CN102617760B - Method for preparing solid catalyst for olefin polymerization - Google Patents
Method for preparing solid catalyst for olefin polymerization Download PDFInfo
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- CN102617760B CN102617760B CN 201110028135 CN201110028135A CN102617760B CN 102617760 B CN102617760 B CN 102617760B CN 201110028135 CN201110028135 CN 201110028135 CN 201110028135 A CN201110028135 A CN 201110028135A CN 102617760 B CN102617760 B CN 102617760B
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Abstract
The invention provides a method for preparing a solid catalyst for olefin polymerization. Components of the solid catalyst comprise: a mixture of magnesium chloride and a magnesium compound with the general formula of MgR<2>R<3>; organic compounds which can dissolve a component a, or a mixture thereof; a titanium compound with the following general molecular formula: Ti(OR<1>)nX4-n; a diester of an aromatic dicarboxylic acid, or an aromatic monoester; an aromatic hydrocarbon or an alkane; and a precipitating aid. The preparation method of the solid catalyst comprises the following steps: mixing the component a, a component b, a component e and a component f to form a solution, allowing the solution to contact with a component c, heating to 30-80DEG C, adding a component d, continuously heating to 90-110DEG C, maintaining for 1-3h, filtering out the resulting liquid phase, washing the resulting solid by the component e at least two times, allowing the resulting solid to contact with a mixed solution of the component c and the component e, filtering, washing the resulting material by the component e three to six times, and drying to form the solid catalyst. The solid catalyst synthesized through the method has the advantages of high polymerization activity and good copolymerization, and is suitable for producing copolymer resins with high ethylene contents.
Description
Technical field
The present invention relates to a kind of method for preparing solid catalyst in olefin polymerization catalyst, specifically, be prepared into solution by the mixture that uses two or more magnesium compounds, then contact crystallization magnesium chloride granules and supported titanium compound activity center with titanium compound, thereby prepare the method for solid catalyst in olefin polymerization catalyst.
Background technology
By magnesium chloride is dissolved in the organic solvent, contact with titanium tetrachloride again and separate out magnesium chloride granules and supported titanium active centre, be widely used in the polypropylene industry with this method for preparing solid catalyst in olefin polymerization catalyst.
Such as, Chinese patent ZL88101916.x discloses in a kind of solution that magnesium chloride, Tetra hydro Phthalic anhydride is dissolved in isooctyl alcohol and decane, then solution is contacted with titanium tetrachloride low temperature, then heat up and add dibutyl phthalate, then the gained solid is continued same titanium tetrachloride reaction, obtain the polyolefine solid catalyst with the inert solvent washing at last.
Chinese patent CN85100997A discloses in a kind of solution that magnesium chloride, Tetra hydro Phthalic anhydride is dissolved in toluene, epoxy chloropropane, tributyl phosphate, then solution is contacted with titanium tetrachloride low temperature, then heating up adds dibutyl phthalate, and the gained solid is continued with obtaining the polyolefine solid catalyst with the inert solvent washing after the titanium tetrachloride reaction.
Above-mentioned two kinds of catalyzer that method is prepared, owing to adopting the single formed solution of magnesium chloride, this solution height is even, the magnesium chloride crystallite of compact structure is arranged in order in separating out magnesium chloride particle process, degree of irregularity is low, cause microvoid structure more single, so activity is lower and copolymerization performance is relatively poor.Therefore, along with the development of polypropylene technology, the catalyzer of this method preparation can not satisfy growing needs on active and copolymerization performance.
Summary of the invention
The object of the present invention is to provide a kind of method that olefin polymerization catalysis is used solid catalyst for preparing, the method has overcome above-mentioned deficiency, be prepared into solution by the mixture that uses two or more magnesium compounds, then contact crystallization magnesium chloride granules and supported titanium compound activity center with titanium compound, thereby prepare the method for solid catalyst in olefin polymerization catalyst, the solid catalyst synthetic by present method has the advantages that polymerization activity is high, copolymerization performance is good, is suitable for producing the copolymer resins of high ethylene content.
