CN100348624C - Catalyst components for olefinic polyreaction and catalyst thereof - Google Patents
Catalyst components for olefinic polyreaction and catalyst thereof Download PDFInfo
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- CN100348624C CN100348624C CNB2005100004817A CN200510000481A CN100348624C CN 100348624 C CN100348624 C CN 100348624C CN B2005100004817 A CNB2005100004817 A CN B2005100004817A CN 200510000481 A CN200510000481 A CN 200510000481A CN 100348624 C CN100348624 C CN 100348624C
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Abstract
The present invention provides a catalyst component for the olefinic polymerization. The catalyst component contains titanium, magnesium, halogen and at least two electron donor compounds a and b, wherein the electron donor compound a is selected from a dibasic acid ester compound shown in a general formula (I). The electron donor compound b is selected from a 1, 3-diether compound. When used for the olefinic polymerization, particularly for the propylene polymerization, the catalyst has high catalytic activity and wide molecular weight distribution.
Description
Technical field
The present invention relates to a kind of catalyst component and catalyzer of for olefines polymerization, and it is at alpha-olefin CH
2Application in the polyreaction of=CHR and composition thereof, wherein R is the alkyl of hydrogen or 1～12 carbon atom.More particularly, relate to a kind of catalyst component and catalyzer and application thereof that contains at least two kinds of electron donor compounds.
Technical background
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component
2=CHR olefinic polyreaction, particularly in alpha-olefine polymerizing, can obtain the polymkeric substance of higher yields and higher tacticity with 3 carbon or more carbon atoms, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.Up to now, existing many patent disclosures the multiple internal electron donor compound that is applicable to the preparation Ziegler-Natta catalyst, and the catalyzer that is used for olefinic polymerization that comprises these internal electron donor compounds.
These internal electron donor compounds mainly comprise: the electron donor compound of European patent EP 0045977 described phthalate, European patent EP 0361493, describe among the EP0728724 1, the 3-diether compound, describe among the Chinese patent CN1105671A 1, the 3-cyclohexadione compounds, Chinese patent CN1236732, CN1236733, CN1236734, the malonic ester compounds of the special replacement of describing among the CN1292800, the succinate compounds of describing in the PCT International Application No. WO 0063261, the beta substitution glutarate compounds of describing in the PCT International Application No. WO 0055215, the cyano group ester compound of describing among the Chinese patent CN1242780, the two amine electron donor compounds of describing among the Chinese patent CN1087918, the electron donor compound of the maleic acid ester class of describing in the PCT International Application No. WO 03022894, and Chinese patent CN1436766A, a kind of special polyol ester compounds of describing among the CN1436796A etc.
Owing to adopt different internal electron donor compounds to make prepared catalyzer have different characteristics, for example some catalyzer has higher activity, some catalyzer has better hydrogen regulation sensitivity, but generally speaking, for the catalyzer that uses single internal electron donor compound, its prepared molecular weight distribution is narrower, has influenced the processing characteristics of resin.For example describe among European patent EP 0361493, the EP0728724 1, the 3-diether compound, when using this compounds as internal electron donor, though can improve the degree of isotacticity of activity of such catalysts and raising polymkeric substance, even when saving the external electron donor component, still can obtain high yield and high normal polymkeric substance.But this class catalyzer gained polymeric molecular weight distribution is narrower, and the poor processability of polymkeric substance has limited the application of polymkeric substance.
In the prior art, people adopt the method that adds multiple internal electron donor compound in catalyst preparation process to improve the over-all properties of catalyzer usually.As disclosing in the Preparation of catalysts process among the Chinese patent CN1268957A, two kinds of electron donor compounds have been used, a kind of ether compound that contains two or more ehter bonds that is selected from, a kind of monocarboxylic acid or polycarboxylic ester cpds of being selected from.Gained catalyst activity height, the polypropylene dimethylbenzene insolubles content height that makes, degree of crystallinity is lower simultaneously, is suitable for preparing Bi-Oriented Polypropylene Films BOPP.And for example WO03/002617 proposes, in catalyst preparation process, add a spot of simple function group compound class earlier, ethyl benzoate for example, in preparation process subsequently, add another kind of electron donor compound then, the content of simple function group compound seldom even can not surveyed in the catalyzer that obtains.But the catalyst activity that obtains, melt flow index etc. have all obtained bigger improvement.Though aforesaid method has had certain improvement to catalyzer, in that widen still can not be satisfactory aspect the molecular weight distribution of polymkeric substance.
The inventor finds in research process, in catalyst preparation process, adds above-mentionedly 1, adds a kind of dibasic ester compound with special construction in the time of 3-two ethers electron donor compounds, can prepare the catalyst component and the catalyzer of high comprehensive performance.It is worthy of note that this catalyzer is being used for olefinic polymerization, is particularly showing the very high activity and the molecular weight distribution of broad during propylene polymerization.
Summary of the invention
The invention provides a kind of catalyst component that is used for olefinic polymerization, this catalyst component comprises titanium, magnesium, halogen and at least two kinds of electron donor compound as and b, and wherein the electron donor compound a is selected from two ester compounds shown in general formula (I):
R ' and R in the formula
1Group is identical or inequality, is selected from the C of replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl; A is that carbon chain length is the divalent linker of 1-10, and it is selected from aliphatics, alicyclic and aromatic divalent group, can have C on the carbon in the described divalent linker
1-C
20Be selected from alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene, the fused ring aryl of straight chain or branching, the substituting group of ester group, preferably, can have C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
2-C
10Alkylene, C
7-C
10Alkaryl or aralkyl, and two or more substituting group can be connected to form saturated or undersaturated monocycle or many rings;
Wherein the electron donor compound b is selected from 1 of general formula (II), 3-diether compound;
R wherein
1, R
II, R
III, R
IV, R
VAnd R
VIIdentical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIICan be identical or different, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring.
In two ester compounds shown in the above-mentioned general formula (I), preferred A is that chain length is the divalent linker of 2 carbon atoms, and R ' is selected to replace or unsubstituted C
6-C
20Aryl, alkaryl or aralkyl.
