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A kind of cycloolefin addition polymerization catalyst system and its application

A catalyst and main catalyst technology, applied in the field of catalysts, can solve the problems of high melting temperature of polymers, complex operation of the catalytic process, and expensive co-catalysts

Inactive Publication Date: 2015-08-05
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 bottle, add 10 ml of toluene, 2 g of norbornene, 2 ml of MMAO (2 M), stir at room temperature for 10 minutes, then add a zero-valent palladium catalyst [(Ph) 3 P] 4 Pd(0) 1.4 mg, dichloromethane 0.5 ml solution. Polymerization was carried out for 30 minutes. After the stirring was stopped, pour it into 100 ml of 1% ethanol hydrochloric acid solution, a white polymer precipitated, filtered, and vacuum-dried at 50°C for 24 hours to obtain 650 mg of polynorbornene. The resulting polymer was insoluble in common organic solvents, and its molecular weight could not be determined.

Embodiment 2

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

Embodiment 3

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

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PUM

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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 present invention relates to a catalyst, more particularly to a cycloolefin addition polymerization catalyst system and its application. Background technique [0002] Norbornene is an important cycloolefin monomer. Due to its special ring structure, the polymerization of this type of monomer can be achieved through ring-opening metathesis polymerization (ROMP), cationic or free radical polymerization, and addition polymerization. way. [0003] Polynorbornene obtained through addition polymerization is a class of high-performance polymers. 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 ring-opening reaction. There is no double bond in the polymer chain skeleton structure, and the chain unit retains the polymerization single body ring structure. The force between the molecular chains of this kind of polymer ...

Claims

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Application Information

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