Conjugated diene and monovinylarene random copolymer, and preparation method thereof

A technology of monovinyl arene and conjugated diene, which is applied in the field of preparation of conjugated diene and monovinyl arene random copolymer, can solve the problems of increasing vinyl structure content, high production cost, butadiene and benzene The problems of incomplete conversion of ethylene monomers, etc., can achieve the effect of increasing the polymerization temperature of the system, increasing the Mw/Mn, and increasing the 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

Examples

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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 continuous polymerization reaction device comprising a plurality of series reactors, the method comprising: under anionic polymerization conditions, The reaction materials containing the first part of conjugated diene, monovinylarene, solvent, gel inhibitor and monoorganolithium initiator are continuously introduced from the first tank of the continuous polymerization reaction device, and successively introduced in the continuous polymerization The continuous copolymerization reaction is carried out in each reactor of the reaction device, wherein the second part of conjugated diene is respectively introduced into each reactor, and the polymerization temperature is controlled at 90-140°C.

[0019] In the present invention, the continuous copolymerization reaction is carried out in a continuous pol...

Embodiment 1

[0058] This example illustrates the preparation of the random copolymer of conjugated diene and monovinylarene of the present invention.

[0059] Three 5-liter polymerization reactors connected in series are used as continuous polymerization reaction devices.

[0060] In the continuous polymerization reaction device, under the protective atmosphere of high-purity nitrogen, the total residence time of the reaction materials in the three tanks is 50 minutes, and the polymerization reaction pressure is controlled at 0.7±0.05MPa:

[0061] (1) Add reaction materials from the bottom of the first kettle: hexane fraction 9180g / h, styrene 1224g / h, 1,3-butadiene 1101.6g / h, n-butyl lithium 20.4mmol / h and 1,2- Butadiene 5.97g / h, carry out first kettle continuous polymerization reaction;

[0062] (2) Add 1,3-butadiene 367.2g / h at the bottom of the second kettle;

[0063] (3) Add 1,3-butadiene 367.2g / h at the bottom of the three-pot;

[0064] (4) Add 0.37 g / h terminator water at the outl...

Embodiment 2

[0074] This example illustrates the preparation of the random copolymer of conjugated diene and monovinylarene of the present invention.

[0075] Three 5-liter polymerization reactors connected in series are used as continuous polymerization reaction devices.

[0076] In the continuous polymerization reaction device, under the protective atmosphere of high-purity nitrogen, the total residence time of the reaction materials in the three tanks is 60 minutes, and the polymerization reaction pressure is controlled at 0.8±0.05MPa:

[0077] (1) Add reaction materials from the bottom of the first kettle: cyclohexane 7956g / h, styrene 448g / h, 1,3-butadiene 538.56g / h, n-butyllithium 10.2mmol / h and 1,2- Butadiene 4.38g / h, carry out first kettle continuous polymerization reaction;

[0078] (2) Add 1,3-butadiene 718.08g / h at the bottom of the second kettle;

[0079] (3) Add 1,3-butadiene 538.56g / h at the bottom of the three-pot;

[0080] (4) Add 0.15 mg / h terminator water at the outlet ...

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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. Thepreparation method 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 first reactor of a continuous polymerization reaction device, the sequential copolymerization reaction is carried outin each reactor of the continuous polymerization reaction device, the second part of conjugated diene is introduced into each reactor, and the polymerization temperature is controlled to be 90-140 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): C08F212/08C08F236/10C08F4/48
CPCC08F212/08C08F236/10C08F4/482
Inventor 吕万树王雪徐林康新贺王妮妮王世朝胡保利董新民
Owner CHINA PETROLEUM & CHEM CORP
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