Comprise the diester compound shown in following general formula (III) in the dibasic ester compound of its preferred described general formula of embodiment (I):
In the formula:
R
1Be C
1-C
20Unsubstituted or the halogen alkyl or the C that replace
6-C
20Unsubstituted or halogen replaces aryl or alkaryl;
R
2-5Identical or different, be hydrogen or C
1-4The alkyl of straight or branched;
R
1-5Identical or different, be hydrogen, halogen, C
1-C
10Unsubstituted or halogen replaces alkyl or C
6-C
20Unsubstituted or halogen replaces aryl or alkaryl or aralkyl.
Above-mentioned halogen is preferably selected from F, Cl, Br.
In above-mentioned general formula (III) compound, preferred R
1Be C
2-C
10The alkyl C of straight or branched
6-C
20Alkaryl.More preferably R
1Be C
2-C
6Alkyl for example ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, the hexyl etc. of straight or branched.
At above-mentioned general formula (III)) in the compound, preferred R
1-5Identical or different, be hydrogen or C
1-C
6The alkyl or the halogenated alkyl of straight or branched, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl etc.
Concrete dibasic ester examples for compounds comprises:
3-benzoyloxy ethyl butyrate, 2-methyl-3-benzoyloxy ethyl butyrate, 2-ethyl-3-benzoyloxy ethyl butyrate, 2-n-propyl-3-benzoyloxy ethyl butyrate, 2-allyl group-3-benzoyloxy ethyl butyrate, 2-sec.-propyl-3-benzoyloxy ethyl butyrate, 2-normal-butyl-3-benzoyloxy ethyl butyrate, 2-isobutyl--3-benzoyloxy ethyl butyrate, the 2-tertiary butyl-3-benzoyloxy ethyl butyrate, 2-benzyl-3-benzoyloxy ethyl butyrate, 2,2-dimethyl-3-benzoyloxy ethyl butyrate, 3-benzoyloxy Valeric acid ethylester, 2-methyl-3-benzoyloxy Valeric acid ethylester, 2-ethyl-3-benzoyloxy Valeric acid ethylester, 2-n-propyl-3-benzoyloxy Valeric acid ethylester, 2-allyl group-3-benzoyloxy Valeric acid ethylester, 2-sec.-propyl-3-benzoyloxy Valeric acid ethylester, 2-normal-butyl-3-benzoyloxy Valeric acid ethylester, 2-isobutyl--3-benzoyloxy Valeric acid ethylester, the 2-tertiary butyl-3-benzoyloxy Valeric acid ethylester, 2-benzyl-3-benzoyloxy Valeric acid ethylester, 2,2-dimethyl-3-benzoyloxy Valeric acid ethylester, 3-benzoyloxy ethyl hexanoate, 2-methyl-3-benzoyloxy ethyl hexanoate, 2-ethyl-3-benzoyloxy ethyl hexanoate, 2-n-propyl-3-benzoyloxy ethyl hexanoate, 2-allyl group-3-benzoyloxy ethyl hexanoate, 2-sec.-propyl-3-benzoyloxy ethyl hexanoate, 2-normal-butyl-3-benzoyloxy ethyl hexanoate, 2-isobutyl--3-benzoyloxy ethyl hexanoate, the 2-tertiary butyl-3-benzoyloxy ethyl hexanoate, 2-benzyl-3-benzoyloxy ethyl hexanoate, 3-benzoyloxy isopropyl butyrate, 2-methyl-3-benzoyloxy isopropyl butyrate, 2-ethyl-3-benzoyloxy isopropyl butyrate, 2-n-propyl-3-benzoyloxy isopropyl butyrate, 2-allyl group-3-benzoyloxy isopropyl butyrate, 2-sec.-propyl-3-benzoyloxy isopropyl butyrate, 2-normal-butyl-3-benzoyloxy isopropyl butyrate, 2-isobutyl--3-benzoyloxy isopropyl butyrate, the 2-tertiary butyl-3-benzoyloxy isopropyl butyrate, 2-benzyl-3-benzoyloxy isopropyl butyrate, 2,2-dimethyl-3-benzoyloxy isopropyl butyrate, 3-benzoyloxy isobutyl butyrate, 2-methyl-3-benzoyloxy isobutyl butyrate, 2-ethyl-3-benzoyloxy isobutyl butyrate, 2-n-propyl-3-benzoyloxy isobutyl butyrate, 2-allyl group-3-benzoyloxy isobutyl butyrate, 2-sec.-propyl-3-benzoyloxy isobutyl butyrate, 2-normal-butyl-3-benzoyloxy isobutyl butyrate, 2-isobutyl--3-benzoyloxy isobutyl butyrate, the 2-tertiary butyl-3-benzoyloxy isobutyl butyrate, 2-benzyl-3-benzoyloxy isobutyl butyrate, 2,2-dimethyl-3-benzoyloxy isobutyl butyrate, 3-benzoyloxy methyl-butyrate, 2-methyl-3-benzoyloxy methyl-butyrate, 2-ethyl-3-benzoyloxy methyl-butyrate, 2-n-propyl-3-benzoyloxy methyl-butyrate, 2-allyl group-3-benzoyloxy methyl-butyrate, 2-sec.-propyl-3-benzoyloxy methyl-butyrate, 2-normal-butyl-3-benzoyloxy methyl-butyrate, 2-isobutyl--3-benzoyloxy methyl-butyrate, the 2-tertiary butyl-3-benzoyloxy methyl-butyrate, 2-benzyl-3-benzoyloxy methyl-butyrate, 2,2-dimethyl-3-benzoyloxy methyl-butyrate.3-cinnamoyloxy group ethyl butyrate, 2-methyl-3-cinnamoyloxy group ethyl butyrate, 2-ethyl-3-cinnamoyloxy group ethyl butyrate, 2-n-propyl-3-cinnamoyloxy group ethyl butyrate, 2-allyl group-3-cinnamoyloxy group ethyl butyrate, 2-sec.-propyl-3-cinnamoyloxy group ethyl butyrate, 2-normal-butyl-3-cinnamoyloxy group ethyl butyrate, 2-isobutyl--3-cinnamoyloxy group ethyl butyrate, the 2-tertiary butyl-3-cinnamoyloxy group ethyl butyrate, 2-benzyl-3-cinnamoyloxy group ethyl butyrate, 2,2-dimethyl-3-cinnamoyloxy group ethyl butyrate, 3-cinnamoyloxy group Valeric acid ethylester, 2-methyl-3-cinnamoyloxy group Valeric acid ethylester, 2-ethyl-3-cinnamoyloxy group Valeric acid ethylester, 2-n-propyl-3-cinnamoyloxy group Valeric acid ethylester, 2-allyl group-3-cinnamoyloxy group Valeric acid ethylester, 2-sec.-propyl-3-cinnamoyloxy group Valeric acid ethylester, 2-normal-butyl-3-cinnamoyloxy group Valeric acid ethylester, 2-isobutyl--3-cinnamoyloxy group Valeric acid ethylester, the 2-tertiary butyl-3-cinnamoyloxy group Valeric acid ethylester, 2-benzyl-3-cinnamoyloxy group Valeric acid ethylester, 2,2-dimethyl-3-cinnamoyloxy group Valeric acid ethylester, 3-cinnamoyloxy group ethyl hexanoate, 2-methyl-3-cinnamoyloxy group ethyl hexanoate, 2-ethyl-3-cinnamoyloxy group ethyl hexanoate, 2-n-propyl-3-cinnamoyloxy group ethyl hexanoate, 2-allyl group-3-cinnamoyloxy group ethyl hexanoate, 2-sec.-propyl-3-cinnamoyloxy group ethyl hexanoate, 2-normal-butyl-3-cinnamoyloxy group ethyl hexanoate, 2-isobutyl--3-cinnamoyloxy group ethyl hexanoate, the 2-tertiary butyl-3-cinnamoyloxy group ethyl hexanoate, 2-benzyl-3-cinnamoyloxy group ethyl hexanoate, 2,2-dimethyl-3-cinnamoyloxy group ethyl hexanoate, 3-cinnamoyloxy group isopropyl butyrate, 2-methyl-3-cinnamoyloxy group isopropyl butyrate, 2-ethyl-3-cinnamoyloxy group isopropyl butyrate, 2-n-propyl-3-cinnamoyloxy group isopropyl butyrate, 2-allyl group-3-cinnamoyloxy group isopropyl butyrate, 2-sec.-propyl-3-cinnamoyloxy group isopropyl butyrate, 2-normal-butyl-3-cinnamoyloxy group isopropyl butyrate, 2-isobutyl--3-cinnamoyloxy group isopropyl butyrate, the 2-tertiary butyl-3-cinnamoyloxy group isopropyl butyrate, 2-benzyl-3-cinnamoyloxy group isopropyl butyrate, 2,2-dimethyl-3-cinnamoyloxy group isopropyl butyrate, 3-cinnamoyloxy group isobutyl butyrate, 2-methyl-3-cinnamoyloxy group isobutyl butyrate, 2-ethyl-3-cinnamoyloxy group isobutyl butyrate, 2-n-propyl-3-cinnamoyloxy group isobutyl butyrate, 2-allyl group-3-cinnamoyloxy group isobutyl butyrate, 2-sec.-propyl-3-cinnamoyloxy group isobutyl butyrate, 2-normal-butyl-3-cinnamoyloxy group isobutyl butyrate, 2-isobutyl--3-cinnamoyloxy group isobutyl butyrate, the 2-tertiary butyl-3-cinnamoyloxy group isobutyl butyrate, 2-benzyl-3-cinnamoyloxy group isobutyl butyrate, 2,2-dimethyl-3-cinnamoyloxy group isobutyl butyrate, 3-cinnamoyloxy group methyl-butyrate, 2-methyl-3-cinnamoyloxy group methyl-butyrate, 2-ethyl-3-cinnamoyloxy group methyl-butyrate, 2-n-propyl-3-cinnamoyloxy group methyl-butyrate, 2-allyl group-3-cinnamoyloxy group methyl-butyrate, 2-sec.-propyl-3-cinnamoyloxy group methyl-butyrate, 2-normal-butyl-3-cinnamoyloxy group methyl-butyrate, 2-isobutyl--3-cinnamoyloxy group methyl-butyrate, the 2-tertiary butyl-3-cinnamoyloxy group methyl-butyrate, 2-benzyl-3-cinnamoyloxy group methyl-butyrate, 2,2-dimethyl-3-cinnamoyloxy group methyl-butyrate, 3-acetoxyl group ethyl butyrate.
Above-mentioned dibasic ester compound can be synthetic by various reactions, wherein can be in the presence of corresponding acid or acyl chlorides, and make the alcohol ester compounds of corresponding general formula (IV) carry out esterification and obtain corresponding diester compound with the acyl compounds that contains R '.
Wherein R ' and R
1The same general formula of definition (I).
The compound of general formula (IV) generally can be obtained by corresponding ketone ester compound reduction, and the synthetic method of ketone ester compound is a lot, wherein can be obtained by the carboxylicesters condensation as beta-diketonate compound.
Wherein the electron donor compound b is selected from 1 of general formula (II), 3-diether compound;
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VIIdentical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIICan be identical or different, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring.
Described 1, the 3-diether compound preferably has the compound of following structure (V):
Further preferably, described 1, the 3-diether compound is selected from the compound of shown in general formula (VI):
Above-mentioned logical formula V or (VI) in R identical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl;
R wherein
1Identical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl:
R wherein
2Identical or inequality, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl.
Described 1, the example of 3-diether compound has:
2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-butyl-1, the 3-Propanal dimethyl acetal, the 2-second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-1, the 3-Propanal dimethyl acetal, 2-cumyl-1, the 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(right-chloro-phenyl-)-1, the 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, the 3-Propanal dimethyl acetal, 2-(1-naphthyl)-1, the 3-Propanal dimethyl acetal, 2-(2-fluorophenyl)-1, the 3-Propanal dimethyl acetal, 2-(1-decahydro naphthyl)-1, the 3-Propanal dimethyl acetal, 2-(right-the tert-butyl phenyl)-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-propyl group-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2, two (right-chloro-phenyl-)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, the 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-(1-the methyl butyl)-2-second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2, two-second month in a season of 2--butyl-1, the 3-Propanal dimethyl acetal, 2,2-two-tert-butyl-1, the 3-Propanal dimethyl acetal, 2,2-di neo-pentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-benzyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal, 1, two (the methoxymethyl)-cyclopentadiene of 1-, 1, two (methoxymethyl)-2,3 of 1-, 4,5-tetramethyl-ring pentadiene, 1, two (methoxymethyl)-2 of 1-, 3,4,5-tetraphenyl cyclopentadiene, 1, two (methoxymethyl)-2,3 of 1-, 4,5-ptfe ring pentadiene, 1, two (methoxymethyl)-3 of 1-, 4-two cyclopentyl cyclopentadiene, 1, two (methoxymethyl) indenes of 1-, 1, two (methoxymethyl)-2 of 1-, 3-dimethoxy indenes, 1, two (methoxymethyl)-4,5 of 1-, 6,7-tetrafluoro indenes, 1, two (methoxymethyl)-2,3 of 1-, 6,7-tetrafluoro indenes, 1, two (methoxymethyl)-4 of 1-, 7-dimethyl indenes, 1, two (methoxymethyl)-3 of 1-, 6-dimethyl indenes, 1, two (the methoxymethyl)-4-phenylindan of 1-, 1, two (the methoxymethyl)-4-phenyl of 1--2-methyl indenes, 1, two (the methoxymethyl)-4-cyclohexyl indenes of 1-, 1, two (methoxymethyl)-7-(3,3, the 3-trifluoro propyl) indenes of 1-, 1, two (the methoxymethyl)-7-trimethyl silyl indenes of 1-, 1, two (the methoxymethyl)-7-trifluoromethyl indenes of 1-, 1, two (methoxymethyl)-4 of 1-, 7-dimethyl-4,5,6, the 7-tetrahydroindene, 1, two (the methoxymethyl)-7-methyl indenes of 1-, 1, two (the methoxymethyl)-7-cyclopentyl indenes of 1-, 1, two (the methoxymethyl)-7-sec.-propyl indenes of 1-, 1, two (the methoxymethyl)-7-cyclohexyl indenes of 1-, 1, two (the methoxymethyl)-7-tert-butyl indenes of 1-, 1, two (the methoxymethyl)-7-tert-butyl of 1--2-methyl indenes, 1, two (the methoxymethyl)-7-phenylindan of 1-, 1, two (the methoxymethyl)-2-phenylindan of 1-, 9, two (methoxymethyl) fluorenes of 9-, 9, two (methoxymethyl)-2,3 of 9-, 6,7-tetramethyl-fluorenes, 9, two (methoxymethyl)-2 of 9-, 3,4,5,6,7-hexafluoro fluorenes, 9, two (methoxymethyl)-2 of 9-, 3 phenylpropyl alcohol indenes, 9, two (methoxymethyl)-2,3 of 9-, 6,7-two phenylpropyl alcohol indenes, 9, two (methoxymethyl)-2 of 9-, 7-two cyclopentyl fluorenes, 9, two (methoxymethyl)-1 of 9-, 8-dichloro fluorenes, 9, two (methoxymethyl)-2 of 9-, 7-two cyclopentyl fluorenes, 9, two (methoxymethyl)-1 of 9-, 8-difluoro fluorenes, 9, two (methoxymethyl)-1,2 of 9-, 3,4-tetrahydrochysene fluorenes, 9, two (methoxymethyl)-1 of 9-, 2,3,4,5,6,7,8-octahydro fluorenes, 9, two (the methoxymethyl)-4-tert-butyl fluorenes of 9-, 1,1-pair (1 '-butoxyethyl group)-cyclopentadiene, 1,1-pair (1 '-isopropoxy-n-propyl) cyclopentadiene, 1-methoxymethyl-1-(1 '-methoxy ethyl)-2,3,4,5-tetramethyl-ring pentadiene, 1, two (α-methoxy-benzyl) indenes of 1-, 1, two (the phenoxymethyl)-indenes of 1-, 1,1-pair (1 '-methoxy ethyl)-5,6-dichloro indenes, 1, two (phenoxymethyl)-3 of 1-, 6-two ring ethyl indenes, 1-methoxymethyl-1-(1 '-methoxy ethyl)-7-tertiary butyl indenes, 1, two [2-(2 ' methoxy-propyl)]-2-methyl indenes of 1-, 9, two (α-p-methoxy-phenyl) fluorenes of 9-, 9,9-pair (1 '-isopropoxy-normal-butyl)-4, the 5-diphenylfluorene, 9,9-pair (1 '-methoxy ethyl) fluorenes, 9-(methoxymethyl)-9-(1 '-methoxy ethyl)-2,3,6,7-tetrafluoro fluorenes, 9-(methoxymethyl)-9-pentyloxy methyl fluorenes, 9-(methoxymethyl)-9-ethoxyl methyl fluorenes, 9-(methoxymethyl)-9-(1 '-methoxy ethyl) fluorenes, 9-(methoxymethyl)-9-[2-(2 ' methoxy-propyl)] fluorenes, 1,1-pair-(methoxymethyl)-2, the 5-cyclohexadiene, 1,1-pair-(methoxymethyl) benzo naphthalene, 7,7-pair-(methoxymethyl) 2, the 5-norbornadiene, 9,9-pair-(methoxymethyl)-1,4-methane dihydronaphthalene, 9,9-pair-(methoxymethyl)-9,1 0-dihydroanthracene, 1,1-pair-(methoxymethyl)-1, the 2-dihydroanthracene, 4,4-pair-(methoxymethyl)-1-phenyl-1, the 4-dihydronaphthalene, 4,4-pair-(methoxymethyl)-1-phenyl-3, the 4-dihydronaphthalene, 5,5-pair-(methoxymethyl)-1,3, the 6-cycloheptatriene.
