CN105440177A - Olefin polymerization catalyst component and preparation method thereof and olefin polymerization catalyst and application thereof - Google Patents
Olefin polymerization catalyst component and preparation method thereof and olefin polymerization catalyst and application thereof Download PDFInfo
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- CN105440177A CN105440177A CN201410404254.XA CN201410404254A CN105440177A CN 105440177 A CN105440177 A CN 105440177A CN 201410404254 A CN201410404254 A CN 201410404254A CN 105440177 A CN105440177 A CN 105440177A
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Abstract
The present invention discloses an olefin polymerization catalyst component and a preparation method thereof and an olefin polymerization catalyst and application thereof. The catalyst component comprises the following the reaction product components: (i) a magnesium-containing compound; (ii) a titanium-containing compound; and (iii) an internal electron donor; wherein the internal electron donor is a combination of an internal electron donor compound a, an internal electron donor compound b and an internal electron donor compound c, the internal electron donor compound a is a diol ester compound shown as a formula I, the internal electron donor compound b is a diether compound shown as a formula II, and the internal electron donor compound c is an alkylene oxide compound shown as a formula III. The olefin polymerization catalyst component during being used in olefin polymerization has high stereoregularity orientation property, meanwhile polymerization activity is high, and a high isotactic index and low ash content olefin polymer can be obtained in the condition of no use or a very small amount of use of an external electron donor.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalyst components and preparation method thereof and olefin polymerization catalysis and application thereof.
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, and its important indicator such as the isotactic index to polymerization activity, polymkeric substance, molecular weight and molecualr weight distribution plays conclusive effect.Along with the development of internal electron donor compound, polyolefin catalyst constantly updates.
The catalyzer containing different internal electron donor is adopted to have different characteristics, such as, some catalyzer has higher polymerization activity, and some catalyzer has good hydrogen response, and the polyolefin resin of some catalyst preparing has wider molecular weight distribution etc.And in polyolefinic industrial production, extremely need the catalyzer with excellent over-all properties, particularly also there is the catalyzer of high directionality while there is high reactivity, high hydrogen response.
The vertical structure directional property of catalyzer decides the isotactic index of polymkeric substance, and the isotactic index performance index that to be of polymkeric substance important, polyacrylic isotactic index is higher, its alignment degree, degree of crystallinity are also higher, the hardness of product, rigidity, modulus, the mechanical property such as fracture and yield strength increase all to some extent, and fusing point, thermostability, ageing resistance and resistance to width penetrate performance also corresponding raising.Therefore, in order to improve the vertical structure directional property of catalyzer, investigators are carrying out a large amount of research work always.Adopt the catalyzer containing two kinds of composite (or two or more) internal electron donors to make up the deficiency of the performance of the catalyzer containing single internal electron donor in some research, thus improve the performance of catalyzer.But composite effect is not the simple superposition of several electron donor performance.Such as, be generally that the polypropylene degree of isotacticity of the catalyzer gained of internal electron donor is low with monocarboxylic ester, product need take off random thing.And WO03002617 disclose a kind of with monocarboxylic ester and dicarboxylic esters with the use of the catalyst component for olefinic polymerization obtained and catalyzer, the hydrogen response of this catalyzer is good, but stereospecificity and polymerization activity are not still very high.
Adopt in catalyst component disclosed in CN101724102A and catalyzer diol-lipid compound and diether compound composite as internal electron donor, when the catalyzer containing this internal electron donor is used for olefinic polymerization, there is the polymerization activity of superelevation and higher vertical structure directional property.Compared with similar catalyst, activity and the vertical structure directional property of this catalyzer are all in higher level.Therefore, if increase the vertical structure directional property of olefin polymerization catalysis on this basis further, be particularly valuable, this is very favorable for producing some polypropylene with high isotactic.
Therefore, develop a kind of catalyzer of high comprehensive performance, namely highly actively have higher vertical structure directional property in maintenance, the catalyzer making olefin polymer have higher isotactic index and lower ash oontent is still the problem that is needed badly solution simultaneously.
