CN105315390A - Catalyst composition for olefin polymerization and application thereof - Google Patents
Catalyst composition for olefin polymerization and application thereof Download PDFInfo
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- CN105315390A CN105315390A CN201410379646.5A CN201410379646A CN105315390A CN 105315390 A CN105315390 A CN 105315390A CN 201410379646 A CN201410379646 A CN 201410379646A CN 105315390 A CN105315390 A CN 105315390A
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Abstract
The invention provides a catalyst composition for olefin polymerization reaction. The catalyst composition comprises a solid catalyst component a, alkyl aluminum b, and an external electron donor, i.e., a malonate compound c with a structure as shown in a general formula (I), wherein the solid catalyst component a contains magnesium, titanium, halogen, and internal electron donor which contains lone pair electrons and is at least one selected from the group consisting of ethers, esters, etc.; the external electron donor c can also be a mixture of a diether compound as shown in a general formula (II), alkoxy silane as shown in a general formula (III) and malonate as shown in the general formula (I); and when the solid catalyst component a is used for olefin polymerization in the presence of the external electron donor, the activity of the solid catalyst component a has the effect of high-temperature self extinguishing.
Description
Technical field
The invention belongs to olefin polymerization catalysis technical field, relate to a kind of catalyst composition for olefinic polymerization and application thereof.
Background technology
As everyone knows, using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basal component, can be used for olefinic polyreaction, particularly can obtain higher yields and the polymkeric substance compared with high isotactic in the alpha-olefine polymerizing with 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalyst component, and the development along with internal electron donor compound result in polyolefin catalyst and constantly updates, external electron donor also needs the supporting development with internal electron donor.At present, disclosed multiple electron donor compound in a large number, such as internal electron donor monocarboxylic ester or multi-carboxylate, ketone, monoether or polyether, amine etc. and derivative thereof, external electron donor conventional for general formula be R
nsi (OR)
4-norganosilicone compounds.This external electron donor coordinates with existing solid catalyst, be applied to catalyzing propone polymerization, higher activity and orientation property can be had, but be applied in some occasion particularly gas phase process time, because gaseous media dispersion is so uneven, heat-transfer effect, also not as in liquid phase medium, causes the focus that there will be local in polymerization process, and catalyzer still has higher activity in high temperature, and then there will be implode phenomenon.
Patent of invention CN101835812A etc. disclose a kind of external electron donor with high temperature self-gravitation, but its usage quantity is very large, and the ratio as the aluminum alkyls that requires and its consumption is less than 4, and orientation property is not high, and activity also has much room for improvement in addition.
Summary of the invention
Now be surprisingly found out that, by general formula R
1r
2c (COOR
3) (COOR
4) the malonic ester compounds of (I) is when coordinating with existing solid catalyst, there is the effect of high temperature self-gravitation, the degree of the activity decrease under the specific activity normal temps namely under high temperature will far above existing catalyst system, simultaneously its consumption is few, and catalyzer orientation property and activity high.
The present invention still further provides the application in olefin polymerization of a kind of catalyst composition of the present invention.For achieving the above object, according to a first aspect of the invention, provide a kind of catalyst composition for the preparation of olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and contains lone-pair electron as the internal electron donor compound containing O, N, P, S;
B. alkylaluminium cpd;
C. as external electron donor, there is general formula R
1r
2c (COOR
3) (COOR
4) the malonic ester compounds of (I).
Wherein, R
1, R
2, R
3and R
4may be the same or different, substituted or unsubstituted C
1-C
20alkyl; R in addition
1and R
2for hydrogen and halogen can be selected from.
For R
3and R
4preferred substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or C
7~ C
10aralkyl, is more preferably substituted or unsubstituted C
2~ C
8straight chained alkyl, C
3~ C
8the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10aralkyl.
R
1and R
2hydrogen, halogen and substituted or unsubstituted C can be preferably selected from
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl; More preferably, R
1and R
2be selected from hydrogen, halogen and substituted or unsubstituted C
1~ C
8alkyl, C
2~ C
8alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl.
