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.