CN102453149B - Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method - Google Patents

Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method Download PDF

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CN102453149B
CN102453149B CN 201010521694 CN201010521694A CN102453149B CN 102453149 B CN102453149 B CN 102453149B CN 201010521694 CN201010521694 CN 201010521694 CN 201010521694 A CN201010521694 A CN 201010521694A CN 102453149 B CN102453149 B CN 102453149B
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ester
acid
ether
glycol monomethyl
monomethyl ether
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CN102453149A (en
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周奇龙
谭忠
严立安
徐秀东
宋维玮
尹珊珊
于金华
李凤奎
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides an olefin polymerization catalyst component, an olefin polymerization catalyst and an olefin polymerization method. According to the invention, an internal electron donor a and an internal electron donor b are used simultaneously as internal electron donors, so that when used for olefin polymerization, the olefin polymerization catalyst component and the olefin polymerization catalyst have higher stereoselectivity and simultaneously have high activity and good hydrogen response, and the prepared olefin polymer has wide molecular weight distribution, wherein the internal electron donor a is a compound as shown in a formula (I) in which R1 and R3 are the same or different and are respectively one of linear or branched alkyl with carbon number of 1-10, naphthenic base with carbon number of 3-10 and substituted or unsubstituted aryl with carbon number of 6-20, R2 is one of linear or branched alkylidene with carbon number of 1-6 and substituted or unsubstituted arylidene with carbon number of 6-20, and n is an integer from 2 to 10.

Description

Olefin polymerization catalyst components and olefin polymerization catalysis and olefine polymerizing process
Technical field
The present invention relates to a kind of olefin polymerization catalyst components, olefin polymerization catalysis and olefine polymerizing process.
Background technology
At present, with magnesium, titanium and the electron donor ingredient of solid catalyst as basal component, namely Ziegler-Natta catalyst known in the field, can be used for CH 2=CHR olefinic polyreaction particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atoms.As everyone knows, interior is one of requisite composition in Ziegler-Natta catalyst to electron compound.From early stage disclosed monocarboxylic acid ester compound, ethyl benzoate for example, the binary aromatic carboxylic acid's ester compound that widely uses up till now, for example n-butyl phthalate or o-benzoic acid diisobutyl ester, arrive again recent disclosed 1,3-two ethers, succinate compound and 1,3-diol-lipid compound, the development of electron donor compound has caused polyolefin catalyst constantly to update just.
CN1436796A and CN1453298A disclose respectively a kind of polyol ester compounds as the olefin polymerization catalysis of electron donor.This olefin polymerization catalysis shows higher polymerization activity and stereospecificity preferably.But the preparation cost of such catalyzer is high, and is difficult to obtain good hydrogen response when using them to carry out olefinic polymerization as olefin polymerization catalysis.
In addition, CN1041752A discloses a class for the preparation of 1 of Ziegler-Natta catalyst, gives electron compound in 3-two ethers, and the catalyst component that obtains has high catalytic activity and hydrogen response preferably when being used for olefinic polymerization.But this compounds preparation cost is high, and the weight of otefi pi polymer narrowly distributing of preparation.
Summary of the invention
The object of the present invention is to provide that a kind of catalytic activity is high, hydrogen response is high, can prepare olefin polymerization catalyst components and olefin polymerization catalysis and the olefine polymerizing process of wide molecular weight distribution polyolefin.
The present inventor is surprised to find that through research, when the compound shown in formula (I) is applied to the electron donor component of Ziegler-Natta catalyst, can obtain high reactivity, high hydrogen response and the catalyst activity component of stereotaxis ability preferably, this catalyst activity component is particularly suitable for by formula CH 2Polymerization, the especially propylene polymerization of the alkene that=CHR represents (wherein R is that hydrogen or carbonatoms are the alkyl of 1-6).
The invention provides a kind of olefin polymerization catalyst components, this catalyst component contains titanium, magnesium and internal electron donor, wherein, described internal electron donor comprises internal electron donor a and internal electron donor b, described internal electron donor a is the compound shown in formula (I), described internal electron donor b is at least a in the binary aliphatic alcohol carboxylicesters shown in the binary aromatic carboxylic acid's ester shown in formula (II) and formula (III)
In formula (I), R 1And R 3Identical or different, a kind of in the replacement of the straight or branched alkyl of the carbonatoms 1-10 that respectively does for oneself, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20 or unsubstituting aromatic yl;
R 2For the replacement of the straight or branched alkylidene group of carbonatoms 1-6 and carbon atom 6-20 or do not replace a kind of in arylidene;
N is the integer of 2-10;
Figure GDA00002918786000022
In formula (II), R 4And R 5Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-8, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl;
R 6, R 7, R 8And R 9Be all hydrogen, perhaps wherein three be hydrogen, another one is that halogen, carbonatoms are a kind of in the straight or branched alkyl of 1-4 and straight or branched alkoxyl group that carbonatoms is 1-4;
R in formula (III) 10And R 11Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-10, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl; R 12And R 13Identical or different, the carbonatoms of respectively doing for oneself is the straight or branched alkyl of 1-10; R 14And R 15Identical or different, a kind of in the straight or branched alkyl of respectively do for oneself hydrogen and carbonatoms 1-10.
