CN100424099C - Catalyst active component, its preparation and catalyst containing it - Google Patents
Catalyst active component, its preparation and catalyst containing it Download PDFInfo
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- CN100424099C CN100424099C CNB200510105626XA CN200510105626A CN100424099C CN 100424099 C CN100424099 C CN 100424099C CN B200510105626X A CNB200510105626X A CN B200510105626XA CN 200510105626 A CN200510105626 A CN 200510105626A CN 100424099 C CN100424099 C CN 100424099C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F10/02—Ethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst active ingredient, its production and catalyst containing it are disclosed. The ingredient consists of magnesium 12.0-18.0 proportion, titanium 4.0-8.0 proportion, alkoxy 1.1-11.0 proportion, silicon 0.5-2.5 and halogen 55.0-75.0 proportion. The process is carried out by preparing magnesium alcoholate slurry, reacting it with electron, pre-carried titanium reacting and carried titanium reacting. It has higher catalytic activity and melt index, better physical mechanical and copolymer performances and hydrogen selectivity, and homogeneous grain distribution.
Description
Technical field
The present invention relates to a kind of catalyst activity component that is used for vinyl polymerization or copolymerization, and preparation method thereof, and the catalyzer that uses this active ingredient.
Background technology
Vinyl polymerization requires catalyzer that advantages of high catalytic activity is arranged usually, and has long-lastingly, simultaneously, also requires polymericular weight and controllable molecular weight distribution system, and has good form, so that process stabilizing improves running usefulness.At present, the Ziegler-Natta type polyethylene catalysts of industrial use is the loading type effective catalyst, and used carrier generally all is a magnesium chloride.Current, polyethylene catalysts has not only required active high, the more important thing is that to require copolymerization performance good, hydrogen transfers susceptibility good, and the poly bulk density of gained is wanted greatly, size-grade distribution is wanted evenly, fine powder is few, characteristics such as the physical and mechanical properties of polymkeric substance is good, this is the direction of following polyethylene catalysts development.This just requires catalyzer need have higher mechanical wear intensity and has good particle form.
CN1085569A discloses a kind of method for preparing titanium catalyst, and the pure and mild hydrocarbon solvent of six carbon atom forms magnesium solution to this method with containing at least with magnesium halide, and then makes solid mangnesium-aluminium complex with the organo-aluminium compound reaction.This solid magnesium aluminum compound is suspended in the hydrocarbon solvent, adds the solid titanium catalyst that tetravalent titanium compound promptly obtains being applicable to vinyl polymerization.
CN1050389A discloses a kind of ethylene rolymerization catalyst, and this catalyzer contains magnesium chloride and silicon-dioxide, and active ingredient is TiX
4, contain complexing agent ROH, electron donor ester and alkylaluminium cpd in addition.This Preparation of catalysts method is that magnesium chloride and silicon-dioxide are mixed, and adds an amount of alcohol again, and making alcohol/magnesium mol ratio is 3～25: 1, stirs down fully reaction, adds aluminum alkyls and ester again, removes unnecessary alcohol, obtains catalyst solid constituent.
Above preparation method neither be very effective, simultaneously, owing to need magnesium chloride load on expensive silica gel, so also to cause the catalyzer cost to improve.
Therefore, modifying magnesium chloride by appropriate chemical also is the research direction of current ethylene rolymerization catalyst to obtain the good catalyzer of form.
The method of chemically modified magnesium chloride has a lot, and CN1118488C has reported a kind of ethylene rolymerization catalyst, and this catalyzer contains halohydrocarbon, and active ingredient is TiX
4, by the modification of halohydrocarbon, the form of magnesium chloride is improved, and not only catalytic activity improves, and the bulk density of resin also obviously increases.But this catalyzer need carry out dealcoholysis with aluminum alkyls, and this certainly will increase the catalyzer cost, and increases environmental issue.
CN1112373C discloses a kind of ethylene rolymerization catalyst, and this catalyzer contains by adding electron donor to be modified catalyzer, and the form of magnesium chloride is improved, and catalytic activity improves, and the bulk density of resin also obviously increases.Though but the added tetraalkoxysilane electron donor of this patent has very big benefit to the form that keeps catalyzer form and resulting polymers, decomposes easily, its degree of decomposition all has a significant impact catalytic activity, polymer morphology and hydrogen response.
Summary of the invention
One of purpose of the present invention provides a kind of catalyst activity component that is used for vinyl polymerization or copolymerization.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyst activity component.
A further object of the present invention provides a kind of catalyzer that comprises above-mentioned active ingredient.
According to technical scheme of the present invention, the invention provides a kind of catalyst activity component that is used for vinyl polymerization or copolymerization, the gross weight based on the catalyst activity component of 100 weight parts comprises: the magnesium of 12.0～18.0 weight parts; 4.0 the titanium of～8.0 weight parts; 1.1 the alkoxyl group of～11.0 weight parts; 0.5 the silicon of～2.5 weight parts; And the halogen of 55.0～75.0 weight parts.
