CN106543312A - A kind of olefin polymerization catalyst system and its application - Google Patents

A kind of olefin polymerization catalyst system and its application Download PDF

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CN106543312A
CN106543312A CN201510612874.7A CN201510612874A CN106543312A CN 106543312 A CN106543312 A CN 106543312A CN 201510612874 A CN201510612874 A CN 201510612874A CN 106543312 A CN106543312 A CN 106543312A
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diethyl
dimethyl
ester
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group
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CN106543312B (en
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张天
张天一
夏先知
刘月祥
张志会
段瑞林
万真
马长友
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to field of olefin polymerisation, discloses a kind of catalyst system, the catalyst system contains：Solids containing titanium catalytic component, alkyl aluminum compound and external donor compound, the solids containing titanium catalytic component contains at least two internal electron donor compound of glycol ester type compound and carboxylate compound, and the external donor compound is ether ester compounds.Present invention also offers application of the catalyst in olefinic polyreaction as above.The present invention is used in the polyreaction of alkene by ether ester compounds are added when olefinic polyreaction is carried out as the ingredient of solid catalyst of internal electron donor using glycol ester type compound and carboxylate compound, the catalyst can not only be made to keep higher polymerization activity, while the hydrogen response of catalyst can also be improved.

Description

Olefin polymerization catalyst system and application thereof
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst system and application thereof in olefin polymerization.
Background
It is known that the catalyst systems used in the homopolymerization or copolymerization of alpha-olefins generally consist of three parts: (1) a main catalyst (solid catalyst), (2) a cocatalyst (usually an alkyl aluminum compound), and (3) an external electron donor compound added during polymerization.
The use of one or more external electron donor compounds to control the stereoregularity and morphology of a polymer during a polymerization reaction is well known to those skilled in the art. In addition to affecting the stereoregularity of the polymer, the external electron donor often affects other properties of the catalyst to varying degrees. Although a wide variety of compounds are known to be available as external electron donors, the use of different external electron donor compounds for a particular catalyst may result in different polymer properties. The choice of a suitable external electron donor may be particularly compatible with a particular catalyst, i.e. finding a suitable external electron donor may significantly improve some aspects of the performance of the polymer product, and it would therefore be highly advantageous to find a set of external electron donors for a particular catalyst that gives polymers with outstanding properties in some respects.
Chinese patents CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN 200410073623.8, CN200410073621.9, etc. describe catalyst components using glycol ester compounds and phthalic acid ester compounds to compound an internal electron donor, when the catalyst components are used for propylene polymerization, the external electron donor used is hydrocarbyl dialkoxy silane which is a commonly used external electron donor in industry at present, such as methylcyclohexyl dimethoxy silane (CHMMS), etc. Although chinese patent CN03109781.2 also used different external electron donors for comparison, for example diisobutyldimethoxysilane, Dicyclopentyldimethoxysilane (DCPMS), bis (cyclobutylmethyl) dimethoxysilane, etc. in addition to methylcyclohexyldimethoxysilane. However, in general, it is difficult to effectively adjust the overall performance of the catalyst by the external electron donor or the external electron donor compound composition in the prior art, and obtain a catalyst with excellent polymerization activity and hydrogen sensitivity.
Disclosure of Invention
The object of the present invention is to overcome the above drawbacks by providing an olefin polymerization catalyst system comprising: a titanium-containing solid catalyst component, an alkyl aluminum compound and an external electron donor compound, wherein,
the titanium-containing solid catalyst component contains a glycol ester compound and a carboxylic ester compound as internal electron donor compounds;
wherein the external electron donor compound is an ether ester compound with a structure shown in a formula (I);
R5-O-R4(R3(COOR1)COOR2)(I)
wherein,
R1、R2each independently is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl of (2), C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl of R1、R2Optionally the same or different;
R3a first organic radical which is trivalent or tetravalent and which is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl radical, C1-C20Linear or branched alkyl of (a);
R4is a reaction with R3By single or double bond connection, R4A second organic group which is divalent or trivalent, the second organic group being C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl group;
R5is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl groups of (1).
In another aspect, the present invention also provides the use of a catalyst system as described above in the polymerisation of olefins.
According to the invention, the ether-based ester compound is added into the solid catalyst component which takes the diol ester compound and the carboxylic ester compound as the internal electron donor, and is used as the external electron donor for the polymerization reaction of the olefin, so that the catalyst can keep higher polymerization activity, and the hydrogen regulation sensitivity of the catalyst can be improved, and the polymerization method is simple.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides an olefin polymerization catalyst system comprising: a titanium-containing solid catalyst component, an alkyl aluminum compound and an external electron donor compound, wherein,
the titanium-containing solid catalyst component contains a glycol ester compound and a carboxylic ester compound as internal electron donor compounds;
wherein the external electron donor compound is an ether ester compound with a structure shown in a formula (I);
R5-O-R4(R3(COOR1)COOR2) (I)
wherein,
R1、R2each independently is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl of (2), C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl of R1、R2Optionally the same or different;
R3a first organic radical which is trivalent or tetravalent and which is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl radical, C1-C20Linear or branched alkyl of (a);
R4is a reaction with R3By single or double bond connection, R4A second organic group which is divalent or trivalent, the second organic group being C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl group;
R5is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl groups of (1).
It is well known to those skilled in the art that in organic materials, carbon atoms and other atoms form 4 pairs of common electron pairs, always having 4 valences. It may be a single bond, a double bond or a triple bond. Herein, the term "divalent organic group" refers to an organic group formed by a carbon atom having a 4-valent bond constituting a 2 pair common electron pair with a hydrogen atom and constituting a 2 pair common electron pair with an atom other than hydrogen in an organic substance. By analogy, the term "trivalent organic group" refers to an organic group formed by a carbon atom with a 4-valent bond and a hydrogen atom forming 1 pair of common electron pairs and atoms other than hydrogen forming 3 pairs of common electron pairs in an organic substance; the "tetravalent organic group" means an organic group in which a carbon atom having a 4-valent bond does not form a pair of electrons in common with a hydrogen atom, but forms a pair of electrons in common with 4 pairs of atoms other than hydrogen in all valences. Note that the valence bond between a carbon atom and an atom other than hydrogen may be a single bond, a double bond, or a triple bond.
The inventors of the present invention have found in the course of research that when the ether ester compound having the structure represented by the above formula (I) of the present invention is added to an olefin polymerization reaction system as an external electron donor, the catalyst not only can maintain a high activity, but also can improve the hydrogen response of the catalyst, and the polymerization method is simple, thereby completing the present invention.
According to the invention, R1、R2Preferably the same.
According to the invention, preferably, R1、R2Each independently is C3-C10Cycloalkyl of, C6-C12Aryl of (C)7-C12Aralkyl or C7-C12Alkylaryl of, C10-C14Condensed ring aryl of (C)2-C10Alkenyl group of (C)1-C10Linear or branched alkyl of (a); further preferably, R1、R2Each independently is C3-C6Cycloalkyl of, C6-C12Aryl of (C)7-C10Phenylalkyl or C7-C10Alkylphenyl radical of (1), C2-C6Alkenyl group of (C)1-C6Linear or branched alkyl groups of (1).
Wherein the cycloalkyl group may be C5Or C6A cycloalkyl group of (a).
Wherein the aryl group may be phenyl.
Wherein the phenylalkyl or alkylphenyl group may have C1-C6Is preferably a phenylalkyl or alkylphenyl radical having a linear or branched alkyl radical of (A), preferably having C1-C4The phenylalkyl group or alkylphenyl group of the straight-chain or branched alkyl group of (1) may be, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, a butylbenzene group, and most preferably a benzyl group or a tolyl group.
Wherein, C2-C6The alkenyl group of (3) is more preferably C2-C4The linear or branched alkenyl group of (2) may specifically be a vinyl group, an allyl group or a 1-butenyl group, and a vinyl group or an allyl group is more preferable.
Wherein, C1-C6Further preferably C1-C4The linear or branched alkyl group of (2) may specifically be a methyl group, an ethyl group, a propyl group or a butyl group, and more preferably a methyl group or an ethyl group.
According to the invention, preferably, R3A first organic radical which is trivalent or tetravalent and which is C3-C6Cycloalkyl of, C6-C12Aryl of (C)7-C10Aralkyl or C7-C10Alkylaryl of, C1-C10Linear or branched alkyl of (a); more preferably, the first organic group is C6-C12Aryl or C of1-C6Linear or branched alkyl groups of (1).
Wherein, the C6-C12Aryl of (b) is preferably phenyl.
Wherein the aralkyl or alkaryl group may be of C1-C6OfPhenylalkyl or alkylphenyl radicals of a chain or branched alkyl radical, preferably having C1-C4The phenylalkyl group or alkylphenyl group of the straight-chain or branched alkyl group of (1) may be, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, a butylbenzene group, and most preferably a benzyl group or a tolyl group.
Wherein, C1-C6Further preferably C1-C4The linear or branched alkyl group of (2) may specifically be a methyl group, an ethyl group, a propyl group or a butyl group, and more preferably a methyl group, an ethyl group or a propyl group.
According to the invention, R4And R3By single or double bond linkage, R4Is a divalent or trivalent second organic group, preferably the second organic group is C1-C10Linear or branched alkyl of (2), C3-C6Cycloalkyl radical, C6-C12Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl group of (1); more preferably C1-C6Linear or branched alkyl or C6-C12Further preferably C1-C4Linear or branched alkyl C of7-C10Alkylaryl or C of7-C10An aralkyl group of (2). Most preferred is methyl, methylene, ethyl, ethylene, benzyl or benzylidene.
According to the invention, preferably, R5Is C3-C6Cycloalkyl of, C6-C12Aryl of (C)7-C10Aralkyl or C7-C10Alkylaryl of, C2-C6Linear or branched alkenyl or C1-C6Linear or branched alkyl groups of (1). More preferably, R5Is phenyl, C6-C8Aralkyl or C6-C8Alkylaryl of, C2-C6Linear or branched alkenyl or C1-C6Linear or branched alkyl groups of (1).
Wherein, the C6-C8The aralkyl or alkaryl group of (a) is preferably benzyl or tolyl.
Wherein, the C6-C12Aryl of (b) is preferably phenyl.
Wherein, C1-C6Further preferably C1-C4The linear or branched alkyl group of (b) may be, for example, a methyl, ethyl, propyl or butyl group, most preferably a methyl or ethyl group.
Wherein, C2-C6The linear or branched alkenyl group of (3) is more preferably C2-C4The linear or branched alkenyl group of (2) may be, for example, a vinyl group, an allyl group, a butenyl group, and more preferably a vinyl group or an allyl group.
