CN1453298A - Catalyst for olefine polymerizing reaction and its components - Google Patents

Catalyst for olefine polymerizing reaction and its components Download PDF

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CN1453298A
CN1453298A CN 03109781 CN03109781A CN1453298A CN 1453298 A CN1453298 A CN 1453298A CN 03109781 CN03109781 CN 03109781 CN 03109781 A CN03109781 A CN 03109781A CN 1453298 A CN1453298 A CN 1453298A
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methyl
dibenzoate
pentanediol
preparation
group
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CN1213080C (en
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高明智
刘海涛
李昌秀
丁春敏
杨燕涛
李威莅
王晓东
李天益
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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 provides one kind catalyst component for CH2=CHR olifine polymerization, where R is H or alkyl radical or aryl radical of C1-C6. The catalyst component contains Mg, Ti, halogen and electron donor.

Description

The catalyst component and the catalyzer thereof that are used for olefinic polyreaction
Technical field
The present invention relates to ingredient of solid catalyst of a kind of diol ester compound that contains special construction and preparation method thereof, contain the catalyzer of this ingredient of solid catalyst and this catalyzer at CH 2Application in the=CHR olefinic polyreaction, wherein R is hydrogen or C 1-C 6Alkyl or aryl, special application in propylene polymerization can obtain the polymkeric substance of high yield, high isotactic and molecular weight distribution broad.
Technical background
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component 2=CHR olefinic polyreaction, particularly in alpha-olefine polymerizing, can obtain the polymkeric substance of higher yields and higher tacticity with 3 carbon or more carbon atoms, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.At present, multiple electron donor compound is disclosed in a large number, for example polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is aromatic carboxylates's class of binary, for example n-butyl phthalate or diisobutyl phthalate etc. can be referring to Chinese patent CN85100997A.
In recent years, the electron donor that people attempt to adopt other compound to be used as in the olefin polymerization catalyst components again uses, for example at Chinese patent CN1042547A and the disclosed catalyst component that is used for olefinic polyreaction of CN1143651A, special 1 of two ether groups that contain have been adopted, the 3-diether compound is as electron donor, 2-sec.-propyl-2-isopentyl-1 for example, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc.At the disclosed ingredient of solid catalyst that is used for olefinic polyreaction of Chinese patent CN1054139A, adopted special 1 of two ketone groups that contain, the 3-cyclohexadione compounds is as electron donor, for example 2,2,4,6,6-pentamethyl--3,5-heptadione and 2,2,6,6-tetramethyl--4-3,5-heptadione etc.
The special dibasic aliphatic carboxylic acid ester compound of one class is disclosed again recently, as (referring to CN1313869A, CN1236373A and CN1236374A) such as succinate, malonic ester, glutarates, the use of this class electron donor compound not only can improve activity of such catalysts, and the molecular weight distribution of gained propene polymer is obviously widened.
Yet, the aromatic carboxylic acid ester compound of the above-mentioned disclosed binary of above-mentioned employing, contain 1 of two ether groups, the catalyzer that is used for olefinic polymerization of 3-diether compound and the preparation of dibasic aliphatic carboxylic acid ester compound all exists certain defective in actual applications, for example adopt the catalytic activity of catalyzer of aromatic carboxylic acid ester compound of binary lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, though the catalyzer of 3-diether compound is active higher, and catalyzer susceptibility that hydrogen is transferred might as well, the narrow molecular weight distribution of resulting polymers is unfavorable for the exploitation of the different trades mark of polymkeric substance; And adopt the catalytic activity of catalyzer of recent disclosed dibasic aliphatic carboxylicesters still on the low side, and when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is lower.
The inventor unexpectedly finds, in olefin polymerization catalysis by using a kind of new diol ester compound that contains special construction as electron donor, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain the polymkeric substance of higher degree of isotacticity, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Summary of the invention
One of purpose of the present invention is to provide a kind of CH of being used for 2The catalyst component of=CHG olefinic polyreaction, wherein R is hydrogen or C 1-C 6Alkyl or aryl, this catalyst component comprises magnesium, titanium, halogen and electron donor, this electron donor is selected from least a diol ester compound in the following general formula (I):
Figure A0310978100061
R wherein 1-R 6Can be identical or inequality, be hydrogen or C 1-C 10The alkyl of straight or branched, C 3-C 10Cycloalkyl, C 6-C 10Aryl, C 7-C 10Alkaryl or aralkyl, but R 1, R 2, R 5, R 6Be not hydrogen simultaneously; R 1-R 6In two or more groups mutually bonding generate one or several condensed ring structure;
R 7And R 8Can be identical or inequality, represent C 1-C 10Straight or branched alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Aryl, the benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl.
In the diol ester compound of wherein said general formula (I), R 1, R 2, R 5And R 6In to have a group at least be hydrogen.But work as R 3And R 4When being methyl simultaneously, R 1, R 2, R 5, R 6When having three to be hydrogen in the group, another group should not be a sec.-propyl.
In above-mentioned diol ester general formula compound, preferred R 1And R 2, R 5And R 6In to have a group respectively at least be not hydrogen, more preferably, R 1And R 2, R 5And R 6In a group is arranged respectively is hydrogen, and another group is methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl.
In above-mentioned propylene glycol ester general formula compound, preferred R 7And R 8Group is selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, aminomethyl phenyl, halogenated aminomethyl phenyl, indenyl, benzyl or phenylethyl.More preferably, R 7And R 8Group is selected from phenyl, halogenated phenyl, aminomethyl phenyl or halogenated aminomethyl phenyl.
Examples of suitable compounds include, but are not limited to: (R) -1 - phenyl-1 ,3 - propanediol dibenzoate, (S) -1 - phenyl-1 ,3 - propanediol dibenzoate, 1,3 - Phenyl-1 ,3 - propanediol dibenzoate, 1,3 - diphenyl-2 - methyl-1,3 - propanediol dibenzoate, 1,3 - Diphenyl-1 ,3 - propylene glycol n-propyl ester, 1,3 - diphenyl-2 - methyl-1,3 - propanediol dipropionate, 1,3 - Diphenyl-2 - methyl-1,3 - propanediol diacetate, 1,3 - diphenyl-2 ,2 - dimethyl-1 ,3 - propanediol benzophenone Ester, 1,3 - diphenyl-2 ,2 - dimethyl-1 ,3 - propanediol dipropionate, 1,3 - di-tert-butyl-2 - ethyl-1 ,3 - Propylene glycol dibenzoate, 1,3 - diphenyl-1 ,3 - propanediol diacetate, 1,3 - diisopropyl-1 ,3 - propanol two (4 - butyl benzoic acid) ester, 1 - phenyl - 2 - amino-1 ,3 glycol benzoate, 1 - phenyl - 2 - methyl-1 ,3 - Butylene glycol benzoate, phenyl-2 - methyl-1,3 - butanediol bis neopentyl ester, 1 - furan-2 - methyl-1 ,3 - D Glycol dibenzoate, 4,4,4 - trifluoro-1 - (2 - naphthyl) - 1,3-butylene glycol dibenzoate, 2,4 - pentyl glycol Benzoate 3 - methyl-2 ,4 - pentanediol dibenzoate 3 - ethyl-2 ,4 - pentanediol dibenzoate 3 - Propyl 2,4 - pentanediol dibenzoate 3 - butyl 2,4 - pentanediol dibenzoate, 3,3 - dimethyl-2 ,4 - Pentanediol dibenzoate, (2S, 4S) - (+) -2,4 - pentanediol dibenzoate, (2R, 4R) - (+) 2,4 - pentanediol dibenzoate, 2,4 - pentanediol di (p-chlorobenzoic acid) ester, 2,4 - pentanediol di (m-chloroperbenzoic Acid) ester, 2,4 - pentanediol di (p-bromo-benzoic acid) ester, 2,4 - pentanediol di (o-bromo-benzoic acid) ester, 2,4 - pentanediol di (p-methylbenzoate) acrylate, 2,4 - pentanediol di (p-tert-butylbenzoic acid) ester, 2,4 - Neopentyl glycol di (p-butyl benzoic acid) ester, 2,4 - pentanediol, cinnamic acid esters, 2,4 - pentanediol two cinnamon Ester, 1,3 - pentanediol dipropionate 2 - methyl-1 ,3 - pentanediol dibenzoate 2 - methyl-1 ,3 - pentanediol Bis (p-chlorobenzoic acid) ester of 2 - methyl-1,3 - pentanediol di (p-methylbenzoate) ester 2 - butyl-1 ,3 - Neopentyl glycol di (p-methylbenzoate) ester of 2 - methyl-1,3 - pentanediol di (p-tert-butylbenzoic acid) ester, 2 - methyl-1,3 - pentanediol, neopentyl ester 2 - methyl-1,3 - pentanediol, cinnamic acid esters, 2,2 - dimethyl-1 ,3 - Pentanediol dibenzoate, 2,2 - dimethyl-1 ,3 - pentanediol, cinnamic acid ester 2 - ethyl-1 ,3 - glutaryl Alcohol dibenzoate 2 - butyl-1 ,3 - pentanediol dibenzoate 2 - allyl 1,3 - pentanediol dibenzoate Esters of 2 - methyl-1,3 - pentanediol, cinnamic acid ester 2 - methyl-1,3 - pentanediol dibenzoate 2 - B Yl 1,3 - pentanediol dibenzoate 2 - propyl-1 ,3 - pentanediol dibenzoate 2 - butyl-1 ,3 - pentanediol Dibenzoate, 2,2 - dimethyl-1 ,3 - pentanediol dibenzoate, 1,3 - pentanediol di (p-chlorobenzoic acid) Ester, 1,3 - pentanediol di (m-chloroperbenzoic acid) ester, 1,3 - pentanediol di (p-bromo-benzoic acid) ester, 1,3 - E Glycol di (o-bromo-benzoic acid) ester, 1,3 - pentanediol di (p-methylbenzoate) acrylate, 1,3 - pentanediol di (p- Tert-butyl benzoic acid) ester, 1,3 - pentanediol di (p-butyl benzoic acid) ester, 1,3 - pentanediol, cinnamic acid Ester, 1,3 - pentyl glycol cinnamate, 1,3 - pentanediol dipropionate 2 - methyl-1,3 - pentanediol benzophenone Ester 2 - methyl-1,3 - pentanediol di (p-chlorobenzoic acid) ester of 2 - methyl-1,3 - pentanediol di (p-methyl Acid) ester of 2 - butyl-1 ,3 - pentanediol di (p-methylbenzoate) ester 2 - methyl-1 - pentyl glycol (Tert-butyl benzoic acid) ester of 2 - methyl-1,3 - pentanediol, neopentyl ester 2 - methyl-1,3 - pentanediol benzoic Cinnamic acid esters, 2, 2 - dimethyl-1 ,3 - pentanediol dibenzoate, 2,2 - dimethyl-1 ,3 - pentanediol benzoic Cinnamic acid ester 2 - ethyl-1 ,3 - pentanediol dibenzoate 2 - butyl-1 ,3 - pentanediol dibenzoate 2 - Allyl 1,3 - pentanediol dibenzoate 2 - methyl-1,3 - pentanediol, cinnamic acid ester, 2,2,4 - trimethoxyphenyl Yl 1,3 - pentanediol, diisopropyl ester, 1 - trifluoromethyl-3 - methyl-2 ,4 - pentanediol dibenzoate, 2,4 - Pentanediol two pairs fluoromethyl benzoate, 2,4 - pentanediol di (2 - furoic acid) ester of 3 - methyl - 3 - D Yl -2,4 - pentanediol dibenzoate 2 - ethyl-1 ,3 - hexanediol dibenzoate 2 - propyl-1 ,3 - hexanediol Dibenzoate 2 - butyl-1 ,3 - hexanediol dibenzoate ester, 4 - ethyl-1,3 - hexanediol dibenzoate ester, 4 - Methyl 1,3 - hexanediol dibenzoate 3 - methyl 1,3 - hexanediol dibenzoate 3 - ethyl-1 ,3 - hexanediol Alcohol dibenzoate, 2,2,4,6,6 - pentamethyl-3, 5 - hexanediol dibenzoate, 6 - heptene 2,4 - heptane diol Benzoate 2 - methyl-6 - heptene 2,4 - heptane diol dibenzoate 3 - methyl-6 - heptene 2,4 - heptane diol Dibenzoate ester, 4 - methyl-6 - heptene 2,4 - heptane diol dibenzoate, 5 - methyl-6 - heptene 2,4 - heptane diol Dibenzoate, 6 - methyl-6 - heptene 2,4 - heptane diol dibenzoate 3 - ethyl-6 - heptene 2,4 - heptane diol Dibenzoate ester, 4 - ethyl-6 - heptene 2,4 - heptane diol dibenzoate, 5 - ethyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate, 6 - ethyl-6 - heptene 2,4 - heptane diol dibenzoate 3 - propyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate ester, 4 - propyl-6 - heptene 2,4 - heptane diol dibenzoate, 5 - propyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate, 6 - propyl-6 - heptene 2,4 - heptane diol dibenzoate 3 - butyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate ester, 4 - butyl-6 - heptene 2,4 - heptane diol dibenzoate, 5 - butyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate, 6 - butyl-6 - heptene 2,4 - heptane diol dibenzoate, 3,5 - dimethyl-6 - heptene-2, 4 - Heptane diol dibenzoate, 3,5 - diethyl-6 - heptene 2,4 - heptane diol dibenzoate, 3,5 - propyl-6 - Heptene 2,4 - heptane diol dibenzoate, 3,5 - butyl-6 - heptene 2,4 - heptane diol dibenzoate, 3,3 - Dimethyl-6 - heptene 2,4 - heptane diol dibenzoate, 3,3 - diethyl-6 - heptene 2,4 - heptane diol benzophenone Ester, 3,3 - propyl-6 - heptene 2,4 - heptane diol dibenzoate, 3,3 - butyl-6 - heptene-2 ​​,4 - heptadienoic Alcohol dibenzoate, 3,5 - heptane diol dibenzoate 2 - methyl-3 ,5 - heptane diol dibenzoate 3 - methyl -3 ,5 - heptane diol dibenzoate ester, 4 - methyl-3 ,5 - heptane diol dibenzoate, 5 - methyl-3 ,5 - heptanediol Dibenzoate, 6 - methyl-3 ,5 - heptane diol dibenzoate 3 - ethyl 3,5 - heptane diol dibenzoate ester, 4 - Ethyl-3 ,5 - heptane diol dibenzoate, 5 - ethyl-3 ,5 - heptane diol dibenzoate 3 - propyl-3 ,5 - pimelic Alcohol dibenzoate ester, 4 - propyl 3,5 - heptane diol dibenzoate 3 - butyl 3,5 - heptane diol dibenzoate, 2,3 - dimethyl-3 ,5 - heptane diol dibenzoate, 2,4 - dimethyl-3 ,5 - heptane diol dibenzoate, 2,5 - Methyl-3 ,5 - heptane diol dibenzoate, 2,6 - dimethyl-3 ,5 - heptane diol dibenzoate, 3,3 - dimethyl-3 ,5 - Heptane glycol dibenzoate, 4,4 - dimethyl-3 ,5 - heptane diol dibenzoate, 6,6 - dimethyl-3 ,5 - heptanedionate Alcohol dibenzoate, 2,6 - dimethyl-3 ,5 - heptane diol dibenzoate, 3,4 - dimethyl -3,5 - diphenyl heptanediol Methyl ester, 3,5 - dimethyl-3 ,5 - heptane diol dibenzoate, 3,6 - dimethyl-3 ,5 - heptane diol dibenzoate, 4,5 - dimethyl-3 ,5 - heptane diol dibenzoate, 4,6 - dimethyl-3 ,5 - heptane diol dibenzoate, 4,4 - Methyl-3 ,5 - heptane diol dibenzoate, 6,6 - dimethyl-3 ,5 - heptane diol dibenzoate, 2 - methyl -3 - acetic -3 ,5 - heptane diol dibenzoate, 2 - methyl -4 - ethyl 3,5 - heptane diol dibenzoate, 2 - methyl -5 - B -3 ,5 - heptane diol dibenzoate 3 - methyl - 3 - ethyl-3 ,5 - heptane diol dibenzoate 3 - methyl - 4 - ethyl -3 ,5 - heptane diol dibenzoate 3 - methyl-5 - ethyl-3 ,5 - heptane diol dibenzoate ester, 4 - methyl - 3 - acetic -3 ,5 - heptane diol dibenzoate ester, 4 - methyl - 4 - ethyl-3,5 - heptane diol dibenzoate ester, 4 - methyl-5 - ethyl -3 ,5 - heptane diol dibenzoate, 2 - methyl -3 - propyl 3,5 - heptane diol dibenzoate, 2 - methyl -4 - C -3 ,5 - heptane diol dibenzoate, 2 - methyl -5 - propyl 3,5 - heptane diol dibenzoate 3 - methyl - 3 - C -3 ,5 - heptane diol dibenzoate 3 - methyl - 4 - propyl 3,5 - heptane diol dibenzoate 3 - methyl-5 - C -3 ,5 - heptane diol dibenzoate ester, 4 - methyl - 3 - propyl-3,5 - heptane diol dibenzoate ester, 4 - methyl - 4 - C -3 ,5 - heptane diol dibenzoate ester, 4 - methyl-5 - propyl 3,5 - heptane diol dibenzoate, 6 - methyl-2 ,4 - Heptane diol di (p-chlorobenzoic acid) ester, 6 - methyl-2 ,4 - heptane diol di (p-methylbenzoate) ester, 6 - methyl-2 ,4 - Heptane glycol di (-methyl benzoic acid) ester, 6 - methyl-2 ,4 - heptane neopentyl glycol ester, 6 - heptene-2 ​​,4 - heptadienoic Neopentyl glycol dimethyl ester, 3,6 - dimethyl 2,4 - heptane diol dibenzoate, 2,2,6,6 - tetramethyl-3 ,5 - heptanediol Dibenzoate ester, 4 - methyl-3,5 - octanediol dibenzoate ester, 4 - ethyl-3,5 - octanediol dibenzoate ester, 4 - Propyl-3 ,5 - dibenzoate octanediol, 5 - propyl 3,5 - octanediol dibenzoate ester, 4 - butyl-3 ,5 - octanediol Alcohol dibenzoate, 4,4 - dimethyl-3 ,5 - dibenzoate octanediol, 4,4 - diethyl 3,5 - diphenyl octanediol Methyl ester, 4,4 - dipropyl-3 ,5 - octanediol dibenzoate ester, 4 - methyl - 4 - ethyl-3,5 - octanediol benzophenone Ester 3 - phenyl-3 ,5 - dibenzoate octanediol, 2 - methyl -3 - ethyl-3 ,5 - dibenzoate octanediol, 2 - methyl -4 - ethyl 3,5 - octanediol dibenzoate, 2 - methyl -5 - ethyl-3 ,5 - dibenzoate octanediol, 2 - methyl-6 - ethyl-3 ,5 - dibenzoate octanediol, 5 - methyl-4 ,6 nonane diol dibenzoate, 5 - ethyl - Nonane diol dibenzoate 4,6, 5 - propyl-nonane diol dibenzoate 4,6, 5 - diphenyl butyl-4 ,6 nonanediol Methyl ester, 5,5 - dimethyl -4,6 nonane diol dibenzoate, 5,5 - diethyl 4,6 nonane diol dibenzoate 5,5 - dipropyl-4 ,6 nonane diol dibenzoate, 5,5 - dibutyl-nonane diol dibenzoate 4,6, 5 - methyl - 4 - ethyl-4 ,6 nonane diol dibenzoate, 5 - phenyl-4 ,6 nonane diol dibenzoate, 4,6 - diphenyl nonanediol Methyl ester 4 - butyl-3 ,5 - heptane diol dibenzoate 3 - methyl - 3 - butyl -2,4 - diphenyl-pentanediol acid Esters. ...
Preferably, the ingredient of solid catalyst that is used for olefinic polymerization of the present invention comprises following titanium compound, magnesium compound and is selected from the have general formula reaction product of diol ester compound of (I).
Wherein used magnesium compound is selected from a kind of in one of them halogen atom alkoxy in the hydrate of magnesium dihalide, alkoxyl magnesium, alkyl magnesium, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula or the halogenated alkoxy institute metathetical derivative or their mixture; The alcohol adduct of preferred magnesium dihalide or magnesium dihalide, for example magnesium dichloride, dibrominated magnesium, two magnesium iodides and their alcohol adduct.
It is TiX that wherein used titanium compound can be selected general formula for use n(OR) 4-nCompound, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.For example: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
What particularly point out is magnesium compound, preferably is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.Wherein organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).
Wherein organo phosphorous compounds comprises the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite benzene methyl.
Can select to press the method for stating and prepare ingredient of solid catalyst of the present invention.
At first, magnesium compound is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, mixes with titanium compound behind the formation homogeneous solution, in the presence of precipitation additive, separate out solids; This solids by using is selected from the propylene glycol ester compound compound of general formula (I) and handles, it is attached on the solids, in case of necessity, with titanium tetrahalide and inert diluent solids is handled again, wherein precipitation additive is a kind of in organic acid anhydride, organic acid, ether, the ketone, or their mixture.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.
Described each component is in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, and organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0～1.0 mole, titanium compound is 0.5～150 mole, and the propylene glycol ester compound of general formula (I) is 0.02～0.4 mole.
According to another kind of method, be to be TiX with general formula n(OR) 4-nTitanium compound, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4, preferred TiCl 4, with general formula be MgCl 2The adducts of pROH reacts and the preparation ingredient of solid catalyst.At MgCl 2Among the pROH, p is 0.1 to 6 number, and is preferred 2 to 3.5, and R is the alkyl with 1-18 carbon atom.Adducts can be made spherical by the following method aptly: not with the miscible unreactive hydrocarbons of adducts in the presence of, pure and mild magnesium chloride is mixed, make the rapid chilling of this emulsion, thereby adducts solidified with the form of spheroidal particle.The adducts that so obtains can be directly and the titanium compound reaction, perhaps it can pass through the dealcoholization (80-130 ℃) of thermal control to obtain a kind of adducts in advance before reacting with titanium compound, wherein Chun mole number generally is lower than 3, preferably between 0.1 and 2.7.Can be by adducts (dealcoholysis or itself) be suspended in cold TiCl 4In (general 0 ℃), and with the mixture temperature programming to 80-130 ℃ and under this temperature, kept 0.1-2 hour, carry out reaction with titanium compound.TiCl 4Processing can be carried out once or repeatedly.Using TiCl 4Can add the above-mentioned dibasic alcohol ester compound of general formula the present invention during the processing and handle, this processing also can repeat once or repeatedly.
