1, p-chloro-styrene, o-chloro-styrene, m ing complexes with the metal components employed in the brono-styrene, p-iodo-styrene, p-fluoro-styrene, 4-chloro present invention is not preferable. For example, ethers vinyl-cyclohexane, p-chloro-allyl-benzene, 2,4-dichloro such as ethylether, tetrahydrofuran and dioxane; ketones Styrene, 2,6-dichloro-styrene, 2,4-difluoro-styrene, 3-tri such as acetone; esters; nitriles and amides such as di fluoromethyl-Styrene, 4-chloro-1-vinyl-naphthalene, vinyl methylformamide are not usable, and alcohols and water idene chloride, vinylidene bromide, 2-chloro-propene-1,1- are neither preferable. 40 brono-1-chloro-ethylene, 2-chloro-allyl chloride, methal In the process of the present invention, when the lyl chloride, and 1,1-bis(p-chlorophenyl)-ethylene. polymerization is effected in the presence of oxygen or In the present invention, the substituted conjugated vinyl an organic peroxide, the reaction is promoted, in general, compound having the formula or the polymerization can be effected by use of a rela tively small amount thereof. It is, however, needless to RII Say that no alternating copolymer can be obtained by RICH=C-Q mere addition of oxygen or an organic perixode to the mixture of an olefinic compound and a substituted con include B-substituted vinyl compounds having the formula jugated vinyl compound. Further, no alternating copolymer RCHFCH-Q and c-substituted vinyl compounds hav can either be obtained by mere use of a catalyst system ing the formula prepared by combining trialkylboron or trialkyl-aluminum RII with oxygen or an organic peroxide. That is, the process of the present invention is different from the mere con CH-C-Q ventionally known radical polymerization reactions using Wherein R and RF are as defined before. As RI, RII hy organic metals. 5 5 drocarbon radicals such as alkyl, aryl, aralkyl, alkylary The promoting mechanism of oxygen and organic per and cycloalkyl; said radicals substituted with halogens or oxide in the process of the present invention is not suffi other inert groups; or halogens are frequently employed. ciently clear, but it is not considered that they show As the halogens, there are used chlorine, bromine, iodine the same roles as those of conventional initiators in radi and fluorine. Further, in Q, the organic radicals having 1 cal polymerization systems in which zinc chloride has 60 to 20 carbon atoms which are represented by R, R and been coordinated with methyl methacrylate or acryloni R', are preferably ordinary hydrocarbon groups, and inert trile. This is clear also from the fact that the polymeriza Substituted groups thereof may also be used. Such groups tion in accordance with the present invention cannot be are, for example, alkyl, aryl, aralkyl, alkylaryl and cyclo promoted by use of all kinds of radical initiators. In alkyl groups. As the halogens employed in Y, there may the process of the present invention, the excellent promot be raised chlorine, bromine, iodine and fluorine. Me rep ing effect can be seen only by addition of oxygen or an resents a monovalent portion of an element of Groups I to organic peroxide, and no effect can be attained at all in the III of the Mendeleev's Periodic Table or an ammonium case of using other radical initiator containing no oxygen, group. Such element includes, for example, lithium, so such as azobisisobutyronitrile. dium, potassium, rubidium, cesium, copper, silver, beryl In the olefinic compounds having the formula: lium, calcium, strontium, barium, magnesium, zinc, cad mium, mercury, boron, aluminum and gallium. The R monovalent portion referred to herein means that in case / a metal element of Groups I to III of the Mendeleev's Pe CH=C riodic Table is represented by Me', the Me belonging to a R2 divalent element means Me"/2 and that of a trivalent 3,629,215 5 6 element is Me"/3. That is, the above concretely corre methylaluminum dibromide, ethylaluminum diiodide, sponds to allylaluminum dichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesqui fluoride, methylaluminum sesquichloride, diethylalumi (non-Z1 -z-Me J2 num chloride, diethylaluminum fluoride, ethylphenylalu minum chloride, dicyclohexylaluminum chloride, methyl in the case of a divalent element, and to boron dichloride, ethylboron dichloride, ethylboron di iodide, butylboron dichloride, hexylboron dichloride, dodecylboron dichloride, phenylboron dichloride, benzyl (CH=CH-i-z)-Me2, J 3 O boron dichloride, cyclohexylboron dichloride, diethylboron in the case of trivalent element. Of these, monovalent salts, chloride, diethylboron bromide, dipropylboron chloride, i.e. salts of elements of Group I, and ammonium salt are dibutylboron chloride, dihexylboron chloride, ethylvinyl particularly preferable. NR'R' includes the case where boron chloride and dicyclopentadienylboron chloride. R" and R'' are mutually bonded at other portion than nitro The compounds having the formula MRIV include tri gen, fo example, morpholino, pyrrolidino and piperadino 5 methylaluminum, triethylaluminum, tripropylaluminum, groups. tributylaluminum, trihexylaluminum, tridecylaluminum, That is, the above compounds includes o- or g- sub triphenylaluminum, tricyclohexylaluminum, tribenzylalu stituted acrylates, thiolacrylates, thionacrylates, dithio minum, trimethylboron, triethylboron, tributylboron, tri acrylates, acrylamide, thioacrylamide, N-substituted acryl hexylboron, diethylphenylboron, diethyl-p-tolylboron and amides, N-substituted thioacrylamides, N,N-disubstituted 20 tricyclohexylboron. The compounds having the formula acrylamides, N,N-disubstituted thioacrylamides, acryloyl M'X's include aluminum trichloride, aluminum tribro halides, thioacryloyl halides, acrylic acid, thiolacrylic mide, aluminum triiodide, partially fluorinated aluminum acid, thionacrylic acid, dithioacrylic acid, salts of these chloride, boron trichloride, boron trifluoride, boron tri acids, acrolein, unsaturated ketones, and acrylonitrile. bromide and boron triiodide. Concretely, examples of these compounds are methyl 25 The organic compounds of metals of Group IIb, IIIb methacrylate, ethyl methacrylate, propyl methacrylate, or IVb of the Mendeleev's Periodic Table which are used butyl methacrylate, octyl methacrylate, octadecyl meth as the catalysts of item (2) are those having, as metal acrylate, benzyl methacrylate, phenyl methacrylate, tolyl components thereof, zinc, cadmium, mercury, boron, alu methacrylate, cyclohexyl methacrylate, 2 - chloroethyl minum, gallium, indium, thallium, germanium, tin and methacrylate, methyl thiolmethacrylate, ethyl thiolmeth 30 lead. Particularly, the metal components of zinc, boron, acrylate, methyl ox-ethylacrylate, ethyl ox-butylacrylate, aluminum and tin are frequently employed. As the or methyl ox-cyclohexylacrylate, methyl ox-phenylacrylate, ganic groups, hydrocarbon groups or substituted groups methyl ox-chloroacrylate, ethyl a-chloroacrylate, methyl thereof are preferable, and those having alkyl, alkenyl, cy-bromoacrylate, methyl ox-chloromethylacrylate, methyl aryl, aralkyl, alkylaryl or cycloalkyl groups are par o-(p-chlorophenyl) acrylate, methacrylamide, N-ethyl ticularly effective. Those organo-metallic compounds in methacrylamide, N-cyclohexyl-methacrylamide, N,N-di clude also the case where other groups than organic methyl methacrylamide, methacrylyl piperidine, ot-ethyl groups are attached to the metal. Particularly useful are acrylamide, c. - chloroacrylamide, ox - ethyl-methacryloyl