CN106496375B - A kind of catalytic component and catalyst for vinyl polymerization - Google Patents
A kind of catalytic component and catalyst for vinyl polymerization Download PDFInfo
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- CN106496375B CN106496375B CN201510559690.9A CN201510559690A CN106496375B CN 106496375 B CN106496375 B CN 106496375B CN 201510559690 A CN201510559690 A CN 201510559690A CN 106496375 B CN106496375 B CN 106496375B
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Abstract
The present invention provides a kind of catalytic components for vinyl polymerization, the catalytic component is in the presence of inert diluent, solution is formed by being dissolved in organo-magnesium compound in the system containing organic epoxide, organo-silicon compound and cyclodextrin or derivatives thereof, then acetyl halide compound is added, is prepared with the halide of titanium or derivatives thereof effect.The present invention also provides the preparation methods of the catalytic component, and the ethylene rolymerization catalyst based on the catalytic component.The preparation process of catalytic component of the present invention is simple, and catalyst activity keeps higher level, and polymer bulk density is higher, and melting means is higher, and hydrogen response is preferable.
Description
Technical field
The present invention relates to a kind of catalytic component for ethylene polymerization, the preparation method of the catalytic component,
And the application of ethylene rolymerization catalyst and the catalyst in vinyl polymerization containing the catalytic component, belong to alkene
Polymerized hydrocarbon field.
Background technique
It occupies an leading position it is well known that the caltalyst of the compound containing Ti/Mg ties up in the industrialized production of polyolefin,
Research core is quick nothing more than the hydrogen tune of the particle shape and particle diameter distribution, catalyst that are the polymerization activity of catalyst, catalyst
Perception and copolymerization performance etc..In the prior art, there is the catalyst of uniform particle diameter and preferable particle shape in order to obtain,
People generally use different magnesium raw materials to prepare catalyst.First method is using magnesium chloride as dissolution of raw material certain molten
Homogeneous solution is obtained in agent, and the solution is mixed again with titanium compound and optional electron donor then, passes through the method for precipitating
The solids containing magnesium, titanium and optional electron donor is obtained, and the solids is handled with excessive liquid titanium compound
After obtain catalyst granules.Such as the preparation method disclosed in CN1099041A, CN1229092, catalyst therein are logical
Cross magnesium halide be dissolved in organic epoxy compound object, organic phosphorus compound add electron donor formed homogeneous solution, then at least
A kind of precipitation additive and the halide of transition metals Ti or derivatives thereof effect and obtain.The shortcomings that this conventional method, is:
The partial size and particle diameter distribution of catalyst granules are entirely by precipitation process, i.e. the recrystallization process of magnesium carrier ingredient controls
, particle shape is more difficult to control, and hydrogen response needs further increase.
Second method is to prepare polyolefin catalyst using organo-magnesium compound as raw material, this kind of method is usually led to
Grain shape is preferable, the preferable catalyst of hydrogen response, but the activity of gained catalyst is relatively low as the activity of raw material compared with using magnesium chloride.
The organo-magnesium compound generallyd use be magnesium ethylate, magnesium ethylate dissolubility is poor, foreign patent US3901863,
It is disclosed in US4617360 and domestic patent CN102344514 and a kind of prepares catalyst by raw material of organo-magnesium compound
Oxygen-containing organo-magnesium compound is mainly dissolved in oxygen-containing organic titanic compound by method, then is reacted with organo-aluminum compound
Form catalyst precipitating.Disclosed in foreign patent US5077357, US6825146 one kind using chlorobenzene as solvent, magnesium ethylate with
Purity titanium tetraethoxide, titanium tetrachloride, phenols and alcohol carry out reaction and form catalyst precursor, then are formed and be catalyzed with titanium tetrachloride reaction
The preparation method of agent.Wherein for phenols as a kind of cutting agent, effect is the magnesium ethylate for opening polymerization, makes magnesium ethylate and other
Component is reacted.If but the phenols being added on a small quantity is not completely removed in catalyst preparation process, and easy residual is led
Cause catalyst poisoning.If residual in the catalyst also can shadow in addition, participating in the organic titanic compound reacted without reacting completely
Ring the activity of catalyst.New cutting agent such as Mg (OEt) (O is mentioned in foreign patent US2001/0039241A12COEt)、B
(OEt)3、CaCO3Deng instead of phenolic compound, it is prepared for polyolefin catalyst, but the bulk density of gained catalyst is lower.