The present invention also provides a kind of olefin polymerization catalysis, and this catalyzer is used for by general formula CH 2The polyreaction of the alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6, described catalyzer comprises the reaction product of following material:
(1) above-mentioned olefin polymerization catalyst components;
(2) as the organo-aluminium compound of promotor;
(3) randomly, external donor compound.
The present invention also provides a kind of olefine polymerizing process, and the method is included under the olefinic polymerization condition, and one or more alkene are contacted with above-mentioned catalyzer, and at least a in described alkene is by general formula CH 2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.
Olefin polymerization catalyst components of the present invention is by using simultaneously internal electron donor a and internal electron donor b as internal electron donor, when making it be used for olefinic polymerization, has higher stereoselectivity, have simultaneously the hydrogen response that high reactivity is become reconciled, prepared olefin polymer has wide molecular weight distribution.
Embodiment
According to olefin polymerization catalyst components provided by the invention, this catalyst component contains titanium, magnesium and internal electron donor, wherein, described internal electron donor comprises internal electron donor a and internal electron donor b, described internal electron donor a is the compound shown in formula (I), described internal electron donor b is at least a in the binary aliphatic alcohol carboxylicesters shown in the binary aromatic carboxylic acid's ester shown in formula (II) and formula (III)
Figure GDA00002918786000041
In formula (I), R 1And R 3Identical or different, a kind of in the replacement of the straight or branched alkyl of the carbonatoms 1-10 that respectively does for oneself, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20 or unsubstituting aromatic yl;
R 2For the replacement of the straight or branched alkylidene group of carbonatoms 1-6 and carbon atom 6-20 or do not replace a kind of in arylidene;
N is the integer of 2-10;
Figure GDA00002918786000042
In formula (II), R 4And R 5Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-8, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl;
R 6, R 7, R 8And R 9Be all hydrogen, perhaps wherein three be hydrogen, another one is that halogen, carbonatoms are a kind of in the straight or branched alkyl of 1-4 and straight or branched alkoxyl group that carbonatoms is 1-4;
Figure GDA00002918786000051
R in formula (III) 10And R 11Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-10, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl; R 12And R 13Identical or different, the carbonatoms of respectively doing for oneself is the straight or branched alkyl of 1-10; R 14And R 15Identical or different, a kind of in the straight or branched alkyl of respectively do for oneself hydrogen and carbonatoms 1-10.
In the present invention, carbonatoms is that the example of the straight or branched alkyl of 1-4 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.Carbonatoms is that the example of the straight or branched alkyl of 1-8 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl and n-octyl.Carbonatoms is that the example of the straight or branched alkyl of 1-10 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and positive decyl.
In the present invention, carbonatoms is that the example of the straight or branched alkoxyl group of 1-4 can comprise: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert.-butoxy.
In the present invention, the example of the cycloalkyl of carbonatoms 3-10 can comprise: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-propyl cyclohexyl and 4-normal-butyl cyclohexyl.
In the present invention, the example of the replacement of carbonatoms 6-20 or unsubstituting aromatic yl can comprise: phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-propyl group phenyl, 4-isopropyl phenyl, 4-n-butylphenyl, 4-tert-butyl-phenyl, 4-p-methoxy-phenyl and 4-ethoxyl phenenyl.
In the present invention, the example of the straight or branched alkylidene group of carbonatoms 1-6 can comprise: methylene radical, ethylidene, inferior n-propyl, isopropylidene, inferior normal-butyl, inferior sec-butyl, isobutylidene, the inferior tertiary butyl, inferior n-pentyl, isopentylidene, inferior tert-pentyl, inferior neo-pentyl and inferior n-hexyl.
Carbonatoms is that the replacement of 6-20 or the example that does not replace arylidene can comprise: phenylene, 2-chlorine phenylene, 3-chlorine phenylene, 4-chlorine phenylene, 2-bromine phenylene, 3-bromine phenylene, 4-bromine phenylene, 4-methylphenylene, 4-ethyl phenylene, 4-propyl group phenylene, 4-sec.-propyl phenylene, 4-normal-butyl phenylene, 4-tertiary butyl phenylene, 4-methoxyl group phenylene and 4-oxyethyl group phenylene.
In the preferred case, in formula (I), described R 1Be the straight or branched alkyl of carbonatoms 1-6, described R 3Be phenyl or the substituted-phenyl of carbonatoms 6-10, described R 2Straight or branched alkylidene group for carbonatoms 2-4.
