CN1153183A - Butadiene-isoprene-styrene block copolymer and preparing method thereof - Google Patents
Butadiene-isoprene-styrene block copolymer and preparing method thereof Download PDFInfo
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Abstract
A process for preparing the block copolymers of butadiene, isoprene and styrene is disclosed. This kind of block copolymers has following three symmetrical structures: (1) S-B-I-B-S, (2) S-I-B-I-S, and (3) S-B/I-S, where S is polystyrene block, B is polybutadiene block, I is polyisopene block, and B/I is the atactic copolymer block of butadiene-isopene. Said block copolymers are prepared by use of bifunctional initiator of alkyl lithium, and features excellent characteristics of SBS or SIS and better comprehensive performance.
Description
The present invention relates to a class divinyl, isoprene, styrene block copolymer and preparation method thereof, this based block copolymer comprises following three kinds of symmetrical structures: (1) S-I-B-I-S; (2) S-B-I-B-S; (3) S-B/I-S; Wherein: S is a polystyrene block, and B is a polybutadiene block, and I is a polyisoprene blocks, and B/I is divinyl, isoprene block of random copolymer.
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).
The objective of the invention is to prepare a class based on divinyl, isoprene, three kinds of monomeric polynary segmented copolymers of vinylbenzene, this based block copolymer is the broad-spectrum thermoplastic elastic material of a class with the performance of SBS and SIS excellence.
Technical characterictic of the present invention is the B section among the common SBS, I section among the SIS are replaced divinyl, two kinds of monomers of isoprene by common a kind of monomer, replaces the B section among the SBS, the I section among the SIS with I-B-I section or B-I-B section or B, I random copolymers section.
Prepared divinyl, isoprene, the styrene block copolymer of the present invention has following symmetrical structure: (1) S-I-B-I-S; (2) S-B-I-B-S; (3) S-B/I-S.The number-average molecular weight of segmented copolymer (Mn) general range is 5 * 10
4-50 * 10
4, optimum range is 10 * 10
4-30 * 10
4The general range of monomer styrene content is 10%-50% (weight percent, below identical), and optimum range is 20%-40%; The general range of isoprene content is 10%-75% (weight percent, below identical), and optimum range is 20%-50%; The general range of butadiene content is 10%-75% (weight percent, below identical), and optimum range is 20%-50%.1,2-polybutadiene content general range is 6%-35% (weight percent, below identical), and optimum range is 10%-20%; 3,4-polyisoprene content general range is 6%-35% (weight percent, below identical), and optimum range is 10%-20%.
Divinyl involved in the present invention, isoprene, styrene block copolymer preparation method are as follows:
The preparation of S-I-B-I-S: in the non-polar hydrocarbon kind solvent, once join divinylic monomer in the reactor by monomer ratio, the general range of butadiene content is 10%-75%, 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
4-50 * 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, the general range of isoprene content is 10%-75%, begin to prepare polyisoprene blocks, after the isoprene total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50%, begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent (1010 with weight ratio 1: 1 mix with 264), anti-aging agent 1010 is four [3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (hereinafter to be referred as 1010), antioxidant 264 is 2,6-di-tert-butyl-4-methy phenol (hereinafter to be referred as 264), aging inhibitor dosage is calculated with 1% of polymer weight, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the S-I-B-I-S segmented copolymer.
The preparation of S-B-I-B-S: in the non-polar hydrocarbon kind solvent, once join isoprene monomer in the reactor by monomer ratio, the general range of isoprene content is 10%-75%, 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
4-50 * 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, once join divinylic monomer in the reactor by monomer ratio again, the general range of butadiene content is 10%-75%, begin to prepare polybutadiene block, after the divinyl total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50%, begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent (1010 with weight ratio 1: 1 mixes with 264), aging inhibitor dosage is with 1% calculating of polymer weight, and the employing traditional method is carried out aftertreatment to the polymkeric substance glue, carry out analytical test behind the product drying, obtain the S-B-I-B-S segmented copolymer.
The preparation of S-B/I-S: in the non-polar hydrocarbon kind solvent, press monomer ratio with divinyl, isoprene monomer once joins in the reactor, the general range of butadiene content is 10%-75%, the general range of isoprene content is 10%-75%, 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
4-50 * 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, work as divinyl, after the isoprene total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50%, begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent (1010 with weight ratio 1: 1 mix with 264), aging inhibitor dosage is calculated with 1% of polymer weight, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the S-B/I-S segmented copolymer.