The present invention above-mentioned 1, the 3-diether compounds is disclosed among Chinese patent CN1020448C and the CN1141285A, its associated viscera is incorporated herein the present invention as a reference.
The mol ratio of two kinds of electron donor compound as and b is generally 0.01～100, is preferably 0.05～1, and more preferably 0.1～0.4.
As above said, except above-mentioned electron donor compound a and b, catalyst component of the present invention also comprises titanium, magnesium and halogen.Usually it contains the reaction product of titanium compound, magnesium compound and at least two kinds of electron donor compound as and b.
Described magnesium compound is selected from the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula a kind of by in-oxyl or the halo-oxyl institute metathetical derivative of a halogen atom, or their mixture.The MgCl of the preferred active state of magnesium dihalide wherein
2, it is widely known by the people in patent documentation as one of component of Ziegler-Natta catalyst.
Described titanium compound has a Ti-halogen bond at least, and its general formula is: TiX
n(OR)
4-n, R is C in the formula
1～C
20Alkyl, be preferably normal-butyl/isobutyl-, 2-ethylhexyl, n-octyl and phenyl; X is a halogen, and n is 1～4.Concrete titanium compound can be selected titanium tetrahalide, particularly titanium tetrachloride for use; Three chlorocarbon oxygen machine base titanium, particularly trichlorine butoxy and Trichlorophenoxy titaniums; Four titan-alkoxides, particularly four titanium butoxide, purity titanium tetraethoxide.
The preparation of catalyst component of the present invention can be carried out according to several different methods.
Usual method is at a kind of MgCl
2.nROH load has the reaction product of above-mentioned titanium compound and described two kinds of electron donor compound as and b, wherein MgCl on the adducts
2.nROH adducts is magnesium dichloride and pure adducts, preferred particle spherical in shape, and wherein n is generally 1.5～4, and preferred 2.0～3.5; R is the alkyl of carbon number 1-4, described alcohol such as ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, isooctyl alcohol etc.Relevant preparation process can be carried out with reference to disclosed method among Chinese patent CN1036011C, the CN1330086A, and disclosed associated viscera is incorporated herein the present invention as a reference.
Also can be prepared with reference to the preparation method of disclosed solids containing titanium catalyst component among the Chinese patent CN85100997, disclosed associated viscera is incorporated herein the present invention as a reference among the CN85100997.
At first, magnesium compound is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, mixes with titanium compound behind the formation homogeneous solution, in the presence of precipitation additive, separate out solids; This solids is with the processing of above-mentioned two kinds of electron donor compound as and b, it is attached on the solids, in case of necessity, it is described and obtain the solids containing titanium catalyst component to handle solids with titanium tetrahalide and inert diluent again, and wherein precipitation additive is a kind of in organic acid anhydride, organic acid, ether, the ketone.Described each component is in every mole of magnesium halide, and organic epoxy compounds is 0.2～10 mole, and organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0.03～1.0 mole, and titanium compound is 0.5～150 mole.
Preparing the another kind of method that ingredient of solid catalyst of the present invention can adopt comprises, magnesium compound is dissolved in the electron donors such as alcohol, ether, with the titanium compound hybrid reaction, to separate out precipitation again, its preparation method is disclosed among the CN1057656 behind the formation homogeneous solution.Also can prepare ingredient of solid catalyst of the present invention in addition with reference to US4866022 and the disclosed method of US4829037.In these methods, can magnesium compound with add above-mentioned two kinds of electron donor compound as of the present invention and b before or after titanium compound contacts.
Electron donor compound a and electron donor compound b can be used in many ways jointly, and preferably both mix back adding or compound a adding earlier in catalyst preparation process.
Ingredient of solid catalyst of the present invention changes into the catalyzer that is used for olefinic polymerization by reacting according to currently known methods and organo-aluminium compound.
In particular, the present invention also provides a kind of alkene that is used for, and particularly uses alpha-olefin CH
2=CHR polymeric catalyzer, wherein R is the alkyl of hydrogen or 1～12 carbon atom, this catalyzer comprises the reaction product between following material:
(1), a kind of above-mentioned catalyst component that contains Mg, Ti and halogen and above-mentioned two kinds of electron donor compound as and b;
(2), a kind of alkylaluminium cpd, and randomly,
(3), one or more electron donor compounds (external electron donor).
The alkylaluminium cpd preferred formula is AIR
nX
3-nCompound, R is the alkyl of hydrogen or carbonatoms 1～20, particularly alkyl, aralkyl, aryl etc. in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Alkylaluminium cpd of the present invention comprises: trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum; Alkyl aluminium hydrides such as one hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum; Aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, aluminum alkyls muriates such as ethyl aluminum dichloride wherein are preferably triethyl aluminum and triisobutyl aluminium.
The consumption of aluminum alkyls is: wherein the mol ratio of titanium is 5-5000 in aluminium and the solid constituent (1), is preferably 20-500.
The external electron donor compound is preferably silicoorganic compound.Its general formula is RnSi (OR ') 4-n, 0＜n in the formula≤3, and R and R ' they are alkyl of the same race or not of the same race, cycloalkyl, aryl, haloalkyl etc. in the general formula, R also can be halogen or hydrogen atom.Silicoorganic compound of the present invention comprise the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, two phenoxy group dimethoxy silane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-methyl dimethoxysilane etc.
The consumption of external electron donor (3) is: the mol ratio of organo-aluminium compound and described external electron donor compound is 0.1～500, and is preferred 1～300, more preferably 3～100.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer in the liquid phase of the solution in inert solvent, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.Testing method:
1. polymericular weight and molecular weight distribution MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method, with PL-GPC220 is that solvent is measured (standard specimen: polystyrene down at 150 ℃ with the trichlorobenzene, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).
