CN1121431C - Butadiene-styrene triblock copolymer and its preparation method - Google Patents
Butadiene-styrene triblock copolymer and its preparation method Download PDFInfo
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- CN1121431C CN1121431C CN00100846A CN00100846A CN1121431C CN 1121431 C CN1121431 C CN 1121431C CN 00100846 A CN00100846 A CN 00100846A CN 00100846 A CN00100846 A CN 00100846A CN 1121431 C CN1121431 C CN 1121431C
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Abstract
The present invention relates to a tri-block copolymer of butadiene and styrene, and a preparation method thereof. The block copolymer has the following symmetrical structure: SBR-B-SBR; in the structure, SBR is the random copolymer block of butadiene and styrene; B is a polybutadiene block; the number average molecular weight of the block copolymer is from 5*10<4> to 35*10<4>; in the butadiene and styrene random copolymer SBR block, the styrene content is from 10 wt% to 50 wt%; the butadiene content is from 50 wt% to 90 wt%; the proportion SBR/B of the butadiene and styrene random copolymer SBR block to the polybutadiene B block is from 10:90 to 90:10(weight ratio).
Description
The present invention relates to a class divinyl, styrene triblock copolymer and preparation method thereof, this based block copolymer has following symmetrical structure: SBR-B-SBR, and wherein: SBR is divinyl, styrene random copolymer block, 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 divinyl and vinylbenzene add fashionable simultaneously, because divinyl is different with cinnamic reactivity ratio, can only obtain containing divinyl, five segmented copolymer S-BS-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, at first carry out the polymerization of polybutadiene block B, carry out the polymerization of random butylbenzene copolymer block SBR again, prepared the SBR-B-SBR triblock copolymer, from truly having realized the chemical composite of random styrene-butadiene rubber and polybutadiene rubber.
The objective of the invention is to prepare a class based on divinyl, two kinds of monomeric triblock copolymers of vinylbenzene, this based block copolymer is the broad-spectrum elastomer material of a class with the performance of random styrene-butadiene rubber and polybutadiene rubber excellence.
Technical characterictic of the present invention is general random butylbenzene copolymer rubber and general polybutadiene rubber are realized that in polymerization reactor in-situ chemical is composite.
Divinyl that the present invention is prepared and styrene triblock copolymer have following symmetrical structure: SBR-B-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 is 50%-90% (weight percent, below identical), and optimum range is 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 polyhutadiene B block ratio SBR/B is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.1.2-polybutadiene content general range is 6%-80% (weight percent, below identical) in the polyhutadiene B block, and preferred range is 6%-55%, and optimum range is 6%-20%.
Divinyl involved in the present invention and styrene triblock copolymer preparation method are as follows: 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, 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 first divinyl total overall reaction finishes, vinylbenzene and second batch of divinylic monomer that will contain polar additive by divinyl and styrene random copolymer block 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 to realize that divinyl and vinylbenzene carry out random copolymerization and is as the criterion, kind on polar compound is decided, 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 the SBR-B-SBR triblock copolymer.
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, ethylene glycol ethyl tertbutyl ether, ethylene glycol propyl group tertbutyl ether, Ethylene Glycol Methyl tertbutyl 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, polyhutadiene two lithium oligopolymers, polyisoprene 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 unrestricted claim protection domain of the present invention.
Embodiment 1
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 140 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
1Butadiene polymerization is all finished when polyreaction proceeds to 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, continues reaction 60 minutes, after divinyl and styrene polymerization reaction are all finished, adding anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) 3.5 restrains, adopt traditional method to carry out the glue aftertreatment, the performance of classical way specimen structure is 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, styrene monomer proportioning difference, the kind of polar additive is different with consumption, has prepared the SBR-B-SBR triblock copolymer, and 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
Annotate: S is the vinylbenzene consumption, and B1 is first divinyl consumption, and B2 is second batch of divinyl consumption, Ai is the polar additive kind, Ai/Li is polar additive consumption (mol ratio), and 1.2-B% is a 1.2-polyhutadiene weight percent content, and Tg is that temperature is changeed in vitrifying.THF is a tetrahydrofuran (THF), and TMEDA is a Tetramethyl Ethylene Diamine, and 2G is a diethylene glycol dimethyl ether.