Above-mentioned catalyst according to the invention active ingredient, wherein based on the catalyst activity component gross weight of 100 weight parts, 1.0 the alkoxyl group of～6.0 weight parts is generated by organic alcohol, described organic alcohol be selected from comprise ethanol, propyl alcohol, butanols, hexanol, 2-methyl amyl alcohol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, and composition thereof group; And, catalyst activity component gross weight based on 100 weight parts, 0.1～2.0 weight part alkoxyl groups are for by decomposing the methoxyl group get to electronics in the preparation process, 0.0～3.0 weight part alkoxyl groups are for by decomposing the oxyethyl group get to electronics in the preparation process, according to the difference of employed electron donor, the electron donor that is added also may not produce oxyethyl group.
According to another technical scheme of the present invention, the present invention also provides the method for preparing above-mentioned catalyst activity component (method 1), said method comprising the steps of:
(1), the preparation of magnesium alcoholate slurries: under 50～180 ℃, in the inert hydrocarbon solvent that contains at least a C6～12 aliphatic hydrocarbons, magnesium compound and the organic alcohol reaction that contains 2～10 carbon atoms 0.5～3 hour, form homogeneous solution, wherein the mol ratio of magnesium/alcohol is 1: 0.5～6, and every mole of magnesium compound uses 1.8～5.0 liters of inert hydrocarbon solvents;
(2), magnesium alcoholate slurries and the electron donor of preparation reacted, wherein temperature of reaction is 20～100 ℃, based on every mole of magnesium compound, adds 0.05～1.0 mole electron donor;
(3), with titanium compound Ti (OR)
4-nX
nAdd and carry out the reaction of preload titanium in the reaction solution in (2), wherein temperature of reaction is-30～20 ℃, and X is a halogen, R is an alkyl, n is 0 or smaller or equal to 4 integer, adds 1.0～80.0 moles described titanium compound based on every mole of magnesium compound, adds titanium compound Ti (OR)
4-nX
nAfter remain on-10～0 ℃ 0.5～3 hour down;
(4), the adding of the reaction solution in (3) halohydrocarbon carries the titanium reaction, wherein in 1～4 hour, temperature of reaction is raised to 70～130 ℃, continue reaction 1～6 hour, the mole dosage of halohydrocarbon is 2～20 times of mole dosage of magnesium compound, and described halohydrocarbon is halogenated alkane or halo naphthenic hydrocarbon;
(5), filter reacting slurry in (4), with solvent wash, drying, obtain solid catalyst.
The method according to this invention, in step (1), preferred every mole of magnesium compound uses 1.8～5.0 liters, more preferably 2.0～3.0 liters of inert hydrocarbon solvents.
The method according to this invention, employed magnesium compound can comprise MgCl for one or more are selected from step (1)
2, MgBr
2, MgI
2, Mg (OEt)
2, Mg (OPr)
2, Mg (OBu)
2The compound of group.
The method according to this invention, the temperature of reaction of preferred steps (1) are that 70～120 ℃, the mol ratio of magnesium/alcohol are 1: 2～4.
The method according to this invention, the temperature of reaction of preferred steps (2) is 40～80 ℃.
Preferably, the method according to this invention, the described electron donor in the step (2) comprises having molecular formula (R for one or more are selected from
1) (R
2) (R
3) (R
4) Si, R
1, R
2, R
3, R
4Whole identical or R
1And R
2Identical or R
1, R
2And R
3Identical, and R
1, R
2, R
3, R
4In can be four alkoxyl groups or three alkoxyl groups or two alkoxyl groups, have an alkoxyl group at least.R
1, R
2, R
3, R
4Be selected from C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Alkoxyl group, C
6～C
9Aryloxy alkyl or C
1～C
12Haloalkyl, C
3～C
6Epoxy group(ing), more preferably described electron donor is selected from and comprises dimethyldimethoxysil,ne, dipropyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dibutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxydiphenylsilane, phenyltrimethoxysila,e, methyltrimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, dimethyldiethoxysilane, the dipropyl diethoxy silane, the di-isopropyl diethoxy silane, the diisobutyl diethoxy silane, the dibutyl diethoxy silane, the cyclohexyl methyl diethoxy silane, cyclohexyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl butyl diethoxy silane, cyclopentyl propyl group diethoxy silane, two cyclopentyl diethoxy silanes, the phenylbenzene diethoxy silane, phenyl triethoxysilane, Union carbide A-162, the butyl triethoxyl silane, the isobutyl-triethoxyl silane, γ-chloropropyl triethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane/and composition thereof group.
Preferably, the method according to this invention, in step (3), the temperature of preload titanium reaction for-20～20 ℃, more preferably-10～10 ℃, most preferably be-5 ℃.