Butyl octyl magnesium is dissolved in ethyl hexanol, o-phthaloyl chloride and chlorobutane and forms lotion by foreign patent US7256150B2,
Polypropylene catalyst is formed with titanium tetrachloride reaction again, which is used for gas phase reaction.But butyl octyl magnesium is as raw material valence
Lattice are more expensive, are unfavorable for industrialized production.
Summary of the invention
To solve the problems, such as that above-mentioned technology exists, the purpose of the present invention is to provide a kind of catalyst for vinyl polymerization
Component.
The present invention also provides the ethylene rolymerization catalysts based on the catalytic component.The catalyst is poly- for ethylene
Higher polymerization activity, preferable hydrogen response and preferable bulk density are shown when conjunction.The method for preparing catalyst
Simply, few with titanium amount, be conducive to simplify subsequent processing work.
The catalytic component is in the presence of inert diluent, by by organo-magnesium compound and organic epoxy compound
Object, organo-silicon compound and cyclodextrin or derivatives thereof reaction form solution, and acetyl halide compound is added, then with the halide of titanium
Or derivatives thereof effect be prepared.
In a specific embodiment of the present invention, the catalytic component is in the presence of inert diluent, by organic-magnesium
Conjunction object, which is dissolved in the system containing organic epoxide, organo-silicon compound and cyclodextrin or derivatives thereof, forms solution, adds
Enter acetyl halide compound, is then gradually precipitated and is formed particle with the halide of transition metals Ti or derivatives thereof effect, solid, remove
The solid for removing unreacted reactant and solvent and being washed using inert diluent, is finally removed inert diluent, obtains the present invention
The catalytic component.
The general formula of the organo-magnesium compound is Mg (OR1)nX2-n, R in formula1It is C2-C20Alkyl, the alkyl is
Saturations or undersaturated straight chain, branch or closed chain；X is halogen, preferably chlorine；And 0≤n≤2.Specific compound is selected from one
Chloromethane epoxide magnesium, a chloroethoxy magnesium, a chlorine isopropoxy magnesium, a neoprene oxygroup magnesium, a chlorine octyloxy magnesium, diethoxy magnesium,
At least one of isopropoxy magnesium, butoxy magnesium, n-octyloxy magnesium and 2- ethyl hexyl oxy magnesium, preferably diethoxy magnesium, two
At least one of propoxyl group magnesium, dibutoxy magnesium and two octyloxy magnesium.
The organic epoxy compound object is selected from aliphatic olefin, alkadienes or the halogenated aliphatic that carbon atom number is 2-8
At least one of the oxide of alkene or alkadienes, glycidol ether and inner ether.Specific compound is selected from ethylene oxide, ring
Ethylene Oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and two are shunk
At least one of glycerin ether；It is preferred that epoxychloropropane and/or tetrahydrofuran.
The general formula of the organo-silicon compound is R2 xR3 ySi(OR4)z, wherein R2And R3Respectively carbon atom number is 1-10
Alkyl or halogen, R4The alkyl for being 1-10 for carbon atom number, wherein x, y and z are positive integer, 0≤x≤2,0≤y≤2, and 0
≤ z≤4, and x+y+z=4.Specific compound is selected from silicon tetrachloride, silicon bromide, tetramethoxy-silicane, tetraethoxy-silicane
Alkane, tetrapropoxysilane, four butoxy silanes, four (2- ethyl hexyl oxy) silane, ethyl trimethoxy silane, three ethoxy of ethyl
Base silane, methyltrimethoxysilane, methyltriethoxysilane, n-propyl triethoxysilane, n-propyl trimethoxy silicon
Alkane, ruthenium trimethoxysilane, ruthenium triethoxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, 2-
Methylcyclopentyl trimethoxy silane, 2,3- dimethylcyclopentyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl
Triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl triethoxysilane, vinyl trimethoxy
Base silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltrimethoxysilane, three ethoxy of normal-butyl
Base silane, trimethoxysilane, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy
Base silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy silane, a chlorine triethoxysilane, second
Three isopropoxy silane of base, vinyltributoxysilane, trimethyl phenoxysilane, methyl triolefin npropoxysilane, ethylene
Base triacyloxysilanes, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diisopropyl dimethoxy silane, two
Isopropyl diethoxy silane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl methyl two
Ethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, methylcyclopentyl diethoxy silane,
Methylcyclopentyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopenta methoxy silanes,
At least one in three cyclopenta Ethoxysilanes, dicyclopentylmethyl methoxy silane and cyclopenta dimethyl methoxy silane
Kind.It is preferred that at least one of tetraethoxysilane, tetramethoxy-silicane and four butoxy silanes.
