CN105622790A - Carrier for ethylene homopolymerization or copolymerization, and catalyst thereof - Google Patents
Carrier for ethylene homopolymerization or copolymerization, and catalyst thereof Download PDFInfo
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Abstract
The present invention relates to a polymer doped carrier for an ethylene polymerization catalyst, an ethylene polymerization catalyst component prepared from the polymer doped carrier, a preparation method of the ethylene polymerization catalyst component, and a catalyst of the polymer doped carrier. According to the present invention, magnesium chloride/organic phosphorus compound/epoxy compound having a carbon-carbon double bond/alcohol compound can form a clear and transparent solution in an inert hydrocarbon solvent, and during the heating process of the solution, the epoxy compound having the carbon-carbon double bond in the system or the reaction product thereof and a subsequently-added free radical polymerization monomer are subjected to a copolymerization reaction so as to precipitate the polymer doped carrier; the polyethylene catalyst prepared from the carrier has characteristics of narrow particle size distribution, high hydrogen response, breaking resistance during the polymerization process, and less fine powder; and the obtained polyethylene powder material has the broad molecular weight distribution.
Description
Technical field
The present invention relates to a kind of for vinyl polymerization or the polymer-doped type carrier of combined polymerization, ingredient of solid catalyst, and the Catalysts and its preparation method containing this ingredient of solid catalyst.
Background technology
The common preparation method of one of Ziegler-Natta type polyolefin catalyst is: first prepare magnesium compound (or magnesium compound and electron donor are formed the solid complex) carrier with certain particle shape and particle size distribution, alkoxyl magnesium carrier as described in patent CN102020534A, or the magnesium chloride/ethanolic vehicle described in patent CN1091748A. Again through the method such as dealcoholysis, chlorination, it is the framing structure of magnesium chloride by vector, completes the preparation process of polyolefin catalyst finally by load titanium chloride.
Modal magnesium compound (or magnesium compound/electron donor) carrier and magnesium chloride/ethanolic vehicle in this area, as described in patent CN1091748A. By introducing polymer in magnesium chloride/ethanolic vehicle, such as polyethers (CN101544710A) and polyester (CN101550205A) etc., it is possible to give the resistant to breakage ability that support/catalyst is higher. Additionally, other method preparing carrier includes: 1, as CN102020534A and CN101663332A etc. discloses the method preparing alkoxyl magnesium carrier; 2, react with epoxide as WO2011/044761A1 discloses magnesium chloride alcohol adduct solution, the method preparing novel ball magnesium compound carrier; 3, such as the CN101554595A preparation method disclosing the polymer-doped type carrier comprising magnesium chloride/styrol copolymer/silica gel/oxolane/butanediol component.
Catalyst whether easily broken mechanical strength being primarily limited to carrier in polymerization, if the mechanical strength of carrier is relatively low, the catalyst being then processed obtaining also is easily broken, and can produce a certain amount of polyethylene fine powder in polymerization, and this is disadvantageous for the stable operation of fluid bed. The mechanical strength strengthening carrier is to avoid catalyst breakage, and then reduces the optimization approach of fine powder content in polymerization technique, and introducing polymer in carrier is effective ways. Accordingly, it would be desirable to prepare a kind of polymer-doped type carrier and catalyst.
Additionally, for the polyolefin products obtaining wide molecular weight distribution, generally introduce multiple electron donor in catalyst, as described in patent CN101554595A. Introduce copolymer in catalytic component, then the different structure unit class of copolymer is similar to different electron donors, it is possible to produces different active center, and then can obtain the polyolefin products of wide molecular weight distribution.
The present inventor it have been investigated that, the solution of magnesium chloride/organic phosphorus compound/can be formed in inert hydrocarbon solvent with the epoxide/alcohol compound of carbon-carbon double bond clear, this solution is in temperature-rise period, system can be copolymerized conjunction reaction with the free yl polymerizating monomer being subsequently added with the epoxide of carbon-carbon double bond or its product such that it is able to precipitate out the carrier of doped polymer. By polyethylene catalysts narrow diameter distribution prepared by this carrier, hydrogen adjusts sensitivity high, not broken in the course of the polymerization process, so fine powder is less, it is also possible to make its gained polyethylene powder have wide molecular weight distribution.
