CN103923235B - Vanadium series catalyst, its preparation method and application - Google Patents
Vanadium series catalyst, its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of vanadium series catalyst, including major catalyst and co-catalyst, and the major catalyst is formed with the compound and electron donor of vanadium, or is formed with the complex and electron donor of vanadium；The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or VOCl3；The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta diketone class, 8-hydroxy-quinoline or oximes；The electron donor is the compound of mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound, the compound of formula (I) structure, the compound of formula (II) structure or formula (III) structure.The vanadium series catalyst strengthens the stability of water, air and oxygen.When for ethene, the copolymerization of propylene, reactivity is high, and the propylene content for being obtained is slightly higher, structure-controllable.
Description
Technical field
Catalyst field the present invention relates to be used to synthesize EP rubbers, more particularly to vanadium series catalyst, its preparation method
And application.
Background technology
EP rubbers is a kind of copolymer rubber with ethene and propylene as basic monomer.It can specifically be divided into binary second third
Rubber and ethylene propylene diene rubber.Compared with other rubber clones, EP rubbers has advantages below：First, double bond is free of in main chain,
It is fully saturated, resistance to ozone, ageing-resistant, chemicals-resistant and high temperature resistant；2nd, light specific gravity；3rd, excellent insulation performance；4th, can be
Highly oil-filled rubber clone.EP rubbers is one of most rising rubber types at present, from its commercially produce with
Come, its application field is constantly expanded, and has been widely used for automobile component, building materials, electric wire, heat-resistant rubber hose, senior sealing
Material, lube oil additive and the aspect such as polyolefin modified.
Production EP rubbers is more with vanadium sub-group compound as major catalyst both at home and abroad, with organo-aluminum compound and activation accelerator
It is co-catalyst.Wherein, it is VX as these vfanadium compound of major catalyst3,VX4,VOX3With VO (OR)3-nXn, X is halogen,
Predominantly chlorine atom, R is 6~12 alkyl of carbon, and n is the integer of 0-2.The catalyst VOCl commonly used in industry3It is by V2O5It is high
Warm chlorination is obtained, and largely the health of operating personnel is not only damaged using chlorine, and cause serious environmental pollution.The opposing party
Face, VOCl3Water very sensitive to water and micro can just be reacted, and generate a large amount of hydrogen chloride gas and five oxidations
The rufous dust of two vanadium, to human body and its harmful, limits the application of such catalyst.
The content of the invention
Present invention solves the technical problem that being to provide a kind of vanadium series catalyst and preparation method thereof, the vanadium series catalyst
Stability to water is strong, and catalysis activity is high.
The invention discloses a kind of vanadium series catalyst, including major catalyst and co-catalyst, it is characterised in that described to sponsor
Compound and the electron donor cooperation of agent vanadium are formed, or are formed with the complex and electron donor of vanadium；
The vfanadium compound is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or
VOCl3；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oxime
Class；The electron donor is mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound, formula (I)
The compound of the compound, the compound of formula (II) structure or formula (III) structure of structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkane virtue
Base；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~
C20 alkaryls.
Preferably, the R1、R2、R3、R4、R5And R6Be independently selected from the alkyl of C2~C10, C3~C10 cycloalkyl,
C6~C10 aryl or C7~C20 alkaryls.
The R7And R8It is the alkyl of C2~C6；R3、R4、R5And R6It is hydrogen.
Preferably, the compound of formula (I) structure is double (methoxyl methyl) -1,3- cyclopentadiene of 1,1-, the double (first of 1,1-
Oxygen methyl) -2,3,4,5- tetramethyl -1,3- cyclopentadiene, double (the methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- rings penta of 1,1-
Double (the methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- cyclopentadiene of diene, 1,1- or the double rings of (methoxyl methyl) -3,4- two of 1,1-
Amyl group -1,3- cyclopentadiene.
Preferably, the compound of formula (II) structure is 2- methyl -2- isopropyl -1,3- dimethoxy propanes, 2,2-
Diisobutyl -1,3- dimethoxy propanes, 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- benzhydryl -1,3- dimethoxies
Base propane, 2,2- double (2- cyclohexyl methyls) -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dibutoxies propane, 2,
2- diisobutyl -1,3- di ethyl propyl ethers, 2- isopentyl -2- isopropyl -1,3- dimethoxy propanes, 2,2,4- trimethyls -
1,3- dimethoxys pentane, 1,1 '-bi-methoxy hexahydrotoluene, 2,2 '-bis- (methoxyl methyl) norbornanes, 2- isopropyls-
2-3,7- dimethyl octyl -1,3- dimethoxy propanes, 2,2- diisopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- hexamethylenes
Base -1,3- dimethoxy propanes, 2- isopropyl -2- cyclopenta -1,3- dimethoxy propanes, 2,2- bicyclopentyl -1,3- diformazans
Epoxide propane, 2- heptyl -2- amyl group -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2- isopropyls
Base -2- isobutyl group -1,3- dimethoxy propanes or 2,2- dipropyl -1,3- dimethoxy propanes.
Preferably, the compound of formula (III) structure be double (methoxyl methyl) fluorenes of 9,9-, 9,9- double (methoxyl methyls)-
Double (the methoxyl methyl) -2,3,4,5,6,7- hexafluoros fluorenes of 2,3,6,7- tetramethyls fluorenes, 9,9-, double (the methoxyl methyl) -2,3- benzene of 9,9-
And double (the methoxyl methyl) -2,3,6,7- dibenzo fluorenes of fluorenes, 9,9-, double (the methoxyl methyl) -2,7- diisopropyls fluorenes of 9,9-, 9,9- are double
Double (the methoxyl methyl) -2,7- bicyclopentyls fluorenes of (methoxyl methyl) -1,8- dichloros fluorenes, 9,9-, double (the methoxyl methyl) -1,8- two of 9,9-
Double (the methoxyl methyl) -1,2,3,4- tetrahydrochysenes fluorenes of fluorine fluorenes, 9,9-, double (the methoxyl methyl) -1,2,3,4,5,6,7,8- octahydro fluorenes of 9,9-
Or double (the methoxyl methyl) -4- tert-butyl group fluorenes of 9,9-.
Preferably, the VOCl3The ratio between the molal quantity of middle vanadium and the molal quantity of electron donor are 1:1~1:10.
The invention discloses a kind of preparation method of the vanadium series catalyst described in above-mentioned technical proposal, comprise the following steps：
(A) vfanadium compound or vanadium complex and electron donor are well mixed in organic solvent, obtain major catalyst；
The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or
VOCl3；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oxime
Class；
(B) major catalyst and co-catalyst are mixed, obtains vanadium series catalyst；
The electron donor be mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound,
The compound of the compound, the compound of formula (II) structure or formula (III) structure of formula (I) structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkane virtue
Base；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~
C20 alkaryls.
Preferably, in the step (A), the temperature of the mixing is 30~70 DEG C.
The invention also discloses the vanadium series catalyst described in a kind of above-mentioned technical proposal or above-mentioned technical proposal methods described
The application of the vanadium series catalyst of preparation.
Compared with prior art, vanadium series catalyst of the invention, including major catalyst and co-catalyst, it is characterised in that
The major catalyst is formed with the compound of vanadium or the complex of vanadium and electron donor；The compound of described vanadium is V
(acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or VOCl3；The part of the complex of the vanadium
It is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oximes；The electron donor is mononuclear aromatics class
Compound, acrylic ester compound, methyl acrylic ester compound, the compound of formula (I) structure, the chemical combination of formula (II) structure
The compound of thing or formula (III) structure.The electronics pair of electron donor, can be coordinated with pentavalent vanadium, play protection pentavalent vanadium
Effect, the major catalyst after coordination strengthens the stability of water, air and oxygen.In the polymerization process for carrying out ethene, propylene, five
Valency vanadium plays main catalytic action, there is the complexation reaction between electron donor and vanadium, can stablize vanadium catalyst, and lifting is anti-
Should be active, effectively improve VOCl3It is low Deng activity under traditional vanadium catalyst high temperature, inactivate fast shortcoming.Further, since electron
The effect of body, can reduce the generation of ethylene propylene diene rubber gel in the course of the polymerization process, enhancing ethene and propylene random copolymerization
Ability, under same polymerizing condition, the propylene content for being obtained is slightly higher, structure-controllable.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of vanadium series catalyst, including major catalyst and co-catalyst, it is characterised in that institute
State major catalyst to be formed with the compound and electron donor of vanadium, or formed with the complex and electron donor of vanadium；
The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or
VOCl3；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oxime
Class；
The electron donor be mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound,
The compound of the compound, the compound of formula (II) structure or formula (III) structure of formula (I) structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkane virtue
Base；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~
C20 alkaryls.