Specifically, the ether-based ester compound of the present invention having the structure shown in formula (I) may be one or more selected from, but not limited to, the following compounds: dimethyl methoxymethylenemalonate, diethyl ethoxymethylenemalonate, dimethyl ethoxymethylenemalonate, diethyl methoxymethylenemalonate, dimethyl 2-methoxymethylene-1, 4-succinate, diethyl 2-ethoxymethylene-1, 4-succinate, dimethyl 2-ethoxymethylene-1, 4-succinate, diethyl 2-methoxymethylene-1, 4-succinate, dimethyl methoxyethylenemalonate, diethyl ethoxyethylenemalonate, dimethyl ethoxyethylenemalonate, diethyl methoxyethylenemalonate, dimethyl 2-methoxyethylenel-1, 4-succinate, diethyl 2-ethoxyethylenel-1, 4-succinate, diethyl ethoxymethylenemalonate, diethyl ethoxymethylethoxymethylethoxymethylbutanemalonate, diethyl ethoxymethylbutanemalonate, diethyl malonate, diethyl ethoxymethylbutanedioate, diethyl-, 2-ethoxyethylene-1, 4-butanedioic acid dimethyl ester, 2-methoxyethylene-1, 4-butanedioic acid diethyl ester, 2-methoxymethylene-1, 5-pentanedioic acid dimethyl ester, 2-ethoxymethylene-1, 5-pentanedioic acid diethyl ester, 2-ethoxymethylene-1, 5-pentanedioic acid dimethyl ester, 2-methoxymethylene-1, 5-pentanedioic acid diethyl ester, 3-methoxymethylene-1, 5-pentanedioic acid dimethyl ester, 3-ethoxymethylene-1, 5-pentanedioic acid diethyl ester, 3-ethoxymethylene-1, 5-pentanedioic acid dimethyl ester, 3-methoxymethylene-1, 5-pentanedioic acid diethyl ester, diethyl ester, Dicyclopentyl methoxymethylenemalonate, dicyclopentyl ethoxymethylenemalonate, dicyclohexyldicyclohexylethoxymethylenemalonate, dicyclohexyldicyclohexylmethoxymethylenemalonate, diphenylmethyl methoxymethylenemalonate, diphenylmethyl ethoxymethylenemalonate, dimethyl phenoxymethylenemalonate, diethyl phenoxymethylenemalonate, dimethyl vinyloxymethylenemalonate, diethyl vinyloxymethylmethylenemalonate, dimethyl allyloxymethylenemalonate, diethyl allyloxymethylenemalonate, dimethyl 3-methoxymethylenephthalate, diethyl 3-ethoxymethylenephthalate, dimethyl 3-ethoxymethylenephthalate, diethyl 3-methoxymethylenephthalate, dimethyl 4-methoxymethylenephthalate, dimethyl ethoxymethylenephthalate, dimethyl ethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymethylethoxymalonate, diethyl 3-methoxymethylenephthalate, dimethyl ethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymalonate, dimethyl, Diethyl 4-ethoxymethylenephthalate, dimethyl 4-ethoxymethylenephthalate, diethyl 4-methoxymethylenephthalate, dimethyl 2-methoxymethyleneterephthalate, diethyl 2-ethoxymethyleneterephthalate, dimethyl 2-ethoxymethyleneterephthalate, diethyl 2-methoxymethyleneterephthalate, dimethyl 3-methoxymethyleneterephthalate, diethyl 3-ethoxymethyleneterephthalate, dimethyl 3-ethoxymethyleneterephthalate, diethyl 3-methoxymethyleneterephthalate, dimethyl methoxymethylmalonate, diethyl ethoxymethylmalonate, dimethyl ethoxymethylmalonate, diethyl methoxymethylmalonate, diethyl ethoxymethylmalonate, diethyl methoxymethylmalonate, dimethyl ethoxymethylmalonate, and the like, 2-methoxymethyl-1, 4-succinic acid dimethyl ester, 2-ethoxymethyl-1, 4-succinic acid diethyl ester, 2-ethoxymethyl-1, 4-succinic acid dimethyl ester, 2-methoxymethyl-1, 4-succinic acid diethyl ester, methoxyethyl malonic acid dimethyl ester, ethoxyethyl malonic acid diethyl ester, ethoxyethyl malonic acid dimethyl ester, methoxyethyl malonic acid diethyl ester, 2-methoxyethyl-1, 4-succinic acid dimethyl ester, 2-ethoxyethyl-1, 4-succinic acid diethyl ester, 2-ethoxyethyl-1, 4-succinic acid dimethyl ester, 2-methoxyethyl-1, 4-succinic acid diethyl ester, 2-methoxymethyl-1, 5-dimethyl glutarate, diethyl 2-ethoxymethyl-1, 5-glutarate, dimethyl 2-ethoxymethyl-1, 5-glutarate, diethyl 2-methoxymethyl-1, 5-glutarate, dimethyl 3-methoxymethyl-1, 5-glutarate, diethyl 3-ethoxymethyl-1, 5-glutarate, dimethyl 3-ethoxymethyl-1, 5-glutarate, diethyl 3-methoxymethyl-1, 5-glutarate, dimethyl 2-methoxymethyl-1, 5-glutarate, diethyl 2-ethoxymethyl-1, 5-glutarate, dimethyl 2-ethoxymethyl-1, 5-glutarate, Diethyl 2-methoxymethyl-1, 5-glutarate, dimethyl 3-methoxymethyl-1, 5-glutarate, diethyl 3-ethoxymethyl-1, 5-glutarate, dimethyl 3-ethoxymethyl-1, 5-glutarate, diethyl 3-methoxymethyl-1, 5-glutarate, dicyclopentyl methoxymethylmalonate, dicyclopentyl ethoxymethylmalonate, dicyclohexyl methoxymethylmalonate, diphenylmethyl ethoxymethylmalonate, dimethyl phenoxymethylmalonate, diethyl phenoxymethylmalonate, dimethyl vinyloxymethylmalonate, diethyl vinyloxymethylmalonate, dimethyl allyloxymethylmalonate, dimethyl ethoxymethylmalonate, dimethyl (ethoxymethylmalonate), dimethyl (allyloxymethyl) malonate, dimethyl, Diethyl allyloxymethylmalonate, dimethyl 3-methoxymethylphthalate, diethyl 3-ethoxymethylphthalate, dimethyl 3-ethoxymethylphthalate, diethyl 3-methoxymethylphthalate, dimethyl 4-methoxymethylphthalate, diethyl 4-ethoxymethylphthalate, dimethyl 4-ethoxymethylphthalate, diethyl 4-methoxymethylphthalate, dimethyl 2-methoxymethylphthalate, diethyl 2-ethoxymethylterephthalate, dimethyl 2-ethoxymethylterephthalate, diethyl 2-methoxymethylphthalate, dimethyl 3-methoxymethylphthalate, diethyl 3-ethoxymethylterephthalate, diethyl 2-ethoxymethylterephthalate, diethyl 3-ethoxymethylterephthalate, diethyl ester, and mixtures thereof, Dimethyl 3-ethoxymethyl terephthalate, diethyl 3-methoxymethyl terephthalate, dimethyl 4-methoxyphenylmethylenemalonate, diethyl 4-methoxyphenylmethylenemalonate, dipropyl 4-methoxyphenylmethylenemalonate, dibutyl 4-methoxyphenylmethylenemalonate, dimethyl 4-ethoxyphenylenemalonate, diethyl 4-ethoxyphenylenemalonate, dipropyl 4-ethoxyphenylenemalonate, dibutyl 4-ethoxybenzylidenemalonate, dimethyl 4-methoxyphenylethylenemalonate, diethyl 4-methoxyphenylethylenemalonate, dipropyl 4-methoxyphenylethylenemalonate, dibutyl 4-methoxyphenylethylenemalonate, dimethyl 3-methoxyphenylmethylenemalonate, dimethyl 4-methoxyphenylmethylenemalonate, dimethyl-ethoxyphenyl malonate, dimethyl-4-ethoxyphenyl, Diethyl 4-methoxybenzylmalonate, dipropyl 4-methoxybenzylmalonate, dibutyl 4-methoxybenzylmalonate, dimethyl 4-ethoxybenzylmalonate, diethyl 4-ethoxybenzylmalonate, dipropyl 4-ethoxybenzylmalonate, dibutyl 4-ethoxybenzylmalonate, dimethyl 4-methoxyethylmalonate, diethyl 4-methoxyphenylethylmalonate, dipropyl 4-methoxyphenylethylmalonate, and dibutyl 4-methoxyphenylethylmalonate.
The catalyst system of the invention, wherein the diol ester type compound has a structure as described in formula (III),
wherein, R'1And R'2Identical or different, each independently is halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C7-C20Aralkyl of (2), C7-C20Alkylaryl of, C2-C20Linear or branched alkenyl or C10-C20A condensed ring aryl group of (4);
preferably, R'1And R'2Each independently is C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C7-C10Phenylalkyl of, C7-C10Alkylphenyl radical of (1), C2-C10Linear or branched alkenyl or C10-C15A condensed ring aryl group of (2).
Wherein, the C1-C10Of (2) straight-chain or branchedAlkyl is further preferably C1-C7The straight-chain or branched alkyl group of (1) may specifically be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group or a heptyl group.
Among them, preferred is C3-C10Cycloalkyl of (C) is preferably C5-C6A cycloalkyl group of (a).
Among them, preferred is C7-C10Phenylalkyl or C7-C10The alkylphenyl group (b) is preferably a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolyl group, an ethylphenyl group, a propylphenyl group or a butylbenzene group.
Among them, preferred is C2-C10The linear or branched alkenyl group of (3) is more preferably C2-C6Linear or branched alkenyl groups of (1).
R”’3、R”’4、R”’5、R”’6And R1-R2nThe same or different, each independently is hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Linear or branched alkenyl or C10-C20A condensed ring aryl group of (4); or, R'3、R”’4、R”’5、R”’6And R1-R2nTwo or more of them are bonded to each other to form a ring; wherein, R'3、R”’4、R”’5、R”’6And R1-R2nOptionally including one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus and halogen atoms as substituents of carbon or hydrogen atoms or both; n is an integer of 0 to 10. Preferably, R'3、R”’4、R”’5、R”’6And R1-R2nOne or more of the groups are optionally linked to form a ring.
Wherein, preferably, said C1-C20The linear or branched alkyl group of (1) is preferably C1-C10The straight or branched alkyl group of (1), further preferably C1-C7The straight-chain or branched alkyl group of (1) may specifically be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group or a heptyl group.
Wherein, preferably, said C3-C20Cycloalkyl of (C) is preferably C3-C10Is more preferably C5-C6A cycloalkyl group of (a).
Among them, preferred is C7-C20Alkylaryl or C of7-C20The aralkyl group of (A) is preferably C7-C10Phenylalkyl or C7-C10The alkylphenyl group of (2) is more preferably a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolyl group, an ethylphenyl group, a propylphenyl group or a butylbenzene group.
Among them, preferred is C2-C10The linear or branched alkenyl group of (3) is more preferably C2-C6Linear or branched alkenyl groups of (1).
More preferably, according to the catalyst system of the present invention, the glycol ester type compound has a structure represented by formula (IV) or formula (V),
wherein, formula (IV) is a structural formula in the case that n is 1 in formula (III), it can be understood that the definitions of other groups are as described in formula (III).
In the formula (V), R' are the same or different hydrogen, halogen atom, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl of (2), othersThe definition of each group is as described in formula (III).
Wherein, preferably, said C1-C20The linear or branched alkyl group of (1) is preferably C1-C10The straight or branched alkyl group of (1), further preferably C1-C7The straight-chain or branched alkyl group of (1) may specifically be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group or a heptyl group.
Wherein, preferably, said C3-C20Cycloalkyl of (C) is preferably C3-C10Is more preferably C5-C6A cycloalkyl group of (a).
Among them, preferred is C7-C20Alkylaryl or C of7-C20The aralkyl group of (A) is preferably C7-C10Phenylalkyl or C7-C10The alkylphenyl group of (2) is more preferably a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolyl group, an ethylphenyl group, a propylphenyl group or a butylbenzene group.
More preferably, the glycol ester compound is one or more of 2-isopropyl-2-isoamyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and 9, 9-bis (phenylmethylcarboxymethyl) fluorene.
According to the catalyst system of the present invention, preferably, the carboxylate compound is a mono-or poly-aliphatic carboxylate and/or an aromatic carboxylate, preferably one or more selected from the group consisting of alkyl diesters, alkenyl diesters, benzoates, phthalates and succinates.
Preferably, the phthalate type compound is a compound represented by formula (III),
in the formula (3), R "1And R "2Identical or different, each independently is C1-C10Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-Cl0Aryl of (C)7-Cl0Alkylaryl or C of7-C20An aromatic hydrocarbon group of (1); r'3、R”4、R”5And R "6Are the same or different and are each independently hydrogen or Cl-Cl0Straight or branched alkyl, C3-Cl0Cycloalkyl of, C6-Cl0Aryl of (C)7-Cl0Alkylaryl or arylalkyl of, and R "3、R”4、R”5And R "6Two or more of them are bonded to each other to form a ring.
Preferably, the succinate compound is a compound shown as a formula (VI),
in the formula (VI), R "ⅠAnd R "ⅡIdentical or different, each independently is C1-C20Straight or branched alkyl or C3-C20Cycloalkyl groups of (a);
R”Ⅲ、R”Ⅳ、R”Ⅴand R "ⅥThe same or different, each independently is hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20Or one of the alkylaryl groups of (A), or, R "Ⅲ、R”Ⅳ、R”ⅤAnd R "ⅥTwo or more of them are bonded to each other to form a ring.
More preferably, the carboxylic acid ester is selected from the group consisting of ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl phthalate, di-octyl phthalate, di-n-butyl, One or more of diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl hemitrimellitate, tributyl hemitrimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate.
According to the catalyst system, the titanium-containing solid catalyst component, the alkyl aluminum compound and the external electron donor compound can be independently stored, or the alkyl aluminum compound and the external electron donor compound can be mixed according to a predetermined proportion and then stored.
According to the present invention, the amount of the aluminum alkyl compound, the titanium-containing solid catalyst component and the external electron donor may be those conventionally used in the art, and generally, in the catalyst for olefin polymerization, the molar ratio of aluminum in the aluminum alkyl compound to titanium in the catalyst component may be 1 to 1000: 1, preferably 50 to 1000: 1, more preferably 200-: 1; the molar ratio of the external electron donor to the amount of aluminum alkyl compound may be 0.001 to 1: 1, preferably 0.01 to 0.8: 1, most preferably 0.02-0.4: 1.
According to the invention, the amount of the ether-based ester compound used in the catalyst can be selected within a wide range, and preferably, the molar ratio of the ether-based ester compound to the aluminum alkyl compound calculated on the basis of aluminum element is 0.001-1: 1, preferably 0.01 to 0.8: 1, more preferably 0.02 to 0.4: 1.
according to the catalyst system of the invention, the titanium-containing solid catalyst component isLoaded with a compound of the formula Ti (OR)w)4-kXkAnd a magnesium halide alcoholate of at least two internal electron donors of the above diol ester compound and the carboxylate compound;
wherein R iswPreferably selected from C1-C20More preferably C1-C14Further preferably C1-C8Alkyl groups of (a), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like; x is preferably selected from chlorine, bromine and iodine, k is an integer from 0 to 4; preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride. Preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride.
Among them, preferably, the magnesium halide alcoholate is MgCl2·nRqOH magnesium chloride alcoholate; among them, preferred is RqThe number of carbon atoms being C1-C18And n is 0.1 to 6.
According to the present invention, the amount of the internal electron donor can be the amount of the internal electron donor conventionally used in the art, and preferably, the amount of the internal electron donor is 0.01 to 5mol, preferably 0.05 to 1mol, based on 1mol of magnesium in the titanium-containing solid catalyst component.
Preferably, the molar ratio of the diol ester type compound to the carboxylate ester compound is 0.01 to 0.5: 1. within such preferred ranges, the performance of the catalyst and the performance of the resulting polymer can be further improved.
The diol ester compound and the carboxylic ester compound are added in no sequence, and can be used in different steps and under different conditions or added simultaneously. In the production process of the titanium-containing solid catalyst component of the present invention, the diol ester compound is used in an amount of preferably 0.001 to 0.5 mol, more preferably 0.001 to 0.1 mol, per mol of magnesium; the amount of the carboxylate compound to be used is preferably 0.01 to 5mol, more preferably 0.05 to 1 mol.
According to the present invention, the titanium-containing solid catalyst component can be prepared according to conventional methods, for example, the method disclosed in chinese patent CN93102795.0 can be referred to. The magnesium halide alcoholate can be prepared according to the methods disclosed in Chinese patents CN1091748, CN330086A and CN101050245, and the contents disclosed in the above patents are incorporated by reference in the present invention and will not be described in detail.
According to a specific embodiment of the present invention, the specific preparation method of the magnesium halide alcoholate carrier comprises: mixing anhydrous magnesium halide and low-carbon alcohol, heating to react to generate magnesium halide alcohol compound melt, wherein the reaction temperature is 90-140 ℃, putting the magnesium halide alcohol compound melt into a cooled inert medium after high shearing action in a dispersion medium to form spherical magnesium halide alcohol compound particles, and washing and drying to obtain the spherical carrier. High shear may be achieved by conventional means such as high speed stirring (eg CN1330086), spraying (eg US6020279) and high gravity rotating beds (eg CN1580136A) and emulsifying machine (CN 1463990A). The dispersant system adopts hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.
The method for synthesizing the catalyst component of the component (1) of the present invention may comprise: suspending the magnesium halide alcoholate obtained above in a precooled titanium compound or a mixture of the titanium compound and an inert solvent such as hexane, heptane, octane, decane, toluene and the like at a temperature of-30 ℃ to 0 ℃, preferably-20 ℃ to-10 ℃; then heating the mixture to 80-130 ℃, and adding at least two internal electron donors in the process of heating. And then treated one or more times with a titanium compound. Finally, washing with an inert solvent for a plurality of times to obtain the solid catalyst component.
According to the invention, the alkylaluminum compound of component (2) of the invention, of which the general formula may be AlR'3R "" is the same or different C1-C8One or two of the alkyl groups of (1) may be substituted with chlorine, and one or more alkyl aluminum groups may be used in combination, preferably triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, alkyl aluminum chloride, Al (n-C)6H13)3、Al(n-C8H17)3、AlEt2Cl, etc., generally in an Al/Ti molar ratio of 1 to 1000: 1 the above-mentioned alkyl aluminum compound is used.
According to the present invention, in the preparation of the catalyst for olefin polymerization, the aluminum alkyl compound and the external electron donor compound may be mixed with the titanium-containing solid catalyst component for olefin polymerization and then reacted, or the aluminum alkyl and the external electron donor compound may be mixed with the titanium-containing solid catalyst component for olefin polymerization and then reacted, which are conventional technical means in the field, and the skilled person can select them according to the actual situation.
In a second aspect, the present invention also provides the use of a catalyst as described above in the polymerisation of olefins.