The method according to this invention in step (3), preferably, adds 1.0～50.0 moles, more preferably 20.0～50.0 moles described titanium compound based on every mole of magnesium compound.
Preferably, the method according to this invention, the described titanium compound Ti (OR) in the step (3)
4-nX
nComprise in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium for being selected from, and composition thereof group.
Preferably, the method according to this invention in step (4), was raised to 90～110 ℃ with temperature of reaction in 2～3 hours, continued reaction 2～4 hours, and the mole dosage of halohydrocarbon is 5～20 times of mole dosage of magnesium compound.
Preferably, the method according to this invention, employed halohydrocarbon comprises 1 for being selected from the step (4), 2-ethylene dichloride, 1,3-propylene dichloride, 1,4-dichlorobutane, 1,6-dichloro hexane, a chlorine hexanaphthene, dichloro hexanaphthene, a chlorine pentamethylene, dichloro pentamethylene, and composition thereof group.
In addition, catalyst according to the invention active ingredient (method 2) preparation by the following method:
(1), the preparation of magnesium alcoholate slurries: except that every mole of magnesium compound use 0.2～1.0, preferred 0.5～0.8 liter of inert hydrocarbon solvent, identical with the step (1) of method 1;
(2), the reaction of magnesium alcoholate slurries and electron donor, identical with method 1;
(3), the reaction solution in (2) is slowly joined titanium compound Ti (OR)
4-nX
nCarry out the reaction of preload titanium in the solution, wherein temperature of reaction is-30～20 ℃, preferred-10～10 ℃, and X is a halogen, and R is an alkyl, n is 0 or smaller or equal to 4 integer, adds 10.0～80.0 moles, preferred 20.0～50.0 moles described titanium compound based on every mole of magnesium compound;
(4), the reaction solution in (3) adds and carry titanium behind the halohydrocarbon and react, and is identical with method 1;
(5), filter reacting slurry in (4), with solvent wash, drying, obtain solid catalyst.
Comparative approach 1 and 2 as can be seen, both differences mainly are: in method 1, consumption by increasing inert hydrocarbon solvent and in the reaction of preload titanium compound titanium solution being joined in the magnesium alcoholate slurries, like this, the consumption of titanium compound reduces greatly.Yet in method 2, the magnesium alcoholate slurries of step (2) preparation are added in the compound titanium solution, and the consumption of titanium compound is higher like this.Therefore, method 1 more preferably.
The present invention also provides a kind of catalyzer that is used for vinyl polymerization or copolymerization that comprises above-mentioned catalyst activity component and promotor, and described promotor is organo-aluminium compound R
3-nAlX
n, wherein X is a halogen, and R is C1～C6 alkyl, and n is 0～3 integer; The mol ratio of the titanium in aluminium in the promotor and the catalyst activity component is 20～800, preferred 50～300.
Above-mentioned catalyst according to the invention can be used to prepare the high-density high-strength polyethylene.And can be fit to existing vinyl polymerization slurry process and gas-phase process, can produce parallel connection or series connection trade mark polyethylene.
The present invention proposes a kind of catalyzer that is used for olefinic polymerization or copolymerization in order to overcome the shortcoming that exists in the above-mentioned prior art, introduces not labile electron donor, and electron donor and halohydrocarbon are incorporated in the middle of the titaniferous active ingredient simultaneously.Adopting in the method according to the invention increases quantity of solvent simultaneously, and the gained granules of catalyst is big like this; And, in the preparation process of catalyst activity component, only need a little amount of titanium compound; Need in the time of polymeric, not add halohydrocarbon to improve catalyst activity; Another characteristics of catalyzer of the present invention are that the hydrogen response that can improve catalyzer behind the introducing electron donor to a great extent is good; The present invention also has a characteristic to need not exactly to use the aluminum alkyls dealcoholysis, has reduced cost and has reduced environmental pollution.
Catalyzer of the present invention has overcome deficiency of the prior art, has following characteristics:
1) because the granules of catalyst of the present invention's preparation is big, and the settling velocity of granules of catalyst is fast, therefore washing easily makes Preparation of catalysts more simple, and preparation cycle shortens greatly, and this industrial production for catalyzer is very favourable.
2) the catalyzer hydrogen response height of the present invention's preparation, comparable similar catalyzer exceeds one times.
3) in catalyst preparation process, exempted and used the aluminum alkyls dealcoholysis, also reduced TiC1 simultaneously
4Consumption, thus pollution reduced to environment.
4) catalyzer of the present invention has good polymerization, and the polymerization efficiency of catalyzer is more than 50,000 times, and the particle form of polymkeric substance and bulk density also are better than prior art.
5) adding of electron donor can have dual mode, and a kind of is to add in reactions steps (2); The second way is to add a part of electron donor, preferred 90～110 ℃ when earlier temperature of reaction being controlled to 60～130 ℃; And then according to working as the other a part of electron donor of adding in the reactions steps (2).
