CN101838351B - Catalyst for vinyl polymerization and method for preparing same - Google Patents

Catalyst for vinyl polymerization and method for preparing same Download PDF

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Publication number
CN101838351B
CN101838351B CN2009100803451A CN200910080345A CN101838351B CN 101838351 B CN101838351 B CN 101838351B CN 2009100803451 A CN2009100803451 A CN 2009100803451A CN 200910080345 A CN200910080345 A CN 200910080345A CN 101838351 B CN101838351 B CN 101838351B
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ethylene polymerization
polymerization catalysts
mother liquor
electron donor
compound
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CN101838351A (en
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闫力欣
张彤瑄
王如恩
徐世媛
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a catalyst for vinyl polymerization. The catalyst contains titanium-containing active components and active agent components (organic aluminum compound), wherein an inorganic oxide carrier is loaded with at least one kind of magnesium dihalide, one kind of aluminum halide, at least one kind of titanium halide and at least one kind of electron donor, and the electron donor compound is ether, ester or ketone; and the general formula of the organic aluminum compound is AlRnX3-n, R is alkyl of which the number of hydrogen or carbon atoms is 1 to 20, X is halogen, and n is a numeral which is more than 1 and less than or equal to 3. When the catalyst is used for the vinyl polymerization, the catalyst has higher polymerization activity and hydrogen-adjusting sensitivity, and simultaneously the molecular weight distribution of the obtained polymers is wider.