Cyclodextrin is one that amylose generates under the cyclodextrin glycosyltransferase effect generated by bacillus
The general name of series of annular oligosaccharide usually contains 6-12 D- glucopyranose units.Wherein study more and there is weight
Want practical significance is to be referred to as α-, β-and gamma-cyclodextrin containing the molecule of 6,7,8 glucose units.It is brilliant according to X- line
Body diffraction, infrared spectroscopy and spectral analysis of the nuclear magnetic resonance as a result, determining each D (+)-glucopyra for constituting cyclodextrin molecular
Sugar is all chair conformation.Each glucose unit combines cyclization with Isosorbide-5-Nitrae-glycosidic bond.Due to connecting the glycosidic bond of glucose unit
It cannot rotate freely, cyclodextrin is not cylindric molecule but the annulus that tapers slightly.Cyclodextrin of the present invention or its spread out
Biology in alpha-cyclodextrin or derivatives thereof, beta-cyclodextrin or derivatives thereof or gamma-cyclodextrin or derivatives thereof at least one
Kind；Specific compound be selected from alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, Hydroxyproply-α-cyclodextrin, methyl-B-cyclodextrin,
Hydroxypropyl-β-cyclodextrin, hydropropyl-y-cyclodextrin, Sulfobutyl ether β _ cyclodextrin and above-mentioned cyclodextrin derivative in extremely
Few one kind；At least one of more preferable alpha-cyclodextrin, Hydroxyproply-α-cyclodextrin and hydroxypropyl-β-cyclodextrin.
The general formula of the acetyl halide compound is R5(COX)a, wherein R5The aliphatic alkyl for being 1-10 for hydrogen, carbon atom number
Or the carbon atom number being optionally substituted by halogen is the aliphatic alkyl of 1-10, or the aromatic hydrocarbyl for being 6-10 for carbon atom number；X is
Halogen, preferably chlorine；And a is 1 or 2.Specific compound is selected from chloroacetic chloride, oxalyl chloride, chloracetyl chloride, dichloroacetyl chloride, three
Chloracetyl chloride, propionyl chloride, 2- chlorpromazine chloride, 3- chlorpromazine chloride, n-butyryl chloride, isobutyryl chloride, valeric chloride, 5-Chlorovaleryl Chloride, oneself
Acyl chlorides, caprylyl chloride, decanoyl chloride, chlorobenzoyl chloride, 2- chlorobenzoyl chloride, 3- chlorobenzoyl chloride, 4- chlorobenzoyl chloride, to methylbenzene first
Acyl chlorides, o-methyl-benzene formyl chloride, phenyllacetyl chloride, 2,4- dichlorobenzoyl chloride, o-phthaloyl chloride, m-phthaloyl chloride and to benzene
At least one of dimethyl chloride, preferably chloroacetic chloride and/or chlorobenzoyl chloride.
The general formula of the titanium-containing compound is Ti (OR6)aX1 b, R in formula6The aliphatic alkyl for being 1-14 for carbon atom number
Or aromatic hydrocarbyl, X1For halogen, the integer that a 0,1 or 2, b are 0 to 4, and a+b=3 or 4.Specific compound is selected from four
Titanium chloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanium trichloride, dichloro two
At least one of one ethanolato-titanium of ethanolato-titanium and trichlorine, preferably titanium tetrachloride.