6) in the prior art, halohydrocarbon be carry the titanium reaction finish after or be added into during in olefinic polymerization, yet, the present invention finds that halohydrocarbon can be added in a year titanium reaction process, also can after finishing, a year titanium reaction be added into, but in carrying the titanium reaction process, be added into, to improve catalytic activity, to increase the polymer stacks density effect more obvious, and operation is also more simple.
Catalyzer of the present invention has excellent copolymerization performance; this respect is better than prior art greatly; when adding a spot of comonomer; do not collect oligopolymer in the ethane; more for a long time, can collect small amounts of oligomer, and prior art can produce a large amount of low-molecular weight copolymers that can be dissolved in ethane usually at comonomer; gained copolymerized polymer particle form and bulk density also are better than prior art, and this has suitable importance for the exploitation of product innovation and the long-term operation of device.Catalyzer of the present invention is the catalytic activity height not only, copolymerization performance is good, and hydrogen response is very good, melting index will exceed more than one times than prior art resulting polymers, and good, the even particle distribution of the polyethylene product form that makes, the bulk density height, simultaneously, the physical and mechanical properties of polymkeric substance is good, and is especially excellent in cushion effect, can produce the high-density high-strength polyethylene.Because granules of catalyst form of the present invention is good, not only is fit to existing vinyl polymerization slurry process and can also be used for gas-phase process, and can produce parallel connection or series connection trade mark polyethylene.
Embodiment
Below by example in detail the present invention, should be expressly understood that form of the present invention as described herein only is illustrative, does not mean that restriction the present invention.Present invention includes all improvement in the claim scope.
Embodiment 1
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL isooctyl alcohol (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 15mmol dipropyl dimethoxy silane electron donor, continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 2～16
Except using diisopropyl dimethoxy silane respectively, second, isobutyl dimethoxy silane, butyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, dicyclopentyl dimethoxyl silane generation, dimethoxydiphenylsilane, phenyltrimethoxysila,e generation, methyltrimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane replaces outside the dipropyl dimethoxy silane, uses the method identical with embodiment 1 to prepare ingredient of solid catalyst.
Embodiment 17～49
Except that the consumption of employed electron donor and component are as shown in table 1, use the method identical to prepare ingredient of solid catalyst with embodiment 1.
Table 1
Embodiment 50
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL isooctyl alcohol (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 80 ℃, be cooled to 50 ℃ in adding the reaction of 5mmol tetraethoxysilane under this temperature again after 60 minutes, under this temperature, add 10mmol dipropyl dimethoxy silane electron donor, continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 51～61
Except that the consumption of employed electron donor and component are as shown in table 2, use the method identical to prepare ingredient of solid catalyst with embodiment 50.
Table 2
Embodiment 62
4.76 gram (0.05mol) MgCl
2, 30mL decane and 20mL isooctyl alcohol (0.125mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 15mmol dipropyl dimethoxy silane electron donor, continue reaction 60 minutes, be cooled to room temperature after.Slowly it is dripped at 150mLTiCl with 90 fens clock times down at-10 ℃
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 63～72
Except that the consumption of employed electron donor and component are as shown in table 3, use the method identical to prepare ingredient of solid catalyst with embodiment 62.
Table 3
Embodiment 73
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL isooctyl alcohol (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 10mmol dipropyl dimethoxy silane and 10.0mmol γ-r-chloropropyl trimethoxyl silane electron donor, continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 74～82
Except that the consumption of employed electron donor and component are as shown in table 4, use the method identical to prepare ingredient of solid catalyst with embodiment 73.
Table 4
Embodiment 83
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL butanols (0.2mol) (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 15mmol dipropyl dimethoxy silane and continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 84～91
Except that replacing the dipropyl dimethoxy silane with diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, γ-r-chloropropyl trimethoxyl silane respectively, use the method identical to prepare ingredient of solid catalyst with embodiment 83.
Embodiment 92
4.76 gram (0.05mol) MgCl
2, 100mL decane and 23.4mL isooctyl alcohol (0.15mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 15mmol dipropyl dimethoxy silane and continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 93～100
Except that replacing the dipropyl dimethoxy silane with diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, γ-r-chloropropyl trimethoxyl silane respectively, use the method identical to prepare ingredient of solid catalyst with embodiment 92.
Embodiment 101
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL isooctyl alcohol (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 1.5mmol γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane and 13.5mmol γ-r-chloropropyl trimethoxyl silane continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Embodiment 102
Except that the decane consumption changes into the 90mL, use the method identical to prepare ingredient of solid catalyst with embodiment 1.
Embodiment 103
Except that the decane consumption changes into the 250mL, use the method identical to prepare ingredient of solid catalyst with embodiment 1.