In the present invention, the vanadium series catalyst includes major catalyst and co-catalyst, wherein, the major catalyst is by vanadium
Compound or vanadium complex and electron donor coordinate form.The electronics of the electron donor with pentavalent vanadium to that can match somebody with somebody
Position, plays a part of to protect pentavalent vanadium.The molal quantity of vanadium and rubbing for electron donor in the compound of the vanadium or the complex of vanadium
The ratio between your number is preferably 1:1~1:10, more preferably 1:1.05~1:8.
The electron donor be mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound,
The compound of the compound, the compound of formula (II) structure or formula (III) structure of formula (I) structure.The mononuclear aromatics class chemical combination
Thing is preferably benzene, toluene or styrene；The methyl acrylic ester compound is preferably methyl methacrylate (MMA) or first
Base Isooctyl acrylate monomer (EHMA).
In the compound of formula (I) structure, R1、R2And R3Can with identical or difference, be independently selected from C1~
The alkyl of C18, cycloalkyl, aryl or alkaryl, the preferably alkyl of C2~C10, C3~C10 cycloalkyl, C6~C10 aryl or
C7~C20 alkaryls；R1And R2It is asynchronously H, methyl or n-propyl.It is double that the compound of formula (I) structure is preferably 1,1-
Double (the methoxyl methyl) -2,3,4,5- tetramethyl -1,3- cyclopentadiene of (methoxyl methyl) -1,3- cyclopentadiene, 1,1-, 1,1- are double
Double (the methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- rings of (methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- cyclopentadiene, 1,1-
Pentadiene or double (the methoxyl methyl) -3,4- bicyclopentyl -1,3- cyclopentadiene of 1,1-.
In the compound of formula (II) structure, R1、R2、R3、R4、R5And R6Can be with identical or different, choosing independently
From hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkaryl, preferably the alkyl of C2~C10, C3~C10 cycloalkyl, C6~
C10 aryl or C7~C20 alkaryls；R1And R2It is asynchronously H, methyl or n-propyl；R7And R8Can be independent with identical or different
Selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~C20 alkaryls, preferably
The alkyl of Cl, F, C2~C15, C5~C15 cycloalkyl, C8~C15 aryl or C8~C15 alkaryls, more preferably C2~C6's
Alkyl.R1To R4One or more groups can bonded formation cyclic structure.R is preferably in the compound of formula (II) structure7With
R8It is the alkyl of C2~C6；R3、R4、R5And R6It is hydrogen.The compound of formula (II) structure is more preferably 2- methyl -2- isopropyls
Base -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- diphenyl -1,3- dimethoxys third
Alkane, 2,2- benzhydryl -1,3- dimethoxy propanes, 2,2- double (2- cyclohexyl methyls) -1,3- dimethoxy propanes, 2,2- bis-
Isobutyl group -1,3- dibutoxies propane, 2,2- diisobutyl -1,3- di ethyl propyl ethers, 2- isopentyl -2- isopropyls -1,3-
Dimethoxy propane, 2,2,4- trimethyl -1,3- dimethoxys pentane, 1,1 '-bi-methoxy hexahydrotoluene, 2,2 '-bis- (first
Oxygen methyl) norbornane, 2- isopropyl -2-3,7- dimethyl octyl -1,3- dimethoxy propanes, 2,2- diisopropyls -1,3- two
Methoxy propane, 2- isopropyl -2- cyclohexyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclopenta -1,3- dimethoxys
Propane, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2- heptyl -2- amyl group -1,3- dimethoxy propanes, the hexamethylenes of 2,2- bis-
Base -1,3- dimethoxy propanes, 2- isopropyl -2- isobutyl group -1,3- dimethoxy propanes or 2,2- dipropyl -1,3- dimethoxies
Base propane.
