CN1749290A - Polarized SEBS and its preparing mthod - Google Patents
Polarized SEBS and its preparing mthod Download PDFInfo
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- CN1749290A CN1749290A CN 200410046769 CN200410046769A CN1749290A CN 1749290 A CN1749290 A CN 1749290A CN 200410046769 CN200410046769 CN 200410046769 CN 200410046769 A CN200410046769 A CN 200410046769A CN 1749290 A CN1749290 A CN 1749290A
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- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 title claims abstract 8
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 239000012190 activator Substances 0.000 claims abstract description 3
- 229920002223 polystyrene Polymers 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- -1 methyl acrylic ester Chemical class 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 229920003046 tetrablock copolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 30
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a kind of polarized SEBS and its preparation process. The product may be expressed as SEBS-P, where S expresses polystyrene block, EB hydrogenated polybutadiene block, and P polarized block formed via polymerizing polar vinyl pyridine or methacrylate monomer. The preparation process adopts butyl lithium as initiator, tetrahydrofuran as activator and cyclohexane as solvent and includes the steps of the first preparing four block SBS-P polymer, and the subsequent selective hydrogenation to obtain polar SEBS. The present invention produces and polarizes SEBS simultaneously, and thus has high polar monomer converting rate, no need of single treatment of un-converted monomer, simple operation and low production cost. The prepared polar SEBS has obvious polarity, excellent performance, and expanded application field.
Description
Technical field
The present invention relates to SEBS of a kind of polar and preparation method thereof.
Background technology
Hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS) is a kind of novel thermoplastic elastomer, and it is the new modified elastomerics that rubber segments polyhutadiene unsaturated double-bond makes through selecting hydrogenation in styrene-butadiene-styrene triblock copolymer (SBS) molecule.SBS behind the hydrogenation in the middle of it polybutadiene block become SEBS with regard to the random copolymerization section that changes into ethene and butene-1.Compare with SBS, SEBS has excellent ageing-resistant performance, thermotolerance and stability, can be widely used in and produce high-grade elastomerics, modifying plastics, the stopping composition of electric wire and sheath material etc., but it is as a kind of non-polar material, uses in some field to be restricted, during particularly as plastic modifier and the polar polymer consistency relatively poor.In order to improve this shortcoming, improve the polarity of SEBS, patent EP0743330 adopts dilithium initiator, after the SBS polymerization is finished, cooling, add after the agent of attaching the names of pre-determined candidates attaches the names of pre-determined candidates, but polar monomer (methyl) esters of acrylic acid that adds anionoid polymerization again is-78 ℃ of polymerizations, contain polarity segmental polarity S BS thereby make two ends, more this polarity S BS carried out selective hydrogenation and make and contain polarity segmental SEBS, it adopted in the production process of SEBS, directly carry out polar-modified, but its polar-modified condition harshness, polymer concentration is low, and suitability for industrialized production yields poorly, the production cost height; In addition, extensively the post-modification method that adopts is the toxilic acid anhydridization of sulfonation, acetylize, carboxylation, chloromethylation, methylolation and EB section in the PS section, the esterification of esters of acrylic acid etc., carries out free radical initiation grafting modification by copolymerization.As (" SCIs " 1997 such as Jiang Ming, 18 (2), 309-312) sulfonation modifying, (" SCI " 1995 such as Shen Chong are carried out in employing on the phenyl ring of SEBS, 20 (5), 827-829) studied chloromethylation and hydroxymethylation on the SEBS phenyl ring; Guo Yan etc. (88-91) studied and utilize Banbury mixer to carry out SEBS grafted maleic anhydride reaction by " polymer material science and engineering " 2003,19 (6); (" polymer science and engineering " 2003 such as Liu Chengmei, 19 (5), 54-56) studied with solution graft copolymerization vinylformic acid and carried out the polar modification, (" synthetic resins and plastics " 2003 such as Wang Xiaolan, 20 (4), 51-55) studied with twin screw reaction extrusion molding glycidyl methacrylate (GMA) has been grafted to SEBS; This post-modification method exists monomer conversion low, and product is easily crosslinked, complex process, shortcomings such as cost height.
Summary of the invention
The object of the present invention is to provide and a kind ofly in the building-up process of SEBS, directly carry out the polar modification and obtain SEBS of polar and preparation method thereof.
The present invention selects for use vinyl pyridine class and methyl acrylic ester etc. can carry out the polar monomer of active anionic polymerization as properties-correcting agent, in the SEBS production process, after the SBS three stage polymerization is intact, the polar monomer that adds the carried out active anionic polymerization of 0.1% ∽ 30% is proceeded polymerization, thereby make end and contain one section polar monomer segmental polarity S BS, again this polarity S BS is proceeded selective hydrogenation, contain polarity segmental SEBS thereby make, the degree of hydrogenation of conjugated diolefine section is greater than 95%.
The SEBS of polar provided by the invention is a kind of Tetrablock copolymer, its structure can be represented with SEBS-P, wherein S represents polystyrene block, EB represents the hydrogenated diblock of polyhutadiene, P represents polar block, and polar block is obtained by vinyl pyridine class, the polymerization of methyl acrylic ester polar monomer.