Summary of the invention
Object of the present invention overcomes the above-mentioned defect of olefin polymerization catalysis in prior art and provides a kind of olefin polymerization catalyst components and preparation method thereof and olefin polymerization catalysis and application thereof.
The present inventor is in the favorite outer discovery of research process, employing diol-lipid compound and diether compound composite as the basis of internal electron donor adding a small amount of alkylene oxides compound, can make olefin polymerization catalysis under the prerequisite keeping high polymerization activity, vertical structure directional property is further improved.Thus, when using this catalyst component to prepare olefin polymer, the olefin polymer of high isotactic index and low ash content can be obtained when not using or use the external electron donor of seldom amount.
The invention provides a kind of olefin polymerization catalyst components, this catalyst component contains the reaction product of following component:
(i) magnesium-containing compound;
(ii) titanium-containing compound; And
(iii) internal electron donor;
Wherein, described internal electron donor is the combination of internal electron donor compound a, internal electron donor compound b and internal electron donor compound c, described internal electron donor compound a is the diol ester compound shown in formula I, described internal electron donor compound b is the diether compound shown in formula II, described internal electron donor compound c is the alkylene oxides compound shown in formula III
In formula I, R
1and R
2identical or different, be C independently of one another
1-C
10straight 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
7-C
20substituted or unsubstituted alkaryl in one, the aromatic ring in described aryl, aralkyl or alkaryl is optionally selected from halogen, C
1-C
6straight or branched alkyl and C
1-C
6alkoxyl group in one or more replace;
R
3, R
4, R
5, R
6and 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 alkaryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
10straight or branched alkylene and C
10-C
20fused ring aryl in one, R
3, R
4, R
5, R
6and R
1-R
2noptionally containing heteroatoms, described heteroatoms is one or more in nitrogen, oxygen, sulphur, silicon, halogen and phosphorus;
Or, R
3, R
4, R
5, R
6and R
1-R
2nin two or more mutual bondings, to form ring;
N is the integer of 0-10;
In formula II, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6identical 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 and C
7-C
20substituted or unsubstituted alkaryl in one;
R '
7and R '
8identical or different, be 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
7-C
20substituted or unsubstituted alkaryl in one;
Or, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6in two or more mutual bondings, to form ring;
In formula III, R "
1and R "
2identical or different, be hydrogen, C independently of one another
1-C
5straight or branched alkyl or haloalkyl.
Present invention also offers a kind of preparation method of above-mentioned olefin polymerization catalyst components, the method comprises reacts above-mentioned magnesium-containing carrier and described titanium compound, and adds described internal electron donor in one or more time periods before and after, during described magnesium-containing carrier and described titanium compound react.
In addition, the present invention also provides a kind of olefin polymerization catalysis, and 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 the application of above-mentioned olefin polymerization catalysis in olefinic polyreaction.
Olefin polymerization catalyst components of the present invention is by adopting diol ester compound, diether compound and alkylene oxides compound composite as internal electron donor component, when making it for olefinic polymerization, there is high vertical structure directional property, polymerization activity is higher simultaneously, and can obtain the olefin polymer of high isotactic index and low ash content when not using or use the external electron donor of seldom amount.
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 the reaction product of following component:
(i) magnesium-containing compound;
(ii) titanium-containing compound; And
(iii) internal electron donor;
Wherein, described internal electron donor is the combination of internal electron donor compound a, internal electron donor compound b and internal electron donor compound c.