Embodiment 104～105
Remove a year titanium temperature and change 70 ℃, 120 ℃ respectively into; The temperature of reaction of magnesium alcoholate slurries and electron donor changes 40 ℃, 120 ℃ respectively into; The temperature of preload titanium reaction is respectively outside-10 ℃, 10 ℃, uses the method identical with embodiment 1 to prepare ingredient of solid catalyst.
Comparing embodiment 1
4.76 gram (0.05mol) MgCl
2, 100mL decane and 31mL isooctyl alcohol (0.2mol), be heated to 130 ℃ of reactions 180 minutes, be cooled to 50 ℃, under this temperature, add 15mmol tetraethoxysilane electron donor, continue reaction 60 minutes, be cooled to room temperature after.Following at 0 ℃ with 90 fens slow Dropwise 5 0mLTiCl of clock time
4In mixing solutions, dropwise the back and kept 0 ℃ of temperature following 60 minutes, add the 25mL chlorocyclohexane then and slowly be warming up to 110 ℃ with 120 fens clock times and reacted 120 minutes, obtain solid catalyst, after stopping to stir, can find that the solid catalyst particle settling velocity is very fast.Reaction finishes after heat and filters out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Comparing embodiment 2
MgCl
24.76 gram adds 50mL decane and 31mL isooctyl alcohol, is heated to 130 ℃ of back flow reaction 180 minutes, is cooled to 50 ℃, adds the 3.3mL tetraethoxysilane and continue reaction 60 minutes under this temperature, be cooled to room temperature after.Slowly drip 200mLTiCl with 90 fens clock times down at 0 ℃
4In mixing solutions, dropwise the back and slowly be warming up to 110 ℃ of reactions 120 minutes with 90 fens clock times, reaction finishes, and after stopping to stir, finds that the solid catalyst particle settling velocity is very slow.Heat filtering goes out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Comparing embodiment 3
MgCl
24.76 gram adds 150mL decane and 13.5mL ethanol, is incubated 30 ℃ and reacts 120 minutes down, under this temperature, drip aluminium diethyl monochloride (being mixed with the hexane solution of 2.23 volumetric molar concentrations) 21.6mL again, continue down reaction 90 minutes in 35 ℃, be warming up to 60 ℃ after following 30 minutes, slowly drip 16mLTiCl
4In mixing solutions, be warming up to 65 ℃ of reactions 120 minutes after dropwising, reaction finishes, and after stopping to stir, finds that the solid catalyst particle settling velocity is very slow.Heat filtering goes out solid catalyst.Use hexane wash, each 40mL is colourless to filtrate substantially, and wherein free titanium content gets solid catalyst less than 0.3mg/mL after the drying.
Test the composition of the catalyst activity component of each embodiment and comparative example preparation, the result as shown in the following Table 5.
The composition of each embodiment of table 5 and comparative example's catalyst activity component
1.2-ethyl hexyl oxy group;
2.Butoxy radicals
Preparation embodiment 1: vinyl polymerization
In 10 liters of stainless steel autoclaves, behind nitrogen replacement, add 3 liters of dehydration hexanes successively, the hexane solution of triethyl aluminum (is 200 by the Al/Ti mol ratio), and the catalyzer 20mg of the foregoing description 1 preparation, feed hydrogen to 0.2Mpa (gauge pressure), give birth to temperature to 70 ℃, feed ethene to still again and press for 0.8Mpa (gauge pressure), at 80 ℃, keep still to press and be polyreaction under the 0.8Mp 2 hours, obtain polyethylene product.
Each embodiment and comparative example's catalyst system therefor, catalytic activity and polyethylene rerum natura see Table 6.Polyethylene melting index (MI) is measured with the ASTM-D-1238 method, and apparent density is measured with the ASTM-D-1895 method.
Table 6
Preparation embodiment 2 ethene and alpha-olefin copolymer close
In 10 liters of stainless steel autoclaves, behind nitrogen replacement, add 3.5 liters of dehydration hexanes successively, the hexane solution of triethyl aluminum (is 200 by the Al/Ti mol ratio), and the catalyzer 20mg of the foregoing description 1 preparation, add 20 gram propylene and 40 gram butene-1s respectively, feed hydrogen (gauge pressure behind deduction propylene or the butene-1 pressure) to 0.2Mpa, give birth to temperature to 70 ℃, feeding ethene to still again presses for 0.8Mpa (gauge pressure behind deduction propylene or the butene-1 pressure), at 80 ℃, keep still to press and be polyreaction under the 0.8Mp 2 hours, obtain polyethylene product.
Each embodiment and comparative example's catalyst system therefor, catalytic activity and polyethylene rerum natura see Table 7 and table 8 respectively.Polyethylene melting index (MI) is measured with the ASTM-D-1238 method, and apparent density is measured with the ASTM-D-1895 method.
