Process for preparing alternating copolymer of butadiene and α-olefine and novel alternating copolymer of butadiene and α-olefine containing cis-configuration butadiene unit

Abstract

A process for preparing alternating copolymer of butadiene and α-olefine which comprises contacting butadiene and the α-olefine in liquid phase with a catalyst system comprising the first component of AIR 3 wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical in which at least one R is selected from the group consisting of alkyl having at least 3 carbon atoms per one molecule, aryl and cycloalkyl radical and the second component of TiX' 4 wherein X' is selected from the group consisting of chlorine, bromine and iodine, or a catalyst system comprising the first component of AlR 3 wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical, and the second component of TiX' 4 wherein X' is the same as that defined above and the third component of a carbonyl group-containing compound. An alternating copolymer of butadiene and α-olefine, the microstructure of butadiene unit of the alternating copolymer contains cis-configuration. The alternating copolymers are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.

What we claim is: 
     
       1. A process for preparing a 1:1 copolymer of butadiene and an alpha-olefin having alternating butadiene and alpha-olefin units, said alpha-olefin having the general formula of CH 2  =CHR'  wherein R' represents a phenyl radical or a C 1  to C 4  normal or branched chain alkyl radical, which comprises contacting butadiene and the alpha-olefin in liquid phase at a temperature of from -100° C. to 50° C. with a catalyst system comprising a first component of an organoaluminum compound having the general formula of AlR 3  wherein R represents a hydrocarbon radical selected from the group consisting of an alkyl radical, an aryl radical and a cycloalkyl radical, a second component of titanium tetrahalide having the general formula TiX' 4  wherein X' is selected from the group consisting of chlorine, bromine and iodine, and a third component of a carbonyl group-containing compound, wherein the molar ratio of said organoaluminum compound to said titanium tetrahalide is from greater than 1.5 to 20 and the molar ratio of butadiene to said alpha-olefin in the initial monomer composition is within a range of from 20:80 to 80:20. 
     
     
       2. A process as claimed in claim 1, wherein the catalyst system contains a material selected from the group consisting of a metal oxide, a metalloid oxide, a halogen and a halogen compound as a fourth component. 
     
     
       3. A process as claimed in claim 1, wherein the molar ratio of the organoaluminum compound to the titanium tetrahalide is approximately 1.5-10. 
     
     
       4. A process as claimed in claim 1, wherein said halogen compound is selected from the group consisting of a halogen compound having Lewis acid property, a Lewis acid-base complex of a halogen compound having Lewis acid property, an organoaluminum compound having an Al-X linkage, an organotransition-metal compound having a transition metal-X linkage and an alkane compound having a C-X linkage, wherein X represents halogen. 
     
     
       5. A process as claimed in claim 1 wherein the polymerization reaction is carried out in the presence of a hydrocarbon diluent. 
     
     
       6. A process as claimed in claim 1 wherein the molar ratio of butadiene to the alpha-olefin in the initial monomer composition is substantially 50:50. 
     
     
       7. A process as claimed in claim 1, wherein said α-olefin is styrene. 
     
     
       8. A process as claimed in claim 1, wherein said α-olefin is selected from the group consisting of propylene, butene-1, pentene-1 and hexene-1. 
     
     
       9. A process as claimed in claim 1, werein said α-olefin is 4-methyl pentene-1.