In order to realize the object of the invention, the invention provides a kind of method for preparing solid catalyst for olefin polymerization, its composition comprises:
(a) magnesium chloride and general formula are MgR
2R
3The mixture of magnesium compound, R wherein
2, R
3Represent that respectively halogen, carbonatoms are 1～8 alkyl or-oxyl, R
2, R
3Can be identical or different;
(b) organic compound or its mixture that can dissolved constituent a;
(c) has the titanium compound of following general molecular formula: Ti (O R
1)
nX
4-n(R
1Refer to C
1-4Alkyl; X refers to chlorine, bromine, iodine atom; N is between 0～3);
(d) a kind of diester of aromatic binary carboxylic acid or aromatic series monoesters;
(e) aromatic hydrocarbons or alkane;
(f) precipitation additive;
Its preparation process is:
First component a and components b, component e and component f are mixed and made into solution, then contact with amount of component b, be warming up to 30～80 ℃, add again component d, continue to be warming up to 90～110 ℃ and kept the elimination liquid phase 1～3 hour, solids is washed 2 times with component e at least, mixed solution with amount of component b and component e contacts and filters again, washs 3～6 times (also can again add component d in follow-up washing or treating processes) finally by component e, and drying forms.
Wherein, described MgR
2R
3Magnesium compound specifically comprise: magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, magnesium methylate, magnesium ethylate, propoxy-magnesium, butoxy magnesium, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl-magnesium-chloride, chlorination propyl group magnesium, butyl magnesium chloride, chlorination amyl group magnesium, chlorination hexyl magnesium, butyl magnesium ethylate, ethyl-butyl magnesium, preferably magnesium ethylate, chlorination magnesium ethylate, propoxy-magnesium or chlorination propoxy-magnesium.
Component a is preferred, adopts magnesium chloride to mix with magnesium ethylate, and magnesium chloride mixes with dipropoxy magnesium, or magnesium chloride mixes with the chlorination magnesium ethylate.
Consumption those skilled in the art between the component a mixture can adjust as required, wherein take magnesium chloride and general formula as MgR
2R
3The weight ratio of magnesium compound be 1～50: 1～5 for good.
Described components b be can the dissolved magnesium compound organic compound or its mixture; Specifically comprise: be liquid alcohol under the normal temperature, such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol etc.; Ether is such as methyl ether, ether, propyl ether, butyl ether, amyl ether, hexyl ether etc.; Organic epoxy compounds is such as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, tetrahydrofuran (THF) etc.; Organophosphorous compounds are such as trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate etc.Preferably, hexanol, enanthol, isooctyl alcohol, propyl ether, butyl ether, butylene oxide ring, epoxy chloropropane, tricresyl phosphate propyl ester or tributyl phosphate.
Amount of component b in the preparation solid catalyst is one or more titanium tetrachlorides or alkoxyl group halogenated titanium, and the general molecular formula is as follows: Ti (OR
1)
nX
4-n
Described amount of component b comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, alkoxyl group halogenated titanium such as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.Can use one or more in these halogenated titaniums and mix use.Wherein adopt the titanium tetrachloride best results.
Described component d is the diester of aromatic binary carboxylic acid, such as Bisphthalate or bis--terephthalate, Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, the Methyl Benzene-o-dicarboxylate ethyl ester, the Methyl Benzene-o-dicarboxylate isopropyl ester, the Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), the ethyl phthalate(DEP) isobutyl ester, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2,2-dimethyl hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2,2-dimethyl heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can use in independent or multiple mixing.
The bis--terephthalate comprises: dimethyl terephthalate (DMT), diethyl terephthalate, the terephthalic acid di-n-propyl ester, the terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutyl ester), terephthalic acid two n-pentyl esters, the terephthalic acid diisoamyl ester, the terephthalic acid dihexyl, terephthalic acid two positive heptyl esters, the terephthalic acid di-n-octyl, terephthalic acid two different n-octyls, terephthalic acid two (2,2-dimethyl hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, the terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester), with terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can use in independent or multiple mixing.
Recommendation diethyl phthalate in these diester, the dipropyl phthalic butyl ester, the terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, the terephthalic acid di-n-octyl, the terephthalic acid di-isooctyl, the mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or the Di Iso Decyl Phthalate.