Summary of the invention
The preparation method that the technical problem to be solved in the present invention is to provide the polymer-doped type carrier that a kind of ethylene rolymerization catalyst uses, the method is simple to operate, it is not necessary to conventional equipment is adjusted. Additionally providing a kind of ethene polymerization catalyst component prepared by polymer-doped type carrier, its catalytic component and promoter can polymerising ethylenes. The polyethylene catalysts prepared by this carrier not only has the feature of narrow diameter distribution, and not broken, and hydrogen response is high, and the particle size distribution of gained polymerization powder is concentrated especially, fine powder is less and molecular weight distribution is wider.
Polymer-doped type carrier used by a kind of ethylene rolymerization catalyst of the present invention, this carrier includes the product of following component: (1) magnesium compound; (2) organic phosphorus compound; (3) with the epoxide of carbon-carbon double bond; (4) alcohol compound; (5) free yl polymerizating monomer;
Described magnesium compound in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula one of them halogen atom by the one in the replaced derivant of oxyl or halo oxyl, or their mixture;
Described organic phosphorus compound is hydrocarbyl carbonate or the halohydrocarbyl ester of orthophosphoric acid or phosphorous acid;
The described epoxide with carbon-carbon double bond includes with at least one in the aliphatic alkene of carbon-carbon double bond, alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether;
Described alcohol compound include carbon number 1��18 fatty alcohol or aromatic alcohol at least one;
Described free yl polymerizating monomer is acrylate and derivant, Styrene and its derivatives and acrylonitrile and derivant thereof.
Specifically, the magnesium compound described in component (1) includes MgCl2��MgBr2��MgI2, MgCl (OEt), MgCl (OBu) and MgCl2-mROH etc.
Organic phosphorus compound described in component (2) is triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, NSC 5284, tributyl phosphite, at least one in di-n-butyl phosphite.
The epoxide with carbon-carbon double bond described in component (3) includes glycidyl methacrylate and glycidyl acrylate etc.
Alcohol compound described in component (4) includes at least one in methanol, ethanol, propanol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, hexanol, Hexalin, capryl alcohol, isooctanol, benzyl alcohol, phenethanol.
Free yl polymerizating monomer described in component (5) is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, 2-(Acryloyloxy)ethanol, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, styrene, at least one in chlorostyrene, acrylonitrile etc.
Ratio between each reactant is in every mole of magnesium, and organic phosphorus compound is 0.1��5.0 mole, and the epoxide with carbon-carbon double bond is 0.1��5.0 mole, and alcohol compound is 0.1��5.0 mole, and free yl polymerizating monomer is 0.1��5.0 mole.
The preparation method of a kind of polymer-doped type carrier used by ethylene rolymerization catalyst of the present invention, comprises the steps:
(1) magnesium compound described in component (1) is dispersed in hydro carbons atent solvent, obtains suspension;
(2) in suspension, add the organic phosphorus compound described in component (2), the epoxide with carbon-carbon double bond described in component (3) and the alcohol compound described in component (4), after reacting certain time at 20-50 DEG C, form homogeneous transparent solution;
(3) at 20��50 DEG C, the free yl polymerizating monomer described in component (5) is added in the homogeneous transparent solution of step (2), slow temperature-rise period precipitates out solids, after the reaction regular hour, remove unreacted reactant, and adopt inert diluent to wash, obtain the polymer-doped type carrier of the present invention.
