CN110407964A - Catalyst component for olefin and preparation method thereof - Google Patents
Catalyst component for olefin and preparation method thereof Download PDFInfo
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- CN110407964A CN110407964A CN201810402018.2A CN201810402018A CN110407964A CN 110407964 A CN110407964 A CN 110407964A CN 201810402018 A CN201810402018 A CN 201810402018A CN 110407964 A CN110407964 A CN 110407964A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention discloses a kind of catalyst component for olefin, form it includes the reaction product of following components or by the reaction product of following components: (1) magnesium compound；(2) lewis base compound；(3) general formula is R2The acetyl halide compound of COX, wherein R2It is halogen for hydrogen, substituted or unsubstituted C1-C10 alkyl or epoxy group, X；(4) contain the compound of two hydroxyl groups；(5) oxygen-containing titanium-containing compound；(6) titanium tetrahalide.In the present invention, in the preparation process of catalytic component, acetyl halide compound generates diol ester with the compound containing two hydroxyl groups, gained catalyst and a kind of organo-silicon compound are compounded, the catalyst of high comprehensive performance can be obtained, when being used for olefinic polymerization, for obtained polymer in the very high situation of its stereoselectivity, the activity of catalyst is higher.
Description
Technical field
The invention belongs to olefin polymerization technology field, it is related to a kind of catalyst component for olefin and preparation method thereof.
Background technique
In recent years, olefin polymetiation process is quickly grown, and at the same time, the catalyst to match with olefinic polymerization is also quick
Development.Ziegler-Natta catalyst system is to prepare main catalyst in polyene hydrocarbon reaction.From United States Patent (USP)
US4495388 propose by magnesium halide in active as the carrier of Ziegler-Natta catalyst after, high-effective carrier catalyst obtains
It is fast-developing.Such catalyst is using magnesium, titanium, halogen and internal electron donor as main component；Using organo-aluminum compound as helping
Catalytic component, in addition, as needed, when polymerization, is additionally added external electron donor component organo-silicon compound.In such catalyst
In, the development of internal electron donor compound is so that polypropylene catalyst is kept updating.Several major companies are in the world in order to improve
The competitiveness of its catalyst strengthens the research-and-development activity of novel electron donor, further improves titanium system efficient catalytic
The performance of agent.Common electron donor compound include polybasic carboxylic acid, monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether or
Polyether, alcohol, amine etc. and its derivative, wherein more the most commonly used is binary aromatic carboxylic acid's esters, such as n-butyl phthalate
Or diisobutyl phthalate etc., such as United States Patent (USP) US4784983.Research has shown that phthalate compound can be right
Reproductive system, immune system and digestive system of human body etc. bring harm, such as damage male reproductive function, promote female precocious puberty
Deng.Thus various countries have put into effect the corresponding laws and regulations that limitation benzoic ether substance is used in every profession and trade in succession, therefore without neighbour
Phthalates compound gets the attention and applies as the catalyst of internal electron donor, it is also very desirable to seek one kind
Without phthalate electron donor and preparation method is simple, catalyst of function admirable.
Recent study, which develops, uses glycol ester compounds as internal electron donor, but uses glycol ester compounds at present
As in the catalyst preparation of internal electron donor, glycol ester compounds needs are pre-synthesis, in the preparation process of catalyst again
It is added into.And the synthesis of glycol ester compounds and purification process are complicated, cause catalyst preparation high expensive, are unfavorable for such
The popularization and application of catalyst.
Summary of the invention
The present invention has found in the course of the research, in olefin polymerization catalysis in preparation process, can use containing diolation
It closes object and acetyl halide compound reaction in-situ generates glycol ester compounds and directly participates in the synthesis of catalytic component.Gained is catalyzed
Agent and a kind of organo-silicon compound are compounded, and the catalyst of high comprehensive performance can be obtained, and when being used for olefinic polymerization, are obtained
Polymer in the very high situation of its stereoselectivity, catalyst activity it is higher.The preparation process is without using epoxies
Cosolvent and phthalic anhydride class settling aids, can be to avoid the generation of phthalic acid esters compound in reaction process.Due to diol ester
Class electron donor in-situ preparation reduces glycol ester compounds and process is prepared separately, and makees catalyst with glycol ester compounds
For electron donor excellent performance while simplify the preparation process of catalyst.
According to the first aspect of the invention, a kind of catalyst component for olefin is provided.
Catalyst component for olefin provided by the invention, the reaction product comprising following components or by following components
Reaction product composition: (1) magnesium compound；(2) lewis base compound；(3) general formula is R2The acetyl halide compound of COX, wherein R2
It is halogen for hydrogen, substituted or unsubstituted C1-C10 alkyl or epoxy group, X；(4) contain the compound of two hydroxyl groups；(5) contain
Oxygen titanium-containing compound；(6) titanium tetrahalide.
According to the preferred embodiment of the present invention, the magnesium compound is formula M gR1 nX2-nCompound represented or its water
Close object or alcohol adduct, wherein X is halogen, preferably chlorine, bromine or iodine, most preferably Cl, R1For C1-C20 alkyl, alkoxy or
Halogenated alkoxy, the preferably alkyl of C1-C5, alkoxy or halogenated alkoxy, 0≤n≤2, it is preferable that the magnesium compound choosing
From one of magnesium dihalide (including magnesium dichloride, magnesium dibromide, magnesium diiodide), the alcohol adduct of magnesium dihalide and alkoxyl magnesium
Or it is a variety of.
According to the preferred embodiment of the present invention, the lewis base compound is organic phosphorus lewis base compound, excellent
It is selected as phosphate, including phosphate monoester, di-phosphate ester, phosphotriester, more preferably trialkylphosphate, it is preferable that tricresyl phosphate
Arrcostab is by shown in formula (I):
Wherein, R7-R9Methyl, ethyl, C3-C10 linear or branched alkyl group group are each independently selected from (for example, positive third
Base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl and isohesyl etc.).It is specific real at of the invention one
It applies in mode, the trialkylphosphate is tributyl phosphate.
According to the preferred embodiment of the present invention, X is preferably chlorine in the acetyl halide compound.The alkyl includes aliphatic hydrocarbon
Base and aryl radical.Preferably, R2For the substituted or unsubstituted phenyl of halogen, C1-C4 alkyl or furyl, it is preferable that described
Acetyl halide compound is selected from chloroacetic chloride, propionyl chloride, isopropyl acyl chlorides, butyl chloride, isobutyryl chloride, chlorobenzoyl chloride, o-phthaloyl chloride, grass
One of acyl chlorides and furoyl chloride are a variety of, further preferably chlorobenzoyl chloride, o-phthaloyl chloride and 2- furoyl
One of chlorine is a variety of.
According to the preferred embodiment of the present invention, shown in the formula (II) for containing two hydroxyl groups:
Wherein, R1-R6Group is identical or different, be independently selected from H, halogen, C1-C20 linear chain or branched chain alkyl,
C3-C20 naphthenic base, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkylene or fused ring aryl, R1-R6
It cannot simultaneously be hydrogen；Preferably, R1、R2In at least one be not H, for example, it may be R1For H, R2It is not H；Or R2For H, R1No
For H；Or R1、R2It is not H.
R1-R6The selection of group can be exemplified as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, phenyl,
Alkyl-substituted phenyl, naphthalene, vinyl, acrylic etc..
According to the preferred embodiment of the present invention, the compound for containing two hydroxyl groups is symmetrical compound, that is, two
The substituent group on C that a hydroxyl is connected is identical.
According to the preferred embodiment of the present invention, the example of the compound for containing two hydroxyl groups includes, but unlimited
In, 1,3- diphenyl -2- methyl-1,3-propanediol, 1,3- diphenyl -2,2-dimethyl-1,3-propanediol, the tertiary fourth of 1,3- bis-
Base -2- ethyl -1,3-PD dibenzoate, 1,3- diisopropyl -1,3-PD, 1- phenyl -2- amino -1,3 the third two
Alcohol, 1- phenyl -2- methyl-1,3- butanediol, 1- furans -2- methyl-1,3- butanediol, 4,4,4- tri- fluoro- 1- (2- naphthalene) -1,3-
Butanediol, 2,4- pentanediol, 3- methyl -2,4- pentanediol, 3- ethyl -2,4- pentanediol, 3- propyl -2,4- pentanediol, 3- fourth
Base -2,4- pentanediol, 3,3- dimethyl -2,4- pentanediol, (2S, 4S)-(+) -2,4- pentanediol, (2R, 4R)-(+) -2,4- penta
Glycol, 1,3- pentanediol, 2- methyl-1,3- pentanediol, 2- ethyl -1,3- pentanediol, 2- butyl -1,3- pentanediol, 2,2- bis-
Methyl-1,3- pentanediol, 2,2,4- trimethyl -1,3- pentanediol of 2- allyl -1,3- pentanediol, 1- trifluoromethyl -3- methyl -
2,4- pentanediols, 3- methyl -3- butyl -2,4- pentanediol, 2- ethyl -1,3- hexylene glycol, 2- propyl -1,3- hexylene glycol, 2- fourth
Base -1,3- hexylene glycol, 4- ethyl -1,3- hexylene glycol, 4- methyl-1,3- hexylene glycol, 3- methyl-1,3- hexylene glycol, ethyl -1 3-,
3- hexylene glycol, 2,2,4,6,6- pentamethyl -3,5- hexylene glycols, 6- heptene -2,4- heptandiol, 2- methyl -6- heptene -2,4- heptan two
Alcohol ester, 3- methyl -6- heptene -2,4- heptandiol, 4- methyl -6- heptene -2,4- heptandiol, 5- methyl -6- heptene -2,4- heptan two
Alcohol, 6- methyl -6- heptene -2,4- heptandiol, 3- ethyl -6- heptene -2,4- heptandiol, 4- ethyl -6- heptene -2,4- heptan two
Alcohol, 5- ethyl -6- heptene -2,4- heptandiol, 6- ethyl -6- heptene -2,4- heptandiol, 3- propyl -6- heptene -2,4- heptan two
Alcohol, 4- propyl -6- heptene -2,4- heptandiol, 5- propyl -6- heptene -2,4- heptandiol, 6- propyl -6- heptene -2,4- heptan two
Alcohol, 3- butyl -6- heptene -2,4- heptandiol, 4- butyl -6- heptene -2,4- heptandiol, 5- butyl -6- heptene -2,4- heptan two
Alcohol, 6- butyl -6- heptene -2,4- heptandiol, 3,5- dimethyl -6- heptene -2,4- heptandiol, heptene -2 3,5- diethyl -6-,
4- heptandiol, 3,5- dipropyl -6- heptene -2,4- heptandiol, 3,5- dibutyl -6- heptene -2,4- heptandiol ester, 3,3- diformazan
Base -6- heptene -2,4- heptandiol, 3,3- diethyl -6- heptene -2,4- heptandiol, 3,3- dipropyl -6- heptene -2,4- heptan two
Alcohol, 3,3- dibutyl -6- heptene -2,4- heptandiol, 3,5- heptandiol, 2- methyl -3,5- heptandiol, 3- methyl -3,5- heptan two
Alcohol, 4- methyl -3,5- heptandiol, 5- methyl -3,5- heptandiol, 6- methyl -3,5- heptandiol, 3- ethyl -3,5- heptandiol, 4-
Ethyl -3,5- heptandiol, 5- ethyl -3,5- heptandiol, 3- propyl -3,5- heptandiol, 4- propyl -3,5- heptandiol, 3- butyl -
3,5- heptandiols, 2,3- dimethyl -3,5- heptandiol, 2,4- dimethyl -3,5- heptandiol, 2,5- dimethyl -3,5- heptandiol,
2,6- dimethyl -3,5- heptandiols, 3,3- dimethyl -3,5- heptandiol, 4,4- dimethyl -3,5- heptandiol, 6,6- dimethyl -
3,5- heptandiols, 2,6- dimethyl -3,5- heptandiol, 3,4- dimethyl -3,5- heptandiol, 3,5- dimethyl -3,5- heptandiol,
3,6- dimethyl -3,5- heptandiols, 4,5- dimethyl -3,5- heptandiol, 4,6- dimethyl -3,5- heptandiol, 4,4- dimethyl -
3,5- heptandiols, 6,6- dimethyl -3,5- heptandiol, 2- methyl -3- ethyl -3,5- heptandiol, 2- methyl -4- ethyl -3,5-
Heptandiol, 2- methyl -5- ethyl -3,5- heptandiol, 3- methyl -3- ethyl -3,5- heptandiol, 3- methyl -4- ethyl -3,5- heptan
Glycol, 3- methyl -5- ethyl -3,5- heptandiol, 4- methyl -3- ethyl -3,5- heptandiol, 4- methyl -4- ethyl -3,5- heptan two
Alcohol, 4- methyl -5- ethyl -3,5- heptandiol, 2- methyl -3- propyl -3,5- heptandiol, 2- methyl -4- propyl -3,5- heptan two
Alcohol, 2- methyl -5- propyl -3,5- heptandiol, 3- methyl -3- propyl -3,5- heptandiol, 3- methyl -4- propyl -3,5- heptan two
Alcohol, 3- methyl -5- propyl -3,5- heptandiol, 4- methyl -3- propyl -3,5- heptandiol, 4- methyl -4- propyl -3,5- heptan two
Alcohol, 4- methyl -5- propyl -3,5- heptandiol, 6- methyl -2,4- heptandiol, 6- heptene -2,4- heptandiol, dimethyl -2 3,6-,
4- heptandiol, 2,2,6,6- tetramethyl -3,5- heptandiols, 4- methyl -3,5- ethohexadiol, 4- ethyl -3,5- ethohexadiol, 4- third
Base -3,5- ethohexadiol, 5- propyl -3,5- ethohexadiol, 4- butyl -3,5- ethohexadiol, 4,4- dimethyl -3,5- ethohexadiol, 4,4-
Diethyl -3,5- ethohexadiol, 4,4- dipropyl -3,5- ethohexadiol, 4- methyl -4- ethyl -3,5- ethohexadiol, 3- phenyl -3,5-
Ethohexadiol, 2- methyl -3- ethyl -3,5- ethohexadiol, 2- methyl -4- ethyl -3,5- ethohexadiol, 2- methyl -5- ethyl -3,5- are pungent
Glycol, 2- methyl -6- ethyl -3,5- ethohexadiol, 5- methyl -4,6 nonanediol, 5- ethyl -4,6 nonanediol, 5- propyl -4,6 nonyl
Glycol, 5- butyl -4,6 nonanediol, 5,5- dimethyl -4,6 nonanediol, 5,5- diethyl -4,6 nonanediol, dipropyl -4 5,5-,
6 nonanediols, 5,5- dibutyl -4,6 nonanediol, 5- methyl -4- ethyl -4,6 nonanediol, 5- phenyl -4,6 nonanediol, 4,6- nonyl
One of glycol, 4- butyl -3,5- heptandiol and 3- methyl -3- butyl -2,4- pentanediol are a variety of.
According to the preferred embodiment of the present invention, the oxygen-containing titanium-containing compound is general formula Ti (OR ")pX4-pShown in change
Close object, wherein X is halogen, preferably chlorine, bromine, iodine, and R " is C1-C20 alkyl, preferably C1-C14 alkyl, as methyl, ethyl,
Propyl, butyl, amyl etc., 0 p≤4 <.
According to the preferred embodiment of invention, the oxygen-containing titanium-containing compound is selected from four titanium butoxides, purity titanium tetraethoxide, one
One of one ethanolato-titanium of chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium and trichlorine is a variety of.It is preferred that four titanium butoxides.
According to the preferred embodiment of the present invention, the titanium tetrahalide is titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide and four
One of titanium iodide is a variety of.It is preferred that titanium tetrachloride.
According to the preferred embodiment of the present invention, in the catalytic component, the feeding quantity of each component is with every mole of magnesium
Close object meter, lewis base compound is 0.01-20 moles, preferably 0.2-12 moles, for example, can for 0.2,0.5,1.0,1.5,
2.0,2.5,3.0,3.5,4,5,6,7,8,9,10,11,12 moles and arbitrary value between them；Change containing two hydroxyl groups
Closing object is 0.1-10 moles, preferably 0.25-1 moles, such as can for 0.25,0.3,0.35,0.4,0.45,0.5,0.6,0.7,
0.75,0.8,0.9,1 mole and arbitrary value between them；Oxygen-containing titanium-containing compound is 0.1-10 moles, and preferably 1.0-5 rubs
You, such as can be 1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0 moles and arbitrary value between them；Four halogenations
Titanium is 1-5 moles, such as can be 1.0,1.5,2.0,2.5,3.0,3.5,4.0,5.0 moles and arbitrary value between them；
Acetyl halide compound is 0.1-10, preferably 0.5-4.0 moles, more preferable 1-2 moles, for example, can for 1.0,1.05,1.10,
1.15,1.20,1.25,1.3,1.35,1.4,1.45,1.50,1.55,1.6,1.7,1.8,1.9,2.0 moles and they it
Between arbitrary value.
It according to the preferred embodiment of the present invention, is unfavorable containing alcohol in the catalytic component, that is to say, that no
Containing contain two hydroxyl groups compound, pair it is advantageous in the present invention that acetyl halide compound with contain two hydroxyl groups chemical combination
The molar ratio of object is 2-3, such as can be between 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0 and they
Arbitrary value, preferably 2.2-2.6.
There is provided the preparation methods of above-mentioned catalytic component for another aspect of the present invention.
According to the present invention, the preparation method of above-mentioned catalytic component, comprising the following steps:
(i) magnesium compound, lewis base compound, the compound containing two hydroxyl groups and oxygen-containing titanium-containing compound are connect
Touching reaction, obtains haptoreaction product；
(ii) the haptoreaction product is mixed with acetyl halide compound, obtains mixture；
(iii) clear solution and titanium tetrahalide haptoreaction are obtained into solid precipitation, the as described catalytic component.
According to the preferred embodiment of the present invention, in the preparation method of the catalytic component, step (i) is magnesium chemical combination
The mixed dissolution process of object, lewis base compound and compound, oxygen-containing titanium-containing compound containing two hydroxyl groups.In step
(i) in, optionally in the presence of inert diluent, at 0-200 DEG C, for example, 0 DEG C, 1 DEG C, 4 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20
℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95
DEG C, 98 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C and
At arbitrary temperature between them, by magnesium compound, lewis base compound, containing two hydroxyl bases preferably at 25-150 DEG C
The compound of group and oxygen-containing titanium-containing compound haptoreaction.The inert diluent can be exemplified as benzene,toluene,xylene, different
Butane, pentane, hexane, heptane, hexamethylene, 1,2- dichloroethanes, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.This
The 'inertia' that place is said refers to that the diluent is not involved in reaction and will not have an adverse effect to the dissolution of magnesium compound.
According to the preferred embodiment of the present invention, haptoreaction product and carboxylic acid halides in step (ii), in step (i)
When compound mixes, acetyl halide compound is added drop-wise in the haptoreaction product, make acetyl halide compound and contains two hydroxyl bases
The compound of group sufficiently reacts, and preferably carries out at -30-150 DEG C.
According to the preferred embodiment of the present invention, after obtaining the mixture in step (ii), further including will be described mixed
It closes object and is warming up to 80-200 DEG C, obtain clear solution, which usually carries out at a relatively high temperature, but should be anti-
The decomposition temperature of object or less is answered to carry out.After forming clear solution, mixing further can be diluted with inert diluent.Make
For inert diluent, for example, it may be selected from benzene,toluene,xylene, iso-butane, pentane, hexane, heptane or hexamethylene etc.
Aliphatic or aromatic hydrocarbon and their mixture.It is excellent as inert diluent in an embodiment of the invention
It is selected as toluene or hexane.Step (iii) is then carried out again after obtaining clear solution, and the clear solution is contacted with titanium tetrahalide
Reaction obtains solid precipitation.
According to the preferred embodiment of the present invention, in step (iii), at -35 DEG C -60 DEG C, for example, -30 DEG C, -25
℃、-20℃、-15℃、-10℃、-5℃、0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50
DEG C, 55 DEG C, 58 DEG C, at 60 DEG C and the arbitrary temperature between them, it is preferably under the conditions of -30-25 DEG C, the mixing is molten
Liquid is contacted with titanium compound, which can be slowly dropped to titanium compound in the mixed solution, described can also will be mixed
It closes solution to be added drop-wise in the titanium compound, it is preferable that the dropwise addition process control is within the scope of 10min-1h.Optionally, in institute
It states during mixture contacts with titanium compound, other electron donor compound such as alkoxy silanes can be added.It is added dropwise
After the completion, -30-150 DEG C, preferably 20-130 DEG C are raised the temperature to, so that the mixed solution is reacted precipitation with titanium compound solid
Body, it is preferable that be gradually heated to reaction temperature in 30min-5h, preferably 30min-1h.
In the present invention, the preparation method of the catalytic component further includes the step post-processed to the catalytic component
Suddenly (iv) includes curing, washing to solid precipitating post-processing and is dried.According to the preferred embodiment of the present invention, the step
Solid is precipitated using titanium tetrahalide in rapid and carries out maturation process, it is preferable that the titanium tetrahalide used is titanium tetrachloride.In the step
In rapid, the titanium tetrahalide can be added at one time or be added portionwise.According to the preferred embodiment of the present invention, in the step
In, it is come into full contact with to precipitate titanium tetrahalide with solid, model of the reaction temperature condition at 70-150 DEG C when titanium tetrahalide is added
It encloses, preferably 90-130 DEG C of range, the specific number that cures is 1-5 times, preferably 2-3 times.