In the present invention, in formula (I), n can be the integer of 2-10, and preferably, n is the integer of 2-6.More preferably, n is 2-4.Most preferably, n is 2 or 3.
in the preferred case, can be for being selected from the diethylene glycol monomethyl ether acetic ester by the examples of compounds shown in formula (I), the diethylene glycol monomethyl ether propionic ester, the diethylene glycol monomethyl ether benzoic ether, diethylene glycol monomethyl ether (Chlorodracylic acid) ester, di-alcohol monomethyl ether (m-chlorobenzoic acid) ester, di-alcohol monomethyl ether (parabromobenzoic acid) ester, diethylene glycol monomethyl ether (m-bromobenzoic acid) ester, diethylene glycol monomethyl ether (o-bromobenzoic acid) ester, diethylene glycol monomethyl ether (p-methylbenzoic acid) ester, diethylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, diethylene glycol monomethyl ether (to butylbenzoic acid) ester, diethylene glycol monomethyl ether (anisic acid) ester, diethylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the diethylene glycol monoethyl ether acetic ester, the diethylene glycol monoethyl ether propionic ester, the diethylene glycol monoethyl ether benzoic ether, diethylene glycol monoethyl ether (Chlorodracylic acid) ester, single ether (m-chlorobenzoic acid) ester of di-alcohol, single ether (parabromobenzoic acid) ester of di-alcohol, diethylene glycol monoethyl ether (m-bromobenzoic acid) ester, diethylene glycol monoethyl ether (o-bromobenzoic acid) ester, diethylene glycol monoethyl ether (p-methylbenzoic acid) ester, diethylene glycol monoethyl ether (p-tert-butyl benzoic acid) ester, diethylene glycol monoethyl ether (to butylbenzoic acid) ester, diethylene glycol monoethyl ether (anisic acid) ester, diethylene glycol monoethyl ether (o-methoxybenzoic acid) ester, the triethylene glycol monomethyl ether acetic ester, the triethylene glycol monomethyl ether propionic ester, the triethylene glycol monomethyl ether benzoic ether, triethylene glycol monomethyl ether (Chlorodracylic acid) ester, two contracting three ethanol monomethyl ether (m-chlorobenzoic acid) esters, two contracting three ethanol monomethyl ether (parabromobenzoic acid) esters, triethylene glycol monomethyl ether (m-bromobenzoic acid) ester, triethylene glycol monomethyl ether (o-bromobenzoic acid) ester, triethylene glycol monomethyl ether (p-methylbenzoic acid) ester, triethylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, triethylene glycol monomethyl ether (to butylbenzoic acid) ester, triethylene glycol monomethyl ether (anisic acid) ester, triethylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the triethylene glycol monoethyl ether acetic ester, the triethylene glycol monoethyl ether propionic ester, the triethylene glycol monoethyl ether benzoic ether, triethylene glycol monoethyl ether (Chlorodracylic acid) ester, two contracting three ethanol list ether (m-chlorobenzoic acid) esters, two contracting three ethanol list ether (parabromobenzoic acid) esters, triethylene glycol monoethyl ether (m-bromobenzoic acid) ester, triethylene glycol monoethyl ether (o-bromobenzoic acid) ester, triethylene glycol monoethyl ether (p-methylbenzoic acid) ester, triethylene glycol monoethyl ether (p-tert-butyl benzoic acid) ester, triethylene glycol monoethyl ether (to butylbenzoic acid) ester, triethylene glycol monoethyl ether (anisic acid) ester, triethylene glycol monoethyl ether (o-methoxybenzoic acid) ester, the dipropylene glycol monomethyl ether acetic ester, the dipropylene glycol monomethyl ether propionic ester, the dipropylene glycol monomethyl ether benzoic ether, dipropylene glycol monomethyl ether (Chlorodracylic acid) ester, dipropylene glycol monomethyl ether (m-chlorobenzoic acid) ester, dipropylene glycol monomethyl ether (parabromobenzoic acid) ester, dipropylene glycol monomethyl ether (m-bromobenzoic acid) ester, dipropylene glycol monomethyl ether (o-bromobenzoic acid) ester, dipropylene glycol monomethyl ether (p-methylbenzoic acid) ester, dipropylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, dipropylene glycol monomethyl ether (to butylbenzoic acid) ester, dipropylene glycol monomethyl ether (anisic acid) ester, dipropylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the DPE acetic ester, the DPE propionic ester, the DPE benzoic ether, DPE (Chlorodracylic acid) ester, two propyl alcohol list ether (m-chlorobenzoic acid) esters, two propyl alcohol list ether (parabromobenzoic acid) esters, DPE (m-bromobenzoic acid) ester, DPE (o-bromobenzoic acid) ester, DPE (p-methylbenzoic acid) ester, DPE (p-tert-butyl benzoic acid) ester, DPE (to butylbenzoic acid) ester, DPE (anisic acid) ester, DPE (o-methoxybenzoic acid) ester, the tripropylene glycol methyl ether acetate, tripropylene glycol monomethyl ether propionic ester, tripropylene glycol monomethyl ether