CN104592026B - A kind of compound, catalytic component and its catalyst - Google Patents

A kind of compound, catalytic component and its catalyst Download PDF

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Publication number
CN104592026B
CN104592026B CN201310535019.1A CN201310535019A CN104592026B CN 104592026 B CN104592026 B CN 104592026B CN 201310535019 A CN201310535019 A CN 201310535019A CN 104592026 B CN104592026 B CN 104592026B
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bis
compound
tartrate
tartaric acid
magnesium
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CN104592026A (en
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张锐
宋维玮
周奇龙
谭忠
徐秀东
严立安
李凤奎
于金华
尹珊珊
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • C07C69/70—Tartaric acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention discloses a kind of compound of new structure, its structure shown in formula I,Wherein R1、R2、R3And R4It may be the same or different, be each independently selected from substituted or unsubstituted C1‑C20Alkyl, be preferably selected from substituted or unsubstituted C1‑C10Aliphatic group, C3‑C10Cycloalkyl, C6‑C20Aryl and C7‑C20Alkaryl；R3And R4It is optionally cyclic or not cyclic.The present invention is used as internal electron donor compound by using compound shown in the Formulas I of new structure, it can obtain the catalyst of high comprehensive performance, when the catalyst is used for olefinic polymerization, with preferable polymerization activity, the bulk density of obtained polymer is high, isotacticity is high and high melt index, and with good hydrogen response, be conducive to the exploitation of different trade mark polymer.

Description

A kind of compound, catalytic component and its catalyst
Technical field
It is internal electron donor compound containing the compound the present invention relates to a kind of compound of new structure（Solid） Catalyst component and preparation method thereof.The invention further relates to containing above-mentioned（Solid）The catalyst of catalyst component and the catalyst exist Application in olefinic polymerization.
Background technology
The catalyst that solid titanium catalyst component using magnesium, titanium, halogen and internal electron donor as basis is constituted, i.e., Ziegler-Natta catalyst known in the field, available for CH2=CHR olefinic polyreactions.Particularly when described When Ziegler-Natta catalyst is used to have 3 carbon or more the alpha-olefine polymerizing of carbon atom, can obtain higher yields and The polymer of higher stereospecificity.It is well known that interior Donor compound is must not in Ziegler-Natta catalyst component One of composition that can be less.From early stage disclosed monocarboxylic acid esters compound, such as ethyl benzoate, to widely used at present Binary aromatic carboxylic acid's ester type compound, such as n-butyl phthalate or o- benzoic acid diisobutyl ester, then disclosed to recent The ethers of 1,3- bis-（CN1020448C）, succinate compound（CN1313869）With 1,3- diol-lipids（CN1213080C）Chemical combination The development of thing, exactly internal electron donor compound result in polyolefin catalyst and be continuously updated the replacement.
The need for adapting to the olefinic polymerization continued to develop, it is desirable to develop new internal electron donor system, obtain To the catalyst of high comprehensive performance.
The content of the invention
In view of the shortcomings of the prior art, the present inventor be passed through in-depth study there is provided one kind contain specific knot The catalyst component of the electron donor compound of structure and the catalyst comprising the catalytic component, the catalyst are used for olefinic polymerization When there is high activity, good stereoselectivity and hydrogen regulation performance.
According to an aspect of the invention, there is provided a kind of compound of new structure, its structure shown in formula I,
Wherein R1-R4It may be the same or different, be each independently selected from substituted or unsubstituted C1-C20Alkyl, be preferably selected from Substituted or unsubstituted C1-C10Aliphatic group, C3-C10Cycloalkyl, C6-C20Aryl and C7-C20Alkaryl；R3And R4 It is optionally cyclic or not cyclic.
According to the present invention, the substituted alkyl refers to that alkyl includes aliphatic group, cycloalkyl, aryl etc. as described Deng substituted group, thereon on hydrogen atom optionally by halogen（It is miscellaneous）On atom, alkyl or alkoxy substitution, the main chain Carbon atom is optionally exchanged for heteroatoms.In the present invention, the aliphatic group can be straight or branched structure, include saturation Alkyl and undersaturated group such as alkenyl etc..The hetero atom is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom etc..
According to the specific embodiment of the present invention, the R1And R2Group is selected from substituted or unsubstituted C1-C10Fat Alkyl, C3-C10Cycloalkyl, C6-C20Aryl.The R1And R2Group is preferably substituted or unsubstituted C1-C6Hydrocarbon Base, is preferably selected from methyl, ethyl and isopropyl.
According to another specific embodiment of the present invention, the R3And R4Group is selected from substituted or unsubstituted C1-C10Fat Fat alkyl, C3-C10Cycloalkyl, C6-C20Aryl, be preferably selected from substituted or unsubstituted C1-C4Alkyl and C6-C12's Aryl, such as methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, pi-allyl, phenyl, benzene Methyl, menaphthyl etc..
According to compound of the present invention, the compound shown in the suitable Formulas I includes but is not limited to：L-(+)- (2,3- diacetyls) dimethyl tartrate, L- (+)-(propionos of 2,3- bis-) dimethyl tartrate, L- (+)-(butyryl of 2,3- bis- Base) dimethyl tartrate, L- (+)-(isobutyryls of 2,3- bis-) dimethyl tartrate, L- (+)-(valeryls of 2,3- bis-) tartaric acid Dimethyl ester, L- (+)-(2,3- bis- (1- methyl) bytyry) dimethyl tartrate, L- (+)-(2,3- diisoamyls acyl group) tartaric acid Dimethyl ester, L- (+)-(2,3- bis- (2,2- pivaloyl groups) dimethyl tartrate, L- (+)-(caproyls of 2,3- bis-) tartaric acid diformazan Ester, L- (+)-(2,3- bis- (1- methyl) valeryl) dimethyl tartrate, L- (+)-(2,3- bis- (2- methyl) valeryl) winestone Dimethyl phthalate, L- (+)-(isocaproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- bis- (1,1- dimethyl) bytyry) Dimethyl tartrate, L- (+)-(the special caproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- bis- (1,2- dimethyl) butyryl Base) dimethyl tartrate, L- (+)-(2,3- diene propiono) dimethyl tartrate, L- (+)-(2,3- dibenzoyls) winestone Dimethyl phthalate, L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, L- (+)-(2,3- bis- (2- naphthoyls)) wine Stone dimethyl phthalate, L- (+)-(p-toluenesulfonyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- diacetyls) tartaric acid Dimethyl ester, D- (+)-(propionos of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- dibutyryls) dimethyl tartrate, D- (+)-(isobutyryls of 2,3- bis-) dimethyl tartrate, D- (+)-(valeryls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- Two (1- methyl) bytyries) dimethyl tartrate, D- (+)-(2,3- diisoamyls acyl group) dimethyl tartrate, D- (+)-(2,3- Two (2,2- pivaloyl groups) dimethyl tartrates, D- (+)-(caproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- bis- (1- methyl) valeryl) dimethyl tartrate, D- (+)-(2,3- bis- (2- methyl) valeryl) dimethyl tartrate, D- (+)- (isocaproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- bis- (1,1- dimethyl) bytyry) dimethyl tartrate, D- (+)-(the special caproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) tartaric acid diformazan Ester, D- (+)-(2,3- diene propiono) dimethyl tartrate, D- (+)-(2,3- dibenzoyls) dimethyl tartrate, D- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, D- (+)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, D- (+)-(p-toluenesulfonyls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- diacetyls) ethyl tartrate, L- (+)-(propionos of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- dibutyryls) ethyl tartrate, L- (+)-(2,3- bis- Isobutyryl) ethyl tartrate, L- (+)-(valeryls of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- bis- (1- methyl) Bytyry) ethyl tartrate, L- (+)-(2,3- diisoamyls acyl group) ethyl tartrate, L- (+)-((2,2- spy penta by 2,3- bis- Acyl group) ethyl tartrate, L- (+)-(caproyls of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- bis- (1- methyl) valeryl Base) ethyl tartrate, L- (+)-(2,3- bis- (2- methyl) valeryl) ethyl tartrate, L- (+)-(the dissident's acyls of 2,3- bis- Base) ethyl tartrate, L- (+)-(2,3- bis- (1,1- dimethyl) bytyry) ethyl tartrate, L- (+)-(2,3- bis- is special Caproyl) ethyl tartrate, L- (+)-(2,3- bis- (1,2- dimethyl) bytyry) ethyl tartrate, L- (+)-(2,3- Diene propiono) ethyl tartrate, L- (+)-(2,3- dibenzoyls) ethyl tartrate, L- (+)-((the 1- naphthalenes of 2,3- bis- Formoxyl)) ethyl tartrate, L- (+)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, L- (+)-(2,3- bis- is to first Benzenesulfonyl) ethyl tartrate, D- (+)-(2,3- diacetyls) ethyl tartrate, D- (+)-(propionos of 2,3- bis-) wine Stone diethyl phthalate, D- (+)-(2,3- dibutyryls) ethyl tartrate, D- (+)-(isobutyryls of 2,3- bis-) tartaric acid diethyl Ester, D- (+)-(valeryls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- bis- (1- methyl) bytyry) ethyl tartrate, D- (+)-(2,3- diisoamyls acyl group) ethyl tartrate, D- (+)-(2,3- bis- (2,2- pivaloyl groups) ethyl tartrate, D- (+)-(caproyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- bis- (1- methyl) valeryl) ethyl tartrate, D- (+)-(2,3- bis- (2- methyl) valeryl) ethyl tartrate, D- (+)-(isocaproyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- bis- (1,1- dimethyl) bytyry) ethyl tartrate, D- (+)-(the special caproyls of 2,3- bis-) tartaric acid diethyl Ester, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) ethyl tartrate, D- (+)-(2,3- diene propiono) tartaric acid Diethylester, D- (+)-(2,3- dibenzoyls) ethyl tartrate, D- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid two Ethyl ester, D- (+)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, D- (+)-(p-toluenesulfonyls of 2,3- bis-) tartaric acid Diethylester, L- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, L- (+)-(propionos of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, L- (+)-(isobutyryls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1- methyl) bytyry) tartaric acid diisopropyl ester, L- (+)-(2,3- diisoamyls acyl group) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl Ester, L- (+)-(caproyls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1- methyl) valeryl) tartaric acid two are different Propyl ester, L- (+)-(2,3- bis- (2- methyl) valeryl) tartaric acid diisopropyl ester, L- (+)-(isocaproyls of 2,3- bis-) tartaric acid Diisopropyl ester, L- (+)-(2,3- bis- (1,1- dimethyl) bytyry) tartaric acid diisopropyl ester, L- (+)-(special hexanoyls of 2,3- bis- Base) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1,2- dimethyl) bytyry) tartaric acid diisopropyl ester, L- (+)-(2,3- Diene propiono) tartaric acid diisopropyl ester, L- (+)-(2,3- dibenzoyls) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester, L- (+)- (p-toluenesulfonyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, D- (+)- (propionos of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- Isobutyryl) tartaric acid diisopropyl ester, D- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-((the 1- first of 2,3- bis- Base) bytyry) tartaric acid diisopropyl ester, D- (+)-(2,3- diisoamyls acyl group) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl ester, D- (+)-(caproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1- methyl) valeryl) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (2- methyl) valeryl) tartaric acid diisopropyl ester, D- (+)-(isocaproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1,1- dimethyl) bytyry) tartaric acid two are different Propyl ester, D- (+)-(the special caproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) wine Stone acid diisopropyl ester, D- (+)-(2,3- diene propiono) tartaric acid diisopropyl ester, D- (+)-(2,3- dibenzoyls) winestone Sour diisopropyl ester, D- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid diisopropyl ester, D- (+)-((the 2- naphthalene formyls of 2,3- bis- Base)) tartaric acid diisopropyl ester and D- (+)-(2,3- bis- p-toluenesulfonyl) tartaric acid diisopropyl ester, be preferably selected from L- (+)- (2,3- diacetyls) dimethyl tartrate, L- (+)-(propionos of 2,3- bis-) dimethyl tartrate, L- (+)-(butyryl of 2,3- bis- Base) dimethyl tartrate, L- (+)-(isobutyryls of 2,3- bis-) dimethyl tartrate, L- (+)-(valeryls of 2,3- bis-) tartaric acid Dimethyl ester, L- (+)-(2,3- diisoamyls acyl group) dimethyl tartrate, L- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid two Methyl esters, L- (+)-(caproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(isocaproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(the special caproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- bis- (1,2- dimethyl) bytyry) tartaric acid diformazan Ester, L- (+)-(2,3- diene propiono) dimethyl tartrate, L- (+)-(2,3- dibenzoyls) dimethyl tartrate, L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, L- (+)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, L- (+)-(p-toluenesulfonyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- diacetyls) dimethyl tartrate, D- (+)-(propionos of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- dibutyryls) dimethyl tartrate, D- (+)-(2,3- bis- Isobutyryl) dimethyl tartrate, D- (+)-(valeryls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- diisoamyls acyl group) Dimethyl tartrate, D- (+)-(2,3- bis- (2,2- pivaloyl groups) dimethyl tartrate, D- (+)-(caproyls of 2,3- bis-) winestone Dimethyl phthalate, D- (+)-(isocaproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(the special caproyls of 2,3- bis-) tartaric acid diformazan Ester, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) dimethyl tartrate, D- (+)-(2,3- diene propiono) tartaric acid Dimethyl ester, D- (+)-(2,3- dibenzoyls) dimethyl tartrate, D- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid two Methyl esters, D- (+)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, D- (+)-(p-toluenesulfonyls of 2,3- bis-) tartaric acid Dimethyl ester, L- (+)-(2,3- diacetyls) ethyl tartrate, L- (+)-(propionos of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- dibutyryls) ethyl tartrate, L- (+)-(isobutyryls of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- Two valeryls) ethyl tartrate, L- (+)-(2,3- diisoamyls acyl group) ethyl tartrate, L- (+)-((2,2- is special by 2,3- bis- Valeryl) ethyl tartrate, L- (+)-(caproyls of 2,3- bis-) ethyl tartrate, L- (+)-(isocaproyls of 2,3- bis-) wine Stone diethyl phthalate, L- (+)-(the special caproyls of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- bis- (1,2- dimethyl) butyryl Base) ethyl tartrate, L- (+)-(2,3- diene propiono) ethyl tartrate, L- (+)-(2,3- dibenzoyls) winestone Diethyl phthalate, L- (+)-(2,3- bis- (1- naphthoyls)) ethyl tartrate, L- (+)-(2,3- bis- (2- naphthoyls)) wine Stone diethyl phthalate, L- (+)-(p-toluenesulfonyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- diacetyls) tartaric