Description

A kind of ethylene polymerization catalysts and preparation method thereof that is used for
Technical field
The present invention relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, and this Preparation of catalysts method and purposes.
Technical background
In the copolymerization of the polyreaction of ethene or ethene and terminal olefin, adopt with titanium, magnesium, halogen and electron donor compound catalyzer mostly as basal component.When this type catalyst applications is in industry; Catalyzer shows as to have higher activity, catalyzer and polymkeric substance thereof and has particle form and high tap density preferably; But the hydrogen response of catalyzer is not ideal usually, and good that hydrogen response can make the density of polymkeric substance and molecular weight regulate easily.
As everyone knows, be used for ethylene polymerization catalysts mostly with magnesium halide as carrier, comprising magnesium chloride, magnesium bromide and magnesium iodide.
In disclosed patent CN1041763, the high activated catalyst of a kind of ethene gas-phase homopolymerization and copolymerization is provided, with MgCl 2, ZnCl2 and SiO2 be complex carrier, is Primary Catalysts with TiCl4, forms compound accelerant by SiCl4 and organic-magnesium complex compound, this catalyzer has greater activity, can make hydrogen transfer the molecular weight effect to significantly improve.
In disclosed patent CN1693316, a kind of low carried titanium MgCl is provided 2/ AlCl 3The complex carrier propylene polymerization is used catalyzer, and this catalyzer prepares with abrasive method.The catalyst Ti content of this method preparation is controlled, preparation technology is simple, cost is low, environmental pollution is little, is easy to industrial production; But with this catalyzer catalyzing propone polymerization, the preparation raw or low grade polypropylene.But activity was very low when this catalyzer was used for vinyl polymerization.
In disclosed patent CN1837247, a kind of low carried titanium MgCl is disclosed 2/ MnCl 2The complex carrier propylene polymerization is with catalyzer and preparation method, and this Preparation of catalysts is to adopt single tank ball milling.Activity was very low when equally, this catalyzer was used for vinyl polymerization.
The inventor finds through lot of test, is used for ethylene polymerization catalysts in preparation, adopts MgCl 2/ AlCl 3As complex carrier, the catalyzer that obtains not only has very high activity, demonstrates higher hydrogen response simultaneously, and the polymkeric substance that obtains has wider molecular weight distribution.
Summary of the invention
The object of the present invention is to provide a kind of ethylene polymerization catalysts that is used for, it comprises the reaction product of following component:
(1) titaniferous active ingredient: load has at least a magnesium dihalide on inorganic oxide carrier, a kind of aluminum halide, and at least a halogenated titanium, at least a electron donor compound, wherein said electron donor compound is selected from ether, ester or ketone;
(2) activator component: general formula is AlR nX 3-nBasic aluminum compound is arranged, and R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, and X is a halogen, and n is the number of 1＜n≤3.
Above titaniferous active ingredient can adopt following method preparation:
(1) preparation of mother liquor:
In electronic donor compound capable, magnesium dihalide, halogenated titanium and aluminum halide are reacted the preparation mother liquor;
Described electronic donor compound capable is selected from ether, ester or ketone, concrete as: C 1～C 4The alkyl ester of aliphatic saturated monocarboxylic acid, C 7～C 8The alkyl ester of aromatic carboxylic acid, C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6A kind of in the saturated fatty ketone or their mixture, preferred: methyl-formiate, ETHYLE ACETATE, butylacetate, ether, hexyl ether, THF, acetone and MIBK etc., most preferably THF.They can use separately or several kinds of mixing are used.
Described halogenated titanium is titanium chloride or titanium bromide, preferred TiCl 3Or TiCl 4
Described magnesium dihalide is magnesium dichloride, dibrominated magnesium or two magnesium iodides, preferred magnesium dichloride.
Described aluminum halide is aluminum chloride, aluminum bromide or aluminum iodide, preferred aluminum chloride.
In preparation mother liquor process, each component ratio preferably is controlled to be: the mol ratio of said Ti and magnesium halide is 1: 0.1～10; The mol ratio of said Ti and aluminum halide is 1: 0.1～5; Preferred 1: 0.5～3.Generally be controlled at every mole of Ti for the electron donor(ED) add-on and be approximately 1～600 mole, preferred 20～200 moles.
(2) silica gel blending: with the mother liquor and the oxide carrier blending of preparation in the step (1);
Described oxide compound is generally the oxide compound of silicon and/or aluminium, and particle diameter is generally 0.01～1000 micron, and preferable particle size is less than 2 microns, and more preferably 0.1～2 micron, 0.1～1 micron silica gel most preferably.Oxide compound need be dryness in use, does not promptly have the water of absorption.Should the carrier of sufficient amount be mixed with mother liquor mutually, formation is suitable for carrying out spray-dired slurry, and the content of this carrier is 5～50 in slurry, preferred 5～30 weight %.
(3) spray shaping carries out spraying drying with the mixture that obtains in the step (2), obtains ingredient of solid catalyst;