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 45 ℃, add bifunctional alkyl lithium initiator 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, initiator amount is 15 * 104 calculating with the multipolymer number-average molecular weight, the isoprene polymerization reaction is all finished when polyreaction proceeds to 30 minutes, add 105 gram divinyl again and continue reaction 45 minutes, after butadiene conversion reaches 100%, add 105 gram vinylbenzene again, continue reaction 35 minutes, after styrene polymerization reaction is all over, add anti-aging agent (1010 with weight ratio 1: 1 mixes with 264) 3.5 and restrain, the employing traditional method is carried out the glue aftertreatment, classical way specimen structure and mechanical property are adopted in dry back, and the result is as shown in table 1.Embodiment 2
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 140 gram divinyl, be warmed up to 45 ℃, add bifunctional alkyl lithium initiator 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, initiator amount is 15 * 10 with the multipolymer number-average molecular weight
4Calculate, butadiene polymerization is all finished when polyreaction proceeds to 30 minutes, add 105 gram isoprene again and continue reaction 60 minutes, after the isoprene transformation efficiency reaches 100%, add 105 gram vinylbenzene again, continue reaction 45 minutes, after the styrene polymerization reaction is all over, adding anti-aging agent (1010 with weight ratio 1: 1 mix with 264) 3.5 restrains, adopt traditional method to carry out the glue aftertreatment, classical way specimen structure and mechanical property are adopted in dry back, and the result is as shown in table 1.Embodiment 3
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 175 gram divinyl, 70 gram isoprene, be warmed up to 45 ℃, add bifunctional alkyl lithium initiator 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, initiator amount is 15 * 10 with the multipolymer number-average molecular weight
4Calculate, after divinyl, isoprene transformation efficiency reach 100% when polyreaction proceeds to 90 minutes, add 105 gram vinylbenzene again, continue reaction 30 minutes, after styrene polymerization reaction is all over, add anti-aging agent (1010 with weight ratio 1: 1 mixes with 264) 3.5 and restrain, the employing traditional method is carried out the glue aftertreatment, classical way specimen structure and mechanical property are adopted in dry back, and the result is as shown in table 1.Embodiment 4
Polymerization process and processing condition are with embodiment 2, be vinylbenzene, isoprene, divinylic monomer proportioning difference, and employing bifunctional alkyl lithium initiator 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, prepared the S-I-B-I-S segmented copolymer, polymerization process condition, product structure transitivity test result are distinguished as shown in table 1.Embodiment 5
Polymerization process and processing condition are with embodiment 3, be vinylbenzene, isoprene, divinylic monomer proportioning difference, and employing bifunctional alkyl lithium initiator 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, prepared the S-B/I-S segmented copolymer, polymerization process condition, product structure transitivity test result are distinguished as shown in table 1.Embodiment 6,7
Polymerization process and processing condition are with embodiment 2, and just vinylbenzene, isoprene, divinylic monomer proportioning difference have prepared the S-I-B-I-S segmented copolymer, and polymerization process condition, product structure transitivity test result are distinguished as shown in table 1.
Table 1 polymerization process condition and product rerum natura
Annotate: S is a styrene content, and I is an isoprene content, and B is a butadiene content, and S/I/B is vinylbenzene, isoprene, divinylic monomer proportioning, and kind A is that S-B-I-B-S, B are that S-I-B-I-S, C are the S-B/I-S structure.
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 |
| Kind | ????A | ????B | ????C | ????B | ????C | ????B | ????B |
| ??S(g) | ????105 | ????105 | ????105 | ????140 | ????140 | ????70 | ???70 |
| ??I(g) | ????140 | ????105 | ????70 | ????105 | ????70 | ????140 | ???105 |
| ??B(g) | ????105 | ????140 | ????175 | ????105 | ????140 | ????140 | ????175 |
| ??S/I/B | ???3/4/3 | ???3/3/4 | ???3/2/5 | ???4/3/3 | ???4/2/4 | ???2/4/4 | ???2/3/5 |
| Tensile strength (MPa) | ???26.5 | ???26.0 | ???24.8 | ????28.0 | ????26.7 | ????24.6 | ????23.8 |
| Elongation at break (%) | ????950 | ???1050 | ???1100 | ????960 | ????900 | ????1080 | ????1150 |
| Hardness (Shao Shi A) | ????60 | ????65 | ????70 | ????70 | ????75 | ????55 | ????50 |
Claims (54)
1. a class divinyl, isoprene, styrene block copolymer is characterized in that this multipolymer has following symmetrical structure: S-I-B-I-S, and wherein: S is a polystyrene block, and I is a polyisoprene blocks, and B is a polybutadiene block.