In order to keep dissolution more abundant, inert diluent can be optionally added during the preparation process, usual this inertia is dilute
Release the halides that agent includes arene compounds or alkane derivative or both the above compound.The arene compounds
And its halides are in benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene and monochlorotoluene and its derivative
At least one；The alkane derivative and its halides are selected from the linear paraffin and halogenated straight alkane that carbon atom number is 3-20
Hydrocarbon, branched paraffin and halogenated branched paraffin or at least one of cycloalkane and halogenated cycloalkane, such as butane, pentane, hexane, ring
Hexane, heptane, 1,2- dichloroethanes etc., as long as facilitating can using for organo-magnesium compound dissolution.Above-mentioned inertia is dilute
Releasing agent can be used alone, and also can be used in combination.
Ratio between each reactant is calculated with every mole of organo-magnesium compound, usually the dosage of organic epoxy compound object
It is 0.0001-1 moles, the dosage of organo-silicon compound is 0.0001-1 moles, and the dosage of cyclodextrin or derivatives thereof is
0.0001-0.001 moles, the dosage of acetyl halide compound is 0.0001-6 moles, and the dosage of titanium compound is 0.001-10 moles.
The present invention also provides a kind of preparation methods of catalytic component for vinyl polymerization, comprising the following steps:
In the presence of inert diluent by organo-magnesium compound be dissolved in containing organic epoxide, organo-silicon compound and cyclodextrin or its
Homogeneous solution is formed in the system of derivative, solution temperature is 0-120 DEG C；After reaction 0-6 hours, preferably 1-6 hours, cooling
To -40 to 10 DEG C and acetyl halide compound is added dropwise, reacts 0-10 hours；Above-mentioned solution and titanium compound are carried out at -40 to 10 DEG C
Haptoreaction obtains mixture, and mixture is to slowly warm up to 50-120 DEG C, and solids is gradually precipitated and forms particle；It will be upper
It states solids and removes unreacted reactant and solvent, and washed with inert diluent, obtain the catalytic component.
The present invention also provides a kind of catalyst for vinyl polymerization, comprising: (1) of the present invention poly- for ethylene
The catalytic component of conjunction；(2) organo-aluminum compound.
The general formula of the organo-aluminum compound is AlR7 nX2 3-n, R in formula7The alkyl for being 1-20 for hydrogen or carbon atom number, X2
For halogen, and 0≤n≤3.Specific compound is selected from triethyl aluminum, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethyl
In aluminium, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine diisopropyl aluminium, chloromethyl n-propyl aluminium and a chlorodiphenyl base aluminium
It is at least one.Wherein at least one of preferred aluminium diethyl monochloride, one aluminium ethide of dichloro and triethyl aluminum.
Slurry polymerization can be used when the catalyst is used for vinyl polymerization, gas-phase polymerization can also be used.
Slurry polymerization medium includes: iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvents such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
Catalyst of the present invention has many advantages, such as that catalytic activity is high, hydrogen response is good, polymer bulk density is high, is suitable for
In the slurry polymerization processes and gas-phase polymerization process of ethylene.
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
Test mode
1, the measurement (titration) of catalyst Ti content: the 722 type grating beam splitting luminosity that analysis instrument factory produces in Shanghai
It is measured on instrument.
2, it the measurement of the bulk density of polymer: is measured according to ASTM-D1895 standard method.
3, the measurement of the melt index of polymer: according to ASTM-D1238 standard method, in Italian CEAST company 6932
It is measured on fusion index instrument, 190 DEG C of measuring temperature, measures load 2.16kg.
Embodiment 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, sequentially add 4.5g diethoxy magnesium, toluene 120ml,
Epoxychloropropane 10.0ml, silester 10.0ml, Hydroxyproply-α-cyclodextrin 0.01g are warming up to 90 DEG C under stirring, in the temperature
Degree lower reaction 3 hours, obtain emulsion form reaction system.Then 50 DEG C are cooled to, 3.0ml chlorobenzoyl chloride is added, is reacted 1 hour.
