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Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method

A technology of Natta catalyst and copolymer carrier, which is applied in the field of olefin polymerization catalysts, and can solve problems such as specific surface area, small pore volume, poor compatibility between polyvinyl chloride and polyethylene, and limited catalytic productivity

Inactive Publication Date: 2007-04-18
吉林市朋力科技开发有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

US6413901, US6448348 announced a kind of Z-N catalyst that uses polyvinyl chloride as carrier, although catalytic activity has been greatly improved, its specific surface area, pore volume are small, limit the raising of catalytic productivity, and polyvinyl chloride and polyvinyl chloride The miscibility of ethylene is extremely poor, which has a certain adverse effect on the appearance quality of the product; US5290745 has announced a Z-N catalyst made by spray drying, and its catalytic productivity is 2 to 3 times higher than that of the traditional one. According to ASTM D-1922 standard It is measured that the appearance quality of the film product has increased from +10 to +30, but a silica gel CAB-O-SIL (white carbon black TS-610) with a diameter of 0.06-0.2um and no micropores has been added to the preparation of the catalyst , it is insoluble in solvents and incompatible with polyolefins

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Catalyst preparation

[0041] The preparation of poly(styrene-acrylic acid) copolymer carrier: 60Kg dioxane, 20Kg styrene / acrylic acid are added in the reactor, and styrene / acrylic acid mol ratio is 80: 20, add reactant weight (20Kg) 1.5 % (Wt) azobisisobutyronitrile / benzoyl peroxide mixed initiator. After the reaction vessel was evacuated with nitrogen, the temperature was raised to 95°C at a rate of 1°C / min, the temperature was stopped and circulating cooling water was introduced to lower the temperature, the polymerization time was 4 hours, and the polymer was introduced into another tank containing a large amount of hexane / water. In the container, the volume ratio of hexane and water is 1:2. Under vigorous stirring, the copolymer was allowed to separate out. The copolymer was vacuum-dried at 60° C. for 48 hours to obtain a poly(styrene-acrylic acid) copolymer. Measure the viscosity average molecular weight W of the copolymer η for 38430.

[0042] Preparation of...

Embodiment 2

[0044] Catalyst preparation

[0045] The preparation of poly(styrene-acrylic acid) copolymer carrier: 80Kg dioxane, 20Kg styrene / acrylic acid are added in the reactor, and styrene / acrylic acid mol ratio is 70: 30, add reactant weight (20Kg) 3.0 % (Wt) azobisisobutyronitrile / benzoyl peroxide mixed initiator, the temperature was raised to 95° C. for 2 hours to polymerize. Other steps and process conditions are the same as the preparation of the copolymer carrier in Example 1. Measured copolymer viscosity average molecular weight W η for 18300.

[0046] Preparation of poly(styrene-acrylic acid) polymer carrier catalyst: Take 500 g of the styrene copolymer prepared above, 5 L of THF, 180 g of magnesium dichloride, and 68 g of titanium trichloride. Other steps are identical with the preparation steps of example 1 polymer carrier catalyst. The composition of the polymer carrier catalyst is Ti 1.97% (wt); Mg 4.02% (wt); THF 18.2% (wt), and the rest is polymer carrier.

Embodiment 3

[0048] Catalyst preparation

[0049] The preparation of poly(styrene-propylene alcohol) copolymer carrier: 60Kg dioxane, 20Kg styrene / propylene alcohol are added in the reactor, and styrene / propylene alcohol mol ratio is 80: 20, then add reactant weight ( 20Kg) 2.5% (Wt) azobisisobutyronitrile / benzoyl peroxide mixed initiator. Other steps and process conditions are the same as the preparation of the copolymer carrier in Example 1. The viscosity-average molecular weight of the copolymer was measured by the viscosity method W η for 31000.

[0050] The preparation of poly(styrene-propylene alcohol) copolymer carrier catalyst: get the poly(styrene-propylene alcohol) copolymer carrier 500g of above-mentioned preparation, join in 5L THF, add 170g magnesium dichloride, titanium trichloride 60g, other Steps and process conditions are the same as the preparation steps of Example 1 polymer carrier catalyst. The composition of the polymer carrier catalyst is Ti1.58% (wt); Mg 3.80% (w...

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Abstract

This invention relates to a Z-N catalyst that uses polymer as carrying agent is utilized for aethylenum homopolymerization / alpha- alkenes copolymerization and its preparation. The expression of this catalyst is P-S .Mgx MClY(nTHF),in the expression M is titanium or Vanadium; X=1-40,Y=5-96,n=5-10;P-S is benzene vinyl copolymer carrying agent containing Lewis base functional group-OH,-COOH,-COOR, -CONH2, ixo-equal molecular weight is 10000-40000.Its preparation: First stated copolymer carrying agent that contains Lewis base functional group is dissolved in polar solvent and agretopes with magnesic chloride, second generating emboliform catalyst by the method that it is resolved with chloride of metal titanium or Vanadium and THF by nonpolar solvent or drying spray. This catalyst has very high catalytic activity to aethylenum polymerization, Applied to gas and slurry polymerization process, its products don't have inorganic ash content contained in common inorganic carrying agent.

Description

technical field [0001] The invention belongs to the field of olefin polymerization catalysts, in particular to a polymer carrier Ziegler-Natta catalyst for ethylene homopolymerization or ethylene / α-olefin copolymerization and a preparation method. Background technique [0002] Ziegler-Natta (Zigeler-Natta) polyolefin catalysts are composed of chlorides of certain metals (titanium, vanadium, etc.) In the 1950s, it is still the main catalyst for olefin polymerization so far, and it occupies an important position both in the field of industrial applications and in the field of research and development. People continue to improve its catalytic productivity and performance, but for more than 50 years, the traditional preparation method is still used, that is, the active components of the catalyst are supported on a carrier with a moderate specific surface area and pore volume that is insoluble in solvents. These carriers include: inorganic substances such as ...

Claims

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Application Information

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IPC IPC(8): C08F10/02C08F4/643C08F2/34C08F4/02
Inventor 刘超曲雅焕
Owner 吉林市朋力科技开发有限公司
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