Described component d also can be the aromatic series monoesters, and it comprises: a kind of in methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl-benzoate, phenylformic acid heptyl ester, n-octyl benzoate, phenylformic acid ester in the ninth of the ten Heavenly Stems, the n-decyl benzoate or their mixture.
Component e for the preparation of solid catalyst of the present invention is that a kind of room temperature is liquid aromatic hydrocarbons or alkane.Described aromatic hydrocarbons is: benzene,toluene,xylene, ethylbenzene, propyl benzene or trimethylbenzene etc., preferably use toluene or dimethylbenzene.In addition, also can use other solvents of inertia, these organic solvents are saturated hydro carbons-alkane, comprising: hexane, heptane or hexanaphthene, aromatic hydrocarbons and alkane can use separately also can mix use.
Described precipitation additive is Tetra hydro Phthalic anhydride or aromatic binary carboxylic acid ester; Described aromatic binary carboxylic acid ester is diethyl phthalate, dipropyl phthalate, the terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, the terephthalic acid di-n-octyl, the terephthalic acid di-isooctyl, the mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or the Di Iso Decyl Phthalate.
The present invention is in the process of preparation solid catalyst, and each component is preferably: component a is the mixture of magnesium chloride and diethoxy magnesium, or the mixture of magnesium chloride and dipropoxy magnesium; Components b is one or more in isooctyl alcohol, epoxy chloropropane or the tributyl phosphate; Amount of component b is titanium tetrachloride; Component d is diester or the phenylformic acid monoesters of phthalic acid; Specifically use one or more diethyl phthalates, n-propyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (ethylhexyl) diester and didecyl phthalate, methyl benzoate, ethyl benzoate; Component e is toluene, dimethylbenzene or hexane; Component f is Tetra hydro Phthalic anhydride.
The mol ratio of the add-on of components b and component a is 0.1～50, is preferably 0.1～20, is preferably 0.5～10.
When contacting with component a for the first time for amount of component b, the two ratio is 1～50, is preferably 2～20, is preferably 5～20.
Mol ratio for the add-on of component d and component a is 0.001～10, is preferably 0.01～1, is preferably 0.02～0.6.
The mol ratio of the add-on of component e and component a is 0.001～500, is preferably 0.001～100, is preferably 0.005～50.
Solid catalyst of the present invention preferably adopts the following methods preparation:
First with component a and components b, component e was-10～130 ℃ of reactions 0.1～10 hour, form homogeneous solution, add again component f, stirred 1～3 hour, then lower-30～80 ℃ (being preferably-30～40 ℃) and in the presence of component e, contact with amount of component b, be warming up to 30～80 ℃, add again component d, continuing to be warming up to 90～110 ℃ kept 1～3 hour, the elimination liquid phase is washed solids 2 times with component e at least, and the mixed solution with amount of component b and component e contacts and filters again, wash 3～6 times (also can again add component d in follow-up washing or treating processes) finally by component e, drying forms.
The solid catalyst of gained of the present invention can be used for preparing olefin polymerization catalysis, and described olefin polymerization catalysis comprises following component:
(A) ingredient of solid catalyst of the present invention (being called for short component A)
(B) a kind of organo-aluminium compound (abbreviation B component), the general molecular formula is as follows: R
2 PAlQ
3-P(R
2Refer to C
1-4Alkyl; Q refers to hydrogen atom or halogen atom (such as chlorine, bromine, iodine), and the value of P is 0-3)
(C) a kind of silicoorganic compound (being called for short component C), the general molecular formula is as follows: R
3 qSi (OR
4)
4-q(R
3And R
4Refer to C
1-12Alkyl, C
1-12Cycloalkyl, phenyl, allyl group, aralkyl, vinyl, these groups can be the same or different, the value of q is: 1-3).
Wherein: B component is preferably triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, diethyl aluminum bromide or ADEH.The organism of these aluminium can use separately or two or more simultaneously use.What effect was best is triethyl aluminum and triisobutyl aluminium.