According to the present invention, described internal electron donor compound a is the diol ester compound shown in formula I,
In formula I, R
1and R
2identical or different, be C independently of one another
1-C
10straight 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
7-C
20substituted or unsubstituted alkaryl in one, the aromatic ring in described aryl, aralkyl or alkaryl is optionally selected from halogen, C
1-C
6straight or branched alkyl and C
1-C
6alkoxyl group in one or more replace; In formula I, 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
3, R
4, R
5, R
6and 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 alkaryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
10straight or branched alkylene and C
10-C
20fused ring aryl in one, R
3, R
4, R
5, R
6and R
1-R
2noptionally containing heteroatoms, described heteroatoms is one or more in nitrogen, oxygen, sulphur, silicon, halogen and phosphorus;
Or, R
3, R
4, R
5, R
6and 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, in the diol ester compound shown in formula I, substituting group is R
3, R
4carbon atom directly and substituting group be R
5, R
6carbon atom key connect;
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
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, aminomethyl phenyl, ethylphenyl, 4-tert-butyl-phenyl 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.
In the present invention, C
1-C
6the example of alkoxyl group can include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, tertiary pentyloxy and hexyloxy.
In the present invention, C
2-C
10the example of straight or branched alkylene can include but not limited to: vinyl, propenyl, butenyl, pentenyl, octenyl etc.
In the present invention, C
10-C
20the example of fused ring aryl can include but not limited to: naphthyl, anthryl, phenanthryl, pyrenyl etc.
According to the present invention, the example of described internal electron donor compound a 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 etc.
Under preferable case, described internal electron donor compound a is the diol ester compound shown in formula IV,
In formula IV, R
7, R
8, R
9, R
10, R
11and R
12identical 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 a is 2,4-glycol dibenzoate and/or 3,5-heptanediol dibenzoate.
According to the present invention, described internal electron donor compound b is the diether compound shown in formula II,
In formula II, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6identical 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 and C
7-C
20substituted or unsubstituted alkaryl in one;
R '
7and R '
8can be identical or different, and be 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
7-C
20substituted or unsubstituted alkaryl in one;
Or, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6in two or more mutual bondings, to form saturated or undersaturated ring.
In preferred situation, described internal electron donor compound b is 1,3-diether compound shown in formula V,
In formula V, R '
9and R '
10can be identical or different, be hydrogen, halogen, C independently of one another
1-C
18straight or branched alkyl, C
3-C
18substituted or unsubstituted cycloalkyl, C
6-C
18substituted or unsubstituted aryl and C
7-C
18substituted or unsubstituted aralkyl in one, or, R '
9and R '
10mutual bonding, to form ring; R '
11and R '
12can be identical or different, be C independently of one another
1-C
10straight or branched alkyl.
According to the present invention, the example of described internal electron donor compound b can include but not limited to: 2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-butyl-1,3-Propanal dimethyl acetal, 2-sec-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-1,3-Propanal dimethyl acetal, 2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1,3-Propanal dimethyl acetal, 2-(2-cyclohexyl-ethyl)-1,3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1,3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1,3-Propanal dimethyl acetal, two (2-cyclohexyl-ethyl)-1, the 3-Propanal dimethyl acetal of 2,2-, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two (cyclohexyl methyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-sec-butyl-1,3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec-butyl 1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec-butyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-sec-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal, 9,9-dimethoxy-methyl fluorenes.
Under most preferred case, described internal electron donor compound b is 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and/or 9,9-dimethoxy-methyl fluorenes.
In the present invention, described 1,3-diether compound can synthesize with reference to method disclosed in CN1020448C, CN100348624C and CN1141285A.Repeat no more herein.
According to the present invention, described internal electron donor compound c is the alkylene oxides compound shown in III,
In formula III, R "
1and R "
2identical or different, be hydrogen, C independently of one another
1-C
5straight or branched alkyl or haloalkyl, preferably, R "
1and R "
2identical or different, be hydrogen, C independently of one another
1-C
3straight or branched alkyl or haloalkyl, further in preferred situation, R "
1and R "
2can be hydrogen, methyl, ethyl, propyl group, chloromethyl, Chloroethyl, chloro propyl group, bromomethyl, bromoethyl or Bromopropyl.
