CN1121434C - Butadiene-isoprene-styrene pentablock copolymer and its preparation method - Google Patents

Butadiene-isoprene-styrene pentablock copolymer and its preparation method Download PDF

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CN1121434C
CN1121434C CN00100850A CN00100850A CN1121434C CN 1121434 C CN1121434 C CN 1121434C CN 00100850 A CN00100850 A CN 00100850A CN 00100850 A CN00100850 A CN 00100850A CN 1121434 C CN1121434 C CN 1121434C
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block
sbr
lithiums
divinyl
polybutadiene
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CN1263120A (en
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李杨
陆兴军
杨力
徐宏德
洪定一
王玉荣
顾明初
杨锦宗
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China Petroleum and Chemical Corp
Beijing Research Institute of Beijing Yanshan Petrochemical Corp
China Petrochemical Corp
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China Petroleum and Chemical Corp
Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Priority to CN00100850A priority Critical patent/CN1121434C/en
Priority to PCT/CN2000/000228 priority patent/WO2001060879A1/en
Priority to AU2000265534A priority patent/AU2000265534A1/en
Priority to DE60024880T priority patent/DE60024880T2/en
Priority to EP00952839A priority patent/EP1266916B1/en
Publication of CN1263120A publication Critical patent/CN1263120A/en
Priority to US10/152,184 priority patent/US6777499B2/en
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Abstract

The present invention relates to a penta-block copolymer of butadiene, isoprene and styrene, and a preparation method thereof. The block copolymer has the following symmetrical structure: SBR-I-B-I-SBR, wherein SBR is a butadiene and styrene random copolymer block; I is a polyisoprene block; B is a polybutadiene block; the proportion SBR/(B+I) of the butadiene and styrene random copolymer SBR block and a poly-conjugated dialkene block (the sum of the polybutadiene B block and the polyisoprene I block) is from 10:90 to 90:10(weight ratio); in the poly-conjugated dialkene block, the proportion B/I of the polybutadiene B block and the polyisoprene I block is from 10:90 to 90:10(weight ratio).