Above-mentioned malonic ester compounds has particularly: diethyl malonate, dipropyl malonate, Diisopropyl malonate, butyl ethyl malonate, propanedioic acid diisobutyl ester, propanedioic acid di tert butyl carbonate, methyl-malonic ester, Methylpropanedioic acid dipropyl, Methylpropanedioic acid diisopropyl ester, Methylpropanedioic acid di-n-butyl, Methylpropanedioic acid diisobutyl ester, Methylpropanedioic acid di tert butyl carbonate, ethyl malonic acid diethylester, ethyl malonic acid dipropyl, ethyl malonic acid diisopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester, ethyl malonic acid di tert butyl carbonate, propylmalonic acid diethyl ester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propylmalonic acid di-n-butyl, propylmalonic acid diisobutyl ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl-malonic acid dipropyl, isopropyl-malonic acid diisopropyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid diisobutyl ester, isopropyl-malonic acid di tert butyl carbonate, phenyl ethyl malonate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester, phenylmalonic acid di-n-butyl, phenylmalonic acid diisobutyl ester, phenylmalonic acid di tert butyl carbonate, Bian propylmalonic acid diethyl ester, Bian propylmalonic acid dipropyl, Bian propylmalonic acid diisobutyl ester, dimethyl malonic ester, diethyl malonic ester, methylethyl diethyl malonate, methyl butyl diethyl malonate, methyl-isobutyl diethyl malonate, methyl-propyl diethyl malonate, isopropyl methyl diethyl malonate, diη-propyl diethyl malonate, di-n-butyl diethyl malonate, di-isopropyl diethyl malonate, diisobutyl diethyl malonate and diallyl diethyl malonate.
For the component C in catalyst combination, general formula R can also be contained
5r
6c (CH
2oR
7)
2(II) 1,3-diether compounds.
In general formula (II), R5 with R6 can be identical or not identical, for substituted or unsubstituted C1 ~ C10 straight chained alkyl, C3 ~ C15 branched-chain alkyl, C3 ~ C15 cycloalkyl, C6 ~ C20 aryl or C7 ~ C20 alkaryl or aralkyl, be preferably substituted or unsubstituted C2 ~ C10 straight chained alkyl, C3 ~ C10 branched-chain alkyl, C3 ~ C10 cycloalkyl, C6 ~ C15 aryl or C7 ~ C15 alkaryl or aralkyl; R5 and R6 optionally can be keyed to ring or not Cheng Huan.And R7 is methyl or ethyl; The ratio of 1,3-diether and malonic ester is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol), is more preferably 0.2 ~ 5 (mol/mol).
Described 1,3-diether compounds has 2-sec.-propyl-2-isopentyl-1 particularly, 3-Propanal dimethyl acetal, 9,9-bis-(methoxymethyl) fluorenes, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyls-1,3-Propanal dimethyl acetal and 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal.
In addition for the component C in catalyst combination, can also be R containing general formula
1 nsi (OR
2)
4-n(III) alkoxysilane compound containing trialkylsilyl group in molecular structure (the middle n=0 or 1 or 2 or 3, R of general formula (III)
1and R
2for substituted or unsubstituted C
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl); The ratio of organoalkoxysilane and malonic ester is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol), is more preferably 0.2 ~ 5 (mol/mol);
Described organoalkoxysilane has Cyclohexyl Methyl Dimethoxysilane particularly, diphenyl dimethoxy silicon, butyl sec.-propyl dimethoxysilane, diisopropyl dimethoxy silane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, dibutyldimethoxysilane, cyclohexyl trimethoxy silane, butyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, phenyltrimethoxysila,e, cyclopentyl-trimethoxy-silane, ethyl trimethoxy silane.
For in the ingredient of solid catalyst a in catalyst composition, described internal electron donor compound is preferably from the compound containing O atom, as ethers, ester class, phenolic ether class, phenolic ester class and ketone, preferred benzoic acid ester compounds, phthalate compound, 1,3-diether, polybasic ester compound, polyvalent alcohol/phenolic ester compound, wherein 1, 3-diether compound has 2-propyl group-2-sec.-propyl-1 particularly, 3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1, 3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1, 3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1, 3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1, 3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1, 3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1, 3-Propanal dimethyl acetal, 2, 2-bis-(2-methyl butyl)-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, 2-bis-(2-ethylhexyl)-1, 3-Propanal dimethyl acetal and 9, 9-bis-(methoxymethyl) fluorenes.
And polybasic ester compound is preferably selected from malonate compound, succinate compound, glutarate compound, phthalate compound.More preferably diethyl phthalate is selected from, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, four tetramethyl-n-butyl phthalates, tetramethyl-diisobutyl phthalate, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, 2, 3-diη-propyl ethyl succinate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-n-butyl ethyl succinate, 2, 3-diisobutyl ethyl succinate, 2, 3-diη-propyl di-iso-octyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-n-butyl di-iso-octyl succinate and 2, one or more in 3-diisobutyl di-iso-octyl succinate etc.
