CN1141928A - Butadiene styrene block copolymer and preparation method thereof - Google Patents
Butadiene styrene block copolymer and preparation method thereof Download PDFInfo
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Abstract
This block copolymer has a symmetrical structure of PS-HVBR-LVBR-HVBR-PS, in which PS is polystyrene block, HVBR is high-vinyl polybutadiene block, LVBR is low-vinyl polybutadiene block. Said block copolymer has better mechanical properties, and compared with the general butadiene and phenylethylene three-block copolymer (SBS) it has the advantage of: reduced amount of phenylethylene to be used under the condition of a certain molecular weight without clear reducing of its mechanical properties; clear improved mechanical propenties under the same monomer ratio of butadiene and phenylethylene; obvious increased polymerizing reaction speed and clear shortened polymerizing reaction period.
Description
The present invention relates to a class divinyl, vinylbenzene five segmented copolymers and preparation method thereof, this segmented copolymer has the A-B-C-B-A symmetrical structure, wherein: A is polystyrene block (being called for short the PS section), B is high vinyl polybutadiene block (being called for short the HVBR section), C is low vinyl polybutadiene block (being called for short the LVBR section), and the structure of this five segmented copolymers is: PS-HVBR-LVBR-HVBR-PS.The prepared segmented copolymer of the present invention has better mechanical property, and adopts this preparation method, and the polyreaction cycle is obviously shortened.
Divinyl, styrene block copolymer be the A-C-A structure normally, as divinyl, styrene triblock copolymer (be referred to as SBS), wherein polybutadiene block (being the B section among the SBS) is a low vinyl polybutadiene block (contents of ethylene is generally 8%-20%).Under the condition of certain molecular weight, the method that SBS improves its mechanical property normally increases cinnamic content, but because styrene resource shortage, price are more expensive, and the increase of styrene content causes, and copolymer product hardness increases, flexibility decrease, and therefore the use of this method is subjected to restriction to a certain degree.
The objective of the invention is to prepare a class divinyl, vinylbenzene five segmented copolymers, to obtain following positive effect: compare with SBS, (1) reduces cinnamic consumption under the condition of certain molecular weight, and the mechanical property of copolymer product does not have remarkable decline; (2) under the condition of identical divinyl, styrene monomer proportioning, the mechanical property of copolymer product obviously improves; (3) polymerization rate is significantly accelerated, and the polyreaction cycle obviously shortens.
Technical characterictic of the present invention is the B section among the common SBS is replaced upright structure three block structures of HVBR-LVBR-HVBR by common single LVBR structure, promptly replace " hard-soft-hard " segment structure by common single soft segment structure, improve the mechanical property of copolymer product effectively, and can reduce cinnamic consumption.Owing to when preparation HVBR block, added polar additive, improved the speed of response of polyreaction middle and later periods effectively, shortened the polyreaction cycle.Key problem in technology of the present invention just is to control the block ratio of HVBR and LVBR, contents of ethylene in the control HVBR block, the molecular weight of control multipolymer.
Prepared divinyl, vinylbenzene five segmented copolymers of the present invention have following symmetrical structure: PS-HVBR-LVBR-HVBR-PS, wherein: PS, HVBR, LVBR connotation as mentioned above, 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
4Vinylbenzene, divinylic monomer proportioning (S/B) general range are 15/85-45/55 (weight ratio, below identical), and optimum range is 20/80-35/65; HVBR, LVBR block are 10/90-60/40 (weight ratio, below identical) than (HVBR/LVBR) general range, and optimum range is 20/80-40/60; The contents of ethylene general range is 6%-35% (weight percent, below identical) in the LVBR block, and optimum range is 10%-20%; The contents of ethylene general range is 35%-100% (weight percent, below identical) in the HVBR block; Optimum range is 75%-100%.