organo-metallic compounds having the formula: chloride, methacrylic acid, thiomethacrylic acid, sodium methacrylate, zinc methacrylate, aluminum methacrylate, 40 ammonium ox-fluoroacrylate, methacrolein, methyl-iso wherein M' is a metal of Group IIb, IIIb or IVb of the propenyl-ketone, 1 - chloro-butenyl-ethyl-ketone, meth Mendeleev's Periodic Table; RV is a hydrocarbon group acrylonitrile, or - ethyl-acrylonitrile, ox-cyclohexyl-acrylo having 1 to 20 carbon atoms or a substituted hydrocarbon nitrile, a-chloroacrylonitrile, ox-chloromethyl acrylonitrile, group thereof; p is the valency of the metal; and n is an methyl crotonate, ethyl crotonate, butyl crotonate, phenyl 45 arbitrary number of 1 to p. The organo-metallic com crotonate, cyclohexyl crotonate, crotonamide, crotonic pounds are particularly effective when n=p. Of course, acid chloride, crotonitrile, methyl cinnamate, ethyl cin other organic compounds of metals of Group IIb, IIIb or namate, butyl cinnamate, chloromethyl cinnamate, cin IVb of the Mendeleev's Periodic Table may also be used, namic nitrile, methyl (3-ethyl acrylate and methyl 3-chloro if necessary. These compounds include, for example, di methyl acrylate. 50 ethylzinc, ethylzinc chloride, diethylcadmium, diethyl The catalyst components to be used in the process of mercury, diphenylmercury, triethylboron, tributylboron, the present invention are (1) compounds having the tricyclohexylboron, ethylboron bromide, triethylalu formula MR'X, M'RTV or M'X' wherein M, M minum, tributylaluminum, trihexylaluminum, tricyclo and M' are aluminum or boron; R'' and RV are organic heXylaluminum, vinyldiethylaluminum, diethylaluminum radicals; X and X’ are halogen atoms; and n is an arbitrary 55 chloride, ethylaluminum sesquichloride, ethylaluminum, number of 1 to 2, or (2) (a) organic compounds of dichloride, trimethylgallium, triethylgallium, triethylindi metals of Group IIb, IIIb or IVb of the Mendeleev's um, tetraethylgermanium, tetramethyltin, tetraethyltin, Periodic Table and (b) halides of metals of Group IIIb tetraisobutyltin dimethyldiethyltin, tetraphenyltin, tetra or IVb of the Periodic Table. benzyltin, diethyldiphenyltin, triethyltin chloride, diethyl In the aluminum or boron compounds having the 60 tin dichloride, ethyltin trichloride, tetramethyllead, tetra formula MR'X - MRIV or M'X', R'' and RV are ethyllead, dimethyl-diethylead and triethyllead chloride. preferably hydrocarbon radicals having 1 to 20 carbon On the other hand, the metal halides to be employed atoms, or inert substituted groups thereof may be effec are halides of metals of Group IIIb or IVb of the tively used. For example, compounds having alkyl, Mendeleev's Periodic Table and include, for example, alkenyl, aryl, aralkyl, alkylaryl or cycloalkyl groups are 65 compounds of boron, aluminum, gallium, indium, thal particularly effective. Examples thereof are methyl, ethyl, lium, germanium, tin and lead. As the halogen, any of propyl, butyl, hexyl, octyl, decyl, dodecyl, stearyl, phenyl, chlorine, bromine, iodine and fluorine are used. As these tolyl, naphthyl, benzyl, cyclopentadienyl and cyclohexyl. metal halides, those having other groups than halogen As the X and X, there are used chlorine, bromine, iodine may also be used. Particularly useful metal halides in the and fluorine. 70 process of the present invention are compounds having the Concretely, compounds having the formula MR'Xa-n formula include, for example, methylaluminum dichloride, ethyl aluminum dichloride, isobutylaluminum dichloride, hexyl MIV 'mRV-m aluminum dichloride, dodecylaluminum dichloride, phen wherein MIV is a metal of Group IIIb or TVb of the ylaluminum dichloride, cyclohexylaluminum dichloride, 5 Mendeleev's Periodic Table; X' is a halogen atom; RIV 3,629,215 7 8 is a hydrocarbon group having 1 to 20 carbon atoms or a ponents can be effectively used even at higher or lower substituted hydrocarbon group thereof; q is the valency concentraitons than above. Generally speaking, desirable of the metal; and m is an arbitrary number of 1 to q. results are obtained by contacting and coordinating the Generally, favorable results are easily obtained when halogen-containing metal compound with the substituted m= q. Of course, other halides of metals of Group IIIb conjugated vinyl compound in such a state that no oxygen or IVb of the Mendeleev's Periodic Table may also be or organic peroxide is present. Depending on the condi used, if necessary. Examples of metal halides useful for itons, however, the catalyst components may be added the process of the present invention are boron trichloride, later to the monomer mixture. boron trifluoride, boron tribromide, boron triiodide, ethyl As the polymerization temperature, there may be boron dichloride, diethylboron chloride, aluminum tri 10 selected any temperature ranging from such a low tem chloride, aluminum tribromide, aluminum triiodide, perature as -150° C. to such a temperature as -- 100° C. partially fluorinated aluminum chloride, ethylaluminum The copolymerization reaction in accordance with the dichloride, methylaluminum dibromide, ethylaluminum process of the present invention quickly progresses even sesquichloride, diethylaluminum chloride, gallium tri at markedly low temperatures. This fact suggests that the chloride, gallium dichloride, germanium tetrachloride, tin activation energy is markedly small. tetrachloride, tin tetrabromide, tin tetraiodide, ethyltin In the practice of the process of the present invention, trichloride, methyltin trichloride, phenyltin trichloride, di bulk-polymerization can be effected in liquid monomers, methyltin dibromide, diethyltin dichloride, diisobutyltin but ordinary inert solvents may also be used. As such sol dichloride, triethyltin chloride, lead tetrachloride and di vents, there are employed for example ordinary hydro ethylead dichloride. 20 carbons or halogen-containing hydrocarbon compounds. In the catalysts of item (2), where is used the combi These solvents include, for example, propane, butane, pen nation of an organic compound of Group IIb, IIIb or IVb tane, hexane, heptane, octane, ligroin, petroleum ether, of the Mendeleev's Periodic Table and a halide of a metal other petroleum series mixed solvents, benzene, toluene, of Group IIIb or IVb of the Periodic Table, the organo xylene, cyclohexane, methyl-cyclohexane, methylene di metallic compound and the metal halide are employed chloride, ethylene dichloride, trichloroethylene, tetrachlo without previous mixing. The mixing of said components roethylene, butyl chloride, chlorobenzene and bromobenz should be effected in the presence of at least said sub ene. As has been mentioned, compounds forming stable stituted conjugated vinyl compound. Particularly favor complexes with the catalyst components are not preferable able results are obtained when the organo-metallic com as Solvents. pound is added after the substituted conjugated compound 30 After completion of the polymerization reaction, after and the metal halides have been mixed. treatments are effected according to ordinary procedures The organic peroxides to be used in the process of the to purify and recover polymerization resultants. As such present invention are the general organic compounds hav procedures there is optionally adopted, for example, alco ing peroxide linkages, and include, for example, diacyl hol treatment, alcohol-hydrochloric acid treatment, hydro peroxides, ketone peroxides, aldehyde