The above catalyst of the present invention is particularly suitable for CH2CHRy (where Ry is hydrogen or C)1-C6Alkyl or aryl) and mixtures containing, if necessary, small amounts of diolefins.
According to the invention, the polymerization of the olefins can be carried out according to known methods, in liquid phase with the monomer or monomers dissolved in an inert solvent, or in gas phase, or by a combined polymerization process in gas-liquid phase. The polymerization temperature is generally from 0 to 150 ℃ and preferably from 50 to 100 ℃. The polymerization pressure is normal pressure or higher.
According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the alkyl aluminum compound, and the external electron donor according to the present invention may be added to the polymerization reactor separately, or may be mixed and added to the polymerization reactor, or the olefin may be prepolymerized and added to the polymerization reactor by a prepolymerization method known in the art.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
1. polymer melt index (used to characterize the hydrogen response of the catalyst): the greater the polymer melt index, the better the hydrogen response of the catalyst, as determined according to astm d 1238-99.
2. Polymer isotacticity: the determination is carried out by adopting an n-heptane extraction method (boiling extraction for 6 hours) that 2g of dried polymer sample is taken and put in an extractor to be extracted for 6 hours by boiling heptane, then the residue is dried to constant weight, and the ratio of the obtained polymer weight (g) to 2 is the isotacticity. Indicating the catalyst's ability to orient.
3. Polymerization activity of catalyst: the amount of polymer obtained in kg over a period of time (here 1 hour) was divided by the amount of catalyst added in g.
4. And (3) testing molecular weight and distribution: the molecular weight and molecular weight distribution MWD (MWD. Mw/Mn) of the polymer were measured by PL-GPC220 using trichlorobenzene as a solvent at 150 ℃ (standard: PS, flow rate: 1.0ml/min, column: 3xPlgel 10um M1 xED-B300 x7.5nm).
Preparation example
Adding 100ml titanium tetrachloride into a 300ml glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding a spherical magnesium chloride alcohol compound (the preparation method is shown in Chinese patent CN1330086A), slowly heating to 110 ℃, adding 2.5mol of diol ester compound and 3.9mmol of carboxylic ester compound in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for two times, washing with hexane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component A.
Examples
The polymerization of propylene was carried out according to the ingredients in examples 1 to 14 and comparative examples 1 to 4 in Table 1 with reference to the following conditions.
In a 5 l autoclave, purged with a stream of nitrogen at 70 ℃ for 1 hour, then the polymerization vessel was replaced 3 times with gaseous propylene, and 5ml of an alkylaluminum compound (triethylaluminum concentration 0.5mmol/ml), 1ml of a hexane solution of an external electron donor (external electron donor concentration 0.1mmol/ml), 10ml of anhydrous hexane and 8 to 12mg of the titanium-containing solid catalyst component A were introduced under nitrogen protection. Closing the autoclave, introducing a certain volume of hydrogen (measured at 25 ℃ under normal pressure) (L) and 1.0-1.2Kg of liquid propylene; the internal kettle temperature was rapidly increased to 70 ℃ with stirring. After polymerization at 70 ℃ for 1 hour, the stirring was stopped, the unpolymerized propylene monomer was removed, and the polymer was collected and vacuum-dried at 70 ℃ for 1 hour. The polymerization activity, polymer melt index and polymer isotacticity of the catalyst were measured, and the results are shown in Table 1.
In addition, the molecular weight distribution width of the polymers obtained in examples 1 and 6 and comparative examples 1 and 3 was determined by GPC (gel permeation chromatography) molecular weight measurement. Where Mn represents a number average molecular weight, Mw represents a weight average molecular weight, and PD ═ Mw/Mn, and the larger PD represents the broader molecular weight distribution. The results are shown in Table 2.
As can be seen from the following Table 1, the use of the ether-based ester compound of the present invention as an external electron for the polymerization of olefins can improve the polymerization activity of the catalyst, improve the hydrogen response of the catalyst, and also maintain the isotacticity of the catalyst, that is, the orientation ability of the catalyst at an effective level.
As can be seen from Table 2 below, the molecular weight distribution of the polymer obtained by using the ether-based ester compound of the present invention as an external electron for the polymerization of olefin is broadened.
TABLE 1
Note: EMME: ethoxymethylenemalonic acid diethyl ester
DMMMM: methoxymethylenemalonic acid dimethyl ester
DMPMBM: 4-Methoxyphenylmethylenemalonic acid dimethyl ester
C or C-donor: methylcyclohexyldimethoxysilane
D or D-donor: dicyclopentyl dimethoxy silane
a: 2, 4-Pentanediol dibenzoate
b: dibutyl phthalate
c 4-Ethyl-3, 5-heptanediol dibenzoate
di-isobutyl phthalate
TABLE 2
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (14)

1. An olefin polymerization catalyst system, the catalyst system comprising: a titanium-containing solid catalyst component, an alkyl aluminum compound and an external electron donor compound, which is characterized in that,
the titanium-containing solid catalyst component contains a glycol ester compound and a carboxylic ester compound as internal electron donor compounds;
wherein the external electron donor compound is an ether ester compound with a structure shown in a formula (I);
R5-O-R4(R3(COOR1)COOR2) (I)
wherein,
R1、R2each independently is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl of (2), C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl of R1、R2Optionally the same or different;
R3a first organic radical which is trivalent or tetravalent and which is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl radical, C1-C20Linear or branched alkyl of (a);
R4is a reaction with R3By single or double bond connection, R4A second organic group which is divalent or trivalent, the second organic group being C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl group;
R5is C3-C20Cycloalkyl of, C6-C24Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, C10-C22Condensed ring aryl of (C)2-C20Linear or branched alkenyl or C1-C20Linear or branched alkyl groups of (1).