The invention still further relates to a kind of catalytic component for vinyl polymerization, it comprises the product of following component:
(1) above-mentioned polymer-doped type carrier;
(2) one or more are by formula Ti (OR)nX4-nShown titanium compound, in formula, R is C1��C8Alkyl, X is halogen atom, 0��n��4;
(3) one or more are by formula AlR 'aXbHcShown organo-aluminum compound, in formula, R ' is C1��C14Alkyl, X is halogen, and a, b, c are the integer of 0��3 and a+b+c=3;
(4) one or more electron donor compounds, selected from carboxylate, aromatic ester, aliphatic ether and cycloaliphatic ether etc.;
Wherein the ratio between each reactant is in every mole of magnesium in the polymer-doped type carrier described in component (1), and component (2) titanium compound is 0.1��15.0 mole; Component (3) organo-aluminum compound is 0.1��5.0 mole; Component (4) electron donor compound is 0.1��5.0 mole.
Titanium compound formula described in component (2) is Ti (OR)nX4-n, in formula, R is C1��C8Alkyl, X is halogen atom, 0��n��3, including TiCl4��TiBr4��TiI4��Ti(OC2H5)Cl3��Ti(OCH3)Cl3��Ti(OC4H9)Cl3��Ti(OC2H5)Br3��Ti(OC2H5)2Cl2��Ti(OCH3)2Cl2��Ti(OCH3)2I2��Ti(OC2H5)3Cl��Ti(OCH3)3Cl��Ti(OC2H5)3I etc.
The formula of the organo-aluminum compound described in component (3) is AlR 'aXbHcShown in, in formula, R ' is C1��C14Alkyl, X is halogen, and a, b, c are the integer of 0��3 and a+b+c=3. Particular compound such as Al (CH3)3��Al(CH2CH3)3��Al(i-Bu)3��Al(n-C6H13)3��AlH(CH2CH3)2��AlH(i-Bu)2�� AlCl(CH2CH3)2��Al2Cl3(CH2CH3)3��AlCl(CH2CH3)2��AlCl2(CH2CH3) etc. alkyl aluminum compound, wherein be preferably Al (CH2CH3)3��Al(n-C6H13)3��Al(i-Bu)3. It most preferably is Al (CH2CH3)3. These organo-metallic compounds both may be used alone, two or more kinds can also be used in combination.
Electron donor compound described in component (4) is selected from carboxylate, aliphatic ether, cyclic aliphatic ether or aliphatic ketone, it is preferred to C1��C4The Arrcostab of aliphatic saturated monocarboxylic acid, C1��C8The Arrcostab of aromatic carboxylic acids, C2��C12Aliphatic ether, C3��C4Cyclic ethers, C3��C6Saturated fat ketone. Particular compound such as methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate, ether, hexyl ether, oxolane, acetone and methyl iso-butyl ketone (MIBK) etc., these electron donor compounds both may be used alone, two or more kinds can also be used in combination.
The preparation method of the catalytic component for ethylene polymerization of the present invention, it comprises the following steps:
(1) by the polymer-doped type support dispersion described in component (1) in hydro carbons atent solvent, suspension is obtained;
(2) suspension is carried out haptoreaction in-40��50 DEG C with component (3) organo-aluminum compound and one or more electron donor compounds of component (4);
(3) mixture of step (2) is to slowly warm up to 20��60 DEG C, after the reaction regular hour, removes unreacted reactant, and adopt inert diluent to wash;
(4) add component (2) titanium compound to react, then adopt inert diluent washing, obtain the catalytic component of the present invention.
Present invention also offers a kind of catalyst for vinyl polymerization or combined polymerization, it comprises the product of following components:
(1) catalytic component of the invention described above;
(2) formula is AlRdX3-dOrgano-aluminum compound, in formula, R is hydrogen or carbon number is the alkyl of l��20, and X is halogen atom, 0 < d��3.