In the compound of formula (III) structure, R4And R5Be independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl,
The alkyl of aryl or alkaryl, preferably C2~C10, C3~C10 cycloalkyl, C6~C10 aryl or C7~C20 alkaryls；R7
It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~C20 alkaryls, preferably
It is the alkyl of Cl, F, C2~C15, C5~C15 cycloalkyl, C8~C15 aryl or C8~C15 alkaryls, more preferably C2~C6
Alkyl.The compound of formula (III) structure is preferably double (methoxyl methyl) fluorenes of 9,9-, double (methoxyl methyl) -2,3 of 9,9-,
Double (the methoxyl methyl) -2,3,4,5,6,7- hexafluoros fluorenes of 6,7- tetramethyls fluorenes, 9,9-, double (the methoxyl methyl) -2,3- benzfluorenes of 9,9-,
Double (the methoxyl methyl) -2,3,6,7- dibenzo fluorenes of 9,9-, double (the methoxyl methyl) -2,7- diisopropyls fluorenes of 9,9-, the double (methoxies of 9,9-
Methyl) -1,8- dichloros fluorenes, double (the methoxyl methyl) -2,7- bicyclopentyls fluorenes of 9,9-, double (the methoxyl methyl) -1,8- difluoros fluorenes of 9,9-,
Double (the methoxyl methyl) -1,2,3,4- tetrahydrochysenes fluorenes of 9,9-, double (the methoxyl methyl) -1,2,3,4,5,6,7,8- octahydros fluorenes of 9,9- or 9,9-
Double (methoxyl methyl) -4- tert-butyl group fluorenes.
The co-catalyst is commonly used in the art, including organo-aluminum compound and accelerative activator.Organic calorize
Compound is preferably one or more in the aluminium of ethylaluminum two, ethyl aluminum dichloride, aluminium diethyl monochloride and dichloro aluminium isobutyl,
One or two more preferably in ethyl aluminum dichloride and aluminium diethyl monochloride.Source of the present invention to the alkyl aluminum compound
Also it is not particularly limited, can be bought by market.The activation accelerator is preferably halogenated alkane or esters, more preferably trichlorine
Ethyl acetate, CH3Cl、CH2Cl2Or CHCl3.The present invention does not do especially limit for the usage ratio of major catalyst and co-catalyst
System, according to the conventional selection of those skilled in the art.
The invention discloses a kind of preparation method of the vanadium series catalyst described in above-mentioned technical proposal, comprise the following steps：
(A) complex and electron donor of the compound of vanadium or vanadium are well mixed in organic solvent, obtain main catalytic
Agent；
The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4Or
VOCl3；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oxime
Class；
(B) major catalyst and co-catalyst are mixed, obtains vanadium series catalyst；
The electron donor be mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound,
The compound of the compound, the compound of formula (II) structure or formula (III) structure of formula (I) structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkane virtue
Base；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~
C20 alkaryls.
In the present invention, the complex and electron donor of the compound of vanadium or vanadium are mixed in organic solvent first
It is even, obtain major catalyst.The ratio between molal quantity of the molal quantity of vanadium and electron donor in the compound of the vanadium or the complex of vanadium
Preferably 1:1~1:10, more preferably 1:1.05~1:8.The organic solvent is preferably the alkane or C6~C15 of C5~C10
Aromatic hydrocarbon, more preferably hexane, heptane, benzene or toluene.The temperature of the mixing is preferably 30~70 DEG C, more preferably 40~
60℃.The time of the mixing is preferably 20~40 minutes, more preferably 30~38 minutes.
After obtaining major catalyst, major catalyst and co-catalyst are mixed, obtain vanadium series catalyst.The co-catalyst is
Commonly used in the art, including organo-aluminum compound and accelerative activator.The organo-aluminum compound is preferably ethylaluminum two
One or more in aluminium, ethyl aluminum dichloride, aluminium diethyl monochloride and dichloro aluminium isobutyl, more preferably ethyl aluminum dichloride and
One or two in chlorodiethyl aluminium.The present invention is also not particularly limited to the source of the alkyl aluminum compound, Ke Yiyou
Buy in market.The activation accelerator is preferably halogenated alkane or esters, more preferably ethyl trichloroacetate, CH3Cl、CH2Cl2
Or CHCl3.The present invention is not particularly limited for major catalyst with the usage ratio of co-catalyst, according to those skilled in the art
Conventional selection.