Vinyl pyridine class polar monomer comprises 2-vinyl pyridine, 4-vinylpridine and isomer thereof, its chemical structural formula such as figure below:
Wherein R=H, CH
3, C
2H
5
The methyl acrylic ester polar monomer comprises methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate, Octyl methacrylate and isomer thereof, and its chemical general formula is: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8).
Weight content at product Semi-polarity block is 0.1%～30%; The ratio of S/EB is 5%～95%/95%～5%; The degree of hydrogenation of conjugated diolefine section is greater than more than 95%, and the number-average molecular weight of product is 10,000～300,000, and molecular weight distributing index is 1.02～2.00.
Preparation method of the present invention is, with the butyllithium is initiator, tetrahydrofuran (THF) is an activator, hexanaphthene is a solvent, concentration 8% ∽ 18% of polymkeric substance in solvent, earlier vinylbenzene is joined and be heated to more than 50 ℃ the back in the hexanaphthene and add butyllithium and carry out initiated polymerization, after first section polymerization is intact, add divinyl and vinylbenzene in succession respectively and carry out second section and three stage polymerization, after three stage polymerization is intact, continue to add vinyl pyridine or methyl acrylic ester monomer again, carry out the 4th section polymerization, promptly get SBS-P four block polymers, the 4th section polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1～120 minute.Above-mentioned SBS-P four block polymers are carried out selective hydration, make Primary Catalysts with the dicyclopentadiene titanium dichloride, methyl benzoate is made promotor, and hydrogenation reaction 1 ∽ is 2 hours under the pressure of 115 ℃ of 45 ℃ of ∽ and 0.5 ∽ 15MPa, can make the SEBS of polar.
The present invention has when producing SEBS, realizes the production of polar SEBS simultaneously, and the transformation efficiency height of polar monomer does not need unconverted monomer is carried out special disposal, and easy and simple to handle, production cost is low; The polar SEBS of preparation has obvious polarity, has more superior performance than common SEBS, can widen Application Areas greatly.
Embodiment
Embodiment 1: in the 5L polymeric kettle, add 3L hexanaphthene and 100ml vinylbenzene and a small amount of tetrahydrofuran (THF), be warmed up to the catalyzer butyllithium that adds after 60 ℃ through calculating, initiated polymerization is after one-step polymerization is finished, add 435ml divinyl and 100ml vinylbenzene respectively and carry out two sections and three stage polymerization, two, after trimerization is finished, promptly get active SBS, the maintenance system temperature is 50-90 ℃, continue to add 10ml 2-vinyl pyridine and carry out the 4th section polymerization, polymerization time is controlled to be 5 minutes.After polymerization is intact, glue is changed in 10 liters of hydrogenation stirring tanks, heat up, logical hydrogen adds promotor methyl benzoate 0.15mmol after waiting the still temperature to reach 50 ℃, continues to stir 20min, be warming up to 70 ℃ simultaneously, to join in the hydrogenation reaction kettle with toluene dissolved 0.65mmol dicyclopentadiene titanium dichloride solution in advance, logical hydrogen reaction, reaction is 2 hours under 1.2MPa pressure, reaction product is carried out stripping, remove hexanaphthene,, promptly get polarity S EBS again with product drying.The product number-average molecular weight is 106758, and molecular weight distributing index is 1.17, the degree of hydrogenation 98.6 of conjugated diene section.
Embodiment 2: change the 10ml 2-vinyl pyridine of the 4th section adding into the 20ml methyl methacrylate, other raw material and manufacture method can make the polarity S EBS that contains methyl methacrylate all with example 1.The product number-average molecular weight is 98480, and molecular weight distributing index is 1.13, the degree of hydrogenation 98.3 of conjugated diene.
Embodiment 3～8: raw material add-on of first three section and polymerization process are all with example 1, and the polar monomer kind of adding and add-on and the 4th section polymeric temperature and time have all obtained polar monomer modified polarity S EBS respectively as following table.
| Sequence number | Polar monomer | Add-on (ml) | The 4th section polymerization temperature (℃) | The 4th section polymerization time (min) | Mn | D | The degree of hydrogenation of conjugated diolefine section |
| Example 3 | 4-vinylpridine | 5 | 100 | 1 | 121678 | 1.16 | 97.8 |
| Example 4 | The 2-vinyl pyridine | 200 | 10 | 20 | 10720 | 1.89 | 98.4 |
| Example 5 | Jia Jibingxisuanyizhi | 20 | 30 | 10 | 90472 | 1.12 | 97.1 |
| Example 6 | Vinyl pyrrolidone | 50 | 0 | 30 | 64789 | 1.21 | 96.5 |
| Example 7 | Butyl methacrylate | 100 | 50 | 2 | 89625 | 1.09 | 97.6 |
| Example 8 | The 2-vinyl pyridine | 300 | 80 | 40 | 167608 | 1.08 | 98.6 |
Claims (2)
1, a kind of SEBS of polar, it is characterized in that it is a kind of Tetrablock copolymer, its structure can be represented with SEBS-P, wherein S represents polystyrene block, EB represents the hydrogenated diblock of polyhutadiene, P represents polar block, and polar block is obtained by vinyl pyridine class, the polymerization of methyl acrylic ester polar monomer; Vinyl pyridine class polar monomer comprises 2-vinyl pyridine, 4-vinylpridine and isomer thereof, its chemical structural formula such as figure below:
Wherein R=H, CH
3, C
2H
5
The methyl acrylic ester polar monomer comprises methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate, Octyl methacrylate and isomer thereof, and its chemical general formula is: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8);
Wherein the weight content of polar block is 0.1%～30%; The ratio of S/EB is 5%～95%/95%～5%; The degree of hydrogenation of conjugated diolefine section is greater than more than 95%, and the number-average molecular weight of product is 10,000～300,000, and molecular weight distributing index is 1.02～2.00.