Component C specifically can be: the trimethylammonium methoxy silane, trimethylethoxysilane, three n-propyl methoxy silane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silane, the triisobutyl Ethoxysilane, the thricyclohexyl methyl-monosilane, the thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, the diη-propyl diethoxy silane, the di-isopropyl diethoxy silane, the di-n-butyl diethoxy silane, the diisobutyl diethoxy silane, di-t-butyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, the di-t-butyl diethoxy silane, the di-n-butyl diethoxy silane, n-butylmethyldimethoxyforane, two (2-ethylhexyl) dimethoxy silane, two (2-ethylhexyl) diethoxy silane, Dicyclohexyldimethoxysilane, the dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexyl Methyl Dimethoxysilane, the cyclohexyl methyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclohexyl n-propyl dimethoxy silane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silane, the amyl group methyl dimethoxysilane, the amyl group methyldiethoxysilane, amyl group ethyl dimethoxy silane, amyl group ethyl diethoxy silane, cyclohexyl dimethyl methyl TMOS, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl Ethoxysilane, 2-ethylhexyl Trimethoxy silane, cyclohexyl dimethoxy silane, the cyclohexyl diethoxy silane, 2-ethylhexyl triethoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, the isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, the cyclopentyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-ethylhexyl Trimethoxy silane, 2-ethylhexyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane, 3,5-Dimethylcyclohexyl cyclopentyl dimethoxy silane, 3-methylcyclohexyl cyclohexyl dimethoxy silane, two (3-methylcyclohexyl) dimethoxy silane, 4-methylcyclohexyl cyclohexyl dimethoxy silane, two (4-methylcyclohexyl) dimethoxy silane, 3,5-Dimethylcyclohexyl cyclohexyl dimethoxy silane, two (3,5-Dimethylcyclohexyl) dimethoxy silane, tetrapropoxysilane, four butoxy silanes.First-selected in these silicoorganic compound: diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, the di-n-butyl diethoxy silane, tert-butyl trimethoxy silane, Dicyclohexyldimethoxysilane, the dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl ethyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, the cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane and 3,5-dimethylcyclopentyl dimethoxy silane etc.Use can be used separately or mix to these Compound C.
The catalyzer of using among the present invention carries out olefinic polymerization, and homopolymerization and copolymerization can be used above-mentioned by component A, B, the prepared catalyzer of C.Usually the mol ratio of B component and component A is 1～1000 (wherein component A is in the amount of titanium atom among the component A), is preferably 50～800; The mol ratio of component C and B component is 0.002～10, is preferably 0.01～2, is preferably 0.01～0.5.
The order of addition(of ingredients) of each component is arbitrarily, joins at first in the paradigmatic system with B component, then adds component C, and it is good adding at last component A.
Polymerization technique among the present invention can be in the situation that have solvent or do not have solvent to carry out.Olefinic monomer can be gas phase or liquid phase.Further add hydrogen and can be used as molecular weight regulator.Certainly polymerization can be in the situation that there be molecular weight regulator to carry out yet.Polymerization temperature is not higher than 200 ℃, had better not be above 100 ℃.Polymerization pressure does not surpass 10MPa, had better not surpass 5MPa.Successive polymerization or batchwise polymerization technique can be used.And polyreaction can divide a step, two steps or multistep to carry out.
Use the alkene that catalyzer of the present invention carries out homopolymerization or copolymerization and comprise normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is such as 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is such as divinyl, vinyl cyclopentenes and vinyl cyclohexene.Catalyzer of the present invention preferably is applied in polyethylene and the polypropylene.These alkene can use in independent or multiple mixing.
Use the polymerization (referring to the main body polymerization here) of the alkene that catalyst component A of the present invention, B, C carry out, recommend to carry out the degree of isotacticity, particle properties of the reactive polymer of the incompatible increase catalyzer of pre-polymerization etc.This prepolymerization technology can be used for the vinylbenzene homopolymerization equally.
The order of addition(of ingredients) of each component and monomer is arbitrarily in prepolymerization technology.Preferably first B component is joined and contain inertia and maybe will carry out in the alkene gas of polymerization, then after adding component A, add one or more alkene of wanting polymerization.In using the prepolymerized process of alkene of organosilane, suggestion joins B component in the prepolymerization system of olefin gas that rare gas element maybe will carry out polymerization, then adds component C, then adds component A, adds at last alkene again.