acid Diethylester, D- (+)-(propionos of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- dibutyryls) ethyl tartrate, D- (+)-(isobutyryls of 2,3- bis-) ethyl tartrate, D- (+)-(valeryls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- Diisoamyl acyl group) ethyl tartrate, D- (+)-(2,3- bis- (2,2- pivaloyl groups) ethyl tartrate, D- (+)-(2,3- bis- Caproyl) ethyl tartrate, D- (+)-(isocaproyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- bis- special caproyl) Ethyl tartrate, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) ethyl tartrate, D- (+)-(acrylyls of 2,3- bis- Base) ethyl tartrate, D- (+)-(2,3- dibenzoyls) ethyl tartrate, D- (+)-(2,3- bis- (1- naphthoyls)) Ethyl tartrate, D- (+)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, D- (+)-(tolysulfonyl of 2,3- bis- Base) ethyl tartrate, L- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, L- (+)-(propionos of 2,3- bis-) tartaric acid Diisopropyl ester, L- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, L- (+)-(isobutyryls of 2,3- bis-) tartaric acid two are different Propyl ester, L- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- diisoamyls acyl group) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl ester, L- (+)-(caproyls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(isocaproyls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(the special caproyls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1,2- dimethyl) bytyry) tartaric acid diisopropyl ester, L- (+)-(2,3- diene propiono) tartaric acid two are different Propyl ester, L- (+)-(2,3- dibenzoyls) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid two Isopropyl ester, L- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester, L- (+)-(p-toluenesulfonyls of 2,3- bis-) wine Stone acid diisopropyl ester, D- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, D- (+)-(propionos of 2,3- bis-) tartaric acid two Isopropyl ester, D- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, D- (+)-(isobutyryls of 2,3- bis-) tartaric acid diisopropyl Ester, D- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- diisoamyls acyl group) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl ester, D- (+)-(caproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(isocaproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(the special caproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1,2- dimethyl) bytyry) tartaric acid diisopropyl ester, D- (+)-(2,3- diene propiono) tartaric acid two are different Propyl ester, D- (+)-(2,3- dibenzoyls) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid two Isopropyl ester, D- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester and D- (+)-(p-toluenesulfonyls of 2,3- bis-) wine Stone acid diisopropyl ester, is more preferably selected from L- (+)-(2,3- diacetyl) dimethyl tartrate, L- (+)-(2,3- bis- propiono) Dimethyl tartrate, L- (+)-(2,3- dibutyryls) dimethyl tartrate, L- (+)-(isobutyryls of 2,3- bis-) tartaric acid two Methyl esters, L- (+)-(valeryls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- diisoamyls acyl group) dimethyl tartrate, L- (+)-(2,3- bis- (2,2- pivaloyl groups) dimethyl tartrate, L- (+)-(caproyls of 2,3- bis-) dimethyl tartrate, L- (+)- (isocaproyls of 2,3- bis-) dimethyl tartrate, L- (+)-(2,3- diene propiono) dimethyl tartrate, L- (+)-(2,3- bis- Benzoyl) dimethyl tartrate, L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, L- (+)-((2- of 2,3- bis- Naphthoyl)) dimethyl tartrate, L- (+)-(p-toluenesulfonyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- diethyls Acyl group) dimethyl tartrate, D- (+)-(propionos of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- dibutyryls) tartaric acid Dimethyl ester, D- (+)-(isobutyryls of 2,3- bis-) dimethyl tartrate, D- (+)-(valeryls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- diisoamyls acyl group) dimethyl tartrate, D- (+)-(2,3- bis- (2,2- pivaloyl groups) dimethyl tartrate, D- (+)-(caproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(isocaproyls of 2,3- bis-) dimethyl tartrate, D- (+)-(2,3- Diene propiono) dimethyl tartrate, D- (+)-(2,3- dibenzoyls) dimethyl tartrate, D- (+)-((the 1- naphthalenes of 2,3- bis- Formoxyl)) dimethyl tartrate, D- (+)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, D- (+)-(2,3- bis- is to first Benzenesulfonyl) dimethyl tartrate, L- (+)-(2,3- diacetyls) ethyl tartrate, L- (+)-(propionos of 2,3- bis-) wine Stone diethyl phthalate, L- (+)-(2,3- dibutyryls) ethyl tartrate, L- (+)-(isobutyryls of 2,3- bis-) tartaric acid diethyl Ester, L- (+)-(valeryls of 2,3- bis-) ethyl tartrate, L- (+)-(2,3- diisoamyls acyl group) ethyl tartrate, L- (+)- (2,3- bis- (2,2- pivaloyl groups) ethyl tartrate, L- (+)-(caproyls of 2,3- bis-) ethyl tartrate, L- (+)-(2, The isocaproyls of 3- bis-) ethyl tartrate, L- (+)-(2,3- diene propiono) ethyl tartrate, L- (+)-(2,3- hexichol Formoxyl) ethyl tartrate, L- (+)-(2,3- bis- (1- naphthoyls)) ethyl tartrate, L- (+)-((the 2- naphthalenes of 2,3- bis- Formoxyl)) ethyl tartrate, L- (+)-(p-toluenesulfonyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- diacetyl Base) ethyl tartrate, D- (+)-(propionos of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- dibutyryls) tartaric acid two Ethyl ester, D- (+)-(isobutyryls of 2,3- bis-) ethyl tartrate, D- (+)-(valeryls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- diisoamyls acyl group) ethyl tartrate, D- (+)-(2,3- bis- (2,2- pivaloyl groups) ethyl tartrate, D- (+)-(caproyls of 2,3- bis-) ethyl tartrate, D- (+)-(isocaproyls of 2,3- bis-) ethyl tartrate, D- (+)-(2,3- Diene propiono) ethyl tartrate, D- (+)-(2,3- dibenzoyls) ethyl tartrate, D- (+)-((the 1- naphthalenes of 2,3- bis- Formoxyl)) ethyl tartrate, D- (+)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, D- (+)-(2,3- bis- is to first Benzenesulfonyl) ethyl tartrate, L- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, L- (+)-(propionos of 2,3- bis-) Tartaric acid diisopropyl ester, L- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, L- (+)-(isobutyryls of 2,3- bis-) winestone Sour diisopropyl ester, L- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- diisoamyls acyl group) tartaric acid two Isopropyl ester, L- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl ester, L- (+)-(caproyls of 2,3- bis-) tartaric acid two Isopropyl ester, L- (+)-(isocaproyls of 2,3- bis-) tartaric acid diisopropyl ester, L- (+)-(2,3- diene propiono) tartaric acid two are different Propyl ester, L- (+)-(2,3- dibenzoyls) tartaric acid diisopropyl ester, L- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid two Isopropyl ester, L- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester, L- (+)-(p-toluenesulfonyls of 2,3- bis-) wine Stone acid diisopropyl ester, D- (+)-(2,3- diacetyls) tartaric acid diisopropyl ester, D- (+)-(propionos of 2,3- bis-) tartaric acid two Isopropyl ester, D- (+)-(2,3- dibutyryls) tartaric acid diisopropyl ester, D- (+)-(isobutyryls of 2,3- bis-) tartaric acid diisopropyl Ester, D- (+)-(valeryls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- diisoamyls acyl group) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (2,2- pivaloyl groups) tartaric acid diisopropyl ester, D- (+)-(caproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(isocaproyls of 2,3- bis-) tartaric acid diisopropyl ester, D- (+)-(2,3- diene propiono) tartaric acid diisopropyl ester, D- (+)-(2,3- dibenzoyls) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid diisopropyl ester, D- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester, D- (+)-(p-toluenesulfonyls of 2,3- bis-) tartaric acid two are different Propyl ester.