The ester formed for polyvalent alcohol/phenol is preferably selected from 1,3-diol ester compound and 1,2-biphenol ester cpds, is more preferably selected from 2,4-glycol dibenzoate, 2,4-pentanediol two aligns propylbenzoic acid ester, 2,4-pentanediol two cuminic acid ester, 2,4-pentanediol, two pairs of isobutyl-benzene manthanoate, 2,4-pentanediol, two pairs of n-butylbenzoic acid esters, 2,4-pentanediol two p-tert-butyl benzoic acid ester, 3,5-heptanediol dibenzoate, 3,5-heptanediol two p-methylbenzoic acid ester, 3,5-heptanediol two p-ethylbenzoic acid ester, 3,5-heptanediol two aligns propylbenzoic acid ester, 3,5-heptanediol two cuminic acid ester, 3,5-heptanediol, two pairs of isobutyl-benzene manthanoate, 3,5-heptanediol, two pairs of n-butylbenzoic acid esters, 3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol two p-methylbenzoic acid ester, 4-ethyl-3,5-heptanediol two p-ethylbenzoic acid ester, 4-ethyl-3,5-heptanediol two n-propyl benzoate ester, 4-ethyl-3,5-heptanediol two pairs of butylbenzoic acid esters, 4-ethyl-3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-propyl group-1,2-biphenol dibenzoate, 1,2-biphenol two aligns propylbenzoic acid ester, 1,2-biphenol two cuminic acid ester, 1,2-biphenol, two pairs of isobutyl-benzene manthanoate, 1,2-biphenol, two pairs of n-butylbenzoic acid esters, 1,2-biphenol two p-tert-butyl benzoic acid ester, the 4-tertiary butyl-1,2-biphenol two aligns propylbenzoic acid ester, 4,5-dipropyl-1,2-biphenol two cuminic acid ester, 4-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate, 4-sec.-propyl-1,2-biphenol two pairs of n-butylbenzoic acid esters, 4-isopentyl-1,2-biphenol two p-tert-butyl benzoic acid ester, 2-ethyl-1,2-biphenol two aligns propylbenzoic acid ester, 4-isobutyl--5-ethyl-1,2-biphenol two cuminic acid ester, one or more in the 4-tertiary butyl-5-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate etc.
Catalyst composition for the preparation of olefin polymer provided by the invention, its preferred ingredient comprises following:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and is selected from phthalate compound, 1,3-diether compounds, 1,3-malonate compound, succinate compound, 1, the internal electron donor compound of one or more in 3-diol ester compound, 1,2-diphenol ester cpds;
B. alkylaluminium cpd;
C. as external electron donor, there is general formula R
1r
2c (COOR
3) (COOR
4) (I) malonic ester compounds (in general formula I, R
1, R
2, R
3and R
4may be the same or different, substituted or unsubstituted C
1-C
20alkyl, be preferably selected from hydrogen, halogen and substituted or unsubstituted C
1-C
10alkyl; R in addition
1and R
2for hydrogen and halogen can be selected from) and general formula be R
nsi (OR ')
4-n(III) (in general formula (III), n=0 or 1 or 2 or 3, R and R ' is substituted or unsubstituted C to alkoxysilane compound containing trialkylsilyl group in molecular structure
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl).The ratio of malonic ester and organoalkoxysilane is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol).
In ingredient of solid catalyst a in above-mentioned catalyst composition, based on the gross weight of ingredient of solid catalyst a, the content of described titanium is 1wt% ~ 7wt%, and the content of magnesium is 8wt% ~ 20wt%; Preferably, the content of described titanium is 1.5wt% ~ 4.5wt%, and the content of magnesium is 15wt% ~ 20wt%.
For the b component in catalyst composition, the general formula of described alkylaluminium cpd is AlRbnX3-n, and wherein Rb is hydrogen or C
1~ C
20alkyl, X is halogen, 1 < n≤3.
And in described catalyst system, the mol ratio of component a and components b is with titanium: aluminium counts 1: (5 ~ 1000), preferably 1: (20 ~ 250); The mol ratio of component a and amount of component b is with titanium: external donor compound counts 1: (0.1 ~ 200), preferably 1: (0.2 ~ 50), be more preferably 1: (0.2 ~ 10), wherein the amount of amount of component b refers to general formula (I), the summation of the compound of (II) and (III).Amount of component b also can be diluted with alkane in addition, and preferably alkane is selected from C
6~ C
10alkane, be more specifically selected from one or more in hexane, heptane, octane, nonane and decane, and the mol ratio of external electron donor and thinner alkane is 1: 0.1 ~ 10.
