CN1454911A - Polarized SDS and preparation method thereof - Google Patents
Polarized SDS and preparation method thereof Download PDFInfo
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- CN1454911A CN1454911A CN 03118381 CN03118381A CN1454911A CN 1454911 A CN1454911 A CN 1454911A CN 03118381 CN03118381 CN 03118381 CN 03118381 A CN03118381 A CN 03118381A CN 1454911 A CN1454911 A CN 1454911A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 4
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 4
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 229920003046 tetrablock copolymer Polymers 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- 229920013730 reactive polymer Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006000 epoxidized styrene-butadiene-styrene block copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010550 living polymerization reaction 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
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a polarized SDS, it is a kind of tetrablock copolymer, the structure is "SDSM", wherein S stands for the polystyrene block, D stands for the polybutadiene block or polyisoprene block, M stands for the polar block, the polar block is represented by the chemical formula: CH 2CHC(CH3)COO(CnH2n+1) (n-1-8) by polymerizing a polar monomer; the ratio of S/D is 5% -95%/95% -5%; the weight content of M is 0.1-50%; the 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 is that in the production process of SDS, after the third section polymerization, the polar monomer capable of making active polymerization is added into the obtained SDS triblock active polymer to make continuous polymerization so as to obtain the polar SDS whose end contains a section of polar monomer chain segment. The polarized SDS is a block copolymer, the content of polar monomers can be controlled at will, and the polarized SDS can be used as an adhesive, so that the adhesive property of the polarized SDS to polar materials can be greatly improved, and compared with SBS or SIS, the peel strength can be improved by more than 50%; the preparation method is simple and convenient to operate and low in production cost.
Description
Technical field
The present invention relates to SDS of a kind of polar and preparation method thereof.
Background technology
(S represents polystyrene block to thermoplastic elastomer SDS, D represents polybutadiene block or polyisoprene blocks) compare with General Purpose Rubber and have a series of high-performances, obtained application more and more widely in a lot of fields such as sole material, tackiness agent, asphalt modification at present.But SDS is as a kind of non-polar material, and it exists and the not enough defective of polar material cohesive strength when using as tackiness agent.In order to improve this shortcoming of SDS, need carry out the polar modification to SDS.
In the prior art, the method that SDS is carried out the polar modification is to carry out the free radical grafting copolymerization modification with SDS epoxidation, sulfonation or with polymerisable monomers such as maleic anhydride, esters of acrylic acids.As document (1) " Speciality Petrochemicals " in September, 2002, the fifth phase, P23-25 " sulfonation modifying of SBS " Wei Yi etc., the SBS that will be dissolved in the hexanaphthene with the vitriol oil carries out sulfonation reaction, made the polarity SBS of sulfonation modifying, sulfonated SBS is compared with common SBS, and it obviously improves the cohesive strength of polar material; Document (2) " Chinese tackiness agent " 2000, the 9th volume first phase, P5-6 " development of epoxidized SBS tackiness agent " Di Mingwei, make oxygenant with the peroxyformic acid that hydrogen peroxide and formic acid reaction generate, two keys in soft section of the divinyl among the SBS are carried out epoxidation reaction, can make the polarity SBS of epoxidation modification, the adhesive property to polar material when being used for tackiness agent obviously improves; Document (3) " synthetic resins and plastics " 1997,14 (2), P30-32 " research of SBS Graft Adhesive " Zhang Changde etc., with methyl methacrylate and butyl acrylate as grafted monomer, as initiator SBS solution is carried out graft reaction with dibenzoyl peroxide, made the polarity SBS of methyl methacrylate and butyl acrylate graft modification, the adhesive property to polar material during as tackiness agent obviously improves.
Above-mentioned polarity SBS all adopts the preparation of post-modification method, and there is following shortcoming in product: the percentage of grafting of (1) modified SBS is not high, and general percentage of grafting only is 1%-5%, and the cohesive force of glue is not strong, and difficulty satisfies the shoemaking industry requirement.(2) production cost height generally adopts grafting solution method, the price height of solvent, but also to purify and wash the cost height of modified SBS.
Summary of the invention
In order to improve the shortcoming that prior art Semi-polarity SDS exists, the invention provides a kind of polar SDS, it is a kind of Tetrablock copolymer, structure is " SDSM ", wherein S represents polystyrene block, D represents polybutadiene block or polyisoprene blocks, and M represents polar block, and polar block by chemical general formula is: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8) polar monomer polymerization obtains; The ratio of S/D is 5%～95%/95%～5%; The weight content of M is 0.1%～50%; The molecular-weight average of product is 10,000～300,000, and molecular weight distributing index is 1.02～2.00.
Polar SDS provided by the invention is in the SDS production process, behind three stage polymerization, in the SDS three block reactive polymers that obtain, adding can be carried out the polar monomer of living polymerization and proceed polymerization, contains one section polar monomer segmental polarity S DS thereby make end.Its technical scheme is, in the anionoid polymerization system of preparation SDS, earlier vinylbenzene is heated to more than 50 ℃, add lithium alkylide and carry out initiated polymerization, after first section polymerization is intact, adds divinyl or pentadiene and vinylbenzene in succession respectively and carry out second section and three stage polymerization, after three stage polymerization is intact, obtain SBS or SIS three block reactive polymers, continuation adding chemical general formula is again: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8) polar monomer carries out the 4th section polymerization, the 4th section polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1 minute～120 minutes, thus preparation polar SDS.
