CN103772536B - A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst thereof - Google Patents
A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for ethylene polymerization, comprise the ingredient of solid catalyst of following component: A, titaniferous, it is to react with organic epoxide, organic phosphorus compound, organic alcohol compound by magnesium halide to form homogeneous solution, then mix with the halide or derivatives thereof of aromatic ester compound, transition metals Ti, obtain ingredient of solid catalyst; B, organo-aluminum compound, its general formula is AlRnX3-n, in formula, R is the alkyl that hydrogen or carbon number are 1～20, and X is halogen atom, and n is the integer of 0 < n≤3. This catalyst has higher catalytic activity, good hydrogen response, and polymer has very high bulk density, is applicable to the equal polymerization of ethene or the combined polymerization of ethene and other alpha-olefin.
Description
Technical field
The present invention relates to a kind of catalytic component for vinyl polymerization or copolymerization, this catalyst groupThe preparation method who divides and its catalyst. More particularly, relate to a kind of aromatic ester that adds in preparation processThe catalytic component of compounds, the preparation method of this catalytic component and its catalyst.
Background technology
As everyone knows, tie up in polyolefinic suitability for industrialized production and account for master containing the caltalyst of Ti/Mg compoundLead status, its research core is nothing more than being the polymerization activity of catalyst, particle shape and the grain of catalystThe hydrogen response of footpath distribution, catalyst and copolymerization performance etc. And in the slurry polymerization processes of ethene,Except requiring catalyst should have higher catalytic activity, control the polyvinyl particle diameter of producing largeIt is very important that little and particle diameter distributes. In olefinic polymerization, particularly in the slurry polymerization process of ethene,Be easy to produce thinner polymer particle, this fine powder easily produces static, causes " airborne dust " phenomenon, hasIn time, also easily lumps, and causes the obstruction of equipment pipe. And particle size and the particle diameter of controlling polymer distributeEffective method is that particle diameter and the particle diameter of controlling catalyst distribute.
In the prior art, in order to obtain having the catalyst of single-size diameter and better particle shape,People adopt two following class methods to carry out Kaolinite Preparation of Catalyst conventionally.
The first is that the magnesium compounds such as magnesium chloride are dissolved in and in some solvent, obtain homogeneous solution, and thenBy this solution and titanium compound and optionally electron donor mix, obtain containing magnesium, titanium by the method for precipitationWith the solids of optional electron donor, and this solids is processed with excessive liquid titanium compoundAfter obtain catalyst granules. For example, in CN1099041A, CN1229092 disclosed. This tradition sideThe shortcoming of method is that particle diameter and the particle diameter distribution of catalyst granules is to be magnesium carrier composition by precipitation process completelyRecrystallization process control, its stability more difficult control.
The second is that catalyst activity component is directly carried on to inert carrier as on silica gel etc., due to siliconThe particle diameter of glue is easily controlled, and particle shape is better, therefore can obtain evengranular catalystParticle. But because the load capacity of active component on carrier is restricted, the catalysis that therefore this method makesIn agent, Ti content is lower, and polymerization activity is not high. For example: in CN1268520 with magnesium chloride, silicaFor carrier, titanium tetrachloride is active component, and the preparation method of catalyst is as follows: by MgCl2At tetrahydrochysene furanIn muttering with TiCl4Reaction, then with the SiO processing through alkyl aluminum2Mix, remove after oxolane and make and urgeAgent component. When for vinyl polymerization, because the Ti content in catalyst is lower, thus polymerization activityLower. Therefore, although this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethene, byBe difficult to be applicable in the slurry polymerization processes of ethene in lower catalytic activity.
As everyone knows, in the slurry polymerization processes of ethene, except requiring catalyst should there is higher catalysisOutside activity and particle diameter distribution preferably, also should there is higher bulk density and good hydrogen response.And the bulk density of the catalyst system that above-mentioned two kinds of methods make and hydrogen response also do not make us fullMeaning.
