CN101423571A - Catalyst component for olefin polymerization and catalyst thereof - Google Patents
Catalyst component for olefin polymerization and catalyst thereof Download PDFInfo
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- CN101423571A CN101423571A CNA2007101766662A CN200710176666A CN101423571A CN 101423571 A CN101423571 A CN 101423571A CN A2007101766662 A CNA2007101766662 A CN A2007101766662A CN 200710176666 A CN200710176666 A CN 200710176666A CN 101423571 A CN101423571 A CN 101423571A
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- hept
- ene
- bicyclo
- dicarboxylic acid
- dimethyl
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Abstract
The invention relates to an olefinic-polymerized catalytic composition, which adopts at least one succinate in a general formula (I) as an internal electron donor. The catalytic composition is used for olefin, and can obtain a polymer with quite high stereospecificity particularly when propylene is copolymerized. The invention also discloses a catalyst containing the catalytic composition.
Description
Technical field
The present invention relates to poly-catalyst component of a kind of alkene and catalyzer thereof, particularly a kind of catalyst component and catalyzer thereof that is used for propylene polymerization.
Background technology
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 can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atoms.Wherein, electron donor is one of requisite composition in the catalyst component, and along with the development of electron donor compound has caused polyolefin catalyst constantly to update.
Previously, reported multiple electron donor compound in the document in a large number, for example polycarboxylic acid, monobasic or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is binary aromatic carboxylic acid's ester class, as n-butyl phthalate or diisobutyl phthalate (CN85100997A) etc.
In recent years, people attempt adopting other compounds as the electron donor in the olefin polymerization catalyst components, US4971937, US2004014597 and EP728769 have adopted special 1, the 3-diether compound is as electron donor, as 2, and 2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc. also can be referring to CN1042547A, CN1143651A, US2003027715 and WO03076480.The disclosed catalyst component that is used for olefinic polyreaction of CN1054139A, it is special 1 to adopt, and the 3-cyclohexadione compounds is as electron donor, as 2,2,6,6-tetramethyl--3,5-heptadione and 2,2,4,6,6-pentamethyl--3,5-heptadione etc.
Disclose special dibasic aliphatic carboxylic acid esters and the diol-lipid compound of a class recently again, given body (referring to CN1313869A, CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) as the internal electron of olefin polymerization catalysis as succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and hexylene glycol ester etc.The use of these electron donor compounds not only can improve activity of such catalysts, and the polyacrylic molecular weight distribution of gained is obviously widened.But when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is still lower.US6818583 and WO2004024785 disclose the succinate that replaces and have given body as internal electron, succinate compound wherein structurally 2, and 3-bit substituent group is not bonded to ring mutually, and the synthetic difficulty of compound is big, the cost height.
Summary of the invention
The object of the present invention is to provide a kind of CH of being used for
2=CHR catalyst component in olefin polymerisation, wherein R is hydrogen or the hydrocarbyl group with 1-12 carbon atom.Another object of the present invention provides the catalyzer that contains above-mentioned catalyst component.
The contriver is by discovering, the succinate that contains 5-norbornylene structure can be given body as the internal electron of olefin polymerization catalysis effectively, and the synthetic method of this compound is simple, side reaction is few, productive rate is high, easy to utilize.
Based on above-mentioned research, the present invention proposes a kind of olefin polymerization catalytic component, by weight percentage, comprise 10-25% magnesium, 1-10% titanium, 40-60% halogen and 1-30% internal electron donor, described internal electron donor is selected from least a succinate in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, the optional heteroatoms that contains; Radicals R
3To R
10Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, optional heteroatoms and the R of containing
3-R
10In two or more groups mutually bonding generate one or several condensed ring structure.
In above-mentioned general formula compound, R
1And R
2Be preferably C
1-C
10Alkyl, cycloalkyl or arylalkyl, further preferred C
1-C
10Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or neo-pentyl, preferred especially ethyl, n-propyl, sec.-propyl or normal-butyl.
In above-mentioned general formula compound, preferred R
3And R
4, R
5And R
6, R
7And R
8, R
9And R
10In to have one group of group at least be hydrogen, more preferably, radicals R
7And R
8Be hydrogen.
The example of suitable above-mentioned general formula compound includes but not limited to:
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
, Diethyl bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, bicyclo [2.2.1] hept-5 - ene-2 ,3 -
Dicarboxylic acid isopropyl ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid isobutyl ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester 2 - methyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid methyl ester 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Acid diethyl ester 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl 2 - methyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl
Di-n-butyl 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester 2 - methyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl
Dimethyl 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester 2 - ethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diisopropyl
Esters of 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2 - ethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl
Esters of 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate 2 - isopropyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-propyl
Esters of 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester 2 - isopropyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Butyl 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - dimethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Acid diethyl ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3 - dimethyl
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - diethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Acid, diethyl 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3 - diethyl
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - diethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - diisopropyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl, diethyl 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl,
2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-isobutyl, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl
, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - dimethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Carboxylic acid di-n-propyl, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4 -
Dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Neopentyl, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - diethyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 -
Dimethyl di-n-propyl, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4 -
Diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Neopentyl, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - diisopropyl-
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diisopropyl
, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - diisopropyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid neopentyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 5,6 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Isopropyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 5,6 - dimethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 5,6 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Isopropyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 5,6 - diethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 5,6 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid isopropyl ester, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl
Ester, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 5,6 - diisopropyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 7,7 -
Dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
N-butyl, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 7,7 - dimethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 7,7 -
Diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
N-butyl, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 7,7 - diethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylate, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester,
7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-butyl, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,2,3,4 - tetramethyl-
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dimethyl, diethyl 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid is
Propyl, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,2,3,4 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 1,2,3,4 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl ester, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid dimethyl
Esters of 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,2,3,4 - tetraethyl
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-
-5 - Ene -2,3 - dicarboxylic acid isopropyl ester, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-butyl 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester,
1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,2,3,4 - tetraisopropyl
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-
-5 - Ene -2,3 - dimethyl, diethyl 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-propyl, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester,
1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 1,2,3,4 - tetraisopropoxide
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl
Dimethyl 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3,5,6 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-butyl 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Butyl, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 -
Tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3,5,6 - tetraethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-propyl, 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester,
2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2,3,5,6 - tetraethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Dimethyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 -
Tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3,5,6 - tetraisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Diisobutyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester,
1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4,5,6 - tetramethyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Propyl, 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-butyl 1,4,5,6 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4,5,6 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester,
1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 1,4,5,6 - tetraethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Iso-butyl 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,4,5,6 -
Tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4,5,6 - tetraisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Iso-propyl, 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl,
1,4,5,6 - four isopropyl - bicyclo [2.2.1] hept-5 - ene -2,3 - dimethyl diisobutyl or 1,4,5,6 - tetra-iso-
Propyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl.
...
The synthetic of above-mentioned general formula compound can be adopted known method, promptly obtained through esterification by corresponding precursor compound, and its precursor compound can utilize diels-alder reaction (Diels-Alder reaction) to prepare.Pertinent literature is specifically referring to Org.React.1998, and 52,1.; Furuta K.; IwanagaK.Yamamoto H.Tetrahedron Lett.1986,27 (37), 4507..
Magnesium in the catalyst component can be by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0 ≦ m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
Magnesium halide in the magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate, preferred magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol, preferred alcohol.
After magnesium halide alcohol adduct adopts magnesium halide and alcohol to be total to heat of solution, high pressure ejection or high-speed stirring, the method that is solidified into microsphere particle in heat-eliminating medium obtains, and concrete grammar is referring to the associated description among the US4399054.
Titanium in the catalyst component can be TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.Concrete compound is as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
The preparation method of catalyst component of the present invention comprises: (1) joins spherical magnesium halide alcohol adduct in-40～10 ℃ the titanium compound, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1:5～1:50; (2) be warming up to 30～80 ℃, add the internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2:1～15:1; (3) be warming up to 100～150 ℃ again, reacted 1～4 hour; (4) add titanium compound with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, more after filtration, washing obtained after the drying.