2. polymkeric substance degree of isotacticity II adopts the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3. melting index MFI measures according to ASTM D1238-99.
The preparation of embodiment 1:3-benzoyloxy ethyl butyrate
1) preparation of ethyl 3-hydroxybutanoate
In the there-necked flask of titration apparatus is housed, add the 1.5g sodium borohydride successively, 0.02g sodium hydroxide, 13ml water mixes.Ice-water bath, the interior mixed solution that drips 0.1mol methyl aceto acetate and 15ml anhydrous methanol of slowly past reaction flask under the agitation condition.Drip off the back and continue reaction 2hr.Utilize Rotary Evaporators solvent evaporated methyl alcohol and big portion moisture to residuum to be solid phase.Anhydrous diethyl ether extraction 24hr under the agitation condition.Filter extraction liquid, anhydrous sodium sulfate drying.Solvent evaporated gets product ethyl 3-hydroxybutanoate 0.052mol.Productive rate 52%.
2) preparation of 3-benzoyloxy ethyl butyrate
Under the anhydrous and oxygen-free nitrogen atmosphere, add 50mlTHF, 0.04mol3-3-hydroxyethyl butyrate, 0.06mol pyridine successively, slowly be added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, filter, solid components washs three times with anhydrous diethyl ether.Merge organic phase, the saturated aqueous common salt thorough washing is used anhydrous sodium sulfate drying at last.The Rotary Evaporators solvent evaporated is carried out column chromatography with the component that obtains, the final product 3-benzoyloxy ethyl butyrate 0.32mol that gets.Productive rate 80%.
At CDCl
3In, under 300MHz, make internal standard substance with TMS, product 3-benzoyloxy ethyl butyrate
1The H-NMR data are as follows:
7.4-8.0 5H phenyl ring
5.3 H CH
4.1 2H CH
2
2.6 2H CH
2
1.3 3H CH
3
1.2 3H CH
3
The preparation of embodiment 2 2-methyl-3-benzoyloxy Valeric acid ethylester
1) preparation of Alpha-Methyl Propionylacetic acid ethyl ester
Under the anhydrous and oxygen-free nitrogen protection condition, in the there-necked flask of titration apparatus is housed, add 0.15mol potassium tert.-butoxide, 150ml tetrahydrofuran (THF) successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.12mol Propionylacetic acid ethyl ester.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.18mol methyl iodide under the normal temperature, after dropwising, continue reaction 24hr at normal temperatures.After reaction was finished, the Rotary Evaporators solvent evaporated added saturated aqueous common salt to just dissolving fully of solid mixture, separates organic phase, and water merges organic phase with an amount of anhydrous diethyl ether extraction three times, and saturated aqueous common salt is fully washed, and uses anhydrous sodium sulfate drying at last.Rotary Evaporators solvent evaporated, underpressure distillation get the 0.054mol product.Productive rate 45%.
2) preparation of 2-methyl-3-hydroxypentanoic acid ethyl ester
In the there-necked flask of titration apparatus is housed, add the 1.5g sodium borohydride successively, 0.02g sodium hydroxide, 13ml water mixes.Ice-water bath, the interior mixed solution that drips 0.1mol α-ethyl Propionylacetic acid ethyl ester and 15ml anhydrous methanol of slowly past reaction flask under the agitation condition.Drip off the back and continue reaction 2hr.Utilize Rotary Evaporators solvent evaporated methyl alcohol and big portion moisture to residuum to be solid phase.Anhydrous diethyl ether extraction 24hr under the agitation condition.Filter extraction liquid, filtrate is through anhydrous sodium sulfate drying.Solvent evaporated gets product 2-methyl-3-hydroxypentanoic acid ethyl ester 0.06 mol.Productive rate 60%.
3) preparation of 2-methyl-3-benzoyloxy Valeric acid ethylester
Under the anhydrous and oxygen-free nitrogen atmosphere, add 50mlTHF, 0.04mol2-ethyl-3-hydroxypentanoic acid ethyl ester, 0.06mol pyridine successively, slowly be added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, filter, solid components washs three times with anhydrous diethyl ether.Merge organic phase, the saturated aqueous common salt thorough washing is used anhydrous sodium sulfate drying at last.The Rotary Evaporators solvent evaporated is carried out column chromatography for separation with the component that obtains, the final product 2-methyl-3-benzoyloxy Valeric acid ethylester 0.30mol that gets.Productive rate 75%.
At CDCl
3In, under 300MHz, make internal standard substance with TMS, product 2-methyl-3-benzoyloxy Valeric acid ethylester
1The H-NMR data are as follows:
7.4-8.1 5H phenyl ring
5.3 H CH
4.0 2H CH
2
2.5 1H CH
1.7 3H CH
3
1.1 3H CH
3
0.9 3H CH
3
The preparation of embodiment 3 3-benzoyloxy isobutyl butyrates
1) preparation of 3-hydroxybutyric acid isobutyl ester
In the there-necked flask of titration apparatus is housed, add the 1.5g sodium borohydride successively, 0.02g sodium hydroxide, 13ml water mixes.Ice-water bath, the interior mixed solution that drips 0.1mol isobutyl acetoacetate and 15ml anhydrous methanol of slowly past reaction flask under the agitation condition.Drip off the back and continue reaction 2hr.Utilize Rotary Evaporators solvent evaporated methyl alcohol and big portion moisture to residuum to be solid phase.Anhydrous diethyl ether extraction 24hr under the agitation condition.Filter extraction liquid, filtrate is through anhydrous sodium sulfate drying.Solvent evaporated gets product 3-hydroxybutyric acid isobutyl ester 0.052 mol.Productive rate 52%.