Component (2) formula of is AlRdX3-dOrgano-aluminum compound, in formula, R can be hydrogen or carbon number be the alkyl of l��20, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; 0 < d��3. Particular compound such as Al (CH3)3��Al(CH2CH3)3��Al(i-Bu)3��AlH(CH2CH3)2��AlH(i-Bu)2��AlCl(CH2CH3)2��Al2Cl3(CH2CH3)3��AlCl(CH2CH3)2��AlCl2(CH2CH3) etc. alkyl aluminum compound. It is preferably Al (CH2CH3)3��Al(i-Bu)3. Wherein in component (2), aluminum is 5��500 with the mol ratio of titanium in component (1), it is preferable that 20��200.
Liquid polymerization medium includes: iso-butane, hexane, heptane, hexamethylene, Petroleum, raffinate oil, the atent solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogasoline, kerosene, benzene,toluene,xylene.
In order to regulate the molecular weight of final polymer, hydrogen is adopted to make molecular weight regulator.
The present inventor it have been investigated that, the solution of magnesium chloride/organic phosphorus compound/can be formed in inert hydrocarbon solvent with the epoxide/alcohol compound of carbon-carbon double bond clear, this solution is in temperature-rise period, system can be copolymerized conjunction reaction with the free yl polymerizating monomer being subsequently added with the epoxide of carbon-carbon double bond or its product such that it is able to precipitate out the carrier of doped polymer. By polyethylene catalysts narrow diameter distribution prepared by this carrier, hydrogen adjusts sensitivity high, not broken in the course of the polymerization process, so fine powder is less, it is also possible to make its gained polyethylene powder have wide molecular weight distribution.
Detailed description of the invention
Method of testing:
1. the relative weight percents of titanium elements in catalyst system: adopt spectrophotography;
2. the relative weight percents of polymer in catalyst system: adopt core magnetic survey;
3, the molecular weight of polymer in catalyst system, is measured by gel chromatography PL220;
4, the mensuration (MI/2.16Kg) of melt index: according to ASTMD1238-99;
With embodiment the present invention described below, but and the unrestricted scope of the invention.
Embodiment 1
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 90ml toluene, 20ml TRI N BUTYL PHOSPHATE, 8.0ml glycidyl methacrylate, 1ml ethanol join in reactor, when speed of agitator 450rpm, temperature are 40 DEG C, and constant temperature 2 hours. Adding 3ml methyl methacrylate to system, be to slowly warm up to 90 degree, carrier particle precipitates out gradually. Constant temperature 1 hour, elimination mother solution, washs for several times through inert diluent. Transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtain the polymer-doped type carrier of narrow diameter distribution.
Embodiment 2
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 80ml toluene, 18ml triethyl phosphate, 6.0ml glycidyl acrylate, 2ml ethanol join in reactor, when speed of agitator 450rpm, temperature are 40 DEG C, and constant temperature 2 hours. Adding 3ml acrylonitrile to system, be to slowly warm up to 90 degree, carrier particle precipitates out gradually. Constant temperature 1 hour, elimination mother solution, washs for several times through inert diluent. Transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtain the polymer-doped type carrier of narrow diameter distribution.
Embodiment 3
The preparation of polymer-doped type carrier
By 3.0 grams of magnesium chlorides, 80ml toluene, 18ml tricresyl phosphate propyl ester, 10.0ml glycidyl acrylate, 2ml ethanol join in reactor, when speed of agitator 450rpm, temperature are 40 DEG C, and constant temperature 2 hours. Adding 6ml hydroxyethyl methylacrylate to system, be to slowly warm up to 90 degree, carrier particle precipitates out gradually. Constant temperature 1 hour, elimination mother solution, washs for several times through inert diluent. Transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtain the polymer-doped type carrier of narrow diameter distribution.
Embodiment 4
(1) preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into the polymer-doped type carrier of 4.0g (being prepared by embodiment 1), hexane 100ml, stirring borehole cooling is to-10 DEG C, the hexane solution (triethyl aluminum: 1.2M) of dropping 40ml triethyl aluminum and 0.5ml ethyl benzoate, then heat to 50 DEG C, and maintain reaction 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate hexane is room temperature washing twice. Add 100ml hexane, this system is cooled to 0 DEG C, is slowly added dropwise titanium tetrachloride 6ml, be warming up to 60 DEG C afterwards, react 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate, with, after hexanes wash twice, being transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution. Catalyst forms in Table 1.