Description

Divinyl, isoprene, vinylbenzene five segmented copolymers and preparation method thereof
The present invention relates to a class divinyl, isoprene, vinylbenzene five segmented copolymers and preparation method thereof, this based block copolymer has following symmetrical structure: SBR-I-B-I-SBR, wherein: SBR is divinyl, styrene random copolymer block, I is a polyisoprene blocks, and B is a polybutadiene block.
Usually based on divinyl, isoprene, three kinds of monomeric segmented copolymers of vinylbenzene SBS, SIS are arranged; SBS is a divinyl, (wherein: B is a polybutadiene block to styrene triblock copolymer; S is a polystyrene block), SIS is isoprene, styrene triblock copolymer
(wherein: I is a polyisoprene blocks, and S is a polystyrene block).With the bifunctional lithium alkylide is initiator, change the order of addition(of ingredients) of divinyl, isoprene, styrene monomer, can obtain the segmented copolymer of different structure, this based block copolymer comprises following symmetrical structure: (1) S-I-B-I-S (divinyl, isoprene, vinylbenzene add in proper order); (2) S-B-I-B-S (isoprene, divinyl, vinylbenzene add in proper order); (3) S-I-BI-B-BI-I-S (divinyl and isoprene once add, vinylbenzene list add); (4) S-BS-B-I-B-BS-S (the isoprene list adds, divinyl and vinylbenzene add simultaneously); (5) S-IS-I-B-I-IS-S (the divinyl list adds, isoprene and vinylbenzene add simultaneously); (6) S-IS-I-BI-B-BI-I-IS-S (divinyl, isoprene and vinylbenzene add simultaneously); Wherein: S is a polystyrene block, B is a polybutadiene block, and I is a polyisoprene blocks, and BI is divinyl, the trapezoidal copolymer block of isoprene, BS is divinyl, the trapezoidal copolymer block of vinylbenzene, and IS is isoprene, the trapezoidal copolymer block of vinylbenzene.When the isoprene list adds, divinyl and vinylbenzene add fashionable simultaneously, because divinyl is different with cinnamic reactivity ratio, can only obtain containing divinyl, seven segmented copolymer S-BS-B-I-B-BS-S of the trapezoidal copolymer block of vinylbenzene, in order to change divinyl and cinnamic reactivity ratio, at divinyl, add polar additive in the time of styrene charge, make divinyl, cinnamic polymerization is carried out according to random mode, finally obtain random butylbenzene copolymer block, the present invention is just from such polymer design, SBR-I-B-I-SBR five segmented copolymers have been prepared, from truly having realized random styrene-butadiene rubber, polybutadiene rubber and polyisoprene rubber chemical composite.
The objective of the invention is to prepare a class based on divinyl, isoprene, three kinds of monomeric five segmented copolymers of vinylbenzene, this based block copolymer is the broad-spectrum elastomer material of a class with the performance of random styrene-butadiene rubber SBR, polybutadiene rubber B and polyisoprene rubber I excellence.
Technical characterictic of the present invention is general random butylbenzene copolymer rubber SBR and general polybutadiene rubber B and polyisoprene rubber I in-situ accomplishes chemistry in polymerization reactor composite.
Prepared divinyl, isoprene, vinylbenzene five segmented copolymers of the present invention have following symmetrical structure: SBR-I-B-I-SBR.The number-average molecular weight of segmented copolymer (Mn) general range is 5 * 10 4-35 * 10 4, optimum range is 10 * 10 4-25 * 10 4Consisting of of divinyl and styrene random multipolymer SBR block: the general range of styrene content is 10%-50% (weight percent, below identical), and optimum range is 15%-35%; The general range of butadiene content be 50%-90% (weight percent, below mutually good scope be 65%-85%; 1.2-the polybutadiene content general range is 6%-80% (weight percent, below identical), optimum range is 10%-50%.The general range of divinyl and styrene random multipolymer SBR block and poly-conjugated-diolefin block (polybutadiene