Polysiloxane compound, modified conjugated diene-vinyl aromatic copolymer and preparing method thereof
The present invention relates to a polysiloxane compound having a structure represented by formula 1: wherein each of F 1 , F 2 , F 3 and F 4 is individually selected from one of a first group, a second group, a third group and a fourth group, the first group is selected from a C 2 ˜C 10 hydrocarbon group having amino group(s), a C 2 ˜C 10 hydrocarbon group having epoxy group(s), a C 2 ˜C 10 hydrocarbon group having carbonyl group(s) or a C 2 ˜C 10 hydrocarbon group having alkoxy group(s), the second group is a C 2 ˜C 10 hydrocarbon group having amino group(s), the third group is selected from a C 2 ˜C 10 hydrocarbon group having epoxy group(s), a C 2 ˜C 10 hydrocarbon group having carbonyl group(s), a C 2 ˜C 10 hydrocarbon group having SiCl group(s) or a C 2 ˜C 10 hydrocarbon group having alkoxy group(s), the fourth group is selected from a C 2 ˜C 10 hydrocarbon group having aryl group(s) or a C 2 ˜C 10 hydrocarbon group having alkoxy group(s).
1. A method for preparing a modified conjugated diene-vinyl aromatic copolymer, comprising:
polymerizing an organic alkali metal compound with conjugated diene monomers and vinyl aromatic hydrocarbon monomers to obtain a conjugated diene-vinyl aromatic copolymer, wherein a weight ratio of the conjugated diene monomers and the vinyl aromatic hydrocarbon monomers ranges from 2:1 to 5:1; and
reacting the conjugated diene-vinyl aromatic copolymer with a polysiloxane compound to form the modified conjugated diene-vinyl aromatic copolymer, wherein the polysiloxane compound having a structure represented by formula 1:
wherein each of F 1 , F 2 , F 3 and F 4 is different from each other, wherein F 1 and F 2 is individually selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one epoxy group, a C 2 ˜C 10 hydrocarbon group having at least one carbonyl group, a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one SiCl group, F 3 is a C 2 ˜C 10 hydrocarbon group having at least one amino group, F 4 is selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one aryl group, n is an integer from 1 to 60, m is an integer from 1 to 60, X is an integer from 1 to 60, Y is an integer from 1 to 60, and Z is an integer from 0 to 300.
2. The method of claim 1 , wherein with respect to a total amount of the conjugated diene monomers and the vinyl aromatic hydrocarbon monomers as 100 parts by weight, an amount of the organic alkali metal compound ranges from 0.01 parts by weight to 0.5 parts by weight and an amount of the polysiloxane compound ranges from 0.01 parts by weight to 1.0 part by weight.
3. The method of claim 1 , wherein the polysiloxane compound has a structure represented by formula 2:
wherein n is an integer from 15 to 20, m is an integer from 15 to 20, X is an integer from 1 to 10, Y is an integer from 15 to 20, Z is an integer from 0 to 10 and a is an integer from 4 to 10, R 1 ˜R 4 is individually a C 2 ˜C 4 alkyl group, R 5 is a C 1 ˜C 3 alkyl group or a C 1 ˜C 3 alkoxy group, and R 6 ˜R 11 is individually a C 1 ˜C 3 alkyl group.
4. The method of claim 1 , further comprising adding a microstructural modifying agent during the reaction of the conjugated diene monomers and the vinyl aromatic hydrocarbon monomers.
5. The method of claim 4 , wherein with respect to the total amount of the conjugated diene monomers and the vinyl aromatic hydrocarbon monomers as 100 parts by weight, an amount of the microstructural modifying agent ranges from 0.05 parts by weight to 0.5 parts by weight.
6. The method of claim 4 , wherein the microstructural modifying agent includes an ether, a tertiary amine compound, an alkali metal alkoxide compound, a phosphine compound, an alkyl sulfonate compound, an aryl sulfonate compound or the combinations thereof.
7. The method of claim 1 , wherein the conjugated diene monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-butadiene, 2-methyl-pentadiene, 4-methyl-pentadiene, 2,4-hexadiene or the combinations thereof.
8. The method of claim 1 , wherein the vinyl aromatic hydrocarbon monomers include styrene, alpha-methyl styrene, divinylbenzene or the combinations thereof.