This method is directly to carry out modification in the SDS production process, and easy and simple to handle, production cost is low.The polar SDS that this method is produced is a segmented copolymer, and the content of polar monomer can be controlled arbitrarily, as tackiness agent, can improve it greatly to the adhesiveproperties between the polar material, compares with SBS or SIS, and stripping strength can improve more than 50%.
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, be cooled to 40 ℃, continue to add the 50ml methyl methacrylate and carry out four sections polymerizations, polymerization time is controlled to be 30 minutes.After polymerization is intact reaction product is carried out stripping, remove hexanaphthene,, promptly get the polarity SBS again with product drying.The product number-average molecular weight is 86754, and molecular weight distributing index is 1.08.
Embodiment 2: change the divinyl of second section adding into pentadiene, other raw material and manufacture method can make polar SIS all with example 1.The product number-average molecular weight is 74490, and molecular weight distributing index is 1.02.
Embodiment 3～8: raw material add-on of first three section and polymerization process are all with example 1, and the kind of the polar monomer of adding and add-on and the 4th section polymeric temperature and time see Table 1, have obtained diverse polarity SBS.
Table 1
| Sequence number | The polar monomer kind | Add-on (ml) | The 4th section polymerization temperature (℃) | The 4th section polymerization time (min) | ????Mn | ????D |
| Example 3 | Methyl methacrylate | ????5 | ????60 | ????5 | ??121678 | ??1.06 |
| Example 4 | Methyl methacrylate | ????400 | ????10 | ????20 | ??10720 | ??1.89 |
| Example 5 | Jia Jibingxisuanyizhi | ????50 | ????30 | ????10 | ??90472 | ??1.12 |
| Example 6 | Butyl methacrylate | ????100 | ????0 | ????30 | ??64789 | ??1.21 |
| Example 7 | Octyl methacrylate | ????200 | ????50 | ????2 | ??89625 | ??1.02 |
| Example 8 | Methyl methacrylate | ????300 | ????80 | ????40 | ??167608 | ??1.08 |
Claims (2)
1, a kind of polar SDS is characterized in that it is a kind of Tetrablock copolymer, and structure is " SDSM ", and wherein S represents polystyrene block, and D represents polybutadiene block or polyisoprene blocks, and M represents polar block, and polar block by chemical general formula is: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8) polar monomer polymerization obtains; The ratio of S/D is 5%～95%/95%～5%; The weight content of M is 0.1%～50%; The molecular-weight average 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 polar SDS, it is characterized in that in the anionoid polymerization system of preparation SDS, earlier vinylbenzene is heated to more than 50 ℃, add lithium alkylide and carry out initiated polymerization, after first section polymerization is intact, adds divinyl or pentadiene and vinylbenzene in succession respectively and carry out second section and three stage polymerization, after three stage polymerization is intact, obtain SBS or SIS three block reactive polymers, continuation adding chemical general formula is again: CH
2CHC (CH
3) COO (C
nH
2n+1) (n=1-8) polar monomer carries out the 4th section polymerization, the 4th section polymeric temperature is controlled at-10 ℃～100 ℃, and polymerization time was controlled at 1 minute～120 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118381 CN1454911A (en) | 2003-05-14 | 2003-05-14 | Polarized SDS and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118381 CN1454911A (en) | 2003-05-14 | 2003-05-14 | Polarized SDS and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1454911A true CN1454911A (en) | 2003-11-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03118381 Pending CN1454911A (en) | 2003-05-14 | 2003-05-14 | Polarized SDS and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1454911A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072744A (en) * | 2014-07-10 | 2014-10-01 | 大连理工大学 | Polyethylene oxide block containing polarized butadiene/isoprene/styrol copolymer 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 |
| CN106220798A (en) * | 2016-08-30 | 2016-12-14 | 广东众和化塑有限公司 | A kind of high melting means, high transparency SIS elastomer and preparation method thereof |
| CN106397695A (en) * | 2016-08-30 | 2017-02-15 | 广东众和化塑有限公司 | High-melting-point high-transparency SBS (Styrene Butadiene Styrene) elastomer 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 |
-
2003
- 2003-05-14 CN CN 03118381 patent/CN1454911A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072744A (en) * | 2014-07-10 | 2014-10-01 | 大连理工大学 | Polyethylene oxide block containing polarized butadiene/isoprene/styrol copolymer 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 |
| CN104072744B (en) * | 2014-07-10 | 2016-08-24 | 大连理工大学 | A kind of polar butadiene/isoprene/styrol copolymer containing poly-ethylene 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 |
| CN106220798A (en) * | 2016-08-30 | 2016-12-14 | 广东众和化塑有限公司 | A kind of high melting means, high transparency SIS elastomer and preparation method thereof |
| CN106397695A (en) * | 2016-08-30 | 2017-02-15 | 广东众和化塑有限公司 | High-melting-point high-transparency SBS (Styrene Butadiene Styrene) elastomer and preparation method thereof |
| CN106220798B (en) * | 2016-08-30 | 2019-02-26 | 广东众和化塑有限公司 | A kind of high melting means, high transparency SIS elastomer and preparation method thereof |
| CN106397695B (en) * | 2016-08-30 | 2019-04-30 | 广东众和化塑有限公司 | A kind of high melting means, high transparency SBS elastomer and preparation method thereof |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |