Synthesis of isoprene-butadiene copolymer rubbers
It has been unexpectedly found that certain neodymium catalyst systems can be used to copolymerize isoprene and 1,3-butadiene to produce random isoprene-butadiene copolymer rubbers which are not tapered. These random isoprene-butadiene copolymer rubbers have properties which are beneficial for use in rubber formulations for manufacturing a wide variety of rubber products, such as tires, hoses, conveyor belts, power transmission belts, and shoe soles. These random isoprene-butadiene rubbers are synthesized by copolymerizing (a) isoprene monomer or a substituted isoprene monomer and (b) 1,3-butadiene monomer in the presence of a neodymium catalyst system, wherein the neodymium catalyst system is prepared by (1) reacting a neodymium carboxylate with an organoaluminum compound in the presence of a conjugated diolefin monomer to produce neodymium-aluminum catalyst component, and (2) subsequently reacting the neodymium-aluminum catalyst component with an alkyl aluminum chloride to produce the neodymium catalyst system.
1 . A process for the synthesis of an isoprene-butadiene rubber which comprises copolymerizing (a) isoprene monomer or a substituted isoprene monomer and (b) 1,3-butadiene monomer in the presence of a neodymium catalyst system, wherein the neodymium catalyst system is prepared by (1) reacting a neodymium carboxylate with an organoaluminum compound in the presence of a conjugated diolefin monomer to produce neodymium-aluminum catalyst component, and (2) subsequently reacting the neodymium-aluminum catalyst component with an alkyl aluminum chloride to produce the neodymium catalyst system, where from 40 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 60 weight percent 1,3-butadiene.
2 . The process as specified in claim 1 wherein the neodymium catalyst is prepared at a temperature that is within the range of about −60° C. to about 150° C.
3 . The process as specified in claim 2 wherein the mole ratio of the organoaluminum compound to the neodymium carboxylate is within the range of about 4/1 to about 200/1.
4 . The process as specified in claim 2 wherein the organoaluminum compound is selected from the group consisting of trialkylaluminum compounds and dialkylaluminum hydride compounds.
5 . The process as specified in claim 4 wherein the mole ratio of the organoaluminum compound to the neodymium carboxylate is within the range of about 10/1 to about 50/1.
6 . The process as specified in claim 2 wherein the polymerization is carried out at a temperature within the range of about 10° C. to about 130° C. in an organic solvent.
7 . The process as specified in claim 2 wherein said organoaluminum compound is selected from the group consisting of diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolyethylalumin hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, ethylaluminum dihydride, butylaluminum dihydride, isobutylaluminum dihydride, octylaluminum dihydride, amylaluminum dihydride, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolyaluminum, tribenylaluminum, ethyldiphenylaluminum, ethyl-di-p-tolylaluminum, ethyldibenzylaluminum, diethylphenylaluminum, diethyl-p-tolylaluminum, and diethylbenzylaluminum.
8 . The process as specified in claim 7 wherein the alkyl aluminum chloride is a dialkyl aluminum chloride, and wherein the dialkyl aluminum chloride is selected from the group consisting of dimethyl aluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, dihexylaluminum chloride, diisobutylaluminum chloride, and didodecyaluminum chloride.
9 . The process as specified in claim 1 wherein the polymerization is terminated by the addition of an alkaline aqueous neutralizer solution, wherein the alkaline aqueous neutralizer solution has a pH within the range of 7.1 to 9.5.
10 . The process as specified in claim 9 wherein the alkaline aqueous neutralizer solution is an aqueous solution of sodium bicarbonate.
11 . The process as specified in claim 9 wherein the alkaline aqueous neutralizer solution has a pH within the range of 7.5 to 9.0.
12 . The process as specified in claim 9 wherein the alkaline aqueous neutralizer solution has a pH within the range of 8.0 to 8.5.
13 . The process as specified in claim 1 where from 45 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 55 weight percent 1,3-butadiene.
14 . The process as specified in claim 1 where from 50 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 50 weight percent 1,3-butadiene.
15 . The process as specified in claim 1 where from 55 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 45 weight percent 1,3-butadiene.
16 . The process as specified in claim 1 where from 60 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 40 weight percent 1,3-butadiene.
17 . The process as specified in claim 3 wherein the neodymium catalyst is prepared at a temperature which is within the range of about 5° C. to about 15° C.
18 . The process as specified in claim 3 wherein the molar ratio of the dialkyl aluminum chloride to neodymium is within the range of about 0.5:1 to about 3.5:1.
19 . A process for the synthesis of an isoprene-butadiene rubber which comprises copolymerizing (a) isoprene monomer or a substituted isoprene monomer and (b) 1,3-butadiene monomer in the presence of a neodymium catalyst system, wherein the neodymium catalyst system is prepared at a temperature that is within the range of about −60° C. to about 150° C. by (1) reacting a neodymium carboxylate with an organoaluminum compound in the presence of a conjugated diolefin monomer to produce neodymium-aluminum catalyst component, wherein the organoaluminum compound is selected from the group consisting of trialkylaluminum compounds and dialkylaluminum hydride compounds, and (2) subsequently reacting the neodymium-aluminum catalyst component with an alkyl aluminum chloride to produce the neodymium catalyst system, where from 40 weight percent to 70 weight percent isoprene is copolymerized with 30 weight percent to 60 weight percent 1,3-butadiene and the molar ratio of isoprene monomer to neodymium ranges from about 5/1 to about 500/1.
20 . The process as specified in claim 19 wherein the neodymium carboxylate is selected from the group consisting of neodymium octoate, neodymium neodecanoate, and neodymium 2-ethyl hexanoate.