Another object of the present invention is to provide a kind of CH of being used for 2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C 1-C 6Alkyl or aryl, comprise the reaction product of following component: (1) a kind of above-mentioned propylene glycol ester compound that contains magnesium, titanium, halogen and be selected from general formula (I): ingredient of solid catalyst; (2) alkylaluminium cpd; (3) randomly, external electron donor component.
Wherein alkylaluminium cpd is that general formula is AlR nX 3-nCompound, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, X is a halogen, n is the number of 1＜n≤3; Specifically can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
When needing the very high olefin polymer of taxis to use, need to add (3) external electron donor compound, for example general formula is R nSi (OR) 4-nSilicoorganic compound, 0≤n in the formula≤3, R and R Be of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, R also can be halogen or hydrogen atom.For example: the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, two (cyclobutylmethyl) dimethoxy silane.
The ratio between component (1), component (2) and the component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500; Be preferably 1: 25～100: 25～100.
Above-mentioned external electron donor component also can be selected from monobasic or polybasic organic acid ester, for example monobasic or polybasic benzoates.Preferred monobasic benzoates.
1 of the also optional self-drifting of above-mentioned external electron donor component (II), 3-two ethers:
R wherein I, R II, R III, R IV, R VAnd R VIIdentical or different, for hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom, and R VIIAnd R VIIICan be identical or different, for having the hydrocarbyl group of 1 to 18 carbon atom; R I-R VIIIGroup in one or morely can link up into ring.Preferably, R VIIAnd R VIIIBe selected from C 1-C 4Alkyl group, R IIIAnd R IVForm undersaturated condensed ring, and R I, R H, R V, and R VIBe hydrogen.For example: 9, two (methoxymethyl) fluorenes of 9-.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, perhaps also can carry out under the operation of liquid and gas polymerization stage combination.Adopt conventional technology such as slurry process, gas-phase fluidized-bed etc., wherein alkene is selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1 hexene, the equal polymerization of special propylene with or the copolymerization of other alkene of propylene.Be to adopt following reaction conditions preferably:
Polymerization temperature: 0～150 ℃, preferred 60～90 ℃.
Catalyzer of the present invention can directly add and be used for polymerization process in the reactor.Perhaps, catalyzer can carry out prepolymerization before adding first polymerization reactor.In the present invention, term " pre-polymerized catalyst " means with the catalyzer of low transforming degree through polymerization procedure.According to the present invention, described pre-polymerized catalyst comprises the prepolymer that above-mentioned ingredient of solid catalyst and alkene carry out the prepolymerization gained, and the pre-polymerization multiple is 0.1-1000g olefin polymer/g ingredient of solid catalyst.
Can adopt the alpha-olefin identical to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene with aforementioned alkene.Specifically, particularly preferably be, the mixture that adopts ethene or itself and amount to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is that about 0.2 gram is to about 500 gram polymkeric substance/gram ingredients of solid catalyst.
The prepolymerization operation can under preferred 0 to the 50 ℃ temperature, be carried out in liquid or in the gas phase at-20 to 80 ℃.Prepolymerization step can be used as online the carrying out of a part in the continuous polymerization technique, or carries out independently in periodical operation.For preparation amount is the polymkeric substance of 0.5-20g/g catalyst component, the batch pre-polymerization of preferred especially catalyzer of the present invention and ethene.Polymerization pressure is 0.01-10MPa.
Catalyzer of the present invention also is applicable to produces polyethylene and ethene and alpha-olefin, as the multipolymer of propylene, butylene, amylene, hexene, octene, 4-methylpentene-1.
It is worthy of note that the present invention is by adopting novel internal electron donor diol ester compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain the polymkeric substance of higher degree of isotacticity, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment embodiment given below is for the present invention is described, rather than limits the invention.Testing method: 1, fusing point: adopt XT4A micro melting point apparatus (temperature control type).2, the mensuration of nucleus magnetic resonance: use Bruke dmx300 nuclear magnetic resonance analyser Instrument measuring 1H-NMR (300MHz, solvent C DCl 3, TMS is interior mark, measures temperature 300K).3, polymericular weight and molecular weight distribution MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method,
With PL-GPC220 is that solvent is measured (standard specimen: polystyrene, flow velocity: 1.0 down at 150 ℃ with the trichlorobenzene
Ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).4, the polymkeric substance degree of isotacticity adopts the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant are poly-
Laminate samples was placed in the extractor with the extracting of boiling heptane after 6 hours, and the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.5, the mensuration of infrared spectrum: adopt the MAGNA-IR 760 type infrared spectrometers of NICOLET company, conventional method of analysis.6, the mensuration of melt index: according to ASTM D1238-99 measure one, the synthetic embodiment 12 of diol ester compound, 4-pentanediol dibenzoate synthetic
The preparation of (1) 2,4-pentanediol
10g 2, and 4-diacetylmethane and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.1g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets colourless liquid 2,4-pentanediol 9.4g, yield 90%.The IR spectrogram is at 3400cm -1There is strong absorption peak at the place, and at 1700cm -1About do not have absorption peak, prove that reduction reaction carries out fully.
The preparation of (2) 2,4-pentanediol dibenzoates
2, (3.1g, 0.03mol) middle 30ml tetrahydrofuran (THF) and 7.1g (0.09mol) pyridine of adding under agitation adds 10.5g (0.075mol) Benzoyl chloride, reflux 4h to the 4-pentanediol.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol dibenzoate 8.9g, yield 95%.
1H NMR (TMS, CDCl 3, ppm): δ 1.3～1.4 (8H, m, methyl H), 2.0～2.1 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H) embodiment 2 (2S, 4S)-(+)-2,4-pentanediol dibenzoate synthetic
(2S, 4S)-(+)-2,4-pentanediol 3.1g adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine among the 0.03mol, under agitation add the 0.075mol Benzoyl chloride, reflux 4 hours.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography get colourless liquid (2S, 4S)-(+)-2,4-pentanediol dibenzoate 8.9g, yield 95%.
1H NMR (TMS, CDCl 3, ppm): δ 1.2～1.4 (8H, m, methyl H), 2.0～2.1 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), δ 7.3～8.0 (10H, m, phenyl ring H).Embodiment 3 (2R, 4R)-(+)-2,4-pentanediol dibenzoate synthetic
Method is preparation embodiment 2 together, just use (2R, 4R)-(+)-2, the replacement of 4-pentanediol (2S, 4S)-(+)-2, the 4-pentanediol. 1HNMR (TMS, CDCl 3, ppm): δ 1.3～1.4 (8H, m, methyl H), 2.0～2.1 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).Embodiment 42, the preparation of 4-pentanediol two (m-chlorobenzoic acid) ester
0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol m-chlorobenzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 2,4-pentanediol two (m-chlorobenzoic acid) ester, yield 95%. 1HNMR (TMS, CDCl 3) δ (ppm): 1.3～1.4 (6H, d, methyl H), 1.9～2.3 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.3～8.1 (8H, m, phenyl ring H).Embodiment 52, the preparation of 4-pentanediol two (parabromobenzoic acid) ester
The preparation method just replaces m-chlorobenzoyl chloride with parabromobenzoyl chloride with preparation embodiment 4, gets colourless liquid 2,4-pentanediol two (parabromobenzoic acid) ester, yield 90% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.3～1.4 (6H, d, methyl H), 1.8～2.2 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.4～7.9 (8H, m, phenyl ring H).Embodiment 62, the preparation of 4-pentanediol two (o-bromobenzoic acid) ester
The preparation method just replaces m-chlorobenzoyl chloride with adjacent bromo-benzoyl chloride with preparation embodiment 4, gets colourless liquid 2,4-pentanediol two (o-bromobenzoic acid) ester, yield 90% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.3～1.4 (6H, m, methyl H), 2.06～2.09 (2H, d, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.3～7.9 (8H, m, phenyl ring H).Embodiment 72, the preparation of 4-pentanediol two (aligning butylbenzoic acid) ester
The preparation method just uses the n-butylbenzene formyl chloride is replaced m-chlorobenzoyl chloride with preparation embodiment 4, gets colourless liquid 2,4-pentanediol two (aligning butylbenzoic acid) ester, yield 90% at last. 1HNMR (TMS, CDCl 3, ppm): δ 0.91～0.98 (6H, m, the methyl H of butyl), 1.3～1.4 (8H, m, the methylene radical H of butyl), 1.5～1.6 (6H, m, methyl H), 2.0～2.1 (2H, t, methylene radical H), 2.6～2.7 (4H, t, the methylene radical H of butyl), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).Embodiment 82, the preparation of 4-pentanediol phenylformic acid laurate
0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.04mol pyridine in the 4-pentanediol, under agitation add the 0.03mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml tetrahydrofuran (THF) and 0.05mol pyridine, under agitation adds the 0.04mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol phenylformic acid laurate, yield 89%.
1HNMR (TMS, CDCl 3, ppm): δ 0.8～1.4 (8H, m, methyl H), 1.9～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 6.2～8.0 (12H, m, phenyl ring and two key H).Embodiment 92, the preparation of 4-pentanediol two laurates
The preparation method just replaces m-chlorobenzoyl chloride with cinnamyl chloride with preparation embodiment 4, gets colourless viscous liquid 2,4-pentanediol two laurates, yield 88% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.2～1.3 (6H, m, methyl H), 2.0～2.1 (2H, d, methylene radical H), 5.1～5.2 (2H, m, the methyne H of ester group), 6.3～7.6 (14H, m, phenyl ring and two key H).Embodiment 102, the preparation of 4-pentanediol dipropionate
The preparation method just replaces m-chlorobenzoyl chloride with propionyl chloride with preparation embodiment 4, gets colourless liquid 2,4-pentanediol dipropionate, yield 95% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.0～1.1 (6H, d, methyl H), 1.21～1.24 (6H, t, methyl H), 1.74～1.77 (2H, m, methylene radical H), 2.2～2.3 (4H, m, the methylene radical H of propionyloxy), 5.1～5.2 (2H, m, the methyne H of ester group) embodiment 112-methyl-2, the preparation of 4-pentanediol dibenzoate
0.03mol 2-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 2-methyl-2,4-pentanediol dibenzoate, yield 88%. 1HNMR (TMS, CDCl 3, ppm): δ 1.42～1.43 (3H, d, methyl H), 1.68 (6H, s, methyl H), 2.2～2.7 (2H, d, methylene radical H), 5.53～5.58 (1H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).Embodiment 123, the preparation of 5-heptanediol dibenzoate
The preparation of (1) 3,5-heptanediol
14.2g 3,5-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, get white solid 3,5-heptanediol, yield 90%.The IR spectrogram is at 3400cm -1There is strong absorption peak at the place, and at 1700cm -1About do not have absorption peak, prove that reduction reaction carries out fully.m.p.60～65℃。
The preparation of (2) 3,5-heptanediol dibenzoates
0.03mol 3, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 3,5-heptanediol dibenzoate, yield 92%. 1HNMR (TMS, CDCl 3, ppm): δ 0.9～1.0 (6H, m, methyl H), 1.7～1.8 (4H, m, the methylene radical H of ethyl), 2.0～2.1 (2H, m, methylene radical H), 5.21～5.27 (2H, m, the methyne H of ester group), 7.3～8.1 (10H, m, phenyl ring H).Embodiment 132,6-dimethyl-3, the preparation of 5-heptanediol dibenzoate
(1) 2,6-dimethyl-3, the preparation of 5-heptanediol
The preparation method is with 2 with preparation embodiment 12 (1), 6-dimethyl-3, and the 5-heptadione replaces 3, the 5-heptadione, last underpressure distillation is collected cut and is got colourless liquid 2,6-dimethyl-3,5-heptanediol, yield 90%.
