CN104250321A - Catalyst component, catalyst and method for olefin polymerization - Google Patents
Catalyst component, catalyst and method for olefin polymerization Download PDFInfo
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- CN104250321A CN104250321A CN201310269152.7A CN201310269152A CN104250321A CN 104250321 A CN104250321 A CN 104250321A CN 201310269152 A CN201310269152 A CN 201310269152A CN 104250321 A CN104250321 A CN 104250321A
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Abstract
The invention provides a catalyst component, a catalyst and a method for olefin polymerization. The catalyst component comprises magnesium, titanium, halogen and an internal electron donor, the internal electron donor comprises an internal electron donor compound a and an internal electron donor compound b with the mole ratio of 0.007-2:1, the internal electron donor compound a is a malonate compound shown as the formula I/II, the internal donor compound b is a diol ester compound shown as the formula III, and the catalyst component uses the malonate compound and the diol ester compound as internal electron donor compounds, so that when the catalyst component is used for olefin polymerization, the catalyst component has higher vertical structural capacity, a polymer with high isotactic index can be obtained, and the catalyst component has high activity.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalyst components and olefin polymerization catalysis and olefine polymerizing process.
Background technology
As everyone knows, the solid titanium series catalysts component being basal component with magnesium, titanium, halogen and electron donor compound, for olefinic polyreaction, particularly has higher polymerization activity and vertical structure directional property when propylene polymerization.Wherein, electron donor compound is one of requisite composition in catalyst component, it plays conclusive effect to important indicators such as polymerization activity, polymkeric substance degree of isotacticity, molecular weight and molecualr weight distributions, along with the development of internal electron donor compound, polyolefin catalyst constantly updates.
Phthalate compound is polypropylene catalyst electron donor the most frequently used at present, and finds according to the study, its to animal grow and reproductive system can cause serious harm, meanwhile, also may produce similar impact to the mankind.In addition, use phthalate compound as internal electron donor catalyzer be used for olefinic polymerization time, the molecular weight distribution of the polymkeric substance obtained is narrower, and toughness and processing characteristics all can not be satisfactory, limit its range of application.Therefore, the internal electron donor compound that can substitute it is found to be the problem being badly in need of at present solving.
Find under study for action to adopt carboxylic acid diol-lipid compound as internal electron donor, prepared catalyzer is used for propylene polymerization, has the advantages that polymerization activity is higher and molecular weight distribution is wide.Such as, individually disclose a kind of carboxylic acid diol-lipid compound and catalyzer thereof in CN1436766 and CN1552740.But when the spherical catalyst (magnesium chloride alcohol adduct is carrier) of this carboxylic acid diol-lipid internal electron donor is for propylene polymerization, vertical structure orientation property is poor, and the polyacrylic degree of isotacticity obtained is lower.
In addition, it is known in the art for applying some malonate compound as the internal electron donor of catalyst for polymerization of propylene, such as: EP0045977, EP0086473, EP0086644.The polymerization result reported from above-mentioned application, the shortcoming adopting malonic ester class internal electron donor obtains lower polymerization yield and/or lower isotactic index.
Summary of the invention
The above-mentioned defect that the object of the invention is to overcome prior art provides a kind of olefin polymerization catalyst components and olefin polymerization catalysis and olefine polymerizing process.
The present inventor is surprised to find that after deliberation, by shown in formula I and/or the malonate compound shown in formula II and the component as in olefin polymerization catalyst components internal electron donor composite using specific ratio of the diol ester compound shown in formula III time, when for olefinic polymerization, can obtain the olefin polymer that isotactic index is higher, and this catalyst component has higher polymerization activity.
The invention provides a kind of olefin polymerization catalyst components, this catalyst component contains magnesium, titanium, halogen and internal electron donor, wherein, described internal electron donor contains internal electron donor compound a and internal electron donor compound b, and the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.007-2:1, described internal electron donor compound a is the malonate compound shown in formula I and/or formula II, described internal electron donor b compound is the diol ester compound shown in formula III
formula I,
formula II,
In formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
1and R
2mutual bonding, to form ring;
In formula II, R
1' be C
1-C
20alkoxyl group,
In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
3and R
4mutual bonding, to form ring;
formula III,
In formula III, R
5and R
6identical or different, be halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
2-C
20straight or branched alkylene;
R
7, R
8, R
9, R
10and R
1-R
2nidentical or different, be hydrogen, halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
20straight or branched alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20straight or branched alkyl, containing heteroatomic C
3-C
20substituted or unsubstituted cycloalkyl, containing heteroatomic C
6-C
20substituted or unsubstituted aryl, containing heteroatomic C
7-C
20substituted or unsubstituted aralkyl and containing heteroatomic C
2-C
20straight or branched alkylene in one; Or, R
7, R
8, R
9, R
10and R
1-R
2nin two or more mutual bondings, to form ring; Described heteroatoms is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus,
N is the integer of 0-10.
