CN1048022C - Butadiene styrene block copolymer and preparation method thereof - Google Patents
Butadiene styrene block copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN1048022C CN1048022C CN96106448A CN96106448A CN1048022C CN 1048022 C CN1048022 C CN 1048022C CN 96106448 A CN96106448 A CN 96106448A CN 96106448 A CN96106448 A CN 96106448A CN 1048022 C CN1048022 C CN 1048022C
- Authority
- CN
- China
- Prior art keywords
- block
- hvbr
- lithiums
- lvbr
- polar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a penta-block copolymer of butadiene and styrene, and a preparation method thereof. The penta-block copolymer has a PS-HVBR-LVBR-HVBR-PS symmetrical structure, wherein PS is a polystyrol block, HVBR is a high vinyl polybutadiene block, and LVBR is a low vinyl polybutadiene block. The block copolymer prepared by the present invention has better mechanical properties. Compared with universal tri-block copolymers (SBS) of butadiene and styrene, under the condition of certain molecular weight, the amount of styrene is reduced, and the mechanical properties of the copolymer product have no obvious decrease; under the condition of the same proportion of butadiene monomers and styrene monomers, the mechanical properties of the copolymer product are obviously enhanced; the polymerization reaction speed is obviously improved, and the polymerization reaction period is obviously shortened.
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
1, 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
| Sequence number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| S/B | 300/70 | 300/70 | 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 |
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.
Claims (17)
1 one kinds of divinyl, vinylbenzene five segmented copolymers, it is characterized in that this multipolymer has following symmetrical structure: PS-HVBR-LVBR-HVBR-PS, wherein: PS is a polystyrene block, HVBR is the high vinyl polybutadiene block, LVBR is the low vinyl polybutadiene block, contents of ethylene is 35%-100% (weight percent) in the HVBR block, contents of ethylene is 6%-35% (weight percent) in the LVBR block, HVBR/LVBR block content is than being 10/90-60/40 (weight ratio), and monomer ratio vinylbenzene is 15/85-45/55 (weight ratio) than divinyl.
2 segmented copolymers according to claim 1, wherein contents of ethylene is 75%-100% (weight percent) in the HVBR block, contents of ethylene is 10%-20% (weight percent) in the LVBR block.
3 segmented copolymers according to claim 1, wherein HVBR/LVBR block content ratio is 20/80-40/60 (weight ratio).
4 segmented copolymers according to claim 1, wherein monomer ratio vinylbenzene is 20/80-35/65 (weight ratio) than divinyl.
5 segmented copolymers according to claim 1, wherein the number-average molecular weight of segmented copolymer is 5 * 10
4-35 * 10
4
6 segmented copolymers according to claim 5, wherein the number-average molecular weight of segmented copolymer is 10 * 10
4-25 * 10
4
7 one 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 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, at first cause polymerizing butadiene and prepare the LVBR block, the initiation reaction temperature is 30 ℃-80 ℃, and the number-average molecular weight of segmented copolymer is 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, contents of ethylene is 35%-100% (weight percent) in the HVBR block, HVBR/LVBR block content ratio be 10/90-60/40 (weight ratio), after the divinyl total overall reaction finishes, add vinylbenzene again, begin to prepare the PS block, the monomer ratio phenylethylene/butadiene 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.
8 methods according to claim 7 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.
9 according to Claim 8 methods wherein contain oxygen polar additive R
1OCH
2CH
2OR
2And R
1OCH
2CH
2OCH
2CH
2OR
2In R
1, R
2Has different structure.
10 methods according to claim 7, wherein nitrogenous compound is selected from triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
11 methods according to claim 10, wherein nitrogenous compound is selected from Tetramethyl Ethylene Diamine.
12 methods according to claim 7, 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.
13 methods according to claim 12, wherein conjugated diene is selected from divinyl, isoprene, and oligomerisation degree n is 3-6.
14 methods according to claim 7, 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.