(2) 2,6-dimethyl-3, the preparation of 5-heptanediol dibenzoate
The preparation method is with 2 with preparation embodiment 12 (2), 6-dimethyl-3, and the 5-heptanediol replaces 3, and the 5-heptanediol gets colourless liquid 2,6-dimethyl-3,5-heptanediol dibenzoate, yield 88% at last. 1HNMR (TMS, CDCl 3, ppm): δ 0.95～0.99 (12H, m, methyl H), 1.9～2.0 (4H, m, methylene radical and methyne H), 5.10～5.17 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H).Embodiment 146-methyl-2, the preparation of 4-heptanediol dibenzoate
(1) 6-methyl-2, the preparation of 4-heptanediol
The preparation method is with preparation embodiment 12 (1), and just with 6-methyl-3, the 5-heptadione replaces 3, the 5-heptadione, and last underpressure distillation is collected cut and is got colourless liquid 3-methyl-3-butyl-2,4-pentanediol, yield 90%.
(2) 6-methyl-2, the preparation of 4-heptanediol dibenzoate
The preparation method is preparation embodiment 12 (2) together, and just with 6-methyl-3, the 5-heptanediol replaces 3, and the 5-heptanediol gets colourless liquid 6-methyl-2,4-heptanediol dibenzoate, yield 95% at last. 1HNMR (TMS, CDCl 3, ppm): δ 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 5.3～5.5 (2H, m, methyne H), 7.2～8.0 (10H, m, phenyl H).Embodiment 156-methyl-2, the preparation of 4-heptanediol two (p-methylbenzoic acid) ester
The preparation method just uses methyl benzoyl chloride is replaced Benzoyl chloride with preparation embodiment 12 (2), gets colourless liquid 6-methyl-2,4-heptanediol two (p-methylbenzoic acid) ester, yield 95% at last. 1HNMR (TMS, CDCl 3, ppm): δ 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 2.3～2.4 (6H, m, arylmethyl H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～7.9 (8H, m, phenyl H).Embodiment 163-methyl-2, the preparation of 4-pentanediol dibenzoate
(1) 3-methyl-2, the preparation of 4-diacetylmethane
0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 2, the 4-diacetylmethane.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect 84～86 ℃/4kPa of cut (normal pressure is 165～166 ℃), yield 94%.
(2) 3-methyl-2, the preparation of 4-pentanediol
The preparation method is with preparation embodiment 12 (1), and just with 3-methyl-2, the 4-diacetylmethane replaces 3, the 5-heptadione, and last underpressure distillation is collected cut and is got colourless liquid 3-methyl-2,4-pentanediol, yield 90%.
(3) 3-methyl-2, the preparation of 4-pentanediol dibenzoate
The preparation method is preparation embodiment 12 (2) together, and just with 3-methyl-2, the 4-pentanediol replaces 3, and the 5-heptanediol gets colourless liquid 3-methyl-2,4-pentanediol dibenzoate, yield 95%. 1HNMR (TMS, CDCl 3, ppm): δ 1.1～1.2 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 2.0～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).Embodiment 173-methyl-2, the preparation of 4-pentanediol two (Chlorodracylic acid) ester
The preparation method just replaces Benzoyl chloride with parachlorobenzoyl chloride with preparation embodiment 16 (3), gets colourless liquid 3-methyl-2,4-pentanediol two (Chlorodracylic acid) ester, yield 92% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.0～1.1 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.9～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 7.3～7.9 (8H, m, phenyl ring H).Embodiment 183-methyl-2, the preparation of 4-pentanediol two (p-methylbenzoic acid) ester
The preparation method just uses methyl benzoyl chloride is replaced Benzoyl chloride with preparation embodiment 16 (3), gets white solid 3-methyl-2,4-pentanediol two (p-methylbenzoic acid) ester, yield 92% at last.m.p.91～92℃。 1HNMR (TMS, CDCl 3, ppm): δ 1.1～1.2 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 2.1～2.2 (1H, m, methyne H), 2.3～2.4 (6H, m, the methyl H of phenyl ring), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).Embodiment 193-butyl-2, the preparation of 4-pentanediol two (p-methylbenzoic acid) ester
The preparation method is preparation embodiment 12 together, and just with 3-butyl-2, the 4-diacetylmethane replaces 3, and the 5-heptadione gets colourless liquid 3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester, yield 95% at last. 1HNMR δ (TMS, CDCl 3, ppm): 0.8～0.9 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.5～1.7 (6H, m, methylene radical H), 1.9～2.0 (1H, m, methyne H), 2.3～2.4 (6H, m, the methyl H of phenyl ring), 5.3～5.4 (2H, m, the methyne H of ester group), 7.0～8.0 (8H, m, phenyl ring H).Embodiment 203-methyl-2, the preparation of 4-pentanediol two (p-tert-butyl benzoic acid) ester
The preparation method just uses the tert.-butylbenzene formyl chloride is replaced Benzoyl chloride with preparation embodiment 16 (3), gets colourless liquid 3-methyl-2,4-pentanediol two (p-tert-butyl benzoic acid) ester, yield 90% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.1～1.4 (27H, m, methyl H), 2.0～2.1 (1H, m, methyne H), 5.2～5.4 (2H, m, the methyne H of ester group), 7.4～8.1 (8H, m, phenyl ring H) embodiment 213-methyl-2, the preparation of 4-pentanediol phenylformic acid laurate
The preparation method is preparation embodiment 8 together, and just with 3-methyl-2, the 4-pentanediol replaces 2, and the 4-pentanediol gets colourless viscous liquid 3-methyl-2,4-pentanediol phenylformic acid laurate, yield 86% at last. 1HNMR (TMS, CDCl 3, ppm): δ 0.8～1.4 (9, m, methyl H), 1.9～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 6.2～8.0 (12H, m, phenyl ring and two key H).Embodiment 223,3-dimethyl-2, the preparation of 4-pentanediol dibenzoate
(1) 3,3-dimethyl-2, the preparation of 4-diacetylmethane
0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.12mol 3-methyl-2, the 4-diacetylmethane.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect 82～84 ℃/1kPa of cut, yield 98%.
(2) 3,3-dimethyl-2, the preparation of 4-pentanediol
The preparation method is with 3 with preparation embodiment 12 (1), 3-dimethyl-2, and the 4-diacetylmethane replaces 3, the 5-heptadione, last underpressure distillation is collected cut and is got colourless liquid 3,3-dimethyl-2,4-pentanediol, yield 90%.
(3) 3,3-dimethyl-2, the preparation of 4-pentanediol dibenzoate
The preparation method is preparation embodiment 12 (2) together,, just with 3,3-dimethyl-2, the 4-pentanediol replaces 3, and the 5-heptanediol gets colourless liquid 3,3-dimethyl-2,4-pentanediol dibenzoate, yield 95% at last. 1HNMR (TMS, CDCl 3, ppm): δ 1.1～1.2 (6H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.4～8.1 (10H, m, phenyl ring H).Embodiment 233,3-dimethyl-2, the preparation of 4-pentanediol one phenylformic acid one laurate
0.03mol 3,3-dimethyl-2 adds 30ml tetrahydrofuran (THF) and 0.04mol pyridine in the 4-pentanediol, under agitation add the 0.03mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml tetrahydrofuran (THF) and 0.05mol pyridine, under agitation adds the 0.04mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate, yield 88%. 1HNMR (TMS, CDCl 3, ppm): δ 1.0～1.1 (6H, m, methyl H), 1.2～1.3 (6H, m, methyl H), 5.0～5.2 (2H, m, the methyne H of ester group), 6.3～8.0 (12H, m, phenyl ring and two key H).Embodiment 243-ethyl-2,4-pentanediol dibenzoate synthetic
(1) 3-ethyl-2, the preparation of 4-diacetylmethane
In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol iodoethane under the normal temperature, after dropwising, continue reaction 48hr at normal temperatures.
After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 6.5g product.
(2) 3-ethyl-2, the preparation of 4-pentanediol
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively 4, 100mlTHF.Slowly be added dropwise to 0.04mol3-ethyl-2 under the ice-water bath condition, 4-diacetylmethane, normal temperature continue reaction 48hr down.
Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 3.4g product.
(3) 3-ethyl-2, the preparation of 4-pentanediol dibenzoate
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol3-ethyl-2 successively, 4-pentanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, use anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 5.1g product. 1HNMR (TMS, CDCl 3, ppm): δ 7.25～8.17 (10H, phenyl ring H), 5.39～5.47 (2H, CH), 1.80 (1H, CH), 1.66 (2H, CH 2), 1.1～1.42 (9H, CH 3).Embodiment 253-butyl-2, the preparation of 4-pentanediol dibenzoate
(1) 3-butyl-2, the preparation of 4-pentanediol
The preparation method is preparation embodiment 12 (1) together, and just with 3-butyl-2, the 4-diacetylmethane replaces 3, and the 5-heptadione gets colourless liquid 3-butyl-2,4-pentanediol, yield 90% at last.
(2) 3-butyl-2, the preparation of 4-pentanediol dibenzoate
The preparation method is preparation embodiment 12 (2) together, and just with 3-butyl-2, the 4-pentanediol replaces 3, and the 5-heptanediol gets colourless liquid 3-butyl-2,4-pentanediol dibenzoate, yield 95% at last. 1HNMR (TMS, CDCl 3, ppm): 0.8～0.9 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.5～1.6 (6H, m, methylene radical H), 2.0～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H).Embodiment 264-methyl-3, the preparation of 5-heptanediol dibenzoate
(1) 4-methyl-3, the preparation of 5-heptadione
0.02mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.02mol 3, the 5-heptadione.Finish and stir 0.5h, slowly drip 0.04mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, separate out white solid.Filter, washing gets white solid 4-methyl-3,5-heptadione, yield 94% after the drying.m.p.91～92℃。
(2) 4-methyl-3, the preparation of 5-heptanediol
The preparation method is preparation embodiment 12 (1) together, and just with 4-methyl-3, the 5-heptadione replaces 3, and the 5-heptadione gets colourless liquid 4-methyl-3,5-heptanediol, yield 90% at last.