Present invention also offers a kind of olefin polymerization catalysis, wherein, this catalyzer contains:
(1) above-mentioned olefin polymerization catalyst components;
(2) as the alkylaluminium cpd of promotor; And
(3) optionally, external donor compound.
Present invention also offers a kind of olefine polymerizing process, under the method is included in olefin polymerization conditions, make one or more alkene and above-mentioned catalyst exposure, at least one in described alkene is by formula CH
2the alkene that=CHR represents, wherein R is hydrogen or C
1-C
6alkyl.
Olefin polymerization catalyst components of the present invention by by shown in formula I and/or the propylene glycol ester compound shown in formula II and the diol ester compound shown in formula III using the composite component as internal electron donor of specific ratio, when making it for olefinic polymerization, can obtain the olefin polymer that isotactic index is higher, and this catalyst component has higher polymerization activity.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of olefin polymerization catalyst components, this catalyst component contains magnesium, titanium, halogen and internal electron donor, wherein, described internal electron donor contains internal electron donor compound a and internal electron donor compound b, and the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.007-2:1.
According to the present invention, described internal electron donor compound a is the malonate compound shown in formula I and/or formula II,
formula I,
formula II,
In formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
1and R
2mutual bonding, to form ring;
In formula II, R
1' be C
1-C
20alkoxyl group;
In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
3and R
4mutual bonding, to form ring;
In the present invention, C
1-C
20the example of straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, tetrahydrochysene geranyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base, NSC 77136 base and NSC 62789 base.
In the present invention, C
2-C
20the example of straight or branched alkylene can include but not limited to: vinyl, allyl group, pseudoallyl, 1-propenyl, 2-methyl-1-propylene base, 1-butylene base, crotyl, 3-butenyl, 2-ethyl-1-butylene base, 3-methyl-2-butene base, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, geranyl, 1-decene base, tetradecene base, 1-vaccenic acid base, 9-vaccenic acid base, 1-eicosylene base and 3, 7, 11, phytanetriol-cetene base.
In the present invention, C
3-C
20the example of substituted or unsubstituted cycloalkyl can include but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propyl cyclohexyl, 4-normal-butyl cyclohexyl, ring undecyl and cyclo-dodecyl.
In the present invention, C
6-C
20the example of substituted or unsubstituted aryl can include but not limited to: phenyl, 4-tert-butyl-phenyl, naphthyl, anthryl, indenyl etc.
In the present invention, C
7-C
20substituted or unsubstituted aralkyl refer to that carbonatoms is the alkyl group with aryl substituent of 7-20.C
7-C
20the example of substituted or unsubstituted aralkyl can include but not limited to: 3-phenyl propyl, benzyl etc.
In the present invention, C
7-C
20substituted or unsubstituted alkaryl refer to that carbonatoms is the aromatic yl group with alkyl substituent of 7-20.C
7-C
20the example of substituted or unsubstituted alkaryl can include but not limited to: aminomethyl phenyl, ethylphenyl etc.
According to the present invention, the example of described internal electron donor compound a can include but not limited to: 2-isopropyl-malonic acid di-n-butyl, 2-isopropyl-malonic acid diisobutyl ester, 2-isopropyl-malonic acid two peopentyl ester, 2-decyl propanedioic acid di-n-butyl, 2-(2-amyl group) diethyl malonate, 2-cyclohexyl diethyl malonate, 2-cyclohexyl methyl diethyl malonate, 2-cyclohexyl methyl dimethyl malonate, 2, 2-dibenzyl diethyl malonate, 2-normal-butyl-2-isobutyl-dimethyl malonate, 2-sec.-propyl-2-diethyl butylmalonate, ethoxy methylene diethyl malonate, ethoxymeyhylene dimethyl malonate, methoxymethylene diethyl malonate, methoxymethylene dimethyl malonate.
Under preferable case, in formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
2-C
10straight or branched alkylene, C
3-C
10substituted or unsubstituted cycloalkyl, C
6-C
10substituted or unsubstituted aryl, C
7-C
10substituted or unsubstituted aralkyl and C
7-C
10substituted or unsubstituted alkaryl in one; In formula II, R
1' be C
1-C
10alkoxyl group; In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
10straight or branched alkyl, C
2-C
10straight or branched alkylene, C
3-C
10substituted or unsubstituted cycloalkyl, C
6-C
10substituted or unsubstituted aryl, C
7-C
10substituted or unsubstituted aralkyl and C
7-C
10substituted or unsubstituted alkaryl in one.。
More preferably in situation, in formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
6straight or branched alkyl and C
2-C
6straight or branched alkylene in one; In formula II, R
1' be C
1-C
6alkoxyl group; In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
3straight or branched alkyl.
