CN1676539A - Polarized SDS and preparation method thereof - Google Patents
Polarized SDS and preparation method thereof Download PDFInfo
- Publication number
- CN1676539A CN1676539A CN 200410023077 CN200410023077A CN1676539A CN 1676539 A CN1676539 A CN 1676539A CN 200410023077 CN200410023077 CN 200410023077 CN 200410023077 A CN200410023077 A CN 200410023077A CN 1676539 A CN1676539 A CN 1676539A
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- China
- Prior art keywords
- polar
- block
- sds
- polymerization
- vinyl pyridine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 25
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 3
- 239000004793 Polystyrene Substances 0.000 claims abstract description 3
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 3
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 3
- 229920002223 polystyrene Polymers 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229920013730 reactive polymer Polymers 0.000 claims description 2
- 229920003046 tetrablock copolymer Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- -1 methyl acrylic ester compound Chemical class 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- VFNSMNYXBSDMNK-UHFFFAOYSA-N penta-1,3-diene styrene Chemical compound C=CC1=CC=CC=C1.C=CC=CC.C=CC1=CC=CC=C1 VFNSMNYXBSDMNK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention provides a polarized SDS, it is a four block copolymer, its structure can be represented by SDSP, wherein S stands for the polystyrene block, D stands for the polybutadiene block or polyisoprene block, P stands for the polar block, the polar block is polymerized from vinyl pyridine and its polar monomer of derivative; the weight content of the polar block in the polymer is 0.1-50 percent; the ratio of S/D in the SDS chain segment is 5% -95%/95% -5%; the number average molecular weight of the product is 1-30 ten thousand, and the molecular weight distribution index is 1.02-2.00. The preparation method comprises the steps of adding vinylpyridine and a derivative monomer thereof after three-stage polymerization in the SDS production process, and carrying out fourth-stage polymerization at-10-100 ℃ for 1-120 minutes to obtain the product. The method has the advantages that the conversion rate of polar monomers is high and is more than 99 percent, and the unconverted monomers do not need to be specially treated, so the method is simple and convenient to operate and has low production cost; the prepared polarized modified SBS (SIS) has obvious polarity, has more excellent performance than common SBS and can greatly widen the application field.
Description
Technical field
The present invention relates to SDS of a kind of polar and preparation method thereof.
Background technology
Styrene-butadiene-styrene triblock copolymer (SBS) and vinylbenzene-pentadiene-styrene triblock copolymer (SIS) all are the thermoplastic elastomers that adopts anionic polymerisation process to make, and have been widely used in every field such as sole material, tackiness agent, asphalt modification, modifying plastics.But they are as a kind of non-polar material, use in some field to be restricted.In order to improve this shortcoming, improve the polarity of SDS, prior art generally adopts the method for post-modification, is about to SDS epoxidation, sulfonation or carries out the free radical initiation grafting modification by copolymerization of polymerisable monomers such as maleic anhydride, esters of acrylic acid.There is complex process in this post-modification method, the cost height, and the product over-all properties is improved shortcomings such as amplitude is little.
SDS of a kind of polar and preparation method thereof (application number: 03118381), this method is when SDS produces, behind three stage polymerization, adding can be carried out the polar monomer methyl acrylic ester compound of living polymerization and proceed polymerization, contains one section carboxylic acid esters polar monomer segmental polarity S DS thereby make end.This method has obvious superiority than traditional post-modification technology, but still there are some shortcomings, mainly be that the methyl acrylic ester monomer is under higher temperature conditions during polymerization, there is side reaction, monomer conversion is lower, cause existing in the polymer solvent system unconverted monomer, need carry out special disposal, increased the difficulty of postprocessing working procedures.
Summary of the invention
The objective of the invention is to improve the methyl acrylic ester polar monomer and when polymerization, have the low shortcoming of transformation efficiency, the present invention selects for use the pyridines polar monomer as properties-correcting agent, in the SDS production process, behind three stage polymerization, adding can be carried out the pyridines polar monomer of living polymerization and proceed polymerization, thereby make end and contain one section pyridines polar monomer segmental polarity S DS, this method is directly carried out modification in the SDS production process, monomer conversion improves greatly, do not need unconverted monomer in the system is carried out aftertreatment, thus easy and simple to handle, and the modification cost is low, simultaneously, the polar SDS performance that adopts this monomer to make is more superior.
The SDS of polar provided by the invention is a kind of Tetrablock copolymer, its structure can be represented with SDSP, wherein S represents polystyrene block, D represents polybutadiene block or polyisoprene blocks, P represents polar block, polar block comprises that by vinyl pyridine and derivative thereof the polar monomer polymerization of 2-vinyl pyridine, 4-vinylpridine and isomer thereof obtains.
2-vinyl pyridine, 4-vinylpridine and isomer thereof, its chemical structural formula such as figure below:
Wherein R=H, CH
3, C
2H
5
Weight content at polymkeric substance Semi-polarity block is 0.1%～50%; The ratio of S/D is 5%～95%/95%～5% in the SDS segment; 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, 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 (or pentadiene) and vinylbenzene in succession respectively and carry out second section and three stage polymerization, after three stage polymerization is intact, promptly get SBS or SIS three block reactive polymers, continue again to add vinyl pyridine and derivatives monomer thereof, carry out the 4th section polymerization, the polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1～120 minute.