Under most preferred case, described internal electron donor compound c is one or more in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
The present inventor finds in research process, adopt 2, 4-glycol dibenzoate and/or 3, 5-heptanediol dibenzoate is as internal electron donor compound a, adopt 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal and/or 9, 9-dimethoxy-methyl fluorenes is as internal electron donor compound b, and employing oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, one or more in epoxy bromopropane and epoxy n-butyl bromide are as internal electron donor compound c, by internal electron donor compound a, when interior electron compound b and internal electron donor compound c is used for olefinic polymerization with the use of the olefin polymerization catalyst components prepared, there is high vertical structure directional property, polymerization activity is higher simultaneously, and the olefin polymer of high isotactic index and low ash content can be obtained when not using or use the external electron donor of seldom amount.
According to olefin polymerization catalyst components of the present invention, the present invention obtains the olefin polymer with high isotactic index and low ash content by using internal electron donor compound a, internal electron donor compound b and internal electron donor compound c to combinationally use as internal electron donor component, in preferred situation, in described catalyst component, the mol ratio of described internal electron donor compound a, described internal electron donor compound b and described internal electron donor compound c consumption is 0.5-10:1-12:1; Further in preferred situation, the mol ratio of described internal electron donor compound a, described internal electron donor compound b and described internal electron donor compound c consumption is 1-7:1.5-10:1.
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 diol ester compound shown in formula I as the diether compound shown in internal electron donor compound a and formula II as internal electron donor compound b and using the alkylene oxides compound shown in formula III as internal electron donor compound c, and triplicity is used as internal electron donor, when making this catalyst component for olefinic polymerization, there is high vertical structure directional property, polymerization activity is higher simultaneously, and high isotactic index and low-ash olefin polymer can be obtained when not using or use the external electron donor of seldom amount.In the present invention, when preparing described catalyst component, to described magnesium-containing compound, there is no particular limitation for the mol ratio of described titanium-containing compound and described internal electron donor amounts of components, can change in wider scope, under preferable case, described magnesium-containing compound, the mol ratio of described titanium-containing compound and described internal electron donor consumption is 1:10-200:0.04-0.8, under further preferable case, described magnesium-containing compound, the mol ratio of described titanium-containing compound and described internal electron donor consumption is 1:20-180:0.05-0.5, under further preferable case, described magnesium-containing compound, the mol ratio of described titanium-containing compound and described internal electron donor consumption is 1:50-120:0.2-0.4.
According to the present invention, described catalyst component is prepared preferably by following methods: above-mentioned magnesium-containing compound and above-mentioned titanium-containing compound are reacted, and adds described internal electron donor in one or more time periods before and after, during described magnesium-containing compound and described titanium-containing compound react.
According to the present invention, in preferred situation, described magnesium-containing compound can be the adducts of the magnesium-containing compound shown in the magnesium-containing compound shown in formula VI and/or formula VI,
MgR
13r
14formula VI,
In formula VI, R
13and R
14can be identical or different, be 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-containing compound shown in described formula VI refers to MgR
13r
14fR
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 be in 0.1-6 scope within, be preferably 2-3.5; E is a kind of electron donor compound, and this electron donor can be various 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 VI, R
13and R
14being 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-containing 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-containing 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, wherein, R
0for C
1-C
18alkyl, be preferably C
1-C
5alkyl, be more preferably methyl, ethyl, n-propyl and sec.-propyl.Magnesium dichloride and R
0the mol ratio of OH can be 1:1-6, is preferably 1:2-4.
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-containing compound, internal electron donor compound a, internal electron donor compound b and internal electron donor compound c are reacted and obtain.
In the present invention, the titanium-containing compound that described titanium-containing compound can be commonly used for this area.Preferably, described titanium compound is the compound shown in formula VII and/or formula VIII:
TiX
p(OR
15)
4-pformula VII,
TiX
q(OR
15)
3-qformula VIII,
In formula VII and formula VIII, X is halogen, R
15for 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-containing 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-containing compound is titanium tetrachloride.