In the present invention, maturation process is precipitated after reaction to solid using titanium tetrahalide in step (iv), passes through washing
The by-product formed in excessive reactant and preparation process is removed, the catalysis that solid particulate can be obtained then is dried
Agent component.In the present invention, cleaning solvent used in the washing step is not particularly limited, any one can be selected
Atent solvent, for example, iso-butane, pentane, hexane, heptane, hexamethylene, toluene etc. can be selected as cleaning solvent.
The present invention also provides a kind of catalyst for olefines polymerizing comprising:
(1) above-mentioned catalytic component；
(2) alkyl aluminum compound；Preferably general formula AlR3 qX3-qShown in alkyl aluminum compound, R in formula3For hydrogen or C1-
The alkyl of C20, X are halogen, 0 q≤3 <；
(3) optionally, external electron donor component.
" optionally, the external electron donor component " means as needed, and selection adds or be not added external electron donor chemical combination
Object.For needing the very high olefin polymer of stereoregularity in application, needing that (3) external electron donor component is added, according to this hair
Bright preferred embodiment, the external electron donor are general formula (R4)kSi(OR5)4-kCompound represented, 0≤k≤3, R in formula4
And R5It is identical or different, R5For C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl and amino, R4Selected from halogen, hydrogen atom and
C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl or amino.The example of the external electron donor includes, but are not limited to front three
Methoxylsilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diphenyl two
Methoxy silane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyl trimethoxy
Base silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, two
Isobutyl group dimethoxysilane, di-n-butyl dimethoxysilane, dicyclopentyl dimethoxyl silane, two (cyclobutylmethyls) two
Methoxy silane, preferably Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silicon
Alkane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxysilane, dicyclopentyl dimethoxyl silane and two (cyclobutyl
Methyl) one of dimethoxysilane or a variety of.
Preferably, catalytic component is in terms of titanium, and alkyl aluminum compound is in terms of aluminium, and external electron donor component is in terms of silicon, component
(1), component (2), the molar ratio of component (3) are 1:5-1000:0-500；Preferably 1:25-100:25-100.
Of the invention additionally provides the application of the catalytic component or the catalyst in olefin polymerization, wherein described
Alkene preferred formula CH2Alkene shown in=CHR, wherein R is hydrogen or C1-C12Alkyl or aryl group.
Olefin polymerization of the invention is carried out according to well known polymerization, can be carried out in liquid phase or gas phase, or
Person can also carry out under the operation that liquid and gas polymerization stage combines.Using conventional technique such as slurry process, gas phase fluidization
Bed etc., wherein alkene is preferably selected from one of ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexene or a variety of, special
Be not propylene homopolymerization with or propylene and other alkene combined polymerization.Polymerization temperature is generally 0-150 DEG C, preferably 60-90 DEG C.
Catalytic component provided by the invention, which is utilized, generates diol ester containing diol compound and acetyl halide compound reaction in-situ
Compound and the synthesis for directly participating in catalytic component.Gained catalyst and a kind of organo-silicon compound are compounded, can be obtained
To the catalyst of high comprehensive performance, when being used for olefinic polymerization, obtained polymer is in the very high situation of its stereoselectivity
Under, the activity of catalyst is higher.The preparation process, can be to avoid anti-without using epoxies cosolvent and phthalic anhydride class settling aids
The generation of phthalic acid esters compound during answering.Due to diol-lipid electron donor in-situ preparation, reduce glycol esterification
It closes object and process is prepared separately, simplify catalyst while there is excellent performance of the glycol ester compounds as electron donor and urge
The preparation process of agent.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
Test method
Polymer isotacticity II: using the measurement of heptane extraction process (heptane boiling extracting 6 hours): 2 grams of dry polymer
Sample is placed in extractor after being extracted 6 hours with boiling heptane, and residue is dry to the resulting polymer weight (g) of constant weight
Ratio with 2 is isotacticity.
Melt index MI: it using fusion index instrument under 230 DEG C, 2.16kg pressure, " uses and squeezes according to ASTM D1238-99
The standard test method of compactibility meter measurement thermoplasticity fusing flow rate " measurement.
The preparation of ingredient of solid catalyst
Embodiment 1
It in the reactor being sufficiently displaced from by high pure nitrogen, sequentially adds magnesium chloride 4.8g (0.05mol), is being added four just
Titanium butoxide 35mL (0.10mol), 2,4- pentanediol 0.025mol, tributyl phosphate 12.5mL (0.46mol) stir lower heating
It to 60 DEG C, is slowly added dropwise chlorobenzoyl chloride 5.8mL (0.05mol), maintains 2.5 hours；Then heat to 140 DEG C, be stirred to react to
Magnesium chloride is completely dissolved；Then solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour436mL(0.32mol)；Slowly rise
Temperature maintains 1 hour to 80 DEG C, after filtering, toluene 70mL is added, washed once；Add toluene 60mL, TiCl440mL, heating
It to 110 DEG C, maintains 2 hours, filtering；Same operation is repeated 1 times, and is added toluene 60mL and is washed 5 minutes at 110 DEG C, is filtered
After add hexane 60mL and washed twice at 68 DEG C, 5 minutes every time, add under hexane 60mL room temperature and wash twice, every time 5
Minute, obtain solid main catalyst component.
Embodiment 2
It is same as Example 1, only 2,4- pentanediol is substituted with compound 3- methyl -2,4- pentanediol.