2) preparation of 3-benzoyloxy isobutyl butyrate
Under the anhydrous and oxygen-free nitrogen atmosphere, add 50mlTHF, 0.04mol3-hydroxybutyric acid isobutyl ester, 0.06mol pyridine successively, slowly be added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, filter, solid components washs three times with anhydrous diethyl ether.Merge organic phase, the saturated aqueous common salt thorough washing is used anhydrous sodium sulfate drying at last.The Rotary Evaporators solvent evaporated is carried out column chromatography for separation with the component that obtains, the final product 3-benzoyloxy isobutyl butyrate 0.3mol that gets.Productive rate 75%.
At CDCl
3In, under 300MHz, make internal standard substance with TMS, product 3-benzoyloxy isobutyl butyrate
1The H-NMR data are as follows:
7.4-8.0 5H phenyl ring
5.3 H CH
4.3 2H CH
2
2.6 2H CH
2
1.5 H CH
1.3 3H CH
3
1.2 6H CH
3
Embodiment 4:
The preparation of catalyst component: in through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml, 3-benzoyloxy ethyl butyrate 0.7mmol, be warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, add Tetra hydro Phthalic anhydride 1.4g, continued to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour
456ml slowly is warming up to 80 ℃, separates out solids in temperature-rise period gradually, adds 9,9-two (methyl methoxy base) fluorenes 6mmol, and holding temperature 1 hour after the filtration, adds toluene 70ml, and the washing secondary obtains solid sediment.Add toluene 60ml then, TiCl
440ml is warmed up to 100 ℃ and handled 2 hours, after the venting filtrate, adds toluene 60ml again, TiCl
440ml is warmed up to 100 ℃ and handled venting filtrate 2 hours.Add toluene 60 ml boiling attitude washing 5 minutes, suction filtration adds hexane 60ml again, and boiling attitude washed twice adds hexane 60ml, after the washed twice, obtains ingredient of solid catalyst under the normal temperature.
Polymerization experiment: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
32.5mmol methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds the foregoing description 1 solid ingredient 8-10mg and 1.2NL hydrogen respectively, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour, pressure is put in cooling, obtains the PP resin.The results are shown in Table 1.
Embodiment 5:
The preparation of catalyst component: with embodiment 4, just replace 3-benzoyloxy ethyl butyrate with 3-benzoyloxy isobutyl butyrate, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal replaces 9,9-two (methyl methoxy base) fluorenes.
Polymerization experiment:, obtain the PP resin with embodiment 4.The results are shown in Table 1.
Embodiment 6:
The preparation of catalyst component:, just replace the 3-benzoyloxy ethyl butyrate of 0.7mmol with 2-methyl-3-benzoyloxy Valeric acid ethylester of 2.0mmol with embodiment 4.
Polymerization experiment:, obtain the PP resin with embodiment 4.The results are shown in Table 1.
Embodiment 7:
The preparation of catalyst component:, just replace 3-benzoyloxy ethyl butyrate with 5-isobutyl--4-benzoyloxy ethyl hexanoate with embodiment 4.
Polymerization experiment:, obtain the PP resin with embodiment 4.The results are shown in Table 1.
Comparative example 1:
The preparation of catalyst component: except not adding 3-benzoyloxy ethyl butyrate, all the other obtain ingredient of solid catalyst with embodiment 4.
Polymerization experiment:, obtain the PP resin with embodiment 4.The results are shown in Table 1.
Comparative example 2:
The preparation of catalyst component: except not adding 3-benzoyloxy isobutyl butyrate, all the other obtain ingredient of solid catalyst with embodiment 5.
Polymerization experiment:, obtain the PP resin with embodiment 4.The results are shown in Table 1.
Table 1 polymerization catalyst result
| Catalyzer | Polymerization activity KgPP/gcat | MFI g/10min | II ％ | Mw/Mn |
| Embodiment 4 | 41.9 | 4.1 | 98.9 | 6.8 |
| Embodiment 5 | 39.8 | 4.0 | 99.1 | 6.6 |
| Embodiment 6 | 38.5 | 3.6 | 98.7 | 7.5 |
| Embodiment 7 | 45.8 | 4.1 | 98.5 | 6.4 |
| Comparative example 1 | 58.1 | 4.2 | 99.2 | 4.0 |
| Comparative example 2 | 55.4 | 4.5 | 99.5 | 4.1 |
From table 1 embodiment and the data of Comparative Examples more as can be seen, used behind two kinds of electron donor compounds the molecular weight distribution of resulting polymers also to have significantly in the present invention and improved.
Claims (18)
1, the catalyst component that is used for olefinic polymerization, this catalyst component comprise titanium, magnesium, halogen and at least two kinds of electron donor compound as and b, and wherein the electron donor compound a is selected from two ester compounds shown in general formula (I):
R ' and R in the formula
1Group is identical or inequality, is selected from the C of replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl; A is that carbon chain length is the divalent linker of 1-10, and it is selected from aliphatics, alicyclic and aromatic divalent group, can have C on the carbon in the described divalent linker
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
2-C
10Alkylene, C
7-C
10Alkaryl or aralkyl, and two or more substituting group can be connected to form saturated or undersaturated monocycle or many rings;
Wherein the electron donor compound b is selected from 1 of general formula (II), the 3-diether compound,
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VIIdentical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIICan be identical or different, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring.
2, the catalyst component that is used for olefinic polymerization according to claim 1, in the diester compound of its formula of (I), A is that chain length is the divalent linker of 1-6 carbon atom.
3, the catalyst component that is used for olefinic polymerization according to claim 1, in the diester compound of its formula of (I), R ' and R
1Group is identical or inequality, is selected from the C of replacement or unsubstituted straight or branched
1-C
10Alkyl, C
6-C
10Aryl or alkaryl or aralkyl.
4, the catalyst component that is used for olefinic polymerization according to claim 1, in the diester compound of its formula of (I), R ' is selected from C
6-C
10Aryl or alkaryl or aralkyl.