The catalyst that CN1958620A and CN102295717A are prepared above-mentioned two kinds of methods changesEnter, these two sections of patents disclose the preparation method for the catalytic component of ethylene polymerization.CN1958620A discloses in this catalyst preparation and has added the more lower boiling of tetraethoxy-silicane alkanesOrgano-silicon compound, itself and titanium tetrachloride boiling point approach, and in the recovery process of producing, hold at CatalystEasily azeotropic steams together with titanium tetrachloride, but affects the purity of titanium tetrachloride. CN102295717A disclosesA kind of method for preparing catalyst, catalyst prepared by the method all increases at active, hydrogen response,But owing to having added two kinds of electron donors in system, in suitability for industrialized production, adding of electron donor is easyProduce oligomer, stop up rectifying column, be unfavorable for the recovery of toluene and titanium tetrachloride.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of ethylene polymerization ingredient of solid catalyst, and this is solidBody catalyst component has higher catalytic activity, higher hydrogen response, and polymer has very highBulk density.
A kind of catalyst for ethylene polymerization, comprises following component:
The ingredient of solid catalyst of A, titaniferous, it is by magnesium halide and organic epoxide, organicPhosphorus compound, organic alcohol compound reaction form homogeneous solution, then with aromatic ester compound, transitionThe halide or derivatives thereof of Titanium mixes, and obtains ingredient of solid catalyst;
B, organo-aluminum compound, its general formula is AlRnX3-n, in formula R be hydrogen or carbon number be 1～20 alkyl, X is halogen atom, n is the integer of 0 < n≤3;
Ratio between B component and component A, taking the molar ratio computing of magnesium and titanium as 5～500;
The general formula of wherein said aromatic ester compound is R1 nR2 mC6H5-n-m-x［(CH2)yCOOR3］x，Wherein R1，R2That carbon number is 1～20 alkyl, aryl, alcyl or alkoxyl, R3That carbon is formerSubnumber is 1～20 alkyl, aryl, alcyl, 0≤n <, 5,0≤m <, 5,0 < x <, 5,0≤y≤9, n, m, x, y is integer, and n+m+x < 5;
Wherein said organic alcohol compound is that carbon number is 1～10 straight chain, side chain or cycloalkylAlcohol or carbon number are 6～20 alcohol that contain aryl;
Wherein magnesium halide, organic epoxide, organic phosphorus compound, organic alcohol compound, aromatic esterThe feed molar ratio of the halide or derivatives thereof of compounds, transition metals Ti, in every mole of magnesium halide,Organic epoxide 0.2～10mol mole, organic phosphorus compound 0.1～10mol mole, Organic Alcohol0～6 mole of compound, 0.1～1 mole of aromatic ester compound, the halide of transition metals Ti or its1～20 mole, derivative.
Detailed description of the present invention:
The preparation of magnesium halide solution: magnesium halide solution is that magnesium halide is dissolved in organic epoxide and organicThe homogeneous solution that the dicyandiamide solution of phosphorus compound composition obtains, in the process that forms solution or solution shapeAfter one-tenth, add organic alcohol compound, the reaction regular hour obtains reaction solution; Here the solvent body of indicationSystem comprises use or does not use inert diluent.
The described magnesium halide of catalytic component of the present invention (A) comprises water or the alcohol of magnesium dihalide, magnesium dihalideReplaced by oxyl or halogen oxyl Deng one of them halogen atom in complex compound, magnesium dihalide molecular formulaA kind of or its mixture in derivative, above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, twoMagnesium iodide. Wherein taking magnesium dichloride as best.
The magnesium halide granularity using is dissolved as under stirring, and solution temperature is-10 DEG C～150 DEG C, with20 DEG C～130 DEG C for well. When dissolving, can add or not with inert diluent as: benzene,toluene,xylene,1,2-dichloroethanes, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound. Wherein benzene, toluene, twoToluene is that toluene, dimethylbenzene are best preferably.
Organic epoxide comprises that carbon number is 2～8 aliphatic alkene, alkadienes, halo fatThe compounds such as the oxide of fat family alkene or alkadienes, glycidol ether, inner ether. Particular compound as:Oxirane, expoxy propane, epoxy butane, epoxychloropropane, methyl glycidyl ether, two shrink sweetOil ether, oxolane etc. Wherein, be preferably oxirane, expoxy propane, epoxychloropropane,Oxolane, taking oxolane, epoxychloropropane as best.