| Embodiment | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 |
| ?S(g) | ?35 | ?105 | ?105 | ?35 | ?70 | ?70 | ?70 |
| ?B1(g) | ?140 | ?105 | ?70 | ?105 | ?70 | ?140 | ?105 |
| ?B2(g) | ?175 | ?140 | ?175 | ?210 | ?210 | ?140 | ?175 |
| ?Ai | ?TMEDA | ?THF | ?THF | ?2G | ?THF | ?THF | ?TMEDA |
| ?Ai/Li | ?1.0 | ?6 | ?8 | ?0.5 | ?35 | ?40 | ?0.5 |
| ?1.2-B％ | ?52 | ?25 | ?28 | ?57 | ?32 | ?35 | ?40 |
| ?Tg(℃) | ?-55 | ?-30 | ?-50 | ?-58 | ?-52 | ?-40 | ?-43 |
Claims (20)
1. a class divinyl, styrene triblock copolymer, it is characterized in that this multipolymer has following symmetrical structure: SBR-B-SBR, wherein: SBR is divinyl, styrene random copolymer block, and B is a 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, and divinyl and styrene random multipolymer SBR block and polyhutadiene B block ratio SBR/B weight ratio are 10/90-90/10.
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 polyhutadiene B block ratio SBR/B weight ratio are 30/70-70/30.
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, the 1.2-polybutadiene content is 6%-35% by weight percentage in the polyhutadiene B block.
8. segmented copolymer according to claim 7, the 1.2-polybutadiene content is 10%-20% by weight percentage in the polyhutadiene B block.
9. a class divinyl, the preparation method of styrene triblock copolymer SBR-B-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, 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 the SBR-B-SBR triblock copolymer.
10. method according to claim 9, 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.
11. method according to claim 10, wherein conjugated diene is selected from divinyl, isoprene, and oligomerisation degree n is 3-6.
12. method according to claim 9, 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.
13. method according to claim 9, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
14. method according to claim 9, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
15. method according to claim 14, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
16. method according to claim 9 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.
17. method according to claim 16 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.
18. method according to claim 9, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
19. method according to claim 18, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine.
20. method according to claim 9, 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.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100846A CN1121431C (en) | 2000-02-17 | 2000-02-17 | Butadiene-styrene triblock copolymer and its preparation method |
| AU2000265534A AU2000265534A1 (en) | 2000-02-17 | 2000-08-10 | Multiblock copolymer the preparing method thereof |
| EP00952839A EP1266916B1 (en) | 2000-02-17 | 2000-08-10 | Multiblock copolymer and the preparing method thereof |
| PCT/CN2000/000228 WO2001060879A1 (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 |
| US10/152,184 US6777499B2 (en) | 2000-02-17 | 2002-05-20 | Multiblock interpolymers and processes for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100846A CN1121431C (en) | 2000-02-17 | 2000-02-17 | Butadiene-styrene triblock copolymer and its preparation method |
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| CN1263116A CN1263116A (en) | 2000-08-16 |
| CN1121431C true CN1121431C (en) | 2003-09-17 |
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|---|---|---|---|
| CN00100846A Expired - Lifetime CN1121431C (en) | 2000-02-17 | 2000-02-17 | Butadiene-styrene triblock copolymer and its preparation method |
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| CN101255223B (en) * | 2007-02-28 | 2010-12-01 | 中国石油化工股份有限公司 | Terpolymer rubber having low rolling resistance and high wet-sliding resistant performance, preparation and uses thereof |
| CN104558456B (en) * | 2013-10-28 | 2017-03-22 | 中国石油化工股份有限公司 | Block copolymer, block copolymer composition, vulcanized rubber, application of block copolymer, block copolymer composition and vulcanized rubber and block copolymer preparation method |
| CN106699999B (en) * | 2015-08-05 | 2019-02-19 | 中国石油化工股份有限公司 | Type SBS and preparation method thereof and oil-filled glue and modified pitch |
Citations (1)
| 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 |
-
2000
- 2000-02-17 CN CN00100846A patent/CN1121431C/en not_active Expired - Lifetime
Patent Citations (1)
| 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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