The compound provided according to the present invention, it can be prepared by the method for following steps：Method one, passes through tartaric acid two Arrcostab and corresponding acylating reagent（Such as alkyl acyl chloride）Reaction obtains the compound shown in Formulas I；Method two, by dialkanoyl wine Stone acid and halide reagent（Such as alkyl halide）Reaction, obtains the compound shown in Formulas I.In a specific example, tartaric acid two Arrcostab is in the presence of excessive alkali, and the excessive alkyl acyl chloride with addition is reacted, and reacts after terminating through separation, purifying Handle to obtain final product.In another specific example, by dialkanoyl tartaric acid in phase transfer catalyst（Such as tetrabutyl bromine Change ammonium）Catalysis under with excessive alkyl halide（Such as bromoethane）Reacted, reaction is obtained finally after terminating through separation, purification process Product.
The compound of the new structure provided according to the present invention, available for olefinic polymerization, such as catalyst solid constituent Internal electron donor, obtained catalyst has good combination property, with broad application prospect.
According to another aspect of the present invention, a kind of catalytic component for olefinic polymerization is additionally provided（Or urge Agent solid constituent）, including titanium, magnesium, halogen and above-mentioned formula（I）Shown compound.
According to catalytic component of the present invention（In the present invention or ingredient of solid catalyst, catalyst solid constituent Deng）, the titanium（Element）Content be 1.0-8.0wt%, preferably 1.6-6.0wt%；The magnesium（Element）Content be preferably 10-70wt%, preferably 15-40wt%；The halogen（Element）Content be 20-85wt%, preferably 30-80%；The Formulas I institute The compound shown（Internal electron donor compound）Content be 2-30wt%, preferably 3-20wt%.
According to another aspect of the present invention there is provided a kind of method for preparing described catalytic component, including will Compound shown in magnesium compound, titanium compound and Formulas I carries out haptoreaction in a solvent.For preparing the catalytic component Titanium compound, magnesium compound and Formulas I shown in the consumption of compound be not particularly limited, can be respectively the routine of this area Material and consumption.
In a preferred embodiment of catalytic component preparation method of the present invention, the magnesium compound is selected from formula MgR4R5Shown magnesium compound, formula M gR4R5·pH2The hydrate and formula M gR of magnesium compound shown in O4R5·qR6OH In the alcohol adducts of shown magnesium compound, formula, R4 and R5 are each independently selected from halogen, C1-C8Straight or branched alkane Epoxide and C1-C8Straight or branched alkyl；P and q are separately selected from 0.1-6, preferably 2-3.5；R6For C1-C18Alkyl, Preferably C1-C8Alkyl, be more preferably selected from methyl, ethyl, n-propyl and isopropyl.Magnesium compound can be diformazan as described Epoxide magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, Two epoxide magnesium, two (2- ethyls) epoxide magnesium, methoxy magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, ethyoxyl chlorine Change magnesium, ethyoxyl magnesium bromide, ethyoxyl magnesium iodide, propoxyl group magnesium chloride, propoxyl group magnesium bromide, propoxyl group magnesium iodide, butoxy Magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, methyl-magnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, Amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, dibrominated magnesium Alcohol adducts and magnesium diiodide at least one of alcohol adducts.Most preferably, the magnesium compound contains diethoxy At least one of magnesium, butylmagnesium chloride, ethyoxyl magnesium chloride, magnesium dichloride.
In another preferred embodiment of catalytic component preparation method of the present invention, the titanium compound it is logical Formula is TiXm (OR7) 4-m, in formula, X is halogen, R7For C1-C20Alkyl, preferably C1-C5Alkyl, m be 0-4 integer.Example Such as：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen At least one of base titanium and the ethanolato-titanium of trichlorine one.Most preferably, the titanium compound is titanium tetrachloride.
In the specific embodiment of the inventive method, catalyst component exemplary is prepared such as by following methods.
Method one, alkoxyl magnesium or Alkoxymagnesium halides are suspended in inert diluent and form suspension, then this is hanged Supernatant liquid contacts to obtain solids dispersion, commonly referred to as mother liquor with above-mentioned titanium compound, internal electron donor mixing.By mother liquor mistake Filter, gained solid matter is suspended in progress contact processing in the solution containing titanium tetrachloride, and commonly referred to as titanium is handled；Then pass through Filter, washing can be prepared by the catalyst solid constituent of the present invention.
As the specific example of above-mentioned alkoxyl magnesium, can enumerate dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, Diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two hexyloxy magnesium, two (2- ethyls) hexyloxy magnesium Deng or its mixture, preferably diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesiums mixture.The alkoxyl magnesium The preparation method of compound, can be prepared by method well known in the art, as disclosed in patent CN101906017A by magnesium metal with Fatty alcohol is prepared in the presence of a small amount of iodine.
As the specific example of above-mentioned Alkoxymagnesium halides, methoxy magnesium chloride, ethyoxyl magnesium chloride, the third oxygen can be enumerated Base magnesium chloride, butoxy magnesium chloride etc., preferably ethyoxyl magnesium chloride.The preparation method of the alkoxy magnesium compound, can be by Prepared by method well known in the art, such as mix to prepare with purity titanium tetraethoxide and tetraethoxy-silicane by RMgBr butylmagnesium chloride Ethyoxyl magnesium chloride.
Inert diluent used in the formation of mother liquor in the above method one can using hexane, heptane, octane, decane, At least one of benzene, toluene and dimethylbenzene.The consumption of each composition used in the formation of mother liquor, in terms of every mole of magnesium, titanizing 0.5-100 moles of the usage amount of compound, preferably 1-50 moles；The usage amount of inert diluent is usually 0.5-100 moles, excellent Elect 1-50 moles as；The total amount of electronic donor compound is usually 0.005-10 moles, preferably 0.01-1 moles.The shape of mother liquor Into when each component Contact Temperature be usually -40~200 DEG C, be preferably -20~150 DEG C；Time of contact is usually 1 point Clock -20 hours, preferably -8 hours 5 minutes.
