CN1263117A - Isoprene-butadiene-styrene triblock copolymer and its preparation method - Google Patents
Isoprene-butadiene-styrene triblock copolymer and its preparation method Download PDFInfo
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Abstract
The present invention relates to an isoprene, butadiene and styrene triblock copolymer and its preparation method. It possesses the following symmetrical structure: SBR-I-SBR, in which SBR is butadien styrene random copolymer block, I is polyisoprene block, and number-average molecular weight of the block copolymer is 5 X 10 to the power 4-35X10 to the power 4, the styrene content in the butadiene and styrene random copolymer SBR block is 10%-50% (wt%), the butadiene content is (wt%) 50%-90%, and the ratio of SBR block and I block is 10/90-90/10 (weight ratio).
Description
The present invention relates to an isoprenoid, divinyl, styrene triblock copolymer and preparation method thereof, this based block copolymer has following symmetrical structure: SBR-I-SBR, wherein: SBR is divinyl, styrene random copolymer block, and I is a polyisoprene blocks.
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, prepared the SBR-I-SBR triblock copolymer, from truly having realized the chemical composite of random styrene-butadiene rubber and polyisoprene rubber.
The objective of the invention is to prepare a class based on divinyl, isoprene, three kinds of monomeric triblock copolymers of vinylbenzene, this based block copolymer is the broad-spectrum elastomer material of a class with the performance of SBR and I excellence.
Technical characterictic of the present invention is general random butylbenzene copolymer rubber SBR and general polyisoprene rubber I in-situ accomplishes chemistry in polymerization reactor composite.
Prepared isoprene, divinyl, the styrene triblock copolymer of the present invention has following symmetrical structure: SBR-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 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 polyisoprene I block ratio SBR/I is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.3.4-polyisoprene content general range is 6%-35% (weight percent, below identical) in the polyisoprene I block, and optimum range is 10%-20%.
Isoprene involved in the present invention, divinyl, the styrene triblock copolymer preparation method is as follows: once join isoprene monomer in the reactor by monomer ratio in the non-polar hydrocarbon kind solvent, look the polyisoprene microtexture and require to determine whether to use polar additive, and the kind of polar additive and consumption are decided on the design load of 3.4-polyisoprene content in the polyisoprene blocks, 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, the two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof, after the isoprene total overall reaction finishes, the divinyl and the styrene monomer that will contain polar additive by monomer ratio once joins in the reactor again, begins to prepare the SBR block.The purpose that adds polar additive is to change divinyl and cinnamic reactivity ratio, realizes divinyl and cinnamic random copolymerization, obtains 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 weight ratio 1: 1 mix with 2.6.4), the employing traditional method is carried out aftertreatment to the polymkeric substance glue, carries out analytical test behind the product drying, obtains the SBR-I-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), 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, 140 gram isoprene, 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
4The isoprene polymerization reaction 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, 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 isoprene, divinyl, styrene monomer proportioning difference, the kind of polar additive is different with consumption, prepared the SBR-I-SBR triblock copolymer, 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, I is the isoprene consumption, B is the divinyl consumption, Ai is the polar additive kind, Ai/Li is polar additive consumption (mol ratio), 1.2-B% is a 1.2-polyhutadiene weight percent content, and 3.4-I% is a 3.4-polyisoprene weight percent content, and Tg is a second-order transition temperature.THF is a tetrahydrofuran (THF), and TMEDA is a Tetramethyl Ethylene Diamine.
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 |
| ????S(g) | ????35 | ????105 | ????105 | ????35 | ????70 | ????70 | ????70 |
| ????I(g) | ????140 | ????105 | ????70 | ????105 | ????70 | ????140 | ????105 |
| ????B(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-I％ | ????14 | ????15 | ????15 | ????13 | ????14 | ????15 | ????13 |
| ????Tg(℃) | ????-58 | ????-37 | ????-55 | ????-61 | ????-56 | ????-45 | ????-48 |
Claims (22)
1. an isoprenoid, divinyl, styrene triblock copolymer, it is characterized in that this multipolymer has following symmetrical structure: SBR-I-SBR, wherein: SBR is divinyl, styrene random copolymer block, and I is a polyisoprene blocks, and the number-average molecular weight of segmented copolymer is 5 * 10
4-35 * 10
4Styrene content is that 10%-50% (weight percent), butadiene content are 50%-90% (weight percent) in divinyl and the styrene random multipolymer SBR block, and divinyl and styrene random multipolymer SBR block and polyisoprene I block ratio SBR/I are 10/90-90/10 (weight ratio).
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% (weight percent) in divinyl and the styrene random multipolymer SBR block, butadiene content is 65%-85% (weight percent).
4. segmented copolymer according to claim 1, divinyl and styrene random multipolymer SBR block and polyisoprene I block ratio SBR/I are 30/70-70/30 (weight ratio).
5. segmented copolymer according to claim 1, the 1.2-polybutadiene content is 6%-80% (weight percent) in divinyl and the styrene random multipolymer SBR block.
6. segmented copolymer according to claim 5, the 1.2-polybutadiene content is 10%-50% (weight percent) in divinyl and the styrene random multipolymer SBR block.
7. segmented copolymer according to claim 1,3.4-polyisoprene content is 6%-35% (weight percent) in the polyisoprene I block.
8. segmented copolymer according to claim 7,3.4-polyisoprene content is 10%-20% (weight percent) in the polyisoprene I block.
9. an isoprenoid, divinyl, the preparation method of styrene triblock copolymer SBR-I-SBR, it is characterized in that: in the non-polar hydrocarbon kind solvent, once join isoprene monomer in the reactor by monomer ratio, look the polyisoprene microtexture and require to determine whether to use polar additive, and the kind of polar additive and consumption are decided on the design load of 3.4-polyisoprene content in the polyisoprene blocks, 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, 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 isoprene total overall reaction finishes, the divinyl 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, nitrogenous, sulfur-bearing, the mixture that contains one or more compounds in Phosphorus polar compound and the alkoxide 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 (1010 with weight ratio 1: 1 mix with 2.6.4), adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the SBR-I-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
2CH2
OR
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 (TMEDA), two piperidines ethane (DPE).
19. method according to claim 18, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine (TMEDA).
20. method according to claim 9, wherein phosphorous polar additive is selected HMPA (HMPA) for use.
21. method according to claim 9, wherein alkoxide compound 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.
22. method according to claim 21, wherein alkoxide compound is selected from: tert.-butoxy potassium, uncle's pentyloxy potassium.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100847A CN1121432C (en) | 2000-02-17 | 2000-02-17 | Isoprene-butadiene-styrene triblock copolymer and its preparation method |
| DE60024880T DE60024880T2 (en) | 2000-02-17 | 2000-08-10 | MULTIBLOCK COPOLYMER AND ITS MANUFACTURING 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 |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100847A CN1121432C (en) | 2000-02-17 | 2000-02-17 | Isoprene-butadiene-styrene triblock copolymer and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1263117A true CN1263117A (en) | 2000-08-16 |
| CN1121432C CN1121432C (en) | 2003-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00100847A Expired - Lifetime CN1121432C (en) | 2000-02-17 | 2000-02-17 | Isoprene-butadiene-styrene triblock copolymer and its preparation method |
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| CN (1) | CN1121432C (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048022C (en) * | 1996-08-14 | 2000-01-05 | 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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