2. segmented copolymer according to claim 1, wherein the number-average molecular weight general range of segmented copolymer is 5 * 10
4-50 * 10
4
3. segmented copolymer according to claim 1, wherein the number-average molecular weight optimum range of segmented copolymer is 10 * 10
4-30 * 10
4
4. segmented copolymer according to claim 1, the general range of monomer styrene content are 10%-50% (weight percent).
5. segmented copolymer according to claim 1, the optimum range of monomer styrene content are 20%-40% (weight percent).
6. segmented copolymer according to claim 1, the general range of monomer isoprene content are 10%-75% (weight percent).
7. segmented copolymer according to claim 1, the optimum range of monomer isoprene content are 20%-50% (weight percent).
8. segmented copolymer according to claim 1, the general range of monomer butadiene content are 10%-75% (weight percent).
9. segmented copolymer according to claim 1, the optimum range of monomer butadiene content are 20%-50% (weight percent).
10. segmented copolymer according to claim 1,1,2-polybutadiene content general range is 6%-35% (weight percent), 3,4-polyisoprene content general range is 6%-35% (weight percent).
11. segmented copolymer according to claim 1,1,2-polybutadiene content optimum range is 10%-20% (weight percent), 3,4-polyisoprene content optimum range is 10%-20% (weight percent).
A 12. class divinyl, isoprene, the preparation method of styrene block copolymer S-I-B-I-S, it is characterized in that: in the non-polar hydrocarbon kind solvent, once join divinylic monomer in the reactor by monomer ratio, the general range of butadiene content is 10%-75% (weight percent), 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
4-50 * 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, the general range of isoprene content is 10%-75% (weight percent), begin to prepare polyisoprene blocks, after the isoprene total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50% (weight percent), begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent, anti-aging agent is four [3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and 2, the 6-di-tert-butyl-4-methy phenol mixes with weight ratio at 1: 1, aging inhibitor dosage is calculated with 1% of polymer weight, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the S-I-B-I-S segmented copolymer.
13. method according to claim 12, 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 generally 2-8.
14. method according to claim 13, wherein conjugated diene is preferably from divinyl, isoprene, and oligomerisation degree n is good with 3-6.
15. method according to claim 12, 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.
16. method according to claim 12, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
17. method according to claim 12, wherein the non-polar hydrocarbon kind solvent generally is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
18. method according to claim 17, wherein the non-polar hydrocarbon kind solvent preferably from: hexane, hexanaphthene, raffinate oil.
19. a class divinyl, isoprene, styrene block copolymer is characterized in that this multipolymer has following symmetrical structure: S-B-I-B-S, wherein: S is a polystyrene block, and I is a polyisoprene blocks, and B is a polybutadiene block.
20. segmented copolymer according to claim 19, wherein the number-average molecular weight general range of segmented copolymer is 5 * 10
4-50 * 10
4
21. segmented copolymer according to claim 19, wherein the number-average molecular weight optimum range of segmented copolymer is 10 * 10
4-30 * 10
4
22. segmented copolymer according to claim 19, the general range of monomer styrene content are 10%-50% (weight percent).
23. segmented copolymer according to claim 19, the optimum range of monomer styrene content are 20%-40% (weight percent).
24. segmented copolymer according to claim 19, the general range of monomer isoprene content are 10%-75% (weight percent).
25. segmented copolymer according to claim 19, the optimum range of monomer isoprene content are 20%-50% (weight percent).
26. segmented copolymer according to claim 19, the general range of monomer butadiene content are 10%-75% (weight percent).
27. segmented copolymer according to claim 19, the optimum range of monomer butadiene content are 20%-50% (weight percent).
28. according to claim 19 described segmented copolymers, 1,2-polybutadiene content general range is 6%-35% (weight percent), 3,4-polyisoprene content general range is 6%-35% (weight percent).
29. segmented copolymer according to claim 19,1,2-polybutadiene content optimum range is 10%-20% (weight percent), 3,4-polyisoprene content optimum range is 10%-20% (weight percent).