(4) prereduction: be applicable to the production ethene polymers in order to make the catalyst component that obtains after the spraying, must adopt organo-aluminium compound that titanium atom in the said catalyst component is reduced into and to make the effective polymeric state of ethene.Usually, in varsol, the catalyst component and the activator component that obtain in (3) are reacted, obtain catalyzer.Also can spraying drying be obtained the solids containing titanium catalyst component and directly in polymerization, contact with activator component, olefinic polymerization is directly caused in the reaction back.
Described activator component is that general formula is AlR nX 3-nBasic aluminum compound is arranged, and R is that hydrogen or carbonatoms are 1～20 alkyl, and X is a halogen, and n is the number of 1＜n≤3, concrete as: triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium or aluminium diethyl monochloride.
Described varsol such as iso-pentane, hexane, heptane, toluene, YLENE, petroleum naphtha and mineral wet goods.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other terminal olefin, and wherein terminal olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the tetramethyl-amylene-1.Polymerization technique adopts vapor phase process, slurry process or solution method, more is applicable to gas-phase fluidized-bed polymerization.
The present invention adopts MgCl 2/ AlCl 3Complex carrier, the catalyzer that obtains not only has very high activity, has improved the catalyzer hydrogen regulation performance simultaneously, and can obtain the polymkeric substance that MWD is widened.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting scope of the present invention.
Testing method:
1, melt index (M.I): measure according to ASTM D1238-99
2, density: ASTM D-1505 measures
3, molecular weight distribution index (Mw/Mn): gel gc (GPC) is measured
4, activity: the weight with every gram catalyzer gained resin is represented
Embodiment 1
1, preparation catalyzer:
In the 250ml there-necked flask that blows row through nitrogen, successively add 0.4 milliliter of (0.7 gram) TiCl 4, the anhydrous MgCl of 4.0 grams 2With the anhydrous AlCl of 1.0 grams 3With the 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot CorporationTS-610 particle diameter 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added, keep 35 ℃ of temperature; Stir after 1 hour; Mother liquor after the silica gel blending is carried out spraying drying with spray-dryer, spray condition: 190 ℃ of inlet temperatures, 105 ℃ of temperature outs; Obtain ingredient of solid catalyst, wherein titanium content is 2.3Wt%.
2, ethylene thick liquid polymerizing:
To pass through and add 1 liter of hexane in 2 liters of polymeric kettles that nitrogen blows row, add triethyl aluminum and the 0.03 gram catalyzer of 1mmol simultaneously, and be warming up to 75 ℃ and add hydrogen 0.18Mpa; After finishing, hydrogenation adds ethene 0.75Mpa; Be warmed up to 85 ℃, react after 2 hours cooling discharge.Polymerization result is seen table 1.
Embodiment 2
1, preparation catalyzer
In the 250ml there-necked flask that blows row through nitrogen, successively add 0.4 milliliter of (0.7 gram) TiCl 4, the anhydrous MgCl of 3.6 grams 2With the anhydrous AlCl of 1.4 grams 3With the 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot CorporationTS-610 particle diameter 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added, keep 35 ℃ of temperature; Stir after 1 hour; Mother liquor after the silica gel blending is carried out spraying drying with spray-dryer, spray condition: 190 ℃ of inlet temperatures, 105 ℃ of temperature outs; Obtain ingredient of solid catalyst, wherein titanium content is 2.3Wt%.2, slurry polymerization
With embodiment 1, polymerization result is seen table 1.
Embodiment 3
1, preparation catalyzer
In the 250ml there-necked flask that blows row through nitrogen, successively add 0.4 milliliter of (0.7 gram) TiCl 4, the anhydrous MgCl of 3.0 grams 2With the anhydrous AlCl of 2.0 grams 3With the 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot CorporationTS-610 particle diameter 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added, keep 35 ℃ of temperature; Stir after 1 hour; Mother liquor after the silica gel blending is carried out spraying drying with spray-dryer, spray condition: 190 ℃ of inlet temperatures, 108 ℃ of temperature outs; Obtain ingredient of solid catalyst, wherein titanium content is 2.2Wt%.
2, slurry polymerization
With embodiment 1, polymerization result is seen table 1.
Comparative example 1
1, preparation catalyzer
In the 250ml there-necked flask that blows row through nitrogen, successively add 0.4 milliliter of (0.7 gram) TiCl 4, the anhydrous MgCl of 4.0 grams 2With the 100ml THF, be warming up to 65 ℃ under stirring, isothermal reaction is 3 hours under this temperature.Be cooled to 35 ℃.
Blow through nitrogen to one and to add 6 gram silica gel (Cabot CorporationTS-610 particle diameter 0.02-0.1 micron) in row's the 250ml there-necked flask, the mother liquor after the cooling is added, keep 35 ℃ of temperature; Stir after 1 hour; Mother liquor after the silica gel blending is carried out spraying drying with spray-dryer, spray condition: 190 ℃ of inlet temperatures, 105 ℃ of temperature outs; Obtain ingredient of solid catalyst, wherein titanium content is 2.4Wt%.
2, slurry polymerization
With embodiment 1, polymerization result is seen table 1
Table 1
Catalyzer Catalyst activity (gram Vilaterm/gram catalyzer 2 hours) Melting index MI (g/10min) Mw/Mn
Embodiment 1 12429 2.19 5.5
Embodiment 2 9800 2.62 6.5
Embodiment 3 9500 2.84 7.5
Comparative Examples 1 10535 0.85 4.2
Data from table 1 can find out that the present invention adopts MgCl 2/ AlCl 3As complex carrier, when the catalyzer that obtains is used for vinyl polymerization, not only have very high activity, under identical hydrogen concentration condition, resulting polymer melt index obviously improves simultaneously, and the MWD of polymkeric substance is obviously widened.

