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Stereo-regular conjugated diene/styrene copolymer and preparation method thereof

A technology of styrene copolymer and conjugated diene, which is applied in the field of stereoregular conjugated diene/styrene copolymer and its preparation, and can solve problems such as low tear strength, increased molecular chain friction, and large hysteresis loss. problems, to achieve the effect of low glass transition temperature, strong resistance to deformation, energy saving and consumption reduction

Active Publication Date: 2013-07-24
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Random styrene-butadiene copolymers have the advantages of good high wet skid resistance and low rolling resistance, but due to cis-1, 4% is low, and the existence of side groups (such as vinyl and phenyl) in the molecular chain makes the macromolecules The chain flexibility is poor, and the friction between molecular chains increases, resulting in poor elasticity and cold resistance, large hysteresis loss, high heat generation, flex cracking resistance and relatively poor adhesion.
[0003] High-cis 1,4-polybutadiene rubber has the advantages of excellent elasticity, cold resistance, wear resistance, hysteresis loss and small heat generation, but has the disadvantages of low tensile strength, low tear strength and poor wet skid resistance.
Regarding the copolymerization of conjugated dienes and styrene catalyzed by titanium-based, cobalt-based and nickel-based systems, there is a key technical problem that the copolymerization activity is low or even inactive.
[0004] CN1057058A discloses a kind of adopting LnL 3 -RX-AlR' m h 3-m -BS k Rare earth catalysts prepare styrene and conjugated diene copolymers, but the sequence structure of the copolymers is not mentioned, and only mentioned in the examples that the glass transition temperature of the butadiene / styrene binary copolymer is 0 °C, Cannot be used as high cold resistance styrene-butadiene rubber
In CN201010191794.6, a high cis-conjugated diene / styrene random copolymer and its preparation method are disclosed. By selecting a suitable composite catalyst system based on rare earth metal carboxylate, styrene and conjugated diene are catalyzed. Coordination copolymerization to prepare high molecular weight, high cis-content random copolymers of conjugated dienes and styrene, but cannot solve the technical problems of block copolymerization and stereoregularity
Disclosed in CN101153069 is a kind of preparation method of high cis-butadiene block copolymer, promptly adopts the method for butadiene and styrene block copolymerization of high-activity rare earth composite catalyst, although can obtain high cis-butadiene block Copolymer, but it is difficult to solve the problem of random copolymerization of butadiene / styrene
Use (C 5 Me 4 C 5 h 4 N) and [Ph 3 C][B(C 6 f 5 ) 4 ] and lanthanide metal compounds can not solve the problem of random copolymerization of butadiene and styrene, only block copolymers of butadiene and styrene can be prepared, and the conversion rate of the copolymerization reaction is low , Copolymer molecular weight is low, the melting point is too high, so it is not easy to process, etc. (see Chemistry European Journal 2010, 16, 14007-14015)
[0005] Therefore, there is no report about a copolymer containing a high-cis conjugated diene / styrene random copolymer segment and a stereoregular polystyrene segment in the prior art

Method used

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  • Stereo-regular conjugated diene/styrene copolymer and preparation method thereof
  • Stereo-regular conjugated diene/styrene copolymer and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0032] At -10°C under nitrogen protection, 1.0mmol Al(i-Bu) 3 (B), 0.1mmol AlH(i-Bu) 2 (B), a mixture of 1.2mmol chloroform (C) and 0.1mmol ethyl trichloroacetate (D) was mixed with 0.06mmol neodymium octanoate (A), reacted for 148 hours to form a homogeneous catalyst, and set aside. Wherein the molar ratio of each component is A:B:C:D=1:16:20:1.5.

[0033] Under nitrogen protection, 10 ml of a mixed solution of styrene (St), butadiene (Bd), hexane and cyclohexane was added to the dry polymerization reactor, wherein Bd / St=1.0 (mass ratio). The above-mentioned homogeneous catalyst was added, and polymerization was carried out at 60° C. for 5 hours. The reaction was terminated with an ethanol solution containing 1% anti-aging agent 1076, and the polymer product was extracted with n-hexane and butanone for 24 hours, washed with water, and dried in a vacuum oven at 40°C until constant weight. M of the resulting copolymer w 4.7×10 5 g / mol, M w / M n 4.3, cis-1, 4 content is 9...