The lotion is cooled to -5 DEG C, 30ml titanium tetrachloride is slowly added dropwise, constant temperature 0.5 hour, 85 DEG C are then to slowly warm up to, at 85 DEG C
Reaction 2 hours.Then cooling down, stop stirring, stand, suspension is layered quickly, and supernatant liquor is extracted, is washed four times with hexane,
High pure nitrogen drying, obtains the ingredient of solid catalyst of good fluidity.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, the triethyl aluminum that concentration is 1M is added
Hexane solution 1L (contains triethyl aluminum 1.0ml), and the solid catalyst of above-mentioned preparation is added, is warming up to 70 DEG C, being passed through hydrogen makes kettle
Interior pressure reaches 0.28Mpa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), and it is small that 2 are polymerize under the conditions of 80 DEG C
When, polymerization result is shown in Table 1.
Embodiment 2
(1) except Hydroxyproply-α-cyclodextrin dosage is changed to 0.005g, chlorobenzoyl chloride dosage is changed to outside 1.5ml, the conjunction of catalyst
At same embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 3
(1) in addition to epoxychloropropane dosage is changed to 5.0ml, the synthesis of catalyst is the same as embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 4
(1) Hydroxyproply-α-cyclodextrin is changed to hydroxypropyl-β-cyclodextrin, dosage is changed to 0.01g, and silester dosage changes
For 12.5ml, chlorobenzoyl chloride dosage is changed to outside 0.5ml, and the synthesis of catalyst is the same as embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Comparative example 1
In the reactor being sufficiently displaced from through high pure nitrogen, 4.5g diethoxy magnesium, 100ml toluene, epoxy are sequentially added
Chloropropane 2.0ml, tributyl phosphate 6.0ml, ethyl alcohol 3.4ml, are warming up to 90 DEG C under stirring, at such a temperature reaction 3 hours, only
Colloid is obtained, emulsion form reaction system is not obtained.The colloid is cooled to -5 DEG C, 65ml titanium tetrachloride, 3.0ml is slowly added dropwise
Tetraethoxysilane, constant temperature 0.5 hour；85 DEG C are to slowly warm up to, is reacted 2 hours at such a temperature.Then cool down, stop stirring
It mixes, stands, hexane washs four times, does not obtain molding catalytic component.
Comparative example 2
(1) synthesis of catalyst is prepared by 1 the method for CN103772548 embodiment.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
1 polymer performance of table
The preparation process that can be seen that catalytic component of the present invention from the experimental data of 1 embodiment of table and comparative example is simple,
Cyclodextrin or derivatives thereof is added and is conducive to dissolution of the organo-magnesium compound in system, gained catalyst activity is kept compared with Gao Shui
Flat, polymer bulk density is higher, and melting means is higher.Wherein comparative example 1 is common BCE method for preparing catalyst, and ethyoxyl
For magnesium in the dissolution system, i.e., the colloid easy to form in tributyl phosphate, epoxychloropropane and ethanol system cannot form stream
The dynamic preferable solid catalyst of property.It is compared with catalyst disclosed in comparative example 2, catalyst obtained by this patent is not only catalyzed work
Property it is high, high melt index illustrates that its hydrogen response significantly improves.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (25)
1. a kind of catalytic component for vinyl polymerization, the catalytic component be in the presence of inert diluent, will be organic
Magnesium compound is dissolved in the system containing organic epoxide, organo-silicon compound and cyclodextrine derivatives and forms solution, adds
Enter acetyl halide compound, is then prepared with the halide of titanium or derivatives thereof effect；The general formula of the organo-magnesium compound
For Mg (OR1)nX2-n, R in formula1It is C2-C20Alkyl, the alkyl be saturations or undersaturated straight chain, branch or closed chain；
X is halogen；The cyclodextrine derivatives are selected from alpha-cyclodextrin derivative, beta-cyclodextrin derivative and gamma-cyclodextrin derivative
At least one of；In terms of every mole of organo-magnesium compound, the dosage of organic epoxy compound object is 0.0001-1 moles, organosilicon
The dosage of compound is 0.0001-1 moles, and the dosage of cyclodextrine derivatives is 0.0001-0.001 moles, acetyl halide compound
Dosage is 0.0001-6 moles, and the dosage of halide of titanium or derivatives thereof is 0.001-10 moles.
