CN105218766A - A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) - Google Patents
A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) Download PDFInfo
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- CN105218766A CN105218766A CN201510756744.0A CN201510756744A CN105218766A CN 105218766 A CN105218766 A CN 105218766A CN 201510756744 A CN201510756744 A CN 201510756744A CN 105218766 A CN105218766 A CN 105218766A
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Abstract
The present invention relates to a kind of synthetic method of styrene isoprene styrene block copolymer (SIS); under the condition of anhydrous and oxygen-free, high pure nitrogen protection; by the mix and blend reaction in polymeric kettle of thinner, polar compound, initiator and total monomer; the polymerisate be precipitated carries out air-dry, dry; by addition sequence, the add-on of strict control material, add indegree; thus could low-gel content be obtained, the styrene isoprene styrene block copolymer (SIS) material that high maximum elongation, physical and mechanical property are good.
Description
Technical field
The present invention relates to the synthetic method of segmented copolymer, particularly relate to a kind of synthetic method of styrene isoprene styrene block copolymer (SIS).
Background technology
Styrene-isoprene-phenylethene (SIS) thermoplastic block copolymers is sisters' product of thermoplastic elastomer SBS's (styrene-butadiene-styrene thermoplastic block copolymers), is all the important kind of SBC (styrene series thermoplastic elastomer).SIS is Philips Petroleum Company of the U.S. and Shell Chemical Co respectively at synchronous development realize the thermoplastic elastomer of new generation of the suitability for industrialized production sixties in last century.It has excellent bellow seal and high temperature confining force; the Microphase Separation structures shape of its uniqueness it there is when being used as tackiness agent unique superiority; the pressure sensitive adhesive be mixed with and hot melt adhesive are widely used in medical treatment, electrical isolation, packaging, protection are sheltered, indicate, the field such as be adhesively fixed; particularly it produces hot-fusible pressure-sensitive adhesive (HMPSA); have not containing solvent, the feature that nuisanceless, energy consumption is little, equipment is simple, bonding scope is wide; receive praises from customers, development in recent years speed is very fast.
Summary of the invention
To the present situation of above-mentioned prior art, technical problem to be solved by this invention be to provide a kind of need not coupling agent, step styrene isoprene styrene block copolymer (SIS) that is simple, that easily realize synthetic method.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of synthetic method of styrene isoprene styrene block copolymer (SIS); under the condition of anhydrous and oxygen-free, high pure nitrogen protection; by the mix and blend reaction in polymeric kettle of thinner, polar compound, initiator and total monomer, the polymerisate be precipitated carries out air-dry, dry.
Further, described total monomer comprises monovinylarene and conjugated diolefine.
Further, comprise the following steps:
(1) at anhydrous and oxygen-free; under the condition of high pure nitrogen protection; thinner, polar compound, initiator and the monovinylarene that accounts for total monomer quality mark 7 ~ 10% of account for thinner total amount 90 ~ 95% are mixed in polymeric kettle, vigorous stirring reaction 15 ~ 30min at 50 ~ 80 DEG C:
(2) at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, join in polymeric kettle by the conjugated diolefine of the massfraction 80 ~ 85% accounting for total monomer quality, continue stirring reaction 20 ~ 40min, temperature of reaction remains on 80 ~ 90 DEG C;
(3), at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, all monovinylarenes of residue are joined in polymeric kettle and continues to stir, the temperature of reaction system still remains on 80 ~ 90 DEG C, after reaction 20 ~ 40min, add butylated hydroxytoluene, termination reaction after 2 ~ 5min;
(4) joined in 100 DEG C of hot water by the liquid obtained in (3) and stir, the polymerisate be precipitated, polymkeric substance is air-dry 24h in ventilation, then at 50 DEG C vacuum-drying 48h.
Further, described monovinylarene is vinylbenzene, and described conjugated diolefine is isoprene, and described thinner is hexanaphthene, and described polar compound is tetrahydrofuran (THF), and described initiator is n-Butyl Lithium.
Further, the massfraction that described initiator amount accounts for total monomer is 0.15% ~ 0.3%.
Further, the mass concentration that described polar compound consumption accounts for thinner is 80-150ppm.
Further, described monovinylarene accounts for the massfraction of total monomer is 15% ~ 22%.
Further, the mass concentration of described total monomer in thinner is 13% ~ 18%.
Further, it is 0.4% ~ 0.6% that described butylated hydroxytoluene consumption accounts for total monomer quality concentration.
Compared with prior art, the invention has the advantages that: synthetic method of the present invention simply, easily prepares styrene isoprene styrene block copolymer (SIS) without the need to coupling, step; Pressure sensitive adhesive, hot melt adhesive, coating, modifying plastics field can be widely used in by the inventive method gained segmented copolymer; The performance of segmented copolymer is subject to order of addition(of ingredients), feeding quantity and adds the impact of indegree very large, the performance difference of the product that different working methods obtains is very large, the present invention by addition sequence, the add-on of strict control material, add indegree, thus could low-gel content be obtained, the styrene isoprene styrene block copolymer (SIS) material that high maximum elongation, physical and mechanical property are good.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with table 1, the present invention is further elaborated.