In methods described one, in the titanium processing procedure, use alternative addition in the solution containing titanium tetrachloride lazy Property diluent, such as at least one of hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene；In the titanium processing procedure, The consumption containing each composition in titanium tetrachloride solution is used, in terms of every mole of magnesium, 0.5-100 moles of the usage amount of titanium compound, Preferably 1-50 moles；The usage amount of inert diluent is usually 0-100 moles, preferably 0-50 moles；Titanium number of processes is 0-10 times, preferably 1-5 times.In the titanium processing procedure, alternative adds above-mentioned electronic donor compound, wherein interior electron Body consumption is usually 0.005-10 moles, preferably 0.01-1 moles.The titanium treatment temperature is usually 0~200 DEG C, is preferably 30~150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -6 hours 5 minutes.
Method two, by magnesium dihalide be dissolved in organic epoxy compound thing, organic phosphorus compound, aliphatic alcohols compound with it is lazy Property diluent composition dicyandiamide solution in, formed homogeneous solution after with above-mentioned titanium compound, electron donor compound haptoreaction, In the presence of precipitation additive, solids is separated out, mother liquor is formed；Mother liquor is filtered, gained solid matter is suspended in containing titanium tetrachloride Solution in carry out contact processing, hereinafter known as titanium handle；Then through filtering, the catalyst that washing can be prepared by the present invention is consolidated Body component.
Precipitation additive used in method two is not particularly limited, as long as solid particle can be made to separate out shaping.Can Have with the example enumerated：At least one of organic acid anhydride, organic acid, ester, ether and ketone.The specific example of the organic acid anhydride can Think at least one of acetic anhydride, phthalic anhydride, succinic anhydride and maleic anhydride etc., the organic acid it is specific Example can be at least one of acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid etc., and the specific example of the ester can Think dibutyl phthalate, 2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 2,3- bis- Isopropyl -1,4- butanediols dibenzoate, 3,5- heptandiols dibenzoate and 4- ethyl -3,5- heptandiol dibenzoates At least one of, the specific example of the ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2- isopropyl -2- isopentyl Dimethoxy propane and 9,9-（Dimethoxy methyl）At least one of fluorenes, the ketone can be acetone, MEK and benzophenone At least one of.
In method two, the organic epoxy compound thing used can be selected from oxirane, expoxy propane, epoxy fourth In alkane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether etc. At least one, preferably epoxychloropropane.The organic phosphorus compound used can for orthophosphoric acid or phosphorous acid hydrocarbyl carbonate or Halogenated hydrocarbons base ester, the specific example of the organic phosphorus compound can be enumerated：Orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid Tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite or phosphorous acid benzene methyl etc., it is excellent Select orthophosphoric acid tributyl.The aliphatic alcohols compound that uses can be carbon number 1-20 straight or branched alkane unitary Or multi-alcohol, preferred carbon number 1-10 straight or branched unitary fatty alcohol, specific example can enumerate：Methanol, second Alcohol, propyl alcohol, isopropanol, butanol, isobutanol, amylalcohol, hexanol, enanthol,（2- ethyls）Hexyl alcohol, octanol, nonyl alcohol, decyl alcohol etc., it is excellent Choosing（2- ethyls）Hexyl alcohol.
In method two, mother liquor, which forms the middle inert diluent used, can use hexane, heptane, octane, decane, benzene, first At least one of benzene and dimethylbenzene.Mother liquor forms the consumption of the middle each composition used, in terms of every mole of magnesium halide, organic epoxidation Compound can be 0.2-10 moles, preferably 0.5-4 moles；Organic phosphorus compound can be 0.1-3 moles, preferably 0.3- 1.5 mole；Fat alcohol compound can be 0.2-10 moles, preferably 0.5-3 moles；Titanium compound can rub for 0.5-20 You, preferably 5-15 moles；It can be 0.01-0.3 moles, preferably 0.02-0.2 moles to help precipitation component；Electron donor Compound total amount can be 0-10 moles, preferably 0.02-0.3 moles.The Contact Temperature of each component leads to during the formation of mother liquor It is often -40~200 DEG C, is preferably -20~150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -8 hours 5 minutes.
In method two, in the titanium processing procedure, use alternative addition inertia in the solution containing titanium tetrachloride dilute Release agent, such as at least one of hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In the titanium processing procedure, made With the consumption containing each composition in titanium tetrachloride solution, in terms of every mole of magnesium, 0.5-100 moles of the usage amount of titanium compound, preferably For 1-50 moles；The usage amount of inert diluent is usually 0-100 moles, preferably 0-50 moles.The titanium number of processes is 0-10 times, preferably 1-5 times.In the titanium processing procedure, alternative adds above-mentioned electronic donor compound, wherein interior electron Body consumption is usually 0.005-10 moles, preferably 0.01-1 moles.The titanium treatment temperature is usually 0~200 DEG C, is preferably 30~150 DEG C；Time of contact is usually -20 hours 1 minute, preferably -6 hours 5 minutes.
Method three, the alcohol adducts of magnesium dihalide are suspended in inert diluent and form suspension, then by the suspension Solids dispersion, hereinafter known as mother liquor are contacted to obtain with above-mentioned titanium compound, internal electron donor mixing.By mother liquor mistake Filter, gained solid matter is suspended in progress contact processing in the solution containing titanium tetrachloride, and hereinafter known as titanium is handled；Then pass through Filter, washing can be prepared by the catalyst solid constituent of the present invention.
In method three, the alcohol adducts of the magnesium dihalide can be made by the following method：Miscible not with adduct Atent solvent（Such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene）In the presence of, by alcohol（Such as methanol, ethanol, third Alcohol or isopropanol etc.）Emulsion is mixed to form with magnesium halide, disperses the rapid chilling of the emulsion, gained spheric granules is dihalide The alcohol adducts of magnesium.
In the above method three, inert diluent used in the formation of mother liquor can using hexane, heptane, octane, decane, At least one of benzene, toluene and dimethylbenzene.The consumption of each composition used in the formation of mother liquor, in terms of every mole of magnesium, titanizing 0.5-100 moles of the usage amount of compound, preferably 1-50 moles；The usage amount of inert diluent is usually 0.5-100 moles, excellent Elect 1-50 moles as；The total amount of electronic donor compound is usually 0.005-10 moles, preferably 0.01-1 moles.The shape of mother liquor Into when each component Contact Temperature be usually -40~200 DEG C, be preferably -20~150 DEG C；Time of contact is usually 1 point Clock -20 hours, preferably -8 hours 5 minutes.
In method three, in the titanium processing procedure, use alternative addition inertia in the solution containing titanium tetrachloride dilute Release agent, such as at least one of hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In titanium processing procedure, use and contain The consumption of each composition in titanium tetrachloride solution, in terms of every mole of magnesium, 0.5-100 moles of the usage amount of titanium compound, preferably 1- 50 moles；The usage amount of inert diluent is usually 0-100 moles, preferably 0-50 moles.Titanium number of processes is 0-10 times, excellent Select 1-5 times.In titanium processing procedure, alternative adds above-mentioned electronic donor compound, and wherein internal electron donor consumption is usually 0.005-10 moles, preferably 0.01-1 moles.Titanium treatment temperature is usually 0~200 DEG C, preferably 30~150 DEG C；During contact Between be usually -20 hours 1 minute, preferably -6 hours 5 minutes.
