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Method for preparing blend of ultra high molecular weight polyolefin and low molecular weight polyolefin

An ultra-high molecular weight, low molecular weight technology, applied in the field of olefin polymerization, can solve the problems of molecular weight drop, bimolecular deactivation, catalytic activity decline, etc., and achieve the effects of avoiding bimetallic deactivation effect, uniform blending, and improving toughness

Active Publication Date: 2020-01-17
HANGZHOU SHUANGAN SCI TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the random distribution of the two catalytic components on the surface of the porous carrier makes the interaction between the catalytic molecules strong, which easily induces bimolecular deactivation, resulting in a decrease in the molecular weight of the high molecular weight part, and a significant decrease in the catalytic activity of each component.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] The reaction device was purged with high-purity nitrogen to remove air and water in the reaction device. Take 1g porous carrier SiO 2 , the pore volume is 0.7g / ml, add styrene, 4-chloromethylstyrene, AIBN initiator total 1ml mixed solution, wherein the molar ratio of 4-chloromethylstyrene and styrene is 0, AIBN and benzene The molar ratio of ethylene was 0.01, and the porous carrier was immersed in the mixed solution for 4 hours at 10°C. After washing to remove the free styrene and initiator outside the porous carrier, heat at 60°C for 4h, then at 100°C for 2h, and finally at 120°C for 2h to obtain a porous carrier filled with styrene-based copolymer. Add 50ml of toluene and 0.15g of FI catalyst to the porous carrier filled with 1g of styrene-based copolymer and stir for 2h, wash with 50ml of toluene for 3 times, and dry to free flow to obtain dry solid particles. Add dry solid particles to 50ml n-hexane, 0.15g Cp 2 ZrCl 2 After the catalyst was stirred for 24 hours...

Embodiment 2

[0045] The reaction device was purged with high-purity nitrogen to remove air and water in the reaction device. Take 1g porous carrier TiO 2 , the pore volume is 10g / ml, add styrene, 4-bromomethylstyrene, azobisisoheptanonitrile total 1ml mixed solution, wherein the molar ratio of 4-bromomethylstyrene to styrene is 10, even The molar ratio of nitrogen diisoheptanonitrile to styrene is 0.001, and the porous carrier is immersed in the mixed solution for 24 hours at 15°C. After washing to remove the free styrene and initiator outside the porous carrier, heat at 40°C for 8h, then at 60°C for 4h, and finally at 180°C for 8h to obtain a porous carrier filled with styrene-based copolymer. Add 50ml of benzene and 0.1g of metallocene catalyst to the porous carrier filled with 1g of styrene-based copolymer and stir for 1h, wash with 50ml of benzene for 3 times, and dry to free flow to obtain dry solid particles. Add 1 g of dry solid particles to 50 ml of cyclohexane and 0.1 g of FI ca...

Embodiment 3

[0048] The reaction device was purged with high-purity nitrogen to remove air and water in the reaction device. Take 1g of porous carrier montmorillonite with a pore volume of 0.01g / ml, add 0.5ml of a mixed solution of styrene, 3-fluoromethylstyrene, and dimethyl azobisisobutyrate, in which 3-fluoromethyl The molar ratio of styrene to styrene was 5, the molar ratio of dimethyl azobisisobutyrate to styrene was 0.1, and the porous carrier was immersed in the mixed solution for 1 hour at 15°C. After washing to remove the free styrene and initiator outside the porous carrier, heat at 50°C for 1 hour, then heat at 120°C for 1 hour, and finally heat at 140°C for 5 hours to obtain a porous carrier filled with styrene-based copolymer. 50ml of xylene and 0.01g of Zeigelr-Natta catalyst were added to the porous carrier filled with 1g of styrene-based copolymer, stirred for 0.5h, washed with 50ml of xylene for 3 times, and dried to free flow to obtain dry solid particles. Add 1 g of dry...

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Abstract

The invention discloses a method for preparing a blend of ultra high molecular weight polyolefin and low molecular weight polyolefin. The method is characterized by comprising the following steps: I,preparing a heterogeneous catalyst, namely (1) adding a porous carrier, styrene and a copolymer monomer and an initiator which are selectively used into a reaction device, and performing impregnationfor 1-24 hours; (2) initializing polymerization of the styrene in pores with the copolymer monomer so as to obtain a porous carrier filled with a styrene-based copolymer; (3) sequentially adding a good solvent of the styrene copolymer and a first catalyst into the porous carrier filled with the styrene copolymer, performing stirring for 10-60 minutes, and performing drying so as to obtain solid particles; and (4) sequentially adding a bad solvent of the styrene copolymer and a second catalyst into the solid particles, performing stirring for 2-24 hours, and performing drying so as to obtain the heterogeneous catalyst; and II, performing an ethylene polymerization reaction. By adopting the method, uniform blending of two components can be achieved in a single reactor, and the molecular weight of the ultra high molecular weight polyolefin can be further increased.

Description

technical field [0001] The invention belongs to the technical field of olefin polymerization, and in particular relates to a preparation method of a blend of ultrahigh molecular weight polyolefin and low molecular weight polyolefin. Background technique [0002] The blending of ultra-high molecular weight polyolefins and ordinary polyolefins can greatly improve the mechanical properties of materials, and is widely used in the development of high-performance polyolefin base resins. However, ultra-high-molecular-weight polyolefins have poor segment mobility and slow diffusion speed due to their ultra-long molecular chains and a large number of chain entanglements, which greatly restricts the miscibility of such polymers with ordinary polyolefins. Take ultra-high molecular weight polyethylene reinforced high-density polyethylene as an example. Although the molecular structure of the two is very similar, due to the huge difference in melt viscosity between the two, through mecha...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F210/16C08F210/06C08F4/02C08F4/64C08L23/08
CPCC08F210/06C08F210/16C08L23/0815C08L23/14C08L2205/025C08L2308/00C08F4/027C08F4/025C08F4/642
Inventor 历伟吴雁捷曹禺唐鑫赵彬清
Owner HANGZHOU SHUANGAN SCI TECH
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