15 methods according to claim 7, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
16 methods according to claim 7, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil,
17 methods according to claim 16, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106448A CN1048022C (en) | 1996-08-14 | 1996-08-14 | Butadiene styrene block copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106448A CN1048022C (en) | 1996-08-14 | 1996-08-14 | Butadiene styrene block copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1141928A CN1141928A (en) | 1997-02-05 |
| CN1048022C true CN1048022C (en) | 2000-01-05 |
Family
ID=5119174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106448A Expired - Lifetime CN1048022C (en) | 1996-08-14 | 1996-08-14 | Butadiene styrene block copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048022C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN104164035A (en) | 2005-11-14 | 2014-11-26 | 克拉通聚合物研究有限公司 | Process for preparing a bituminous binder composition |
| MX2009011561A (en) | 2007-05-01 | 2009-11-10 | Kraton Polymers Us Llc | Bituminous binder composition and process for preparing the same. |
| CN105218767B (en) * | 2014-06-25 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of butadiene block copolymer and preparation method thereof |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118335A (en) * | 1993-10-25 | 1995-05-09 | Japan Synthetic Rubber Co Ltd | Hydrogenated diene copolymer |
-
1996
- 1996-08-14 CN CN96106448A patent/CN1048022C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118335A (en) * | 1993-10-25 | 1995-05-09 | Japan Synthetic Rubber Co Ltd | Hydrogenated diene copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1141928A (en) | 1997-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101974139B (en) | Star-shaped high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof | |
| CN1048022C (en) | Butadiene styrene block copolymer and preparation method thereof | |
| CN101899135A (en) | Starlike high impact polystyrene and preparation method thereof | |
| EP1333042B1 (en) | Star block copolymer and preparing method thereof | |
| CN1048262C (en) | Butadiene-isoprene-styrene block copolymer and preparing method thereof | |
| CN1048261C (en) | Block polymer of isoprene and styrene and preparation thereof | |
| CN1118498C (en) | Star-shaped isoprene, butadiene and styrene block copolymer and its prepn | |
| CN1118497C (en) | Star-shaped butadiene-styrene block copolymer and its prepn | |
| CN1133672C (en) | Star-shaped butadiene, isopene and styrene block copolymer and its prepn | |
| CN102108114B (en) | Impact-resistant transparent linear asymmetric block copolymer of vinyl aromatic hydrocarbon and conjugated diene and preparation method of block copolymer | |
| CN1108320C (en) | Preparation of block copolymer of butadiene, isoprene and styrene | |
| CN1121431C (en) | Butadiene-styrene triblock copolymer and its preparation method | |
| CN1108322C (en) | Seven block co-polymer of butadiene, isoprene and styrene, and method for prepn. of same | |
| CN1108323C (en) | Seven block co-polymer of isoprene, butadiene and styrene, and method for prepn. of same | |
| CN1108321C (en) | Three block-co-polymer of isoprene-butadiene-isoprene, and prepn. method thereof | |
| CN1121433C (en) | Isoprene-butadiene-styrene pentablock copolymer and its preparation method | |
| CN1047390C (en) | Process for preparing stereoblock poly-isoprene | |
| CN1045090C (en) | Method for prepn of double functional group lithium alkylide initiation agent | |
| CN1121432C (en) | Isoprene-butadiene-styrene triblock copolymer and its preparation method | |
| CN1121434C (en) | Butadiene-isoprene-styrene pentablock copolymer and its preparation method | |
| CN1133673C (en) | Star-shaped conjugated diolefine-styrene block copolymer and its prepn | |
| CN1108324C (en) | Nine block copolymer of butadiene, isoprene and styrene, and method for prepn. of same | |
| CN1124298C (en) | Butadiene-isoprene-styrene heptablock copolymer and its preparation method | |
| CN1133674C (en) | Star-shaped styrene-conjugated diolefine block copolymer and its prepn | |
| CN101168588B (en) | Crystallization-amorphism-crystallization stereo triblock polybutadiene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1016062 Country of ref document: HK |
|
| CX01 | Expiry of patent term |
Granted publication date: 20000105 |
|
| EXPY | Termination of patent right or utility model |