(3) 4-methyl-3, the preparation of 5-heptanediol dibenzoate
The preparation method is preparation embodiment 12 (2) together, and just with 4-methyl-3, the 5-heptanediol replaces 3, and the 5-heptanediol gets colourless liquid 4-methyl-3,5-heptanediol dibenzoate, yield 88% at last.
1HNMR (TMS, CDCl 3, ppm): δ 0.9～1.0 (6H, m, methyl H), 1.1～1.2 (3H, m, methyl H), 1.7～1.8 (4H, m, the methylene radical H of ethyl), 2.1～2.2 (1H, m, methylene radical H), 5.21～5.27 (2H, m, the methyne H of ester group), 7.3～8.1 (10H, m, phenyl ring H).Embodiment 272-ethyl-1, the preparation of 3-hexylene glycol dibenzoate
0.03mol 2-ethyl-1 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 3-hexylene glycol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 2-ethyl-1,3-hexylene glycol dibenzoate, yield 91%.
1HNMR (TMS, CDCl 3, ppm): δ 0.9～1.1 (6H, m, methyl H), 1.4～1.6 (6H, m, methylene radical H), 2.2～2.3 (1H, m, methyne H), 4.3～4.5 (2H, m, the methylene radical H of ester group), 5.42～5.44 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).Embodiment 281, the preparation of 3-cyclohexane diol dibenzoate
0.03mol 1, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 3-cyclohexane diol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds the 20ml saturated aqueous common salt, ethyl acetate extraction, and anhydrous Na 2SO4 drying is removed and is desolvated.Column chromatography gets colourless liquid 1,3-cyclohexane diol dibenzoate, yield 95%. 1HNMR (TMS, CDCl 3, ppm): δ 1.2～2.1 (8H, m, the methylene radical H of hexanaphthene), 5.1～5.4 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).Embodiment 294-methyl-3,5-ethohexadiol dibenzoate synthetic
The preparation of (1) 3,5-acetyl caproyl
Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol butanone under the agitation condition.Dropwise post-heating backflow 4hr.Solvent evaporated and boiling point were in the component below 110 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated, the final 2.4g product that gets.
(2) 4-methyl-3, the preparation of 5-acetyl caproyl
In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol methyl iodide under the normal temperature, after dropwising, continue reaction 48hr at normal temperatures.After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets product.
(3) 4-methyl-3, the preparation of 5-ethohexadiol
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively 4, 100mlTHF.Slowly be added dropwise to 0.04mol3-ethyl-2 under the ice-water bath condition, 4-diacetylmethane, normal temperature continue reaction 48hr down.Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets product.
(4) 4-methyl-3, the preparation of 5-ethohexadiol dibenzoate
The preparation method is with aforementioned method.
1HNMR：δ(ppm)7.8(10H，ArH)，5.28(2H，CH)，1.8(4H，CH 2)，1.18(2H，CH 2)，1.0(9H，CH 3)。Synthesizing of embodiment 305-methyl-4,6 nonanediol dibenzoate
(1) 4,6 the ninth of the ten Heavenly Stems diketone preparation
Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol2-pentanone under the agitation condition.Dropwise post-heating backflow 4hr.Solvent evaporated and boiling point were in the component below 110 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated, the final 2.6g product that gets.
(2) preparation of 5-methyl-4,6 nonanediol dibenzoate
Similar step preparation according to (2)～(4) among the preparation embodiment 30.
1HNMR：δ(ppm)7.85(10H，ArH)，5.38(2H，CH)，1.7(4H，CH 2)，1.3(4H，CH 2)，2.45(1H，CH)，1.0(9H，CH 3)。Embodiment 311,3-phenylbenzene-1, ammediol dibenzoate synthetic
According to being similar to the method preparation for preparing among the embodiment 12.
1HNMR (TMS, CDCl 3, ppm): δ 7.13～7.35 (10H, aromatic hydrocarbons H), 5.7 (2H, CH), 2.6 (2H, CH 2), 2.0 (6H, CH 3).Embodiment 321,3-phenylbenzene-2-methyl isophthalic acid, 3-third dibenzoate synthetic
(1) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of 3-propanedione
In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol diphenylpropane-1,3-dione(DPPO).After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol methyl iodide under the normal temperature, after dropwising, continue reaction 48hr at normal temperatures.After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 12g product.
(2) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively 4, 100mlTHF.Slowly be added dropwise to 0.04mol 1 under the ice-water bath condition, 3-phenylbenzene-2-methyl isophthalic acid, 3-propanedione, normal temperature continue reaction 48hr down.Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 5.9g product.
(3) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of 3-third dibenzoate
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 7.3g product. 1HNMR(TMS，CDCl 3，ppm)：δ7.5(20H，ArH)，5.93(2H，CH)，1.24(1H，CH)，0.95(3H，CH 3)。Embodiment 331,3-phenylbenzene-1, ammediol two n Propanoic acid esters synthetic
(1) 1,3-phenylbenzene-1, the preparation of ammediol
The preparation method is with among the preparation embodiment 33 (2).
(2) 1,3-phenylbenzene-1, the preparation of ammediol two n Propanoic acid esters
The preparation method is with among the preparation embodiment 33 (3).Just change Benzoyl chloride into positive propionyl chloride. 1HNMR (TMS, CDCl 3, ppm): δ 7.13～7.36 (10H, aromatic hydrocarbons H), 5.76 (2H, CH), 2.5 (4H, CH 2), 2.11 (2H, CH 2), 1.1 (6H, CH 3).Embodiment 341,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate synthetic
According to being similar to the method preparation for preparing embodiment 33 (3), just change Benzoyl chloride into propionyl chloride. 1HNMR (TMS, CDCl 3, ppm): δ 7.25 (10H, aromatic hydrocarbons H), 5.76 (2H, CH), 2.5 (4H, CH 2), 2.11 (2H, CH 2), 1.1 (6H, CH 3).Embodiment 351,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters synthetic
According to being similar to the method preparation for preparing embodiment 33 (3), just change Benzoyl chloride into Acetyl Chloride 98Min.. 1HNMR (TMS, CDCl 3, ppm): δ 7.3 (10H, aromatic hydrocarbons), 5.6 (2H, CH), 2.4 (1H, CH), 1.0 (9H, CH 3).Embodiment 361-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate synthetic
(1) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-dimethyl diketone
The preparation method is with among the preparation embodiment 33 (1).Just change the raw material diphenylpropane-1,3-dione(DPPO) into 1-phenyl-1, the 3-dimethyl diketone changes iodoethane into methyl iodide.
(2) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol
The preparation method is with among the preparation embodiment 33 (2).Just change the reductive agent lithium aluminum hydride into sodium borohydride.
(3) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol dibenzoate
The preparation method is with among the preparation embodiment 33 (3).
1HNMR(TMS，CDCl 3，ppm)：8.2(15H，ArH)，5.6(2H，CH)，2.1(H，CH)，1.2(6H，CH 3)。Embodiment 376-heptene-2,4-heptanediol two pivalates synthetic
The preparation method is with among the preparation embodiment 33 (3).Just change Benzoyl chloride into tertiary butyl formyl chloride. 1HNMR(TMS，CDCl 3，ppm)：δ5.6(1H，＝CH-)，5.1(2H，CH)，4.8(2H，＝CH 2)，2.2(2H，CH 2)，1.7(2H，CH 2)，1.2(24H，CH 3)。Embodiment 382,2,4,6,6-pentamethyl--3,5-heptanediol dibenzoate synthetic
From two pivalyl methane is starting raw material, prepare according to being similar to the method for preparing embodiment 33, 1HNMR (TMS, CDCl 3, ppm): δ 8.0 (10H, aromatic hydrocarbons H), 5.3 (2H, CH), 2.1 (1H, CH), 1.3 (1H, CH 3).Embodiment 392,2,6,6-tetramethyl--4-ethyl-3,5-heptanediol dibenzoate synthetic
According to being similar to the method preparation for preparing embodiment 33. 1HNMR (TMS, CDCl 3, ppm): δ 8.0 (10H, aromatic hydrocarbons H), 5.3 (2H, CH), 2.1 (H, CH), 1.58 (2H, CH 2), 1.3 (21H, CH 3).Embodiment 40
1-furans-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate synthetic
With 1-furans-1, the 3-dimethyl diketone is a raw material, according to being similar to the method preparation for preparing embodiment 33.
1HNMR (TMS, CDCl 3, ppm): δ 8.9 (3H, furan nucleus H), 7.8 (10H, aromatic hydrocarbons H), 5.1 (2H, CH), 2.15 (1H, CH), 1.0 (6H, CH 3).Embodiment 411-trifluoromethyl-3-methyl-2,4-pentanediol benzoic ether
Synthetic method gets product 4.3g with preparation embodiment 2.Raw material: 1-trifluoromethyl-3-methyl-2,4-pentanediol (3.4g), Benzoyl chloride (4g), pyridine (4.5g) and tetrahydrofuran (THF) (70ml). 1HNMR(TMS，CDCl 3，δppm)：1.4(6H)，2.22.4(2H)，5.1～2.6(1H)，5.8(1H)，7.3～7.9(10H)。Embodiment 421-three fluoro-4-naphthyls-2,4-butyleneglycol two furancarboxylic acid esters
Synthetic method gets product 5.2g with preparation embodiment 2.Raw material: 1-three fluoro-4-naphthyls-2,4-butyleneglycol (3.8g), furoyl chloride (4.5g), pyridine (4.5g) and tetrahydrofuran (THF) (70ml). 1HNMR(TMS，CDCl 3，ppm)：1.4(3H)，2.2～2.4(2H)，5.3～2.7(2H)，5.8(1H)，7.3～7.9(10H)。Embodiment 432, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol
Synthetic method gets product 3.5g with preparation embodiment 2.Raw material: 2,4-pentanediol (2.1g), to fluoro methyl benzoyl chloride (9.2g), pyridine (6g) and tetrahydrofuran (THF) (70ml). 1HNMR(TMS，CDCl 3，ppm)：1.4(6H)，1.9～2.2(2H)，5.3～5.4(2H)，7.4～8.2(8H)。Embodiment 443,6-dimethyl-2, the preparation of 4-heptanediol dibenzoate
(1) 3,6-dimethyl-2, the preparation of 4-heptadione
0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 6-methyl-2, the 4-heptadione.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect 88～90 ℃/1kPa of cut, yield 94%.
(2) 3,6-dimethyl-2, the preparation of 4-heptanediol
14.2g 3,6-dimethyl-2,4-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3,6-dimethyl-2,4-heptanediol, yield 90%.The IR spectrogram is at 3400cm -1There is strong absorption peak at the place, and at 1700cm -1About do not have absorption peak, prove that reduction reaction carries out fully.