With above-mentioned catalyst component is main ingredient, and the present invention also can further be provided for the catalyzer of olefinic polymerization.Catalyzer specifically comprises:
(a) contain magnesium, titanium, halogen and be selected from the catalyst component of at least a succinate in the general formula (I);
(b) alkylaluminium cpd;
(c) randomly, external electron donor.
Wherein, alkylaluminium cpd (b) is selected from trialkyl aluminium compound, as the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
The external electron donor component can add as required selectively.Obtain the olefin polymer of taxis very high (as isotactic index greater than 99%) for needs, suggestion adds the external electron donor compound.
It is R that external electron donor can be selected general formula
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R ', the optional heteroatoms that contains; R also can be halogen or hydrogen atom.Concrete silicoorganic compound are as the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
1 of the also optional self-drifting of external electron donor (II), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VICan be identical or different, can be hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom; R
VIIAnd R
IIICan be identical or different, can be hydrocarbyl group with 1 to 18 carbon atom; R
I-R
VIIIGroup in one or morely can also link up into ring.Preferably, R
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl group, R
IIIAnd R
IVForm undersaturated condensed ring and R
I, R
II, R
VAnd R
VIBe hydrogen.Especially preferably use 9, two (methoxymethyl) fluorenes of 9-.
With titanium: aluminium: the molar ratio computing between the external electron donor compound (c), the amount ratio in the catalyzer between each component are 1:5-1000:0-500; Be preferably 1:25-100:25-300.
Catalyzer of the present invention is used for olefinic polymerization, can access the polymkeric substance of very high isotactic index when the equal polymerization of special propylene or the copolymerization of propylene and other alkene.Simultaneously, do not get rid of the copolymerization that is applicable to production polyethylene and ethene and alpha-olefin such as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene or 1-octene yet.
Can adopt the whole bag of tricks of the prior art when being used for propylene polymerization, can in liquid phase or gas phase, carry out, also can under the combination operation of liquid and gas polymerization stage, carry out.Polymerization is carried out at 0～150 ℃ usually, preferred 40～90 ℃.Polymerization pressure is 0.01～10MPa.The hydrogen of chain-transfer agent effect or other compounds can be played and the molecular weight of controlling polymers can be used for.
The present invention is by adopting novel internal electron donor succinate compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene (being total to) polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain high normal polymkeric substance, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
Embodiment given below is for the present invention is described better, rather than limits the invention.
Testing method:
1, polymericular weight and molecular weight distribution MWD (MWD=M
w/ M
n): adopting the gel permeation chromatography method, is that solvent is measured down at 135 ℃ with the orthodichlorobenzene with Alliance-GPCV2000.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 8 hours), promptly 1 restrain the exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 8 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 1 ratio.
3, the mensuration of melt index: measure according to μ PXRZ-400C.
4, the mensuration of titanium percentage composition: according to spectrophotometry.
5, the mensuration of internal electron donor percentage composition: according to the Autosystem XL of PE company gas chromatograph for determination.
One, succinate compound is synthetic
Only with dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboxylate synthesize example, concrete grammar is as follows:
Add 16.4gNA acid anhydrides, 50ml dehydrated alcohol and 1.0g tosic acid in the 100ml flask, reflux is 12 hours under stirring.After reaction mixture is chilled to room temperature, add saturated aqueous common salt, extracted with diethyl ether 3 times, combining extraction liquid is used anhydrous sodium sulfate drying, filters, solvent evaporated, column chromatography for separation gets oily liquids product 22.6g, yield 95%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 6.19 (q, 2H, alkene H); δ 4.00 (q, 4H, CH
2CH
3); δ 3.22 (q, 2H, CHCO); δ 3.10 (m, 2H, CH); δ 1.39 (q, 2H, CH
2); δ 1.17 (t, 6H, CH
3).
