CN1133673C - Star-shaped conjugated diolefine-styrene block copolymer and its prepn - Google Patents
Star-shaped conjugated diolefine-styrene block copolymer and its prepn Download PDFInfo
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- CN1133673C CN1133673C CNB001301837A CN00130183A CN1133673C CN 1133673 C CN1133673 C CN 1133673C CN B001301837 A CNB001301837 A CN B001301837A CN 00130183 A CN00130183 A CN 00130183A CN 1133673 C CN1133673 C CN 1133673C
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Abstract
The present invention relates to a star-shaped block copolymer of conjugated dialkene and styrene, and a preparation method thereof. The copolymer comprises the following structure: (SBR-A1-A2)n-C; in the structure, SBR is the random copolymer block of butadiene and styrene; A1 and A2 are two kinds of different conjugated dialkene homopolymer blocks; when A1 is a butadiene homopolymer block BR and A2 is an isoprene homopolymer block IR; the star-shaped block copolymer is (SBR-BR-IR)n-C; when A1 is an isoprene homopolymers block IR and A2 is a butadiene homopolymer block BR, the star-shaped block copolymer is (SBR-IR-BR)n-C; C is a polyfunctional group lithium initiating agent residue; n is larger or equal to 3.
Description
The present invention relates to a class conjugated diene, vinylbenzene star block copolymer and preparation method thereof, this class star block copolymer has following structure: (SBR-A1-A2) n-C, wherein: SBR is divinyl, styrene random copolymer block, A1, A2 are two kinds of different conjugated diolefin homopolymerization thing blocks, A1, A2 are selected from divinyl or isoprene usually, when A1 be divinyl, when A2 is isoprene, star block copolymer is (SBR-BR-IR) n-C, wherein: BR is a polybutadiene block, and IR is a polyisoprene blocks; When A1 be isoprene, when A2 is divinyl, star block copolymer is (SBR-IR-BR) n-C, C is a polyfunctional group lithium initiator residue, n is the initiator functionality, n is more than or equal to 3.
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 when isoprene and vinylbenzene department (the divinyl list adds, add); (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 SBR, the present invention is just from such polymer design, adopt the polyfunctional group lithium initiator, at first carry out the polymerization of A1 homopolymer block, carry out the polymerization of A2 homopolymer block again, carry out the polymerization of random butylbenzene copolymer block SBR at last, prepared (SBR-A1-A2) n-C star block copolymer, from truly having realized the chemical composite of random styrene-butadiene rubber and poly-conjugated-diolefin rubber, and realize that the composite traditional method of rubber is various rubber to be carried out physical mixed on mill or Banbury mixer, obviously, composite method is simple for chemistry of the present invention, effect is better.
The object of the present invention is to provide a class based on conjugated diene, the monomeric star block copolymer of vinylbenzene two classes, this class star block copolymer is the broad-spectrum elastomer material of a class with the performance of styrene butadiene rubber sbr, polybutadiene rubber BR and polyisoprene rubber IR excellence.
Another object of the present invention is to provide a kind of method for preparing above-mentioned star block copolymer.
Technical characterictic of the present invention is general Butadiene random copolymer rubber SBR and general polybutadiene rubber BR, polyisoprene rubber IR in-situ accomplishes chemistry in polymerization reactor composite.
Prepared conjugated diene, the vinylbenzene star block copolymer of the present invention has following structure: (SBR-A1-A2) n-C, wherein: SBR is divinyl, styrene random copolymer block, A1, A2 are two kinds of different conjugated diolefin homopolymerization thing blocks, A1, A2 are selected from dienite B block R or isoprene homopolymer block IR, C is a polyfunctional group lithium initiator residue, n is the initiator functionality, n is more than or equal to 3, n is generally at 3-150, preferred range is at 3-50, and optimum range is at 3-10.When A1 is dienite B block R, A2 when being isoprene homopolymer block IR, star block copolymer is (SBR-BR-IR) n-C.When A1 is isoprene homopolymer block IR, A2 when being dienite B block R, star block copolymer is (SBR-IR-BR) n-C.
The prepared conjugated diene of the present invention, number-average molecular weight (Mn) general range of vinylbenzene star block copolymer ((SBR-A1-A2) n-C) are 5 * 10
4-50 * 10
4, optimum range is 10 * 10
4-30 * 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 poly-conjugated-diolefin block ratio SBR/ (A1+A2) is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.The general range of the ratio A1/A2 of poly-conjugated-diolefin block A1 and A2 is 10/90-90/10 (weight ratio, below identical), and optimum range is 30/70-70/30.Wherein A1, A2 are two kinds of different conjugated diolefin homopolymerization thing blocks, when A1, A2 are dienite B block R or isoprene homopolymer block IR, 1.2-polybutadiene content general range is a 6%-80% (weight percent in the polyhutadiene BR block, below identical), preferred range is 6%-55%, and optimum range is 6%-20%.3.4-polyisoprene content general range is 6%-80% (weight percent, below identical) in the polyisoprene IR block, and preferred range is 6%-55%, and optimum range is 6%-20%.
Divinyl involved in the present invention, the preparation method of vinylbenzene star block copolymer (SBR-A1-A2) n-C is as follows: press monomer ratio with a kind of conjugated diene monomer in the non-polar hydrocarbon kind solvent, optional polar additive joins in the reactor, add the polyfunctional group lithium initiator, preparation conjugated diene homopolymers block A2, after this conjugate diene monomer total overall reaction finishes, press monomer ratio again with another kind of conjugated diene monomer, optional polar additive joins in the reactor, preparation conjugated diene homopolymers block A1, after this conjugate diene monomer total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, termination reaction, obtain (SBR-A1-A2) n-C star block copolymer, A1 wherein, A2 is two kinds of different conjugated diolefin homopolymerization thing blocks, A1, A2 is selected from dienite B block R or isoprene homopolymer block IR (down together).
Conjugated diene involved in the present invention and vinylbenzene star block copolymer preparation method's preferred version is as follows: press monomer ratio with a kind of conjugated diene monomer (monomer of preparation conjugated diene homopolymers block A2) in the non-polar hydrocarbon kind solvent, optional polar additive joins in the reactor, look the poly-conjugated-diolefin 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 1.2-polybutadiene content in the poly-conjugated-diolefin block or 3.4-polyisoprene content, 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 ℃, add the polyfunctional group lithium initiator, begin to prepare conjugated diene homopolymers block A2, the consumption of polyfunctional group lithium initiator is decided according to the size of multipolymer number-average molecular weight, and the number-average molecular weight scope of star block copolymer of the present invention is generally 5 * 10
4-50 * 10
4After this conjugate diene monomer total overall reaction finishes, press monomer ratio again with another kind of conjugated diene monomer (monomer of preparation conjugated diene homopolymers block A1), optional polar additive joins in the reactor, begin to prepare conjugated diene homopolymers block A1, look the poly-conjugated-diolefin 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 1.2-polybutadiene content in the poly-conjugated-diolefin block or 3.4-polyisoprene content, after this conjugate diene monomer total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare divinyl and styrene random copolymer block SBR, the various monomeric total concn that each step of control is added is 10%-20% (weight percent), the purpose that adds polar additive is to change divinyl and cinnamic reactivity ratio, realize divinyl and cinnamic random copolymerization, obtain random butylbenzene copolymer block 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 terminator, stop polyreaction, also can randomly add conventional additives, as anti-aging agent Irganox1010 (trade(brand)name, Ciba-Geigy company is on sale) and Antigene BHT or 2.6.4 (trade(brand)name, SUMITOMO CHEMICAL KCC is on sale), adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain (SBR-A1-A2) n-C star block 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 disclosed any polyfunctional group lithium initiator of prior art, is selected from the mixture of a kind of polyfunctional group lithium initiator or several polyfunctional group lithium initiators, as: RLi
n, T (RLi) n, wherein: R is that carbonatoms is the alkyl of 4-20, R can be alkyl or aryl, T is an atoms metal, is generally metallic elements such as tin Sn, silicon Si, plumbous Pb, titanium Ti, germanium Ge, and n is the initiator functionality, n is more than or equal to 3, n is generally at 3-150, and preferred range is at 3-50, and optimum range is at 3-10.The polyfunctional group lithium initiator can be a multi-chelate organolithium initiator, reacts the various multi-chelate organolithium initiators that obtain as Vinylstyrene (DVB) and the lithium alkylide of mentioning in the patents such as GB2124228A, US3280084, EP0573893A2, CN1197806A.Polyfunctional group lithium initiator RLi
nAlso can be to contain above-mentioned metal species multifunctional group organic lithium initiator T (RLi) n, polyfunctional group lithium initiator T (RLi)
nGenerally be selected from stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
n, as the stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi) that mentions among the patent CN1148053A
4The polyfunctional group lithium initiator can also be that other functionality that can be used in initiation divinyl, isoprene equiconjugate diolefine and styrene monomer is not less than 3 polyfunctionality organic lithium initiator, as the various multifunctional group organic lithium initiators of mentioning among patent US5262213, the US5595951.
The consumption of initiator is decided according to the size of multipolymer number-average molecular weight, and the consumption of initiator makes that the number-average molecular weight of star block copolymer is 5 * 10 in the present invention
4-50 * 10
4
The used terminator of the present invention is the disclosed any terminator that can be used for anionic polymerisation of prior art, as water, methyl alcohol, ethanol or Virahol etc.
Further specify the present invention below in conjunction with embodiment, but and the scope of unrestricted claim protection of the present invention.
The used multifunctional group organic lithium initiator of following examples is a multi-chelate organolithium initiator; synthetic method is as follows: under the high pure nitrogen protection; by proportioning hexanaphthene 160 grams, 1; 3-divinyl 11 grams, tetrahydrofuran (THF) (THF) 80mmol, Vinylstyrene (DVB) 100mmol join in 500 milliliters of exsiccant saline bottles; after mixing; add n-Butyl Lithium 100mmol with syringe; after reacting 30 minutes under 70 ℃; generate scarlet homogeneous phase multi-chelate organolithium initiator solution, initiator concentration adopts two volumetrys to record.
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 the polyfunctional group lithium initiator, making 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 THF again, THF/Li (mol ratio) is 35, continue reaction 60 minutes, after the reaction of divinyl and styrene polymerization is all finished, add anti-aging agent (Irganox 1010 mixes with weight ratio with 2.6.4 at 1: 1) 3.5 grams, 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 order of addition(of ingredients) difference of divinyl, isoprene, prepared (SBR-A1-A2) n-C star block 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, A1, I during A2 is capable, B represents isoprene respectively, divinyl, B2 is a divinyl consumption in the SBR block, S/B2 is a vinylbenzene in the SBR block, divinylic monomer proportioning (weight ratio), SBR/ (A1+A2) is SBR block and conjugated diene polymer block weight ratio, A1/A2 is that two kinds of conjugated diene polymer blocks are than (weight ratio), 1.2-BR%+3.4-IR% is 1.2-polyhutadiene and 3.4-polyisoprene content sum, HI for the molecular weight distributing index that adopts gel permeation chromatography (GPC) to record (ratio of weight-average molecular weight and number-average molecular weight, Mw/Mn).
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| S(g) | 35 | 105 | 105 | 35 | 70 | 70 | 70 |
| A1(g) | I：70 | I：45 | I：35 | I：45 | B：35 | B：70 | B：60 |
| A2(g) | B：70 | B：60 | B：35 | B：60 | I：35 | I：70 | I：45 |
| B2(g) | 175 | 140 | 175 | 210 | 210 | 140 | 175 |
| SBR /(A1+A2) | 60 /40 | 70 /30 | 80 /20 | 70 /30 | 80 /20 | 60 /40 | 70 /30 |
| S/B2 | 17/83 | 42/58 | 37/53 | 14/86 | 25/75 | 33/67 | 28/72 |
| A1/A2 | 1/1 | 3/4 | 1/1 | 3/4 | 1/1 | 1/1 | 4/3 |
| 1.2-BR％ +3.4- IR％ | 17.5 | 18.6 | 17.8 | 22.4 | 21.7 | 17.6 | 18.8 |
| HI | 1.31 | 1.44 | 1.39 | 1.37 | 1.36 | 1.38 | 1.41 |
Claims (31)
1. a class conjugated diene, vinylbenzene star block copolymer, it is characterized in that this multipolymer has following structure: (SBR-A1-A2) n-C, wherein: SBR is divinyl, styrene random copolymer block, A1, A2 are two kinds of different conjugated diolefin homopolymerization thing blocks, A1, A2 are selected from dienite B block R or isoprene homopolymer block IR, and C is a polyfunctional group lithium initiator residue, and n is the initiator functionality, n is 3-150, and the number-average molecular weight of star block copolymer is 5 * 10
4-50 * 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, divinyl and styrene random multipolymer SBR block and conjugation diene homopolymers block ratio SBR/ (A1+A2) are 10/90-90/10 (weight ratio), and the ratio A1/A2 of conjugated diolefin homopolymerization thing block A1 and A2 is 10/90-90/10 (weight ratio).
2. star block copolymer according to claim 1, wherein when A1 be dienite B block R, A2 when being isoprene homopolymer block IR, star block copolymer is (SBR-BR-IR) n-C.
3. star block copolymer according to claim 1, wherein when A1 be isoprene homopolymer block IR, A2 when being dienite B block R, star block copolymer is (SBR-IR-BR) n-C.
4. star block copolymer according to claim 1, wherein the number-average molecular weight of star block copolymer is 10 * 10
4-30 * 10
4
5. star block copolymer according to claim 1, wherein styrene content is 15%-35% (weight percent) in divinyl and the styrene random multipolymer SBR block, butadiene content is 65%-85% (weight percent).
6. star block copolymer according to claim 1, wherein divinyl and styrene random multipolymer SBR block and conjugation diene homopolymers block ratio SBR/ (A1+A2) are 30/70-70/30 (weight ratio).
7. star block copolymer according to claim 1, wherein the ratio A1/A2 of conjugated diolefin homopolymerization thing block A1 and A2 is 30/70-70/30 (weight ratio).
8. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-80% (weight percent) in divinyl and the styrene random multipolymer SBR block.
9. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 10%-50% (weight percent) in divinyl and the styrene random multipolymer SBR block.
10. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-80% (weight percent) among the dienite B block R.
11. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-55% (weight percent) among the dienite B block R.
12. star block copolymer according to claim 1, wherein the 1.2-polybutadiene content is 6%-20% (weight percent) among the dienite B block R.
13. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-80% (weight percent) among the isoprene homopolymer block IR.
14. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-55% (weight percent) among the isoprene homopolymer block IR.
15. star block copolymer according to claim 1, wherein 3.4-polyisoprene content is 6%-20% (weight percent) among the isoprene homopolymer block IR.
16. each described conjugated diene of claim 1-15, the preparation method of vinylbenzene star block copolymer (SBR-A1-A2) n-C, it is characterized in that: in the non-polar hydrocarbon kind solvent, press monomer ratio a kind of conjugated diene monomer, optional polar additive joins in the reactor, when the initiation reaction temperature reaches 30 ℃-80 ℃, add the polyfunctional group lithium initiator, preparation conjugated diolefin homopolymerization thing block A2, after this conjugate diene monomer total overall reaction finishes, press monomer ratio again with another kind of conjugated diene monomer, optional polar additive joins in the reactor, preparation conjugated diolefin homopolymerization thing block A1, after this conjugate diene monomer total overall reaction finishes, the vinylbenzene and the divinylic monomer that will contain polar additive by monomer ratio once joins in the reactor again, begin to prepare divinyl and styrene random copolymer block SBR, after divinyl and vinylbenzene total overall reaction are finished, termination reaction, obtain (SBR-A1-A2) n-C star block copolymer, A1 wherein, A2 is two kinds of different conjugated diolefin homopolymerization thing blocks, A1, A2 is selected from dienite B block R or isoprene homopolymer block IR, C is a polyfunctional group lithium initiator residue, n is the initiator functionality, and n is 3-150.
17. method according to claim 16, wherein the polyfunctional group lithium initiator is selected from RLi
n, a kind of polyfunctional group lithium initiator among T (RLi) n or the mixture of several polyfunctional group lithium initiators, wherein: R is that carbonatoms is the alkyl of 4-20, T is tin Sn, silicon Si, plumbous Pb, titanium Ti, germanium Ge atoms metal, and n is the initiator functionality, and n is 3-150.
18. method according to claim 17, wherein polyfunctional group lithium initiator RLi
nBe selected from the various multi-chelate organolithium initiators that the reaction of Vinylstyrene and lithium alkylide obtains.
19. method according to claim 17, wherein polyfunctional group lithium initiator T (RLi)
nBe selected from stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
n
20. method according to claim 19, wherein stanniferous Sn class multifunctional group organic lithium initiator Sn (RLi)
nBe selected from Sn (RLi)
4
21. method according to claim 16, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
22. method according to claim 21, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
23. method according to claim 16, wherein polar additive is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, contains one or more compounds in Phosphorus polar compound and the alkoxide compound.
24. method according to claim 23 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
2Identical or different.
25. method according to claim 24 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.
26. method according to claim 23, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
27. method according to claim 26, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine.
28. method according to claim 23, wherein phosphorous polar additive is selected HMPA for use.
29. method according to claim 23, 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.
30. method according to claim 29, wherein alkoxide compound is selected from: tert.-butoxy potassium, uncle's pentyloxy potassium.
31. method according to claim 16, the various monomeric total concn that is wherein added are 10%-20% (weight percent).
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001301837A CN1133673C (en) | 2000-10-19 | 2000-10-19 | Star-shaped conjugated diolefine-styrene block copolymer and its prepn |
| US09/982,255 US6462137B2 (en) | 2000-10-19 | 2001-10-18 | Star-block interpolymers and preparation of the same |
| PCT/CN2001/001489 WO2002059174A1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
| EP01273428A EP1333042B1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
| JP2002559472A JP4213468B2 (en) | 2000-10-19 | 2001-10-19 | Star-block interpolymers and their manufacture |
| KR1020037005519A KR100806402B1 (en) | 2000-10-19 | 2001-10-19 | Star block copolymer and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001301837A CN1133673C (en) | 2000-10-19 | 2000-10-19 | Star-shaped conjugated diolefine-styrene block copolymer and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1350013A CN1350013A (en) | 2002-05-22 |
| CN1133673C true CN1133673C (en) | 2004-01-07 |
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| JP4480675B2 (en) * | 2003-12-04 | 2010-06-16 | コリア クムホ ペトロケミカル カンパニー，リミテッド | Radial polystyrene-polyisoprene block copolymer having hetero branches and method for producing the same |
| CN105622845A (en) * | 2014-11-25 | 2016-06-01 | 中国石油化工股份有限公司 | Hydrogenated multi-arm star butadiene/isoprene random copolymer, preparation method thereof and application thereof |
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