2, the preparation method of a kind of SEBS of polar, it is characterized in that with the butyllithium being initiator, tetrahydrofuran (THF) is an activator, hexanaphthene is a solvent, concentration 8% ∽ 18% of polymkeric substance in solvent earlier joins vinylbenzene and is heated to more than 50 ℃ the back in the hexanaphthene and adds butyllithium and carry out initiated polymerization; After first section polymerization is intact, adds divinyl and vinylbenzene in succession respectively and carry out second section and three stage polymerization; After three stage polymerization is intact, continue again to add vinyl pyridine or methyl acrylic ester monomer, carry out the 4th section polymerization, promptly get SBS-P four block polymers, the 4th section polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1～120 minute; Above-mentioned SBS-P four block polymers are carried out selective hydration, adopt the dicyclopentadiene titanium dichloride to make Primary Catalysts, methyl benzoate is made promotor, and hydrogenation reaction 1 ∽ is 2 hours under the pressure of 115 ℃ of 45 ℃ of ∽ and 0.5 ∽ 15MPa, can make the SEBS of polar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100467693A CN1326899C (en) | 2004-09-14 | 2004-09-14 | Polarized SEBS and its preparing mthod |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100467693A CN1326899C (en) | 2004-09-14 | 2004-09-14 | Polarized SEBS and its preparing mthod |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749290A true CN1749290A (en) | 2006-03-22 |
| CN1326899C CN1326899C (en) | 2007-07-18 |
Family
ID=36604961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100467693A Expired - Lifetime CN1326899C (en) | 2004-09-14 | 2004-09-14 | Polarized SEBS and its preparing mthod |
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| Country | Link |
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| CN (1) | CN1326899C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781391B (en) * | 2010-01-18 | 2012-05-23 | 苏州大学 | Preparation method of controllable modified SEBS rubber |
| CN103804615A (en) * | 2012-11-06 | 2014-05-21 | 中国石油化工股份有限公司 | Polar diene polymer and preparation method thereof |
| CN105218768A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | Hydrogenated styrene-butadiene-styrene block copolymers synthetic method |
| CN105237696A (en) * | 2015-11-09 | 2016-01-13 | 宁波科元特种橡胶有限公司 | Novel hydrogenated styrene-butadiene-styrene segmented copolymer synthesis method |
| CN106543937A (en) * | 2015-09-17 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of SBS aqueous binders and preparation method thereof |
| CN113416288A (en) * | 2021-06-01 | 2021-09-21 | 广东众和化塑股份公司 | Preparation method of environment-friendly gel-free grafted diene polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0743330B1 (en) * | 1995-05-16 | 2001-08-16 | Shell Internationale Researchmaatschappij B.V. | Selectively hydrogenated symmetrical linear block copolymers |
| AU2001220309A1 (en) * | 2000-12-18 | 2002-07-01 | Samsung General Chemicals Co., Ltd. | Syndiotactic polystyrene compositions having improved impact strength |
| KR100416035B1 (en) * | 2001-02-23 | 2004-02-05 | 삼성종합화학주식회사 | Flame Retardant Syndiotactic Polystyrene Resin Composition |
-
2004
- 2004-09-14 CN CNB2004100467693A patent/CN1326899C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781391B (en) * | 2010-01-18 | 2012-05-23 | 苏州大学 | Preparation method of controllable modified SEBS rubber |
| CN103804615A (en) * | 2012-11-06 | 2014-05-21 | 中国石油化工股份有限公司 | Polar diene polymer and preparation method thereof |
| CN103804615B (en) * | 2012-11-06 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of polarity diene polymer and preparation method thereof |
| CN106543937A (en) * | 2015-09-17 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of SBS aqueous binders and preparation method thereof |
| CN105237696A (en) * | 2015-11-09 | 2016-01-13 | 宁波科元特种橡胶有限公司 | Novel hydrogenated styrene-butadiene-styrene segmented copolymer synthesis method |
| CN105218768A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | Hydrogenated styrene-butadiene-styrene block copolymers synthetic method |
| CN113416288A (en) * | 2021-06-01 | 2021-09-21 | 广东众和化塑股份公司 | Preparation method of environment-friendly gel-free grafted diene polymer |
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| Publication number | Publication date |
|---|---|
| CN1326899C (en) | 2007-07-18 |
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