Two, the preparation of catalyst component
Embodiment 1-27
Under the anhydrous and oxygen-free condition, in 500 milliliter of four neck round-bottomed flask of a process abundant metathetical of high pure nitrogen, add TiCl
4100ml and toluene 60ml are cooled to-20 ℃, add 10.0gMgCl
22.8CH
3CH
2OH ball type carrier (according to the method preparation of USP4399054).Rise to 0 ℃ in 1 hour, continuing to heat up rose to 20 ℃ in 2 hours, and continuing to heat up rose to 40 ℃ in 1 hour, add corresponding succinate compound in the table 1 (adopting aforesaid method preparation) 7.4mmol respectively, be warming up to 100 ℃ in 1 hour, and kept venting filtrate 2 hours.Add TiCl
4100ml rose to 120 ℃ in 1 hour, kept venting filtrate 2 hours.Add anhydrous hexane 60ml, boiling attitude washing 5 times adds anhydrous hexane 60ml then, and normal temperature washing 3 times is at last with the catalyst component vacuum-drying that obtains.
Comparative example 1-4
Press the preparation method of the foregoing description catalyst component, just internal electron donor is replaced with n-butyl phthalate, dibutyl succinate, 2 respectively, 3-di-isopropyl ethyl succinate and 2,4-pentanediol dibenzoate.
Three, propylene polymerization experiment
The catalyst component of the foregoing description 1-27 and comparative example 1-4 is carried out propylene polymerization respectively.Usually step is: volume is the stainless steel autoclave of 5L, after high pure nitrogen is fully replaced, adds AlEt
32.5mmol external electron donor methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds catalyst component 10mg and the 1.2L hydrogen of the foregoing description 1-27 again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release to 1 normal atmosphere obtains the PP powder.Polymerization result is listed in table 1.
Table 1. propylene polymerization result
Four, the propylene polymerization that does not add external electron donor
According to above-mentioned polymerization procedure, but do not add external electron donor, the ingredient of solid catalyst of embodiment 1-3 and comparative example 3-4 is carried out propylene polymerization respectively, the polymerization result of polymerization result and methylate cyclohexyl dimethoxy silane (CHMMS) external electron donor relatively list in table 2.
Table 2. adds and the polymerization result that does not add external electron donor
| Embodiment | Internal electron donor | CHMMS/AlEt 3 mol/mol | Polymerization activity kgPP/gcat | Degree of isotacticity (%) | Molecular weight distribution |
| Embodiment 1 | Dicyclo [2.2.1] heptan-5-alkene-2,3-dioctyl phthalate dimethyl ester | 0.04 | 62 | 99.0 | 8.9 |
| Embodiment 1 | The same | 0 | 65 | 97.5 | 8.8 |
| Embodiment 2 | Dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboxylate | 0.04 | 68 | 99.5 | 9.3 |
| Embodiment 2 | The same | 0 | 73 | 98.3 | 9.1 |
| Embodiment 3 | Dicyclo [2.2.1] heptan-5-alkene-2,3-dioctyl phthalate diisopropyl ester | 0.04 | 58 | 99.2 | 8.8 |
| Embodiment 3 | The same | 0 | 61 | 98.1 | 8.7 |
| Comparative example 3 | 2,3-di-isopropyl succsinic acid diethyl ester | 0.04 | 40 | 94.7 | 8.6 |
| Comparative example 3 | The same | 0 | 43 | 87.4 | 8.5 |
| Comparative example 4 | 2,4-pentanediol dibenzoate | 0.04 | 48 | 95.3 | 5.8 |
| Comparative example 4 | The same | 0 | 50 | 88.7 | 6.0 |
The result can see from table 2, under the situation that does not add external electron donor, adopt ingredient of solid catalyst of the present invention to carry out polymerization and still can obtain quite high degree of isotacticity, and the polymerization activity that polymerization activity is a little higher than to be obtained when adding external electron donor.And adopt the catalyzer (comparative example 3 and comparative example 4) of prior art to carry out polymerization, under the situation that does not add external electron donor, the degree of isotacticity of the polymkeric substance that obtains is very low.