2. The catalyst system according to claim 1, wherein, in formula (I), R1、R2Each independently is C3-C6Cycloalkyl of, C6-C12Aryl of (C)7-C10Aralkyl or C7-C10Alkylaryl of, C2-C6Linear or branched alkylene of (2), C1-C6Linear or branched alkyl of (a);
the first organic group is C3-C6Cycloalkyl of, C6-C12Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl radical, C1-C6Linear or branched alkyl of (a);
the second organic group is C3-C6Cycloalkyl radical, C6-C12Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl of (2), C1-C10Linear or branched alkyl of (a);
R5is C6-C12Aryl of (C)7-C10Aralkyl or C7-C10Alkylaryl of, C2-C6Linear or branched alkenyl or C1-C6Linear or branched alkyl groups of (1).
3. The catalyst system of claim 2, wherein the ether-based ester compound is selected from one or more of the following compounds:
dimethyl methoxymethylenemalonate, diethyl ethoxymethylenemalonate, dimethyl ethoxymethylenemalonate, diethyl methoxymethylenemalonate, dimethyl 2-methoxymethylene-1, 4-succinate, diethyl 2-ethoxymethylene-1, 4-succinate, dimethyl 2-ethoxymethylene-1, 4-succinate, diethyl 2-methoxymethylene-1, 4-succinate, dimethyl methoxyethylenemalonate, diethyl ethoxyethylenemalonate, dimethyl ethoxyethylenemalonate, diethyl methoxyethylenemalonate, dimethyl 2-methoxyethylenel-1, 4-succinate, diethyl 2-ethoxyethylenel-1, 4-succinate, diethyl ethoxymethylenemalonate, diethyl ethoxymethylethoxymethylethoxymethylbutanemalonate, diethyl ethoxymethylbutanemalonate, diethyl malonate, diethyl ethoxymethylbutanedioate, diethyl-, 2-ethoxyethylene-1, 4-butanedioic acid dimethyl ester, 2-methoxyethylene-1, 4-butanedioic acid diethyl ester, 2-methoxymethylene-1, 5-pentanedioic acid dimethyl ester, 2-ethoxymethylene-1, 5-pentanedioic acid diethyl ester, 2-ethoxymethylene-1, 5-pentanedioic acid dimethyl ester, 2-methoxymethylene-1, 5-pentanedioic acid diethyl ester, 3-methoxymethylene-1, 5-pentanedioic acid dimethyl ester, 3-ethoxymethylene-1, 5-pentanedioic acid diethyl ester, 3-ethoxymethylene-1, 5-pentanedioic acid dimethyl ester, 3-methoxymethylene-1, 5-pentanedioic acid diethyl ester, diethyl ester, Dicyclopentyl methoxymethylenemalonate, dicyclopentyl ethoxymethylenemalonate, dicyclohexyldicyclohexylethoxymethylenemalonate, dicyclohexyldicyclohexylmethoxymethylenemalonate, diphenylmethyl methoxymethylenemalonate, diphenylmethyl ethoxymethylenemalonate, dimethyl phenoxymethylenemalonate, diethyl phenoxymethylenemalonate, dimethyl vinyloxymethylenemalonate, diethyl vinyloxymethylmethylenemalonate, dimethyl allyloxymethylenemalonate, diethyl allyloxymethylenemalonate, dimethyl 3-methoxymethylenephthalate, diethyl 3-ethoxymethylenephthalate, dimethyl 3-ethoxymethylenephthalate, diethyl 3-methoxymethylenephthalate, dimethyl 4-methoxymethylenephthalate, dimethyl ethoxymethylenephthalate, dimethyl ethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymethylethoxymalonate, diethyl 3-methoxymethylenephthalate, dimethyl ethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymethylethoxymalonate, dimethyl ethoxymethylethoxymalonate, dimethyl, Diethyl 4-ethoxymethylenephthalate, dimethyl 4-ethoxymethylenephthalate, diethyl 4-methoxymethylenephthalate, dimethyl 2-methoxymethyleneterephthalate, diethyl 2-ethoxymethyleneterephthalate, dimethyl 2-ethoxymethyleneterephthalate, diethyl 2-methoxymethyleneterephthalate, dimethyl 3-methoxymethyleneterephthalate, diethyl 3-ethoxymethyleneterephthalate, dimethyl 3-ethoxymethyleneterephthalate, diethyl 3-methoxymethyleneterephthalate, dimethyl methoxymethylmalonate, diethyl ethoxymethylmalonate, dimethyl ethoxymethylmalonate, diethyl methoxymethylmalonate, diethyl ethoxymethylmalonate, diethyl methoxymethylmalonate, dimethyl ethoxymethylmalonate, and the like, 2-methoxymethyl-1, 4-succinic acid dimethyl ester, 2-ethoxymethyl-1, 4-succinic acid diethyl ester, 2-ethoxymethyl-1, 4-succinic acid dimethyl ester, 2-methoxymethyl-1, 4-succinic acid diethyl ester, methoxyethyl malonic acid dimethyl ester, ethoxyethyl malonic acid diethyl ester, ethoxyethyl malonic acid dimethyl ester, methoxyethyl malonic acid diethyl ester, 2-methoxyethyl-1, 4-succinic acid dimethyl ester, 2-ethoxyethyl-1, 4-succinic acid diethyl ester, 2-ethoxyethyl-1, 4-succinic acid dimethyl ester, 2-methoxyethyl-1, 4-succinic acid diethyl ester, 2-methoxymethyl-1, 5-dimethyl glutarate, diethyl 2-ethoxymethyl-1, 5-glutarate, dimethyl 2-ethoxymethyl-1, 5-glutarate, diethyl 2-methoxymethyl-1, 5-glutarate, dimethyl 3-methoxymethyl-1, 5-glutarate, diethyl 3-ethoxymethyl-1, 5-glutarate, dimethyl 3-ethoxymethyl-1, 5-glutarate, diethyl 3-methoxymethyl-1, 5-glutarate, dimethyl 2-methoxymethyl-1, 5-glutarate, diethyl 2-ethoxymethyl-1, 5-glutarate, dimethyl 2-ethoxymethyl-1, 5-glutarate, Diethyl 2-methoxymethyl-1, 5-glutarate, dimethyl 3-methoxymethyl-1, 5-glutarate, diethyl 3-ethoxymethyl-1, 5-glutarate, dimethyl 3-ethoxymethyl-1, 5-glutarate, diethyl 3-methoxymethyl-1, 5-glutarate, dicyclopentyl methoxymethylmalonate, dicyclopentyl ethoxymethylmalonate, dicyclohexyl methoxymethylmalonate, diphenylmethyl ethoxymethylmalonate, dimethyl phenoxymethylmalonate, diethyl phenoxymethylmalonate, dimethyl vinyloxymethylmalonate, diethyl