In most preferred situation, described internal electron donor compound a is the malonate compound shown in formula II, in formula II, and R
1' be oxyethyl group, R
3and R
4be respectively ethyl, described internal electron donor compound a is ethoxy methylene diethyl malonate.
According to the present invention, described internal electron donor compound b is the diol ester compound shown in formula III,
formula III,
In formula III, R
5and R
6identical or different, be halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
2-C
20straight or branched alkylene; In formula III, the contents table of bracket " [] " is shown with n carbon atom key company successively, and each carbon atom also replaces base key even with 2, i.e. total n carbon atom and R in bracket
1, R
2, R
3r
2ndeng 2n substituting group;
R
7, R
8, R
9, R
10and R
1-R
2nidentical or different, be hydrogen, halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
20straight or branched alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20straight or branched alkyl, containing heteroatomic C
3-C
20substituted or unsubstituted cycloalkyl, containing heteroatomic C
6-C
20substituted or unsubstituted aryl, containing heteroatomic C
7-C
20substituted or unsubstituted aralkyl and containing heteroatomic C
2-C
20straight or branched alkylene in one, described heteroatoms is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus; Or, R
7, R
8, R
9, R
10and R
1-R
2nin two or more mutual bondings, to form saturated or unsaturated ring; N is the integer of 0-10, and as n=0, then in the dibasic alcohol ester compound shown in formula III, substituting group is R
7, R
8carbon atom directly and substituting group be R
9, R
10carbon atom key connect.
According to the present invention, the example of described internal electron donor compound b can include but not limited to: 1,3-PD dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2-propyl group-1,3-PD dibenzoate, 2-butyl-1,3-PD dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, 2-ethyl-2-butyl-1,3-PD dibenzoate, 2,2-diethyl-1,3-PD dibenzoate, 2-methyl-2-propyl-1,3-PD dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-PD dibenzoate, 2,4-glycol dibenzoate, 3-methyl-2,4-glycol dibenzoate, 3-ethyl-2,4-glycol dibenzoate, 3-propyl group-2,4-glycol dibenzoate, 3-butyl-2,4-glycol dibenzoate, 3,3-dimethyl-2,4-glycol dibenzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2,2-dimethyl-1,3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-propyl group-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2,2-dimethyl-1,3-glycol dibenzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2,2-dimethyl-1,3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2,2,4-trimethylammonium-1,3-glycol dibenzoate, 3-methyl-3-butyl-2,4-glycol dibenzoate, 2,2-dimethyl-1,5-PD dibenzoate, 1,6-hexylene glycol dibenzoate, 6-heptene-2,4-heptanediol dibenzoate, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl group-6-heptene-2,4-heptanediol dibenzoate, 4-propyl group-6-heptene-2,4-heptanediol dibenzoate, 5-propyl group-6-heptene-2,4-heptanediol dibenzoate, 6-propyl group-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 3-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 5-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 3-propyl group-3,5-heptanediol dibenzoate, 4-propyl group-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,3-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,4-dimethyl-3,5-heptanediol dibenzoate, 3,5-dimethyl-3,5-heptanediol dibenzoate, 3,6-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-5-ethyl-3,5-heptanediol dibenzoate, 2-methyl-3-propyl group-3,5-heptanediol dibenzoate, 2-methyl-4-propyl group-3,5-heptanediol dibenzoate, 2-methyl-5-propyl group-3,5-heptanediol dibenzoate, 3-methyl-3-propyl group-3,5-heptanediol dibenzoate, 3-methyl-4-propyl group-3,5-heptanediol dibenzoate, 3-methyl-5-propyl group-3,5-heptanediol dibenzoate, 4-methyl-3-propyl group-3,5-heptanediol dibenzoate, 4-methyl-4-propyl group-3,5-heptanediol dibenzoate, 4-methyl-5-propyl group-3,5-heptanediol dibenzoate.
Under preferable case, in described catalyst component, described internal electron donor compound b is the diol ester compound shown in formula IV,
formula IV,
In formula IV, R
11, R
12, R
13, R
14, R
15and R
16identical or different, be hydrogen or C independently of one another
1-C
20straight or branched alkyl.
Under most preferred case, described internal electron donor compound b is 2,4-glycol dibenzoate and/or 3,5-heptanediol dibenzoate.
According to olefin polymerization catalyst components of the present invention, to the content of described internal electron donor, there is no particular limitation, can change in wider scope, under preferable case, with the gross weight of described catalyst component for benchmark, the content of described internal electron donor is 5-25 % by weight, under further preferable case, with the gross weight of described catalyst component for benchmark, the content of described internal electron donor is 10-22 % by weight.