Five, the propylene polymerization result of different external electron donors relatively
Catalyst component is with embodiment 2, and polymerization process is with aforementioned, and just external electron donor changes down the external electron donor described in the tabulation into.
The polymerization result of the different external electron donors of table 3. relatively
| External electron donor | Polymerization activity kgPP/gcat | Degree of isotacticity (%) | Molecular weight distribution | Melting index g/10min |
| Methylcyclohexyl dimethoxy silane | 68 | 99.5 | 9.3 | 0.9 |
| Dicyclopentyl dimethoxyl silane | 67 | 99.2 | 8.4 | 0.9 |
| Diisopropyl dimethoxy silane | 65 | 99.3 | 7.6 | 0.9 |
| Di-n-butyl dimethoxy silane | 66 | 99.1 | 7.4 | 1.0 |
| Second, isobutyl dimethoxy silane | 70 | 99.0 | 7.7 | 1.2 |
| 9, two (methoxymethyl) fluorenes of 9- | 71 | 99.4 | 6.8 | 0.9 |
Six, vinyl polymerization experiment
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the catalyst solid constituent and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 2 gained under nitrogen protection in still
3After being warming up to 75 ℃, in still, replenish an amount of high-purity hydrogen, make that hydrogen partial pressure is 0.3Mpa in the still, after 5 minutes in still make-up ethylene gas make its dividing potential drop reach 0.75MPa, the dividing potential drop of keeping ethylene gas is constant, make system temperature keep 80 ℃, after 3 hours, cooling discharge, polymkeric substance except that desolvating, is obtained polyethylene 275g after the thorough drying.
Seven, ethene and copolymerization of propylene experimental result
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the catalyst solid constituent and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 2 gained under nitrogen protection in still
3Feed liquid propene 2.3L, be warming up to 75 ℃ after, in still, replenish an amount of high-purity hydrogen, making the interior hydrogen partial pressure of still is 0.3MPa, make-up ethylene gas makes its dividing potential drop reach 0.75MPa in still then, and the dividing potential drop of keeping ethylene gas is constant, makes system temperature keep 80 ℃, after 3 hours, cooling discharge except that desolvating, obtains polymer powders 493g with polymkeric substance after the thorough drying.
Claims (23)
1. olefin polymerization catalytic component by weight percentage, comprises 10%-25% magnesium, 1%-10% titanium, 40%-60% halogen and 1%-30% internal electron donor, it is characterized in that described internal electron donor is selected from least a succinate in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, the optional heteroatoms that contains; Radicals R
3To R
10Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, optional heteroatoms and the R of containing
3-R
10In two or more groups mutually bonding generate one or several condensed ring structure.
2. catalyst component according to claim 1 is characterized in that in the ester class general formula compound R
1And R
2Be C
1-C
10Alkyl, cycloalkyl or arylalkyl.
3. catalyst component according to claim 2 is characterized in that in the ester class general formula compound R
1And R
2Be C
1-C
10Alkyl.
4. catalyst component according to claim 3 is characterized in that in the ester class general formula compound R
1And R
2Be ethyl, n-propyl, sec.-propyl or normal-butyl.
5. catalyst component according to claim 1 is characterized in that in the ester class general formula compound R
3And R
4, R
5And R
6, R
7And R
8, R
9And R
10In to have one group of group at least be hydrogen.
6. catalyst component according to claim 5 is characterized in that in the ester class general formula compound R
7And R
8Be hydrogen.