Claims (11)

1. one kind is used for ethylene polymerization catalysts, and it comprises the reaction product of following component:
(1) titaniferous active ingredient: at least a electron donor compound, at least a magnesium dihalide, at least a halogenated titanium and a kind of aluminum halide are reacted the preparation mother liquor; Carry out spraying drying after mother liquor that obtains and the inorganic oxide carrier blending, obtain the titaniferous active ingredient; Wherein when mother liquor prepared, the mol ratio of Ti and magnesium halide was 1:0.1～10; The mol ratio of Ti and aluminum halide is 1:0.5～3, counts 1 ~ 600 mole with every mole of Ti for the add-on of electronic donor compound capable, and described electron donor compound is selected from ether, ester or ketone;
(2) activator component: general formula is AlR nX 3-nBasic aluminum compound is arranged, and R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, and X is a halogen, and n is the number of 1＜n ≦ 3.
2. the ethylene polymerization catalysts that is used for according to claim 1, wherein said aluminum halide is an aluminum chloride.
3. the ethylene polymerization catalysts that is used for according to claim 1, wherein said inorganic oxide carrier are that particle diameter is 0.1 ~ 1000 micron the silicon and/or the oxide compound of aluminium.
4. the ethylene polymerization catalysts that is used for according to claim 3, wherein said inorganic oxide carrier are that particle diameter is 0.1 ~ 2 micron the silicon and/or the oxide compound of aluminium.
5. the ethylene polymerization catalysts that is used for according to claim 4, the particle diameter of wherein said inorganic oxide carrier are 0.1 ~ 1 micron the silicon and/or the oxide compound of aluminium.
6. the ethylene polymerization catalysts that is used for according to claim 1, wherein said halogenated titanium is TiCl 3Or TiCl 4
7. the ethylene polymerization catalysts that is used for according to claim 1, wherein said electron donor compound is selected from C 1～C 4The alkyl ester of aliphatic saturated monocarboxylic acid, C 7～C 8The alkyl ester of aromatic carboxylic acid, C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6A kind of in the saturated fatty ketone or their mixture.
8. the ethylene polymerization catalysts that is used for according to claim 7, wherein said electron donor compound are selected from a kind of or their mixture in methyl-formiate, ETHYLE ACETATE, butylacetate, ether, hexyl ether, THF, acetone and the MIBK.
9. the ethylene polymerization catalysts that is used for according to claim 8, wherein said electron donor compound is a THF.
10. the said Preparation of catalysts method of one of claim 1-9 comprises the steps:
(1) mother liquor preparation: in the electron donor compound, magnesium dihalide, halogenated titanium and aluminum halide are reacted the preparation mother liquor;
(2) silica gel blending: with mother liquor that obtains in the step (1) and inorganic oxide carrier blending;
(3) spray shaping: the mixture that obtains in the step (2) is carried out spraying drying, obtain ingredient of solid catalyst;
(4) prereduction: in varsol, the catalyst component and the activator component that obtain in the step (3) are reacted, obtain catalyzer.
11. the application of the described catalyzer of one of claim 1-9 in vinyl polymerization or copolymerization.
CN2009100803451A 2009-03-20 2009-03-20 Catalyst for vinyl polymerization and method for preparing same Active CN101838351B (en)

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Publication number Priority date Publication date Assignee Title
CN104761665B (en) * 2014-04-18 2018-03-02 陈伟 A kind of ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof
BR102015027108B1 (en) 2014-10-27 2021-01-12 China Petroleum & Chemical Corporation polyethylene composition and film
CN109438595B (en) * 2018-09-29 2021-05-04 吉化集团吉林市天龙催化剂有限公司 Ethylene gas phase polymerization slurry type catalyst and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030069372A1 (en) * 2001-10-09 2003-04-10 Formosa Plastics Corporation, U.S.A. Olefin polymerization catalyst and process for preparing polyolefins with said catalyst
CN1493599A (en) * 2002-10-31 2004-05-05 中国石油化工股份有限公司 Catalyst for ethylene polymerization
CN101260165A (en) * 2008-04-29 2008-09-10 郭琦 Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030069372A1 (en) * 2001-10-09 2003-04-10 Formosa Plastics Corporation, U.S.A. Olefin polymerization catalyst and process for preparing polyolefins with said catalyst
CN1493599A (en) * 2002-10-31 2004-05-05 中国石油化工股份有限公司 Catalyst for ethylene polymerization
CN101260165A (en) * 2008-04-29 2008-09-10 郭琦 Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof

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