Organic phosphorus compound comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid. Concrete as: justTrimethyl phosphate, orthophosphoric acid triethyl, orthophosphoric acid tributyl, triphenyl phosphite, Trimethyl phosphite,Triethyl phosphite, tributyl phosphite, triphenyl phosphite, phosphorous acid benzene methyl etc. Wherein betterBe orthophosphoric acid trimethyl, orthophosphoric acid triethyl and orthophosphoric acid tributyl, orthophosphoric acid tributyl is best.
Catalytic component of the present invention (A) described organic alcohol compound comprises that carbon number is 1～10The alcohol of straight chain, side chain or cycloalkyl or carbon number are 6～20 alcohol that contain aryl. The example of alcohol comprisesFatty alcohol: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, glycerine, hexanol, 2-firstBase amylalcohol, 2-ethyl butanol, n-heptanol, n-octyl alcohol, decyl alcohol etc.; Cyclic alkanol, as cyclohexanol, methylCyclohexanol etc.; Aromatic alcohol, as phenmethylol, methylbenzyl alcohol, ɑ-methylbenzyl alcohol, ɑ, ɑ-dimethylPhenmethylol etc. Preferred alcohol, butanols, 2-Ethylhexyl Alcohol, glycerine. To each alcohol in alcohol compositionRatio has no particular limits.
The described magnesium halide of catalytic component of the present invention (A) forms in the process of homogeneous solution in dissolving,Also can add alkyl metal cpd as zinc alkyl and or alkyl aluminum.
Aromatic ester compound of the present invention comprises: methyl benzoate, ethyl benzoate, benzoic acidPropyl ester, isopropyl benzoate, butyl benzoate, t-butyl perbenzoate, hexyl-benzoate, benzoic acid are pungentEster, benzoic acid cyclohexyl, benzoic acid 2-methyl cyclohexyl, o-toluic acid ethyl ester, to methylbenzene firstAcetoacetic ester, 2,4-mesitylenic acid ethyl ester, 2,6-mesitylenic acid ethyl ester, 3,5-dimethyl benzeneEthyl formate, 2,4,6-triisopropyl ethyl benzoate, benzoic acid methoxy ethyl ester, benzoic acid methoxy thirdEster, benzoic acid methoxy butyl ester, the own ester of benzoic acid methoxy, benzoic acid methoxy monooctyl ester, benzoic acid ethoxy ethyl ester,Benzoic acid ethoxy propyl ester, benzoic acid ethoxy butyl ester, the own ester of benzoic acid ethoxy, benzoic acid ethoxy monooctyl ester, benzeneFormic acid fourth 2-ethoxyethyl acetate, benzoic acid fourth oxygen butyl ester, the own ester of benzoic acid fourth oxygen, 5-acetyl group-2-ethoxy benzonitrileAcetoacetic ester, 3-, 4,5-trimethoxybenzoic acid ethyl ester, methyl phenylacetate, ethyl phenylacetate, phenylacetic acidPropyl ester, Isopropyl phenylacetate, butyl phenylacetate, the phenylacetic acid tert-butyl ester, the own ester of phenylacetic acid, phenylacetic acid are pungentEster, cyclohexanol phenylacetate, phenylacetic acid 2-methyl cyclohexyl, o-Tolylacetic acid ethyl ester, to methylbenzene secondAcetoacetic ester, 2,4-dimethyl phenyl acetic acid ethyl ester, 2,6-dimethyl phenyl acetic acid ethyl ester, 3,5-dimethyl benzeneEthyl acetate, 2,4,6-triisopropyl ethyl phenylacetate, phenylacetic acid methoxy ethyl ester, phenylacetic acid methoxy thirdEster, phenylacetic acid methoxy butyl ester, the own ester of phenylacetic acid methoxy, phenylacetic acid methoxy monooctyl ester, phenylacetic acid ethoxy ethyl ester,Phenylacetic acid ethoxy propyl ester, phenylacetic acid ethoxy butyl ester, the own ester of phenylacetic acid ethoxy, phenylacetic acid ethoxy monooctyl ester, benzeneAcetic acid fourth 2-ethoxyethyl acetate, phenylacetic acid fourth oxygen butyl ester, the own ester of phenylacetic acid fourth oxygen, 5-acetyl group-2-ethoxybenzene secondAcetoacetic ester, 3-, 4,5-trimethoxy ethyl phenylacetate, methyl phenylpropionate, benzenpropanoic acid ethyl ester etc. PreferablyEthyl benzoate, propyl benzoate, benzoic acid ethoxy ethyl ester, ethyl phenylacetate, propyl phenylacetate.