Present invention also offers a kind of olefine polymerizing process, described alkene above-mentioned catalyst composition or effect under be polymerized.And the general formula of described alkene is CH
2=CHR, wherein R is hydrogen or C
1~ C
12alkyl or aryl; Preferred described alkene is propylene.Olefine polymerizing process of the present invention, is particularly suitable for carrying out in gas-phase polymerization process.And at present the gas-phase polymerization process of alkene particularly propylene the most frequently used have fluidized-bed process if UNIPOL propylene polymerization process, vertical stirred tank technique are if Novolen propylene polymerization process and horizontal agitated vessel technique are as Innovene propylene polymerization process etc., particularly in UNIPOL and Novolen technique because catalyst combination provided by the invention has the function of high temperature self-gravitation, and make it greatly reduce the possibility occurring caking or implode, improve the time that device runs continuously.
Ingredient of solid catalyst a for olefinic polymerization of the present invention, preferably comprises the reaction product of titanium compound, magnesium compound and above-mentioned internal electron donor compound.Consumption for the preparation of the titanium compound of described catalyst solid constituent, magnesium compound and internal electron donor compound is not particularly limited, and can be respectively the conventional amount used of this area.
Magnesium compound wherein used be selected from one of them halogen atom in magnesium dihalide, alkoxyl magnesium, alkyl magnesium, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by-oxyl or halo-oxyl the derivative of replacing; Be preferably the alcohol adduct of magnesium dihalide or magnesium dihalide.Specific examples is as magnesium dichloride, dibrominated magnesium, diiodinating magnesium and their alcohol adduct.
Titanium compound wherein used can select general formula to be TiX
m(OR
1) 4-mcompound, R in formula
1for C
1~ C
20alkyl, X is halogen, 1≤m≤4.Such as: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
Ingredient of solid catalyst a described in the present invention is by the following method preparation enumerated.
Method one: as the method Kaolinite Preparation of Catalyst component disclosed according to patent CN1506384.First, magnesium compound is mixed with organic alcohol compound and inert solvent, rising temperature for dissolving, then add phthalic anhydride mixing.Then contact with the titanium compound of precooling, after being warming up to certain temperature, adding internal electron donor compound and react for some time at a certain temperature, then with titanium compound process gained solid, repeatedly wash solid particulate with inert solvent again, after drying, obtain catalyst component.
Method two: be first dissolved in by magnesium compound in the solvent system comprising organic epoxy compounds, organo phosphorous compounds and inert diluent composition, mix after forming homogeneous solution with titanium compound, under precipitation additive exists, separates out solids; This solids contacts with internal electron donor compound, makes it be attached on solids, if desired, then processes solids with titanium tetrahalide and inert diluent.
Method three: by titanium compound of the present invention is concrete as TiCl
4, be MgCl with general formula
2the adducts of pROH reacts and prepares ingredient of solid catalyst.At MgCl
2in pROH, p is the number of 0.1 ~ 6, preferably 2 ~ 3.5, and R is the alkyl with 1 ~ 18 carbon atom.Adducts can be made spherical by diverse ways.Specifically can according to the method Kaolinite Preparation of Catalyst component disclosed in patent CN1091748.
Method four: also can add in arene compound with dialkoxy magnesium and stir, forms suspension; Suspension tetravalence titanium chloride process, and add internal electron donor and react, the solid arene compound obtained washs; And then with the process of tetravalence titanium chloride, finally with inert solvent washing, drain, obtain ingredient of solid catalyst.
Method five: according to the method Kaolinite Preparation of Catalyst component disclosed in patent US4540679.First, magnesium alkoxide and carbon dioxide reaction obtain alkyl magnesiumcarbonate carrier.Then transistion metal compound (be preferably tetravalent titanium compound) and alkyl magnesiumcarbonate carrier and internal electron donor react in certain proportion in inert solvent, and obtain solid catalyst.
Prepare the method for ingredient of solid catalyst a, as in addition magnesium compound, electron donor etc. formed emulsion in thinner, adding titanium compound and making it fixedly obtain spherical solid, more treatedly obtain ingredient of solid catalyst.In the above-mentioned preparation method of any one, required internal electron donor compound both can add with the form of compound; Also can add in other manners, as can be obtained by the precursor original position adopting internal electron donor compound to be applicable to, this precursor becomes required electron donor compound by example chemical reaction as is known such as esterification etc.
According to the present invention, state on the invention in catalyst composition, the general formula of described alkylaluminium cpd b is AlRbnX3-n, and in formula, Rb is hydrogen or C
1~ C
20alkyl, X is halogen, 1 < n≤3.