Embodiment 3
It is same as Example 1, compound 3 is only used, 5- heptandiol substitutes 2,4- pentanediol.
Embodiment 4
Same as Example 1, only 2,4- pentanediol dosage is 0.0125mol, and chlorobenzoyl chloride dosage is 0.025mol.
Embodiment 5
Same as Example 1, only 2,4- pentanediol dosage is 0.05mol, and chlorobenzoyl chloride dosage is 0.1mol.
Embodiment 6
Same as Example 1, only chlorobenzoyl chloride dosage is 0.55mol.
Embodiment 7
Same as Example 1, only chlorobenzoyl chloride dosage is 0.06mol.
Embodiment 8
It is same as Example 1, only with the chlorobenzoyl chloride in m-chlorobenzoyl chloride alternate embodiment 1.
Embodiment 9
It is same as Example 1, only chlorobenzoyl chloride is replaced with tert-butyl acyl chlorides.
Embodiment 10
It is same as Example 1, only 2,4- pentanediol is replaced with 2- ethyl -2,4- pentanediol.
Embodiment 11
It is same as Example 1, only 2,4- pentanediol is replaced with 2- ethyl -1,3- pentanediol.
Embodiment 12
Same as Example 1, only 2,4- pentanediol dosage is 0.03mol, and chlorobenzoyl chloride dosage is 0.06mol.
Embodiment 13
Same as Example 1, only 2,4- pentanediol dosage is 0.0125mol.
Embodiment 14
Same as Example 1, only chlorobenzoyl chloride dosage is 0.065mol.
Embodiment 15
Same as Example 1, only chlorobenzoyl chloride dosage is 0.075mol.
Embodiment 16
Same as Example 1, only chlorobenzoyl chloride dosage is 0.10mol.
Embodiment 17
It is same as Example 1, toluene 46mL is only added, and 35mLTiCl is added dropwise in 1 hour4With mixing for 50mL toluene
Close solution.
Embodiment 18
Same as Example 1, only diethoxy magnesium replaces magnesium chloride.
Embodiment 19
Same as Example 1, only 2,4- pentanediol dosage is 0.06mol, and chlorobenzoyl chloride dosage is 0.12mol.
Embodiment 20
It is same as Example 1, only 2,4- pentanediol is replaced with 4- methyl -4- ethyl -3,5- heptandiol.
Embodiment 21
It is same as Example 1, only 2,4- pentanediol is replaced with 4- methyl -4- butyl -3,5- heptandiol.
Comparative example 1
It is same as Example 1, only 2,4- pentanediol is replaced with ethyl alcohol.
Comparative example 2
It is same as Example 1, only chlorobenzoyl chloride is replaced with o-phthaloyl chloride.
Comparative example 3
It is same as Example 1, only 2,4- pentanediol is replaced with 1,4-butanediol.
Comparative example 4
It is same as Example 1, only 0.05mol chlorobenzoyl chloride is replaced with 0.025mol o-phthaloyl chloride.
Propylene polymerization experiment
Above-mentioned resulting catalytic component is subjected to propylene polymerization respectively.Propylene polymerization program are as follows: volume is the stainless of 5L
AlEt is added after gaseous propylene is sufficiently displaced from steel reaction kettle32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS)
0.1mmol adds above-mentioned ingredient of solid catalyst 8-10mg and 1.2L hydrogen, is passed through liquid propene 2.3L, is warming up to 70
DEG C, maintain this temperature 1 hour.Cooling, pressure release obtain PP powder.Polymerization result is listed in table 1.
Table 1
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 (10)
1. a kind of catalyst component for olefin, it includes the reaction product of following components or by the reaction product of following components
Composition: (1) magnesium compound；(2) lewis base compound；(3) general formula is R2The acetyl halide compound of COX, wherein R2For hydrogen, replace
Or unsubstituted C1-C10 alkyl or epoxy group, X are halogen；(4) contain the compound of two hydroxyl groups；(5) oxygen-containing to contain titanizing
Close object；(6) titanium tetrahalide.
2. catalytic component according to claim 1, which is characterized in that the magnesium compound is formula M gR1 nX2-nIt is shown
Compound or its hydrate or alcohol adduct, wherein X is halogen, R1It is excellent for C1-C20 alkyl, alkoxy or halogenated alkoxy
It is selected as the alkyl, alkoxy or halogenated alkoxy of C1-C5,0≤n≤2, the magnesium compound is preferably selected from magnesium dihalide, dihalo-
Change one of alcohol adduct and alkoxyl magnesium of magnesium or a variety of；And/or
The lewis base compound is organic phosphorus lewis base compound, preferably phosphate, more preferably trialkylphosphate
Ester, it is preferable that trialkylphosphate is by shown in formula (I):
Wherein, R7-R9It is each independently selected from methyl, ethyl, C3-C10 linear or branched alkyl group group.
3. catalytic component according to claim 1 or 2, which is characterized in that R2For the substituted or unsubstituted phenyl of halogen,
C1-C4 alkyl or furyl, it is preferable that the acetyl halide compound is selected from chloroacetic chloride, propionyl chloride, isopropyl acyl chlorides, butyl chloride, isobutyl
One of acyl chlorides, chlorobenzoyl chloride and furoyl chloride are a variety of.