(2) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, add the ingredient of solid catalyst (containing 0.6 milligram of titanium) prepared by said method, it is warming up to 70 DEG C, passes into hydrogen and make pressure in still reach 0.28Mpa, then pass into ethylene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), being polymerized 2 hours under 80 DEG C of conditions, polymerization result is in Table 2.
(3) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, add the ingredient of solid catalyst (containing 1.8 milligrams of titaniums) prepared by said method, it is warming up to 70 DEG C, passes into hydrogen and make pressure in still reach 0.58Mpa, then pass into ethylene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), being polymerized 2 hours under 80 DEG C of conditions, polymerization result is in Table 3.
Embodiment 5
(1) preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into the polymer-doped type carrier of 5.0g (being prepared by embodiment 2), hexane 100ml, stirring borehole cooling is to-10 DEG C, the hexane solution (triethyl aluminum: 1.2M) of dropping 50ml triethyl aluminum and 0.5ml acetic acid n-octyl, then heat to 50 DEG C, and maintain reaction 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate hexane is room temperature washing twice. Add 100ml hexane, this system is cooled to 0 DEG C, is slowly added dropwise titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate, with, after hexanes wash twice, being transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution. Catalyst forms in Table 1.
(2) polyreaction: with embodiment 4, polymerization result is in Table 2.
Embodiment 6
(1) preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into the polymer-doped type carrier of 3.0g (being prepared by embodiment 3), hexane 100ml, stirring borehole cooling is to-10 DEG C, the hexane solution (tri-n-hexyl aluminum: 1.0M) of dropping 40ml tri-n-hexyl aluminum and 0.5ml butyl benzoate, then heat to 50 DEG C, and maintain reaction 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate hexane is room temperature washing twice. Add 100ml hexane, this system is cooled to 0 DEG C, is slowly added dropwise titanium tetrachloride 6ml, be warming up to 60 DEG C afterwards, react 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate, with, after hexanes wash twice, being transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution. Catalyst forms in Table 1.
(2) polyreaction: with embodiment 4, polymerization result is in Table 2 and table 3.
Comparative example 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 4.0g ball type carrier MgCl2��2.6C2H5OH, hexane 100ml, stirring borehole cooling, to-10 DEG C, drips the hexane solution (triethyl aluminum: 1.2M) of 40ml triethyl aluminum, then heats to 50 DEG C, and maintains reaction 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate hexane is room temperature washing twice. Add 100ml hexane, this system is cooled to 0 DEG C, is slowly added dropwise titanium tetrachloride 6ml, be warming up to 60 DEG C afterwards, react 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate, with, after hexanes wash twice, being transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtains the solid spherical catalytic component of good fluidity, narrow particle size distribution. Catalyst forms in Table 1.
(2) polyreaction: with embodiment 4, polymerization result is in Table 2 and table 3.
Comparative example 2
(1) preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 5.0g ball type carrier MgCl2��2.6C2H5OH, hexane 100ml, stirring borehole cooling, to-10 DEG C, drips the hexane solution (tri-n-hexyl aluminum: 1.0M) of 50ml tri-n-hexyl aluminum, ethyl benzoate 2ml, then heats to 50 DEG C, and maintains reaction 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate hexane is room temperature washing twice. Add 100ml hexane, this system is cooled to 0 DEG C, is slowly added dropwise titanium tetrachloride 6ml, be warming up to 60 DEG C afterwards, react 2 hours. Stopping stirring, stand, suspension is quickly layered, and extracts the supernatant, and precipitate, with, after hexanes wash twice, being transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtains the solid spherical catalytic component of good fluidity, narrow particle size distribution. Catalyst forms in Table 1.