Because the solution that the present invention takes different magnesium compounds to make, it is when again separating out the magnesium chloride particle, the crystallite arrangement of magnesium chloride is more disorderly, the inside particles structure is looser, pore structure is abundanter, macropore increases, so the solid catalyst activity by method preparation of the present invention is higher, copolymerization performance is stronger, is particularly suitable for producing the copolymer resins product of high ethylene content.
Embodiment
The below further describes the present invention with embodiment, is conducive to the understanding to the present invention and advantage thereof, better effects if, but described embodiment only is used for explanation the present invention rather than restriction the present invention.
Embodiment 1
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 5g magnesium chloride, 1g magnesium ethylate, 30ml toluene, 25ml isooctyl alcohol, 8ml tributyl phosphate 130 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.7g in the solution, mixture is 130 ℃ of lower stirrings 1 hour, then the solution that obtains is added 50ml toluene and cools to-20 ℃, the titanium tetrachloride that adds 60ml, then be warming up to 80 ℃, add again the 5ml diisobutyl phthalate, continue to be warming up to 110 ℃ of reactions 1 hour, the elimination liquid phase is with solid part 60ml toluene wash 3 times, processed three times in 30 hours with 80ml toluene and 110 ℃ of constant temperature of 20ml titanium tetrachloride mixed solution again, filter, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtain the 5.5g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 2.16 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
Carry out the polymerization evaluation with solid catalyst as the component of olefin polymerization catalysis:
The propylene homopolymerization: at 5 liters of stainless steel cauldrons after nitrogen is fully replaced, add 5 ml concns and be 10 milligrams of the catalyzer of the triethyl aluminum hexane solution of 0.5 mol/L and Cyclohexylmethyldimethoxysilane hexane solution that 1 ml concn is 0.1 mol/L and embodiment 1 preparation, then add 10 milliliters of hexane flushing charge lines, add again 2 liters of (under the standard state) hydrogen, with 2.5 liters of refining propylene, the control reaction was 20 ℃ of pre-polymerizations 5 minutes, be warming up to 70 ℃, polyreaction is 1 hour under this temperature.Evaluation result sees Table 1.
The ethylene, propylene copolymerization: at 5 liters of stainless steel cauldrons after nitrogen is fully replaced, add 5 ml concns and be 10 milligrams of the catalyzer of the triethyl aluminum hexane solution of 0.5 mol/L and Cyclohexylmethyldimethoxysilane hexane solution that 2.5 ml concns are 0.1 mol/L and embodiment 1 preparation, then add 10 milliliters of hexane flushing charge lines, add again 2.5 liters of (under the standard state) hydrogen, with 2 liters of refining propylene, the control reaction was 20 ℃ of pre-polymerizations 5 minutes, be warming up to 70 ℃, polyreaction is 1 hour under this temperature, then bleed off unnecessary propylene, adding ethene and propylene mol ratio are 6: 4 gas mixture, the control reactor continued polyreaction 45 minutes at 80 ℃ under the 1.0MPa condition.Evaluation result sees Table 2.