As claimed in claim 1, wherein the catalytic component, wherein the ester is a bicyclic compound of the formula
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester,
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Isopropyl ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, bicyclo [2.2.1] hept-5 - ene-2 ,3 -
Dicarboxylic acid isobutyl ester, bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester 2 - methyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid methyl ester 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Diethyl 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl 2 - methyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl
Esters of 2 - methyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester 2 - methyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid dimethyl
Esters of 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester 2 - ethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid, n-propyl 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester,
2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2 - ethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid isobutyl ester 2 - ethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester,
2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid methyl ester 2 - isopropyl - bicyclo [2.2.1] hept-
-5 - Ene -2,3 - dicarboxylic acid diethyl ester 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-propyl
Esters of 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester 2 - isopropyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Butyl 2 - isopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - dimethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Acid diethyl ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3 - dimethyl
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 2,3 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - diethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Acid, diethyl 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3 - diethyl
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - diethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 2,3 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 2,3 - diisopropyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl, diethyl 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl,
2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-isobutyl, 2,3 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl
, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - dimethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - two
Carboxylic acid di-n-propyl, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4 -
Dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 1,4 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Neopentyl, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - diethyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 -
Dimethyl di-n-propyl, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4 -
Diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Neopentyl, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4 - diisopropyl-
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diisopropyl
, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 1,4 - diisopropyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4 - diisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid neopentyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 5,6 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Isopropyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 5,6 - dimethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 5,6 - dimethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 5,6 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Isopropyl, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl, 5,6 - diethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 5,6 - diethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate,
5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 5,6 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid isopropyl ester, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl
Ester, 5,6 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 5,6 - diisopropyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 7,7 -
Dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - dimethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
N-butyl, 7,7 - dimethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl, 7,7 - dimethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester, 7,7 -
Diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - diethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
N-butyl, 7,7 - diethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 7,7 - diethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylate, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester,
7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 7,7 - diisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-butyl, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl
Ester, 7,7 - diisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,2,3,4 - tetramethyl-
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dimethyl, diethyl 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid is
Propyl, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,2,3,4 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 1,2,3,4 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,2,3,4 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl acid neopentyl ester, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid dimethyl
Esters of 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,2,3,4 - tetraethyl
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-
-5 - Ene -2,3 - dicarboxylic acid isopropyl ester, 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-butyl 1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester,
1,2,3,4 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,2,3,4 - tetraisopropyl
- Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-
-5 - Ene -2,3 - dimethyl, diethyl 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-propyl, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester,
1,2,3,4 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 1,2,3,4 - tetraisopropoxide
Yl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,2,3,4 - tetraisopropyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl
Dimethyl 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3,5,6 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-butyl 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Butyl, 2,3,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 -
Tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 2,3,5,6 - tetraethyl - bicyclo [2.2.1]
Hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Di-n-propyl, 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester,
2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl 2,3,5,6 - tetraethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 2,3,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid neopentyl ester, 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Dimethyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 2,3,5,6 -
Tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 2,3,5,6 - tetraisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate
Diisobutyl 2,3,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester,
1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4,5,6 - tetramethyl - bis
Ring [2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid iso
Propyl, 1,4,5,6 - tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-butyl 1,4,5,6 -
Tetramethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isobutyl ester, 1,4,5,6 - tetramethyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid diethyl ester,
1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid, n-propyl, 1,4,5,6 - tetraethyl -
Bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid isopropyl ester, 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 -
Ene-2 ,3 - dicarboxylic acid n-butyl 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Iso-butyl 1,4,5,6 - tetraethyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl ester, 1,4,5,6 -
Tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylate, 1,4,5,6 - tetraisopropyl - bicyclo
[2.2.1] hept-5 - ene-2 ,3 - dimethyl, diethyl 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene
-2,3 - Dimethyl di-n-propyl, 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid
Iso-propyl, 1,4,5,6 - tetraisopropyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid n-butyl,
1,4,5,6 - four isopropyl - bicyclo [2.2.1] hept-5 - ene -2,3 - dimethyl diisobutyl or 1,4,5,6 - tetra-iso-
Propyl - bicyclo [2.2.1] hept-5 - ene-2 ,3 - dicarboxylic acid neopentyl.
...