2. catalytic component according to claim 1, which is characterized in that in the general formula of the organo-magnesium compound, X is
Chlorine；And 0≤n≤2.
3. catalytic component according to claim 2, which is characterized in that the organo-magnesium compound is selected from a chloroethene oxygen
Base magnesium, a chlorine isopropoxy magnesium, a neoprene oxygroup magnesium and a chlorine octyloxy magnesium, diethoxy magnesium, isopropoxy magnesium, butoxy
At least one of magnesium, n-octyloxy magnesium and 2- ethyl hexyl oxy magnesium.
4. catalytic component according to claim 2, which is characterized in that the organo-magnesium compound is selected from diethoxy
At least one of magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
5. catalytic component according to claim 1, which is characterized in that the organic epoxy compound object is selected from carbon atom
It counts in the oxide, glycidol ether and inner ether of aliphatic olefin, alkadienes or the halogenated aliphatic alkene or alkadienes that are 2-8
At least one.
6. catalytic component according to claim 5, which is characterized in that the organic epoxy compound object is selected from epoxy second
In alkane, propylene oxide, epoxy butane, butadiene oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether
It is at least one.
7. catalytic component according to any one of claim 1 to 6, which is characterized in that the organo-silicon compound
General formula be R2 xR3 ySi(OR4)z, wherein R2And R3Respectively alkyl or halogen of the carbon atom number for 1-10, R4It is for carbon atom number
The alkyl of 1-10, wherein x, y and z are positive integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4.
8. catalytic component according to claim 7, which is characterized in that the organo-silicon compound are selected from four chlorinations
Silicon, silicon bromide, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2- ethyl hexyl oxygen
Base) silane, ethyl trimethoxy silane, n-propyl triethoxysilane, n-propyl trimethoxy silane, decyl trimethoxy silicon
Alkane, ruthenium triethoxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, 2- methylcyclopentyl trimethoxy
Base silane, 2,3- dimethylcyclopentyl trimethoxy silane, methyltrimethoxysilane, methyltriethoxysilane, ethyl three
Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, normal-butyl three
Methoxy silane, ne-butyltriethoxysilaneand, trimethoxysilane, isobutyl triethoxy silane, cyclohexyl three
Ethoxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy
Silane, a chlorine triethoxysilane, three isopropoxy silane of ethyl, vinyltributoxysilane, trimethyl phenoxysilane,
Methyl triolefin npropoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diisopropyl dimethoxy silicon
Alkane, diisopropyldiethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl
Methyldiethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, methylcyclopentyl diethoxy
Silane, methylcyclopentyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopentylmethoxies
In silane, three cyclopenta Ethoxysilanes, dicyclopentylmethyl methoxy silane and cyclopenta dimethyl methoxy silane extremely
Few one kind.
9. catalytic component according to claim 8, which is characterized in that the organo-silicon compound are selected from tetraethoxy
At least one of silane, tetramethoxy-silicane and four butoxy silanes.
10. catalytic component according to claim 1, which is characterized in that the cyclodextrine derivatives are selected from hydroxypropyl-
Alpha-cyclodextrin, methyl-B-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydropropyl-y-cyclodextrin, in Sulfobutyl ether β _ cyclodextrin extremely
Few one kind.
11. catalytic component according to any one of claim 1 to 6, which is characterized in that the acetyl halide compound
General formula is R5(COX)a, wherein R5It is hydrogen, the aliphatic alkyl of 1-10 or the carbon atom number that is optionally substituted by halogen for carbon atom number is 1-
10 aliphatic alkyl, or the aromatic hydrocarbyl for being 6-10 for carbon atom number；X is halogen.
12. catalytic component according to claim 11, which is characterized in that in the general formula of the acetyl halide compound, X is
Chlorine；And a is 1 or 2.
13. catalytic component according to claim 12, which is characterized in that the acetyl halide compound be selected from chloroacetic chloride,
Oxalyl chloride, chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride, propionyl chloride, 2- chlorpromazine chloride, 3- chlorpromazine chloride, n-butyryl chloride,
Isobutyryl chloride, valeric chloride, 5-Chlorovaleryl Chloride, caproyl chloride, caprylyl chloride, decanoyl chloride, chlorobenzoyl chloride, 2- chlorobenzoyl chloride, 3- chlorobenzene
Formyl chloride, 4- chlorobenzoyl chloride, to methyl benzoyl chloride, o-methyl-benzene formyl chloride, phenyllacetyl chloride, 2,4- dichlorobenzoyl chloride,
At least one of o-phthaloyl chloride, m-phthaloyl chloride and paraphthaloyl chloride.