peroxides, ether chloric acid-water treatment, or any after-treatment pro peroxides, hydroperoxides, dihydrocarbyl peroxides, per cedures employed in conventional cation polymerization acid esters, dihydrocarbyl percarbonates and percarba using Lewis acids or in polymerization using Ziegler-Natta mates. Examples of these compounds are benzoyl per type catalysts. However, it is also possible to adopt pro oxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, 4 cedures of separating and recovering catalyst components chlorobenzoyl peroxide, acetyl peroxide, stearoyl peroxide, 40 from polymerization resultants, without decomposition of phthaloyl peroxide, methylethylketone peroxide, cyclo the catalyst components, by addition of compounds form hexanone peroxide, t-butyl hydroperoxide, p-menthane ing complexes with said components. hydroperoxide, diisopropylbenzene hydroperoxide, cumene The following examples illustrate the invention further hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t in detail, but the invention is not limited thereto at all. butyl-cumyl peroxide, t-butyl perbenzoate, t-butyl periso butyrate, t-butyl peroxypivalate, phenyl percarbamate, di EXAMPLE 1. isopropyl percarbonate and t-butyl perisopropyl carbon A 200 ml. three-necked flask provided with a stirrer ate, but the compounds are not limited thereto. There is Was evacuated and flushed with nitrogen, then, was cooled observed such a tendency that the larger the rate of de to -78° C. Into the flask, 60 ml. of toluene and 3.2 g. of composition of the peroxide, the higher the promoting ac methyl methacrylate were added. To the mixture, 8 mmol. tion of it. of ethylaluminum sesquichloride (Al2EtCls, as 0.2 g/ml. In practicing the present invention, the catalyst com toluene solution) was added in nitrogen atmosphere. The ponents may be used at any proportions, but a proportion mixture was elevated in temperature to 25 C. with of 0.005-10 moles, particularly 0.02-1.5 moles, per mole thorough stirring. To the mixture, 5 g. of styrene was add of the substituted conjugated vinyl compound is frequently ed and polymerization was effected for 5 hours. After employed. Generally speaking, favorable results are liable terminating the polymerization by addition of methanol, to be obtained when the substituted conjugated vinyl com the content was charged in a large amount of methanol, pound is used in combination with a substantially equi and insolubles were recovered, were thoroughly washed molar amount of the halogen-containing metal compound. with methanol and were then dried at 50° C. under re Of course, the metal compound may be used in excess or 60 duced pressure to obtain 1.54 g. of a white solid copoly in less amount. However, in case the halogen-containing mer. This copolymer was soluble in acetone and insoluble metal component is used in excessively smaller amount in methanol and water. After reprecipitation and purifica than the substituted conjugated compound, the polymeri tion with acetone-methanol, the copolymer was dissolved zation activity is greatly lowered in some cases and there in benzene and was subjected to viscosity measurement at fore it is not desirable to make the concentration thereof 30 C. to obtain an intrinsic viscosity of 2.02 dl./g. The excessively low. Generally, at relatively low concentra results of elementary analysis of the copolymer were C: tions, it is effective to carry out the polymerization partic 76.12% and H: 7.80%, and well coincided with the calcu ularly in the presence of an organic peroxide or oxygen. lated values C: 76.40% and H: 7.90% as a 1:1 alter The effects of organic peroxide or oxygen are marked even nating copolymer. Further, the copolymer melted and at such a low temperature of -78° C., for example. Even softened at 231-233 C. and, when pressed, gave a trans when these components are used in relatively small parent film excellent in properties. The specific gravity of amounts, sufficiently high effects can be expected. For the film measured at 23° C. was 1.119. Even when the example, promoting action is observed by addition of said polymerization was effected under the same conditions components in amounts of about 0.01-5% of the sub while variously changing the proportion of monomers, the stituted conjugated vinyl compound. Of course, the com result of the elementary analysis of the product always 3,629,215 10 showed 1:1 compositions. In addition, the nuclear mag nitrogen atmosphere. To the mixture, 30 g. of vinyl chlo netic resonance spectra of the products were obviously ride and further a solution of 30 mg. of benzoyl peroxide different from the random copolymer having 1:1 mono in 20 ml. of toluene was added, with stirring. Thereafter, mer composition obtained by ordinary radical polymeriza the temperature was elevated to 0 C, and polymeriza tion, and it was clarified that the products showed the tion was effected for 24 hours to obtain 320 g. of a white characteristics of alternating copolymers. From these facts, solid copolymer. The results of elementary analysis of the it was understood that the products obtained were alternat copolymer were C: 51.80%, H: 6.73% and Cl: 21.80% ing copolymers. and well coincided with the calculated values for as alter Similar copolymers were obtained when there was used, nating copolymer C: 51.70%, H: 6.82% and Cl: 21.80%. under the same conditions, diethylboron chloride, methyl 10 Similar copolymers were obtained when, under the same aluminum sesquibromide or a mixture of trihexyl-alumi conditions, vinyl bromide, vinylidene chloride, allyl chlo num and aluminum chloride, respectively, in place of ride or 2-chloro-propene-1 was used, respectively, in the ethylaluminum sesquichloride. Further, similar results place of the vinyl chloride. were obtained in the case where p-bromostyrene or iso propenylbenzene was used, respectively, in place of the 5 EXAMPLE 6 styrene. A 200 ml. three-necked flask provided with a stirrer EXAMPLE 2 was evacuated and flushed with nitrogen and was cooled A 300 ml. autoclave with a stirrer was evacuated and to -78 C. Into the flask, 50 ml. of cyclohexane, 20 flushed with nitrogen, then was cooled to -78 C. Into mmol. of boron trichloride and 10 g. of methyl meth the autoclave, 100 g. of ethylene, 25 mmol. of ethyl 20 acrylate were added in a nitrogen atmosphere, and the aluminum sesquichloride (as 0.4 g/ml. heptane solution) compounds, were thoroughly stirred. To the mixture, 11.8 and 20 ml. of heptane were added, and the compound g. of allylbenzene and further 20 mmol. of diethylzinc were homogeneously admixed. To the mixture, 4 g. of (as 0.2 g/ml. cyclohexane solution) were added. There methyl methacrylate was added and polymerization was after, the temperature was elevated at 0° C. and polym effected with stirring for 3 hours. Thereafter, the same 25 erization was effected with stirring for 48 hours, while treatment as in Example 1 was conducted to obtain 0.35 g. injecting a nitrogen gas containing 5% of oxygen, to ob of a white solid copolymer. The infrared absorption spec tain 1.45 g. of a white solid copolymer. trum of the copolymer showed no absorption in the neigh borhood of 720 cm., and it was known that the copoly EXAMPLE 7 mer had no repetition of more than 4 methylene Se 30 A 200 ml. three-necked flask provided with a stirrer quences. This indicates the fact that no ethylene-ethylene was evacuated and flushed with nitrogen and was cooled chain exists in the copolymer, and