In one particular embodiment of the present invention, described alkylaluminium cpd comprises triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium etc.
According to the present invention, in described catalyst composition, the mol ratio of described component a and components b is with titanium: aluminium counts 1: (5 ~ 1000).Be preferably 1: (20 ~ 250).The mol ratio of described component a and amount of component b is with titanium: c counts 1: (0.1 ~ 100).Be preferably 1: (0.5 ~ 50).
According to a second aspect of the invention, provide a kind of pre-polymerized catalyst composition for olefinic polymerization, it comprises the prepolymer that the above-mentioned catalyst composition of at least one and alkene carry out prepolymerization gained, the pre-polymerization multiple of described prepolymer is 0.1 ~ 1000g olefin polymer/g component a, and described alkene is preferably propylene.In the present invention, " pre-polymerized catalyst " refers to the catalyzer of lower transforming degree through polymerization procedure.According to the present invention, the alpha-olefin identical with being polymerized alkene used can being adopted to carry out prepolymerization, wherein carrying out prepolymerized alkene and being preferably propylene.Specifically, particularly preferably be, the mixture adopting propylene or itself and amount to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2 ~ 500 gram of polymkeric substance/gram ingredient of solid catalyst a.
Prepolymerization operation can at-20 ~ 80 DEG C, preferably at the temperature of 0 ~ 50 DEG C, carry out in a liquid or in gas phase.Prepolymerization step can carry out online as the part in continuous polymerization technique, or carries out independently in periodical operation.For the polymkeric substance that preparation amount is 0.5 ~ 20g/g catalyst component, the particularly preferably batch pre-polymerization of catalyzer of the present invention and propylene.Polymerization pressure is 0.01 ~ 10MPa.
According to a third aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the effect of above-mentioned catalyst composition or above-mentioned pre-polymerized catalyst composition.
In the present invention, the general formula of described alkene is CH2=CHR, and wherein R is alkyl or the aryl of hydrogen or C1 ~ C12.Such as, described alkene comprises ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, and preferred described alkene is propylene.
In a specific embodiment of the present invention, above-mentioned catalyst composition of the present invention or above-mentioned catalyst composition may be used for propylene all polymerization with or other alkene of propylene copolymerization reaction in.
Catalyzer of the present invention can directly add in polymerization process in reactor, or catalyzer and alkene pre-polymerization obtain pre-polymerized catalyst after add in reactor.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, or also can carry out under the operation of liquid and gas polymerization stage combination.Adopt conventional technology as slurry process, gas-phase fluidized-bed etc.Adopt following reaction conditions preferably: polymerization temperature 0 ~ 150 DEG C, preferably 60 ~ 90 DEG C.
The present inventor, through many experiments, have been surprisingly found that, the present invention by adopt general formula be (I) malonate compound as external electron donor for alkene especially propylene polymerization time, there is the effect of high temperature self-gravitation.
Embodiment
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment, these embodiments only play illustrative effect, are not limited to range of application of the present invention, NM specific experiment method in the following example, conveniently experimental technique carries out usually.
Testing method:
Polymkeric substance isotactic index adopts heptane extraction process to measure (heptane boiling extracting 6 hours): the polymer samples of 2g drying, be placed in extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to the polymer weight (g) of constant weight gained and be isotactic index with the ratio of 2.
Embodiment
Propylene polymerization is tested
The purified nitrogen of the reaction flask of one 250ml is fully replaced, then 150ml is added through fully dry decane, fully saturated with polymerization-grade propylene again and nitrogen completely in replacement(metathesis)reaction bottle, reaction system is carried out completely under the atmosphere of propylene, after system temperature is risen to temperature of reaction, (triethyl aluminum consumption is AlEt to add a certain amount of triethyl aluminum and external electron donor
3/ Ti=100mol/mol, Ti are the content in added ingredient of solid catalyst a, AlEt
3/ external electron donor=20mol/mol), add ingredient of solid catalyst a and be about 60mg, start to carry out propylene polymerization, in process, pass into propylene continuously, and keep reaction flask pressure to be 0.01MPa, the temperature of reaction of maintenance setting 1 hour, then add the ethanol termination reaction of 30ml, obtain solids after filtration, and fully dry, obtain polymkeric substance, the ratio that the activity of catalyzer is obtained polymkeric substance and added solid catalysis dosage.
Aforesaid propylene polymerization result is in table 1 and table 2.