Embodiment 2
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 5g magnesium chloride, 1g chlorination magnesium ethylate, 30ml toluene, 25ml isooctyl alcohol, 8ml tributyl phosphate 130 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.7g in the solution, mixture is 130 ℃ of lower stirrings 1 hour, then the solution that obtains is added 50ml toluene and cools to-20 ℃, the titanium tetrachloride that adds 60ml, then be warming up to 70 ℃, add again 5ml diisobutyl phthalate reaction 1 hour, the elimination liquid phase, with solid part 60ml toluene wash 3 times, processed three times in 30 hours with 80ml toluene and 110 ℃ of constant temperature of 20ml titanium tetrachloride mixed solution again, filter, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtains the 5.3g pressed powder and is ingredient of solid catalyst, and analyzing titanium content is 2.21 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
Embodiment 3
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 5g magnesium chloride, 1g magnesium ethylate, 30ml toluene, 2ml ethanol, 20ml isooctyl alcohol, 2ml epoxy chloropropane, 5ml tributyl phosphate 100 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.7g in the solution, mixture is 100 ℃ of lower stirrings 1 hour, then the solution that obtains is added 50ml toluene and cools to-20 ℃, the titanium tetrachloride that adds 60ml, then be warming up to 60 ℃, add again 5ml diisobutyl phthalate reaction 1 hour, the elimination liquid phase, with solid part 60ml toluene wash 3 times, processed three times in 30 hours with 80ml toluene and 110 ℃ of constant temperature of 20ml titanium tetrachloride mixed solution again, filter, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtains the 5.2g pressed powder and is ingredient of solid catalyst, and analyzing titanium content is 2.32 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
Embodiment 4
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 5g magnesium chloride, 1g magnesium ethylate, 30ml toluene, 25ml isooctyl alcohol, 8ml tributyl phosphate 130 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.7g in the solution, mixture is 130 ℃ of lower stirrings 1 hour, then the solution that obtains is cooled to-20 ℃, the mixed solution that adds the titanium tetrachloride of 50ml toluene and 60ml, then be warming up to 80 ℃, add again 5ml diisobutyl phthalate reaction 1 hour, the elimination liquid phase, with solid part 60ml toluene wash 3 times, processed three times in 30 hours with 80ml toluene and 110 ℃ of constant temperature of 20ml titanium tetrachloride mixed solution again, filter, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtains the 5.6g pressed powder and is ingredient of solid catalyst, and analyzing titanium content is 2.43 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
Embodiment 5
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 5g magnesium chloride, 1g magnesium ethylate, 30ml toluene, 32ml isooctyl alcohol 130 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.7g in the solution, mixture is 130 ℃ of lower stirrings 1 hour, then the solution that obtains is added 50ml toluene and cools to-20 ℃, the titanium tetrachloride that adds 60ml, then be warming up to 80 ℃, add again 5ml diisobutyl phthalate reaction 1 hour, the elimination liquid phase, with solid part 60ml toluene wash 3 times, processed three times in 30 hours with 80ml toluene and 110 ℃ of constant temperature of 20ml titanium tetrachloride mixed solution, then with 100ml hexane washing 5 times, elimination liquid is also dry again, obtain the 5.4g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 2.29 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
The comparative example 1
The preparation of solid catalyst:
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen, add 7.14g magnesium chloride, 37.5ml decane, 35.1ml isooctyl alcohol 130 ℃ of reactions 2 hours, form homogeneous solution.Add Tetra hydro Phthalic anhydride 1.67g in the solution, mixture is 130 ℃ of lower stirrings 1 hour, then the solution that obtains is joined in-20 ℃ the titanium tetrachloride of 200ml, then be warming up to 110 ℃ and add 5ml diisobutyl phthalate reaction 2 hours, the elimination liquid phase, solid part was processed 2 hours with 110 ℃ of 275ml titanium tetrachlorides, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtains the 6.9g pressed powder and is ingredient of solid catalyst, and analyzing titanium content is 2.31 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
The comparative example 2
The preparation of solid catalyst:
fully replace through nitrogen with 5 mouthfuls of flasks that stir in, add successively 5g magnesium chloride, 75ml toluene, 8ml epoxy chloropropane, 8ml tributyl phosphate and be warming up to 60 ℃ of reactions 2 hours, then add the 1.2g Tetra hydro Phthalic anhydride and keep again reaction 1 hour.Solution is cooled to-25 ℃ and adds the 55ml titanium tetrachloride, then be warming up to 80 ℃ and add 3.3ml diisobutyl phthalate reaction 1 hour, elimination liquid, then use 100ml toluene wash solid 2 times, then process twice with 90 ℃ of 60ml toluene 40ml titanium tetrachloride mixed solutions, then with 100ml hexane washing 5 times, elimination liquid is also dry, obtain the 4.8g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 2.02 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result sees Table 1, table 2.
Table 1 catalyzer propylene homopolymerization performance comparison table
Table 2 catalyzer ethylene, propylene copolymerization performance contrast table
Can find out by table 1, table 2, the method among employing the present invention can significantly improve activity and the olefin-copolymerization performance of catalyzer.
Although the present invention has been described in detail and has quoted as proof some specific exampless, for a person skilled in the art, only otherwise leave the spirit and scope of the present invention, it is obvious making various changes or revising.