can be evidence to to -78 C. To the flask, 20 ml. of toluene, 2.5 g. of n prove that the copolymer is an alternating copolymer. butyl methacrylate and 12.5 mmol. of ethylaluminum sesquichloride (as 0.2g./ml. toluene solution) were added EXAMPLE 3 in a nitrogen atmosphere, and the temperature was ele A 300 ml. threee-necked flask equipped with a stirrer vated to 0 C. with thorough stirring. Into the mixture, was evacuated, flushed with nitrogen and then, was cooled 15 g, of styrene was further charged, and polymeriza to -78° C. Into the flask, 30 g. of propylene and 4 g. of tion was effected at 25 C. for 5 hours to otbain 1.69 g. methyl methacrylate were added in a nitrogen atmosphere. of a white solid copolymer. The copolymer was repre To the mixture, 50 mmol. of ethylaluminum dichloride 40 cipitated and purified with acetone-methanol, was then (AlEtCl, as 0.4 g/ml. heptane solution) was added and dissolved in benzene and was subjected to viscosity meas polymerization was effected for 20 hours to obtain 0.27 urement at 30° C. to obtain an intrinsic viscosity of 2.95 g. of a white solid copolymer. This copolymer was soluble dl./g. The results of elementary analysis of the copolymer in acetone. The copolymer was reprecipitated and purified were C: 78.40% and H: 8.41%, and well coincided with with acetone-methanol, was dissolved in benzene and was the calculated value for an alternating copolymer C: subjected to viscosity measurement at 30° C. to obtain 78.01% and H: 9.00%. an intrinsic viscosity of 0.62 dll/g. The results of ele mentary analysis of the copolymer well coincided with EXAMPLE 8 the calculated values as an alternating copolymer. The co A 200 ml. three-necked flask provided with a stirrer polymer melted at 163-166° C. and gave an excellent 50 was evacuated and flushed with nitrogen, and was cooled film by hot press. The specific gravity of the copolymer to -78° C. Into the flask, 60 ml. of toluene, 3.8 g. of measured at 23° C. was 1.103. methyl ox-chloroacrylate and 8 mmol. of ethylaluminum Sesquichloride (as 0.2 g/ml. toluene solution) were EXAMPLE 4 added in a nitrogen atmosphere, and the temperature was A 300 ml. glass autoclave with stirrer was evacuated, elevated to 25 C. with thorough stirring. To the mix flushed with nitrogen and was cooled to -78 C. Into the ture, 5 g. of styrene was further charged, and polymeriza autoclave, 50 ml. of toluene, 4 g. of methyl methacrylate tion was effected at 25 C. for 2 hours to obtain 3.65 g. and 40 mmol. of tin tetrachloride (as 1.3 g. /ml. toluene of a white solid copolymer. The results of elementary solution) were added. To the mixture, 34 g. of propylene analysis of the copolymer were C: 64.30%, H: 5.99% and and 40 mmol. of triethylaluminum (as 0.2 g/ml. toluene 60 Cl: 14.15%, and well coincided with the calculated values solution) were further added. The temperature was ele for an alternating copolymer C: 64.15%, H: 5.83% and wated to 0° C. with stirring, and polymerization was Cl: 15.78%. effected for 41 hours to obtain 0.13 g. of a white Solid Similar copolymers were obtained in the case where, copolymer. under the same conditions, methyl ox-ethyl-acrylate, Similar results were obtained as well in the case where methyl cy-chloromethyl-acrylate, methyl thiomethacrylate, combinations of aluminum bromide-tributyl aluminum or ethyl methacrylate, methyl isopropenyl ketone, sodium of boron trifluoride-tetraethyl tin was used, respectively, methacrylate or methacryloyl chloride was used, respec as catalysts in place of the combination of tin tetrachlo tively, in place of the methyl ox-chloroacrylate. ride and triethyl aluminum. EXAMPLE 5 70 EXAMPLE 9 A 200 ml. of three-necked flask provided with a stirrer A 300 ml. glass autoclave provided with a stirrer was was evacuated and flushed with nitrogen, and then was cooled to -78° C. Into the autoclave, 3 g. of methyl cooled to -78° C. Into the flask, 60 ml. of toluene, 2.8 methacrylate and 12.5 mmol. of ethyl-aluminum sesqui g. of c-chloroacrylonitrile and 8 mmol. of ethylalumi chloride (as 0.2 g/ml. toluene solution) were added in a 75 num sesquichloride (as 0.2 g/ml. toluene solution) were 3,629,215 2 added in a nitrogen atmosphere, and the temperature Was ing copolymer of monomer (A) and monomer (B), elevated to 25 C. with thorough stirring. Into the mix wherein monomer (A) is an olefinic compound having ture, 5 g. of styrene was charged, and polymerization was the formula: effected for 5 hours to obtain 2.19 g. of a white solid R copolymer. The copolymer was reprecipitated and purified 5 / with acetone-methanol, was dissolved in dimethylform CH=C amide and was subjected to viscosity measurement at R2 30° C. to obtain an intrinsic viscosity of 0.20 dil./g. The wherein R1 and R2 each are a hydrogen atom or a hydro results of elementary analysis of the copolymer were C: carbon radical having 1 to 20 carbon atoms selected 69.19%, H: 5.89%, N: 7.01%, and Cl: 17.23% and well O from the group consisting of alkyl, aryl, aralkyl, alkyl coincided with the calculated value for an alternating co aryl and cycloalkyl, and wherein monomer (B) is a sub polymer C: 68.93%, H: 5.26%, N: 7.31% and Cl: stituted conjugated vinyl compound having the formula: 18.50%. RII EXAMPLE 10 RICH=CH-CSN or CH=C-CEN A 200 ml. three-necked flask provided with a stirrer wherein RI and RII represent a hydrocarbon radical hav was evacuated and flushed with nitrogen, and was cooled ing 1 to 20 carbon atoms. to -78 C. Into the flask, 60 ml. of toluene, 2.1 g. of 2. A copolymer according to claim 1, wherein R and methacrylonitrile and 8 mmol. of ethylaluminum ses RII are alkyl having 1 to 20 carbon atoms. quichloride (as 0.2 g/ml. toluene solution) in a nitrogen 3. A copolymer according to claim 1, wherein R and atmosphere, and the temperature was elevated to 25 C. 20 RII are aryl, aralkyl, alkylaryl or cycloalkyl having 1 Into the mixture, 5 g. of styrene was further charged, to 20 carbon atoms. and polymerization was effected at 25 C. for 18 hours 4. A copolymer consisting essentially of a 1:1 alter to obtain 0.36 g. of a white solid copolymer. The co nating copolymer of monomer (A) and monomer (B), polymer was reprecipitated and purified with acetone 25 wherein monomer (A) is an olefinic compound having methanol, was dissolved in dimethylformamide and was the formula: subjected to viscosity measurement at 30° C. to obtain an intrinsic viscosity value of 0.54 d./g. The results of R1 elementary analysis of the copolymer were C: 84.26%, H: 7.92% and N: 8.19%, and well coincided with the 30 R2 calculated values of an alternating copolymer C: 84.17%, wherein R1 and R2 each are a hydrogen atom or a hydro H: 7.65% and N: 8.18%. The copolymer melted at carbon radical having 1 to 20 carbon atoms Selected from 160-165 C. and, when pressed, gave a film. The specific the group consisting of alkyl, aryl, aralkyl, alkylaryl and viscosity of the film measured at 23° C. was 1.0215. cycloalkyl, and wherein monomer (B) is a Substituted EXAMPLE 11 conjugated vinyl compound having the formula: A 200 ml. three-necked flask provided with a stirrer RII was evacuated and flushed with nitrogen and was cooled to -78. C. Into the flask, 10 ml. of toluene, 4.3 g. of RICH=CH-CEN or CH=C-CeN methacrylamide and 12.5 mmol. of ethylaluminum ses 40 wherein RI and RTI represent a halogen-containing hydro quichloride (as 0.2 g/ml. toluene solution) were added carbon radical having 1 to 20 carbon atoms or a halogen in a nitrogen atmosphere, and