The halide or derivatives thereof general formula of transition metals Ti of the present invention is Ti (OR)aXb, R in formulaFor C1～C14Alkyl, X is halogen atom, a is 1 to 4 integer, b is 1 to 4 integer,And a+b=3 or 4, comprising: TiCl4、TiBr4、TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2l2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、 Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)4Deng. Preferably TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC4H9)4. With TiCl4For the best.
Magnesium halide of the present invention, organic epoxide, organic phosphorus compound, organic alcohol compound,The halide or derivatives thereof of transition metals Ti, the feed molar ratio of aromatic ester compound, with every mole of halogenationMagnesium meter, 0.2～10.0 mole of organic epoxide, preferably 0.3～4.0 mole; Organic phosphorus compound0.1～10.0 mole, preferably 0.2～4.0 mole; 0～6 mole of organic alcohol compound, preferably 0～2Mole; 1～20 mole of the halide or derivatives thereof of transition metals Ti, preferably 1～15 mole; Fragrance0.1～1 mole of ester type compound, preferably 0.1～0.5 mole.
In the catalytic component obtaining in the present invention, titanium: 1～10%, magnesium: 10～30%(weight containsAmount).
The present invention also provides the preparation method of a kind of component A of catalyst for ethylene polymerization, comprises followingStep: under agitation magnesium halide is dissolved in to organic epoxide, organic phosphorus compound and forms evenly thoroughlyBright solution, forming in the process of solution or solution adds organic alcohol compound after forming, reacts certainTime obtains reaction solution, and solution temperature is 50～90 DEG C; Then at-30 DEG C～0 DEG C, above-mentioned reactionSolution mixes with the halide or derivatives thereof of aromatic ester compound, transition metals Ti, will mixThing is slowly warming up to 50～120 DEG C, and particle is separated out and formed to solids gradually, filters, removes mother liquor,Wash solids with atent solvent, make the ingredient of solid catalyst of titaniferous.
Organo-aluminum compound of the present invention, its general formula is AlRnX3-n, in formula, R is hydrogen or carbon atomNumber is 1～20 alkyl, and X is halogen atom, and n is the integer of 0 < n≤3; Preferably AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc.
In catalyst system of the present invention, in component (B), in aluminium and component (A), the mol ratio of titanium is5～500, with 20～200 for well.
Catalyst of the present invention is applicable to the equal polymerization of ethene or the combined polymerization of ethene and other alpha-olefin, itsMiddle alpha-olefin adopts in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methylpentene-1A kind of. When polymerization, can adopt slurry polymerization, also can adopt gas-phase polymerization.
Slurry polymerization medium comprises: iso-butane, hexane, heptane, cyclohexane, naphtha, raffinate oil,The atent solvents 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, adopt hydrogen to make molecular weight regulator.
Owing to adding aromatic ester compound, gained catalyst of the present invention has higher catalytic activity andGood hydrogen response, polymer has good bulk density; Catalyst preparation process is simple, veryBe applicable to the slurry polymerization processes of ethene and need high-bulk-density polymer, high hydrogen response catalystPolymerization mix technique in.
Detailed description of the invention
With embodiment, the present invention is described below, but and unrestricted invention scope.