4. catalytic component according to any one of claim 1-3, which is characterized in that described to contain two hydroxyl groups
Shown in formula (II):
Wherein, R1-R6Group is identical or different, is independently selected from H, halogen, the alkyl of C1-C20 linear chain or branched chain, C3-
C20 naphthenic base, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkylene or fused ring aryl, R1-R6No
It can simultaneously be hydrogen；Preferably, R1、R2In at least one be not H；The compound for containing two hydroxyl groups is preferably selected from 1,3-
Diphenyl -2- methyl-1,3-propanediol, 1,3- diphenyl -2,2-dimethyl-1,3-propanediol, 1,3- di-t-butyl -2- second
Base -1,3-PD dibenzoate, 1,3- diisopropyl -1,3-PD, 1- phenyl -2- amino -1,3 propylene glycol, 1- benzene
Base -2- methyl-1,3- butanediol, 1- furans -2- methyl-1,3- butanediol, 4,4,4- tri- fluoro- 1- (2- naphthalene) -1,3-BDOs,
2,4- pentanediols, 3- methyl -2,4- pentanediol, 3- ethyl -2,4- pentanediol, 3- propyl -2,4- pentanediol, 3- butyl -2,4-
Pentanediol, 3,3- dimethyl -2,4- pentanediol, (2S, 4S)-(+) -2,4- pentanediol, (2R, 4R)-(+) -2,4- pentanediol, 1,
3- pentanediol, 2- methyl-1,3- pentanediol, 2- ethyl -1,3- pentanediol, 2- butyl -1,3- pentanediol, dimethyl -1 2,2-,
3- pentanediol, 2,2,4- trimethyl -1,3- pentanediol of 2- allyl -1,3- pentanediol, 1- trifluoromethyl -3- methyl -2,4- penta
Glycol, 3- methyl -3- butyl -2,4- pentanediol, 2- ethyl -1,3- hexylene glycol, 2- propyl -1,3- hexylene glycol, 2- butyl -1,3-
Hexylene glycol, 4- ethyl -1,3- hexylene glycol, 4- methyl-1,3- hexylene glycol, 3- methyl-1,3- hexylene glycol, 3- ethyl -1,3- oneself two
Alcohol, 2,2,4,6,6- pentamethyl -3,5- hexylene glycols, 6- heptene -2,4- heptandiol, 2- methyl -6- heptene -2,4- heptandiol ester,
3- methyl -6- heptene -2,4- heptandiol, 4- methyl -6- heptene -2,4- heptandiol, 5- methyl -6- heptene -2,4- heptandiol, 6-
Methyl -6- heptene -2,4- heptandiol, 3- ethyl -6- heptene -2,4- heptandiol, 4- ethyl -6- heptene -2,4- heptandiol, 5- second
Base -6- heptene -2,4- heptandiol, 6- ethyl -6- heptene -2,4- heptandiol, 3- propyl -6- heptene -2,4- heptandiol, 4- third
Base -6- heptene -2,4- heptandiol, 5- propyl -6- heptene -2,4- heptandiol, 6- propyl -6- heptene -2,4- heptandiol, 3- fourth
Base -6- heptene -2,4- heptandiol, 4- butyl -6- heptene -2,4- heptandiol, 5- butyl -6- heptene -2,4- heptandiol, 6- fourth
Base -6- heptene -2,4- heptandiol, 3,5- dimethyl -6- heptene -2,4- heptandiol, 3,5- diethyl -6- heptene -2,4- heptan two
Alcohol, 3,5- dipropyl -6- heptene -2,4- heptandiol, 3,5- dibutyl -6- heptene -2,4- heptandiol ester, 3,3- dimethyl -6-
Heptene -2,4- heptandiol, 3,3- diethyl -6- heptene -2,4- heptandiol, 3,3- dipropyl -6- heptene -2,4- heptandiol, 3,
3- dibutyl -6- heptene -2,4- heptandiol, 3,5- heptandiol, 2- methyl -3,5- heptandiol, 3- methyl -3,5- heptandiol, 4-
Methyl -3,5- heptandiol, 5- methyl -3,5- heptandiol, 6- methyl -3,5- heptandiol, 3- ethyl -3,5- heptandiol, 4- ethyl -
3,5- heptandiols, 5- ethyl -3,5- heptandiol, 3- propyl -3,5- heptandiol, 4- propyl -3,5- heptandiol, 3- butyl -3,5-
Heptandiol, 2,3- dimethyl -3,5- heptandiol, 2,4- dimethyl -3,5- heptandiol, 2,5- dimethyl -3,5- heptandiol, 2,6-
Dimethyl -3,5- heptandiol, 3,3- dimethyl -3,5- heptandiol, 4,4- dimethyl -3,5- heptandiol, 6,6- dimethyl -3,5-
Heptandiol, 2,6- dimethyl -3,5- heptandiol, 3,4- dimethyl -3,5- heptandiol, 3,5- dimethyl -3,5- heptandiol, 3,6-
Dimethyl -3,5- heptandiol, 4,5- dimethyl -3,5- heptandiol, 4,6- dimethyl -3,5- heptandiol, 4,4- dimethyl -3,5-
Heptandiol, 6,6- dimethyl -3,5- heptandiol, 2- methyl -3- ethyl -3,5- heptandiol, 2- methyl -4- ethyl -3,5- heptan two
Alcohol, 2- methyl -5- ethyl -3,5- heptandiol, 3- methyl -3- ethyl -3,5- heptandiol, 3- methyl -4- ethyl -3,5- heptan two
Alcohol, 3- methyl -5- ethyl -3,5- heptandiol, 4- methyl -3- ethyl -3,5- heptandiol, 4- methyl -4- ethyl -3,5- heptan two
Alcohol, 4- methyl -5- ethyl -3,5- heptandiol, 2- methyl -3- propyl -3,5- heptandiol, 2- methyl -4- propyl -3,5- heptan two
Alcohol, 2- methyl -5- propyl -3,5- heptandiol, 3- methyl -3- propyl -3,5- heptandiol, 3- methyl -4- propyl -3,5- heptan two
Alcohol, 3- methyl -5- propyl -3,5- heptandiol, 4- methyl -3- propyl -3,5- heptandiol, 4- methyl -4- propyl -3,5- heptan two
Alcohol, 4- methyl -5- propyl -3,5- heptandiol, 6- methyl -2,4- heptandiol, 6- heptene -2,4- heptandiol, dimethyl -2 3,6-,