the temperature was ele aton. vated to 0°C. To the mixture, 5.2 g. of styrene Was 5. A copolymer according to claim 4, wherein R and further added, and polymerization was effected at 0° C. RI are a halogen atom or halogen substituted alkyl, for 22 hours to obtain 1.27 g. of a copolymer. aryl, aralkyl, alkylaryl or cycloalkyl having 1 to 20 car EXAMPLE 12 bon atoms. A 200 ml. three-necked flask provided with a stirrer 6. A copolymer consisting essentially of a 1:1 alter was evacuated and flushed with nitrogen and was cooled nating copolymer of monomer (A) and monomer (B), to -15° C. Into the flask, 40 ml. of heptane, 5 g. of wherein (A) is an olefinic compound having the formula: methyl crotonate and 50 mmol. of ethylaluminum dichlo R1 ride (as 0.4 g. /ml. heptane solution) were added in a / nitrogen atmosphere. Into the mixture, propylene was CH=C injected, and reaction was effected at -15° C. for 2 hours R2 to obtain 0.18 g. of a white solid copolymer. After purifi wherein R1 and R2 are a hydrogen atom, a halogen atom cation, the copolymer showed an intrinsic viscosity of 5 5 or a halogen-containing hydrocarbon radical having 1 to 0.26 d1./g. when measured at 30° C. in benzene solu 20 carbon atoms wherein the hydrocarbon portion there tion. The results of elementary analysis of the copoly of is selected from the group consisting of alkyl, aryl, mer were C.: 67.99% and H: 10.60%, and well coincided aralkyl, alkylaryl and cycloalkyl, provided that both R1 with the calculated values for an alternating copolymer, and R2 are not hydrogen at the same time, and wherein C: 67.57% and H: 99.92%. 60 monomer (B) is a substituted conjugated vinyl com EXAMPLE 1.3 pound having the formula: A 200 ml, three-necked flask provided with a stirrer RII was evacuated and flushed with nitrogen and was cooled RICH=CH-CN or CH-scC-CEN to -78° C. To the flask, 30 ml. of toluene, 10 g. of methyl cinnanate and 25 mmol. of ethylaluminum Ses wherein RI and RII represent a hydrocarbon radical hav quichloride were added, and the temperature was ele ing 1 to 20 carbon atoms, a halogen-containing hydro wated to 25° C. To the mixture, 20 g. of styrene was carbon radical having 1 to 20 carbon atoms or a halogen added, and polymerization was effected at 25 C. for 54 atom. hours to obtain 0.41 g. of a white Solid copolymer. After 7. A copolymer according to claim 6, wherein RI and purification, the copolymer showed an intrinsic viscosity R are a halogen atom or unsubstituted or halogen-sub of 0.66 dl./g. when measured at 30° C. in benzene Solu stituted alkyl, aryl, aralkyl, alkylary or cycloalkyl having tion. 1 to 20 carbon atoms. We claim: 8. A copolymer consisting essentially of a 1:1 alter i. A copolynner consisting essentially of a 1:1 alternat nating copolymer of monomer (A) and monomer (B). 3,629,215 3 4. wherein monomer (A) is an olefinic compound having the group, wherein Y is ZPH, Z2R, -Z2}Me, NR'R'', R, a formula: halogen atom or a hydrogen atom; in which Z1 and Z2 R1 each is an oxygen or a sulfur atom; R is a hydrocarbon or / halohydrocarbon radical having 1 to 20 carbon atoms; CH=C R and R' each represents a hydrogen atom or hydro R2 carbon or halohydrocarbon radical having 1 to 20 carbon wherein R and Reach are a hydrogen atom, a halogen atoms, including the case where R' and R'' are mutually atom, a hydrocarbon radical having 1 to 20 carbon atoms bonded at other portion than nitrogen; and Me represents selected from the group consisting of alkyl, aryl, aralkyl, an element of Groups I to III of Mendeleev's Periodic O Table, wherein k is equal to the valency of Me, or an am alkylaryl and cycloalkyl or a halogen-containing hydro monium group. carbon radical having 1 to 20 carbon atoms wherein the 1. A copolymer according to claim wherein mono hydrocarbon portion thereof is selected from the group ner (B) is methacrylonitrile. consisting of alkyl, aryl, aralkyl, alkylary and cyclo 12. A copolymer according to claim 1 wherein mono alkyl; and wheerin monomer (B) is a substituted conju mer (B) is g-ethylacrylonitrile. gated vinyl compound having the formula: 13. A copolymer according to claim 3 wherein mono RII mer (B) is a-cyclohexyl-acrylonitrile. 14. A copolymer according to claim 4 wherein mono RICH=CH-Q or CH-C-Q mer (B) is o-chloroacrylonitrile or a-chloromethyl acryl 20 onitrile. wherein RI and RTI represent a hydrocarbon radical hav 15. An alternating copolymer according to claim 6 ing 1 to 20 carbon atoms, a halogen-containing hydro Wherein monomer (B) is methacrylonitrile, o-ethyl-acryl carbon radical having 1 to 20 carbon atoms or a halogen onitrile, c-cyclohexyl-acrylonitrile, c-chloroacrylonitrile atom, and Q is a or c-chloromethyl acrylonitrile. 25 16. An alternating copolymer according to claim 8 wherein monomer (B) is a conjugated vinyl compound group, wherein Y is Z2H, Z2R-Z29.Me, NR'R'', R, a Substituted in the c- or g-position with a radical selected halogen atom or a hydrogen atom; in which Z and Z from the class consisting of a hydrocarbon radical having each is an oxygen or a sulfur atom; R is a hydrocarbon 1 to 20 carbon atoms, a halogen-containing hydrocarbon or halohydrocarbon radical having 1 to 20 carbon atoms; 30 radical having 1 to 20 carbon atoms and a halogen atom R and R' each represents a hydrogen atom or hydro and wherein Said conjugated vinyl compound is selected carbon or halohydrocarbon radical having 1 to 20 carbon from the group consisting of an acrylate, a thiolacrylate, atoms, including the case where R and R'' are mutually a thionacrylate, a dithioacrylate, an acrylamide, a thio bonded at other portion than nitrogen; and Me represents acrylamide, an N-substituted acrylamide, an N-substituted an element of Groups I to III of Mendeleev's Periodic 35 thioacrylamide, an N,N-disubstituted acrylamide, an N,N- Table, wherein k is equal to the valency of Me, or an disubstituted thioacrylamide, an acryloyl halide, a thio ammonium group. acryloyl halide, an acrylic acid, a thiolacrylic acid, a thion 9. An alternating copolymer according to claim 8, acrylic acid, a dithioacrylic acid, Groups I to III metal wherein RI and RTI are a halogen atom or unsubstituted Salts or ammonium salts of said acids, acrolein, and an or halogen-substituted alkyl, aryl, aralkyl, alkylary or 40 unsaturated ketone. cycloalkyl having 1 to 20 carbon atoms; wherein R is an 17. An alternating copolymer according to claim 8, unsubstituted or halogen substituted alkyl, aryl, aralkyl, wherein said Substituted conjugated vinyl compound is alkylaryl or cycloalkyl having 1 to 20 carbon atoms; and a conjugated vinyl compound having a group in the o wherein R and R' are unsubstituted or halogen-Sub or g-position selected from the class consisting of a hydro stituted alkyl, aryl, aralkyl, alkylaryl or cycloalkyl having 45 carbon group having 1 to 20 carbon atoms, a halogen 1 to 20 carbon atoms or a hydrogen atom. containing hydrocarbon group having 1 to 20 carbon 10. A copolymer consisting essentially of a 1:1 alter atoms, and a halogen atom and wherein said conjugated nating copolymer of monomer (A) and monomer (B), vinyl compound is selected from the group consisting of wherein monomer (A) is an olefinic compound having an acrylate, a thiolacrylate, acrylamide, an N-substituted the formula: 50 acrylamide, an N,N-disubstituted acrylamide, an acryloyl R1 halide, an acrylic acid, a thiolacrylic acid, Groups I to III / metal Salts or ammonium salts of said acids, acrolein CH=C and an unsaturated