benzoic ether, tripropylene glycol monomethyl ether (Chlorodracylic acid) ester, tripropylene glycol monomethyl ether (m-chlorobenzoic acid) ester, tripropylene glycol monomethyl ether (parabromobenzoic acid) ester, tripropylene glycol monomethyl ether (m-bromobenzoic acid) ester, tripropylene glycol monomethyl ether (o-bromobenzoic acid) ester, tripropylene glycol monomethyl ether (p-methylbenzoic acid) ester, tripropylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, tripropylene glycol monomethyl ether (to butylbenzoic acid) ester, tripropylene glycol monomethyl ether (anisic acid) ester, tripropylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the tripropylene glycol monoethyl ether acetate, tripropylene glycol list ether propionate ester, tripropylene glycol list ether benzoic ether, tripropylene glycol list ether (Chlorodracylic acid) ester, tripropylene glycol list ether (m-chlorobenzoic acid) ester, tripropylene glycol list ether (parabromobenzoic acid) ester, tripropylene glycol list ether (m-bromobenzoic acid) ester, tripropylene glycol list ether (o-bromobenzoic acid) ester, tripropylene glycol list ether (p-methylbenzoic acid) ester, tripropylene glycol list ether (p-tert-butyl benzoic acid) ester, tripropylene glycol list ether (to butylbenzoic acid) ester, at least a in tripropylene glycol list ether (anisic acid) ester and tripropylene glycol list ether (o-methoxybenzoic acid) ester.Compound shown in the formula of using in the present invention (I) all can be commercially available, perhaps obtains through esterification or transesterification and etherificate by corresponding precursor compound.
according to olefin polymerization catalyst components of the present invention, because the present invention is hydrogen response when improving olefin polymerization catalyst components and be used for olefinic polymerization as internal electron donor with internal electron donor a and internal electron donor b, so as long as contain internal electron donor a and internal electron donor b in internal electron donor of the present invention, for described internal electron donor, the content of titanium and magnesium is not particularly limited, in the preferred case, take olefin polymerization catalyst components as benchmark, the content of described internal electron donor a can be the 1-10 % by weight, the content of described internal electron donor b is the 1-10 % by weight.Hydrogen response when being used for olefinic polymerization in order further to improve olefin polymerization catalyst components, take olefin polymerization catalyst components as benchmark, the content of described internal electron donor a is preferably the 2-7 % by weight, and the content of described internal electron donor b is preferably the 3-8 % by weight.In preferred situation, the internal electron donor a in described internal electron donor and the mol ratio of internal electron donor b can be 0.1-10:1, are preferably 0.2-5:1.
According to olefin polymerization catalyst components of the present invention, what described halogen can be in fluorine, chlorine, bromine and iodine is at least a, is preferably chlorine and/or bromine.
described internal electron donor b is for being selected from least a in the dibasic aliphatic carboxylicesters shown in the binary aromatic carboxylic acid esters shown in formula (II) and formula (III), be preferably diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, the O-phthalic di-isooctyl, 2-sec.-propyl-2-isopentyl-1, 3 propylene glycol dibenzoates, 2, 4-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 2, 3-di-isopropyl-1, 4-butyleneglycol dibenzoate, 3, 5-heptanediol dibenzoate and 4-ethyl-3, at least a in 5-heptanediol dibenzoate etc., dibutyl phthalate particularly preferably, diisobutyl phthalate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate and 4-ethyl-3, at least a in 5-heptanediol dibenzoate.
According to olefin polymerization catalyst components of the present invention, wherein, described catalyst component can be the reaction product of titanium compound, magnesium compound and internal electron donor.Consumption for the preparation of titanium compound, magnesium compound and the internal electron donor of described olefin polymerization catalyst components is not particularly limited, and can be respectively conventional substances and the consumption of this area.
In the preferred case, what described magnesium compound can be in the alcohol adducts of the hydrate of the magnesium compound shown in the magnesium compound shown in formula (IV), formula (IV) and the magnesium compound shown in formula (IV) is at least a,
MgR 16R 17 （IV）
In formula (IV), R 16And R 17Respectively do for oneself halogen, carbonatoms is a kind of in the straight or branched alkoxyl group of 1-5 and straight or branched alkyl that carbonatoms is 1-5.