(2) polyreaction: with embodiment 4, polymerization result is in Table 2.
The composition of table 1 catalytic component
From the data of table 1 it can be seen that by gained catalytic component Unusually narrow particle size distribution of the present invention, span value is not higher than 0.7. The narrower span value of polymer-doped type carrier comes from its slow precipitation mode. And the span value of comparative example catalyst is limited to the particle size distribution of spherical magnesium chloride/ethanolic vehicle. Wherein the definition of Span is as follows: [(particle diameter of 90% cumulative particle sizes)-(particle diameter of 10% cumulative particle sizes)]/(particle diameter of 50% cumulative particle sizes), term 90%/10%/50% cumulative particle sizes represents granularity limit value, and the granule at the cumulative amount at limit value place 90%/10%/50% is both less than this granularity limit value.
Table 2 catalyst and properties of powder
From the data of table 2 it can be seen that the polyethylene powder gone out by gained catalyst preparing of the present invention, melt index is higher, and the fine powder content below 190 orders is less than 0.5% (wt), and molecular weight distribution is wider. As can be seen here, gained catalyst particle of the present invention is not broken in the course of the polymerization process.
The hydrogen of table 3 catalyst adjusts sensitivity
From the data of table 3 it can be seen that the catalyst hydrogen response of the present invention is good.
Claims (17)
1. the polymer-doped type carrier used by ethylene rolymerization catalyst, this carrier includes the product of following component:
(1) magnesium compound;
(2) organic phosphorus compound;
(3) with the epoxide of carbon-carbon double bond;
(4) alcohol compound;
(5) free yl polymerizating monomer;
Described magnesium compound in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula one of them halogen atom by the one in the replaced derivant of oxyl or halo oxyl, or their mixture;
Described organic phosphorus compound is hydrocarbyl carbonate or the halohydrocarbyl ester of orthophosphoric acid or phosphorous acid;
The described epoxide with carbon-carbon double bond is with at least one in the aliphatic alkene of carbon-carbon double bond, alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether;
Described alcohol compound be carbon number 1��18 fatty alcohol or aromatic alcohol at least one;
Described free yl polymerizating monomer is acrylate and derivant, Styrene and its derivatives and acrylonitrile and derivant thereof.
2. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterized in that the ratio between each reactant is in every mole of magnesium, organic phosphorus compound is 0.1��5.0 mole, epoxide with carbon-carbon double bond is 0.1��5.0 mole, alcohol compound is 0.1��5.0 mole, and free yl polymerizating monomer is 0.1��5.0 mole.
3. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterized in that described free yl polymerizating monomer is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, 2-(Acryloyloxy)ethanol, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, styrene, at least one in chlorostyrene, acrylonitrile etc.
4. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that the described epoxide with carbon-carbon double bond is selected from glycidyl methacrylate and glycidyl acrylate.
5. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterized in that described organic phosphorus compound is triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, NSC 5284, tributyl phosphite, at least one in di-n-butyl phosphite.
6. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that described alcohol compound at least one in methanol, ethanol, propanol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, hexanol, Hexalin, capryl alcohol, isooctanol, benzyl alcohol, phenethanol.
7. the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that described magnesium compound is selected from MgCl2��MgBr2��MgI2, MgCl (OEt), MgCl (OBu) and MgCl2-mROH��
8. the preparation method of the polymer-doped type carrier used by a kind of ethylene rolymerization catalyst one of claim 1-7 Suo Shu, comprises the steps:
(1) described magnesium compound is dispersed in hydro carbons atent solvent, obtains suspension;
(2) in suspension, add described organic phosphorus compound, with the epoxide of carbon-carbon double bond and alcohol compound, form homogeneous transparent solution after reacting certain time at 20��50 DEG C;
(3) at 20��50 DEG C, described free yl polymerizating monomer is added in the homogeneous transparent solution of step (2), slow temperature-rise period precipitates out solids, after the reaction regular hour, remove unreacted reactant, and adopt inert diluent to wash, obtain the polymer-doped type carrier of the present invention.