ketone. R2 18. An alternating copolymer according to claim 8 55 wherein monomer (B) is selected from the group con wherein R1 and R2 each are a hydrogen atom, a halogen sisting of methyl methacrylate, ethyl methacrylate, atom, a hydrocarbon radical having 1 to 20 carbon atoms propyl methacrylate, butyl methacrylate, octyl methacry selected from the group consisting of alkyl, aryl, aralkyl, late, octadecyl methacrylate, benzyl methacrylate, phen alkylaryl and cycloalkyl or a halogen-containing hydro yl methacrylate, tolyl methacrylate, cyclohexyl methac carbon radical having 1 to 20 carbon atoms wherein the 60 rylate, 2-chloroethyl methacrylate, methyl thiolmethac hydrocarbon portion thereof is selected from the group rylate, ethyl thiolmethacrylate, methyl cy-ethylacrylate, consisting of alkyl, aryl, aralkyl, alkylaryl and cycloalkyl, ethyl ox-butylacrylate, methyl ox-cyclohexylacrylate, meth and wheerin monomer (B) is a substituted conjugated yl ox-phenylacrylate, methyl ox-chloroacrylate, ethyl vinyl compound having the formula: C - chloroacrylate, methyl C. - bromoacrylate, methyl a 65 chloromethylacrylate, methyl ox-(p-chlorophenyl) acry RII late, methacrylamide, N-ethyl methacrylamide, N-cyclo hexyl-methacrylamide, N,N - dimethyl methacrylamide, RICH=CH-Q or CH-C-Q methacrylyl piperidine, co-ethyl-acrylamide, cy-chloroac wherein R and RTI represent a hydrocarbon radical hav rylamide, ox-ethyl-methacryloyl chloride, methacrylic ing 1 to 20 carbon atoms, a halogen-containing hydrocar 70 acid, thiolmethacrylic acid, sodium methacrylate, zinc bon radical having 1 to 20 carbon atoms or a halogen methacrylate, aluminum methacrylate, ammonium cy atom; and Q is a nitrile or fluoroacrylate, methacrolein, methyl-isopropenyl-ketone, 1-chloro-butenyl-ethyl-ketone, methyl crotonate, ethyl Crotonate, butyl crotonate, phenyl crotonate, cyclohexyl 75 Crotonate, crotonamide, crotonic acid chloride, cro 3,629,215 15 16 tonitrile, methyl cinnamate, ethyl cinnamate, butyl cin about -150° C. to about 100° C. monomer (A) and namate, chloromethyl cinnamate, cinnamic nitrile, meth monomer (B) defined in claim 8 with (1) an organo yl (3-ethyl acrylate and methyl 6-chloromethyl acrylate. metal halide having the formula: 19. An alternating copolymer according to claim 8 wherein R and R are a hydrogen atom, a halogen atom, or an unsubstituted or halogen-substituted alkyl, aryl, wherein M is aluminum or boron; R' is a hydrocarbon aralkyl, alkylaryl or cycloalkyl having 1 to 20 carbon radical having 1 to 20 carbon atoms; X is a halogen atomS. atom; and n is an arbitrary number of from 1 to 2, or 20. An alternating copolymer according to claim 8 with a mixture of at least two compounds having the wherein monomer (A) is selected from the group con IO following formulae: sisting of ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1, heptene-1, octene-1, 2-methyl (A) MR'X' (B) MRIV and (C) M'X'. butene-1, 3 - methyl-butene - 1, 2-methyl-pentene-1, 4 methyl-pentene - 1, 4 - methyl-hexene-1, decene-1, do wherein M, M' and M'' each represents aluminum or decene-1, octadecene-1, 4-phenyl-butene-1, styrene, ox boron; R'' and RV each represents a hydrocarbon methyl-styrene, a - butyl-styrene, p - methyl-styrene, radical having 1 to 20 carbon atoms; X and X’ each rep m-methyl-styrene, vinyl-cyclobutane, vinyl-cyclohexane, resents a halogen atom; and n is an arbitrary number isopropenyl-benzene, vinyl-naphthalene, 1-methylene-cy from 1 to 2, or with a catalyst (2) comprising component clobutane and alkyl-benzene, vinyl chloride, vinyl bro (a) an organo-compound having the formula: mide, vinyl iodide, allyl chloride, allyl bromide, allyl 20 iodide, 4-chloro-butene-1, 4,44 - trichloro-butene-1, p M'RV,X"-n chloro-styrene, o - chloro-styrene, m-bromo-styrene, p wherein M' is a metal of Group IIb, IIIb, or IVb of iodo-styrene, p - fluoro-styrene, 4 - chloro-vinyl-cyclo Mendeleev's Periodic Table; RV is a hydrocarbon group hexane, p-chloro-allyl-benzene, 2,4 - dichloro-styrene, having 1 to 20 carbon atoms; p is the valency of the 2,6 - dichlorostyrene, 2,4 - difluoro-styrene, 3-trifluoro 25 metal; and n is an arbitrary number of 1 to p, and com methyl-styrene, 4-chloro-1-vinyl-naphthalene, vinylidene ponent (b) a halogeno-compound having the formula: chloride, vinylidene bromide, 2-chloro-propene-1, 1-bro mo-1-chloro-ethylene, 2-chloro-allyl chloride, methallyl www. chloride and 1,1-bis(p-chlorophenyl)-ethylene. MTVX"RV'm 2i. An alternating copolymer according to claim 8 30 wherein MIV is a metal of Group IIIb or IVb of the wherein said monomer (A) is selected from the group Periodic Table; X' is a halogen atom; RVT is a hydro consisting of propylene, isobutylene, Styrene, vinyl ha carbon group having 1 to 20 carbon atoms; q is the lide and vinylidene halide. valency of the metal; and m is an arbitrary number of 22. An alternating copolymer according to claim 8 1 to q, provided that the metal of at least one of com wherein said monomer (A) is selected from the group ponents (a) and (b) is aluminum or boron, provided consisting of propylene, isobutylene, styrene, a vinyl ha that components (a) and (b) are different and provided lide and a vinylidene halide, and said monomer (B) is a that catalyst component (a) is contacted with catalyst conjugated vinyl compound substituted in the a- or (3- component (b) in the presence of at least the conjugated position by a radical selected from the group consisting vinyl compound monomer of Group (B). of methyl, ethyl, phenyl, chloromethyl, 2-chloroethyl, 40 27. A process for producing an alternating copolymer, chlorine and bromine, and wherein said conjugated which comprises contacting at a temperature of from vinyl compound is selected from the group consisting of about -150° C. to about --100° C. monomer (A) and an acrylate, an acrylamide, and acrylic acid. monomer (B) as defined in claim 8 with a catalyst (1) an 23. An alternating copolymer according to claim 22 organo-metal halide having the formula: wherein the monomer (B) is a methacrylate, an ox-chloro acrylate, methacrylic acid, a methacrylamide, an o chloromethyl acrylate, a crotonate or a cinnamate. 24. An alternating copolymer according to claim 9 wherein M is aluminum or boron; R' is a hydrocarbon wherein R and R2 each are a hydrogen atom, a halogen radical of 1 to 20 carbon atoms; X is a halogen atom; and atom, or an unsubstituted or halogen-substituted alkyl, n is an arbitary number of from 1 to 2, or with a catalyst aryl, aralkyl, alkylaryl or cycloalkyl having 1 to 20 car (2) comprising bon atoms. 