In olefin polymerization catalyst components of the present invention, the hydrate of the magnesium compound shown in described formula (IV) refers to MgR 4R 5QH 2O, wherein, q be in the scope of 0.1-6 within, be preferably 2-3.5.In the present invention, described alcohol adducts refers to MgR 16R 17PR 0OH, wherein, R 0Be the alkyl of 1-18 for carbonatoms, be preferably the alkyl that carbonatoms is 1-5, more preferably methyl, ethyl, n-propyl and sec.-propyl; P is preferably 2-3.5 within being in the scope of 0.1-6.Preferably, in formula (IV), R 16And R 17The halogen of respectively doing for oneself, for example can be in chlorine, bromine and iodine a kind of.
in the preferred case, described magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-methyl) hexyloxy magnesium, methoxyl group chlorination magnesium, the methoxyl group magnesium bromide, the methoxyl group magnesium iodide, the oxyethyl group magnesium chloride, the oxyethyl group magnesium bromide, the oxyethyl group magnesium iodide, the propoxy-magnesium chloride, the propoxy-magnesium bromide, the propoxy-magnesium iodide, the butoxy magnesium chloride, the butoxy magnesium bromide, the butoxy magnesium iodide, magnesium dichloride, dibrominated magnesium, two magnesium iodides, the alcohol adducts of magnesium dichloride, at least a in the alcohol adducts of the alcohol adducts of dibrominated magnesium and two magnesium iodides.Most preferably, described magnesium compound is diethoxy magnesium or magnesium dichloride.
According to olefin polymerization catalyst components of the present invention, wherein, described titanium compound is the compound shown in formula V,
TiX m(OR 18) 4-m （V）
In formula V, X is halogen, R 18Be the alkyl of 1-20 for carbonatoms, m is the integer of 1-4.M can be 0,1,2,3 or 4.Described halogen can be chlorine, bromine or iodine.
In the preferred case, in formula V, X is halogen, R 18Be the alkyl of 1-5 for carbonatoms, for example: at least a in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
In the present invention, the method for preparing olefin polymerization catalyst components of the present invention by titanium compound, magnesium compound and internal electron donor are reacted can be undertaken by the method for preparing the alkene catalyst component of this area routine.For example can prepare olefin polymerization catalyst components of the present invention by following method.
Method one, alkoxyl magnesium or alkoxyl group magnesium halide are suspended in form suspended emulsion in inert diluent, again this suspension is mixed with above-mentioned titanium compound and contact to get solids, and then solids is contacted with b with internal electron donor a, it is attached on solids, can makes olefin polymerization catalyst components of the present invention.
Object lesson as above-mentioned alkoxyl magnesium, can enumerate dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-methyl) hexyloxy magnesium etc. or its mixture, be preferably the mixture of diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesium.The preparation method of this alkoxyl magnesium compound can be by method preparation well known in the art, as the preparation under a small amount of iodine exists with MAGNESIUM METAL and Fatty Alcohol(C12-C14 and C12-C18).
As the object lesson of above-mentioned alkoxyl group magnesium halide, can enumerate methoxyl group chlorination magnesium, oxyethyl group magnesium chloride, propoxy-magnesium chloride, butoxy magnesium chloride etc., preferred oxyethyl group magnesium chloride.The preparation method of this alkoxyl group halogenated magnesium compound can be by method preparation well known in the art, as the Grignard reagent butylmagnesium chloride is mixed to prepare the oxyethyl group magnesium chloride with purity titanium tetraethoxide and tetraethoxy-silicane.
The inert diluent that uses in aforesaid method one can adopt at least a in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.
The consumption of each composition that uses in method one in every mole of magnesium chloride, the usage quantity 0.5-100 of titanium compound mole, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; The total amount of electronic donor compound capable is generally 0.005-10 mole, is preferably 0.01-1 mole.
The Contact Temperature of described each component is generally-40～200 ℃, is preferably-20～150 ℃; Be generally 1 minute duration of contact-20 hours, be preferably 5 minutes-8 hours.
Method two is dissolved in magnesium dihalide in the solvent system of organic epoxy compounds, organo phosphorous compounds and inert diluent composition, mixes with titanium compound after the formation homogeneous solution, under precipitation additive exists, separates out solids; And then this solids is contacted with b with internal electron donor a, it is attached to obtains ingredient of solid catalyst on solids.
The precipitation additive that uses in method two can be as in organic acid anhydride, organic acid, ether and ketone at least a.The object lesson of described organic acid anhydride can be in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried and MALEIC ANHYDRIDE etc. at least a, described organic acid object lesson can be in acetic acid, propionic acid, butyric acid, vinylformic acid and methacrylic acid etc. at least a, the object lesson of described ether can be in methyl ether, ether, propyl ether, butyl ether and amyl ether at least a, what described ketone can be in acetone, methylethylketone and benzophenone is at least a.
The organic epoxy compounds that uses in method two can be for being selected from least a in oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether and diglycidylether etc., preferred epoxy chloropropane.
The organo phosphorous compounds that uses in method two can be hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, the object lesson of this organo phosphorous compounds can be enumerated: 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 or phosphorous acid benzene methyl etc., preferred ortho-phosphoric acid tri-n-butyl.
The inert diluent that uses in method two can adopt in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene at least a.