4- heptandiol, 2,2,6,6- tetramethyl -3,5- heptandiols, 4- methyl -3,5- ethohexadiol, 4- ethyl -3,5- ethohexadiol, 4- third
Base -3,5- ethohexadiol, 5- propyl -3,5- ethohexadiol, 4- butyl -3,5- ethohexadiol, 4,4- dimethyl -3,5- ethohexadiol, 4,4-
Diethyl -3,5- ethohexadiol, 4,4- dipropyl -3,5- ethohexadiol, 4- methyl -4- ethyl -3,5- ethohexadiol, 3- phenyl -3,5-
Ethohexadiol, 2- methyl -3- ethyl -3,5- ethohexadiol, 2- methyl -4- ethyl -3,5- ethohexadiol, 2- methyl -5- ethyl -3,5- are pungent
Glycol, 2- methyl -6- ethyl -3,5- ethohexadiol, 5- methyl -4,6 nonanediol, 5- ethyl -4,6 nonanediol, 5- propyl -4,6 nonyl
Glycol, 5- butyl -4,6 nonanediol, 5,5- dimethyl -4,6 nonanediol, 5,5- diethyl -4,6 nonanediol, dipropyl -4 5,5-,
6 nonanediols, 5,5- dibutyl -4,6 nonanediol, 5- methyl -4- ethyl -4,6 nonanediol, 5- phenyl -4,6 nonanediol, 4,6- nonyl
One of glycol, 4- butyl -3,5- heptandiol and 3- methyl -3- butyl -2,4- pentanediol are a variety of.
5. catalytic component described in any one of -4 according to claim 1, which is characterized in that the oxygen-containing titanium-containing compound is
General formula Ti (OR ")pX4-pCompound represented, wherein X is halogen, and R " is C1-C20 alkyl, preferably C1-C4 alkyl, 0 < p
≤ 4, the oxygen-containing titanium-containing compound is preferably selected from four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen
One of one ethanolato-titanium of base titanium and trichlorine is a variety of；And/or
The titanium tetrahalide is one of titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide and titanium tetra iodide or a variety of.
6. catalytic component according to any one of claims 1-5, which is characterized in that in the catalytic component, respectively
For the feeding quantity of component in terms of every mole of magnesium compound, lewis base compound is 0.01-20 moles, preferably 0.2-12 moles；With/
Or, the compound containing two hydroxyl groups is 0.1-10 moles, preferably 0.25-1 moles；And/or oxygen-containing titanium-containing compound is
0.1-10 moles, preferably 1.0-5 moles；And/or titanium tetrahalide is 1-5 moles；And/or acetyl halide compound 0.1-10, it is excellent
Select 0.5-4.0 moles, more preferable 1-2 moles, it is preferable that the molar ratio of acetyl halide compound and the compound containing two hydroxyl groups
For 2-3, preferably 2.2-2.6.
7. the preparation method of catalytic component described in any one of claim 1-6, comprising the following steps:
(i) magnesium compound, lewis base compound, the compound containing two hydroxyl groups and oxygen-containing titanium-containing compound are contacted anti-
It answers, obtains haptoreaction product；It is preferred that catalytic temperature is 0-200 DEG C, more preferably 25-150 DEG C；
(ii) the haptoreaction product is mixed with acetyl halide compound, obtains mixture；It is preferred that being mixed at -30-150 DEG C
Obtain mixture；
(iii) mixture and titanium tetrahalide haptoreaction are obtained into solid precipitation, the as described catalytic component.
8. the method according to the description of claim 7 is characterized in that further including after obtaining the mixture in step (ii)
The mixture is warming up to 80-200 DEG C, obtains clear solution, is then carried out again step (iii).
9. a kind of catalyst for olefines polymerizing comprising:
(1) it is urged made from any one of the described in any item catalytic components of claim 1-7 or claim 7 or 8 the method
Agent component；
(2) alkyl aluminum compound；Preferably general formula AlR3 qX3-qShown in alkyl aluminum compound, R in formula3For hydrogen or C1-C20
Alkyl, X are halogen, 0 q≤3 <；
(3) optionally, external electron donor component, preferably general formula (R4)kSi(OR5)4-kCompound represented, 0≤k≤3 in formula,
R4And R5It is identical or different, R5For C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl and amino, R4Selected from halogen, hydrogen atom
And C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl or amino；
Preferably, catalytic component is in terms of titanium, alkyl aluminum compound in terms of aluminium, external electron donor component in terms of silicon, component (1),
Component (2), the molar ratio of component (3) are 1:5-1000:0-500；Preferably 1:25-100:25-100.
10. the application of catalyst described in claim 9 in olefin polymerization, wherein the alkene preferred formula CH2Shown in=CHR
Alkene, wherein R be hydrogen or C1-C12Alkyl or aryl group.
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