According to another aspect of the present invention there is provided a kind of catalyst for olefines polymerizing, it includes following components Reaction product：
A. above-mentioned catalytic component；
B. organo-aluminum compound；
C. optionally, external donor compound.
Can be olefinic polymerization as the organo-aluminum compound of co-catalyst according to olefin polymerization catalysis of the present invention The organo-aluminum compound of the conventional various co-catalysts that can act as Ziegler-natta catalyst in field.It is preferred that described have Machine aluminium compound is formula AlR'n'X'3-n'Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkyl and C6- C20Aryl；X' is halogen, and n' is 1-3 integer.
In above-mentioned catalyst, described organo-aluminum compound preferably is selected from least one of following compound：Trimethyl aluminium, Triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine two At least one of aluminium isobutyl, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferably triethyl aluminum and/or triisobutyl Aluminium.
In above-mentioned catalyst, the consumption of the organo-aluminum compound can be the conventional amount used of this area.Usually, it is described The mol ratio of aluminium in organo-aluminum compound and the titanium in the catalyst is 5-5000：1；Preferably 20-1000：1；More preferably For 50-500：1.
In above-mentioned catalyst, " optionally, the external donor compound " means that the catalyst can include component a With b reaction product, component a, b and c reaction product can be also included.It is described according to olefin polymerization catalysis of the present invention External electron donor component can be various external electron donors known in the industry, be not particularly limited.
In above-mentioned catalyst, the external electron donor is preferably general formula R1″m″R2″n″Si(OR3Having shown in ") 4-m "-n " In organic silicon compound, formula, R1" and R2" it is identical or different, it is each independently selected from：Halogen, hydrogen atom, C1-C20Alkyl, C3- C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；R3" it is selected from C1-C20Alkyl, C3-C20Cycloalkyl, C6- C20Aryl and C1-C20Haloalkyl；M " and n " respectively 0-3 integers, and m "+n "<4.Preferably, it is described siliconated Compound is selected from least one of following compound：Trimethylmethoxysilane, diisopropyl dimethoxy silane, diisobutyl Dimethoxysilane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxy Silane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopenta Methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl diformazan It is TMOS, double（2- methylcyclopentyls）Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, Phenyl triethoxysilane, MTMS, MTES, ethyl trimethoxy silane, propyl group front three TMOS, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy Silane, butyl triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, Isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, Diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, ethene Ethyl triethoxy silicane alkane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes；These organo-silicon compound can divide It is not used alone, two or more can also be applied in combination.
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In preferred feelings Under condition, the mol ratio of aluminium and the external donor compound in the organo-aluminum compound is 0.1-500：1, preferably 1- 300：1, more preferably 3-100：1.I.e. when the external donor compound selects organo-silicon compound, the organo-aluminium chemical combination The mol ratio of thing and organo-silicon compound is calculated as 0.1 with aluminium/silicon:1-500:1, preferably 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention there is provided a kind of olefine polymerizing process, the alkene is in above-mentioned catalyst It is polymerize in the presence of component or above-mentioned catalyst.
According to the olefine polymerizing process of the present invention, it can be not only used for the homopolymerization of alkene, it can also be used to the copolymerization of alkene.
According to the present invention, the formula of the alkene is CH2=CHR, R are hydrogen or C1-C12Alkyl, preferably hydrogen or C1- C6Alkyl.Alkene is preferably selected from least one of following compound as described：Ethene, propylene, 1- n-butenes, 1- positive penta Alkene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene；It is more preferably selected from least one of ethene, propylene and 1- butylene.
According to olefine polymerizing process of the present invention, the olefin polymerization conditions are that the temperature of olefinic polymerization is 0-150 DEG C, preferably 60-130 DEG C；Time is 0.1-5 hours, and preferably 0.5-4 hours, pressure was 0.01-10MPa, preferably 0.5- 5MPa.The consumption of catalyst can be the consumption of the various catalyst of prior art.
According to the present invention, obtained by using the compound shown in new structure Formulas I as internal electron donor compound Catalyst, can replace phthalate internal electron donor compound the most frequently used in the prior art（It has been found to unfavorable In the fecundity of people）Catalyst, with higher security；And obtained polymer has higher bulk density and molten Melt index（Mean that catalyst has preferable hydrogen regulation performance）.In accordance with the invention it is possible to obtain the catalysis of high comprehensive performance Agent, polymerization activity is suitable, the stereotaxis ability of catalyst is good and hydrogen response is good；For olefinic polymerization, especially third When alkene polymerize, gratifying polymerization yield rate can be obtained, and the bulk density of polymer is high, isotacticity is good, melt index Height, is conducive to the exploitation of different trade mark polymer.According to the new catalyst that provides of the present invention, with excellent comprehensive Can, with broad application prospect.
Embodiment
Example given below is used to further illustrate the present invention, but does not constitute any limitation of the invention.
Method of testing：
1st, the Ti content in catalyst：Tested according to 721 spectrophotometers.
2nd, catalyst grain size distribution：Measured according to the n-hexane dispersant laser diffractometry of Malvern 2000.
3rd, the measure of melt index：Determined according to GB/T3682-2000.
4th, polymer isotacticity is determined using heptane extraction process：2 grams of dry polymer samples, are placed in extractor with boiling After rising heptane extracting 6 hours, by the polymer weight obtained by residue drying to constant weight（g）With 2（g）Ratio be isotactic Degree.
5、1H NMR are determined：Use Bruker dmx nmr determinations（300MHz, solvent C DCl3, internal standard TMS, survey Constant temperature degree 300K）.
6th, internal electron donor content uses Agilent7890Series gas Chromatographic Determinations.