According to olefin polymerization catalyst components of the present invention, the present invention is by using internal electron donor compound a and internal electron donor compound b using specific ratio with the use of improving olefin polymerization catalyst components as internal electron donor for vertical structure orientation property during olefinic polymerization and polymkeric substance isotactic index, in described catalyst component, the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.007-2:1; In preferred situation, the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.05-1.2:1.
According to the present invention, in described catalyst component, ethoxy methylene diethyl malonate is as internal electron donor compound a, and adopt 2,4-glycol dibenzoate and/or 3,5-heptanediol dibenzoate is as internal electron donor compound b, and the mol ratio of described internal electron donor compound a and described internal electron donor compound b is when being 0.007-2:1, the catalyzer that vertical structure orientation property is higher can be obtained, make the isotactic index of olefin polymer higher, and this catalyst component have higher polymerization activity.
Improvement mainly of the present invention is the improvement to the internal electron donor in olefin polymerization catalyst components, in the present invention, using the malonate compound shown in formula I and/or formula II as the diol ester compound shown in internal electron donor a and formula III as internal electron donor b, and by both with the composite component being used as internal electron donor of specific ratio, when making this catalyst component for olefinic polymerization, the olefin polymer that isotactic index is higher can be obtained.In described olefin polymerization catalyst components, for the content of titanium, magnesium, halogen and internal electron donor, there is no particular limitation, reasonably can select according to the consumption of this area routine.Under preferable case, in the titanium of titanium elements, in the magnesium of magnesium elements, in the weight ratio of the halogen of halogens and internal electron donor for 1:3-15:8-30:2-12; Under further preferable case, in the titanium of titanium elements, in the magnesium of magnesium elements, in the weight ratio of the halogen of halogens and internal electron donor for 1:5-12:10-25:3-10.
According to the present invention, described halogen can be at least one in fluorine, chlorine, bromine and iodine, is preferably chlorine and/or bromine.
According to the present invention, described catalyst component can adopt the method for well known to a person skilled in the art to obtain.Such as magnesium compound and titanium compound are reacted, and add described internal electron donor in one or more time periods before and after, during described magnesium compound and titanium compound react, wherein, the above-mentioned internal electron donor of described internal electron donor compound.
According to the present invention, in preferred situation, described magnesium compound can be the adducts of the magnesium compound shown in the magnesium compound shown in formula V and/or formula V,
MgR
17r
18formula V,
In formula V, R
17and R
18be halogen, C independently of one another
1-C
5straight or branched alkoxyl group and C
1-C
5straight or branched alkyl in one.
In olefin polymerization catalyst components of the present invention, the adducts of the magnesium compound shown in described formula V refers to MgR
17r
18fR
0oHgEhH
2o, wherein, R
0for C
1-C
18alkyl, be preferably C
1-C
5alkyl, be more preferably methyl, ethyl, n-propyl and sec.-propyl; F is within the scope of 0.1-6, is preferably 2-3.5; E is a kind of electron donor compound, and described electron donor compound can be electron donor compound known in the field, and g is within the scope of 0-2; H is within the scope of 0-0.7.Preferably, in formula V, R
17and R
18being halogen independently of one another, such as, can be the one in chlorine, bromine and iodine.
According to the present invention, in preferred situation, described magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, methoxyl group magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, oxyethyl group magnesium chloride, oxyethyl group magnesium bromide, oxyethyl group magnesium iodide, propoxy-magnesium chloride, propoxy-magnesium bromide, propoxy-magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, magnesium dichloride, dibrominated magnesium, diiodinating magnesium, the alcohol adducts of magnesium dichloride, at least one in the alcohol adducts of dibrominated magnesium and the alcohol adducts of diiodinating magnesium.
Under further preferable case, described magnesium compound is the alcohol adducts of magnesium dichloride, and the alcohol adducts of described magnesium dichloride is spheroidal particle.
In the present invention, described magnesium compound is method known in the art preparation, such as, can prepare with reference to the preparation method of the carrier of adduct of magnesium halides disclosed in CN1091748A, CN101050245A, CN101486722A, CN102796132A, CN102796129A and CN102796128A.
Usually, the preparation method of the alcohol adducts of described spherical magnesium dichloride can comprise: by by magnesium dichloride and R
0oH carries out high-shear in dispersion medium at the temperature of 90-140 DEG C, then the reaction product obtained is placed in the heat-eliminating medium that temperature is-20 DEG C to 0 DEG C, thus forms spheroidal particle, through washing and the dry alcohol adducts that can obtain spherical magnesium dichloride.The method of described high-shear can be such as method disclosed in method disclosed in method disclosed in method disclosed in CN1330086, US6020279, CN1580136A and CN1463990A.Described dispersion medium can be hydrocarbon system solvent, such as: kerosene, white oil, silicone oil, paraffin oil and vaseline oil.Described heat-eliminating medium can be raffinating oil in pentane, hexane, heptane, sherwood oil and petroleum refining process.