Method of testing:
Melt index (MI): measure according to ASTMD1238-99
Embodiment 1
(1) preparation of catalytic component
In the reactor of fully replacing through high pure nitrogen, add successively 4.0g magnesium dichloride, toluene50ml, epoxychloropropane 3.0ml, tributyl phosphate 9.0ml, ethanol 4.4ml, be warming up under stirring70 DEG C, after dissolving the solution that forms homogeneous completely, solid reacts 2 hours at 70 DEG C. By cooling this systemTo-10 DEG C, be slowly added dropwise to ethyl benzoate 4.0ml, constant temperature drips 60ml titanium tetrachloride after 10 minutes.Slowly be warming up to 85 DEG C, react 2 hours. Stop stirring, leave standstill, the very fast layering of suspension, extractsThe layer stillness of night, hexane washing four times. High pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adds hexane 1L, denseSpend the triethyl aluminum 1.0ml of 1M, add the solid catalyst of above-mentioned preparation, be warming up to 80 DEG C, pass intoHydrogen makes still internal pressure reach 0.60Mpa, then passes into ethene and make stagnation pressure in still reach 1.0Mpa(gauge pressure),Polymerization 2 hours under 90 DEG C of conditions, polymerization result is in table 1.
Embodiment 2
(1) catalyst is synthetic with embodiment 1. Just ethyl benzoate changes benzoic acid ethoxy ethyl ester into.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in table 1.
Embodiment 3
(1) catalyst is synthetic with embodiment 1. Just ethyl benzoate changes propyl benzoate into.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in table 1.
Embodiment 4
(1) catalyst is synthetic with embodiment 1. Just ethyl benzoate changes ethyl phenylacetate into.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in table 1.
Embodiment 5
(1) catalyst is synthetic with embodiment 1. Just ethyl benzoate changes propyl phenylacetate into
(2) vinyl polymerization is with embodiment 1. Polymerization result is in table 1.
Embodiment 6
(1) catalyst is synthetic with embodiment 1. Just ethyl benzoate changes 2-chlorobenzene acetic acid ethyl ester into.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in table 1.
Comparative example 1
(1) prepared by catalytic component the synthetic method described in CN1958620A embodiment 1 of press.
(2) vinyl polymerization condition is with embodiment 1. Polymerization result is in table 1.
Comparative example 2
(1) prepared by catalytic component the synthetic method described in CN102295717A embodiment 1 of press.
(1) vinyl polymerization condition is with embodiment 1. Polymerization result is in table 1.
Table 1 polymerization result
Can find out from the data of table 1, under same polymerizing condition, catalyst of the present invention hasHigh catalytic activity, good hydrogen response, polymer has very high bulk density.
Claims (8)
1. a catalyst for ethylene polymerization, comprises following component:
The ingredient of solid catalyst of A, titaniferous, it is by magnesium halide and organic epoxide, organophosphorCompound, organic alcohol compound reaction form homogeneous solution, then with aromatic ester compound, transition metalThe halide or derivatives thereof of titanium mixes, and obtains ingredient of solid catalyst;
B, organo-aluminum compound, its general formula is AlRnX3-n, in formula, R is that hydrogen or carbon number are 1～20Alkyl, X is halogen atom, n is the integer of 0 < n≤3;
Ratio between B component and component A, taking the molar ratio computing of aluminium and titanium as 5～500;
The general formula of wherein said aromatic ester compound is R1 nR2 mC6H5-n-m-x[(CH2)yCOOR3]x，Wherein R1，R2That carbon number is 1～20 alkyl or alkoxyl, R3That carbon number is 1～20 alkaneBase, 0≤n <, 5,0≤m < 5,0 < x <, 5,0≤y≤9, n, m, x, y is integer, and n+m+x < 5;
Wherein said organic alcohol compound is that carbon number is the alcohol of 1～10 straight chain, side chain or cycloalkylOr carbon number is 7～20 alcohol that contain aryl;
Wherein magnesium halide, organic epoxide, organic phosphorus compound, organic alcohol compound, aromatic esterThe feed molar ratio of the halide or derivatives thereof of compound, transition metals Ti, in every mole of magnesium halide, organic0.2～10 mole of epoxide, 0.1～10 mole of organic phosphorus compound, organic alcohol compound 0～6 is rubbedYou, 0.1～1 mole of aromatic ester compound, 1～20 mole of the halide or derivatives thereof of transition metals Ti.
