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Functional highly-isotactic polystyrene and preparation method thereof

A technology of isotactic polystyrene and styrene, applied in the field of polymers, can solve the problems of low selectivity, loss of activity, inability to obtain high isotactic polystyrene, etc., and achieve high isotactic selectivity and high conversion rate. Effect

Active Publication Date: 2016-03-30
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In the prior art, alkoxy-functionalized styrene can obtain functionalized polystyrene through cationic polymerization and anionic polymerization, but the resulting polymer has low selectivity, such as o-methoxy Both functionalized styrene and p-methoxy functionalized polystyrene have random structures (Makromol.Chem., 1962, 58, 217-225); o-methoxy functionalized polystyrene obtained at low temperature by anionic polymerization Ethylene isotropic selectivity is low, mm is only 90% (J.Polym.Sci., PartA-1, 1969, 7, 1933-1946)
For Ziegler-Natta coordination polymerization catalysts, functionalized highly isotactic polystyrene cannot be obtained because the heteroatoms on the functionalized styrene monomer will coordinate with the active center to deactivate it

Method used

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  • Functional highly-isotactic polystyrene and preparation method thereof
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  • Functional highly-isotactic polystyrene and preparation method thereof

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preparation example Construction

[0056] The preparation method of the functionalized high isotactic polystyrene provided by the present invention comprises: performing a polymerization reaction on the functionalized styrene under the action of a catalyst to obtain the functionalized high isotactic polystyrene;

[0057] The functionalized styrene has a structure shown in formula II:

[0058]

[0059] In formula II, F is sulfur or oxygen;

[0060] T 1 An alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms;

[0061] T is an alkoxy group with 1 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an alkylthio group with 1 to 20 carbon atoms, an arylthio group with 6 to 20 carbon atoms, An alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms; T is substituted at any position on the benzene ring;

[0062] n represents the number of substituent T, 0≤n≤4;

[0063] The catalysts include rare earth complexes, organoboron compounds and organoalum...

Embodiment 1

[0118] Under anhydrous and oxygen-free conditions, 5mL of tetrahydrofuran solution with a concentration of 0.1mol / L having a ligand shown in formula 16 and 0.31mL of a n-hexane solution of n-butyl lithium with a molar concentration of 1.6mol / L were mixed in React at 0°C for 1 hour to obtain the first intermediate product; at 25°C, add 5 mL of the tetrahydrofuran solution of the first intermediate product with a concentration of 0.1 mol / L dropwise to 2 mL of YCl with a concentration of 0.25 mol / L 3 In the tetrahydrofuran suspension, react for 4 hours, obtain the second intermediate product; In the second intermediate product, add the LiCH of 1.0mmol 2 SiMe 3 After reacting for 12 hours, the obtained reaction product was desolventized, extracted with toluene and concentrated to obtain 0.24 g of the rare earth complex having the structure shown in Formula 1, and the yield of the rare earth complex having the structure shown in Formula 1 was 81%.

[0119]

[0120] Terminal gro...

Embodiment 2

[0122] According to the method described in Example 1, the rare earth complex with the structure shown in Formula 2 was prepared, and the difference from Example 1 was that the ligand with the structure shown in Formula 17 was used to replace the ligand with the structure shown in Formula 16 in Example 1. .

[0123] Example 2 of the present invention prepared 0.27 g of the rare earth complex having the structure shown in Formula 2, and the yield of the rare earth complex having the structure shown in Formula 2 was 84%.

[0124]

[0125] Terminal groups not given in Formula 17 are methyl groups.

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Abstract

The present invention provides functional highly-isotactic polystyrene comprising repeating units having the structure of formula I, in the formula I, E is sulfur or oxygen, R1 is an alkyl group having 1-10 carbon atoms or an aryl group having 6-10 carbon atoms, R is an alkoxy group having 1-20 carbon atoms or an aryloxy having 6-20 carbon atoms, the R can substitute arbitrary position on a benzene ring; m represents the number of substituent groups R, and the m is greater than or equal to 0 and less than or equal to 4. The present invention provides a preparation method of the functional highly-isotactic polystyrene comprising the repeating units having the structure of the formula I, the method comprises polymerization of functionalized styrene to obtain the functional highly-isotactic polystyrene under the role of a catalyst, the functionalized styrene has a structure of formula II, and the catalyst comprises a rare earth complex, an organic boron compound and an organic aluminum compound. The functional highly-isotactic polystyrene has high isotactic selectivity.

Description

technical field [0001] The invention relates to the technical field of polymers, in particular to a functionalized high isotactic polystyrene and a preparation method thereof. Background technique [0002] Polystyrene is one of the very important engineering materials. According to its microstructure, it can be divided into isotactic polystyrene, syndiotactic polystyrene and random polystyrene. Among them, polystyrene with isotactic structure can pass Ziegler-Natta Catalyst preparation. However, because the polymer molecule does not contain polar groups, the polarity of this polystyrene is poor, which in turn leads to the poor bonding performance, dyeing performance and compatibility with other polar polymers of this polystyrene. Poor, limiting the application of polystyrene products. Therefore, the use of styrene monomers with polar groups to synthesize functionalized highly isotactic polystyrene has attracted people's attention. [0003] In the prior art, alkoxy-functio...

Claims

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Application Information

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IPC IPC(8): C08F112/14C08F112/32C08F4/54
Inventor 崔冬梅刘东涛
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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