CN1108320C - Preparation of block copolymer of butadiene, isoprene and styrene - Google Patents
Preparation of block copolymer of butadiene, isoprene and styrene Download PDFInfo
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- CN1108320C CN1108320C CN99111137A CN99111137A CN1108320C CN 1108320 C CN1108320 C CN 1108320C CN 99111137 A CN99111137 A CN 99111137A CN 99111137 A CN99111137 A CN 99111137A CN 1108320 C CN1108320 C CN 1108320C
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Abstract
The present invention relates to a block copolymer of butadiene, isoprene and styrene, and a preparation method thereof. The block copolymer comprises the following symmetrical structures: S-B-I-B-S, S-I-B-I-S and S-B/I-S, in the symmetrical structures, S is a polystyrol block; B is a polybutadiene block; I is a polyisoprene block; B/I is the random copolymer block of butadiene and isoprene. The block copolymer referred by the present invention is prepared from double-functional group alkyl lithium initiating agents, simultaneously has the good characteristics of SBS and SIS and has a good combination property.
Description
The application is that publication number is dividing an application of CN1153183A, and its applying date is 96.10.09, and application number is 96120017.0, and denomination of invention is divinyl, isoprene, styrene block copolymer and preparation method thereof.
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
4One 50 * 10
4, optimum range is 10 * 10
4-25 * 10
4The general range of monomer styrene consumption is 10%-50% (weight percent, below identical), and optimum range is 20%-40%; The general range of isoprene consumption is 10%-75%, and optimum range is 20%-50%; The general range of divinyl consumption is 10%-75%, and optimum range is 20%-50%.1.2-the polybutadiene content general range is 6%-35% (weight percent, below identical), optimum range is 10%-20%; 3.4-polyisoprene content general range is 6%-35% (weight percent, below identical), 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, 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, begin to prepare polyisoprene blocks, after the isoprene total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, 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 2.6.4), the consumption of anti-aging agent calculates 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, 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, begin to prepare polybutadiene block, after the divinyl total overall reaction finishes, once join styrene monomer in the reactor by monomer ratio again, 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 2.6.4), the consumption of anti-aging agent calculates 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.
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, 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, 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 2.6.4), the consumption of anti-aging agent calculates 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, 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 105 gram divinyl again and continue reaction 30 minutes, after butadiene conversion reaches 100%, add 105 gram vinylbenzene again, continue reaction 25 minutes, after styrene polymerization reaction is all over, add anti-aging agent (1010 with weight ratio 1: 1 mixes with 2.6.4) 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 2-7
Polymerization process and processing condition are with embodiment 1, be vinylbenzene, isoprene, divinylic monomer proportioning difference, order of addition(of ingredients) difference, prepared S-B-I-B-S, S-I-B-I-S, S-B/I-S segmented 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 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 (7)
1. a class divinyl, isoprene, the preparation method of styrene block copolymer, this multipolymer has following symmetrical structure: S-B-I-B-S, wherein: S is a polystyrene block, I is a polyisoprene blocks, B is a polybutadiene block, it is characterized in that: in the non-polar hydrocarbon kind solvent, once join isoprene monomer in the reactor by monomer ratio, 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 of segmented copolymer is 5 * 10
4-50 * 10
4The bifunctional alkyl lithium initiator is selected from two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, the two lithiums of naphthalene class, a kind of bifunctional alkyl lithium initiator in two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof or the mixture of several bifunctional alkyl lithium initiators, after the isoprene total overall reaction finishes, once join divinylic monomer in the reactor by monomer ratio again, 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, 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.
2. method according to claim 1, 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.
3. method according to claim 2, wherein conjugated diene is selected from divinyl, isoprene, and oligomerisation degree n is 3-6.
4. method according to claim 1, 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.
5. method according to claim 1, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
6. method according to claim 1, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
7. method according to claim 6, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99111137A CN1108320C (en) | 1999-07-28 | 1999-07-28 | Preparation of block copolymer of butadiene, isoprene and styrene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN99111137A CN1108320C (en) | 1999-07-28 | 1999-07-28 | Preparation of block copolymer of butadiene, isoprene and styrene |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96120017 Division CN1048262C (en) | 1996-10-09 | 1996-10-09 | Butadiene-isoprene-styrene block copolymer and preparing method thereof |
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| CN1244541A CN1244541A (en) | 2000-02-16 |
| CN1108320C true CN1108320C (en) | 2003-05-14 |
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| WO2001060879A1 (en) * | 2000-02-17 | 2001-08-23 | China Petroleum & Chemical Corporation | Multiblock copolymer the preparing method thereof |
| CN105218766A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) |
| CN108178819B (en) * | 2016-12-08 | 2020-11-10 | 中国石油化工股份有限公司 | H-type polymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782119A (en) * | 1984-08-27 | 1988-11-01 | Japan Synthetic Rubber Co., Ltd. | Rubber composition comprising a styrene-butadiene block copolymer having two kinds of blocks |
| US5462994A (en) * | 1994-01-27 | 1995-10-31 | The Dow Chemical Company | Preparation of conjugated diene-monoalkenyl arene block copolymers having a low polydispersity index |
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1999
- 1999-07-28 CN CN99111137A patent/CN1108320C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782119A (en) * | 1984-08-27 | 1988-11-01 | Japan Synthetic Rubber Co., Ltd. | Rubber composition comprising a styrene-butadiene block copolymer having two kinds of blocks |
| US5462994A (en) * | 1994-01-27 | 1995-10-31 | The Dow Chemical Company | Preparation of conjugated diene-monoalkenyl arene block copolymers having a low polydispersity index |
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