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Fluorine-containing syndiotactic polystyrene and preparation method thereof

A polystyrene and styrene technology, applied in the field of fluorine-containing syndiotactic polystyrene and its preparation, can solve the problems of fluorine atom poisoning, catalyst deactivation, monomer conversion rate not exceeding 2%, and achieve high conversion rate , high selectivity, to achieve complete conversion effect

Active Publication Date: 2020-11-10
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

However, fluorinated non-polar and insoluble syndiotactic polystyrene is difficult to achieve a high degree of fluorination, and a large amount of highly toxic and corrosive fluorinating agents are wasted
However, direct polymerization of fluorine-containing styrene tends to poison the catalyst with fluorine atoms, leading to catalyst deactivation.
In 1988, Ishihara et al. synthesized a very small amount of syndiotactic p-fluoropolystyrene and syndiotactic meta-fluoropolystyrene using titanocene catalysts, but the monomer conversion rate did not exceed 2%.

Method used

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  • Fluorine-containing syndiotactic polystyrene and preparation method thereof
  • Fluorine-containing syndiotactic polystyrene and preparation method thereof
  • Fluorine-containing syndiotactic polystyrene and preparation method thereof

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preparation example Construction

[0068] The preparation method of the fluorine-containing syndiotactic polystyrene provided by the invention is to copolymerize the reaction monomer styrene and the fluorine-containing styrene under the action of a catalyst, or homopolymerize the reaction monomer fluorine-containing styrene under the action of the catalyst, and react The fluorine-containing syndiotactic polystyrene is obtained; the catalyst includes a rare earth complex and an organoboron compound, or includes a rare earth complex, an organoboron compound and an organoaluminum compound.

[0069] The rare earth complex is preferably a compound having a structure shown in formula (IV) or a compound having a structure shown in formula (V):

[0070]

[0071]

[0072] where: R 1 It is preferably any one of cyclopentadienyl and its derivatives, indenyl and its derivatives, and fluorenyl and its derivatives; more preferably cyclopentadienyl, indenyl or fluorenyl. R 2 preferably C 1～10 Alkyl, C 1～10 silyl gro...

Embodiment 1

[0112] At 25°C, add 10 μmol of the rare earth complex having the structure shown in formula 1, 10 μmol of [Ph 3 C][B(C 6 f 5 ) 4 ], 100 μmol triisobutylaluminum and 5 mL of toluene solvent were mixed for 2 minutes to obtain a molar concentration of the rare earth complex of 2.0 mmol L –1 catalyst solution in toluene.

Embodiment 2～41

[0114] According to the method described in Example 1, the catalyst solutions were prepared using the raw material ratios and reaction conditions in Table 1; Table 1 shows the raw material ratios and reaction conditions in Examples 2-41. The volume of the reaction vessel can be determined by itself according to the volume of the added solvent.

[0115] Raw material ratio and reaction conditions of table 1 embodiment 2~41

[0116]

[0117]

[0118]

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Abstract

The invention relates to fluorine-containing syndiotactic polystyrene and a preparation method thereof, belongs to the technical field of preparation of polymers and solves the technical problems of extremely low polymerization rate and transformation rate of current fluorine-containing polystyrene in coordination polymerization. The fluorine-containing syndiotactic polystyrene comprises a repetition unit with a structure expressed as formula (I) and a repetition unit with a structure expressed as formula (II). The formula (I) and the formula (II) are shown in the description. Experimental results show that the syndiotactic selectivity of the fluorine-containing syndiotactic polystyrene is not less than 90%; the content of structure units of the fluorine-containing styrene can be randomly adjusted between 0 and 100%. The preparation method of the fluorine-containing syndiotactic polystyrene firstly achieves high-activity, high-transformation-rate and high-selectivity coordination polymerization of the fluorine-containing styrene for the first time, achieves copolymerization of the fluorine-containing styrene and styrene under any monomer ratio for the first time, enables the insertion rate of the fluorine-containing styrene to be freely regulated and controlled, and breaks through the limitation that the conventional fluorine-containing styrene is low in possibility of coordination polymerization; through the method, the complete transformation of the monomers can be achieved.

Description

technical field [0001] The invention relates to the technical field of polymer preparation, in particular to a fluorine-containing syndiotactic polystyrene and a preparation method thereof. Background technique [0002] Syndiotactic polystyrene is a semi-crystalline polymer with high crystallinity, high elastic modulus, low dielectric constant, low loss factor, and excellent heat resistance and solvent resistance. It has a very wide range of applications in industry prospect. However, due to the lack of polar groups in syndiotactic polystyrene, its dyeability, adhesion, and wettability are poor, and it is easy to generate static electricity. In addition, the high melting point and low weather resistance also severely limit the processing and application of syndiotactic polystyrene as a material. Therefore, the modification of syndiotactic polystyrene on the basis of keeping the original properties of syndiotactic polystyrene as much as possible has always been a subject th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F212/14C08F212/08C08F4/52C08F112/14C08F212/32
CPCC08F4/52C08F112/14C08F212/08C08F212/14C08F212/32
Inventor 崔冬梅王子川刘东涛
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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