block B and polyisoprene I block sum) ratio SBR/ (B+I) is a 10/90-90/10 (weight ratio, below identical), optimum range is 30/70-70/30.The general range of polybutadiene block B and polyisoprene I block ratio B/I is 10/90-90/10 (weight ratio, below identical) in the poly-conjugated-diolefin block, and optimum range is 30/70-70/30.1.2-polybutadiene content general range is 6%-35% (weight percent, below identical) in the polyhutadiene B block, and optimum range is 10%-20%.3.4-polyisoprene content general range is 6%-35% (weight percent, below identical) in the polyisoprene I block, and optimum range is 10%-20%.
Divinyl involved in the present invention, isoprene, five segmented copolymer preparation methods are as follows for vinylbenzene: by monomer ratio first divinylic monomer is joined in the reactor in the non-polar hydrocarbon kind solvent, look Microstructure of Polybutadiene and require to determine whether to use polar additive, and the kind of polar additive and consumption are decided on the design load of 1.2-polybutadiene content in the polybutadiene block, monomer concentration is 10%-20% (weight percent), the non-polar hydrocarbon kind solvent is selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil, open stirring, after reaching kick off temperature, the initiation reaction temperature is 30 ℃-80 ℃, adding the bifunctional lithium alkylide is initiator, begin to prepare the B block, the consumption of bifunctional alkyl lithium initiator is decided according to the size of multipolymer number-average molecular weight, and the number-average molecular weight scope of segmented copolymer is generally 5 * 10 4-35 * 10 4The bifunctional alkyl lithium initiator is selected from the mixture of a kind of bifunctional alkyl lithium initiator or several bifunctional alkyl lithium initiators, generally be selected from two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, the two lithiums of naphthalene class, two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof, after the divinyl total overall reaction finishes, add isoprene by monomer ratio again, begin to prepare the I block, after the isoprene total overall reaction finishes, the second batch of divinylic monomer and the styrene monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare the SBR block, the purpose that adds polar additive is to change divinyl and cinnamic reactivity ratio, realize divinyl and cinnamic random copolymerization, obtain random butylbenzene copolymer SBR.The polar additive consumption is decided on the kind of polar compound to realize that divinyl and vinylbenzene carry out random copolymerization and is as the criterion.After divinyl and vinylbenzene total overall reaction are finished, add anti-aging agent [1010 with 2.6.4 (2, the 6-di-tert-butyl-4-methy phenol) mixes at 1: 1 with weight ratio], adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain SBR-I-B-I-SBR five segmented copolymers.
Polar additive used in the present invention is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, contains one or more compounds in Phosphorus polar compound and the alkoxide compound, as: (1) oxygenatedchemicals generally is selected from: ether, tetrahydrofuran (THF), R 1OCH 2CH 2OR 2(wherein: R 1, R 2Be that carbonatoms is the alkyl of 1-6, R 1, R 2Can be identical also can be different, with R 1, R 2Be not all good, as glycol dimethyl ether, ethylene glycol diethyl ether), R 1OCH 2CH 2OCH 2CH 2OR 2(wherein: R 1, R 2Be that carbonatoms is the alkyl of 1-6, R 1, R 2Can be identical also can be different, with R 1, R 2Be not all good, as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound generally is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected HMPA (HMPA) for use; (4) alkoxide compound generally is selected from ROM, and wherein: R is that carbonatoms is the alkyl of 1-6, and O is a Sauerstoffatom, and M is metal ion sodium Na or potassium K, preferably certainly: tert.-butoxy potassium, uncle's pentyloxy potassium.