The consumption of each composition that uses in method two, in every mole of magnesium halide, organic epoxy compounds can be 0.2-10 mole, is preferably 0.5-4 mole; Organo phosphorous compounds can be 0.1-3 mole, is preferably 0.3-1.5 mole; Titanium compound can be 0.5-20 mole, is preferably 5-15 mole; Help and separate out component and can be 0.01-0.3 mole, be preferably 0.02-0.08 mole; The electronic donor compound capable total amount can be 0-10 mole, is preferably 0.02-0.3 mole.
Method three 80-130 ℃ of reaction, and then contacts with internal electron donor a of the present invention the alcohol adducts of the titanium compound shown in above-mentioned formula (III) and magnesium dihalide with b, obtain olefin polymerization catalyst components of the present invention.The alcohol adducts of described magnesium dihalide can make by the following method: under not miscible with adducts inert solvent (as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene etc.) exists, alcohol (as methyl alcohol, ethanol, propyl alcohol or Virahol etc.) and magnesium halide are mixed the formation emulsion, make the rapid chilling of this emulsion, the gained spheroidal particle is the alcohol adducts of magnesium dihalide.
In the above-mentioned three kinds any methods that prepare olefin polymerization catalyst components of the present invention, can with described internal electron donor a and b divides out or add with the form of mixture.
In the above-mentioned three kinds any methods that prepare olefin polymerization catalyst components of the present invention, internal electron donor a and b also can be at magnesium compound with before titanium compound contact or add in contact process, as first internal electron donor a and b being joined at alkoxyl magnesium or alkoxyl group magnesium halide in the suspension at inert diluent in method one, then be mixed with olefin polymerization catalysis with titanium compound; In method two with internal electron donor a and b magnesium halide solution with join magnesium halide solution before titaniferous compound contacts.
In the preparation of above-mentioned olefin polymerization catalyst components, the consumption of internal electron donor a and the mol ratio of magnesium atom can be 0.01-1 usually, are preferably 0.05-0.5.The consumption of internal electron donor b and the mol ratio of magnesium atom can be 0.01-1 usually, are preferably 0.05-0.5.
According to olefin polymerization catalysis of the present invention, this catalyzer is used for by general formula CH 2The polyreaction of the alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6, described catalyzer comprises the reaction product of following material:
(1) above-mentioned olefin polymerization catalyst components;
(2) as the organo-aluminium compound of promotor;
(3) randomly, external donor compound.
In above-mentioned olefin polymerization catalysis, described organo-aluminium compound can be the field of olefin polymerisation various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst commonly used.In the preferred case, described organo-aluminium compound can be the compound shown in formula (VI),
AlR' n'X' 3-n' （VI）
In formula (VI), R' is that hydrogen, carbonatoms are that alkyl or the carbonatoms of 1-20 is the aryl of 6-20, and X' is halogen, and n' is the integer of 1-3.The object lesson of described organo-aluminium compound for example can be in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride and ethyl aluminum dichloride at least a.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 5-5000:1.Preferably, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 20-1000:1.More preferably, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 50-500:1.
Owing to only the internal electron donor in olefin polymerization catalyst components being improved in olefin polymerization catalysis of the present invention, therefore, kind and the content of the external electron donor in olefin polymerization catalysis of the present invention are not particularly limited.In the preferred case, the aluminium in described organo-aluminium compound and the mol ratio of described external donor compound are 0.1-500:1, preferred 1-300:1, more preferably 3-100:1.
In above-mentioned olefin polymerization catalysis, described external electron donor component can be the silicoorganic compound shown in formula (VII),
R'' m'Si(OR''') 4-m' （VII）
In formula (VII), R'' be halogen, hydrogen atom, carbonatoms are the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms be 1-20 haloalkyl in a kind of; R''' be carbonatoms is the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms be 1-20 haloalkyl in a kind of; M' is the integer of 1-3.object lesson as described silicoorganic compound can be enumerated the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, two cyclohexyl dimethoxy silane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1, 1, 1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1, 1, 1-three fluoro-2-propyl group) at least a in-methyl dimethoxysilane etc.
According to olefine polymerizing process of the present invention, the method is included under the olefinic polymerization condition, and one or more alkene are contacted with above-mentioned catalyzer, and at least a in described alkene is by general formula CH 2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.
Olefine polymerizing process of the present invention can be used for the equal polymerization of alkene, also can be used for multiple alkene is carried out copolymerization.At least a in described alkene is by general formula CH 2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.Described by general formula CH 2The specific examples of the alkene that=CHR represents comprises: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.Preferably, described alpha-olefin CH 2=CHR is one or more in ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene.More preferably, described by general formula CH 2The alkene that=CHR represents is propylene.
According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be the normal condition of this area.Usually, described olefinic polymerization condition comprises: temperature is 0-150 ℃, and the time is 0.1-5 hour, and pressure is 0.01-10MPa.Preferably, described olefinic polymerization condition comprises: temperature is 60-100 ℃, and the time is 0.5-3 hour, and pressure is 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
Below in conjunction with embodiment, the present invention is described in further detail.