8. catalyst component according to claim 1 is characterized in that magnesium in the catalyst component by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0 ≦ m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
9. catalyst component according to claim 8 is characterized in that providing in the magnesium halide alcohol adduct of magnesium, and magnesium halide is a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol in the magnesium halide alcohol adduct is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
10. catalyst component according to claim 9, it is characterized in that providing the magnesium halide in the magnesium halide alcohol adduct of magnesium is magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is ethanol.
11. catalyst component according to claim 1 is characterized in that the titanium in the catalyst component is TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.
12. catalyst component according to claim 11 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium.
13. catalyst component according to claim 12 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride.
14. a catalyzer that comprises one of the described catalyst component of claim 1 to 13 is characterized in that catalyzer comprises:
A) one of the described catalyst component of claim 1 to 13;
B) alkylaluminium cpd;
C) randomly, external electron donor component.
15. catalyzer according to claim 14 is characterized in that alkylaluminium cpd is a trialkyl aluminium compound.
16. catalyzer according to claim 15, it is characterized in that alkylaluminium cpd is the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
17. catalyzer according to claim 14 is characterized in that external electron donor is that general formula is R
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R '.
18. catalyzer according to claim 17, it is characterized in that external electron donor is the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
19. catalyzer according to claim 14 is characterized in that external electron donor is 1 of a general formula (II), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VICan be identical or different, for hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom; R
VIIAnd R
IIICan be identical or different, for having the hydrocarbyl group of 1 to 18 carbon atom; R
1-RV
IIIGroup in one or morely can link up into ring.
20. catalyzer according to claim 19 is characterized in that in the external electron donor general formula R
VIIAnd R
VIIIBe C
1-C
4Alkyl group; R
IIIAnd R
IVForm undersaturated condensed ring; R
I, R
II, R
VAnd R
VIBe hydrogen.
21. catalyzer according to claim 20 is characterized in that external electron donor is 9, two (methoxymethyl) fluorenes of 9-.
22. catalyzer according to claim 14 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1:5-1000:0-500.
23. catalyzer according to claim 22 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1:25-100:25-300.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399329A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN102399327A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102020731B (en) * | 2009-09-10 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and catalyst thereof |
| CN103304709A (en) * | 2013-07-10 | 2013-09-18 | 河北工业大学 | Solid catalyst for 1-butene polymerization |
| CN104761664A (en) * | 2015-03-13 | 2015-07-08 | 北京肯佰恩科技发展有限公司 | Catalyst composition used in olefin polymerization and application thereof |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE335014T1 (en) * | 1999-04-15 | 2006-08-15 | Basell Poliolefine Srl | COMPONENTS AND CATALYSTS FOR OLEFIN POLYMERIZATION |
| DE60104238T2 (en) * | 2000-02-02 | 2005-07-28 | Basell Poliolefine Italia S.P.A. | COMPONENTS AND CATALYSTS FOR POLYMERIZATION OF OLEFINES |
| CN1274724C (en) * | 2003-09-18 | 2006-09-13 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN100400554C (en) * | 2005-01-13 | 2008-07-09 | 中国石油化工股份有限公司 | Catalyst components for propylene polymerization and catalyst thereof |
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| CN102020731B (en) * | 2009-09-10 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and catalyst thereof |
| CN102399329A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN102399327A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102399327B (en) * | 2010-09-16 | 2013-06-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and its catalyst |
| CN102399329B (en) * | 2010-09-16 | 2013-08-14 | 中国石油化工股份有限公司 | Catalyst component used in alkene polymerization, and catalyst |
| CN103304709A (en) * | 2013-07-10 | 2013-09-18 | 河北工业大学 | Solid catalyst for 1-butene polymerization |
| CN103304709B (en) * | 2013-07-10 | 2016-03-30 | 河北工业大学 | A kind of solid catalyst for 1-butylene polymerization |
| CN104761664A (en) * | 2015-03-13 | 2015-07-08 | 北京肯佰恩科技发展有限公司 | Catalyst composition used in olefin polymerization and application thereof |
| US11530281B2 (en) | 2016-08-19 | 2022-12-20 | Institute Of Chemistry, Chinese Academy Of Sciences | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
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