A 30. class divinyl, isoprene, the preparation method of styrene block copolymer S-B-I-B-S, it is characterized in that: in the non-polar hydrocarbon kind solvent, once join isoprene monomer in the reactor by monomer ratio, the general range of isoprene content is 10%-75% (weight percent), 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
4-50 * 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, once join divinylic monomer in the reactor by monomer ratio again, the general range of butadiene content is 10%-75% (weight percent), begin to prepare polybutadiene block, after the divinyl total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50% (weight percent), begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent, anti-aging agent is four [3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and 2, the 6-di-tert-butyl-4-methy phenol mixes with weight ratio at 1: 1, aging inhibitor dosage is calculated with 1% of polymer weight, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the S-B-I-B-S segmented copolymer.
31. method according to claim 30, 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 generally 2-8.
32. method according to claim 31, wherein conjugated diene is preferably from divinyl, isoprene, and oligomerisation degree n is good with 3-6.
33. method according to claim 30, 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.
34. method according to claim 30, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
35. method according to claim 30, wherein the non-polar hydrocarbon kind solvent generally is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
36. method according to claim 35, wherein the non-polar hydrocarbon kind solvent preferably from: hexane, hexanaphthene, raffinate oil.
37. a class divinyl, isoprene, styrene block copolymer is characterized in that this multipolymer has following symmetrical structure: S-B/I-S, wherein: S is a polystyrene block, and B/I is divinyl, isoprene block of random copolymer.
38. according to the described segmented copolymer of claim 37, wherein the number-average molecular weight general range of segmented copolymer is 5 * 10
4-50 * 10
4
39. according to the described segmented copolymer of claim 37, wherein the number-average molecular weight optimum range of segmented copolymer is 10 * 10
4-30 * 10
4
40. according to the described segmented copolymer of claim 37, the general range of monomer styrene content is 10%-50% (weight percent).
41. according to the described segmented copolymer of claim 37, the optimum range of monomer styrene content is 20%-40% (weight percent).
42. according to the described segmented copolymer of claim 37, the general range of monomer isoprene content is 10%-75% (weight percent).
43. according to the described segmented copolymer of claim 37, the optimum range of monomer isoprene content is 20%-50% (weight percent).
44. according to the described segmented copolymer of claim 37, the general range of monomer butadiene content is 10%-75% (weight percent).
45. according to the described segmented copolymer of claim 37, the optimum range of monomer butadiene content is 20%-50% (weight percent).
46. according to the described segmented copolymer of claim 37,1,2-polybutadiene content general range is 6%-35% (weight percent), 3,4-polyisoprene content general range is 6%-35% (weight is from proportion by subtraction).
47. according to the described segmented copolymer of claim 37,1,2-polybutadiene content optimum range is 10%-20% (weight percent), 3,4-polyisoprene content optimum range is 10%-20% (weight percent).
A 48. class divinyl, isoprene, the preparation method of styrene block copolymer S-B/I-S, it is characterized in that: in the non-polar hydrocarbon kind solvent, press monomer ratio divinyl, isoprene monomer once joins in the reactor, the general range of butadiene content is 10%-75% (weight percent), the general range of isoprene content is 10%-75% (weight percent), 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
4-50 * 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, work as divinyl, after the isoprene total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, the general range of styrene content is 10%-50% (weight percent), begin to prepare polystyrene block, after the vinylbenzene total overall reaction is finished, add anti-aging agent, anti-aging agent is four [3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and 2, the 6-di-tert-butyl-4-methy phenol mixes with weight ratio at 1: 1, aging inhibitor dosage is calculated with 1% of polymer weight, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the S-B/I-S segmented copolymer.
49. according to the described method of claim 48, 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 generally 2-8.
50. according to the described method of claim 49, wherein conjugated diene is preferably from divinyl, isoprene, oligomerisation degree n is good with 3-6.
51. according to the described method of claim 48, 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.
52. according to the described method of claim 48, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
53. according to the described method of claim 48, wherein the non-polar hydrocarbon kind solvent generally is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
54. according to the described method of claim 53, wherein the non-polar hydrocarbon kind solvent preferably from: hexane, hexanaphthene, raffinate oil.
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| CN 96120017 CN1048262C (en) | 1996-10-09 | 1996-10-09 | Butadiene-isoprene-styrene block copolymer and preparing method thereof |
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| CN 96120017 CN1048262C (en) | 1996-10-09 | 1996-10-09 | Butadiene-isoprene-styrene block copolymer and preparing method thereof |
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| CN99111137A Division CN1108320C (en) | 1999-07-28 | 1999-07-28 | Preparation of block copolymer of butadiene, isoprene and styrene |
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| CN1153183A true CN1153183A (en) | 1997-07-02 |
| CN1048262C CN1048262C (en) | 2000-01-12 |
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