Non-polar organic solvent used in the present invention is selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as: Mixed XYLENE), mixing-in fat hydrocarbon (as: raffinating oil), preferably from: hexane, hexanaphthene, raffinate oil.
Initiator used in the present invention is the bifunctional alkyl lithium initiator, be selected from the mixture of a kind of bifunctional alkyl lithium initiator or several bifunctional alkyl lithium initiators, as: two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, as: LiRLi, Li (DO) nR (DO) nLi, wherein: R is that carbonatoms is the alkyl of 4-10, and DO is that carbonatoms is a kind of conjugated diene of 4-8 or the mixture of several conjugated dienes, with 1, the 3-divinyl, isoprene is good, n is the oligomerisation degree, and n is generally 2-8, is good with 3-6, two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof are selected from: 1,4-two lithium butane, 1,2-two lithiums-1,2-diphenylethane, 1,4-two lithiums-1,1,4,4-tetraphenyl butane, 1,4-dimethyl-1,4-diphenyl butane two lithiums, polyisoprene two lithium oligopolymers, polyhutadiene two lithium oligopolymers; The two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium; Two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof are selected from: 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, the two lithiums of 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, 1, the two lithiums of 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer.
Further specify the present invention below in conjunction with embodiment, but and the scope of unrestricted claim protection of the present invention.Embodiment 1
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 70 gram divinyl, be warmed up to 50 ℃, add bifunctional alkyl lithium initiator 1, the two lithiums in 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group], the multipolymer number-average molecular weight is 15 * 10 4Butadiene polymerization is all finished when polyreaction proceeds to 30 minutes, add 70 gram isoprene again, the isoprene polymerization reaction is all finished after polyreaction is carried out 30 minutes, add the 175 gram divinyl and the 35 gram vinylbenzene that contain polar additive TMEDA again, TMEDA/Li (mol ratio) is 1.0, continue reaction 60 minutes, after the reaction of divinyl and styrene polymerization is all finished, adding anti-aging agent (1010 than 1: 1 mix with the 2.6.4 weight/power ratio) 3.5 restrains, adopt traditional method to carry out the glue aftertreatment, classical way specimen structure and performance are adopted in dry back, and the result is as shown in table 1.
Embodiment 2-7
Polymerization process and processing condition are with embodiment 1, be divinyl, isoprene, styrene monomer proportioning difference, the kind of polar additive is different with consumption, prepared SBR-I-B-I-SBR five segmented copolymers, polymerization process condition, product structure transitivity test result are respectively shown in 2-7 in the table 1.
Table 1 polymerization process condition and product rerum natura
Embodiment 1 2 3 4 5 6 7
S(g) 35 105 105 35 70 70 70
I(g) 70 45 35 65 30 70 35
B1(g) 70 60 35 40 40 70 70
B2(g) 175 140 175 210 210 140 175
Ai TMEDA THF THF TMEDA THF THF TMEDA
Ai/Li 1.0 6 8 1.2 35 40 0.5
1.2-B％ 52 25 28 57 32 35 40
3.4-1％ 14 15 15 13 14 15 13
Tg(℃) -60 -37 -57 -65 -59 -47 -50
Annotate: S is the vinylbenzene consumption, I is the isoprene consumption, B1 is first divinyl consumption, B2 is second batch of divinyl consumption, Ai is the polar additive kind, and Ai/Li is polar additive consumption (mol ratio), and 1.2-B% is 1.2-polyhutadiene shared weight percent content in polyhutadiene, 3.4-I% is 3.4-polyisoprene shared weight percent content in polyisoprene, and Tg is a second-order transition temperature.THF is a tetrahydrofuran (THF), and TMEDA is a Tetramethyl Ethylene Diamine.