Table 1:
| Compound used therefor | Consumption | Temperature of reaction | Reaction times |
| Hexanaphthene (thinner) | 32000kg | 55℃ | / |
| THF (polar compound) | 3kg | 55℃ | / |
| N-Butyl Lithium (L initiator) | 3.02kg | 55℃ | / |
| Vinylbenzene (S1) | 245kg | 55℃ | 18min |
| Isoprene | 4650kg | 80℃ | 30min |
| Vinylbenzene (S2) | 425kg | 90℃ | 25min |
As described in Table 1, a kind of synthetic method of styrene isoprene styrene block copolymer (SIS), at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, by thinner, polar compound, initiator and total monomer be mix and blend reaction in polymeric kettle, the polymerisate be precipitated carries out air-dry, dry, described total monomer comprises monovinylarene and conjugated diolefine, comprise the following steps: (1) is at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, by account for thinner total amount 90 ~ 95% thinner, polar compound, initiator mixes in polymeric kettle with the monovinylarene (S1) accounting for total monomer quality mark 7 ~ 10%, vigorous stirring reaction 15 ~ 30min at 50 ~ 80 DEG C, (2) at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, join in polymeric kettle by the conjugated diolefine of the massfraction 80 ~ 85% accounting for total monomer quality, continue stirring reaction 20 ~ 40min, temperature of reaction remains on 80 ~ 90 DEG C, (3) at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, the all monovinylarenes (S2) of residue are joined in polymeric kettle and continues to stir, the temperature of reaction system still remains on 80 ~ 90 DEG C, after reaction 20 ~ 40min, add butylated hydroxytoluene, termination reaction after 2 ~ 5min, (4) joined in 100 DEG C of hot water by the liquid obtained in (3) and stir, the polymerisate be precipitated, polymkeric substance is air-dry 24h in ventilation, then at 50 DEG C vacuum-drying 48h.Described monovinylarene is vinylbenzene, described conjugated diolefine is isoprene, described thinner is hexanaphthene, described polar compound is tetrahydrofuran (THF), described initiator is n-Butyl Lithium, the massfraction that described initiator amount accounts for total monomer is 0.15% ~ 0.3%, the mass concentration that described polar compound consumption accounts for thinner is 80-150ppm, the massfraction that described monovinylarene accounts for total monomer is 15% ~ 22%, the mass concentration of described total monomer in thinner is 13% ~ 18%, it is 0.4% ~ 0.6% that described butylated hydroxytoluene consumption accounts for total monomer quality concentration.
Compared with prior art, the invention has the advantages that: synthetic method of the present invention simply, easily prepares styrene isoprene styrene block copolymer (SIS) without the need to coupling, step; Pressure sensitive adhesive, hot melt adhesive, coating, modifying plastics field can be widely used in by the inventive method gained segmented copolymer; The performance of segmented copolymer is subject to order of addition(of ingredients), feeding quantity and adds the impact of indegree very large, the performance difference of the product that different working methods obtains is very large, the present invention by addition sequence, the add-on of strict control material, add indegree, thus could low-gel content be obtained, the styrene isoprene styrene block copolymer (SIS) material that high maximum elongation, physical and mechanical property are good.
Claims (9)
1. the synthetic method of a styrene isoprene styrene block copolymer (SIS); it is characterized in that; under the condition of anhydrous and oxygen-free, high pure nitrogen protection; by the mix and blend reaction in polymeric kettle of thinner, polar compound, initiator and total monomer, the polymerisate be precipitated carries out air-dry, dry.
2. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 1, is characterized in that, described total monomer comprises monovinylarene and conjugated diolefine.
3. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 2, is characterized in that, comprise the following steps:
(1) at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, thinner, polar compound, initiator and the monovinylarene that accounts for total monomer quality mark 7 ~ 10% of account for thinner total amount 90 ~ 95% are mixed in polymeric kettle, vigorous stirring reaction 15 ~ 30min at 50 ~ 80 DEG C;
(2) at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, join in polymeric kettle by the conjugated diolefine of the massfraction 80 ~ 85% accounting for total monomer quality, continue stirring reaction 20 ~ 40min, temperature of reaction remains on 80 ~ 90 DEG C;
(3), at anhydrous and oxygen-free, under the condition of high pure nitrogen protection, all monovinylarenes of residue are joined in polymeric kettle and continues to stir, the temperature of reaction system still remains on 80 ~ 90 DEG C, after reaction 20 ~ 40min, add butylated hydroxytoluene, termination reaction after 2 ~ 5min;
(4) joined in 100 DEG C of hot water by the liquid obtained in (3) and stir, the polymerisate be precipitated, polymkeric substance is air-dry 24h in ventilation, then at 50 DEG C vacuum-drying 48h.
4. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, it is characterized in that, described monovinylarene is vinylbenzene, described conjugated diolefine is isoprene, described thinner is hexanaphthene, described polar compound is tetrahydrofuran (THF), and described initiator is n-Butyl Lithium.
5. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, is characterized in that, the massfraction that described initiator amount accounts for total monomer is 0.15% ~ 0.3%.
6. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, is characterized in that, the mass concentration that described polar compound consumption accounts for thinner is 80-150ppm.
7. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, is characterized in that, the massfraction that described monovinylarene accounts for total monomer is 15% ~ 22%.
8. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, is characterized in that, the mass concentration of described total monomer in thinner is 13% ~ 18%.
9. the synthetic method of a kind of styrene isoprene styrene block copolymer (SIS) according to claim 3, is characterized in that, it is 0.4% ~ 0.6% that described butylated hydroxytoluene consumption accounts for total monomer quality concentration.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110959927A (en) * | 2019-11-21 | 2020-04-07 | 黄生林 | Antiallergic breathable leg guard |
| CN113461882A (en) * | 2021-07-05 | 2021-10-01 | 淄博鲁华泓锦新材料股份有限公司 | Preparation method of styrene-isoprene-styrene block copolymer |
| CN113831474A (en) * | 2020-06-24 | 2021-12-24 | 中国石油天然气股份有限公司 | Preparation method of hyperbranched and widely distributed butyl rubber |
| CN114796164A (en) * | 2022-05-24 | 2022-07-29 | 河南羚锐制药股份有限公司 | Preparation method of emplastrum matrix for rapidly releasing volatile medicines |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175595A (en) * | 1996-09-02 | 1998-03-11 | 岳阳石油化工总厂合成橡胶厂 | Process for preparing styrene-isoprene block copolymer |
| CN1244541A (en) * | 1999-07-28 | 2000-02-16 | 北京燕山石油化工公司研究院 | Preparation of block copolymer of butadiene, isoprene and styrene |
| CN1376721A (en) * | 2002-03-30 | 2002-10-30 | 巴陵石化岳阳石油化工总厂 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
| CN1421471A (en) * | 2002-12-16 | 2003-06-04 | 江苏圣杰实业有限公司 | Preparation method of conjugated diene and monovinylarene block copolymer |
| CN1676539A (en) * | 2004-04-02 | 2005-10-05 | 中国石化集团巴陵石油化工有限责任公司 | Polarized SDS and its preparing method |
-
2015
- 2015-11-10 CN CN201510756744.0A patent/CN105218766A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175595A (en) * | 1996-09-02 | 1998-03-11 | 岳阳石油化工总厂合成橡胶厂 | Process for preparing styrene-isoprene block copolymer |
| CN1244541A (en) * | 1999-07-28 | 2000-02-16 | 北京燕山石油化工公司研究院 | Preparation of block copolymer of butadiene, isoprene and styrene |
| CN1376721A (en) * | 2002-03-30 | 2002-10-30 | 巴陵石化岳阳石油化工总厂 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
| CN1421471A (en) * | 2002-12-16 | 2003-06-04 | 江苏圣杰实业有限公司 | Preparation method of conjugated diene and monovinylarene block copolymer |
| CN1676539A (en) * | 2004-04-02 | 2005-10-05 | 中国石化集团巴陵石油化工有限责任公司 | Polarized SDS and its preparing method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110959927A (en) * | 2019-11-21 | 2020-04-07 | 黄生林 | Antiallergic breathable leg guard |
| CN113831474A (en) * | 2020-06-24 | 2021-12-24 | 中国石油天然气股份有限公司 | Preparation method of hyperbranched and widely distributed butyl rubber |
| CN113831474B (en) * | 2020-06-24 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of hyperbranched wide-distribution butyl rubber |
| CN113461882A (en) * | 2021-07-05 | 2021-10-01 | 淄博鲁华泓锦新材料股份有限公司 | Preparation method of styrene-isoprene-styrene block copolymer |
| CN113461882B (en) * | 2021-07-05 | 2023-11-17 | 淄博鲁华泓锦新材料集团股份有限公司 | Preparation method of styrene-isoprene-styrene block copolymer |
| CN114796164A (en) * | 2022-05-24 | 2022-07-29 | 河南羚锐制药股份有限公司 | Preparation method of emplastrum matrix for rapidly releasing volatile medicines |
| CN114796164B (en) * | 2022-05-24 | 2022-12-23 | 河南羚锐制药股份有限公司 | Preparation method of emplastrum matrix for rapidly releasing volatile medicines |
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Address after: 315000 Zhejiang Province, Ningbo city Beilun District qijiashan Port Road No. 98, building 1, floor 3, 2 Applicant after: Ningbo Changhong polymer Polytron Technologies Inc Address before: 315000 Zhejiang Province, Ningbo city Beilun District qijiashan Port Road No. 98, building 1, floor 3, 2 Applicant before: Ningbo Changhong Polymer Technology Co Ltd |
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