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Conjugated diene and monovinylarene random copolymer, and preparation method thereof

A technology of monovinyl aromatic hydrocarbons and conjugated dienes, which is applied in the field of preparation of random copolymers of conjugated dienes and monovinyl aromatic hydrocarbons. The conversion of ethylene monomer is not very complete, etc., to achieve the effect of increasing the polymerization temperature of the system, increasing Mw/Mn, and fast monomer conversion rate

Active Publication Date: 2019-10-22
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The random agent can make the vinyl content of the polymer between 10-20% by weight, but the synthesis process of this regulator is complicated and the production cost is high
[0007] Although the use of the above structural regulators or randomizers can effectively inhibit the formation of styrene blocks in styrene-butadiene copolymers, it also has certain limitations: one is to increase the production cost; the other is that some randomizers need It can only be applied after dissolving in polar solvents, but toluene is highly toxic and pollutes the environment; third, structural regulators such as amines will have residues in the product, which does not meet environmental protection requirements; fourth, some structural regulators are reacting The solubility in the system is poor, the repeatability is poor, and the source of raw materials is not smooth; the fourth is that the addition of a structure regulator will lead to an increase in the vinyl structure content of the solution-polymerized styrene-butadiene rubber, and it is impossible to achieve low-vinyl solution-polymerized styrene-butadiene rubber copolymerization preparation
Without the addition of structure regulators and randomizers, at a reaction temperature of 70-100°C, the conversion of butadiene and styrene monomers at the outlet of the second kettle is not complete, which limits its industrial application

Method used

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  • Conjugated diene and monovinylarene random copolymer, and preparation method thereof
  • Conjugated diene and monovinylarene random copolymer, and preparation method thereof
  • Conjugated diene and monovinylarene random copolymer, and preparation method thereof

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preparation example Construction

[0018] The preparation method of the random copolymer of conjugated diene and monovinylarene provided by the present invention is to carry out continuous copolymerization reaction in a single reactor, the method comprises: under the condition of anionic polymerization, will contain the first part of conjugated The reaction materials of olefin, monovinylarene, solvent, gel inhibitor and monoorganolithium initiator are continuously introduced from the bottom of the reactor, and a second part of conjugated diene is continuously introduced in the middle of the reactor, The third part of conjugated diene is continuously introduced into the upper part of the reactor, and the polymerization temperature is controlled at 90-140°C.

[0019] In the present invention, when the vertical distance between the upper and lower vertices of the reactor is used as a reference, the vertical distance between the upper feed port of the reactor and the upper apex is the vertical distance between the u...

Embodiment 1

[0056] This example illustrates the preparation of the random copolymer of conjugated diene and monovinylarene of the present invention.

[0057] A 16-liter tower-type polymerization reactor is used as a continuous polymerization reaction device.

[0058] In the continuous polymerization reaction device, under the protective atmosphere of high-purity nitrogen, the total residence time of the reaction materials in the kettle is 50 minutes, and the polymerization reaction pressure is controlled at 0.7±0.05MPa:

[0059] (1) Add reaction materials from the bottom of the reactor: hexane fraction 9792g / h, styrene 1305.6g / h, 1,3-butadiene 1175g / h, n-butyllithium 21.76mmol / h and 1,2 -Butadiene 6.36g / h, carry out polymerization reaction;

[0060] (2) Add 1,3-butadiene 392g / h in the middle of the reactor;

[0061] (3) Add 1,3-butadiene 392g / h at the top of the reactor;

[0062] (4) Add terminator water at 0.39g / h to terminate the reaction at the top outlet of the reactor (the tempera...

Embodiment 2

[0072] This example illustrates the preparation of the random copolymer of conjugated diene and monovinylarene of the present invention.

[0073] A 16-liter tower-type polymerization reactor is used as a continuous polymerization reaction device.

[0074] In the continuous polymerization reaction device, under the protective atmosphere of high-purity nitrogen, the total residence time of the reaction materials in the kettle is 60 minutes, and the polymerization reaction pressure is controlled at 0.8±0.05MPa:

[0075] (1) Add reaction materials from the bottom of the reactor: cyclohexane 8486g / h, styrene 479g / h, 1,3-butadiene 575g / h, n-butyllithium 10.88mmol / h and 1,2- Butadiene 4.67g / h, carry out first kettle continuous polymerization reaction;

[0076] (2) Add 1,3-butadiene 766g / h in the middle of the reactor;

[0077] (3) Add 1,3-butadiene 574g / h at the top of the reactor;

[0078] (4) Add terminator water at 0.16 mg / h to terminate the reaction at the top outlet of the re...

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Abstract

The invention relates to the field of conjugated diene and monovinylarene random copolymers, and discloses a conjugated diene and monovinylarene random copolymer, and a preparation method thereof. Themethod is the continuous polymerization reaction conducted in each reactor, and includes the following steps that under the condition of anionic polymerization, reaction materials containing the first part of conjugated diene, monovinylarene, solvents, gel inhibitors and single organic lithium initiators are continuously introduced from the bottoms of reactors, the second part of conjugated dieneis introduced in the middles of the reactors, the third part of conjugated diene is continuously introduced on the upper parts of the reactors, and the polymerization temperature is controlled to be90-140 DEG C. According to the preparation method, under the conditions that any structural regulators or random agents are not added, the reaction temperature is high, and residence time is reasonable, the conjugated diene and monovinylarene random copolymer can be prepared with controllable basic molecular weight and low vinyl content.

Description

technical field [0001] The present invention relates to the field of random copolymers of conjugated dienes and monovinylarenes, in particular to a method for preparing random copolymers of conjugated dienes and monovinylarenes and the random copolymer prepared by the method things. Background technique [0002] As a styrene-butadiene copolymer of general-purpose rubber, the styrene structural units on the molecular chain of solution-polymerized styrene-butadiene rubber require an ideal random distribution as much as possible. The presence of styrene blocks will change the dynamic mechanical properties of rubber. When the molecular chain of solution polystyrene-butadiene rubber contains a small amount of styrene blocks, it can cause van der Waals force between the end of the flexible butadiene molecular chain and the styrene block. , thereby increasing the tensile strength. The existence of a large number of styrene blocks will seriously damage the elasticity, strength and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F212/08C08F236/06C08F4/48C08F2/01
CPCC08F236/06C08F212/08C08F4/48C08F2/01
Inventor 吕万树王雪徐林康新贺王妮妮王世朝胡保利
Owner CHINA PETROLEUM & CHEM CORP
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