(3) 3,6-dimethyl-2, the preparation of 4-heptanediol dibenzoate
0.03mol 3,6-dimethyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 3,6-dimethyl-2,4-heptanediol dibenzoate, yield 88%. 1HNMR (TMS, CDCl 3, ppm): δ 0.8～0.9 (6H, m, methyl H), δ 1.0～1.1 (3H, m, methyl H), δ 1.3～1.4 (3H, m, methyl H), δ 1.5～1.7 (2H, m, methylene radical H), δ 1.8～1.9 (1H, m, methyne H), δ 2.0～2.1 (1H, m, methyne H), δ 5.1～5.5 (2H, m, the methyne H of ester group), δ 7.3～8.1 (10H, m, phenyl ring H).Embodiment 452,2,6,6-tetramethyl--3,5-heptanediol dibenzoate synthetic
According to being similar to the method preparation for preparing embodiment 12. 1HNMR (TMS, CDCl 3, ppm): δ 8.0 (10H, aromatic hydrocarbons H), 5.3 (2H, CH), 2.0 (2H, CH 2), 1.3 (1H, CH 3).Embodiment 463-allyl group-2,4-pentanediol dibenzoate synthetic
(1) 3-allyl group-2, the preparation of 4-diacetylmethane
In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol bromopropylene under the normal temperature, after dropwising, continue reaction 48hr at normal temperatures.
After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 7.1g product.
(2) 3-allyl group-2, the preparation of 4-pentanediol
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively 4, 100mlTHF.Slowly be added dropwise to 0.04mol3-allyl group-2 under the ice-water bath condition, 4-diacetylmethane, normal temperature continue reaction 48hr down.
Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 3.7g product.
(3) 3-allyl group-2, the preparation of 4-pentanediol dibenzoate
Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol3-allyl group-2 successively, 4-pentanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 5.3g product.
1HNMR (TMS, CDCl 3, ppm): 7.37～8.13 (10H, aromatic hydrocarbons H), 6.0 (2H ,=CH 2), 5.38 (1H, CH), 5.12 (2H, CH), 2.49 (2H, CH 2), 2.27 (H, CH), 1.38～1.52 (6H, CH 3).Embodiment 473-methyl-3-butyl-2, the preparation of 4-pentanediol dibenzoate
(1) 3-methyl-3-butyl-2, the preparation of 4-diacetylmethane
Be that negative electrode, 0.05molEtNOTs and 50mlDMF are anodic electrolyzer room temperature electrolysis 10h by 0.075mol 2-Pyrrolidone, 0.075mol tetraethyl-tolysulfonyl ammonium (EtNOTs) and 60ml dimethyl formamide (DMF).Electrode is the platinum electrode of 2cm * 2cm, and electric current is the continuous current of 0.2A.Take out negative solution, slowly drip 0.05mol 3-methyl-2, the 4-diacetylmethane, stirring at room 1h drips the 0.075mol butyl iodide, stirring at room 5h.Add the saturated NH of 100ml 4Cl aqueous solution termination reaction, ethyl acetate extraction, anhydrous sodium sulfate drying.Remove and desolvate, underpressure distillation is collected cut 57～59 /0.3kPa, yield 85%.
(2) 3-methyl-3-butyl-2, the preparation of 4-pentanediol
1.3gNaBH 4, 0.1gNaOH and 13ml water slowly drips 15ml methyl alcohol and 0.05mol 3-methyl-3-butyl-2, the mixed solution of 4-diacetylmethane in the ice bath cooling with under stirring.Finish stirring at room 4h.Removal of solvent under reduced pressure adds ethyl acetate and stirs 12h, filters.Filtrate is used anhydrous sodium sulfate drying after dividing water outlet, removes and desolvates.The IR spectrogram shows nothing-CO-peak and very strong-OH peak is arranged.Yield 90%.
(3) 3-methyl-3-butyl-2, the preparation of 4-pentanediol dibenzoate
0.03mol 3-methyl-3-butyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-methyl-3-butyl-2,4-pentanediol dibenzoate, yield 88%. 1HNMR(TMS，CDCl 3，ppm)：δ0.8～0.9(3H，-CH 3)，0.9～1.1(6H，-CH 2-)，1.1～1.5(9H，-CH 3)，5.3～5.5(2H，-CH-)，7.3～8.0(10H，ArH)。Embodiment 484-butyl-3, the preparation of 5-heptanediol dibenzoate
According to being similar to the method preparation for preparing embodiment 48. 1HNMR(TMS，CDCl 3，ppm)：δ0.8～0.9(9H，-CH 3)，1.3～1.7(10H，-CH 2-)，1.8～2.0(1H，-CH-)，5.2～5.3(2H，-CH-)，7.1～8.0(10H，ArH)。Embodiment 494-ethyl-3,5-heptanediol dibenzoate synthetic method is with embodiment 13.
4-ethyl-3,5-heptanediol dibenzoate 1H-NMR (TMS, CDCl 3, ppm): δ 7.8 (10H, aromatic hydrocarbons), δ 5.3 (2H, CH), δ 2.0 (1H, CH), δ 1.9 (2H, CH 2), δ 1.7 (4H, CH 2), δ 1.0 (9H, CH 3Embodiment 503-ethyl-2,4-hexylene glycol dibenzoate synthetic method is with embodiment 13.
3-ethyl-2,4-hexylene glycol dibenzoate 1H-NMR (TMS, CDCl 3, ppm): δ 7.8 (10H, aromatic hydrocarbons H), 5.3 (2H, CH), 2.0 (1H, CH), 1.9 (2H, CH 2), 1.7 (2H, CH 2), 1.0 (9H, CH 3) comparative example 12-sec.-propyl-2-isopentyl-1, ammediol dibenzoate synthetic
(1) synthetic (preparation method is referring to the CN1036846C) of 2-sec.-propyl-5-methyl-2-hexenoic aldehyde
The isovaleric aldehyde of 207g and the OH of 26ml -Amberlite IRA910 resin (the Rohm ﹠amp of form; Hass produces) reflux.Remove the water of generation with water trap, collect stopped reaction behind about 26ml water, filter out resin.Underpressure distillation, the cut of 85～90 ℃/20mmHg of collection.
(2) 2-sec.-propyl-5-methyl hexanal is synthetic
Add 70ml ethanol, the saturated NaHCO of 1ml in above-mentioned synthetic 10g 2-sec.-propyl-5-methyl-2-hexenoic aldehyde 3The Pd of 10% on solution and the 0.25g carbon support.Feed N 2, feed H then 2, install and be with the graduated H of being full of 2Drop-burette link to each other.The normal temperature and pressure stirring reaction is up to H 2Absorption reach calculated value.Filter, filtrate is used for secondary response down.
(3) 2-sec.-propyl-2-isopentyl-1, ammediol synthetic
Add 5.3gK in the above-mentioned filtrate 2CO 3Be dissolved in the solution of 13.1ml water and the CH of 16.9ml60% 2O, reflux 7h.Remove ethanol, tell organic phase and hot water wash up to neutrality.Underpressure distillation gets 2-sec.-propyl-2-isopentyl-1, ammediol, b.p.165 ℃/20mmHg.
(4) 2-sec.-propyl-2-isopentyl-1, ammediol dibenzoate synthetic
9.4g (0.05mol) 2-sec.-propyl-2-isopentyl-1 adds the 50ml tetrahydrofuran (THF) in the ammediol, under agitation add 12.1ml (0.15mol) pyridine.Slowly add 14.5ml (0.125mol) Benzoyl chloride after stirring evenly, stirring at room 1h, reflux 4h then.Add the salt that the 70ml water dissolution generates, ethyl acetate extraction is told organic phase, saturated common salt washing 2 times, anhydrous sodium sulfate drying.Remove and desolvate, underpressure distillation gets light yellow liquid 2-sec.-propyl-2-isopentyl-1, ammediol dibenzoate, yield 91%. 1NMR (TMS, CDCl 3) δ (ppm): 0.88 (d, 6H, the methyl hydrogen of isopentyl), 1.05 (d, 6H, the methyl hydrogen of sec.-propyl), 1.24 (m, 2H, the methylene radical hydrogen of isopentyl), (1.27 m, 2H, the methylene radical hydrogen of isopentyl), 1.58 (m, 1H, the methyne hydrogen of isopentyl), 2.04 (m, 1H, the methyne hydrogen of sec.-propyl), 4.42 (m, 4H, 1, the methoxyl group hydrogen of ammediol), 7.38～8.02 (m, 10H, aromatic ring hydrogen).Comparative example 29,9-two (benzoyl oxygen methyl) fluorenes synthetic
Synthetic (its preparation method is referring to the CN1141285A) of (1) 9,9-two (benzoyl oxygen methyl) fluorenes
(DMSO uses CaH to add the 60ml methyl-sulphoxide in 9g (0.3mol) Paraformaldehyde 96 (vacuum hydro-extraction 8h) 2Dewater) and 0.4gNa and the 8ml dehydrated alcohol alcohol sodium solution after having reacted, the cooling of ice desire.Stir and in 30 seconds, add the DMSO solution that 100ml contains 16.6g fluorenes (0.1mol, vacuum hydro-extraction 8h) down, reaction 10min.
Add the hydrochloric acid termination reaction, and make solution become neutral, be poured in the 300ml saturated aqueous common salt, use ethyl acetate extraction, tell organic phase, saturated common salt washing 2 times, anhydrous sodium sulfate drying.Remove and desolvate, the toluene recrystallization gets white solid 9,9-dihydroxymethyl fluorenes, productive rate 72%, m.p.142-145 ℃.
9,9-dihydroxymethyl fluorenes 1H-NMR (CDCL 3) δ (ppm):
(0.27 t, 2H, hydroxyl hydrogen)
(4.03 t, 4H, methylene radical hydrogen)
(7.3-7.9 m, 8H, aromatic ring hydrogen)
Synthesizing of two (benzoyloxy methyl) fluorenes of (2) 9,9-
At the 11.3g of above-mentioned preparation (0.05mol) 9, in the 9-dihydroxymethyl fluorenes, add the 50ml tetrahydrofuran (THF), under agitation add 12.1ml (0.15mol) pyridine.Slowly add 14.5ml (0.125mol) Benzoyl chloride after stirring evenly, stirring at room 1h, reflux 4h then.
Add the salt that the 70ml water dissolution generates, organic phase is told in the toluene extraction, saturated common salt washing 2 times, anhydrous sodium sulfate drying.Remove and desolvate, get white solid.Use re-crystallizing in ethyl acetate, get white crystal 9,9-two (benzoyl oxygen methyl) fluorenes, yield 89%, m.p.144-146 ℃.