Claims (11)
1. a method for preparing solid catalyst for olefin polymerization is characterized in that, its composition comprises:
(a) magnesium chloride and general formula are MgR
2R
3The mixture of magnesium compound, wherein said MgR
2R
3Magnesium compound be selected from: magnesium bromide, magnesium iodide, magnesium fluoride, magnesium methylate, magnesium ethylate, propoxy-magnesium, butoxy magnesium, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl-magnesium-chloride, chlorination propyl group magnesium, butyl magnesium chloride, chlorination amyl group magnesium, chlorination hexyl magnesium, butyl magnesium ethylate or ethyl-butyl magnesium;
(b) organic compound or its mixture that can dissolved constituent a;
(c) has the titanium compound of following general molecular formula: Ti (OR
1)
nX
4-n, R
1Refer to C
1-4Alkyl; X refers to chlorine, bromine, iodine atom; N is between 0～3;
(d) a kind of diester of aromatic binary carboxylic acid or aromatic series monoesters;
(e) aromatic hydrocarbons or alkane;
(f) precipitation additive;
Its preparation process is:
First component a and components b, component e and component f are mixed and made into solution, then contact with amount of component b, be warming up to 30～80 ℃, add again component d, continue to be warming up to 90～110 ℃ and kept the elimination liquid phase 1～3 hour, solids is washed 2 times with component e at least, mixed solution with amount of component b and component e contacts and filters again, and finally by component e washing 3～6 times, drying forms.
2. method according to claim 1 is characterized in that, described MgR
2R
3Magnesium compound be magnesium ethylate, chlorination magnesium ethylate, propoxy-magnesium or chlorination propoxy-magnesium.
3. method according to claim 2 is characterized in that, component a adopts magnesium chloride to mix with magnesium ethylate, and magnesium chloride mixes with dipropoxy magnesium, or magnesium chloride mixes with the chlorination magnesium ethylate.
4. method according to claim 1 is characterized in that, described magnesium chloride and general formula are MgR
2R
3The weight ratio of magnesium compound be 1～50: 1～5.
5. the described method of any one is characterized in that according to claim 1-4, and described components b is alcohol liquid under the normal temperature, ether, organic epoxy compounds, Organophosphorous compounds.
6. method according to claim 5 is characterized in that, described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol or octanol; Described ether is methyl ether, ether, propyl ether, butyl ether, amyl ether or hexyl ether; Described organic epoxy compounds is oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane or tetrahydrofuran (THF); Described Organophosphorous compounds are trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate or TNPP tri n pentyl phosphate.
7. method according to claim 5 is characterized in that, described components b is hexanol, enanthol, isooctyl alcohol, propyl ether, butyl ether, butylene oxide ring, epoxy chloropropane, tricresyl phosphate propyl ester or tributyl phosphate.
8. the described method of any one is characterized in that according to claim 1-4, and described amount of component b comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkoxyl group halogenated titanium; Component e is one or more in benzene,toluene,xylene, ethylbenzene, propyl benzene, trimethylbenzene, hexane, heptane or the hexanaphthene.
9. method according to claim 8 is characterized in that, described component a is the mixture of magnesium chloride and diethoxy magnesium, or the mixture of magnesium chloride and dipropoxy magnesium; Components b is one or more in isooctyl alcohol, epoxy chloropropane or the tributyl phosphate; Amount of component b is titanium tetrachloride; Component d is diester or the phenylformic acid monoesters of phthalic acid; Component e is toluene, dimethylbenzene or hexane; Component f is Tetra hydro Phthalic anhydride.
10. method according to claim 1, it is characterized in that, its preparation process is: first with component a and components b, component e was-10～130 ℃ of reactions 0.1～10 hour, form homogeneous solution, add again component f, stirred 1～3 hour, then descend and in the presence of component e, contact with amount of component b at-30～80 ℃, be warming up to 30～80 ℃, add again component d, continuing to be warming up to 90～110 ℃ kept 1～3 hour, the elimination liquid phase is washed solids 2 times with component e at least, and the mixed solution with amount of component b and component e contacts and filters again, finally by component e washing 3～6 times, drying forms.
11. solid catalyst for olefin polymerization by the described method preparation of claim 1-10 any one.
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