The invention also discloses the vanadium series catalyst described in a kind of above-mentioned technical proposal or above-mentioned technical proposal methods described
The application of the vanadium series catalyst of preparation.The vanadium catalyst is applied to the synthesis of EPM and three hospital's EP rubbers
In.
For a further understanding of the present invention, with reference to vanadium series catalyst, its preparation side that embodiment is provided the present invention
Method and application are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
So that benzene does part as an example, be modified VOCl3The method of catalyst is as follows：In the ampere bottle for having replaced nitrogen, configuration
The good hexane solution 10ml containing 1mmol benzene, extracts the VOCl containing 1mmol3Solution, squeezes into above-mentioned ampere bottle, rocks
It is even, in case polymerization is used.
Embodiment 2
0.4g ethers 2 (double (the methoxyl methyl) -1,3- cyclopentadiene of 1,1-) of being weighed in glove box are put into and have replaced nitrogen
In ampere bottle, 1ml toluene is squeezed into by syringe, then reinject hexane solution 10ml, make ampere bottle closed with emulsion tube, most
The VOCl containing 1mmol is extracted afterwards3Solution, is squeezed into above-mentioned ampere bottle, and ampere bottle is placed on into 70 DEG C of water-baths of ultrasonator
In, 30min, shaken well are kept, in case polymerization is used.
Embodiment 3
In the ampere bottle for having replaced nitrogen, 1ml styrene is squeezed into by syringe, then reinject hexane solution
10ml, makes ampere bottle closed with emulsion tube, finally extracts the VOCl containing 1mmol3Solution, squeezes into above-mentioned ampere bottle and is put into 30 DEG C
30min, shaken well are kept in water-bath, in case polymerization is used.
Embodiment 4~11
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；Sequentially add 0.1mmol implementations
The method of example 1 is modified different vanadium complexes, the aluminium (Al of 4.0mmol ethylaluminums two of preparation2(C2H5)3Cl3), 0.6mmol trichlorines
Ethyl acetate (ETCA), hexane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure exists
0.4MPa, stirring, 30min is reacted at 20 DEG C, after polymerization terminates, the salt of mass percent 5% is added in polymerizate
Acid-ethanol solution, and washed with ethanol, then obtain EPM under vacuo in drying again.Specific test data is shown in
Table 1.
The modified ligand that embodiment 4~11 is used respectively benzene, toluene, styrene, (i.e. double (the methoxy first of 9,9- of ether 1
Base) fluorenes), ether 2 (i.e. 1,1- double (methoxyl methyl) -1,3- cyclopentadiene), (i.e. double (the methoxyl methyl) -9,10- dihydros of 9,9- of ether 3
Change anthracene), MMA, EHMA.
Comparative example 1
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；0.1mmol is sequentially added not add
Modified VOCl3Catalyst, the aluminium (Al of 4.0mmol ethylaluminums two2(C2H5)3Cl3), 0.6mmol ethyl trichloroacetates
(ETCA), hexane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure is stirred in 0.4MPa
Mix, 30min is reacted at 20 DEG C, after polymerization terminates, add the hydrochloric acid-ethanol of mass percent 5% molten in polymerizate
Liquid, and washed with ethanol, then obtain EPM under vacuo in drying again.Specific test data is shown in Table 1.
The embodiment 4~11 of table 1 and comparative example 1 are compared using the product property that different catalysts are obtained
Embodiment 12~14
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；Sequentially add 0.1mmol implementations
The method of example 1 is using ether 1 compound modified vanadium complex, 4.0mmol aluminium diethyl monochlorides (Al (C2H5)2Cl), 0.6mmol tri-
Ethyl chloroacetate (ETCA), hexane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure exists
0.4MPa, stirring, reacts 30min at 30 DEG C, 40 DEG C, 50 DEG C respectively, after polymerization terminates, quality is added in polymerizate
Hydrochloric acid-the ethanol solution of percentage 5%, and washed with ethanol, then obtain EPM under vacuo in drying again.