9, two (benzoyloxy methyl) fluorenes of 9- 1H-NMR (CDCL 3) δ (ppm):
(4.74 s, 4H, methylene radical hydrogen)
(7.25-7.75 m, 18H, aromatic ring hydrogen).Two, the preparation of embodiment 1～50 and comparative example 1 and 2 ingredients of solid catalyst
The dibasic alcohol ester compound of above-mentioned preparation is prepared catalyst component as follows:
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5ml.Be warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully.Add Tetra hydro Phthalic anhydride 1.4g, continued to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour 456ml.Slowly be warming up to 80 ℃, in temperature-rise period, separate out solids gradually.Add preparation the foregoing description synthetic dibasic alcohol ester compound 6mmol respectively, holding temperature 1 hour.After the filtration, add toluene 70ml, washed twice obtains solid sediment.Add toluene 60ml then, TiCl 440ml is warmed up to 100 ℃, handles two hours, after the venting filtrate, adds toluene 60ml again, TiCl 440ml is warmed up to 100 ℃, handles venting filtrate two hours.Add toluene 60ml, boiling attitude washing three times adds hexane 60ml again, and boiling attitude washed twice adds hexane 60ml, after the normal temperature washed twice, obtains the ingredient of solid catalyst of the foregoing description.Comparative example 3～5: press the preparation method of the ingredient of solid catalyst of the foregoing description, just internal electron donor is replaced with n-butyl phthalate, 9 respectively, 9-two (methyl methoxy base) fluorenes and 2,3-di-isopropyl succsinic acid diethyl ester.Three, propylene polymerization experiment
The catalyst component of the foregoing description is carried out propylene polymerization respectively.The propylene polymerization program is: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt 32.5mmol external electron donor methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds ingredient of solid catalyst 8-10mg and the 1.2L hydrogen of the foregoing description 1-62 again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release obtains the PP powder.Polymerization result is listed in table 1.
By above-mentioned polymerization procedure the ingredient of solid catalyst of Comparative Examples 1,2 and 3 is carried out propylene polymerization respectively, polymerization result is listed in table 2.
Table 1 propylene polymerization result
Embodiment The polyol ester classes of compounds Binary alcohol esters content (wt%) ????Ti ????wt％ Polymerization activity kgPP/gcat Degree of isotacticity (%) Molecular weight distribution Melting index g/10m in
??1 2,4-pentanediol dibenzoate ????18.2 ????2.9 ????51.0 ??99.5 ??5.9 ??0.6
??2 (2S, 4S)-(+)-2,4-pentanediol dibenzoate ????/ ????/ ????17.7 ??95.4 ??8.2 ??4.5
??3 (2R, 4R)-(+)-2,4-pentanediol dibenzoate ????/ ????/ ????18.4 ??94.6 ??8.1 ??4.2
??4 2,4-pentanediol two (m-chlorobenzoic acid) ester ????17.2 ????2.7 ????42.8 ??97.3 ??6.0 ??0.6
??5 2,4-pentanediol two (parabromobenzoic acid) ester ????20.1 ????2.8 ????52.5 ??97.8 ??7.2 ??0.6
??6 2,4-pentanediol two (o-bromobenzoic acid) ester ????21.8 ????3.0 ????47.6 ??96.9 ??7.3 ??1.2
??7 2,4-pentanediol two (to butylbenzoic acid) ester ????22.1 ????3.1 ????64.2 ??98.6 ??9.7 ??0.5
??8 2,4-pentanediol phenylformic acid laurate ????/ ????/ ????50.1 ??96.8 ??7.0 ??1.3
??9 2,4-pentanediol two laurates ????18.2 ????2.8 ????17.5 ??93.8 ??6.7 ??4.5
??10 2,4-pentanediol dipropionate ????/ ????/ ????14.9 ??92.0 ??6.9 ??5.4
??11 2-methyl-2,4-pentanediol dibenzoate ????/ ????/ ????9.4 ??93.7 ??6.9 ??3.4
??12 3,5-heptanediol dibenzoate ????18.7 ????3.2 ????49.5 ??98.5 ??6.3 ??1.5
??13 2,6-dimethyl-3,5-heptanediol dibenzoate ????18.9 ????3.0 ????44.7 ??97.9 ??7.7 ??1.7
??14 6-methyl-2,4-heptanediol dibenzoate ????17.6 ????2.7 ????57.9 ??96.8 ??5.3 ??2.1
??15 6-methyl-2,4-heptanediol two (p-methylbenzoic acid) ester ????19.5 ????2.9 ????59.5 ??98.4 ??6.8 ??1.2
??16 3-methyl-2,4-pentanediol dibenzoate ????18.3 ????3.4 ????55.0 ??99.1 ??6.7 ??0.8
??17 3-methyl-2,4-pentanediol two (Chlorodracylic acid) ester ??20.1 ??3.1 ??54.8 ??98.2 ??6.7 ??0.7
??18 3-methyl-2,4-pentanediol two (p-methylbenzoic acid) ester ??18.9 ??2.9 ??42.7 ??98.2 ??6.6 ??0.6
??19 3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester ??17.8 ??3.1 ??63.2 ??98.8 ??5.7 ??0.4
??20 3-methyl-2,4-pentanediol two (p-tert-butyl benzoic acid) ester ??20.2 ??2.9 ??52.1 ??98.4 ??9.7 ??0.6
??21 3-methyl-2,4-pentanediol one phenylformic acid one laurate ??/ ??/ ??42.0 ??97.2 ??6.2 ??1.4
??22 3,3-dimethyl-2,4-pentanediol dibenzoate ??17.5 ??2.9 ??48.0 ??98.1 ??5.7 ??1.2
??23 3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate ??/ ??/ ??40.5 ??95.7 ??6.6 ??2.8
??24 3-ethyl-2,4-pentanediol dibenzoate ??17.6 ??2.9 ??54.8 ??98.2 ??5.8 ??1.5
??25 3-butyl-2,4-pentanediol dibenzoate ??16.9 ??2.8 ??59.2 ??97.9 ??8.1 ??1.0
??26 4-methyl-3,5-heptanediol dibenzoate ??18.3 ??3.2 ??53.6 ??97.2 ??7.5 ??1.9
??27 2-ethyl-1,3-hexylene glycol dibenzoate ??15.6 ??2.9 ??40.7 ??96.7 ??8.9 ??0.3
??28 1,3-cyclohexane diol dibenzoate ??/ ??/ ??13.5 ??94.3 ??7.2 ??2.4
??29 4-methyl-3,5-ethohexadiol dibenzoate ??17.8 ??3.0 ??54.3 ??96.6 ??7.3 ??1.1
??30 5-methyl-4,6 nonanediol dibenzoate ??19.1 ??3.1 ??53.9 ??97.8 ??6.6 ??2.2
??31 1,3-phenylbenzene-1, ammediol dibenzoate ??/ ??/ ??15.7 ??93.6 ??6.3 ??8.1
??32 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dibenzoate ??/ ??/ ??13.3 ??95.1 ??7.0 ??6.7
??33 1,3-phenylbenzene-1, ammediol two n Propanoic acid esters ??/ ??/ ??20.0 ??94.1 ??6.2 ??5.9
??34 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate ??20.3 ??2.9 ??19.1 ??94.0 ??6.4 ??3.5
??35 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters ??/ ??/ ??1.7 ??94.7 ??4.1
??36 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate ??/ ??/ ??14.0 ??94.9 ??6.7 ??6.6
??37 6-heptene-2,4-heptanediol two pivalates ??/ ??/ ??18.6 ??93.6 ??8.1 ??3.5
??38 2,2,4,6,6-pentamethyl--3,5-heptanediol dibenzoate ??20.8 ??2.9 ??48.0 ??98.2 ??7.6 ??1.2
??39 2,2,6,6-tetramethyl--4-ethyl-3,5-hexylene glycol dibenzoate ??21.6 ??3.2 ??51.6 ??97.9 ??7.8 ??2.3
??40 1-furans-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate ??/ ??/ ??17.0 ??97.1 ??4.7 ??3.4
??41 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate ??/ ??/ ??36.5 ??97.2 ??8.6 ??1.5
??42 1-three fluoro-4-naphthyls-2,4-butyleneglycol two furancarboxylic acid esters ??16.1 ??2.8 ??34.5 ??96.4 ??10.1 ??1.6
??43 2, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol ??16.0 ??2.9 ??52.2 ??98.1 ??7.3 ??0.2
??44 3,6-dimethyl-2,4-heptanediol dibenzoate ??/ ??/ ??53.8 ??98.1 ??7.4 ??2.1
??45 2,2,6,6-tetramethyl--3,5-heptanediol dibenzoate ??19.5 ???3.1 ??57.1 ??97.6 ??6.4 ??0.8
??46 3-allyl group-2,4-pentanediol dibenzoate ??18.2 ???3.0 ??30.2 ??95.8 ??8.2 ??1.5
??47 3-methyl-3-butyl-2,4-pentanediol dibenzoate ??16.9 ???2.7 ??56.9 ??98.6 ??0.8
??48 4-butyl-3,5-heptanediol dibenzoate ??/ ???/ ??47.3 ??98.7 ??1.3
??49 4-ethyl-3,5-heptanediol dibenzoate ??16.2 ???2.6 ??59.5 ??97.2 ??6.4 ??2.1
??50 3-ethyl-2,4-hexylene glycol dibenzoate ??15.4 ???2.8 ??35.5 ??97.8 ??0.7
Compare 1 2-sec.-propyl-2-isopentyl-1, the ammediol dibenzoate ??12.8 ???2.4 ??31.7 ??97.8 ??5.8 ??0.1
Compare 2 9,9-two (benzoyl oxygen methyl) fluorenes ??15.1 ???2.5 ??33.7 ??98.3 ??6.6 ??0.1
As can be seen from Table 1, obviously to be higher than comparative example 1 and comparative example 2 by the resulting polyacrylic melting index of ingredient of solid catalyst of the present invention under the same terms.
The propylene polymerization test of the ingredient of solid catalyst of table 2 comparative example
Sequence number Internal electron donor Internal electron donor (wt%) ????Ti ??(wt％) Active kgPP/gcat Degree of isotacticity % Molecular weight distribution
Embodiment 1 2,4-pentanediol dibenzoate ????18.2 ????2.9 ????51.0 ???99.5 ????5.9
Embodiment 16 3-methyl-2,4-pentanediol dibenzoate ????18.3 ????3.4 ????55.0 ???99.1 ????6.7
Comparative example 3 N-butyl phthalate ????9.6 ????2.0 ????32.5 ???98.7 ????4.4
Comparative example 4 9,9-two (methyl methoxy base) fluorenes ????24.6 ????3.1 ????58.4 ???98.5 ????4.0
Comparative example 5 2,3-di-isopropyl succsinic acid diethyl ester ????14.3 ????2.6 ????39.8 ???98.0 ????8.7
Can see from the comparing result of table 2, adopt the resulting polypropylene of ingredient of solid catalyst of the present invention, not only has higher degree of isotacticity, and polymerization activity is higher, be higher than comparative example 3 and comparative example 5 significantly, and the molecular weight distribution broad of while resulting polymers is better than comparative example 3 and comparative example 4 significantly.Four, the propylene polymerization of no external electron donor
According to above-mentioned polymerization procedure, but do not add external electron donor, the ingredient of solid catalyst of embodiment 1,16 and Comparative Examples 3 carried out propylene polymerization respectively, polymerization result and the polymerization result that adds external electron donor relatively list in table 3.