When the alcohol adducts of described magnesium dichloride is spheroidal particle, be also spheroidal particle by the catalyst component that the alcohol adducts of magnesium dichloride and described titanium compound, internal electron donor compound a and internal electron donor compound b are reacted and obtain.
In the present invention, the titanium compound that described titanium compound can be commonly used for this area.Preferably, described titanium compound is the compound shown in formula VI and/or formula VII:
TiX
p(OR
19)
4-pformula VI,
TiX
q(OR
19)
3-qformula VII,
In formula VI and formula VII, X is halogen, R
19for C
1-C
20alkyl, p is the integer of 1-4, and q is the integer of 1-3.
Under further preferable case, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride, oxyethyl group titanous chloride and titanous chloride.Under most preferred case, described titanium compound is titanium tetrachloride.
In the present invention, the reaction of described magnesium compound and titanium compound can be implemented according to method disclosed in prior art, such as, titanium compound can be cooled to less than 0 DEG C (being preferably-5 to-25 DEG C), then magnesium compound is added, and be uniformly mixed 10-60 minute at such a temperature, be warming up to temperature of reaction (being preferably 60-130 DEG C) afterwards, and maintain 0.5-10 hour under this temperature of reaction.Internal electron donor compound a and internal electron donor compound b is added in temperature-rise period.Then add titanium compound process one or many, finally, repeatedly wash with inert solvent, thus obtain catalyst component.The example of described inert solvent can include but not limited to: hexane, heptane, octane, decane and toluene.
In the preparation method of the described catalyst component for olefinic polymerization, described internal electron donor before and after, during the reaction of described magnesium compound and described titanium compound in one or more time periods in add.Time period before the reaction of described magnesium compound and described titanium compound refers to the time period after described magnesium compound adds in reactor and before being warming up to temperature of reaction.
In the present invention, when preparing described catalyst component, described internal electron donor compound a and internal electron donor compound b can gradation or simultaneously add in the mixture of described magnesium compound and described titanium compound.When described internal electron donor compound a and internal electron donor compound b gradation are added in the mixture of described magnesium compound and described titanium compound, both can first add described internal electron donor compound a, then add described internal electron donor compound b; Also can first add described internal electron donor compound b, then add described internal electron donor compound a.
According to the present invention, when preparing described catalyst component, to the consumption of described magnesium compound, described titanium compound and described internal electron donor, there is no particular limitation, can change in wider scope, under preferable case, the mol ratio of described magnesium compound, described titanium compound and described internal electron donor is 1:20-140:0.1-0.8, and under further preferable case, the mol ratio of described magnesium compound, described titanium compound and described internal electron donor is 1:30-120:0.2-0.6.Wherein, the add-on of described internal electron donor compound a and described internal electron donor compound b in mole, the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.005-3:1, is preferably 0.05-1.8:1.
The present invention also provides a kind of olefin polymerization catalysis, and this olefin polymerization catalysis contains:
(1) above-mentioned olefin polymerization catalyst components;
(2) as the alkylaluminium cpd of promotor; And
(3) optionally, external donor compound.
According to the present invention, in above-mentioned olefin polymerization catalysis, the various alkylaluminium cpds that can be used as the promotor of olefin polymerization catalysis that described alkylaluminium cpd can be commonly used for field of olefin polymerisation.Under preferable case, described alkylaluminium cpd is the compound shown in formula VIII,
AlR '
n'x '
3-n'formula VIII,
In formula VIII, R ' is C
1-C
8alkyl or haloalkyl, X ' is halogen, and n' is the integer of 1-3.In formula VIII, X ' be preferably in chlorine, bromine and iodine one or more, be more preferably chlorine.
Under further preferable case, described alkylaluminium cpd is triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride, Al (n-C
6h
13)
3with Al (n-C
8h
17)
3in one or more.
Most preferably, described alkylaluminium cpd is triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, the consumption of described alkylaluminium cpd can be the conventional amount used of this area.Preferable case, the mol ratio of the titanium in the aluminium in described alkylaluminium cpd and described catalyst component is 1-2000:1.Under further preferable case, the mol ratio of the titanium in the aluminium in described alkylaluminium cpd and described catalyst component is 10-500:1.