Table 1 propylene polymerization result
* CS-1-G is that Yingkou faces south Ke Hua group product; SHAC201 is DOW Chemical product; NG and BCND-II-04 is Sinopec catalyzer company limited product; Ac
100/ Ac
67it is the ratio of the catalyst activity at 100 DEG C and 67 DEG C; External electron donor 1 in embodiment 3,5,8,9,10 and comparative example 3 and the mol ratio of external electron donor 2 are respectively 1: 2,1: 1,3: 2,1: 1,1: 1 and 2: 1.
As can be seen from Table 1, use silicon compound of the present invention for external electron donor, compared with the silane of prior art, catalyzer activity decrease at high temperature obtains faster, avoids, during high temperature polymerization, implode occurs.
Table 2
Note: in table, the number on external electron donor hurdle is the ratio (mol/mol) of two kinds of external electron donors; Comparative example 5, Al/ external electron donor=5 (mol/mol).
Table 2 can be found out, catalyst combination of the present invention has active high, and orientation property is high, and the external electron donor amount of needs is few.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (20)
1., for the preparation of a catalyst composition for olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and contains lone-pair electron as the internal electron donor compound containing O, N, P, S;
B. alkylaluminium cpd;
C. as external electron donor, there is general formula R
1r
2c (COOR
3) (COOR
4) the malonic ester compounds of (I).
Wherein, R
1, R
2, R
3and R
4may be the same or different, be substituted or unsubstituted C
1-C
20alkyl; R in addition
1and R
2for hydrogen and halogen can be selected from.
2. catalyst composition according to claim 1, is characterized in that, the feature of described malonate compound is, R
3and R
4for C
1~ C
10straight-chain alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cycloalkyl, C
6~ C
10aryl, C
7~ C
10alkaryl or C
7~ C
10aralkyl, is preferably C
2~ C
8straight-chain alkyl, C
3~ C
8the alkyl of side chain, C
3~ C
10cycloalkyl or C
7~ C
10alkaryl;
R
1and R
2may be the same or different, be selected from hydrogen, halogen and C
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl; Preferably, R
1and R
2be selected from hydrogen, halogen and C
1~ C
8alkyl, C
2~ C
8alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10aralkyl.
3. according to the catalyst composition in claim 1-2 described in any one, it is characterized in that, described malonic ester compounds is selected from following compound: diethyl malonate, dipropyl malonate, Diisopropyl malonate, butyl ethyl malonate, propanedioic acid diisobutyl ester, propanedioic acid di tert butyl carbonate, methyl-malonic ester, Methylpropanedioic acid dipropyl, Methylpropanedioic acid diisopropyl ester, Methylpropanedioic acid di-n-butyl, Methylpropanedioic acid diisobutyl ester, Methylpropanedioic acid di tert butyl carbonate, ethyl malonic acid diethylester, ethyl malonic acid dipropyl, ethyl malonic acid diisopropyl ester, ethyl malonic acid di-n-butyl, ethyl malonic acid diisobutyl ester, ethyl malonic acid di tert butyl carbonate, propylmalonic acid diethyl ester, propylmalonic acid dipropyl, propylmalonic acid diisopropyl ester, propylmalonic acid di-n-butyl, propylmalonic acid diisobutyl ester, propylmalonic acid di tert butyl carbonate, diethyl isopropyl, isopropyl-malonic acid dipropyl, isopropyl-malonic acid diisopropyl ester, isopropyl-malonic acid di-n-butyl, isopropyl-malonic acid diisobutyl ester, isopropyl-malonic acid di tert butyl carbonate, phenyl ethyl malonate, phenylmalonic acid dipropyl, phenylmalonic acid diisopropyl ester, phenylmalonic acid di-n-butyl, Bian propylmalonic acid diethyl ester, Bian propylmalonic acid dipropyl, Bian propylmalonic acid diisopropyl ester, Bian propylmalonic acid di-n-butyl, Bian propylmalonic acid diisobutyl ester, dimethyl malonic ester, diethyl malonic ester, methylethyl diethyl malonate, methyl butyl diethyl malonate, methyl-isobutyl diethyl malonate, methyl-propyl diethyl malonate, isopropyl methyl diethyl malonate, diη-propyl diethyl malonate, di-n-butyl diethyl malonate, di-isopropyl diethyl malonate, diisobutyl diethyl malonate and diallyl diethyl malonate.
4. catalyst composition according to claim 1, is characterized in that:
Also containing general formula R in c component
5r
6c (CH
2oR
7)
2(II) 1,3-diether compounds.