9. A modified conjugated diene-vinyl aromatic copolymer, wherein the modified conjugated diene-vinyl aromatic copolymer is obtained by:
polymerizing conjugated diene monomers and vinyl aromatic hydrocarbon monomers to obtain a conjugated diene-vinyl aromatic copolymer; and
reacting the conjugated diene-vinyl aromatic copolymer with a polysiloxane compound to form the modified conjugated diene-vinyl aromatic copolymer, wherein the polysiloxane compound having a structure represented by formula 1:
wherein each of F 1 , F 2 , F 3 and F 4 is different from each other, wherein F 1 and F 2 is individually selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one epoxy group, a C 2 ˜C 10 hydrocarbon group having at least one carbonyl group, a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one SiCl group, F 3 is a C 2 ˜C 10 hydrocarbon group having at least one amino group, F 4 is selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one aryl group, n is an integer from 1 to 60, m is an integer from 1 to 60, X is an integer from 1 to 60, Y is an integer from 1 to 60, and Z is an integer from 0 to 300.
10. The copolymer of claim 9 , wherein with respect to a total amount of the conjugated diene monomers and the vinyl aromatic hydrocarbon monomers as 100 parts by weight, an amount of the polysiloxane compound ranges from 0.01 parts by weight to 1.0 part by weight.
11. The copolymer of claim 9 , wherein the conjugated diene monomers are polymerized to form 1,2-polymerized structural units and 1,4-polymerized structural units, and the 1,2-polymerized structural units account for 55%˜70% of a total amount of the 1,2-polymerized structural units and the 1,4-polymerized structural units.
12. The copolymer of claim 9 , wherein the conjugated diene monomers account for 74 wt %˜84 wt % of a total amount of the conjugated diene-vinyl aromatic copolymer, while the vinyl aromatic hydrocarbon monomers account for 16 wt %˜26 wt % of the total amount of the conjugated diene-vinyl aromatic copolymer.
13. The copolymer of claim 9 , wherein the modified conjugated diene-vinyl aromatic copolymer has a weight average molecular weight of 100,000˜700,000, and has a number average molecular weight of 60,000˜400,000.
14. The copolymer of claim 9 , wherein the modified conjugated diene-vinyl aromatic copolymer has a polydispersity index (PDI) of 1.5˜2.0.
15. The copolymer of claim 9 , wherein the first group is selected from a C 2 ˜C 10 hydrocarbon group having ethylene oxide group, a C 2 ˜C 10 hydrocarbon group having propylene oxide group or a C 2 ˜C 10 hydrocarbon group having ethylene oxide-propylene oxide group.
16. The copolymer of claim 9 , wherein the at least one amino group of the second group is represented by formula (iii):
17. The method of claim 1 , wherein each of F 1 , F 2 , F 3 and F 4 is different from each other, F 1 and F 2 is individually selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one epoxy group, F 3 is a C 2 ˜C 10 hydrocarbon group having at least one amino group, F 4 is a C 2 ˜C 10 hydrocarbon group having at least one aryl group, and a molar ratio of alkoxy group:amino group:epoxy group:aryl group is 1˜40:1˜30:0.5˜10:45˜90.
18. The copolymer of claim 9 , wherein each of F 1 , F 2 , F 3 and F 4 is different from each other, F 1 and F 2 is individually selected from the group consisting of a C 2 ˜C 10 hydrocarbon group having at least one alkoxy group and a C 2 ˜C 10 hydrocarbon group having at least one epoxy group, F 3 is a C 2 ˜C 10 hydrocarbon group having at least one amino group, F 4 is a C 2 ˜C 10 hydrocarbon group having at least one aryl group, and a molar ratio of alkoxy group:amino group:epoxy group:aryl group is 1˜40:1˜30:0.5˜10:45˜90.
19. The copolymer of claim 9 , wherein the polysiloxane compound has a structure represented by formula 2:
wherein n is an integer from 15 to 20, m is an integer from 15 to 20, X is an integer from 1 to 10, Y is an integer from 15 to 20, Z is an integer from 0 to 10 and a is an integer from 4 to 10, R 1 ˜R 4 is individually a C 2 ˜C 4 alkyl group, R 5 is a C 1 ˜C 3 alkyl group or a C 1 ˜C 3 alkoxy group, and R 6 ˜R 11 is individually a C 1 ˜C 3 alkyl group.