First, synthesis example：
Compound 1：The synthesis of L- (+)-(2,3- dibenzoyls) dimethyl tartrate：
26g（145.5mmol）L- (+)-dimethyl tartrate, 32.38g（320.0mmol）Triethylamine is mixed, and is dissolved in In the chloroform that 200mL is dried.45g（320mmol）Chlorobenzoyl chloride is dissolved in 150mL chloroforms, and mixing is instilled at room temperature In system, 30 DEG C of reactions 3h, back flow reaction 6h after completion of dropping.Terminate reaction, be filtered to remove solid, be spin-dried for solvent, add 250mL ethyl acetate, 300mL2% sodium carbonate liquor, point liquid, ethyl acetate wash water phase three times（100mL,80mL,60mL）, close And organic item, anhydrous magnesium sulfate drying, filtering, revolve except solvent, crude product recrystallizing methanol obtains sterling 40.9g, yield 72.6%, purity 99.2%（LC）.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.772(s,6H,-CH3),6.001(s,4H,-HC(OC) OCH3),7.451-7.503(m,4H,C6H5-),7.586-7.640(m,2H,C6H5-),8.095-8.123(m,4H,C6H5-)。
Compound 2：The synthesis of D- (-)-(2,3- dibenzoyls) dimethyl tartrate：
Using similar method, D- (-)-(2,3- dibenzoyl) dimethyl tartrate 23.6g, yield has been synthesized 68.6%, purity 98.7%（LC）.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.769(s,6H,-CH3),6.013(s,4H,-HC(OC) OCH3),7.489-7.517(m,4H,C6H5-),7.635-7.702(m,2H,C6H5-),8.134-8.193(m,4H,C6H5-)。
Compound 3：The synthesis of L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate：
Using similar method, L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate 16.3g, yield has been synthesized 71.3%, purity 98.9%（LC）.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.831(s,6H,-OCH3),6.202(s,2H,-HC(OC) OCH3),7.508-7.638(m,6H,C10H9-),7.892-7.923(d,2H,C10H9-),8.069-8.097(d,2H, C10H9-),8.351-8.376(d,2H,C10H9-),8.978-9.031(d,2H,C10H9-)。
Compound 4：The synthesis of L- (+)-(p-toluenesulfonyls of 2,3- bis-) dimethyl tartrate：
20g (112.3mmol) L- (+)-dimethyl tartrate, 30.0g, 41mL (291.9mmol) triethylamine mixing is added The chloroform that 120mL is dried.55.7g (291.9mmol) paratoluensulfonyl chloride is dissolved in the chloroform of 100mL dryings, drop Enter in mixture 1, keeping temperature is stable at 5-10 DEG C during dropwise addition, and completion of dropping is warmed to room temperature stirring 1h naturally, is warming up to Backflow, reacts 6h.Reaction terminates, and is filtered to remove solid, is spin-dried for solvent, adds 250mL ethyl acetate, and 300mL water, point liquid is fitted Measure ethyl acetate aqueous phase extracted three times, merge organic phase, anhydrous magnesium sulfate is dried, filtering is spin-dried for solvent, crude product methanol is tied again Crystalline substance obtains sterling 41.9g, yield 76.7%, purity 96.5%（GC）.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):2.464(s,6H,-(CO)OCH3),3.642(s,4H,-C (CH2O-)2),6.714(s,4H,-CH(CO)OCH3),7.353-7.380(m,4H,C6H5-),7.827-7.855（m,4H, C6H5-）.
Compound 5：The synthesis of L- (+)-(2,3- dibenzoyls) ethyl tartrate：
30.0g (0.084mol) L- (+) dibenzoyl tartaric acid, 2.0g TBABs are dissolved in dried 200mL The in the mixed solvent of dimethylformamide and 100mL acetone.Add 35g (0.252mol) potassium carbonate, 27.5g, 18.8mL （0.252mol）Bromoethane, 25 DEG C of stirrings 2h, 30 DEG C of stirrings 4h, 50 DEG C of stirring 4h.Reaction terminates, and is filtered to remove solid, and rotation is removed Solvent, adds water 300mL, and ethyl acetate is extracted three times, merges organic item, and anhydrous magnesium sulfate is dried, and filtering, rotation removes solvent, obtains To crude product, crude product post separation obtains sterling 51.9g, yield 86.1%, purity 96.5%（GC）.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):1.169-1.217(t,6H,-(CO)OCH2CH3),4.195- 4.270(q,4H,-(CO)OCH2CH3),6.008(s,2H,--CH(CO)OCH2CH3),7.450-7.500(m,4H,C6H5-), 7.583-7.636(m,2H,C6H5-), 8.102-8.113 (m, 4H, C6H5-)。
2nd, application examples
Embodiment 1：
The preparation of alkoxyl magnesium
It is prepared by alkoxyl magnesium：In the 1L reactors with agitator, reflux condensing tube, thermometer and buret, nitrogen is used After gas is sufficiently displaced from, ethanol 550mL, isopropanol 10mL, iodine 0.68g dissolvings are added into reactor.Risen after opening stirring Temperature, until reaching the reflux temperature of reaction system.Then magnesium powder 32g is gradually added；Reaction is untill there is no hydrogen discharge.So Washed, filtered and dried afterwards, obtain bulk density 0.25g/cm3, average grain diameter（D50）47.0 μm of alkoxyl magnesium 147g.
The preparation of ingredient of solid catalyst：
Take alkoxyl magnesium carrier 10g obtained above, toluene 50mL and internal electron donor（Compound 1）2.5g, is configured to Suspension；In the 300mL reactor of displacement is repeated by high pure nitrogen, toluene 40mL and titanium tetrachloride 60mL is added, so The suspension prepared is added in kettle afterwards, 80 DEG C are warming up to, constant temperature is continuously heating to 115 DEG C after 1 hour, constant temperature is after 2 hours By liquid（Mother liquor）Press filtration is clean.It is small that addition toluene 90mL and titanium tetrachloride 60mL mixed liquor is warming up to 110 DEG C of stir process 1 When（Titanium processing）, by liquid（Mother liquor）Press filtration is clean, and the mixed liquor for adding toluene 120mL and titanium tetrachloride 30mL is warming up to 110 DEG C of stir process 2 hours（Titanium processing）, liquid is filtered off, the solid of gained is washed 3 times at 55 DEG C with n-hexane 150mL, in room Temperature washed once with n-hexane, filter off liquid and drying, produce the ingredient of solid catalyst of the present invention.
Propylene polymerization
In a 5L autoclave, after being sufficiently displaced from through gas-phase propene, the hexane that 5mL triethyl aluminums are added at room temperature is molten Liquid (concentration of triethyl aluminum is 0.5mmol/mL), the hexane solution of lmL Cyclohexyl Methyl Dimethoxysilanes (CHMMS) (CHMMS concentration is 0.10mmol/mL), 10mL anhydrous hexanes and the above-mentioned ingredients of solid catalyst prepared of 10mg.Close Autoclave is closed, 4.5 standards is introduced and rises hydrogen and 2L liquid propene；Temperature is risen to 70 DEG C in 10 minutes under agitation.70 Polymerisation stops stirring after 1 hour at DEG C, removes unpolymerized propylene monomer, collected polymer.Catalyst activity is by obtaining Polymer quality (Kg) calculated with the ratio of the catalyst quality (g) used.
Embodiment 2-5：
Step be the same as Example 1, simply respectively by being changed to of internal electron donor during prepared by ingredient of solid catalyst Compound 2-5, consumption 2.5g.
Comparative example 1：
Step be the same as Example 1, is simply changed to adjacent benzene two during prepared by ingredient of solid catalyst by internal electron donor Formic acid di-n-butyl（DNBP）, consumption 2.5g.
Comparative example 2：
Step be the same as Example 1, is simply changed to L- (+)-wine during prepared by ingredient of solid catalyst by electron donor Stone diethyl phthalate, consumption 2.5g.It can not obtain that form is good, workable ingredient of solid catalyst.
Comparative example 3：
Step be the same as Example 1, is simply changed to L- (+)-wine during prepared by ingredient of solid catalyst by electron donor Stone acid diisopropyl ester, consumption 2.5g.Form can not be obtained good, workable ingredient of solid catalyst.
The performance of the catalyst of table 1.
In table, contentaRefer to the mass percent of internal electron donor in catalyst.