The result of table 7 and copolymerization of propylene
| Catalyzer | Catalytic activity * 10 -4gPE/gCat | Bulk density g/cm 3 | Oligopolymer mg/ml | Fusing point ℃ | MI 2.16 g/min | MI 2.16 g/min |
| Embodiment 3 | 6.25 | 0.315 | ＜0.01 | 130.23 | 1.11 | 44.6 |
| Embodiment 5 | 6.51 | 0.31 | ＜0.01 | 130.04 | 1.15 | 46.5 |
| Embodiment 10 | 6.85 | 0.32 | ＜0.01 | 129.25 | 1.41 | 56.2 |
| Embodiment 16 | 7.05 | 0.32 | ＜0.01 | 129.46 | 1.35 | 54.0 |
| Embodiment 17 | 7.25 | 0.34 | ＜0.01 | 130.43 | 0.95 | 38.6 |
| Embodiment 20 | 7.35 | 0.35 | ＜0.01 | 130.03 | 1.16 | 46.4 |
| Embodiment 23 | 7.27 | 0.34 | ＜0.01 | 130.29 | 1.08 | 43.2 |
| Embodiment 35 | 7.64 | 0.35 | ＜0.01 | 130.01 | 1.18 | 47.2 |
| Embodiment 38 | 6.29 | 0.34 | ＜0.01 | 130.56 | 0.98 | 39.2 |
| Embodiment 39 | 6.17 | 0.335 | ＜0.01 | 130.33 | 1.02 | 40.8 |
| Embodiment 40 | 6.40 | 0.34 | ＜0.01 | 129.83 | 1.21 | 48.8 |
| Embodiment 41 | 6.30 | 0.335 | ＜0.01 | 129.36 | 1.38 | 55.5 |
| Embodiment 42 | 6.32 | 0.33 | ＜0.01 | 130.36 | 1.01 | 40.1 |
| Embodiment 43 | 6.31 | 0.34 | ＜0.01 | 130.39 | 1.05 | 42.7 |
| Embodiment 48 | 6.46 | 0.33 | ＜0.01 | 129.78 | 1.21 | 48.5 |
| Embodiment 49 | 6.43 | 0.335 | ＜0.01 | 129.41 | 1.31 | 52.0 |
| Embodiment 51 | 6.53 | 0.32 | ＜0.01 | 130.27 | 1.09 | 43.8 |
| Embodiment 52 | 6.72 | 0.33 | ＜0.01 | 129.45 | 1.32 | 52.8 |
| Embodiment 53 | 6.14 | 0.345 | ＜0.01 | 129.38 | 1.39 | 55.5 |
| Embodiment 54 | 6.61 | 0.325 | ＜0.01 | 130.33 | 1.02 | 40.1 |
| Embodiment 55 | 6.85 | 0.315 | ＜0.01 | 130.29 | 1.06 | 42.7 |
| Embodiment 60 | 7.11 | 0.35 | ＜0.01 | 129.72 | 1.25 | 50.5 |
| Embodiment 61 | 7.21 | 0.345 | ＜0.01 | 129.33 | 1.35 | 54.0 |
| Comparative example 1 | 6.11 | 0.34 | ＜0.01 | 131.23 | 0.80 | 32.0 |
| Comparative example 2 | 5.46 | 0.31 | 0.92 | 131.83 | 0.61 | 20.4 |
| Comparative example 3 | 4.21 | 0.26 | 1.53 | 132.13 | 0.45 | 18.7 |
The result of table 8 and butylene copolymerization
| Embodiment | Catalytic activity * 10 -4gPE/gCat | Bulk density g/cm 3 | Oligopolymer mg/ml | Fusing point ℃ | MI 2.16 g/min | MI 2.16 g/min |
| Embodiment 3 | 5.68 | 0.31 | 0.21 | 129.33 | 1.31 | 52.4 |
| Embodiment 5 | 5.73 | 0.31 | 0.18 | 129.03 | 1.45 | 58.5 |
| Embodiment 10 | 5.91 | 0.32 | 0.24 | 128.53 | 1.61 | 64.2 |
| Embodiment 16 | 6.31 | 0.32 | 0.23 | 128.73 | 1.52 | 60.8 |
| Embodiment 17 | 6.54 | 0.33 | 0.19 | 129.93 | 1.14 | 45.6 |
| Embodiment 20 | 6.68 | 0.34 | 0.23 | 129.23 | 1.36 | 54.4 |
| Embodiment 23 | 6.60 | 0.33 | 0.20 | 129.43 | 1.28 | 51.2 |
| Embodiment 35 | 6.87 | 0.34 | 0.24 | 129.19 | 1.38 | 55.2 |
| Embodiment 38 | 5.66 | 0.33 | 0.26 | 129.81 | 1.18 | 47.2 |
| Embodiment 39 | 5.54 | 0.32 | 0.29 | 129.49 | 1.22 | 48.8 |
| Embodiment 40 | 5.75 | 0.33 | 0.23 | 128.95 | 1.41 | 56.8 |
| Embodiment 41 | 5.67 | 0.32 | 0.25 | 128.39 | 1.65 | 66.2 |
| Embodiment 42 | 5.68 | 0.32 | 0.23 | 129.47 | 1.21 | 48.4 |
| Embodiment 43 | 5.67 | 0.33 | 0.26 | 129.34 | 1.25 | 50.7 |
| Embodiment 48 | 5.81 | 0.32 | 0.24 | 128.85 | 1.41 | 56.4 |
| Embodiment 49 | 5.78 | 0.32 | 0.26 | 128.56 | 1.56 | 62.0 |
| Embodiment 51 | 5.87 | 0.31 | 0.29 | 129.29 | 1.29 | 51.6 |
| Embodiment 52 | 6.04 | 0.32 | 0.25 | 128.61 | 1.52 | 60.8 |
| Embodiment 53 | 5.52 | 0.33 | 0.20 | 128.41 | 1.61 | 64.4 |
| Embodiment 54 | 5.95 | 0.31 | 0.29 | 129.52 | 1.22 | 48.8 |