vinyloxymethylmalonate, dimethyl allyloxymethylmalonate, dimethyl ethoxymethylmalonate, dimethyl (ethoxymethylmalonate), dimethyl (allyloxymethyl) malonate, dimethyl, Diethyl allyloxymethylmalonate, dimethyl 3-methoxymethylphthalate, diethyl 3-ethoxymethylphthalate, dimethyl 3-ethoxymethylphthalate, diethyl 3-methoxymethylphthalate, dimethyl 4-methoxymethylphthalate, diethyl 4-ethoxymethylphthalate, dimethyl 4-ethoxymethylphthalate, diethyl 4-methoxymethylphthalate, dimethyl 2-methoxymethylphthalate, diethyl 2-ethoxymethylterephthalate, dimethyl 2-ethoxymethylterephthalate, diethyl 2-methoxymethylphthalate, dimethyl 3-methoxymethylphthalate, diethyl 3-ethoxymethylterephthalate, diethyl 2-ethoxymethylterephthalate, diethyl 3-ethoxymethylterephthalate, diethyl ester, and mixtures thereof, Dimethyl 3-ethoxymethyl terephthalate, diethyl 3-methoxymethyl terephthalate, dimethyl 4-methoxyphenylmethylenemalonate, diethyl 4-methoxyphenylmethylenemalonate, dipropyl 4-methoxyphenylmethylenemalonate, dibutyl 4-methoxyphenylmethylenemalonate, dimethyl 4-ethoxyphenylenemalonate, diethyl 4-ethoxyphenylenemalonate, dipropyl 4-ethoxyphenylenemalonate, dibutyl 4-ethoxybenzylidenemalonate, dimethyl 4-methoxyphenylethylenemalonate, diethyl 4-methoxyphenylethylenemalonate, dipropyl 4-methoxyphenylethylenemalonate, dibutyl 4-methoxyphenylethylenemalonate, dimethyl 3-methoxyphenylmethylenemalonate, dimethyl 4-methoxyphenylmethylenemalonate, dimethyl-ethoxyphenyl malonate, dimethyl-4-ethoxyphenyl, Diethyl 4-methoxybenzylmalonate, dipropyl 4-methoxybenzylmalonate, dibutyl 4-methoxybenzylmalonate, dimethyl 4-ethoxybenzylmalonate, diethyl 4-ethoxybenzylmalonate, dipropyl 4-ethoxybenzylmalonate, dibutyl 4-ethoxybenzylmalonate, dimethyl 4-methoxyethylmalonate, diethyl 4-methoxyphenylethylmalonate, dipropyl 4-methoxyphenylethylmalonate, and dibutyl 4-methoxyphenylethylmalonate.
4. The catalyst system of claim 1, wherein the glycol ester compound has a structure according to formula (III),
wherein, R'1And R'2Identical or different, each independently is halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C7-C20Aralkyl of (2), C7-C20Alkylaryl of, C2-C20Linear or branched alkenyl or C10-C20A condensed ring aryl group of (4);
R”’3、R”’4、R”’5、R”’6and R1-R2nThe same or different, each independently is hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C7-C20Alkylaryl of, C7-C20Aralkyl of (2), C2-C20Linear or branched alkenyl or C10-C20A condensed ring aryl group of (4); or, R'3、R”’4、R”’5、R”’6And R1-R2nTwo or more groups of (a) are bonded to each other to form a ring; wherein, R'3、R”’4、R”’5、R”’6And R1-R2nOptionally including one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus and halogen atoms as substituents of carbon or hydrogen atoms or both;
n is an integer of 0 to 10.
5. The catalyst system of claim 4, wherein the glycol ester compound has a structure of formula (IV) or formula (V),
wherein, in the formula (IV), R' is selected from hydrogen, halogen atom and C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20An aralkyl group of (2).
6. The catalyst system according to claim 5, wherein the glycol ester compound is selected from one or more of 2-isopropyl-2-isoamyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and 9, 9-bis (phenylmethylcarboxymethyl) fluorene.
7. The catalyst system according to claim 1 or 4, wherein the carboxylate compound is a mono-or poly-aliphatic carboxylate and/or an aromatic carboxylate.
8. The catalyst system of claim 7, wherein the carboxylate compound is selected from the group consisting of ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl phthalate, dibutyl sebacate, and mixtures thereof, One or more of diethyl maleate, di-n-butyl maleate, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate.
9. The catalyst system according to claim 1, wherein the molar ratio of the aluminium in the aluminium alkyl compound to the titanium in the catalyst component is from 1 to 1000: 1.
10. the catalyst system according to claim 1 or 9, wherein the molar ratio of the ether-based ester compound to the aluminum alkyl compound, calculated as aluminum element, is from 0.001 to 1: 1.
11. the catalyst system according to any one of claims 1 to 10, wherein the titanium-containing solid catalyst component is supported with a compound of the general formula Ti (OR)w)4-kXkThe titanium compound, the diol ester type compound and the carboxylic ester compound are magnesium halide alcoholates of at least two internal electron donors;
wherein R iswIs selected from C1-C20X is selected from chlorine, bromine and iodine, and k is an integer of 0 to 4;
preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride.
12. The catalyst system according to claim 11, wherein the internal electron donor is 0.01-5mol, preferably 0.05-1mol, based on 1mol of magnesium in the titanium-containing solid catalyst component.
13. The catalyst system according to claim 1 or 12, wherein the molar ratio of the glycol ester compound and the carboxylic ester compound is 0.01-0.5: 1.
14. use of the catalyst system according to any one of claims 1 to 13 in the polymerization of olefins.
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