Specific test data is shown in Table 2.
Comparative example 2~4
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；Sequentially add 0.1mmol
VOCl3, 4.0mmol aluminium diethyl monochlorides (Al (C2H5)2Cl), 0.6mmol ethyl trichloroacetates (ETCA), hexane 300ml；It is logical
It is 1 to enter ethene, propylene molar ratio：2 mixed gas, control polymerization pressure in 0.4MPa, stirring, respectively 30 DEG C, 40 DEG C, 50
30min is reacted at DEG C, after polymerization terminates, the hydrochloric acid-ethanol solution of mass percent 5% is added in polymerizate, be used in combination
Ethanol is washed, and then obtains EPM under vacuo in drying again.Specific test data is shown in Table 2.
The embodiment 12~14 of table 2 and comparative example 2~4 are compared using the product property that different catalysts are obtained
Embodiment 15~18
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；Sequentially add 0.1mmol implementations
The method of example 1 is using ether 1 compound modified vanadium complex and VOCl3Compound contrast, aluminium diethyl monochloride (Al (C2H5)2Cl)、
0.6mmol ethyl trichloroacetates (ETCA), hexane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control is poly-
In 0.4MPa, 30min is reacted in stirring to resultant pressure at 20 DEG C, the consumption of added alkyl aluminum be followed successively by 1.0mmol, 2.0mmol,
3.0mmol、6.0mmol、8.0mmol.After polymerization terminates, the hydrochloric acid-second of mass percent 5% is added in polymerizate
Alcoholic solution, and washed with ethanol, then obtain EPM under vacuo in drying again.Specific test data is shown in Table 3.
Comparative example 5~8
The reactor used by polymerization is installed, seal is kept, with nitrogen displacement 2-3 times；Sequentially add
0.1mmolVOCl3Compound contrast, aluminium diethyl monochloride (Al (C2H5)2Cl), 0.6mmol ethyl trichloroacetates (ETCA), oneself
Alkane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure is in 0.4MPa, stirring, at 20 DEG C
Reaction 30min, the consumption of added alkyl aluminum is followed successively by 1.0mmol, 2.0mmol, 3.0mmol, 6.0mmol, 8.0mmol.Poly-
After conjunction terminates, the hydrochloric acid-ethanol solution of mass percent 5% is added in polymerizate, and washed with ethanol, then existed again
In drying under vacuum, EPM is obtained.Specific test data is shown in Table 3.
The embodiment 15~18 of table 3 and comparative example 5~8 are compared using the product property that different catalysts are obtained
Embodiment 19~23
Enter 0.1mmol and use the method for embodiment 1 using ether 1 compound modified vanadium complex and VOCl3Compound is contrasted,
4.0mmol Dichlorodiethyls aluminium (Al (C2H5)2Cl2), 0.6mmol ethyl trichloroacetates (ETCA), 2ml ENB, hexane 300ml；
It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure reacts at a certain temperature in 0.4MPa, stirring
30min, after polymerization terminates, adds the hydrochloric acid-ethanol solution of mass percent 5%, and washed with ethanol in polymerizate
Wash, then obtain ethylene propylene diene rubber under vacuo in drying again.Concrete outcome is shown in Table four
The reaction temperature of embodiment 19~23 and comparative example 9~13 is respectively 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C and 60 DEG C.
Comparative example 9~13
Enter 0.1mmolVOCl3, 4.0mmol Dichlorodiethyls aluminium (Al (C2H5)2Cl2), 0.6mmol ethyl trichloroacetates
(ETCA), 2ml ENB, hexane 300ml；It is 1 to be passed through ethene, propylene molar ratio：2 mixed gas, control polymerization pressure exists
0.4MPa, stirring, reacts 30min at a certain temperature, after polymerization terminates, mass percent 5% is added in polymerizate
Hydrochloric acid-ethanol solution, and washed with ethanol, then obtain ethylene propylene diene rubber under vacuo in drying again.Concrete outcome
It is shown in Table 4.