The present invention has and can realize the production of polar modified SBS (SIS) simultaneously when producing SBS (SIS), and the transformation efficiency height of polar monomer greater than 99%, does not need unconverted monomer is carried out special disposal, thereby easy and simple to handle, and production cost is low; The polar modified SBS (SIS) of preparation has obvious polarity, has more superior performance than common SBS, 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 80 ℃, continue to add the 10ml2-vinyl pyridine and carry out the 4th section polymerization, polymerization time is controlled to be 5 minutes.After polymerization is intact reaction product is carried out stripping, remove hexanaphthene,, promptly get polarity S BS again with product drying.The product number-average molecular weight is 96754, and molecular weight distributing index is 1.18.The transformation efficiency of 2-vinyl pyridine is 99.5%.
Embodiment 2: change the divinyl of second section adding into pentadiene, other raw material and manufacture method can make polarity S IS all with example 1.The product number-average molecular weight is 94490, and molecular weight distributing index is 1.12.The transformation efficiency of 2-vinyl pyridine is 99.7%.
Embodiment 3～10: raw material add-on of first three section and polymerization process are all with example 1, and the vinyl pyridine kind of adding and add-on and the 4th section polymeric temperature and time have all obtained the polarity S BS of vinyl pyridine modification respectively as following table.
| Sequence number | Vinyl pyridine | Add-on (ml) | The 4th section polymerization temperature (℃) | The 4th section polymerization time (min) | ??Mn | ????D | Polar monomer transformation efficiency % |
| Example 3 | 4-vinylpridine | ????5 | ????100 | ????1 | ??121678 | ??1.16 | ????99.2 |
| Example 4 | The 2-vinyl pyridine | ????200 | ????10 | ????20 | ??10720 | ??1.89 | ????99.8 |
| Example 5 | 4-vinylpridine | ????20 | ????30 | ????10 | ??90472 | ??1.12 | ????99.7 |
| Example 6 | The 2-vinyl pyridine | ????50 | ????0 | ????30 | ??64789 | ??1.21 | ????99.3 |
| Example 7 | 4-vinylpridine | ????100 | ????50 | ????2 | ??89625 | ??1.09 | ????99.4 |
| Example 8 | The 2-vinyl pyridine | ????300 | ????80 | ????40 | ??167608 | ??1.08 | ????99.9 |
| Example 9 | The 2-vinyl pyridine | ????100 | ????-10 | ????120 | ??297500 | ??1.95 | ????99.2 |
| Example 10 | The 2-vinyl pyridine | ????150 | ????50 | ????15 | ??75620 | ??1.02 | ????99.7 |
Claims (2)
1, a kind of SDS of polar, it is a kind of Tetrablock copolymer, structure can be represented with SDSP, wherein S represents polystyrene block, D represents polybutadiene block or polyisoprene blocks, P represents polar block, it is characterized in that polar block is obtained by the polar monomer polymerization of vinyl pyridine and derivative thereof; The polar monomer of vinyl pyridine and derivative thereof 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 weight content of polymkeric substance Semi-polarity block is 0.1%～50%; The ratio of S/D is 5%～95%/95%～5% in the SDS segment; The number-average molecular weight of product is 10,000～300,000; Molecular weight distributing index is 1.02～2.00.
2, the preparation method of a kind of polar SDS, it is characterized in that with the butyllithium being initiator, tetrahydrofuran (THF) is an activator, hexanaphthene is a 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 (or pentadiene) and vinylbenzene in succession respectively and carry out second section and three stage polymerization, after three stage polymerization is intact, promptly get SBS or SIS three block reactive polymers, continue again to add vinyl pyridine and derivatives monomer thereof, carry out the 4th section polymerization, the polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1～120 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410023077 CN1676539A (en) | 2004-04-02 | 2004-04-02 | Polarized SDS and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410023077 CN1676539A (en) | 2004-04-02 | 2004-04-02 | Polarized SDS and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1676539A true CN1676539A (en) | 2005-10-05 |
Family
ID=35049302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410023077 Pending CN1676539A (en) | 2004-04-02 | 2004-04-02 | Polarized SDS and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1676539A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724240B (en) * | 2008-10-30 | 2012-02-29 | 中国石油化工股份有限公司 | Makrolon/ABS composite material and preparation method thereof |
| CN104072746A (en) * | 2014-07-10 | 2014-10-01 | 大连理工大学 | Polarized SIS (Styrene Isoprene Styrene) containing polyethylene oxide block and preparation method |
| 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) |
| CN105693963A (en) * | 2016-03-04 | 2016-06-22 | 安徽国星生物化学有限公司 | Preparation method of styrene-vinyl pyridine two-block copolymer |
| 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 |
-
2004
- 2004-04-02 CN CN 200410023077 patent/CN1676539A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724240B (en) * | 2008-10-30 | 2012-02-29 | 中国石油化工股份有限公司 | Makrolon/ABS composite material and preparation method thereof |
| CN104072746A (en) * | 2014-07-10 | 2014-10-01 | 大连理工大学 | Polarized SIS (Styrene Isoprene Styrene) containing polyethylene oxide block and preparation 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 |
| 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) |
| CN105693963A (en) * | 2016-03-04 | 2016-06-22 | 安徽国星生物化学有限公司 | Preparation method of styrene-vinyl pyridine two-block copolymer |
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