Preferably, the method of described Kaolinite Preparation of Catalyst component also comprises and to be filtered by liquid and to reclaim solid, the titanium compound (as titanium tetrachloride) of reusable liquid is to the solids wash reclaimed, relative to every gram of magnesium-containing compound, the consumption of the titanium compound of described liquid state is preferably 8mL-40mL, and then repeatedly washs the ingredient of solid catalyst obtained with inert solvent.Described inert solvent can be selected from aliphatic and aromatic hydrocarbons, such as, and hexane, heptane, octane, decane, toluene etc.
In the preparation method of the described catalyst component for olefinic polymerization, described internal electron donor component before and after, during the reaction of described magnesium-containing compound and described titanium-containing compound in one or more time periods in add.Time period before the reaction of described magnesium-containing compound and described titanium-containing 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, internal electron donor compound b and internal electron donor compound c can gradation or simultaneously add in the mixture of described magnesium-containing compound and described titanium-containing compound.When described internal electron donor compound a, internal electron donor compound b and internal electron donor c gradation are added in the mixture of described magnesium-containing compound and described titanium-containing compound, both can first add described internal electron donor compound a and internal electron donor compound b, then add described internal electron donor compound c; Also can first add described internal electron donor compound c, then add described internal electron donor compound a and internal electron donor compound b.Preferably, join after electron donor compound a, b, c mixing together in the mixture of described magnesium-containing compound and described titanium-containing compound.
According to the present invention, the reaction of described magnesium-containing compound and titanium-containing compound can be implemented according to method disclosed in prior art, such as, titanium-containing compound can be cooled to less than 0 DEG C (being preferably-5 to-35 DEG C), then magnesium-containing 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, internal electron donor compound b and internal electron donor compound c is added in temperature-rise period.Then liquid filtered and reclaim solid, and with the solid one or many that liquid titanium compound process is reclaimed, finally, repeatedly washing with inert solvent, thus obtain catalyst component.
The present invention also provides a kind of olefin polymerization catalysis, and this catalyzer 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 Ⅸ,
AlR '
n'x '
3-n'formula Ⅸ,
In formula Ⅸ, R ' is C
1-C
8alkyl or haloalkyl, X ' is halogen, the integer that n ' is 1-3.In formula Ⅸ, 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 1-500:1.Under further preferable case, the mol ratio of the titanium in the aluminium in described alkylaluminium cpd and described catalyst component is 10-300:1, in most preferred situation, the mol ratio of the titanium in the aluminium in described alkylaluminium cpd and described catalyst component is 20-200:1.
Owing to only improving the internal electron donor component 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 consumption is 2-500:1, is more preferably 5-200:1; Or do not use external electron donor.
According to the present invention, 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 Ⅹ,
(R
16)
m '(R
17)
p 'si (OR
18)
q 'formula Ⅹ,
In formula Ⅹ, R
16, R
17and R
18be 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
16and R
17be 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 in a kind of, optionally containing heteroatoms, described heteroatoms is one or more in F, Cl, Br, N and I; R
18for C
1-C
10straight or branched alkyl, be more preferably methyl.
According to the present invention, the specific examples of described silicoorganic 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.
Present invention also offers the application of above-mentioned olefin polymerization catalysis in olefinic polyreaction.
Improvements of the present invention are to have employed a kind of catalyzer for olefinic polymerization newly, and the polymerisation process of the concrete kind of alkene, alkene and condition all can be same as the prior art.
According to the present invention, under the method for olefinic polymerization is included in olefin polymerization conditions, one or more alkene are contacted with above-mentioned olefin polymerization catalysis, and 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.
Olefin polymerization catalysis 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.
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 60-100 DEG C, and the time is 0.5-3 hour, and pressure is 0.5-5MPa.Pressure of the present invention all refers to gauge pressure.The consumption of described olefin polymerization catalysis can be the various conventional amount used of prior art alkene catalyst.In the course of the polymerization process, hydrogen can be used as molecular weight and the melting index that polymericular weight conditioning agent joins telomerized polymer in polymerization container.
