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Preparation method of trans-3,4-poly(1-aryl-1,3-butadiene)

A technology of butadiene and aryl groups, which is applied in the field of preparation of trans 3,4-polymerization and can solve the problems of low polymerization activity and the like

Active Publication Date: 2019-06-14
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

If a cobalt-based metal catalyst is used to catalyze the homopolymerization of 1PB, the 3,4-structural unit content of the obtained polymer can reach 98%, but the polymerization activity is very low, and the molar ratio of the monomer to the catalyst is 200. At 30 ° C, polymerize for 24 hours , the monomer conversion rate reaches 92% (Macromolecules, 1978, 11, 639-644)
Recently, Cui Dongmei's research group used rare earth catalysts to catalyze the homopolymerization of 1-(4-methylphenyl)-1,3-butadiene, and obtained syndiotactic 3,4-polymers. However, in the same Under these conditions, the 3,4-selectivity of the catalyst for 1PB polymerization is only 94.4%, and the polymerization activity of this type of rare earth catalyst is still very low (Macromolecules, 2015, 48, 1999-2005)
So far, there is no literature report on highly 3,4-syndiotactic selective polymerization of 1PB

Method used

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preparation example Construction

[0044] The invention provides a preparation method of trans 3,4-poly(1-aryl-1,3-butadiene), comprising the following steps:

[0045] 1) Under the protection of inert gas nitrogen or argon, the rare earth compound, cocatalyst organoboron salt and / or alkylaluminum compound are dissolved in an organic solvent to obtain a catalyst composition solution;

[0046] 2) 1-aryl-1,3-butadiene monomer is used as a raw material, and the catalyst composition solution is used to catalyze the polymerization reaction. After the reaction is completed, the product is precipitated and dried to obtain 3,4-poly(1-aryl -1,3-butadiene);

[0047] The 1-aryl-1,3-butadiene monomer has the structure shown in (IV):

[0048]

[0049] R is selected from hydrogen, halogen elements, alkyl, isopropenyl, alkoxy, aryloxy, alkylamino, arylamino, alkylthio, arylthio, alkylphosphino or arylphosphino; preferably R is selected from hydrogen, methyl, isopropyl, isopropenyl, methoxy, phenyloxy, methylthio, N,N-dime...

Embodiment 1

[0096] Under anhydrous and oxygen-free conditions, rare earth complex 1 (9.0mg, 10μmol), [Ph 3 C][B(C 6 f 5 ) 4 ] (9.2mg, 10μmol) and Ai i Bu 3 (0.2mL×0.25M) in 2mL of toluene solution was added to 25mL of 1-phenyl-1,3-butadiene (1.30g, 10mmol) monomer in toluene solution (3mL) at 25°C. After reacting with high-speed stirring for 60 minutes, a small amount of ethanol solution was added to terminate the polymerization reaction. Then the reaction solution was poured into a small amount of 100 mL of methanol containing hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was dried in a vacuum oven at 40° C. for 48 hours to obtain a polymer with a net weight of 1.30 g (yield 100%).

[0097] H NMR spectroscopy ( 1 H NMR) and carbon nuclear magnetic resonance ( 13 C NMR) analysis of the obtained 1-aryl-1,3-butadiene homopolymer showed that the syndiotacticity was greater than or equal to 90%; the 3,4 selectivity was greater than 95%. Get its number-average...

Embodiment 2～49

[0099] According to the method described in Example 1, using the raw material ratio and reaction conditions in Table 1, 1-aryl-1,3-butadiene homopolymers were prepared respectively; Table 1 shows Examples 2 to 49 of the present invention Raw material ratio, reaction conditions, and summary of test results.

[0100] Table 1.

[0101]

[0102]

[0103] a chlorobenzene as a solvent; b n-hexane as a solvent; c cyclohexane as a solvent; d decahydronaphthalene as a solvent; e petroleum ether as a solvent; f xylene as a solvent. The solvent is toluene when not indicated.

[0104] The 1-phenyl-1,3-butadiene homopolymer prepared in Example 36 of the present invention was detected by proton nuclear magnetic resonance spectrum and carbon spectrum, and the detection results are shown in figure 1 and figure 2 ,in figure 1 is the H NMR spectrum of the 1-aryl-1,3-butadiene homopolymer prepared in Example 36 of the present invention, figure 2 is the carbon nuclear magnetic resona...

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Abstract

The invention relates to a preparation method of trans-3,4-poly(1-aryl-1,3-butadiene). A catalyst composition used in the invention comprises a rare earth complex represented by formula (A), an organoboron reagent and an alkylaluminum compound, a series of rare earth catalysts having a high syndiotactic 3,4-selectivity for the polymerization of a 1-aryl-1,3-butadiene monomer is found for the firsttime, the syndiotacticity of the obtained polymer reaches up to above 99%, and the 3,4- selectivity can reach up to above 99%; the structure of the trans-3,4-poly(1-aryl-1,3-butadiene) is representedby general formula (I) shown in the description, n in the formula (I) is 250-10000, the syndiotacticity is greater than 90%, and the 3,4- selectivity is 95% or above; and R in the formula (I) is selected from hydrogen, a halogen element, an alkyl group, an isopropenyl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, an alkylthio group, an arylthio group, an alkylphosphino group and an arylphosphino group.

Description

technical field [0001] The invention relates to the technical field of polymer preparation, in particular to a preparation method of trans 3,4-poly(1-aryl-1,3-butadiene), the obtained polymer has high 3,4-syndiotactic Regularity. Background technique [0002] 1-aryl-1,3-butadiene is a 1,3-butadiene monomer whose 1-position is substituted by an aryl group, and can also be regarded as a styrene monomer whose β-position is substituted by ethylene. This unique structure endows it with different polymerization behavior than other conjugated dienes. It was reported that 1-phenyl-1,3-butadiene (1-PB) was polymerized by cationic method to obtain 3,4-based polymers. However, in the cationic polymerization process, about 50% of the double bonds undergo intramolecular cyclization reactions, so the polymer obtained by this method is a polymer with a complex microstructure containing side chain double bonds and alicyclic rings (Polymer Journal. 1976, August, 43-52). The polymerizatio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F136/04C08F4/52
Inventor 崔冬梅姜洋李世辉
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI