CN1293208A - Metallocene catalyst with shell-nuclear compounded carrier and its preparing process - Google Patents
Metallocene catalyst with shell-nuclear compounded carrier and its preparing process Download PDFInfo
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- CN1293208A CN1293208A CN 99121154 CN99121154A CN1293208A CN 1293208 A CN1293208 A CN 1293208A CN 99121154 CN99121154 CN 99121154 CN 99121154 A CN99121154 A CN 99121154A CN 1293208 A CN1293208 A CN 1293208A
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- metallocene
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Abstract
A metallocene catalyst is composed of a metallocene compound containing transition metal in TV B family, a carrier surface treating agent, and a composite sheel-nuclear carrier. Said carrier is prepared through wrapping with the organic polymer containing functional group on the surface of inorganic compound. It can be used to prepare polyethylene products with uniform granularity, high stack density, and uniform distribution of copolymerized monomers on high-molecular chain.
Description
The invention belongs to metallocene catalyst with shell-nuclear compounded carrier and preparation method thereof.
The control that metallocene catalysis system and Zieg1er-Natta catalyst system compare polyolefinic synthesis and structure has greater flexibility and diversity.But be used for suitability for industrialized production to metallocene catalysis system also has many technical problems to solve.Metallocene/methylaluminoxane catalyzer is a homogeneous system, and the polymerisate poor morphology can't be used for gas phase and slurry polymerization processes, and metallocene obtains maximum catalytic activity needs a large amount of promotor methylaluminoxane (MAO).People are seeking solution to the problems described above always, along with going deep into of research and development, find metallocene compound is loaded on the carrier and can well address these problems, and US 4921825 has adopted SiO
2In the carrier as metallocene compound such as porous oxide and polyethylene powders.Catalyzer after the load not only can be used for gas phase, slurry polymerization processes, produces the polymeric articles of narrow size distribution, high bulk density, can also a large amount of consumptions that reduce MAO.The supported material of metallocene is with SiO
2The most general.And result of study shows SiO
2It is uneven that the carrier surface hydroxyl distributes, and some regional local density can differ 5 times from the teeth outwards.The inhomogeneous of hydroxyl distribution not only makes a year zirconium reaction be difficult to carry out, and carry zirconium again after handling with MAO and can cause the catalyst concn of regional area excessive, make the active centre too crowded, the influence of this distribution of comonomer on polymer chain during to the ethylene/alpha-olefin copolymerization is particularly unfavorable.The catalyzer that the load request load of metallocene is got on can not lost the high catalytic activity of homogeneous system, upright structure control and the premium propertiess such as statistical distribution of copolymerization units on macromolecular chain.US 5362824, and US 5463001, and US 5473020, and EP 690076, and EP 700934-35 etc. begins to adopt polymkeric substance to carry out the polymerization of alkene as the carrier of metallocene.Polymer support can swelling in organic solvent, a kind of homogeneous environment is provided can for the metallocene compound of load.The activity of the supported catalyst that obtains by polymer support and homogeneous phase metallocene catalyst quite active, polymer support surface anchoring group is evenly distributed, and distribution density is adjustable, can carry out catalyst design very easily.And because macromolecular effect, the supported catalyst system is to oxygen, and the stability of water increases.But in application, the size and the size distribution of controlling polymers particle are extremely important, polymerisate requires to have higher bulk density, and the catalyzer huge stress that will stand in polymerization process, to produce, and metallocene catalyst is active high, the stress that produces in polymerization process is also corresponding wants big, so big as the requirement of strength of the material of carrier.And general polymerization thing preparing carriers is comparatively complicated, and the polymer support size distribution that obtains is inhomogeneous, and sphericity is very poor.Cause catalyzer after the load property that flows poor.The physical strength of carrier is also less, and broken easily when being used for polymerization, the polymer particle that obtains is more loose.
The purpose of this invention is to provide a kind of organic/inorganic metallocene catalyst with shell-nuclear compounded carrier that is used for olefinic polymerization and preparation method thereof.This catalyst structure is made up of the complex carrier S load metallocene compd A of core-shell structure.Nuclear is granular porous mineral compound C, and shell is the organic polymer B that contains functional group.
Among the present invention the carrier of catalyzer by inorganics as nuclear, utilize a kind of coupling agent to make its surface coat the shell of one deck organic polymer as carrier, on the shell functional group of polymkeric substance can with aluminum alkyls, the reaction of compounds such as metallocene, metallocene is carried on the surface of carrier, catalyzer can swelling in organic solvent, for the metallocene compound of load on it provides a kind of homogeneous environment.And inorganics is as the nuclear of carrier, for carrier provides suitable intensity, and surface-area and sphericity.The carrier size distribution that obtains is even, and is spherical in shape substantially.The polymer morphology that obtains is improved greatly.
In order to realize this purpose, catalyzer of the present invention consists of: I) at least a organic polymer B that contains functional group, II) at least a particle spherical in shape, mass mean diameter is in 10 to 1000 microns mineral compound C, III) a kind of B and C link coupled organic coupling agent D of making form, and wherein the mass content of B in carrier is 5% to 50%, the gained carrier respectively with IV) a kind of surface treatment agent E, V) at least a metallocene compound A contact, dipping, and separate and make with the liquid hydrocarbon washing;
The structure of A is LJMX
2Or LQJMX
2X among the A is a kind of haloid element, is specially chlorine, bromine, iodine; L is a cyclopentadiene or derivatives thereof indenes, and J is a cyclopentadiene or derivatives thereof indenes, and L can be identical with J, also can be inequality; Q is a kind of bridge linkage group that connects L and J, is methylene radical, and ethylidene, dimethylene silicon, M are a kind of metal Ti of group vib, Zr, Hf;
B is a kind of hydroxyl, acid amides, pyridine, carboxyl, the organic polymer of amido functional group.Be specially the styrene-propene amide copolymer of carbonyl, the styrene-propene acid copolymer contains the vinylbenzene-4-vinylpridine multipolymer of nitrogen;
C is a kind of particulate state spherical in shape, the porous mineral compound, and they are oxide S iO of surperficial hydroxyl
2, Al
2O
3, the perhaps MgCl of surperficial chloride element
2
D is a kind of compound with coupled action that contains two or more reactive functionality, and its chemical formula is NCO-P-SiR
3, Cl-P-SiR
3, OH-P-SiR
3Coupling agent, P is-(CH
2)
n-, n=0-6, R are that carbonatoms is alkyl or the alkoxyl group of 1-6;
E is a kind of surface treatment agent of carrier, and its general structure is (1) R ＇
nAl,, n=1-3, R ' they are the alkyl of 1-6 for carbonatoms; (2) [RAIO]
m, m=5-10, R are that carbonatoms is the alkyl of 1-6; (3) chlorosilane, amine, fluorine borane compound.
Preparation of catalysts method branch following steps are finished:
The preparation of complex carrier: at anhydrous and oxygen-free, under the protection of inert gas mineral compound C is contacted with coupling agent D, temperature of reaction 20-80 ℃, stirring reaction 0.5-5 hour, remove unreacted D with the liquid hydrocarbon washing, add organic polymer B, the weight ratio of C and B is 1: 5-10: 1, and the solvent toluene of adding C was at 20-80 ℃ of following continuous impregnating 1-20 hour, with solvent eccysis free C, remove at last and desolvate, obtain granular complex carrier S spherical in shape, contain 5% to 60% B in this complex carrier, its surperficial functional group is evenly distributed, and the granular mass mean diameter is at the 5-500 micron;
The load of metallocene compound: at anhydrous and oxygen-free, under the protection of inert gas carrier S is contacted with activator E earlier in varsol, the weight ratio of S and E is 1: 1-20: 1, under 20-80 ℃, react, 0.5-6.0 after hour, unreacted E is removed in liquid hydrocarbon washing with capacity, add metallocene compound A then, the weight ratio of S and E is 5: 1-100: 1,20-80 ℃ the reaction 1-20 hour after, liquid hydrocarbon with capacity washs the A that removes in the not load, removes and desolvates, and obtains carried catalyst T;
Preparation technology of the present invention is simple, can be fit to slurry, body and vapour phase polymerization mode.Processing parameter in the time of can passing through to regulate catalyst formulation and polymerization, the polyolefin products that obtains is fit to the needs of each side.Can effectively carry out the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin, the alpha-olefin that can be used to carry out with ethylene copolymer contains 3-8 carbon atom, is specially propylene, 1-butylene, 1-hexene, 1-octene.Use catalyzer of the present invention to carry out ethylene polymerization, can adopt slurry process or gas-phase process.Carry out in the polymerization at slurry process, adopt inert saturated alkane or naphthenic hydrocarbon to make solvent, be specially hexane, carry out the vapour phase polymerization of ethene with catalyzer of the present invention, polymerization temperature is at 50 to 120 ℃.In two kinds of polymerization processs, ethylene pressure adopts normal pressure to 4.0MPa, and promotor is selected aluminum alkyls or aikyiaiurnirsoxan beta for use, is specially triethyl aluminum, triisobutyl aluminium or methylaluminoxane.Catalyzer of the present invention can be made promotor with the boron compound that non-aluminum alkyls is, is specially penta phenyl fluoride boron.The poly fusing point that is made by this catalyzer is 110 to 140 ℃, and degree of crystallinity is 30 to 80%, and density is 0.89 to 0.96g/cm
3Bulk density is all at 0.35g/cm
3More than.Poly even particle distribution, mass median diameter are about 500 microns.
Embodiment provided by the invention is as follows:
Embodiment 1
The preparation of carrier
With the pretreated SiO of 10.0g process
2, adding has in the reactor of agitation and filtration device the anhydrous and oxygen-free of reaction system strictness.Entire reaction is carried out under protection of inert gas.In the Preparation of Catalyst bottle, add toluene, under 20 ℃ slowly to SiO
2Toluene suspension in drip 10 mmole NCO-Si (CH
3)
3Be warming up to 50 ℃, reacted 5 hours.Wash 3 times with toluene, in system, slowly drip the toluene solution that contains 10g styrene-propene amide copolymer (PSAm) then.Then be warming up to 75 ℃, nitrogen protection was stirred 10 hours down, with 40 milliliters of toluene wash 5 times, drained solvent at last under vacuum.Obtain complex carrier.When using microscopic examination, this carrier particle spherical in shape, mass mean diameter is 52 microns, particle size dispersion is even.The specific surface of carrier is 201m
2/ g, PSAm weight content in carrier is about 60%.
Embodiment 2
The preparation of carrier
In the Preparation of Catalyst bottle of anhydrous and oxygen-free under protection of inert gas, add 10gMgCl
2And toluene, slowly drip 1 mmole Cl-(CH in the suspension under 50 ℃
2)
3-Si (OC
6H
13)
3Be warming up to 80 ℃, reacted 0.5 hour.Wash 3 times with toluene, in system, slowly drip the vinylbenzene that contains nitrogen-4-vinylpridine multipolymer (PS4VP) toluene solution that contains 1g then.Nitrogen protection was stirred 20 hours down, with 40 milliliters of toluene wash 3 times, drained solvent at last under vacuum.Obtain complex carrier.Mass mean diameter is 10 microns, and particle size dispersion is even, and the specific surface of carrier is 181m
2/ g, PS4VP weight content in carrier is about 5%.
Embodiment 3
The preparation of carrier
In the Preparation of Catalyst bottle of anhydrous and oxygen-free under protection of inert gas, add 10gAl
2O
3And toluene, Dropwise 5 mmole OH-(CH in the suspension slowly under 80 ℃
2)
6-Si (OC
3H
7)
3Be warming up to 50 ℃, reacted 3 hours.Wash 3 times with toluene, in system, slowly drip styrene-propene acid copolymer (PSAA) toluene solution that contains nitrogen that contains 10g then.Nitrogen protection was stirred 1 hour down, kept 60 ℃, with 40 milliliters of toluene wash 5 times, drained solvent at last under vacuum.Obtain complex carrier.Mass mean diameter is 500 microns, and particle size dispersion is even, and the specific surface of carrier is 190m
2/ g, PSAA weight content in carrier is about 29%.
Embodiment 4
Preparation of catalysts
Under the identical situation of condition and embodiment 1, in the Preparation of Catalyst bottle, add prepared complex carrier and 50 milliliters of toluene among the 1.0g embodiment 1, add methylaluminoxane 0.3g again 20 ℃ of reactions 1 hour down, wash 3 times with 40 milliliters of toluene.Add 0.2g Cp again
2ZrCl
2, reacted 20 hours down at 20 ℃, wash 3 times with 40 milliliters of toluene, drain solvent at last catalyst separating is come out, in nitrogen, preserve.It is the spheroidal particle that every gram contains 100 mmole zr elements, and its quantity mean diameter is 55 microns, and particle size dispersion is even.
Embodiment 5
Preparation of catalysts
In the Preparation of Catalyst bottle, add prepared complex carrier and 30 milliliters of toluene among the 1.0g embodiment 2, add methylaluminoxane 3g again and reacted 6 hours down, wash 3 times with 40 milliliters of toluene at 50 ℃.Add 0.01g dimethylene silyl-bridged dichloro two indenyl titaniums again, reacted 1 hour down at 50 ℃, 30 milliliters of toluene are washed 3 times, drain solvent at last catalyst separating is come out, and preserve in nitrogen.It is the spheroidal particle that every gram contains 0.1 mmole titanium elements, and its quantity mean diameter is 5 microns, and particle size dispersion is even.
Embodiment 6
Preparation of catalysts
In the Preparation of Catalyst bottle, add prepared complex carrier and 50 milliliters of toluene among the 1.0g embodiment 3, add methylaluminoxane 0.3g again and reacted 0.5 hour down, wash 3 times with 40 milliliters of toluene at 80 ℃.Add 0.1g ethidene bridged linkage Dicyclopentadiene (DCPD) hafnium dichloride again, reacted 2 hours down at 80 ℃, 30 milliliters of toluene are washed 3 times, drain solvent at last catalyst separating is come out, and preserve in nitrogen.It is the spheroidal particle that every gram contains 15 mmole hafnium elements, and its quantity mean diameter is 500 microns.Embodiment 7
Slurry polymerization
1 liter of industrial hexane, promotor MAO 5.4 mmoles, contain 0.006 mmole zirconium in embodiment 4 preparation catalyzer.Import successively in 60 ℃ under nitrogen pressure and be equipped with in the 2 liter autoclaves that the per minute rotating speed is 250 whipping apptss that change, add the comonomer octene-1, ethene feeds the 1.0MPa that keep-ups pressure continuously, reacts 4.0 hours.Polymerisate is done the dry back of F reclaim the white polyethylene particle that obtains having following characteristic: density is 0.920g/cm
3, tap density is 0.35g/cm
3
Embodiment 8
Pressurization vapour phase polymerization in fluidized-bed reactor
At a diameter is 100mm, and in the gas-phase fluidized-bed reactor of high 1.5m, elder generation adds the polyethylene powders of about 100g oven dry as base-material, and squeezes into water and the impurity of 0.5 milliliter of aluminum alkyls with the system of removing.After for some time, add among the embodiment 5 through the preactivated solid catalyst that contains 0.006 mmole titanium, feeding ethene rising pressure is to 1.0MPa and be warmed up to 80 ℃, reacts 4 hours, and the white polyethylene particles that obtain 138 gram good fluidities and have following characteristic: density is 0.956g/cm
3, tap density is 0.39g/cm
3
Embodiment 9
Gas phase copolymerization in fluidized-bed reactor
At a diameter is 100mm, and in the gas-phase fluidized-bed reactor of high 1.5m, elder generation adds the polyethylene powders of about 100g oven dry as base-material, and squeezes into water and the impurity of 0.5 milliliter of aluminum alkyls with the system of removing.After for some time, add among the embodiment 6 through the preactivated solid catalyst that contains 0.006 mmole hafnium, import in the reactor and contain the ethene of butylene 16% and the gaseous mixture of butylene, rising pressure is to 1.0MPa, and be warmed up to 80 ℃, and reacted 4 hours, reclaim and obtain 690 gram good fluidities, and the white polyethylene particle with following characteristic: melting index M12.16 be 0.2 the gram/10 minutes, density is 0.926g/cm
3, tap density is 0.40g/cm
3
Claims (7)
1. metallocene catalyst with shell-nuclear compounded carrier, it is characterized in that catalyzer consists of: I) at least a organic polymer B that contains functional group, II) at least-kind of particle spherical in shape, mass mean diameter is at 10 to 1000 microns mineral compound C, III) a kind of B and the C link coupled organic coupling agent D of making forms, wherein the mass content of B in carrier is 5% to 50%, the gained carrier respectively with IV) a kind of surface treatment agent E, V) at least a metallocene compound A;
The structure of A is LJMX
2Or LQJMX
2X among the A is a kind of haloid element, is specially chlorine, bromine, iodine; L, J are cyclopentadiene or derivatives thereof indenes, and Q is a kind of bridge linkage group, is specially methylene radical, and ethylidene, dimethylene silicon, M are a kind of metal Ti of group vib, Zr, Hf;
B is a kind of hydroxyl, acid amides, and pyridine, carboxyl, the organic polymer of amido functional group is specially the styrene-propene amide copolymer of carbonyl, and the styrene-propene acid copolymer contains the vinylbenzene-4-vinylpridine multipolymer of nitrogen;
C is a kind of particulate state spherical in shape, the porous mineral compound, and they are SiO
2, Al
2O
3The oxide compound of surface hydroxyl, the perhaps MgCl of surperficial chloride element
2:
D is a kind of compound with coupled action that contains two or more reactive functionality, and its chemical formula is NCO-P-SiR
3, Cl-P-SiR
3, OH-P-SiR
3Coupling agent, P is-(CH
2) n-, n=0 to 6, R are that carbonatoms is 1 to 6 alkyl or alkoxyl group;
E is a kind of surface treatment agent of carrier, and its general structure is (1) R ＇
nAl,, n=1 to 3, R ＇ are that carbonatoms is 1 to 6 alkyl; (2) [RAlO]
m, m=5 to 10, R are that carbonatoms is 1 to 6 alkyl; (3) chlorosilane, amine, fluorine borane compound.
2. the preparation method of a metallocene catalyst with shell-nuclear compounded carrier is characterized in that the branch following steps finish:
The preparation of complex carrier: at anhydrous and oxygen-free, under the protection of inert gas mineral compound B is contacted with coupling agent D, temperature of reaction 20-80 ℃, stirring reaction 0.5 to 5 hour, remove unreacted D with the liquid hydrocarbon washing, add organic polymer C, the weight ratio of C and B is 1: 5 to 10: 1, adds the solvent toluene of C, 20 to 80 ℃ of following continuous impregnatings 5 to 20 hours, with solvent eccysis free C, remove at last and desolvate, obtain granular complex carrier S spherical in shape;
The load of metallocene compound: at anhydrous and oxygen-free; under the protection of inert gas carrier S is contacted with activator E earlier in varsol, the weight ratio of S and E is 1: 1 to 20: 1, reacts under 20 to 80 ℃; 1.0 after 6.0 hours; unreacted E is removed in liquid hydrocarbon washing with capacity, adds metallocene compound A then, and the weight ratio of S and E is 5: 1 to 100: 1; react after 1 to 20 hour; liquid hydrocarbon with capacity washs the A that removes in the not load, removes and desolvates, and obtains carried catalyst T.
3. catalyzer as claimed in claim 1 is characterized in that L, the J in the described A structure is cyclopentadiene.
4. catalyzer as claimed in claim 1 is characterized in that L, the J in the described A structure is indenes.
5. catalyzer as claimed in claim 1, the mineral compound C that it is characterized in that described form of spherical particles is the oxide S iO of surperficial hydroxyl
2, Al
2O
3
6. catalyzer as claimed in claim 1, the mineral compound C that it is characterized in that described form of spherical particles are the muriate MgCl of surperficial chloride element
2
7. catalyzer as claimed in claim 1 is characterized in that (1) is triethyl aluminum among the described surface treatment agent E, and (2) are methylaluminoxane, and (3) are chlorosilane.
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|---|---|---|---|
| CNB991211545A CN1134458C (en) | 1999-10-19 | 1999-10-19 | Metallocene catalyst with shell-nuclear compounded carrier and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991211545A CN1134458C (en) | 1999-10-19 | 1999-10-19 | Metallocene catalyst with shell-nuclear compounded carrier and its preparing process |
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| CN1293208A true CN1293208A (en) | 2001-05-02 |
| CN1134458C CN1134458C (en) | 2004-01-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231393A (en) * | 2014-09-05 | 2014-12-24 | 苏州井上高分子新材料有限公司 | Bimetallic catalyst porous carrier and preparation method and use thereof |
| CN109705242A (en) * | 2018-11-13 | 2019-05-03 | 上海东化环境工程有限公司 | A kind of carried metallocene catalyst and its preparation method and application |
| CN115960279A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460472C (en) * | 2005-12-02 | 2009-02-11 | 中国科学院化学研究所 | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method |
-
1999
- 1999-10-19 CN CNB991211545A patent/CN1134458C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231393A (en) * | 2014-09-05 | 2014-12-24 | 苏州井上高分子新材料有限公司 | Bimetallic catalyst porous carrier and preparation method and use thereof |
| CN109705242A (en) * | 2018-11-13 | 2019-05-03 | 上海东化环境工程有限公司 | A kind of carried metallocene catalyst and its preparation method and application |
| CN109705242B (en) * | 2018-11-13 | 2021-10-29 | 上海东化环境工程有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN115960279A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method and application thereof |
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