5, the catalyst component that is used for olefinic polymerization according to claim 1, its formula of (I) comprises the dibasic ester compound shown in the following general formula (III):
In the general formula (III), R
1Be C
1-C
20Unsubstituted or the halogen alkyl or the C that replace
6-C
20Unsubstituted or halogen replaces aryl or alkaryl;
R
2-5Identical or different, be hydrogen or C
1-4The alkyl of straight or branched;
R
1-5Identical or different, be hydrogen, halogen, C
1-C
10Unsubstituted or halogen replaces alkyl or C
6-C
20Unsubstituted or halogen replaces aryl or alkaryl or aralkyl.
Above-mentioned halogen is selected from F, Cl or Br.
6, the catalyst component that is used for olefinic polymerization according to claim 5, in the wherein said general formula (III), R
1Be C
2-C
10The alkyl or the C of straight or branched
6-C
20Alkaryl.
7, the catalyst component that is used for olefinic polymerization according to claim 5, in the wherein said general formula (III), R
1Be C
2-C
6The alkyl of straight or branched.
8, the catalyst component that is used for olefinic polymerization according to claim 5, in the wherein said general formula (III), R
1-5Identical or different, be hydrogen or C
1-C
6The alkyl or the halogenated alkyl of straight or branched.
9, the catalyst component that is used for olefinic polymerization according to claim 1, it is described 1 to it is characterized in that described electron donor compound b is selected from shown in general formula (VI), the 3-diether compound:
R is identical or inequality in the general formula (VI), is selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl;
R wherein
1Identical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl;
R wherein
2Identical or inequality, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl.
10, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that the mol ratio of described two kinds of electron donor compound as and b is 0.01～100.
11, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that the mol ratio of described two kinds of electron donor compound as and b is 0.05～1.
12, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that the mol ratio of described two kinds of electron donor compound as and b is 0.1～0.4.
13, according to the described catalyst component that is used for olefinic polymerization of one of claim 1-12, it comprises the reaction product of described two kinds of electron donor compound as of titanium compound, magnesium compound and claim 1 and b,
Wherein magnesium compound is selected from a kind of in one of them halogen atom alkoxy in the hydrate of magnesium dihalide, alkoxyl magnesium, alkyl magnesium, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula or the halogenated alkoxy institute metathetical derivative or their mixture;
Wherein titanium compound is that general formula is TiXn (OR)
4-nR is that carbonatoms is 1～20 alkyl in the formula, and X is a halogen, n=1～4.
14, the catalyst component that is used for olefinic polymerization according to claim 13, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
15, the catalyst component that is used for olefinic polymerization according to claim 14, its organic epoxy compounds comprise at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.
16, the catalyst component that is used for olefinic polymerization according to claim 14, its organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
17, a kind of CH that is used for
2=C the catalyzer of R olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, comprise the reaction product of following component:
(1) the described catalyst component of one of claim 1-12;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
18, be used for alkene CH
2=CHR polymeric method, wherein R is hydrogen or C
1-C
6Alkyl or aryl, in the presence of the described catalyzer of claim 17, carry out.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100004817A CN100348624C (en) | 2005-01-13 | 2005-01-13 | Catalyst components for olefinic polyreaction and catalyst thereof |
| US11/117,093 US7351778B2 (en) | 2004-04-30 | 2005-04-28 | Catalyst component for olefin polymerization and catalyst comprising the same |
| EP05754877.8A EP1746110B1 (en) | 2004-04-30 | 2005-04-29 | Catalyst component for olefin polymerization reaction and catalyst thereof |
| PCT/CN2005/000598 WO2005105858A1 (en) | 2004-04-30 | 2005-04-29 | Catalyst component for olefin polymerization reaction and catalyst thereof |
| JP2007509857A JP4769246B2 (en) | 2004-04-30 | 2005-04-29 | Olefin polymerization catalyst component and catalyst containing the same |
| ES05754877.8T ES2537087T3 (en) | 2004-04-30 | 2005-04-29 | Catalyst component for the olefin polymerization reaction and catalyst for it |
| BRPI0510344A BRPI0510344B1 (en) | 2004-04-30 | 2005-04-29 | catalyst component, catalyst, prepolymerized catalyst and olefin polymerization process |
| CA2565111A CA2565111C (en) | 2004-04-30 | 2005-04-29 | Catalyst component for olefin polymerization including dibasic ester, a catalyst comprising the same, and a process |
| MYPI20051912A MY140853A (en) | 2004-04-30 | 2005-04-29 | Catalyst component for olefin polymerization and catalyst comprising the same |
| RU2006142303/04A RU2358987C2 (en) | 2004-04-30 | 2005-04-29 | Catalytic component for polymerising olefins and catalyst, containing such component |
| KR1020067025033A KR101017081B1 (en) | 2004-04-30 | 2005-04-29 | Catalyst component for olefin polymerization reaction and catalyst thereof |
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| CNB2005100004817A CN100348624C (en) | 2005-01-13 | 2005-01-13 | Catalyst components for olefinic polyreaction and catalyst thereof |
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| CN1803863A CN1803863A (en) | 2006-07-19 |
| CN100348624C true CN100348624C (en) | 2007-11-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011044760A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising the same |
| WO2011047522A1 (en) | 2009-10-20 | 2011-04-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| US9499569B2 (en) | 2009-07-15 | 2016-11-22 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| CN107629156A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application |
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| CN102040485A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Diether compound for preparing olefin polymerization catalyst |
| CN102234339B (en) * | 2010-04-22 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst components for olefin polymerization and preparation method thereof |
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| CN104558282B (en) * | 2013-10-18 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application |
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| US9499569B2 (en) | 2009-07-15 | 2016-11-22 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| US10239969B2 (en) | 2009-07-15 | 2019-03-26 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| WO2011044760A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising the same |
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| WO2011047522A1 (en) | 2009-10-20 | 2011-04-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| CN107629156A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application |
| CN107629156B (en) * | 2016-07-18 | 2020-05-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application thereof |
| WO2020078352A1 (en) | 2018-10-19 | 2020-04-23 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| US11970510B2 (en) | 2018-10-19 | 2024-04-30 | China Petroleum & Chemical Corporation | Catalyst component and catalyst for olefin polymerization, and application thereof |
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