Below will be described the present invention by embodiment.
The performance test related in following examples is as follows:
1, polymkeric substance isotactic index: adopt heptane extraction process to measure (heptane boiling extracting 6 hours): by 2 grams of dry polymer samples, be placed on seething with excitement heptane extracting after 6 hours in extractor, the ratio of the polymer weight (g) and 2 (g) that residuum are dried to constant weight gained is isotactic index.
2, the mensuration of polymkeric substance ash oontent: measure according to GB/T9345-1988.
3, the titanium content in olefin polymerization catalyst components adopts spectrophotometry, measures the massfraction of Ti in catalyst component with Shanghai analytical instrument factory 722 type grating spectrophotometer.
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 0.912mol and the hexane of 10mL, be cooled to-20 DEG C, add 8g (0.0372mol) spherical magnesium chloride alcohol adduct (MgCl
22.6C
2h
5oH, disclosed in CN1330086A, method magnesium dichloride and ethanol synthesize), under agitation, slowly heat up stage by stage, 2 are added in temperature-rise period, (internal electron donor compound is 5mmol a) for 4-glycol dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 5mmol and epoxy chloropropane (internal electron donor compound c) 1.5mmol, continue to be warming up to 110 DEG C, reach after temperature after constant temperature 0.5h, suction filtration removing liquid, adds titanium tetrachloride process in the solid phase that filtration obtains.Then wash five times with hexane, after vacuum-drying, obtain spherical catalyst components A1.
Results of elemental analyses shows, and the titanium content in spherical catalyst components A1 is 2.8%.
Propylene polymerization: in the autoclave of a 5L, adopt stream of nitrogen gas to purge, in stream of nitrogen gas, then introduce 0.25mmol triethyl aluminum, 0.01mmol Cyclohexyl Methyl Dimethoxysilane (CHMMS), the anhydrous hexane of 10mL and the spherical catalyst components A1 of 4mg.Close autoclave, the liquid propene of hydrogenation 2NL and 2.3L.Be warmed up to 70 DEG C, be polymerized 1.0 hours.The test result of the polymerization activity of the isotactic index of polymkeric substance and ash oontent and 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.
Prepare olefin polymerization catalyst components according to the method for embodiment 1, and prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, do not introduce Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and 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 adding 2, (internal electron donor compound is 4.5mmol a) for 4-glycol dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 6mmol and epoxy chloropropane (internal electron donor compound c) 4mmol, obtains catalyst component A3.
And prepare polypropylene according to the method for embodiment 1, difference adopts catalyst component A3 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and 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 A4 is prepared according to the method for embodiment 3.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, and prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component A4 to replace catalyst component A1, and do not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and 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, do not add 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, add 9,9-dimethoxy-methyl fluorenes (internal electron donor compound b) 5mmol, obtain catalyst component A5.
And prepare polypropylene according to the method for embodiment 1, difference is, adopts catalyst component A5 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 6
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 A6 is prepared according to the method for embodiment 5.
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, and prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component A6 to replace catalyst component A1, and do not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 7
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, do not add 2,4-glycol dibenzoate, (internal electron donor compound a) 5mmol obtains catalyst component A7 to add 3,5-heptanediol dibenzoate.
And prepare polypropylene according to the method for embodiment 1, difference is, adopts catalyst component A7 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 8
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 A8 is prepared according to the method for embodiment 7.
And prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component A8 to replace catalyst component A1, and do not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 9
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 2, (internal electron donor compound is 3mmol a) for 4-glycol dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 7mmol and epoxy chloropropane (internal electron donor compound c) 1mmol, obtains catalyst component A9.
And prepare polypropylene according to the method for embodiment 1, difference is, adopts catalyst component A9 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 10
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 A10 is prepared according to the method for embodiment 9.
And prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component A10 to replace catalyst component A1, and do not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Embodiment 11
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 2, (internal electron donor compound is 3.5mmol a) for 4-glycol dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 5mmol and epoxy chloropropane (internal electron donor compound c) 0.5mmol, obtains catalyst component A11.
