CN1676539A - Polarized SDS and its preparing method - Google Patents
Polarized SDS and its preparing method Download PDFInfo
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- 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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Abstract
This invention provides a polarized SDS that is a tetra-block multipolymer, and its structure can be expressed by SDSP, S represents PS block, D represents polybutadiene block or PI block, P represents polar block that is polymerized by ethenyl pyridine and the polar monomer of its vibrant; the polar block weight is 0.1%-0.5%, the S/D in SDS chain block is 5%-95%/95%-5%;the molecular weight of the product is 10-300 thousand, the distribution index of molecular is 1.02-2.00. The preparation method is during the manufacturing procedure of SDS, add ethenyl pyridine and monomer of its vibrant after three-block polymerization reaction, and carry out the forth block polymerization in -10deg.C-100deg.C for 1-120 minutes. This invention has high conversion of the polar monomer, which is more than 99%, and does not need specifically treatment of the non-conversed polar monomer, therefore, it has simple operation and low cost. And SBS (SIS) has apparent polarization and has better performance than the usual SBS and can expand the utilization 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410023077 CN1676539A (en) | 2004-04-02 | 2004-04-02 | Polarized SDS and its preparing method |
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|---|---|---|---|
| CN 200410023077 CN1676539A (en) | 2004-04-02 | 2004-04-02 | Polarized SDS and its preparing method |
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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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