| Embodiment 55 | 6.16 | 0.30 | 0.35 | 129.59 | 1.26 | 50.4 |
| Embodiment 60 | 6.41 | 0.34 | 0.18 | 128.66 | 1.48 | 59.5 |
| Embodiment 61 | 6.48 | 0.33 | 0.16 | 128.21 | 1.66 | 66.4 |
| Comparative example 1 | 5.49 | 0.30 | 0.39 | 130.12 | 1.0 | 40.5 |
| Comparative example 2 | 4.12 | 0.29 | 3.92 | 130.89 | 0.81 | 32.6 |
| Comparative example 3 | 3.79 | 0.25 | 17.53 | 131.2 | 0.55 | 21.6 |
Claims (16)
1. method for preparing the catalyst activity component that is used for vinyl polymerization or copolymerization, this method may further comprise the steps:
(1) preparation of magnesium alcoholate slurries: under 50～180 ℃, in the inert hydrocarbon solvent that contains at least a C6～12 aliphatic hydrocarbons, magnesium compound and the organic alcohol reaction that contains 2～10 carbon atoms 0.5～3 hour, form homogeneous solution, wherein the mol ratio of magnesium/alcohol is 1: 0.5～6, and every mole of magnesium compound uses 1.8～5.0 liters of inert hydrocarbon solvents;
(2) with the magnesium alcoholate slurries and the electron donor reaction of preparation, wherein temperature of reaction is 20～100 ℃, based on every mole of magnesium compound, adds 0.05～1.0 mole electron donor, and wherein said electron donor has molecular formula (R for one or more are selected from
1) (R
2) (R
3) (R
4) the represented compound of Si, R
1, R
2, R
3, R
4All identical or part is identical, R
1, R
2, R
3, R
4In at least one be alkoxyl group, and R
1, R
2, R
3, R
4Be selected from C separately
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Alkoxyl group, C
6～C
9Aryloxy alkyl, C
1～C
12Haloalkyl and C
3～C
6Epoxy group(ing);
(3) with titanium compound Ti (OR)
4-nX
nAdd and carry out the reaction of preload titanium in the reaction solution in the step (2), wherein temperature of reaction is-20～20 ℃, and X is a halogen, R is an alkyl, n is 0 or smaller or equal to 4 integer, adds 1.0～50.0 moles described titanium compound based on every mole of magnesium compound, adds titanium compound Ti (OR)
4-nX
nThe back kept 0.5～3 hour down at-10～0 ℃;
(4) adding of the reaction solution in step (3) halohydrocarbon carries the titanium reaction, wherein in 1～4 hour, temperature of reaction is raised to 70～130 ℃, continue reaction 1～6 hour, the mole dosage of halohydrocarbon is 2～20 times of mole dosage of magnesium compound, and described halohydrocarbon is halogenated alkane or halo naphthenic hydrocarbon;
(5) reacting slurry in the filtration step (4) with solvent wash, drying, obtains the solid catalyst active ingredient.
2. the method for claim 1 is characterized in that, in step (1), every mole of magnesium compound uses 2.0～3.0 liters of inert hydrocarbon solvents.
3. the method for claim 1 is characterized in that, in step (1), the mol ratio of described magnesium/alcohol is 1: 2～4.
4. the method for claim 1 is characterized in that, the temperature of reaction of step (1) is 70～120 ℃.
5. the method for claim 1 is characterized in that, the temperature of reaction of step (2) is 40～80 ℃.
6. the method for claim 1 is characterized in that, in step (3), the temperature of preload titanium reaction is-10～10 ℃.
7. the method for claim 1 is characterized in that, in step (3), based on the described titanium compound of 1.0～50.0 moles of every mole of magnesium compound addings.
8. the method for claim 1 is characterized in that, in step (4), in 2～3 hours temperature of reaction is raised to 90～110 ℃, continues reaction 2～4 hours, and the mole dosage of halohydrocarbon is 5～20 times of mole dosage of magnesium compound.
9. the method for claim 1, it is characterized in that, described electron donor is selected from and comprises dimethyldimethoxysil,ne, dipropyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dibutyl dimethoxy silane, cyclohexylmethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxydiphenylsilane, phenyltrimethoxysila,e, methyltrimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, dimethyldiethoxysilane, the dipropyl diethoxy silane, the di-isopropyl diethoxy silane, the diisobutyl diethoxy silane, the dibutyl diethoxy silane, the cyclohexylmethyl diethoxy silane, cyclohexyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl butyl diethoxy silane, cyclopentyl propyl group diethoxy silane, two cyclopentyl diethoxy silanes, the phenylbenzene diethoxy silane, phenyl triethoxysilane, Union carbide A-162, the butyl triethoxyl silane, the isobutyl-triethoxyl silane, γ-chloropropyl triethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, tetramethoxy-silicane, the group of tetraethoxysilane and composition thereof.
10. the method for claim 1 is characterized in that, the described titanium compound Ti (OR) in the step (3)
4-nX
nFor being selected from the group that comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium and composition thereof.
11. the method for claim 1, it is characterized in that, employed halohydrocarbon comprises 1 for being selected from the step (4), 2-ethylene dichloride, 1,3-propylene dichloride, 1,4-dichlorobutane, 1, the group of 6-dichloro hexane, a chlorine hexanaphthene, dichloro hexanaphthene, a chlorine pentamethylene, dichloro pentamethylene and composition thereof.
12. the catalyst activity component that is used for vinyl polymerization or copolymerization by each described method preparation in the claim 1～11 is characterized in that, based on the gross weight of the catalyst activity component of 100 weight parts, this catalyst activity component comprises:
12.0 the magnesium of～18.0 weight parts;
4.0 the titanium of～8.0 weight parts;
1.1 the alkoxyl group of～11.0 weight parts;
0.5 the silicon of～2.5 weight parts; And
55.0 the halogen of～75.0 weight parts.
13. active ingredient as claimed in claim 12 is characterized in that, based on the catalyst activity component gross weight of 100 weight parts, wherein the alkoxyl group of 0.1～2.0 weight part is a methoxyl group.
14. active ingredient as claimed in claim 12 is characterized in that, based on the catalyst activity component gross weight of 100 weight parts, wherein the alkoxyl group of 0.0～3.0 weight part is an oxyethyl group.
15. a catalyzer that is used for olefinic polymerization or copolymerization is characterized in that comprising
(i) the described catalyst activity component of claim 12; With
(ii) promotor, organo-aluminium compound R
3-nAlX
n, wherein X is a halogen, and R is C1～C6 alkyl, and n is 0～3 integer;
Wherein the mol ratio of the titanium in aluminium in the promotor and the catalyst activity component is 20～800.
16. the catalyzer that is used for olefinic polymerization or copolymerization as claimed in claim 15 is characterized in that, wherein the mol ratio of the titanium in aluminium in the promotor and the catalyst activity component is 50～300.
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| CN100484970C (en) * | 2007-04-30 | 2009-05-06 | 中国石油化工股份有限公司 | Method for preparing solid catalyst in olefin polymerization catalyst |
| MY156621A (en) * | 2009-08-21 | 2016-03-15 | China Petroleum & Chemical | A catalyst component for ethylene polymerization, preparation thereof and a catalyst comprising the catalyst component |
| CN102093498B (en) * | 2009-12-11 | 2012-07-18 | 中国石油天然气股份有限公司 | Material special for polyethylene and preparation method thereof |
| CN101880341B (en) * | 2010-06-21 | 2012-05-30 | 中国石油天然气股份有限公司 | Ethylene homopolymerization or copolymerization catalyst and preparation and application thereof |
| CN102329400B (en) * | 2011-06-23 | 2013-03-27 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst containing silane compound, preparation and application thereof |
| CN102863560A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | External electron donor component, alkene polymerization catalyst containing external electron donor component and application thereof |
| CN104098727B (en) * | 2013-04-03 | 2016-11-16 | 中国石油天然气股份有限公司 | A kind of high-density polyethylene resin and preparation thereof and application |
| CN105461745B (en) * | 2015-08-17 | 2019-04-02 | 临邑县鲁晶化工有限公司 | A kind of dialkyl dialkoxy silicane and its synthetic method |
| CN106632743B (en) * | 2015-10-29 | 2020-07-21 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization and use thereof |
| CN105542038B (en) * | 2015-11-14 | 2018-02-09 | 新疆独山子天利高新技术股份有限公司 | Mixture of siloxanes and the method for regulating and controlling small-entity polypropylene process polymerisation speed |
| CN114426596A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer |
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