Owing to only improving the internal electron donor in olefin polymerization catalyst components in olefin polymerization catalysis of the present invention, therefore, there is no particular limitation for the kind of the external electron donor in olefin polymerization catalysis of the present invention and content.In preferred situation, the mol ratio of the aluminium in described alkylaluminium cpd and described external donor compound is 2-200:1, is more preferably 2.5-100:1.
According to the present invention, described external donor compound is combined the isotactic index that can improve the olefin polymer that method according to the present invention obtains further with described internal electron donor compound a and described internal electron donor compound b.The various external donor compounds that can realize above-mentioned purpose that described external donor compound can be commonly used for this area, such as: one or more in carboxylic acid, carboxylic acid anhydride, carboxylicesters, ketone, ether, alcohol, lactone, organo phosphorous compounds and silicoorganic compound.Preferably, described external donor compound is the silicoorganic compound shown in formula Ⅸ,
(R
20)
m '(R
21)
p 'si (OR
22)
q 'formula Ⅸ,
In formula Ⅸ, R
20, R
21and R
22be C independently of one another
1-C
18alkyl, optionally containing heteroatoms, described heteroatoms is one or more in F, Cl, Br, N and I; M ' and p ' is the integer of 0-2 independently of one another, the integer that q ' is 1-3, and m ', p ' and q's ' and be 4.
Under preferable case, R
20and R
21be C independently of one another
3-C
10straight or branched alkyl, C
3-C
10alkylene, C
3-C
10alkylidene group, C
3-C
10substituted or unsubstituted cycloalkyl and C
6-C
10substituted or unsubstituted aryl, optionally containing heteroatoms, described heteroatoms is one or more in F, Cl, Br, N and I; R
22for C
1-C
10straight or branched alkyl, be more preferably methyl.
According to the present invention, the specific examples of described external donor compound can for but be not limited to: one or more in Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, tertiary hexyl Trimethoxy silane and 2-ethyl piperidine base-2-t-butyldimethoxysilane.
Under further preferable case, described external donor compound is Cyclohexyl Methyl Dimethoxysilane and/or dicyclopentyl dimethoxyl silane.
In addition, present invention also offers a kind of olefine polymerizing process, under the method is included in olefin polymerization conditions, one or more alkene are contacted with above-mentioned olefin polymerization catalysis, at least one in described alkene is by formula CH
2the alkene that=CHR represents, wherein R is hydrogen or C
1-C
6straight or branched alkyl.
Olefine polymerizing process of the present invention may be used for all polymerizations of alkene, also may be used for multiple alkene to carry out copolymerization.At least one in described alkene is by formula CH
2the alkene that=CHR represents, wherein R is hydrogen or C
1-C
6straight or branched alkyl.Described by formula CH
2the specific examples of the alkene that=CHR represents can comprise: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.Under preferable case, described by formula CH
2the alkene that=CHR represents is one or more in ethene, propylene, 1-n-butene, 1-n-hexylene and 4-methyl-1-pentene.More preferably, described by formula CH
2the alkene that=CHR represents is propylene.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area.Usually, described olefin polymerization conditions can comprise: temperature is 0-150 DEG C, and the time is 0.1-5 hour, and pressure is 0.01-10MPa.Preferably, described olefin polymerization conditions comprises: temperature is 50-100 DEG C, and the time is 0.5-3 hour, and pressure is 0.5-5MPa.The consumption of described olefin polymerization catalysis can be the various conventional amount used of prior art alkene catalyst.
Below will be described the present invention by embodiment.
The testing method used in following examples is as follows:
1, polymkeric substance isotactic index: adopt heptane extraction process to measure: by 2 grams of dry polymer samples, be placed in Soxhlet extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to constant weight, calculate the isotactic index of polymkeric substance according to the following formula:
Polymer quality/2 × 100 after degree of isotacticity (%)=extracting.
Embodiment 1
The present embodiment is for illustration of olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
In the glass reaction bottle that the 300ml band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 90mL, be cooled to-20 DEG C, under agitation add the alcohol adducts (MgCl of the spherical magnesium dichloride of 8g
22.6C
2h
5oH, disclosed in CN1330086A, method magnesium dichloride and ethanol synthesize), be slowly warming up to 110 DEG C stage by stage, add respectively in temperature-rise period ethoxy methylene diethyl malonate (internal electron donor compound a, formula II, R '
1for oxyethyl group, R
3and R
4for ethyl) 0.0025mol and 2,4-glycol dibenzoate (internal electron donor compound b) 0.0067mol, after 110 DEG C of constant temperature keep 0.5h, elimination liquid, the titanium tetrachloride stir process twice of 80mL is added in the solid phase that filtration obtains, then wash five times with the hexane of 60mL, after vacuum-drying, obtain spherical catalyst components A1.