The embodiment 19~23 of table 4 and comparative example 9~13 are compared using the product property that different catalysts are obtained
Embodiment 24~30
VO (P are respectively adopted204)2、V(acac)3, aliphatic alcohols vanadium complex VOCl33IOOH, amine vanadium complex
VO2ClTOA, phosphoric acid ester vanadium complex VO2The vanadium complex VO (OH) (8HQ) of Cl3TBP, 8-hydroxy-quinoline2, α-benzene
The vanadium complex VO (OH) (DPhOx) of acyloin oxime2As vfanadium compound, carried out using the hexane solution containing 1mmol toluene
The vanadium catalyst of catalyst complex generation, carries out polymerisation under polymerizing condition below：(1) 0.5L reactors；(2) vanadium system urges
Agent：0.10mmol；(3)Al2(C2H5)3Cl3：3.0mmol；(4)ETCA：0.60mmol；(5) 300ml solvent hexanes；(6) mix
Ethene, propylene molar ratio are 1 in conjunction gas：2, pressure：4MPa, 15min is reacted at 20 DEG C.After polymerization terminates, in polymerization
Hydrochloric acid-the ethanol solution of mass percent 5% is added in product, and is washed with ethanol, then obtained under vacuo in drying again
To ethylene propylene diene rubber.Concrete outcome is shown in Table 5.
The Characterization of The Products result that 5 embodiment of table 24~30 is obtained using different catalysts
Comparative example 14~20
VO (P are respectively adopted204)2、V(acac)3, aliphatic alcohols vanadium complex VOCl33IOOH, amine vanadium complex
VO2ClTOA, phosphoric acid ester vanadium complex VO2The vanadium complex VO (OH) (8HQ) of Cl3TBP, 8-hydroxy-quinoline2, α-benzene
The vanadium complex VO (OH) (DPhOx) of acyloin oxime2As vfanadium compound, polymerisation is carried out under polymerizing condition below：(1)
0.5L reactors；(2) vanadium series catalyst：0.10mmol；(3)Al2(C2H5)3Cl3：3.0mmol；(4)ETCA：0.60mmol；(5)
300ml solvent hexanes；(6) ethene, propylene molar ratio are 1 in mixed gas：2, pressure：4MPa, 15min is reacted at 20 DEG C.
After polymerization terminates, the hydrochloric acid-ethanol solution of mass percent 5% is added in polymerizate, and washed with ethanol, then
Again under vacuo in drying, ethylene propylene diene rubber is obtained.Concrete outcome is shown in Table 6.
The comparative example 14~20 of table 6 is compared using the product property that different catalysts are obtained
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (10)
1. a kind of vanadium series catalyst, is made up of major catalyst and co-catalyst, it is characterised in that the major catalyst by vanadium change
Compound and electron donor cooperation are formed；
The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4、VOCl3Or
The complex of vanadium；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oximes；
The electron donor is mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound, formula
(I) compound of the compound of structure, the compound of formula (II) structure or formula (III) structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkaryl；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~C20 alkane
Aryl；
The co-catalyst includes organo-aluminum compound and accelerative activator, and the accelerative activator is halogenated alkane or lipid.
2. vanadium series catalyst according to claim 1, it is characterised in that the R1、R2、R3、R4、R5And R6Independently
Alkyl, C3~C10 cycloalkyl, C6~C10 aryl or C7~C20 alkaryls selected from C2~C10.
3. vanadium series catalyst according to claim 1, it is characterised in that the R7And R8It is the alkyl of C2~C6；R3、R4、
R5And R6It is hydrogen.
4. vanadium series catalyst according to claim 1, it is characterised in that the compound of formula (I) structure is 1,1- double
Double (the methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- rings of (methoxyl methyl) -2,3,4,5- tetramethyl -1,3- cyclopentadiene, 1,1-
Pentadiene or double (the methoxyl methyl) -2,3,4,5- tetraphenyl -1,3- cyclopentadiene of 1,1-.