Table 3 adds with the polymerization result that does not add external electron donor and compares
Internal electron donor CHMMS/AlEt 3??mol/mol Active kgPP/gcat Degree of isotacticity % Molecular weight distribution
Embodiment 1 2,4-pentanediol dibenzoate ?????0.04 ????51.0 ????99.5 ????5.9
Embodiment 1 The same ?????0 ????53.4 ????98.1 ????5.9
Embodiment 16 3-methyl-2,4-pentanediol dibenzoate ?????0.04 ????55.0 ????99.1 ????6.7
Embodiment 16 The same ?????0 ????60.2 ????96.5 ????6.6
Comparative example 3 2,3-di-isopropyl succsinic acid diethyl ester ?????0.04 ????39.8 ????98.0 ????8.7
Comparative example 3 2,3-di-isopropyl succsinic acid diethyl ester ?????0 ????27.4 ????87.3 ????/
The result can see from table 3, under the situation that does not add external electron donor, adopt ingredient of solid catalyst of the present invention to carry out polymerization and still can obtain quite high degree of isotacticity, and polymerization activity is higher than the polymerization activity that obtains when adding external electron donor.And adopt the catalyzer (comparative example 3) of prior art to carry out polymerization, under the situation that does not add external electron donor, the degree of isotacticity of the polymkeric substance that obtains is very low.
The comparing result of consolidated statement 2 and table 3, can think that ingredient of solid catalyst of the present invention is when being used for propylene polymerization, it is higher not only to have higher degree of isotacticity and high polymerization activity, and the molecular weight distribution broad of resulting polymers, be convenient to process processed and applied, under the situation that does not add external electron donor, still can obtain having the polymkeric substance of higher degree of isotacticity simultaneously, therefore can think the catalyzer that a kind of over-all properties is very good.
Five, the polymerization result of different external electron donors relatively
Polymerization process is with aforementioned, and just external electron donor changes down the external electron donor described in the tabulation into.
The polymerization result of the different external electron donors of table 4 relatively
External electron donor Active kgPP/gcat Degree of isotacticity % Molecular weight distribution Melting index g/10min
Methylcyclohexyl dimethoxy silane ????51.0 ????99.5 ????5.9 ????0.6
Second, isobutyl dimethoxy silane ????52.1 ????99.0 ????6.1 ????0.7
Diisopropyl dimethoxy silane ????49.7 ????99.2 ????6.2 ????0.6
Dicyclopentyl dimethoxyl silane ????50.3 ????99.1 ????6.0 ????0.6
Two (cyclobutylmethyl) dimethoxy silane ????47.8 ????99.2 ????7.5 ????0.5
Di-n-butyl dimethoxy silane ????49.0 ????98.8 ????6.1 ????0.7
Ethyl p-methyl benzoate ????45.8 ????98.1 ????6.4 ????0.7
2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal ????52.6 ????99.3 ????6.0 ????0.8
In through the abundant metathetical reactor of high pure nitrogen, add TiCl 460ml and toluene 40ml are cooled to-20 ℃, add 7.0gMgCl 22.4CH 3CH 2OH ball type carrier (preparation method referring to embodiment among the USP4399054 2, but operate in 2800rpm rather than 10000rpm).Rise to 0 ℃ in 1 hour, continuing to heat up rose to 20 ℃ in 2 hours, and continuing to heat up rose to 40 ℃ in 1 hour, add 2 of embodiment 1 preparation, and 4-pentanediol dibenzoate 2.1g rose to 100 ℃ in 1 hour, kept venting filtrate 2 hours.Add TiCl 4100ml rose to 120 ℃ in 1 hour, kept venting filtrate 2 hours.Add hexane 60ml, boiling attitude washing 5 times adds hexane 60ml then, and normal temperature washing 3 times obtains 4.9g spherical catalyst component.Polymerization as stated above, obtaining activity of such catalysts is 42.6kgPP/gcat, and the degree of isotacticity of polymkeric substance is 99.1%, and melting index is 1.2g/10min.
Six, the polymerization under the differing temps
With aforementioned polymerization process, just change 75 ℃ or 80 ℃ into 70 ℃, gained the results are shown in following table
Catalyzer Polymerization temperature ℃ External electron donor Active kgPP/gcat Degree of isotacticity % Melting index g/10min
Embodiment 1 ????75 ??CHMMS ????52.0 ???99.1 ????0.6
Embodiment 1 ????80 ??CHMMS ????53.4 ???99.5 ????0.6
Embodiment 50 ????75 ??CHMMS ????60.7 ???97.8 ????2.2
Embodiment 50 ????80 ??CHMMS ????62.1 ???98.4 ????2.1
Embodiment 50 ????75 ??DIPS ????61.3 ???98.0 ????2.4
Embodiment 50 ????80 ??DIPS ????65.4 ???98.8 ????2.2
Seven, pre-polymerization experimental result
The ingredient of solid catalyst 8mg that in the abundant metathetical reactor of a usefulness nitrogen, adds embodiment 1 gained, the AlEt of 0.5M 3Hexane solution 5ml, 0.05M methylcyclohexyl dimethoxy silane (CHMMS) hexane solution 2ml, under 25 ℃, feed propylene polymerization, making the polymerization multiple is 50gPP/gcat, above-mentioned again reaction product joins through gaseous propylene and fully puts and be equipped with propylene 2.3L and 1.2L hydrogen, and temperature has reached the stainless steel cauldron of 70 ℃ 5L, keep 70 ℃ 1 hour.Cooling, pressure release obtains degree of isotacticity and is 99.1% polymer powders 460g, and polymerization activity is 57.5kgPP/gcat.
Eight; the vinyl polymerization test: volume is the stainless steel autoclave of 2L; after the abundant pump drainage displacement of high-purity hydrogen; start stirring; under nitrogen protection, progressively in still, add the 1L hexane; catalyst solid constituent and promotor triethyl aluminum 2.5mmol with 8mg embodiment 1 gained; after rising to 75 ℃ of temperature; replenish an amount of high-purity hydrogen in still, making the interior hydrogen partial pressure of still is 0.28Mpa, and make-up ethylene gas makes its dividing potential drop reach 0.75Mpa in still then; the dividing potential drop of keeping ethylene gas is constant; make system temperature keep 85 ℃, after 2 hours, cooling discharge; polymkeric substance except that desolvating, is obtained polymkeric substance 225g after the thorough drying.

Claims (21)

1, the catalyst component that is used for olefinic polymerization, it comprises magnesium, titanium, halogen and electron donor, and this electron donor is selected from least a diol ester compound in the following general formula (I):
Figure A0310978100021
R wherein 1-R 6Can be identical or inequality, be hydrogen or C 1-C 10The alkyl of straight or branched, C 3-C 10Cycloalkyl, C 6-C 10Aryl, C 7-C 10Alkaryl or aralkyl, but R 1, R 2, R 5, R 6Be not hydrogen simultaneously; R 1-R 6In two or more groups mutually bonding generate one or several condensed ring structure; R 7And R 8Can be identical or inequality, represent C 1-C 10Straight or branched alkyl, C 3-C 20Cycloalkyl, C 6-C 20Aryl, C 7-C 20Alkaryl or C 7-C 20Aryl, the benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl.
2, the catalyst component that is used for olefinic polyreaction according to claim 1, in the diol ester compound of wherein said general formula (I), R 1, R 2, R 5And R 6In to have a group at least be hydrogen.
3, the catalyst component that is used for olefinic polyreaction according to claim 1, in the diol ester compound of wherein said general formula (I), R 1And R 2, R 5And R 6In to have a group respectively at least be not hydrogen.
4, the catalyst component that is used for olefinic polyreaction according to claim 3, in the diol ester compound of wherein said general formula (I), R 1And R 2, R 5And R 6In a group is arranged respectively is hydrogen, and another group is methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl.
5, the catalyst component that is used for olefinic polyreaction according to claim 1, in the diol ester compound of wherein said general formula (I), described R 7And R 8Group is selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, alkyl phenyl, halogenated alkyl phenyl, indenyl, benzyl or phenylethyl.
6, the catalyst component that is used for olefinic polyreaction according to claim 5, in the diol ester compound of wherein said general formula (I), described R 7And R 8Group has at least one to be selected from phenyl, halogenated phenyl, alkyl phenyl or halogenated alkyl phenyl.
7, the catalyst component that is used for olefinic polyreaction according to claim 4, in the diol ester compound of wherein said general formula (I), described R 7And R 6Group all is selected from phenyl, halogenated phenyl, alkyl phenyl or halogenated alkyl phenyl.
8, according to the described catalyst component that is used for olefinic polymerization of one of claim 1-7, it comprises titanium compound, magnesium compound and is selected from the reaction product of the diol ester compound of general formula (I),
Magnesium compound is selected from a kind of in one of them halogen atom alkoxy in the hydrate of magnesium dihalide, alkoxyl magnesium, alkyl magnesium, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula or the halogenated alkoxy institute metathetical derivative or their mixture;
Titanium compound is that general formula is TiX n(OR) 4-n' R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.
9, the catalyst component that is used for olefinic polymerization according to claim 8, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
10, the catalyst component that is used for olefinic polymerization according to claim 9, its organic epoxy compounds comprise at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.
11, the catalyst component that is used for olefinic polymerization according to claim 9, its organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
12, the catalyst component that is used for olefinic polymerization according to claim 8, the magnesium compound that it adopted is the alcohol adduct of magnesium dihalide.
13, a kind of CH that is used for 2The catalyzer of=CHG olefinic polyreaction, wherein R is hydrogen or C 1-C 6Alkyl or aryl, comprise the reaction product of following component: the described catalyst component of one of (1) claim 1-12; (2) alkylaluminium cpd; (3) randomly, external electron donor component.
14, catalyzer according to claim 13, wherein external electron donor component general formula is R nSi (OR ') 4-nThe external electron donor compound, 0≤n in the formula≤3, R and R Be of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, amido, R also can be halogen or hydrogen atom.
15, catalyzer according to claim 13, wherein the external electron donor component is selected from monobasic or polybasic organic acid ester.
16, catalyzer according to claim 13, wherein the external electron donor component is selected from monobasic or polybasic benzoates.
17, catalyzer according to claim 13, wherein the external electron donor component is selected from 1 of general formula (II), 3-two ethers:
Figure A0310978100041
R wherein I, R H, R III, R IV, R VAnd R VIIdentical or different, for hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom, and R VIIAnd R VIIICan be identical or different, for having the hydrocarbyl group of 1 to 18 carbon atom; R I-R VIIIGroup in one or morely can link up into ring.
18, the catalyzer of claim 17, described 1, R in the general formula of 3-diether (VI) VIIAnd R VIIIBe selected from C 1-C 4Alkyl group, R IIIAnd R IVForm undersaturated condensed ring, and R I, R II, R V, and R VIBe hydrogen.
19, a kind of alkene CH that is used for 2=CHR polymeric pre-polymerized catalyst, wherein R is hydrogen or C 1-C 12Alkyl group, described pre-polymerized catalyst comprises and a kind ofly carries out the prepolymer of prepolymerization gained according to each described ingredient of solid catalyst and alkene among the claim 1-21, the pre-polymerization multiple is 0.1-1000g olefin polymer/g ingredient of solid catalyst.
20, the pre-polymerized catalyst of claim 19, wherein carrying out prepolymerized alkene is ethene or propylene.
21, be used for alkene CH 2=CHR polymeric method, wherein R is the hydrocarbyl group of hydrogen or 1-12 carbon atom, carries out in the presence of each described catalyzer or the pre-polymerized catalyst in claim 1-20.
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