Wherein, R
5and R
6can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
5and R
6optionally can be keyed to ring or not Cheng Huan.R
7for methyl or ethyl; The ratio of 1,3-diether and malonic ester is 0.01 ~ 100 (mol/mol).
5. according to the requirement of right 4, described in it 1,3-diether compounds is selected from 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 9,9-bis-(methoxymethyl) fluorenes, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2, one or more in 2-diisobutyl-1,3-Propanal dimethyl acetal and 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal.
6. catalyst composition according to claim 1, is characterized in that:
Also containing general formula in c component is R
1 nsi (OR
2)
4-n(III) alkoxysilane compound containing trialkylsilyl group in molecular structure (the middle n=0 or 1 or 2 or 3, R of general formula (III)
1and R
2for substituted or unsubstituted C
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl); The ratio of organoalkoxysilane and malonic ester is 0.01 ~ 100 (mol/mol).
7., according to the requirement of right 6, the organoalkoxysilane described in it is selected from one or more in Cyclohexyl Methyl Dimethoxysilane, diphenyl dimethoxy silicon, butyl sec.-propyl dimethoxysilane, diisopropyl dimethoxy silane, dipropyl dimethoxysilane, dicyclopentyl dimethoxyl silane, dibutyldimethoxysilane, cyclohexyl trimethoxy silane, butyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, phenyltrimethoxysila,e, cyclopentyl-trimethoxy-silane, ethyl trimethoxy silane.
8. according to the catalyst composition in claim 1 ~ 7 described in any one, it is characterized in that, in described ingredient of solid catalyst a, the compound of described internal electron donor compound preferably certainly containing O atom, as ethers, ester class, phenolic ether class, phenolic ester class and ketone.
9. according to Claim 8 described in catalyst composition, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from 1,3-diether compound, preferred 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, one or more in 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
10. according to Claim 8 described in catalyst composition, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from polybasic ester; Be preferably selected from malonate compound, succinate compound, glutarate compound, phthalate compound.More preferably diethyl phthalate is selected from, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, four tetramethyl-n-butyl phthalates, tetramethyl-diisobutyl phthalate, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, 2, 3-diη-propyl ethyl succinate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-n-butyl ethyl succinate, 2, 3-diisobutyl ethyl succinate, 2, 3-diη-propyl di-iso-octyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-n-butyl di-iso-octyl succinate and 2, one or more in 3-diisobutyl di-iso-octyl succinate etc.
11. according to Claim 8 described in catalyst composition, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from the ester that polyvalent alcohol or phenol are formed, be preferably selected from 1,3-diol ester compound and 1,2-biphenol ester cpds, be more preferably selected from 2,4-glycol dibenzoate, 2,4-pentanediol two aligns propylbenzoic acid ester, 2,4-pentanediol two cuminic acid ester, 2,4-pentanediol, two pairs of isobutyl-benzene manthanoate, 2,4-pentanediol, two pairs of n-butylbenzoic acid esters, 2,4-pentanediol two p-tert-butyl benzoic acid ester, 3,5-heptanediol dibenzoate, 3,5-heptanediol two p-methylbenzoic acid ester, 3,5-heptanediol two p-ethylbenzoic acid ester, 3,5-heptanediol two aligns propylbenzoic acid ester, 3,5-heptanediol two cuminic acid ester, 3,5-heptanediol, two pairs of isobutyl-benzene manthanoate, 3,5-heptanediol, two pairs of n-butylbenzoic acid esters, 3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol two p-methylbenzoic acid ester, 4-ethyl-3,5-heptanediol two p-ethylbenzoic acid ester, 4-ethyl-3,5-heptanediol two n-propyl benzoate ester, 4-ethyl-3,5-heptanediol two pairs of butylbenzoic acid esters, 4-ethyl-3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-propyl group-1,2-biphenol dibenzoate, 1,2-biphenol two aligns propylbenzoic acid ester, 1,2-biphenol two cuminic acid ester, 1,2-biphenol, two pairs of isobutyl-benzene manthanoate, 1,2-biphenol, two pairs of n-butylbenzoic acid esters, 1,2-biphenol two p-tert-butyl benzoic acid ester, the 4-tertiary butyl-1,2-biphenol two aligns propylbenzoic acid ester, 4,5-dipropyl-1,2-biphenol two cuminic acid ester, 4-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate, 4-sec.-propyl-1,2-biphenol two pairs of n-butylbenzoic acid esters, 4-isopentyl-1,2-biphenol two p-tert-butyl benzoic acid ester, 2-ethyl-1,2-biphenol two aligns propylbenzoic acid ester, 4-isobutyl--5-ethyl-1,2-biphenol two cuminic acid ester, one or more in the 4-tertiary butyl-5-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate etc.