5. vanadium series catalyst according to claim 1, it is characterised in that the compound of formula (II) structure is 2- first
Base -2- isopropyl -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- diphenyl -1,3- two
Double (2- the cyclohexyl methyls) -1,3- dimethoxys third of methoxy propane, 2,2- benzhydryl -1,3- dimethoxy propanes, 2,2-
Alkane, 2,2- diisobutyl -1,3- dibutoxies propane, 2,2- diisobutyl -1,3- di ethyl propyl ethers, -2- is different for 2- isopentyl
Propyl group -1,3- dimethoxy propanes, 2,2,4- trimethyl -1,3- dimethoxys pentane, 2- isopropyl -2-3,7- dimethyl octyls -
1,3- dimethoxy propanes, 2,2- diisopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclohexyl -1,3- dimethoxys
Propane, 2- isopropyl -2- cyclopenta -1,3- dimethoxy propanes, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2- heptyl -
2- amyl group -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2- isopropyl -2- isobutyl groups -1,3-
Dimethoxy propane or 2,2- dipropyl -1,3- dimethoxy propanes.
6. vanadium series catalyst according to claim 1, it is characterised in that the compound of formula (III) structure is 9,9-
Double (the methoxyl methyl) -2,3,6,7- tetramethyls fluorenes of double (methoxyl methyl) fluorenes, 9,9-, double (methoxyl methyl) -2,3,4,5,6 of 9,9-,
Double (the methoxyl methyl) -2,7- diisopropyls fluorenes of 7- hexafluoros fluorenes, 9,9-, double (the methoxyl methyl) -2,7- bicyclopentyls fluorenes or 9 of 9,9-,
Double (the methoxyl methyl) -4- tert-butyl group fluorenes of 9-.
7. vanadium series catalyst according to claim 1, it is characterised in that in the compound of the vanadium molal quantity of vanadium with give
The ratio between molal quantity of electron is 1:1~1:10.
8. a kind of preparation method of the vanadium series catalyst described in claim 1, comprises the following steps：
(A) compound and electron donor of vanadium are well mixed in organic solvent, obtain major catalyst；
The compound of the vanadium is V (acac)3、VO(OR)3、VO(acac)3、VO(OR)2Cl、VO(OR)Cl2、VCl4、VOCl3Or
The complex of vanadium；
The part of the complex of the vanadium is aliphatic alcohols, amine, phosphoric acid ester, beta-diketon class, 8-hydroxy-quinoline or oximes；
(B) major catalyst and co-catalyst are mixed, obtains vanadium series catalyst；
The co-catalyst includes organo-aluminum compound and accelerative activator, and the accelerative activator is halogenated alkane or lipid；
The electron donor is mononuclear aromatics class compound, acrylic ester compound, methyl acrylic ester compound, formula
(I) compound of the compound of structure, the compound of formula (II) structure or formula (III) structure；
Wherein, R1、R2、R3、R4、R5And R6It is independently selected from hydrogen, the alkyl of C1~C18, cycloalkyl, aryl or alkaryl；
R2And R1It is asynchronously H, methyl or n-propyl；
R7And R8It is independent selected from hydrogen, halogen, the alkyl of C1~C20, C3~C20 cycloalkyl, C7~C20 aryl or C7~C20 alkane
Aryl.
9. preparation method according to claim 8, it is characterised in that in the step (A), the temperature of the mixing is 30
~70 DEG C.
10. vanadium system prepared by vanadium series catalyst or claim 8 methods described described in a kind of claim 1~7 any one
Application of the catalyst in EP rubbers is synthesized.
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| FR2541683B1 (en) * | 1983-02-28 | 1986-05-09 | Ato Chimie | PROCESS FOR THE PREPARATION OF AN ACTIVE HYDROCARBON SOLID USEFUL FOR POLYMERIZING OLEFINS, AND PROCESS FOR THE SYNTHESIS OF AN OLEFINIC POLYMER OR COPOLYMER USING SAID ACTIVE HYDROCARBON SOLID AS A SYSTEM |
| US5002916A (en) * | 1990-03-02 | 1991-03-26 | Exxon Chemical Patents Inc. | Silica supported vanadium carboxylate catalysts |
| IT1303771B1 (en) * | 1998-11-19 | 2001-02-23 | Enichem Spa | VANADIUM CATALYSTS, THEIR PREPARATION AND USE IN THE (CO) POLYMERIZATION OF ALFA-OLEFINE. |
| JP2005519172A (en) * | 2002-03-08 | 2005-06-30 | バセル ポリオレフィン イタリア エス．ピー．エー． | Olefin polymerization method |
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