25. An alternating copolymer according to claim 18 M'RVX p-n wherein monomer (A) is selected from the group con wherein M' is a metal of Group IIb, IIIb or TVb of sisting of ethylene, propylene, butene-1, isobutene, pen 55 Mendeleev's Periodic Table; RV is a hydrocarbon group tene-1, hexene-1, heptene-1, octene-1, 2-methyl-butene having 1 to 20 carbon atoms; p is the valency of the metal; 1, 3-methyl-butene-1, 2 - methyl-pentene-1, 4 - methyl and n is an arbitrary number of 1 to p, and component pentene-1, 4 - methyl-hexene-1, decene-1, dodecene-1, (b) a halogeno-compound having the formula: octadecene-1, 4-phenyl-butene-1, styrene, cy-methyl-sty rene, cy-butyl-styrene, p-methyl-styrene, m-methyl-sty 60 rene, vinyl-cyclobutane, vinyl-cyclohexane, isopropenyl benzene, vinyl-naphthalene, 1 - methylene-cyclobutane wherein MIV is a metal of Group IIIb or IVb of the and allyl-benzene, vinyl chloride, vinyl bromide, vinyl Periodic Table; X' is a halogen atom; RV is a hydro iodide, allyl chloride, allyl bromide, allyl iodide, 4 carbon group having 1 to 20 carbon atoms; q is the va chloro-butene-1, 4,44 - trichloro-butene-1, p-chloro-sty 65 lency of the metal; and m is an arbitrary number of 1 to rene, o-chloro-styrene, m-bromo-styrene, p-iodo-styrene, q, provided that the metal of at least one of components p-fluoro-styrene, 4-chlorovinyl-cyclohexane, p-chloro-al (a) and (b) is aluminum or boron, provided that com lyl-benzene, 2,4-dichloro-styrene, 2,6 - dichloro-styrene, ponents (a) and (b) are different, and provided that 2,4-difluoro-styrene, 3-trifluoromethyl-styrene, 4-chloro catalyst component (a) is contacted with catalyst compo 1-vinyl-naphthalene, vinylidene chloride, vinylidene bro 70 nent (b) in the presence of at least the conjugated vinyl mide, 2-chloro-propene-1, 1-bromo-1-chloro-ethylene, 2 compound monomer of Group (B). chloro-allyl chloride, methallyl chloride, and 1,1-bis(p- 28. A process for producing an alternating copolymer, chlorophenyl)-ethylene. which comprises contacting at a temperature of from 26. A process for producing an alternating copolymer, about -150° C. to about --100° C. monomer (A) and which comprises contacting at a temperature of from 75 monomer (B) defined in claim 8 with an organo-metal 3,629,215 17 18 halide selected from the group consisting of the aluminum a hydrocarbon medium or a halogen-containing hydro and boron compounds having the formula: carbon medium. 32. A process according to claim 26, wherein the cata lyst component is used at a proportion of 0.005 to 10 wherein M is aluminum or boron; R' is a hydrocarbon moles per mole of the substituted conjugated vinyl com radical having 1 to 20 carbon atoms; X is a hologen atom; pound. and n is an arbitrary number of from 1 to 2. 33. A process according to claim 26, wherein the 29. A process for producing an alternating copolymer, halogen-containing metal compound is used in an amount which comprises contacting the olefinic compound and substantially equimolar to the amount of the conjugated the substituted conjugated vinyl compound defined in O OOle. claim 8 with a catalyst comprising component (a) an 34. A process for producing an alternating copolymer, organo-compound having the formula: which comprises contacting at a temperature of from about -150° C. to about --100° C. monomer (A) and monomer (B) defined in claim 8 with an organometal wherein M' is a metal of Group IIb, IIIb or IVb of 15 halide selected from the group consisting of alkylalumi Mendeleev's Periodic Table; RV is a hydrocarbon group num dihalide, alkylaluminum sesquihalide, dialkylalumi having 1 to 20 carbon atoms; n is the valency of the num halide, alkylboron, dihalide and dialkylboron halide. metal, and component (b) a halogeno-compound having 35. A process according to claim 26 wherein the com the formula: pound of the formula MR'X3 is selected from the MIVX' m group consisting of methylaluminum dichloride, ethyl wherein MTV is a metal of Group IIIb or IVb of the aluminum dichloride, isobutylaluminum dichloride, hex Periodic Table; X' is a halogen atom; and n is the va ylaluminum dichloride, dodecylaluminum dichloride, lency of the metal, provided that the metal of at least phenylaluminum dichloride, cyclohexylaluminum dichlo one of the components (a) and (b) is aluminum or boron, ride, methylaluminum dibromide, ethylaluminum diio and provided that the catalyst component (a) is contacted 25 dide, allylaluminum dichloride, ethylaluminum sesqui with catalyst component (b) in the presence of at least chloride, ethylaluminumsesquibromide, ethylaluminum the conjugated vinyl compound monomer of Group (B). sesquifluoride, methylaluminum sesquichloride, diethyl 30. A process for producing an alternating copolymer, aluminum chloride, diethylaluminum fluoride, ethylphen which comprises contacting at a temperature of from ylaluminum chloride, dicyclohexylaluminum chloride, about -150° C. to about --100° C. in the presence of 30 methylboron dichloride, ethylboron dichloride, ethyl from about 0.01% to about 5% of oxygen or an organic boron diiodide, butylboron dichloride, hexylboron di peroxide based on the conjugated monomer, the olefinic chloride, dodecylboron dichloride, phenylboron dichlo compound and the substituted conjugated vinyl compound ride, benzylboron dichloride, cyclohexylboron dichloride, defined in claim 8 wherein Q is a nitrile or said diethylboron chloride, diethylboron bromide, dipropyl 35 boron chloride, dibutylboron chloride, dihexylboron chlo ride, ethylvinylboron chloride and dicyclopentadienyl boron chloride, wherein the compound of the formula MRIV is selected from the group consisting of trimethyl group with (1) an organo-metal halide having the for aluminum, triethylaluminum, tripropylaluminum, tribut mula: 40 ylaluminum, trihexylaluminum, tridecylaluminum, tri phenylaluminum, tricyclohexylaluminum, tribenzylalu wherein M is aluminum or boron; R' is a hydrocarbon minum, trimethylboron, triethylboron, tributylboron, tri radical having 1 to 20 carbon atoms; X is a halogen atom; hexylboron, diethylphenylboron, diethyl-p-tolylboron and and n is an arbitrary number of from 1 to 2, or with a tricyclohexylboron; wherein the compound of the formula 45 M'X' is selected from the group consisting of aluminum mixture of at least two compounds having the following trichloride, aluminum tribromide, aluminum triiodide, formulae: partially fluorinated aluminum chloride, boron trichlo (A) MR'X (B) MRIV and (C) M'X's ride, boron trifluoride, boron tribromide and boron tri wherein M, M' and M'' each represents aluminum or iodide; wherein the compound of the formula boron; R'' and RIV each represents a hydrocarbon radical 50 having 1 to 20 carbon atoms: X and X’ each represents a halogen atom; and n is an arbitrary number of from 1 to is selected from the goup consisting of diethylzinc, ethyl 2, or with a catalyst (2) comprising an organo-compound zinc chloride, diethylcadmium, diethylmercury, diphenyl having the formula: mercury, triethylboron, tributylboron, tricyclohexylboron, ethylboron bromide, triethylaluminum, tributylaluminum, trihexylaluminum, tricyclohexylaluminum, vinyldiethyl wherein M' is a metal of Group IIb, IIIb or IVb of aluminum, diethylaluminum chloride, ethylaluminum ses Mendeleev's Periodic Table; RV is a hydrocarbon group quichloride, ethylaluminum dichloride, trimethylgallium, having 1 to 20 carbon atoms; p is the valency of the metal; triethylgallium, triethylindium, tetraethylgermanium, tet and n is an arbitrary number of 1 to p, and component 60 ramethyltin, tetraethyltin, tetraisobutyltin, dimehyldieth (b) a halogeno-compound having the formula: yltin, tetraphenyltin, tetrabenzyltin, diethyldiphenylin, tri ethyltin chloride, diethyltin dichloride, ethyltin trichlo wherein MIV is a metal of Group IIIb or IVb of the ride, tetramethyllead, tetraethyllead, dimethyl-diethyllead Periodic Table; X' is a halogen atom; RV is a hydro 65 and triethyllead chloride; and wherein the compound of carbon group having 1 to 20 carbon atoms; q is the va the formula MTVX'RV is selected from the group lency of the metal; and n is an arbitrary number of 1 to consisting of boron trichloride, boron trifluoride, boron a, provided that the metal of at least one of components tribromide, boron triiodide, ethylboron dichloride, di (a) and (b) is aluminum or boron, provided components ethylboron chloride, aluminum