Olefinic polymerization: in the autoclave of a 5L, stream of nitrogen gas is adopted to purge, then in stream of nitrogen gas, the obtained spherical catalyst components A1 of the above-mentioned preparation example of the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of 5mL, the hexane solution (the concentration 0.1mmol/mL of CHMMS) of Cyclohexyl Methyl Dimethoxysilane (CHMMS) of 1mL, the anhydrous hexane of 10mL and 8mg is introduced to described reactor, close autoclave, add the liquid propene of hydrogen and 2.3L.Be warmed up to 70 DEG C, be polymerized 1 hour, obtain polypropylene.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Embodiment 2
The present embodiment is for illustration of olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.005mol, obtain catalyst component A2.
And prepare polypropylene according to the method for embodiment 1, add the amount of hydrogen in table 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Embodiment 3
The present embodiment is for illustration of olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.0035mol, and add the 4-ethyl-3 of 0.0085mol, 5-heptanediol dibenzoate (internal electron donor compound b) replaces 2,4-glycol dibenzoate, obtains catalyst component A3.
And prepare polypropylene according to the method for embodiment 1, add the amount of hydrogen in table 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Embodiment 4
The present embodiment is for illustration of olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.0004mol, obtain catalyst component A4.
And prepare polypropylene according to the method for embodiment 1, add the amount of hydrogen in table 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Embodiment 5
The present embodiment is for illustration of olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.008mol, obtain catalyst component A5.
And prepare polypropylene according to the method for embodiment 1, add the amount of hydrogen in table 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Comparative example 1
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, in Kaolinite Preparation of Catalyst component process, do not add ethoxy methylene diethyl malonate, only add 2,4-glycol dibenzoate 0.0067mol, obtain catalyst component B1.
Use above-mentioned catalyst component B1 to replace olefin polymerization catalyst components A1, prepare polypropylene according to the method for embodiment 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Comparative example 2
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, in Kaolinite Preparation of Catalyst component process, do not add 2,4-glycol dibenzoate, only add ethoxy methylene diethyl malonate 0.01mol, obtain catalyst component B2.
Use above-mentioned catalyst component B2 to replace olefin polymerization catalyst components A1, and prepare polypropylene according to the method for embodiment 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Comparative example 3
Olefin polymerization catalyst components is prepared according to the method for embodiment 3, unlike, do not add ethoxy methylene diethyl malonate, only add 4-ethyl-3,5-heptanediol dibenzoate 0.0085mol, obtain catalyst component B3.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Use above-mentioned catalyst component B3 to replace olefin polymerization catalyst components A3, and prepare polypropylene according to the method for embodiment 3.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Comparative example 4
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.00001mol, obtain catalyst component B4.
Use above-mentioned catalyst component B4 to replace olefin polymerization catalyst components A1, and prepare polypropylene according to the method for embodiment 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Comparative example 5
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, add ethoxy methylene diethyl malonate 0.008mol, add 2,4-glycol dibenzoate 0.0034mol, obtain catalyst component B5.
Use above-mentioned catalyst component B5 to replace olefin polymerization catalyst components A1, and prepare polypropylene according to the method for embodiment 1.The test result of the polyacrylic isotactic index obtained and the polymerization activity of catalyzer is in table 1.
Table 1
The result of embodiment 1-5 and comparative example 1-5 as can be seen from table 1, adopt malonate compound and the composite component as internal electron donor of diol ester compound, and both mol ratios are in certain scope, can significantly improve than the vertical structure directional property of the catalyzer taking single compound as internal electron donor, the isotactic index of resulting polymers is also significantly improved, and the polymerization activity of catalyzer also significantly increase.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. an olefin polymerization catalyst components, this catalyst component contains magnesium, titanium, halogen and internal electron donor, it is characterized in that, described internal electron donor contains internal electron donor compound a and internal electron donor compound b, and the mol ratio of described internal electron donor compound a and described internal electron donor compound b is 0.007-2:1, described internal electron donor compound a is the malonate compound shown in formula I and/or formula II, described internal electron donor compound b is the diol ester compound shown in formula III
formula I,
formula II,
In formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
1and R
2mutual bonding, to form ring;
In formula II, R
1' be C
1-C
20alkoxyl group;
In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
20straight or branched alkyl, C
2-C
20straight or branched alkylene, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
7-C
20substituted or unsubstituted alkaryl in one; Or, R
3and R
4mutual bonding, to form ring;
formula III,
In formula III, R
5and R
6identical or different, be halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl and C
2-C
20straight or branched alkylene;
R
7, R
8, R
9, R
10and R
1-R
2nidentical or different, be hydrogen, halogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20substituted or unsubstituted cycloalkyl, C
6-C
20substituted or unsubstituted aryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
20straight or branched alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20straight or branched alkyl, containing heteroatomic C
3-C
20substituted or unsubstituted cycloalkyl, containing heteroatomic C
6-C
20substituted or unsubstituted aryl, containing heteroatomic C
7-C
20substituted or unsubstituted aralkyl and containing heteroatomic C
2-C
20straight or branched alkylene in one; Or, R
7, R
8, R
9, R
10and R
1-R
2nin two or more mutual bondings, to form ring; Described heteroatoms is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus,
N is the integer of 0-10.