Five segmented copolymer preparation methods are as follows for divinyl involved in the present invention, vinylbenzene:
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
4-35 * 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, at first cause polymerizing butadiene and prepare the LVBR block, when LVBR block length reaches preset value, add polar additive, begin to prepare the HVBR block, polar additive is selected from and contains oxygen, nitrogenous, sulfur-bearing, a kind of polar compound in the phosphorous polar compound or the mixture of several polar compounds, the consumption of polar additive is looked its kind because of the difference of polarity power, the height of HVBR block contents of ethylene and deciding, the joining day of polar additive decides according to the block ratio of HVBR/LVBR, the contents of ethylene general range is 35%-100% (weight percent) in the HVBR block, the general range of HVBR/LVBR block content ratio is 10/90-60/40 (weight ratio), after the divinyl total overall reaction finishes, add vinylbenzene again, begin to prepare the PS block, monomer ratio phenylethylene/butadiene general range is 15/85-45/55 (weight ratio), after the vinylbenzene total overall reaction is 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 PS-HVBR-LVBR-HVBR-PS 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, as: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as: Mixed XYLENE), mixing-in fat hydrocarbon (as: raffinating oil) etc.
Polar additive used in the present invention is selected from and contains oxygen, nitrogenous, sulfur-bearing, contains a kind of polar compound in the Phosphorus polar compound or the mixture of several polar compounds, as: (1) oxygenatedchemicals is selected from ether, tetrahydrofuran (THF) (being called for short 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
2, R
2Be not all good, as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound is selected from triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), is good with TMEDA; (3) P contained compound is selected HMPA (HMPA) for use.
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, Comparative Examples, 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, 245 gram divinyl, 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
4When butadiene polymerization proceeds to 25 minutes, transformation efficiency reaches 30%, add TMEDA, TMEDA/Li (mol ratio) is 3.0, continue reaction 30 minutes, after butadiene conversion reaches 100%, add 105 gram vinylbenzene again, continue reaction 25 minutes, after the styrene polymerization reaction is all over, add anti-aging agent (1010 with weight ratio 1: 1 mixes with 2.6.4) 3.5 grams, adopt traditional method to carry out the glue aftertreatment, dry after employing classical way specimen structure and mechanical property, the result is as follows: contents of ethylene is 80% in the HVBR block, molecular weight distributing index is 1.21, and tensile strength is 23.4MPa, and 300% tensile modulus is 2.9MPa, elongation at break is 670%, and Shore A hardness is 67.Embodiment 2-7
Polymerization process and processing condition are with embodiment 1, just vinylbenzene, divinylic monomer proportioning difference, HVBR block content difference, HVBR/LVBR block are than different, prepared PS-HVBR-LVBR-HVBR-PS five segmented copolymers, polymerization process condition, product structure transitivity test result are respectively shown in sample 1-6 in the table 1.Comparative Examples 1-2
Polymerization process and processing condition are with embodiment 1, just in the butadiene polymerization process, no longer add polar additive, polyhutadiene all reacts with the LVBR block fashion, the finished product are the PS-LVBR-PS structure, be common SBS, polymerization process condition, product structure and physical property measurement result are respectively shown in sample in the table 17,8.
Table 1 polymerization process condition and product rerum natura
Annotate: S/B is vinylbenzene and divinylic monomer proportioning, and S% is a styrene content, and H1.2% is a contents of ethylene in the HVBR block.
| Sequence number | ????1 | ?2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 |
| ?S/B | ????30/70 | ?30/70 | ????40/60 | ????40/60 | ????40/60 | ????20/80 | ????30/70 | ????40/60 |
| ?S％ | ????30 | ?30 | ????40 | ????40 | ????40 | ????20 | ????30 | ????40 |
| ?HVBR％ | ????20 | ?40 | ????30 | ????20 | ????30 | ????50 | ????0 | ????0 |
| ?LVBR％ | ????50 | ?30 | ????30 | ????40 | ????30 | ????30 | ????70 | ????60 |
| ?H1.2％ | ????82 | ?55 | ????80 | ????85 | ????50 | ????86 | ????- | ????- |
| Tensile strength (MPa) | ????2105 | ?21.0 | ????25.6 | ????23.8 | ????24.0 | ????20.7 | ????18.1 | ????22.3 |
| 300% tensile modulus (MPa) | ????2.6 | ?2.5 | ????3.3 | ????3.1 | ????3.1 | ????2.3 | ????2.0 | ????2.8 |
| Elongation at break (%) | ????690 | ?690 | ????500 | ????506 | ????520 | ????730 | ????710 | ????550 |
| Hardness (Shao Shi A) | ????63 | ?64 | ????84 | ????81 | ????83 | ????75 | ????60 | ????82 |
Claims (20)
1 one kinds of divinyl, vinylbenzene five segmented copolymers is characterized in that this multipolymer has following symmetrical structure:
PS-HVBR-LVBR-HVBR-PS is wherein: PS is a polystyrene block, and HVBR is the high vinyl polybutadiene block, and LVBR is the low vinyl polybutadiene block.
2 segmented copolymers according to claim 1, wherein the contents of ethylene general range is 35%-100% (weight percent) in the HVBR block, the contents of ethylene general range is 6%-35% (weight percent) in the LVBR block.
3 segmented copolymers according to claim 1, wherein the contents of ethylene optimum range is 75%-100% (weight percent) in the HVBR block, the contents of ethylene optimum range is 10%-20% (weight percent) in the LVBR block.
4 segmented copolymers according to claim 1, wherein the general range of HVBR/LVBR block content ratio is 10/90-60/40 (weight ratio).
5 segmented copolymers according to claim 1, wherein the optimum range of HVBR/LVBR block content ratio is 20/80-40/60 (weight ratio).
6 segmented copolymers according to claim 1, wherein monomer ratio vinylbenzene is 15/85-45/55 (weight ratio) than divinyl general range.
7 segmented copolymers according to claim 1, wherein monomer ratio vinylbenzene is 20/80-35/65 (weight ratio) than divinyl optimum range.
8 segmented copolymers according to claim 1, wherein the number-average molecular weight scope of segmented copolymer is generally 5 * 10
4-35 * 10
4
9 segmented copolymers according to claim 1, wherein the number-average molecular weight optimum range of segmented copolymer is 10 * 10
4-25 * 10
4
10 1 kinds of divinyl, the preparation method of vinylbenzene five segmented copolymers, it is characterized in that: in the non-polar hydrocarbon kind solvent, add divinyl, 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, with the bifunctional lithium alkylide is initiator, the 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, at first cause polymerizing butadiene and prepare the LVBR block, the initiation reaction temperature is 30 ℃-80 ℃, and the number-average molecular weight scope of segmented copolymer is generally 5 * 10
4-35 * 10
4When LVBR block length reaches preset value, add polar additive, polar additive is selected from and contains oxygen, nitrogenous, sulfur-bearing, a kind of polar compound in the phosphorous polar compound or the mixture of several polar compounds, begin to prepare the HVBR block, the contents of ethylene general range is 35%-100% (weight percent) in the HVBR block, the general range of HVBR/LVBR block content ratio is 10/90-60/40 (weight ratio), after the divinyl total overall reaction finishes, add vinylbenzene again, begin to prepare the PS block, monomer ratio phenylethylene/butadiene general range is 15/85-45/55 (weight ratio), after the vinylbenzene total overall reaction is finished, adds anti-aging agent, and glue carried out aftertreatment, obtain the PS-HVBR-LVBR-HVBR-PS segmented copolymer.
11 methods according to claim 10 wherein contain the oxygen polar additive and are selected from: ether, tetrahydrofuran (THF), crown ether compound, R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical also can be different.
12 methods according to claim 11 wherein contain oxygen polar additive R
1OCH
2CH
2OR
2And R
1OCH
2CH
2OCH
2CH
2OR
2With R
1, R
2It is good having different structure.