9. the catalytic component for ethylene polymerization, it is characterised in that comprise the product of following component:
(1) the polymer-doped type carrier used by ethylene rolymerization catalyst described for one of claim 1-7;
(2) at least one formula is Ti (OR3)nX4-nTitanium compound, R in formula3For C1��C8Alkyl, X is halogen atom, 0��n��4;
(3) at least one by formula AlRa��XbHcShown organo-aluminum compound, in formula, R ' is C1��C14Alkyl, X is halogen, and a, b, c are the integer of 0��3 and a+b+c=3;
(4) at least one electron donor compound, selected from carboxylate, aromatic ester, aliphatic ether and cycloaliphatic ether;
Wherein the ratio between each reactant is in every mole of magnesium in described polymer-doped type carrier, and titanium compound is 0.1��15.0 mole; Organo-aluminum compound is 0.1��5.0 mole; Electron donor compound is 0.1��5.0 mole.
10. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that the particle size distribution Span of catalytic component is less than or equal to 0.7.
11. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described titanium compound is selected from TiCl4��TiBr4��TiI4��Ti(OC2H5)Cl3��Ti(OCH3)Cl3��Ti(OC4H9)Cl3��Ti(OC2H5)Br3��Ti(OC2H5)2Cl2��Ti(OCH3)2Cl2��Ti(OCH3)2I2��Ti(OC2H5)3Cl��Ti(OCH3)3Cl��Ti(OC2H5)3I��
12. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described organo-aluminum compound is selected from Al (CH3)3��Al(CH2CH3)3��Al(i-Bu)3��Al(n-C6H13)3��AlH(CH2CH3)2��AlH(i-Bu)2��AlCl(CH2CH3)2��Al2Cl3(CH2CH3)3��AlCl(CH2CH3)2��AlCl2(CH2CH3)��
13. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described electron donor compound is selected from methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate, ether, hexyl ether, oxolane, acetone and methyl iso-butyl ketone (MIBK).
14. the preparation method of a kind of catalytic component for ethylene polymerization described in claim 9, comprise the following steps:
(1) by described polymer-doped type support dispersion in hydro carbons atent solvent, suspension is obtained;
(2) suspension is carried out haptoreaction in-40��50 DEG C with organo-aluminum compound and at least one electron donor compound;
(3) mixture of step (2) is to slowly warm up to 20��60 DEG C, after the reaction regular hour, removes unreacted reactant, and adopt inert diluent to wash;
(4) add titanium compound to react, then adopt inert diluent washing, obtain the catalytic component of the present invention.
15. for a catalyst for ethylene polymerization, it comprises the product of following components:
(1) catalytic component described in claim 9;
(2) formula is AlR "dX3-dOrgano-aluminum compound, R in formula " be the alkyl of l��20 for hydrogen or carbon number, X is halogen atom, 0 < d��3.
16. the catalyst for ethylene polymerization according to claim 15, it is characterised in that in component (2), aluminum is 20��200 with the mol ratio of titanium in component (1).
17. the catalyst for ethylene polymerization described in claim 15 closes the application in reaction or copolymerization at ethylene homo.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101554595A (en) * | 2009-05-18 | 2009-10-14 | 浙江大学 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
| CN102020534A (en) * | 2009-09-18 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing amorphous alkoxy magnesium |
| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
| CN103819586A (en) * | 2012-11-16 | 2014-05-28 | 中国石油化工股份有限公司 | Catalyst system for alkene polymerization reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554595A (en) * | 2009-05-18 | 2009-10-14 | 浙江大学 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
| CN102020534A (en) * | 2009-09-18 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing amorphous alkoxy magnesium |
| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
| CN103819586A (en) * | 2012-11-16 | 2014-05-28 | 中国石油化工股份有限公司 | Catalyst system for alkene polymerization reaction |
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