14. catalytic component according to claim 13, which is characterized in that the acetyl halide compound be chloroacetic chloride and/
Or chlorobenzoyl chloride.
15. catalytic component according to any one of claim 1 to 6, which is characterized in that the halide of the titanium or
The general formula of its derivative is Ti (OR6)aX1 b, R in formula6The aliphatic alkyl or aromatic hydrocarbyl for being 1-14 for carbon atom number, X1For
Halogen, the integer that a 0,1 or 2, b are 0 to 4, and a+b=3 or 4.
16. catalytic component according to claim 15, which is characterized in that described halide of titanium or derivatives thereof choosing
From titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanium trichloride, two
At least one of one ethanolato-titanium of chlorine diethoxy titanium and trichlorine.
17. catalytic component according to claim 16, which is characterized in that described halide of titanium or derivatives thereof is
Titanium tetrachloride.
18. catalytic component according to any one of claim 1 to 6, which is characterized in that the inert diluent is virtue
The halides of hydrocarbon compound or alkane derivative or both the above compound.
19. catalytic component according to claim 18, which is characterized in that the arene compounds and its halides choosing
From benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene and at least one of monochlorotoluene and its derivative.
20. catalytic component according to claim 18, which is characterized in that the alkane derivative and its halides choosing
From linear paraffin and halogenated straight alkane, branched paraffin and halogenated branched paraffin or cycloalkane that carbon atom number is 3-20 and halogenated
At least one of cycloalkane.
21. catalytic component according to claim 20, which is characterized in that the alkane derivative and its halides choosing
From at least one of butane, pentane, hexane, hexamethylene, heptane and 1,2- dichloroethanes.
22. being included in inert diluent to the preparation method of catalytic component described in any one of 21 according to claim 1 and depositing
Organo-magnesium compound is dissolved in shape in the system containing organic epoxide, organo-silicon compound and cyclodextrine derivatives lower
At solution, solution temperature is 0-120 DEG C；Reaction is cooled to -40 to 10 DEG C after 0-6 hours and acetyl halide compound is added dropwise, and reacts 0-
10 hours；Above-mentioned solution and titanium compound are subjected to haptoreaction at -40 to 10 DEG C and obtain mixture, and mixture is slowly risen
To 50-120 DEG C, solids is gradually precipitated and forms particle temperature；Above-mentioned solids is removed into unreacted reactant after reaction 0-10 hours
And solvent, and washed with inert diluent, obtain the catalytic component.
23. according to claim 22 the method, which is characterized in that be included in organo-magnesium compound in the presence of inert diluent
It is dissolved in the system containing organic epoxide, organo-silicon compound and cyclodextrin or derivatives thereof and forms solution, dissolution temperature
Degree is 0-120 DEG C；Reaction is cooled to -40 to 10 DEG C after 1-6 hours and acetyl halide compound is added dropwise, and reacts 0-10 hours；- 40 to
Above-mentioned solution and titanium compound are carried out haptoreaction and obtain mixture, and mixture is to slowly warm up to 50-120 DEG C by 10 DEG C,
Solids is gradually precipitated and forms particle；Above-mentioned solids is removed into unreacted reactant and solvent after reaction 1-6 hours, and uses inertia
Diluent washing, obtains the catalytic component.
24. a kind of catalyst for vinyl polymerization, comprising:
(1) catalytic component of vinyl polymerization is used for described in any one of claim 1 to 21；
(2) general formula is AlR7 nX2 3-nOrgano-aluminum compound, R in formula7The alkyl for being 1-20 for hydrogen or carbon atom number, X2For halogen,
0≤n≤3。
25. application of the catalyst described in claim 24 in ethylene homo or copolyreaction.
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| CN103772553A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and its preparation method |
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| CN103772553A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and its preparation method |
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