That uses in following each embodiment except as otherwise noted, reaches the chemical plant as the phthalic ester of internal electron donor b in all available from Luoyang; Anhydrous MgCl 2Available from Qinghai North Star Science and Technology Ltd.; TiCl 4Available from Xingtai non-ferrous metals smelting works; As the silicoorganic compound of external electron donor, organo-aluminium compound is all available from Nanjing communications and liaison chemical industry company limited.The diethylene glycol monomethyl ether benzoic ether that uses, diethylene glycol monoethyl ether benzoic ether, dipropylene glycol monomethyl ether benzoic ether, triethylene glycol monomethyl ether benzoic ether and diethoxy magnesium prepare according to the method for preparation example 1-5 respectively.
In following examples, 1H-NMR adopts the BRUKER AVANCN300 of company type nuclear magnetic resonance analyser to measure; Titanium content in olefin polymerization catalyst components is according to 721 spectrophotometer tests available from An Hemeng (Tianjin) development in science and technology company limited; In olefin polymerization catalyst components, internal electron donor content is measured according to the Waters600E liquid chromatography; The melting index of polymkeric substance is to use available from the model of Changchun new experimental instrument and equipment company limited to measure according to the method for stipulating in GB/T3682-2000 as the XRZ-00 fusion index instrument.
In following examples, the testing method of polymkeric substance degree of isotacticity comprises: the polymer samples of 2 gram dryings, and be placed in extractor and after 6 hours, residuum be dried to constant weight with the extracting of boiling heptane, calculate degree of isotacticity by following formula:
Polymer quality after degree of isotacticity (%)=extracting/2 * 100.
The measuring method of molecular weight distribution MWD (MWD=Mw/Mn) comprises: adopt PL-GPC220 to measure (standard specimen: polystyrene take trichlorobenzene as solvent under 150 ℃, flow velocity: 1.0ml/min, pillar: 3xPlgel10um MlxED-B300x7.5nm).
Preparation example 1
The preparation of diethylene glycol monomethyl ether benzoic ether
Get 0.2mol(24.0g) diethylene glycol monomethyl ether is dissolved in the mixture of the tetrahydrofuran (THF) of 100mL drying and 100mL pyridine, stirs; Stir and add simultaneously 0.25mol(35g) Benzoyl chloride, continue stirring and be warming up to reflux temperature after 1 hour, back flow reaction 6 hours added 50mL water stirring and refluxing 2 hours.Add the 200mL anhydrous diethyl ether, separatory, organic phase uses 1N salt acid elution to pH=4, then uses the saturated common salt solution washing to neutral, and air distillation desolventizes column chromatography for separation (eluent methylene chloride) and gets colourless liquid 33 grams. 1H-NMR（TMS，CDCl 3，ppm）:δ8.05(d,2H),7.55(t,1H),7.42(t,2H),4.47(t,2H),3.84(t,2H),3.51(s,4H),3.30(s,3H)。
Preparation example 2
The preparation of diethylene glycol monoethyl ether benzoic ether
Get 0.2mol(26.8g) diethylene glycol monoethyl ether, be dissolved in the tetrahydrofuran (THF) of 100mL drying and the mixture of 100mL pyridine, stir; Stir and add simultaneously 0.25mol(35g) Benzoyl chloride,, continue stirring and be warming up to reflux temperature, back flow reaction 6 hours after 1 hour; Added 50mL water stirring and refluxing 2 hours.Add the 200mL anhydrous diethyl ether, separatory, organic phase uses 1N salt acid elution to pH=4, then uses the saturated common salt solution washing to neutral, and air distillation desolventizes column chromatography for separation (eluent methylene chloride) and gets colourless liquid 39 grams. 1H-NMR（TMS，CDCl 3，ppm）:δ8.05(d,2H),7.55(t,1H),7.42(t,2H),4.47(t,2H),3.84(t,2H),3.50(m,6H),1.08(t,3H)。
Preparation example 3
The preparation of dipropylene glycol monomethyl ether benzoic ether
Get 0.2mol(29.2g) dipropylene glycol monomethyl ether is dissolved in the tetrahydrofuran (THF) of 100mL drying and the mixture of 100mL pyridine, stirs; Stir and add simultaneously 0.25mol(35g) Benzoyl chloride, continue stirring and be warming up to reflux temperature, back flow reaction 6 hours after 1 hour; Added 50mL water stirring and refluxing 2 hours.Add the 200mL anhydrous diethyl ether, separatory, organic phase uses 1N salt acid elution to pH=4, then uses the saturated common salt solution washing to neutral, and air distillation desolventizes column chromatography for separation (eluent methylene chloride) and gets colourless liquid 39 grams. 1H-NMR（TMS，CDCl 3，ppm）:δ8.05(d,2H),7.55(t,1H),7.42(t,2H),4.27(t,2H),3.32(t,6H),3.30(s,3H),2.10(m,2H),1.75(m,2H),。
Preparation example 4
The preparation of triethylene glycol monomethyl ether benzoic ether