trichloride, aluminum tri (a) and (b) are different and provided that catalyst com 7) bromide, aluminum triiodide, partially fluorinated alumi ponent (a) is contacted with catalyst component (b) in num chloride, ethylaluminum dichloride, methylalumi the presence of at least the conjugated vinyl compound num dibromide, ethylaluminum sesquichloride, diethyl monomer of Group (B). aluminum chloride, gallium trichloride, gallium dichlo 31. A process according to claim 26, wherein the co ride, germanium tetrachloride, tin tetrachloride, tin tetra polymerization reaction is effected in a liquid monomer, 75 bromide, tin tetraiodide, ethyltin trichloride, methyltin 3,629,215 19 20 trichloride, phenyltin trichloride, dimethyltin dibromide, having 1 to 20 carbon atoms; X and X’ each represents a diethyltin dichloride, diisobutyltin dichloride, triethyltin halogen atom; and n is an arbitrary number from 1 to 2, chloride, lead tetrachloride and diethylead dichloride. or with a catalyst (a) comprising component (a) an 36. A process according to claim 30 wherein said or organo-compound having the formula: ganic peroxide is selected from the group consisting of diacyl peroxides, ketone peroxides, aldehyde peroxides, ether peroxides, hydroperoxides, dihydrocarbyl peroxides, wherein M' is a metal of Group IIb, IIIb, or IVb of peracid esters, dihydrocarbyl percarbonates and percar Mendeleev's Periodic Table; RV is a hydrocarbon group bamates. having 1 to 20 carbon atoms; p is the valency of the 37. A process according to claim 36 wherein said or IO metal; and n is an arbitrary number of 1 to p, and com ganic peroxide is selected from the group consisting of ponent (b) a halogeno-compound having the formula: benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, acetyl peroxide, ste aroyl peroxide, phthaloyl peroxide, methylethylketone where MIV is a metal of Group IIIb or IVb of the Peri peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, odic Table; X' is a halogen atom; RVI is a hydrocarbon p-menthane hydroperoxide, diisopropylbenzene hydro group having 1 to 20 carbon atoms; q is the valency of peroxide, cumene hydroperoxide, di-t-butyl peroxide, di the metal; and m is an arbitrary number of 1 to q, pro cumyl peroxide, t-butyl-cumyl peroxide, t-butyl perbenzo vided that the metal of at least one of components (a) ate, t-butyl perisobutyrate, t-butyl peroxypivalate, phenyl and (b) is aluminum or boron, provided that compo percarbamate, diisopropyl percarbonate and t-butyl per 20 nents (a) and (b) are different and provided that cata isopropyl carbonate. lyst component (a) is contacted with catalyst component 38. A process for producing an alternating copolymer, (b) in the presence of at least the conjugated vinyl com which comprises contacting at a temperature of from pound monomer of Group (B). about -150° C. to about 100° C. monomer (A) and 40. A process for producing an alternating copoly monomer (B) defined in claim 1 with (1) an organo 25 mer, which comprises contacting at a temperature of metal halide having the formula: from about -150° C. to about 100° C. monomer (A) and monomer (B) defined in claim 6 with (1) an organo MR p nXan metal halide having the formula: (wherein M is aluminum or boron; R' is a hydrocarbon radical having 1 to 20 carbon atoms; X is a halogen atom; 30 and n is an arbitrary number of from 1 to 2, or with a wherein M is aluminum or boron; R' is a hydrocarbon mixture of at least two compounds having the following radical having 1 to 20 carbon atoms; X is a halogen atom; formulae: and n is an arbitrary number of from 1 to 2, or with a mixture of at least two compounds having the following (A) MR'X (B) MRIV and (C) M'X'. 35 formulae: wherein M, M' and M'' each represents aluminum or boron; R'' and RV each represents a hydrocarbon radi (A) MR'X (B) MRIV and (C) M'X'. cal having 1 to 20 carbon atoms; X and X’ each repre wherein M, M and M'' each represents aluminum or Sents a halogen atom; and n is an arbitrary number from boron; R'' and RW each represents a hydrocarbon radi 1 to 2, or with a catalyst (a) comprising component (a) cal having 1 to 20 carbon atoms; X and X’ each repre an organo-compound having the formula: sents a halogen atom; and n is an arbitrary number from M'RV,X' 1 to 2, or with a catalyst (a) comprising component (a) wherein M' is a metal of Group IIb, IIIb or IVb of an organo-compound having the formula: Mendeleev's Periodic Table; RV is a hydrocarbon group having 1 to 20 carbon atoms; p is the valency of the 45 metal; and n is an arbitrary number of 1 to p, and com wherein M' is a metal of Group IIb, IIIb, or IVb of ponent (b) a halogeno-compound having the formula: Mendeleev's Periodic Table; RV is a hydrocarbon group having 1 to 20 carbon atoms; p is the valency of the metal; and n is an arbitrary number of 1 to p, and com where MV is a metal of Group IIIb or IVb of the Peri 50 ponent (b) a halogeno-compound having the formula: odic Table; X' is a halogen atom; RVI is a hydrocarbon group having 1 to 20 carbon atoms; q is the valency of the metal; and m is an arbitrary number of 1 to q, pro vided that the metal of at least one of components (a) where MTV is a metal of Group IIIb or IVb of the Peri and (b) is aluminum or boron, provided that components odic Table; X' is a halogen atom; RVI is a hydrocarbon (a) and (b) are different and provided that catalyst con group having 1 to 20 carbon atoms; q is the valency of ponent (a) is contacted with catalyst component (b) in the metal; and m is an arbitrary number of 1 to q, pro the presence of at least the conjugated vinyl compound vided that the metal of at least one of components (a) monomer of Group (B). and (b) is aluminum or boron, provided that components 39. A process for producing an alternating copoly 60 (a) and (b) are different and provided that catalyst mer, which comprises contacting at a temperature of component (A) is contacted with catalyst component (b) from about -150° C. to about 100° C. monomer (A) in the presence of at least the conjugated vinyl com and monomer (B) defined in claim 4 with (1) an organo pound monomer of Group (B). metal halide having the formula: 41. A process for producing an alternating copolymer, 65 which comprises contacting at a temperature of from -150° C. to about --100° C. monomer (A) and mon wherein M is aluminum or boron; R' is a hydrocarbon Omer (B) defined in claim 6 with an organo-metal halide radical having 1 to 20 carbon atoms; X is a halogen Selected from the group consisting of the aluminum and atom; and n is an arbitrary number of from 1 to 2, or boron compounds having the formulae: with a mixture of at least two compounds having the fol 7. lowing formulae: MR'X2, MR'sX5 and MR'X wherein M is aluminum or boron; R' is a hydrocarbon (A) MR'X-, (B) MRIV and (C) M'X's radical having 1 to 20 carbon atoms; and X is a halogen wherein M, M' and M'' each represents aluminum or atom. boron; R'' and RV each represents a hydrocarbon radical (References on following page) 3,629,215 21 22 References Cited WILLIAM H. SHORT, Primary Examiner UNITED STATES PATENTS L. L. LEE, Assistant Examiner 3,127,380 3/1964 Welch ------260-85.5 U.S. C. X.R. 3,159,607 12/1964 D'Alelio ------260-82.1 5 3,169,079 2/1965 Ferington et al. ------117 -124 6 260-32.6 R, 32.8 R, 33.6 F, 33.6 UA, 63 R, 63 HA, 3,183,217 5/1965 Serniuk ------260-85.5 67 UA, 79.7, 85.5 XA, 86.3, 87.5 R, 87.5 A, 87.7, 88.1 R, 3,326,870 6/1967 Nakaguchi et al. 260-85.5 88.1 PN, 88.1 PC, 88.3 R