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Metallocene domino catalytic system for preparing branched polyethylene using ethylene as only monomer and use thereof

A technology of branched polyethylene and catalytic system, which is applied in the field of domino catalytic system, can solve the problems of high production cost of branched polyethylene and high synthesis cost of oligomerization catalyst, and achieve the effect of reducing synthesis cost

Inactive Publication Date: 2009-03-25
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In all the above catalytic systems, the synthesis cost of the oligomerization catalyst is relatively high, and most of the cocatalysts used are relatively expensive alkyl aluminoxanes, which makes the production cost of preparing branched polyethylene relatively high.

Method used

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  • Metallocene domino catalytic system for preparing branched polyethylene using ethylene as only monomer and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Add 50ml of xylene distilled by reflux of metal sodium to a 250ml reactor that has been replaced three times with nitrogen and twice with ethylene, stir and raise the temperature to 60°C, and feed ethylene to keep the pressure in the reactor at 3.0MPa. Solvent xylene 6×10 -6 The proportion of mol main catalyst is added to the main catalyst Cp 2 Zr(O-Ph-Me-p) 2 , and the molar ratio of Al to the main catalyst 1 : M=10 oligomerization cocatalyst Al(C 2 h 5 ) 3 , after prepolymerization for 0.5h, keep the reactor at 0.6MPa, temperature 0℃, add the molar ratio of Al to the main catalyst, that is, Al 2 : the co-catalyst MAO of M=50, polyreaction 0.5 hour, finally add 10ml volume percent concentration and be 10% acidified ethanol (that is 37% concentrated hydrochloric acid by volume ratio: dehydrated alcohol=1:9, known in the art) To the termination of the reaction, wash the generated polymer with water and industrial ethanol, filter the polymer, and then dry it in a va...

Embodiment 2

[0031] Add 50ml of xylene distilled by reflux of metal sodium to a 250ml reactor that has been replaced three times with nitrogen and twice with ethylene, stir and heat up to 80°C, feed ethylene to keep the pressure in the reactor at 3.5MPa, Solvent xylene 3×10 -5 The proportion of mol main catalyst is added to the main catalyst CpZrCl 3 , and the molar ratio of Al to the main catalyst 1 : the oligomerization promoter Al(C of M=50 2 h 5 ) 2 Cl, after prepolymerization for 1 hour, keep the reactor at 0.1MPa, temperature 60°C, add the molar ratio of Al to the main catalyst, that is, Al 2 : M=200 co-catalyst co-catalyst EAO, polymerization reaction 1 hour, finally add 10ml10% acidified ethanol to terminate, water, industrial ethanol wash the polymer that generates, filter polymer, then dry 6 hours in 70 ℃ of vacuum ovens, The polymer branched polyethylene was obtained with an activity of 5.6×10 5 g / (molM·h), the degree of branching is 13 / 1000C, the melting point of the poly...

Embodiment 3

[0033] Add 50ml of xylene distilled by reflux of metal sodium into a 250ml reactor that has been replaced three times with nitrogen and twice with ethylene, stir and raise the temperature to 120°C, and feed ethylene to keep the pressure in the reactor at 1.4MPa. Solvent Xylene 5×10 -3 The proportion of mol main catalyst is added to Ind 2 ZrCl(OC 6 h 3 -3,5-Me 2 ), and the molar ratio of Al to the main catalyst 1 : M=50 oligomerization promoter Al(i-Bu) 3 , after pre-polymerization for 0.5h, keep the reactor at 0.4MPa, temperature 20℃, add Al 2 : M=100 co-catalyst BAO, polymerization reaction 0.5 hour, finally add 10ml10% acidified ethanol to terminate, water, industrial ethanol wash the polymer that generates, filter polymer, then dry 6 hours in 70 ℃ of vacuum ovens, The polymer branched polyethylene was obtained with an activity of 9×10 5 g / (molM·h), the degree of branching is 47 / 1000C, the melting point of the polymer branched polyethylene is 106°C, Mw=205000.

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Abstract

The invention discloses a domino catalyzing system of a primary metallocene catalyst, which takes ethane as a sole monomer to prepare branched polyethylene, and the application thereof, which relates to vinyl copolymer. the catalyzing system is a compound catalyzing system consisting of the single primary metallocene catalyst and two different catalyst promoters, wherein, the primary catalyst is a metallocene catalyst with a structural formula of Cp<1>MR<1>R<2>R<3>, Cp<1>Cp<2>MR<1>R<2> or Cp<1>-D-Cp<2>MR<1>R<2>; alkyl aluminium acts as an oligomerization catalyst promoter; methylaluminoxane or triisobutyl aluminium or triethyl aluminum that is not used together with the oligomerization catalyst promoter acts as a copolymerization catalyst promoter; the mole ratio between the oligomerization catalyst promoter and the primary catalyst is 10-1000 to 1, and the mole ratio between the copolymerization catalyst promoter and the primary catalyst is 20-1000 to 1. The catalytic activity of the metallocene domino catalyzing system for preparing the branched polyethylene is 5 multiplied by 10<5> to 5 multiplied by 10<7>gPE / (molM per hour), the degree of branching is 10-200 / 1000C, the molecular weight of the branched polyethylene prepared under the effect of the catalyzing system ranges from 1 multiplied by 10<5> to 4 multiplied by 10<5> and the melting point is below 120 DEG C or even no melting point exists.

Description

technical field [0001] The technical solution of the invention relates to ethylene polymers, in particular to a domino catalytic system and its application of a metallocene main catalyst for preparing branched polyethylene with ethylene as the only monomer. technical background [0002] Since Kaminsky discovered that methylaluminoxane (MAO) as a metallocene cocatalyst can improve the catalytic activity and its polymerization performance (Angew Chem Int Ed Engl, 19, 1980: 396), metallocene catalysts and limited geometry The preparation of copolymers of ethylene, propylene, butene and other α-olefins with conformational catalysts has become a research hotspot of polyolefin materials, such as branched polyethylene. Branched polyethylene includes short-chain branched polyethylene and long-chain branched polyethylene. Linear low-density polyethylene (LLDPE) is short-chain branched polyethylene, which has excellent toughness and environmental stress crack resistance, high impact ...

Claims

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Application Information

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IPC IPC(8): C08F4/6592C08F110/02
Inventor 闫卫东杨敏刘宾元郝小宇刘盘阁温丽芳程曼
Owner HEBEI UNIV OF TECH
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