2. catalyst for ethylene polymerization according to claim 1, is characterized in that described aromatic ester chemical combinationThing is selected from ethyl benzoate, benzoic acid ethoxy ethyl ester, propyl benzoate, ethyl phenylacetate, propyl phenylacetateIn one.
3. catalyst for ethylene polymerization according to claim 1, is characterized in that described magnesium halide is selected from twoOne of them halogen atom quilt in the hydrate of magnesium halide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formulaAt least one in the derivative that oxyl or halo oxyl are replaced.
4. catalyst for ethylene polymerization according to claim 1, is characterized in that described organic alcohol compoundFor the aliphatic alcohol compounds that contains 1～10 carbon atom.
5. catalyst for ethylene polymerization according to claim 1, the transition metals Ti described in it is characterized in thatHalide or derivatives thereof general formula is Ti (OR)aXb, in formula, R is C1～C14Alkyl, X is halogen atom,A is 1 to 4 integer, and b is 1 to 4 integer, and a+b=3 or 4.
6. catalyst for ethylene polymerization according to claim 1, the transition metals Ti described in it is characterized in thatHalide or derivatives thereof is TiCl4。
7. the preparation method of the component A of the catalyst for ethylene polymerization described in one of claim 1～6, under comprisingState step: under agitation magnesium halide is dissolved in to organic epoxide, organic phosphorus compound, forms evenlyClear solution, solution temperature is 50～90 DEG C, forming in the process of solution or solution adds after forming organicAlcoholic compound, the reaction regular hour, obtains reaction solution; Above-mentioned reaction solution and virtue at-30 DEG C～0 DEG CThe halide or derivatives thereof of fragrant ester type compound, transition metals Ti mixes; Mixture is slowly heated upTo 50～120 DEG C, solids is separated out, and filters, removes mother liquor, washs solids with atent solvent, makes and containsThe ingredient of solid catalyst of titanium.
8. the described catalyst of one of claim 1～6 closes the application in reaction or copolymerization at ethylene homo.
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| CN105566524B (en) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for ethylene polymerization |
| CN105482002B (en) * | 2014-10-10 | 2018-03-02 | 中国石油化工股份有限公司 | Catalytic component, catalyst for vinyl polymerization and preparation method thereof |
| CN105566522B (en) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for ethylene polymerization |
| CN105482003B (en) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | Carrier and its catalyst used in a kind of ethylene rolymerization catalyst |
| CN105566523B (en) * | 2014-10-10 | 2018-01-19 | 中国石油化工股份有限公司 | For ethylene homo conjunction or the catalytic component and its catalyst of copolymerization |
| EP3656754A4 (en) | 2017-07-19 | 2021-05-05 | China Petroleum & Chemical Corporation | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| CN111057169B (en) * | 2018-10-16 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
| CN111057168B (en) * | 2018-10-16 | 2022-07-12 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
| CN110240668A (en) * | 2019-06-24 | 2019-09-17 | 天津科技大学 | The internal electron donor of Ziegler-Natta catalyst, catalytic component, preparation method and applications |
| CN112574338B (en) * | 2019-09-29 | 2022-07-05 | 中国石油天然气股份有限公司 | Composite external electron donor composition for olefin polymerization, olefin polymerization catalytic system containing same and olefin polymerization method |
| CN112759683A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application |
| CN116135892A (en) * | 2021-11-16 | 2023-05-19 | 中国石油化工股份有限公司 | Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst used for vinyl polymerizing or copolymerizing and its making method |
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| JPH02170804A (en) * | 1988-12-24 | 1990-07-02 | Toho Titanium Co Ltd | Catalyst for olefin polymerization |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst used for vinyl polymerizing or copolymerizing and its making method |
Non-Patent Citations (1)
| Title |
|---|
| MgCl2负载Ziegler-Natta催化剂内给电子体的研究进展;杜宏斌;《石油化工》;20101031;第39卷(第10期);第1178-1184页 * |
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