As can be seen from Table 1, using the catalytic component for including specific structure internal electron donor of the present invention The catalyst of preparation, is compared with n-butyl phthalate the most frequently used in the prior art, not only increases the peace of catalyst Quan Xing, obtained polymer has higher bulk density and melt index（Mean that catalyst has preferable hydrogen tonality Energy）.Catalyst according to the invention has the advantages that hydrogen regulation performance is good, polymerization activity suitable and stereotaxis ability is good etc.；With When olefinic polymerization, obtained polymer has preferable isotacticity, higher melt index and bulk density.Especially have Higher melt index, it is meant that catalyst has good hydrogen regulation performance, the exploitation suitable for specific acrylic resin.According to this The new catalyst provided is invented, with excellent combination property, with broad application prospect.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used is descriptive With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair It is bright to can be extended to other all methods and applications with identical function.

Claims (23)

1. a kind of catalytic component for olefinic polymerization, including the compound shown in titanium, magnesium, halogen and Formulas I,
Wherein, the compound shown in described Formulas I is selected from L- (+)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, L- (+)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, D- (-)-(2,3- bis- (1- naphthoyls)) dimethyl tartrate, D- (-)-(2,3- bis- (2- naphthoyls)) dimethyl tartrate, L- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid diethyl Ester, L- (+)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, D- (-)-(2,3- bis- (1- naphthoyls)) tartaric acid two Ethyl ester, D- (-)-(2,3- bis- (2- naphthoyls)) ethyl tartrate, L- (+)-(2,3- bis- (1- naphthoyls)) tartaric acid Diisopropyl ester, L- (+)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester, D- (-)-(2,3- bis- (1- naphthoyls)) Tartaric acid diisopropyl ester and D- (-)-(2,3- bis- (2- naphthoyls)) tartaric acid diisopropyl ester.
2. a kind of catalytic component for olefinic polymerization, including titanium, magnesium, halogen and L- (+)-(2,3- bis- p-toluenesulfonyl) Dimethyl tartrate.
3. catalytic component according to claim 1, it is characterised in that compound shown in described Formulas I for L- (+)- (2,3- bis- (1- naphthoyls)) dimethyl tartrate.
4. the catalytic component according to any one in claim 1-3, it is characterised in that the content of the titanium is 1.0- 8.0wt%；The content of the magnesium is 10-70wt%；The content of the halogen is 20-85wt%；Compound shown in the Formulas I Content be 2-30wt%.
5. the catalytic component according to any one in claim 1-3, it is characterised in that the content of the titanium is 1.6- 6.0wt%；The content of the magnesium is 15-40wt%；The content of the halogen is 30-80%；Compound shown in the Formulas I Content is 3-20wt%.
6. a kind of method for preparing catalytic component described in any one in claim 1-5, including magnesium compound, titanizing are closed Compound shown in thing and Formulas I carries out haptoreaction in a solvent.
7. method according to claim 6, it is characterised in that the magnesium compound is selected from formula M gR4R5Shown magnesium Compound, formula M gR4R5·pH2The hydrate and formula M gR of magnesium compound shown in O4R5·qR6Magnesium compound shown in OH Alcohol adducts, in formula, R4And R5It is each independently selected from halogen, C1-C8Straight or branched alkoxy and C1-C8It is straight Chain or branched alkyl；P and q are separately selected from 0.1-6；R6For C1-C18Alkyl.
8. method according to claim 7, it is characterised in that in the magnesium compound, p and q are separately selected from 2- 3.5；R6For C1-C8Alkyl.
9. method according to claim 7, it is characterised in that in the magnesium compound, R6Selected from methyl, ethyl, n-propyl And isopropyl.
10. method according to claim 6, it is characterised in that the formula of the titanium compound is TiXm (OR7) 4-m, formula In, X is halogen, R7For C1-C20Alkyl, m be 0-4 integer.
11. method according to claim 10, it is characterised in that in the formula of the titanium compound, R7For C1-C5Alkane Base.
12. method according to claim 10, it is characterised in that the titanium compound is titanium tetrachloride.
13. a kind of catalyst for olefines polymerizing, it includes the reaction product of following components：
A. any one methods described system in the catalytic component or claim 6-12 in claim 1-5 described in any one Standby catalytic component；
B. organo-aluminum compound；
C. optionally, external donor compound.
14. catalyst according to claim 13, it is characterised in that the organo-aluminum compound is formula AlR'n'X'3-n' Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkyl and C6-C20Aryl；X' is halogen, and n' is 1-3's Integer.
15. catalyst according to claim 13, it is characterised in that the external donor compound is general formula R1” m” R2” n”Si(OR3”)4-m”-n”In shown organo-silicon compound, formula, R1”And R2”It is identical or different, it is each independently selected from：Halogen, Hydrogen atom, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；R3”Selected from C1-C20Alkane Base, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；M " and n " is respectively 0-3 integer, and m "+n "< 4。
16. the catalyst according to any one in claim 13-15, it is characterised in that the organo-aluminum compound with The mol ratio of catalyst solid constituent is calculated as 5 with aluminium/titanium:1-5000:1；Aluminium and outer electron in the organo-aluminum compound The mol ratio of body compound is 0.1:1-500:1.
17. the catalyst according to any one in claim 13-15, it is characterised in that the organo-aluminum compound with The mol ratio of catalyst solid constituent is calculated as 20 with aluminium/titanium:1-1000:1；Aluminium and outer electron in the organo-aluminum compound The mol ratio of body compound is 1:1-300:1.
18. the catalyst according to any one in claim 13-15, it is characterised in that the organo-aluminum compound with The mol ratio of catalyst solid constituent is calculated as 50 with aluminium/titanium:1-500:1；Aluminium and outer electron in the organo-aluminum compound The mol ratio of body compound is 3:1-100:1.
19. a kind of olefine polymerizing process, catalytic component of the alkene in claim 1-5 described in any one, right It is required that catalyst described in any one in catalytic component or claim 13-18 that in 6-12 prepared by any one methods described In the presence of polymerize.
20. method according to claim 19, it is characterised in that the formula of the alkene is CH2=CHR, R are hydrogen or C1- C12Alkyl.
21. method according to claim 20, it is characterised in that R is hydrogen or C in the formula of the alkene1-C6Alkyl.
22. method according to claim 20, it is characterised in that the alkene is selected from ethene, propylene, 1- n-butenes, 1- N-pentene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene.
23. method according to claim 20, it is characterised in that the alkene is selected from ethene, propylene and 1- butylene.
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WO2001092345A1 (en) * 2000-05-31 2001-12-06 Samsung General Chemicals Co., Ltd. A method for producing ethylene homo- and co-polymer
CN101423570A (en) * 2007-11-01 2009-05-06 中国石油天然气股份有限公司 Spherical catalytic component for olefin polymerization and catalyst thereof

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CN1268521A (en) * 1999-03-30 2000-10-04 中国石油化工集团公司北京化工研究院 High-activity catalyst for olefin polymerization, preparation method thereof and application of catalyst
WO2001092345A1 (en) * 2000-05-31 2001-12-06 Samsung General Chemicals Co., Ltd. A method for producing ethylene homo- and co-polymer
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