2. catalyst component according to claim 1, wherein, with the gross weight of catalyst component for benchmark, the content of described internal electron donor is 5-25 % by weight, is preferably 10-22 % by weight.
3. catalyst component according to claim 1, wherein, in formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
2-C
10straight or branched alkylene, C
3-C
10substituted or unsubstituted cycloalkyl, C
6-C
10substituted or unsubstituted aryl, C
7-C
10substituted or unsubstituted aralkyl and C
7-C
10substituted or unsubstituted alkaryl in one; In formula II, R
1' be C
1-C
10alkoxyl group; In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
10straight or branched alkyl, C
2-C
10straight or branched alkylene, C
3-C
10substituted or unsubstituted cycloalkyl, C
6-C
10substituted or unsubstituted aryl, C
7-C
10substituted or unsubstituted aralkyl and C
7-C
10substituted or unsubstituted alkaryl in one.
4. catalyst component according to claim 3, wherein, in formula I, R
1and R
2identical or different, be hydrogen, C independently of one another
1-C
6straight or branched alkyl and C
2-C
6straight or branched alkylene in one; In formula II, R
1' be C
1-C
6alkoxyl group; In formula I and formula II, R
3and R
4identical or different, be C independently of one another
1-C
3straight or branched alkyl, preferably, described internal electron donor compound a is ethoxy methylene diethyl malonate.
5. catalyst component according to claim 1, wherein, in described catalyst component, described internal electron donor compound b is the diol ester compound shown in formula IV,
formula IV,
In formula IV, R
11, R
12, R
13, R
14, R
15and R
16identical or different, be hydrogen or C independently of one another
1-C
20straight or branched alkyl;
Preferably, described internal electron donor compound b is 2,4-glycol dibenzoate and/or 3,5-heptanediol dibenzoate.
6. according to the catalyst component in claim 1-5 described in any one, wherein, described catalyst component is prepared by the following method: magnesium compound and titanium compound are reacted, and adds described internal electron donor in one or more time periods before and after, during described magnesium compound and titanium compound react.
7. an olefin polymerization catalysis, this olefin polymerization catalysis contains:
(1) olefin polymerization catalyst components in claim 1-6 described in any one;
(2) as the alkylaluminium cpd of promotor; And
(3) optionally, external donor compound.
8. an olefine polymerizing process, under the method is included in olefin polymerization conditions, make one or more alkene and catalyst exposure according to claim 7, at least one in described alkene is by formula CH
2the alkene that=CHR represents, wherein R is hydrogen or C
1-C
6straight or branched alkyl.
9. method according to claim 8, wherein, described by formula CH
2the alkene that=CHR represents is at least one in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
10. method according to claim 8, wherein, described olefin polymerization conditions comprises: temperature is 0-150 DEG C, and the time is 0.1-5 hour, and pressure is 0.01-10MPa.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928359A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
-
2013
- 2013-06-28 CN CN201310269152.7A patent/CN104250321B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928359A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
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| CN104558293B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| CN106543314A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The application of catalyst containing ether ester and the catalyst and ether ester in olefinic polyreaction |
| CN106543313A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543312A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543310A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543313B (en) * | 2015-09-23 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543310B (en) * | 2015-09-23 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543314B (en) * | 2015-09-23 | 2019-02-19 | 中国石油化工股份有限公司 | The application of catalyst containing ether ester and the catalyst and ether ester in olefin polymerization |
| CN105085745A (en) * | 2015-09-29 | 2015-11-25 | 李海燕 | Internal electron donor of olefinic polymerization catalyst, catalyst ingredient, and preparation method |
| CN106608937B (en) * | 2015-10-27 | 2019-04-19 | 中国石油化工股份有限公司 | Catalytic component and its preparation method and application for olefinic polymerization |
| CN106608937A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
| CN106608940A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method for catalyst components used for olefin polymerization |
| CN106608940B (en) * | 2015-10-27 | 2019-06-28 | 中国石油化工股份有限公司 | The preparation method of catalytic component for olefinic polymerization |
| 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 |
| CN110511303A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| CN110511303B (en) * | 2018-05-21 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN111072809A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072809B (en) * | 2018-10-19 | 2022-05-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
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