And prepare polypropylene according to the method for embodiment 1, difference is, adopts catalyst component A11 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and 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 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) and epoxy chloropropane (internal electron donor compound c), (internal electron donor compound is 5mmol a), obtains catalyst component B1 only to add 2,4-glycol dibenzoate.
And prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component B1 to replace catalyst component A1, add 2.5mmol triethyl aluminum, 0.1mmol Cyclohexyl Methyl Dimethoxysilane (CHMMS).The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and 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 (interior Donor compound a) and epoxy chloropropane (internal electron donor compound c), only add 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 6.0mmol, obtain catalyst component B2.
And prepare polypropylene according to the method for embodiment 1, difference adopts catalyst component B2 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Comparative example 3
Olefin polymerization catalyst components is prepared according to the method for embodiment 1, unlike, in Kaolinite Preparation of Catalyst component process, do not add epoxy chloropropane (internal electron donor compound c), only add 2, (internal electron donor compound is 5mmol and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 5mmol a), obtains catalyst component B3 for 4-glycol dibenzoate.
And prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, adopt catalyst component B3 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Comparative example 4
Olefin polymerization catalyst components B4 is prepared according to the method for comparative example 3.
And prepare polypropylene according to the method for embodiment 1, unlike, in propylene polymerization processes, difference adopts catalyst component B4 to replace catalyst component A1, and do not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Comparative example 5
Olefin polymerization catalyst components is prepared according to the method for embodiment 9, unlike, in Kaolinite Preparation of Catalyst component process, do not add epoxy chloropropane (internal electron donor compound c), only add 2, (internal electron donor compound is 3mmol and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (internal electron donor compound b) 7mmol a), obtains catalyst component B5 for 4-glycol dibenzoate.
And prepare polypropylene according to the method for embodiment 1, difference adopts catalyst component B5 to replace catalyst component A1.The test result of the polymerization activity of the polyacrylic isotactic index obtained and ash oontent and catalyzer is in table 1.
Comparative example 6
Olefin polymerization catalyst components B6 is prepared according to the method for comparative example 5.
And prepare polypropylene according to the method for embodiment 1, difference is in propylene polymerization processes, adopts catalyst component B6 to replace catalyst component A1, and does not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.
Table 1
As can be seen from table 1, embodiment 1-11 compares with the data of comparative example 1-2, and the polymerization activity of the catalyzer containing the composite catalyst component obtained of internal electron donor compound a, internal electron donor compound b and internal electron donor compound c provided by the invention and vertical structure directional property are all apparently higher than only containing diol-lipid internal electron donor or only containing the catalyzer of two ethers internal electron donors.And the polymkeric substance using polymerization catalyst provided by the invention to obtain, its ash oontent will far below only containing diol-lipid internal electron donor or only containing the polymkeric substance that the polymerization catalyst of two ethers internal electron donors obtains.As can be seen from table 1, embodiment 1-11 compares with the data of comparative example 3-6, the composite catalyzer and 2 obtained of employing of the present invention three kinds of internal electron donor compound, 4-glycol dibenzoate and 2-sec.-propyl-2-isopentyl-1, the composite catalyzer obtained of 3-Propanal dimethyl acetal is compared, while the high reactivity keeping par and low ash content, vertical structure directional property has further raising, and the isotactic index of resulting polymers is all higher.