13 methods according to claim 11, wherein nitrogenous compound is selected from triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
14 methods according to claim 13, wherein nitrogenous compound is preferably from Tetramethyl Ethylene Diamine.
15 methods according to claim 10, 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.
16 methods according to claim 15, wherein conjugated diene is preferably from divinyl, isoprene, and oligomerisation degree n is good with 3-6.
17 methods according to claim 10, 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.
18 methods according to claim 10, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
19 methods according to claim 10, wherein the non-polar hydrocarbon kind solvent generally is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil,
20 methods according to claim 19, wherein the non-polar hydrocarbon kind solvent preferably from: hexane, hexanaphthene, raffinate oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106448A CN1048022C (en) | 1996-08-14 | 1996-08-14 | Butadiene styrene block copolymer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106448A CN1048022C (en) | 1996-08-14 | 1996-08-14 | Butadiene styrene block copolymer and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1141928A true CN1141928A (en) | 1997-02-05 |
| CN1048022C CN1048022C (en) | 2000-01-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| CN1121434C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Butadiene-isoprene-styrene pentablock copolymer and its preparation method |
| CN1121433C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Isoprene-butadiene-styrene pentablock copolymer and its preparation method |
| CN1121431C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Butadiene-styrene triblock copolymer and its preparation method |
| CN1121432C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Isoprene-butadiene-styrene triblock copolymer and its preparation method |
| CN1124298C (en) * | 2000-02-17 | 2003-10-15 | 中国石油化工股份有限公司 | Butadiene-isoprene-styrene heptablock copolymer and its preparation method |
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| CN106699999A (en) * | 2015-08-05 | 2017-05-24 | 中国石油化工股份有限公司 | Linear SBS and preparation method thereof, oil-extended rubber and modified asphalt |
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Family Cites Families (1)
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|---|---|---|---|---|
| JP3460274B2 (en) * | 1993-10-25 | 2003-10-27 | Ｊｓｒ株式会社 | Hydrogenated diene copolymer and resin composition |
-
1996
- 1996-08-14 CN CN96106448A patent/CN1048022C/en not_active Expired - Lifetime
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| CN1121434C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Butadiene-isoprene-styrene pentablock copolymer and its preparation method |
| CN1121433C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Isoprene-butadiene-styrene pentablock copolymer and its preparation method |
| CN1121431C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Butadiene-styrene triblock copolymer and its preparation method |
| CN1121432C (en) * | 2000-02-17 | 2003-09-17 | 中国石油化工股份有限公司 | Isoprene-butadiene-styrene triblock copolymer and its preparation method |
| CN1124298C (en) * | 2000-02-17 | 2003-10-15 | 中国石油化工股份有限公司 | Butadiene-isoprene-styrene heptablock copolymer and its preparation method |
| US7592381B2 (en) | 2005-11-14 | 2009-09-22 | Kraton Polymers U.S. Llc | Process for preparing a bituminous binder composition |
| US7622519B2 (en) | 2007-05-01 | 2009-11-24 | Kraton Polymers U.S. Llc | Bituminous binder composition and process for preparing the same |
| CN101675114B (en) * | 2007-05-01 | 2012-09-26 | 科腾聚合物美国有限责任公司 | Bituminous binder composition and process for preparing the same |
| CN105218767A (en) * | 2014-06-25 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of butadiene block copolymer and preparation method thereof |
| CN106699999A (en) * | 2015-08-05 | 2017-05-24 | 中国石油化工股份有限公司 | Linear SBS and preparation method thereof, oil-extended rubber and modified asphalt |
| CN106699999B (en) * | 2015-08-05 | 2019-02-19 | 中国石油化工股份有限公司 | Type SBS and preparation method thereof and oil-filled glue and modified pitch |
| CN108559218A (en) * | 2018-05-11 | 2018-09-21 | 苏州长振新材料科技有限公司 | A kind of high resilience linear multi-block polymer and preparation method thereof |
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|---|---|
| CN1048022C (en) | 2000-01-05 |
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