Claims (22)

1. a class divinyl, isoprene, vinylbenzene five segmented copolymers, it is characterized in that this multipolymer has following symmetrical structure: SBR-I-B-I-SBR, wherein: SBR is divinyl, styrene random copolymer block, I is that polyisoprene blocks, B are polybutadiene block, and the number-average molecular weight of segmented copolymer is 5 * 10 4-35 * 10 4Styrene content is that 10%-50%, butadiene content are 50%-90% by weight percentage by weight percentage in divinyl and the styrene random multipolymer SBR block, the polymerized conjugated diene block is polybutadiene block B and polyisoprene I block sum, divinyl and styrene random multipolymer SBR block and poly-conjugated-diolefin block ratio SBR/ (B+I) weight ratio are 10/90-90/10, and polybutadiene block B and polyisoprene I block ratio B/I weight ratio are 10/90-90/10 in the poly-conjugated-diolefin block.
2. segmented copolymer according to claim 1, wherein the number-average molecular weight of segmented copolymer is 10 * 10 4-25 * 10 4
3. segmented copolymer according to claim 1, styrene content is 15%-35% by weight percentage in divinyl and the styrene random multipolymer SBR block, butadiene content is 65%-85% by weight percentage.
4. segmented copolymer according to claim 1, divinyl and styrene random multipolymer SBR block and poly-conjugated-diolefin block ratio SBR/ (B+I) weight ratio are 30/70-70/30, and polybutadiene block B and polyisoprene I block ratio B/I weight ratio are 30/70-70/30 in the poly-conjugated-diolefin block.
5. segmented copolymer according to claim 1, the 1.2-polybutadiene content is 6%-80% by weight percentage in divinyl and the styrene random multipolymer SBR block.
6. segmented copolymer according to claim 5, the 1.2-polybutadiene content is 10%-50% by weight percentage in divinyl and the styrene random multipolymer SBR block.
7. segmented copolymer according to claim 1,3.4-polyisoprene content is 6%-35% by weight percentage in the polyisoprene I block.
8. segmented copolymer according to claim 7,3.4-polyisoprene content is 10%-20% by weight percentage in the polyisoprene I block.
9. segmented copolymer according to claim 1, the 1.2-polybutadiene content is 6%-35% by weight percentage in the polyhutadiene B block.
10. segmented copolymer according to claim 9, the 1.2-polybutadiene content is 10%-20% by weight percentage in the polyhutadiene B block.
A 11. class divinyl, isoprene, the preparation method of vinylbenzene five segmented copolymer SBR-I-B-I-SBR, it is characterized in that: in the non-polar hydrocarbon kind solvent, first divinylic monomer is joined in the reactor by monomer ratio, look Microstructure of Polybutadiene and require to determine whether to use polar additive, and the kind of polar additive and consumption are decided on the design load of 1.2-polybutadiene content in the polybutadiene block, monomer concentration is 10%-20% by weight percentage, the non-polar hydrocarbon kind solvent is selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon or the mixture of several varsols, open stirring, after reaching kick off temperature, the initiation reaction temperature is 30 ℃-80 ℃, adding the bifunctional lithium alkylide is initiator, the consumption of bifunctional alkyl lithium initiator is decided according to the size of multipolymer number-average molecular weight, and the number-average molecular weight scope of segmented copolymer is generally 5 * 10 4-35 * 10 4The bifunctional alkyl lithium initiator is selected from the mixture of a kind of bifunctional alkyl lithium initiator or several bifunctional alkyl lithium initiators, generally be selected from two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, the two lithiums of naphthalene class, two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof, after the divinyl total overall reaction finishes, once join isoprene monomer in the reactor by monomer ratio again, after the isoprene total overall reaction finishes, the second batch of divinylic monomer and the styrene monomer that will contain polar additive by monomer ratio once joins in the reactor again, polar additive is selected from and contains oxygen, the mixture of one or more compounds in the nitrogenous class polar compound, the polar additive consumption is to realize that divinyl and vinylbenzene carry out random copolymerization and is as the criterion, kind on polar compound is decided, begin to prepare the SBR block, after divinyl and vinylbenzene total overall reaction are finished, add anti-aging agent, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain SBR-I-B-I-SBR five segmented copolymers.
12. method according to claim 11, two lithiums of wherein two haloalkane hydro carbons and the two lithiums of oligopolymer thereof are selected from: LiRLi, Li (DO) nR (DO) nLi, R is that carbonatoms is the alkyl of 4-10, DO is that carbonatoms is a kind of conjugated diene of 4-8 or the mixture of several conjugated dienes, n is the oligomerisation degree, and n is 2-8.
13. method according to claim 12, wherein conjugated diene is selected from divinyl, isoprene, and oligomerisation degree n is 3-6.
14. method according to claim 11, wherein two lithiums of diene hydro carbons and oligopolymer dilithium initiator thereof are selected from: 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 4-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, the two lithiums of 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer.
15. method according to claim 11, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
16. method according to claim 11, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
17. method according to claim 16, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
18. method according to claim 11 wherein contains the oxygen polar additive and is selected from: ether, tetrahydrofuran (THF), R 1OCH 2CH 2OR 2, R 1OCH 2CH 2OCH 2CH 2OR 2, wherein: R 1, R 2Be that carbonatoms is the alkyl of 1-6, R 1, R 2Can be identical also can be different.
19. method according to claim 18 wherein contains the oxygen polar additive and is selected from: glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, crown ether.
20. method according to claim 11, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
21. method according to claim 20, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine.
22. method according to claim 11, wherein anti-aging agent is 1010 to mix the mixture that obtains at 1: 1 with weight ratio with 2,6 di tert butyl 4 methyl phenol.
CN00100850A 2000-02-17 2000-02-17 Butadiene-isoprene-styrene pentablock copolymer and its preparation method Expired - Lifetime CN1121434C (en)

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Application Number Priority Date Filing Date Title
CN00100850A CN1121434C (en) 2000-02-17 2000-02-17 Butadiene-isoprene-styrene pentablock copolymer and its preparation method
PCT/CN2000/000228 WO2001060879A1 (en) 2000-02-17 2000-08-10 Multiblock copolymer the preparing method thereof
AU2000265534A AU2000265534A1 (en) 2000-02-17 2000-08-10 Multiblock copolymer the preparing method thereof
DE60024880T DE60024880T2 (en) 2000-02-17 2000-08-10 MULTIBLOCK COPOLYMER AND ITS MANUFACTURING METHOD
EP00952839A EP1266916B1 (en) 2000-02-17 2000-08-10 Multiblock copolymer and the preparing method thereof
US10/152,184 US6777499B2 (en) 2000-02-17 2002-05-20 Multiblock interpolymers and processes for the preparation thereof

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1141928A (en) * 1996-08-14 1997-02-05 北京燕山石油化工公司研究院 Butadiene styrene block copolymer and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1141928A (en) * 1996-08-14 1997-02-05 北京燕山石油化工公司研究院 Butadiene styrene block copolymer and preparation method thereof

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