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 (9)
1. an olefin polymerization catalyst components, this catalyst component contains the reaction product of following component:
(i) magnesium-containing compound;
(ii) titanium-containing compound; And
(iii) internal electron donor;
It is characterized in that, described internal electron donor is the combination of internal electron donor compound a, internal electron donor compound b and internal electron donor compound c, described internal electron donor compound a is the diol ester compound shown in formula I, described internal electron donor compound b is the diether compound shown in formula II, described internal electron donor compound c is the alkylene oxides compound shown in formula III
In formula I, R
1and R
2identical or different, be C independently of one another
1-C
10straight 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
7-C
20substituted or unsubstituted alkaryl in one, the aromatic ring in described aryl, aralkyl or alkaryl is optionally selected from halogen, C
1-C
6straight or branched alkyl and C
1-C
6alkoxyl group in one or more replace;
R
3, R
4, R
5, R
6and 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 alkaryl, C
7-C
20substituted or unsubstituted aralkyl, C
2-C
10straight or branched alkylene and C
10-C
20fused ring aryl in one, R
3, R
4, R
5, R
6and R
1-R
2noptionally containing heteroatoms, described heteroatoms is one or more in nitrogen, oxygen, sulphur, silicon, halogen and phosphorus;
Or, R
3, R
4, R
5, R
6and R
1-R
2nin two or more mutual bondings, to form ring;
N is the integer of 0-10;
In formula II, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6identical 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 and C
7-C
20substituted or unsubstituted alkaryl in one;
R '
7and R '
8identical or different, be 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
7-C
20substituted or unsubstituted alkaryl in one;
Or, R '
1, R '
2, R '
3, R '
4, R '
5and R '
6in two or more mutual bondings, to form ring;
In formula III, R "
1and R "
2identical or different, be hydrogen, C independently of one another
1-C
5straight or branched alkyl or haloalkyl.
2. catalyst component according to claim 1, wherein, the mol ratio of described internal electron donor compound a, described internal electron donor compound b and described internal electron donor compound c consumption is 0.5-10:1-12:1, is preferably 1-7:1.5-10:1.
3. catalyst component according to claim 1, wherein, described internal electron donor compound a is the diol ester compound shown in formula IV,
In formula IV, R
7, R
8, R
9, R
10, R
11and R
12identical or different, be hydrogen or C independently of one another
1-C
20straight or branched alkyl;
Preferably, described internal electron donor compound a is 2,4-glycol dibenzoate and/or 3,5-heptanediol dibenzoate.
4. catalyst component according to claim 1, wherein, described internal electron donor compound b is 1,3-diether compound shown in formula V,
In formula V, R '
9and R '
10identical or different, be hydrogen, halogen, C independently of one another
1-C
18straight or branched alkyl, C
3-C
18substituted or unsubstituted cycloalkyl, C
6-C
18substituted or unsubstituted aryl and C
7-C
18substituted or unsubstituted aralkyl in one, or, R '
9and R '
10mutual bonding, to form ring; R '
11and R '
12identical or different, be C independently of one another
1-C
10straight or branched alkyl;
Preferably, described internal electron donor compound b is 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and/or 9,9-dimethoxy-methyl fluorenes.
5. catalyst component according to claim 1, wherein, in formula III, R "
1and R "
2identical or different, be hydrogen, C independently of one another
1-C
3straight or branched alkyl or haloalkyl, preferably, described internal electron donor compound c is one or more in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
6. catalyst component according to claim 1, wherein, the mol ratio of described magnesium-containing compound, described titanium-containing compound and described internal electron donor consumption is 1:10-200:0.04-0.8, is preferably 1:20-180:0.05-0.5.
7. the preparation method of the catalyst component in claim 1-6 described in any one, the method comprises reacts described magnesium-containing compound and described titanium-containing compound, and adds described internal electron donor in one or more time periods before and after, during described magnesium-containing compound and described titanium-containing compound react.
8. an olefin polymerization catalysis, this catalyzer contains:
(1) olefin polymerization catalyst components in claim 1-7 described in any one;
(2) as the alkylaluminium cpd of promotor; And
(3) optionally, external donor compound.
9. the application of olefin polymerization catalysis according to claim 8 in olefinic polyreaction.
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| CN111072810A (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 |
| CN111072813A (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 |
| CN115975084A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
| CN115975079A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
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| CN115975079A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
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|---|---|
| CN105440177B (en) | 2018-08-17 |
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