Embodiment 2

[0035] Under the protection of nitrogen at 15°C, mix 0.12mmol of neodymium (A) with 1.9mmol of Al(i-Bu) 3 (B), 0.2mmol AlH(i-Bu) 2 (B), a mixture of 1.0mmol chloroform (C), 0.2mmol trichloroethane (C) and 0.2mmol tert-butyl trichloroacetate (D) was reacted for 75 minutes to form a homogeneous catalyst and set aside. Wherein the molar ratio of each component is A:B:C:D=1:16:10:0.8.

[0036] Add 10 ml of a mixed solution of styrene (St), isoprene (Ip) and cyclohexane into the dry polymerization reactor under the protection of nitrogen, wherein Ip / St=0.6 (mass ratio). The above-mentioned homogeneous catalyst was added, and polymerization was carried out at 70° C. for 5 hours. The molar ratio of catalyst component A to total monomer is 5.3×10 -3 . The termination reaction and post-treatment method are the same as implementation 1. M of the resulting copolymer w 3.8×10 5 g / mol, M w / M n 3.9, cis-1, 4 content is 96.0% (mol), total styrene binding amount is 10wt%, molecular ...

Embodiment 3

[0038] Add 2.4mmol of Al(i-Bu) to the catalyst preparation device at 45°C under nitrogen protection 3 (B), 0.1mmol AlH(i-Bu) 2 (B), then add a mixed solution of 0.2mmol ethyl trichloroacetate (D) and 3.0mmol chloroform (C), then mix with 0.15mmol neodymium octanoate (A), and react for 1.5 hours to form a homogeneous catalyst. spare. Wherein the molar ratio of each component is A:B:C:D=1:18:20:1.4.

[0039] The polymerization method is the same as in Example 1. After 2 hours of polymerization at 40°C, the temperature is raised to 60°C and the polymerization is continued for 3 hours. The molar ratio of catalyst component A to total monomers is 1.5×10 -3 . The termination reaction and post-treatment method are the same as implementation 1. M of the resulting copolymer w 1.0×10 5 g / mol, M w / M n 5.2, cis-1, 4 content is 93.7% (mol), total styrene binding amount is 44.4wt%, PS segment molecular weight is 4×10 4 g / mol, the tacticity (rrrr sequence) is 80%, the PS segment ca...

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Abstract

The invention relates to a stereo-regular conjugated diene / styrene copolymer and a preparation method thereof. The copolymer is obtained through coordination polymerization by adopting a rare earth metal carboxylate based high-activity composite catalyst and a one-step or two-step charging process, and the weight average molecular weight and the molecular weight distribution index of the copolymer are 8.0*10<4>-1.3*10<6> and 1.7-9.0 respectively; and the molar content of cis-1,4 of a conjugated diene chain link is 90.0-99.5%, the total mass binding capacity of styrene is 3-80%, the molecular weight of a stereo-regular polystyrene chain segment is 1.0*10<4>-4.0*10<5>, and the stereo regularity is 30-95%. The stereo-regular conjugated diene / styrene copolymer has the advantages of good elasticity, strong deformation resistance, excellent wear resistance, low loss modulus, low heat generation, good cold resistance, high ice and snow covered pavement grip, and low rolling resistance.

Description

Technical field: [0001] The invention relates to a stereoregular conjugated diene / styrene copolymer and a preparation method thereof, in particular to a copolymer containing a high-cis conjugated diene / styrene random copolymer segment and stereoregular polystyrene A copolymer composed of chain segments, and a method for preparing the copolymer by using a rare earth catalyst through coordination polymerization. technical background: [0002] At present, the main industrialized product of conjugated diene / styrene copolymer is butadiene / styrene copolymer. Butadiene / styrene copolymers can be divided into butadiene / styrene random copolymers and butadiene / styrene block copolymers according to their chain structure. The butadiene / styrene random copolymer is mainly carried out by radical emulsion polymerization and anionic solution polymerization. In the butadiene / styrene random copolymer prepared by emulsion polymerization, such as ESBR1500, the cis-1,4-content (cis-1, 4%) of its...

Claims

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Application Information

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IPC IPC(8): C08F236/10C08F4/54C08F4/52C08F297/06
Inventor 吴一弦王洁琼朱寒王迪徐日炜
Owner CHINA PETROLEUM & CHEM CORP
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