Tactic styrene type thermoplastic elastomer and preparation method thereof

A thermoplastic elastomer and stereoregular technology, which is applied in the field of stereoregular styrene thermoplastic elastomers and their preparation, and the preparation of such thermoplastic elastomers by coordination polymerization, can solve the problem that the stereoregularity of polystyrene is difficult to improve. The content of polybutadiene cis structure, the difficulty of improving the stereoregularity of polystyrene, the difficulty of coordinating and efficient block copolymerization, etc., to achieve the effects of improving stereoregularity, good elasticity and wear resistance, and increasing service temperature

Active Publication Date: 2017-08-01
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Therefore, there are still the following technical problems in the prior art: it is difficult to coordinate the high-efficiency block copolymerization of two different types of monomers, butadiene and styrene, through a catalyst; Stereoregularity of styrene; it is difficult to increase the cis structure content of polybutadiene while improving the stereoregularity of polystyrene; it is difficult to convert the active chain ends of the two monomers into each other when they are polymerized
Therefore, it is not possible to prepare a stereoregular triblock copolymer thermoplastic elastomer rich in syndiotactic polystyrene and high cis-polybutadiene by using the prior art

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] During the synthesis, all operations were carried out under the protection of nitrogen.

[0030] The catalyst is composed of neodymium (A) 2-ethylhexanoate, triisobutylaluminum, trichloroethane, 2-ethylhexanoic acid and styrene, and the molar ratio of each component is A:B:C:D:E = 1:16:3:3:2.

[0031] (1) In a reaction flask, mix 10 mL of styrene with the above catalyst so that the molar ratio of A / total monomer is 5×10 -3 , polymerized at 35°C for 6.5h to produce stereoregular polystyrene active chains (S s ) solution;

[0032] (2) In (1) system, add 37mL butadiene (Bd) / n-hexane (HEX) / cyclohexane (CHX) solution ([Bd]=2.4M, V CHX :V HEX =1:1), polymerized at 18°C ​​for 8 hours, and obtained active chains of butadiene-styrene diblock copolymers rich in syndiotactic polystyrene and high cis-polybutadiene (S s B cis ) solution.

[0033] (3) Further polymerize styrene at 40°C for 10 h to obtain active chains of styrene-butadiene triblock copolymers rich in syndiotact...

Embodiment 2

[0038] Experimental operation method is the same as embodiment 1.

[0039] The catalyst consists of 2,5-dimethyl-2-ethyl-hexanoic acid neodymium (A), triisobutylaluminum, trichloroethane and 2,5-dimethyl-2-ethyl-hexanoic acid, Wherein the molar ratio of each component is A:B:C:D=1:14:2.4:0.4.

[0040] (1) In a reaction flask, mix a small amount of styrene (A / St=1 / 1.5, molar ratio) with the above-mentioned catalyst, pre-react at 30°C for 0.5h, and then mix with 20mL styrene / cyclohexane solution ([St ]=6M) mixed so that the molar ratio of A / total monomer is 2.5×10 -3 , polymerized at 40°C for 5h to obtain S s active chain solution;

[0041] (2) In (1) system, add 48mL butadiene / n-hexane / cyclohexane solution ([Bd]=2.5M, V CHX :V HEX =1:1), continued polymerization at 15°C for 10h, and obtained S s B ci active chain solution;

[0042] (3) Further polymerize styrene at 55°C for 7 hours to obtain S s B cis S s active chain system.

[0043] (4) termination reaction and af...

Embodiment 3

[0047] Experimental operation method is the same as embodiment 1.

[0048] The catalyst is composed of neodymium (A) 2-ethylhexanoate, triisobutylaluminum, trichloroethane, 2-ethylhexanoic acid and styrene, and the molar ratio of each component is A:B:C:D:E =1:16:2:1.5:1.

[0049] (1) In a reaction flask, mix 20 mL of styrene cyclohexane solution ([St]=6.0 M) with the above catalyst so that the molar ratio of A / total monomer is 1×10 -3 , polymerized at 45°C for 5h to obtain S s active chain solution;

[0050] (2) In the system (1), add 25mL of butadiene / cyclohexane solution ([Bd]=2.4M), polymerize at 23°C for 4.5h, and obtain S s B cis active chain solution;

[0051] (3) Further polymerize styrene at 60°C for 5 hours to obtain S s B cis S s active chain system.

[0052] (4) termination reaction and aftertreatment mode are the same as embodiment 1, obtain S s B cis S s Tri-block copolymer system with a block efficiency of 93%.

[0053] S s B cis S s Number avera...

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Abstract

The invention relates to a tactic styrene type thermoplastic elastomer and a preparation method thereof. The novel tactic styrene type thermoplastic elastomer is prepared by selecting an appropriate rare earth catalyst system, catalyzing styrene and butadiene for coordination copolymerization and considering polymerization activity of two monomers, wherein the content of a cis-1,4 structure of a PB chain segment is greater than 90 percent. The PS chain segment contains rich syndiotactic structures, so that while phase separation of a copolymer is generated, crystallization can be realized, physical crossing points are enhanced and stabilized, a melting point is below 210 DEG C, further the modulus and strength of the segmented copolymer are improved, and meanwhile a material is endowed with excellent workability, heat resistance, abrasive resistance, physical and mechanical properties and the like.

Description

technical field [0001] The invention relates to a stereoregular styrenic thermoplastic elastomer and a preparation method thereof, specifically, to a kind of soft segment is high-cis polybutadiene, and the hard segment is rich in syndiotactic polystyrene Styrenic thermoplastic elastomers, and methods for preparing such thermoplastic elastomers by coordination polymerization. Background technique [0002] Thermoplastic elastomer material (TPE) has the elasticity of rubber at room temperature, and can be plasticized and formed at high temperature, so that it has the mechanical properties and performance of rubber at room temperature, and can be processed according to thermoplastics. It has a very broad application prospect. TPE includes styrene-based thermoplastic elastomers (TPS), polyolefin-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers. Among them, TPS accounts for about half of the total amount of TPE materials, such as polystyrene-polybut...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F297/06C08F4/54C08F4/52
CPCC08F4/52C08F4/545C08F297/06
Inventor 吴一弦蔡春杨朱寒马晓丽
Owner BEIJING UNIV OF CHEM TECH
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