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Cycloolefin addition polymerization catalyst system and application thereof

An addition polymerization and catalyst technology, applied in the field of cycloolefin addition polymerization catalyst systems, can solve the problems of high polymer melting temperature, expensive cocatalysts, and difficult polymer characterization and processing.

Inactive Publication Date: 2013-08-07
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Polymers obtained by divalent palladium catalyst systems have very high melting temperatures and poor solubility in common organic solvents, making such polymers difficult to characterize and process
In 2012, Japanese scientist Yasuo Wakatsuki reported that the zero-valent palladium complex tris(dibenzylideneacetone)dipalladium in equivalent [CPh 3 ][B(C 6 f 5 ) 4 ], under the action of tricyclohexylphosphine to catalyze the polymerization reaction of norbornene-based monomers (Polymer, 2012, 53 308-315), but the catalytic process is complicated to operate and the cocatalyst is expensive

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] In a dry 100 ml polymerization flask, add 10 ml of toluene, 2 g of norbornene, and 2 ml of MMAO (2 M). After stirring at room temperature for 10 minutes, add the zero-valent palladium catalyst [(Ph) 3 P] 4 Pd(0) 1.4 mg, 0.5 ml dichloromethane solution. The polymerization reaction is 30 minutes. After stopping the stirring, pour into 100 ml of 1% hydrochloric acid ethanol solution, white polymer precipitates, filter, and vacuum dry at 50 ℃ for 24 hours to obtain 650 mg of polynorbornene. The obtained polymer is insoluble in common organic solvents, and its molecular weight cannot be measured.

Embodiment 2

[0040] In a dry 100 ml polymerization flask, add 10 ml of toluene, 2.6 g of dicyclopentadiene, and 2 ml of MMAO (2 M). After stirring at room temperature for 10 minutes, add the zero-valent palladium catalyst [(Ph) 3 P] 4 Pd(0) 1.4 mg, 0.5 ml dichloromethane solution. The polymerization reaction is 30 minutes. After the stirring was stopped, poured into 100 ml of 1% hydrochloric acid ethanol solution, white polymer precipitated, filtered and dried under vacuum at 50°C for 24 hours to obtain 870 mg of polynorbornene. The obtained polymer is insoluble in common organic solvents, and its molecular weight cannot be measured.

Embodiment 3

[0042] In a dry 100 ml polymerization flask, add 10 ml of toluene, 2.4 g of 5-vinylnorbornene, and 2 ml of MMAO (2 M). After stirring at room temperature for 10 minutes, add zero-valent palladium catalyst [(Ph) 3 P] 4 Pd(0) 1.4 mg, 0.5 ml dichloromethane solution. The polymerization reaction is 30 minutes. After the stirring was stopped, poured into 100 ml of 1% hydrochloric acid ethanol solution, white polymer precipitated, filtered and dried under vacuum at 50°C for 24 hours to obtain 50 mg of polynorbornene. The obtained polymer is dissolved in toluene, tetrahydrofuran and other solvents. High temperature GPC test results in molecular weight Mn=51000 and PDI=1.68.

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Abstract

The invention discloses a phosphine-palladium complex catalyst system used for catalyzing cycloolefin monomer addition polymerization. The catalyst system provided by the invention is composed of phosphine-ligand-coordinated zero-valent and mono-valent palladium complex and a co-catalyst alkyl aluminum compound. The catalyst system provided by the invention can catalyze norbornene monomer addition polymerization and norbornene monomer copolymerization reactions. The catalyst system provided by the invention is simple and feasible, and has the advantages of high catalysis activity and no need of strict operation condition. The system can be easily applied in industrial implementations. The cycloolefin addition polymerization catalyst system has a good prospect. Especially, the system can be used in addition polymerization of dicyclopentadiene and norbornene.

Description

Technical field [0001] The invention relates to a catalyst, and more particularly, to a cycloolefin addition polymerization catalyst system and its application. Background technique [0002] Norbornene is an important cycloolefin monomer. Because of its special cyclic structure, the polymerization of this type of monomer can be through ring-opening metathesis polymerization (ROMP), cationic or free radical polymerization, and addition polymerization. This way. [0003] Polynorbornene obtained by addition polymerization is a kind of high performance polymer. It is different from the polymer obtained by the mechanism of ring-opening metathesis polymerization. The addition polymerization method only opens the double bond on the ring without the ring-opening reaction. There is no double bond in the polymer chain backbone structure, and the chain unit retains the polymerization unit. The ring structure of the body. This kind of polymer molecular chain with a cyclic structure in ...

Claims

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Application Information

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IPC IPC(8): C08F132/08C08F136/20C08F232/08C08F236/20C08F4/70
Inventor 伍青邓爵安高海洋
Owner SUN YAT SEN UNIV