12. catalyst compositions according to claim 1, is characterized in that comprising following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and is selected from phthalate compound, 1,3-diether compounds, 1,3-malonate compound, succinate compound, 1, the internal electron donor compound of one or more in 3-diol ester compound, 1,2-diphenol ester cpds;
B. alkylaluminium cpd;
C. as external electron donor, there is general formula R
1r
2c (COOR
3) (COOR
4) (I) malonic ester compounds (in general formula I, R
1, R
2, R
3and R
4may be the same or different, substituted or unsubstituted C
1-C
20alkyl, be preferably selected from hydrogen, halogen and substituted or unsubstituted C
1-C
10alkyl; R in addition
1and R
2for hydrogen and halogen can be selected from) and general formula be R
nsi (OR ')
4-n(III) (in general formula (III), n=0 or 1 or 2 or 3, R and R ' is substituted or unsubstituted C to alkoxysilane compound containing trialkylsilyl group in molecular structure
1~ C
10alkyl, C
1~ C
10alkylene, C
3~ C
10cycloalkyl, C
6~ C
10aryl and C
7~ C
10alkaryl or aralkyl).The ratio of malonic ester and organoalkoxysilane is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol).
13. according to the catalyst composition in claim 1 ~ 12 described in any one, it is characterized in that, in described ingredient of solid catalyst a, based on the gross weight of ingredient of solid catalyst a, the content of described titanium is 1wt% ~ 7wt%, and the content of magnesium is 8wt% ~ 20wt%; Preferably, the content of described titanium is 1.5wt% ~ 4.5wt%, and the content of magnesium is 15wt% ~ 20wt%.
14., according to the catalyst system in claim 1 ~ 13 described in any one, is characterized in that, the general formula of described alkylaluminium cpd is AlRbnX3-n, and wherein Rb is hydrogen or C
1~ C
20alkyl, X is halogen, 1 < n≤3.
15., according to the catalyst system in claim 1 ~ 14 described in any one, is characterized in that, the mol ratio of described component a and components b is with titanium: aluminium counts 1: (5 ~ 1000), preferably 1: (20 ~ 250); The mol ratio of component a and amount of component b is with titanium: external donor compound counts 1: (0.1 ~ 100), and preferably 1: (1 ~ 50).
16. 1 kinds of olefine polymerizing process, the catalyst composition of described alkene according to any one of claim 1 ~ 15 or effect under be polymerized.
17. methods according to claim 16, is characterized in that, the general formula of described alkene is CH2=CHR, and wherein R is hydrogen or C
1~ C
12alkyl or aryl; Preferred described alkene is propylene.
18. methods according to claim 16, is characterized in that, described being aggregated in gas-phase polymerization process is carried out.
19. methods according to claim 18, is characterized in that, described gas-phase polymerization process is UNIPOL propylene polymerization process.
20. methods according to claim 18, is characterized in that, described gas-phase polymerization process is Novolen propylene polymerization process.
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| CN108779056A (en) * | 2016-03-28 | 2018-11-09 | 东邦钛株式会社 | The manufacturing method of alkoxyl magnesium, the manufacturing method of alkoxyl magnesium, solid catalyst component for olefin polymerization, polymerization of olefines catalyst and olefin polymer |
| CN109694420A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalyst system and pre-polymerized catalyst and olefine polymerizing process for olefinic polymerization |
| CN115043867A (en) * | 2021-03-09 | 2022-09-13 | 中国科学院化学研究所 | Hexa-membered cyclic aminosilane external electron donor, preparation method and application thereof |
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| CN108779056A (en) * | 2016-03-28 | 2018-11-09 | 东邦钛株式会社 | The manufacturing method of alkoxyl magnesium, the manufacturing method of alkoxyl magnesium, solid catalyst component for olefin polymerization, polymerization of olefines catalyst and olefin polymer |
| CN108779056B (en) * | 2016-03-28 | 2021-12-24 | 东邦钛株式会社 | Magnesium alkoxide, process for producing magnesium alkoxide, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
| CN109694420A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | Catalyst system and pre-polymerized catalyst and olefine polymerizing process for olefinic polymerization |
| CN109694420B (en) * | 2017-10-24 | 2021-08-03 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization, prepolymerized catalyst and olefin polymerization process |
| CN115043867A (en) * | 2021-03-09 | 2022-09-13 | 中国科学院化学研究所 | Hexa-membered cyclic aminosilane external electron donor, preparation method and application thereof |
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