Get 0.2mol(32.8g) triethylene glycol monomethyl ether is dissolved in the tetrahydrofuran (THF) of 100mL drying and the mixture of 100mL pyridine, stirs; Stir and add simultaneously 0.25mol(35g) Benzoyl chloride, continue stirring and be warming up to reflux temperature, back flow reaction 6 hours after 1 hour; Added 50mL water stirring and refluxing 2 hours.Add the 200mL anhydrous diethyl ether, separatory, organic phase uses 1N salt acid elution to pH=4, then uses the saturated common salt solution washing to neutral, and air distillation desolventizes column chromatography for separation (eluent methylene chloride) and gets colourless liquid 41 grams. 1H-NMR（TMS，CDCl 3，ppm）:δ8.03(d,2H),7.54(t, 1H),7.41(t,2H),4.46(t,2H),3.83(t,2H),3.50(s,8H),3.30(s,3H)。
Preparation example 5
The preparation of diethoxy magnesium
In the 1L reactor with agitator, reflux condensing tube, thermometer and drop-burette, after nitrogen displacement fully, add ethanol 550mL in reactor, iodine 0.68g dissolving.Heat up after opening stirring, until reach the reflux temperature of reaction system.Then successively add magnesium powder 32g.Reaction is till no longer include hydrogen and discharge.Then wash, separate and drying, get tap density 0.25g/cm 3, median size (D50) is the diethoxy magnesium of 38.0 μ m.
Embodiment 1
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The preparation of olefin polymerization catalyst components: get diethylene glycol monoethyl ether benzoic ether (electron donor a, R in formula (I) that diethoxy magnesium carrier 88mmol that preparation example 5 makes and toluene 470mmol, preparation example 2 make 1Be ethyl, R 2Be ethyl, R 3Be phenyl, n is 2) 4mmol, n-butyl phthalate (electron donor b) 6mmol, be mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 94mmol and titanium tetrachloride 819mmol, be warming up to 80 ℃, then the suspension for preparing is added in still, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.Then add the mixed solution of toluene 1128mmol and titanium tetrachloride 273mmol to be warming up to 110 ℃ of stir process 1 hour, so process 3 times, elimination liquid, the solid of gained washs 4 times with hexane 1148mmol, elimination liquid is also dry, namely gets olefin polymerization catalyst components A1 of the present invention.
Polyolefine preparation: in 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5mL triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/mL), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A1 for preparing of 10mg of lmL Cyclohexyl Methyl Dimethoxysilane (CHMMS).Close autoclave, introduce the hydrogen of 4.5 standard liters (NL) and the liquid propene of 2L; Temperature is risen to 70 ℃ under agitation 10 minutes., stop stirring after 1 hour 70 ℃ of lower polyreactions, remove unpolymerized propylene monomer, collect and obtain polymer P 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Comparative Examples 1
Get the magnesium ethylate carrier 8.8mmol that preparation example 5 makes, toluene 470mmol and n-butyl phthalate (electron donor b) 10mmol is mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 94mmol and titanium tetrachloride 819mmol, be warming up to 80 ℃, then the suspension for preparing is added in still, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.Then add the mixed solution of toluene 1128mmol and titanium tetrachloride 273mmol to be warming up to 110 ℃ of stir process 1 hour, so process 3 times, elimination liquid, the solid of gained washs 4 times with hexane 1148mmol, and elimination liquid is also dry, namely gets catalyst component B1.
Use above-mentioned catalyst component B1 to replace olefin polymerization catalyst components A1, prepare polymkeric substance D1 according to the polyacrylic method of preparation polyolefine in embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Embodiment 2
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The preparation of olefin polymerization catalyst components: get diethoxy magnesium carrier 88mmol, the toluene 940mmol that preparation example 5 obtains, diethylene glycol monoethyl ether benzoic ether (electron donor a, the R in formula (I) that preparation example 2 makes 1Be ethyl, R 2Be ethyl, R 3Be phenyl, n is 2) 2mmol, n-butyl phthalate (electron donor b) 8mmol, be mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 94mmol and titanium tetrachloride 240mmol, be warming up to 80 ℃, then the suspension for preparing is added in still, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.Then add the mixed solution of toluene 1128mmol and titanium tetrachloride 273mmol to be warming up to 110 ℃ of stir process 1 hour, so process 3 times, elimination liquid, the solid of gained washs 4 times with hexane 1148mmol, elimination liquid is also dry, namely gets olefin polymerization catalyst components A2 of the present invention.
Polyolefine preparation: in 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5 milliliters of triethyl aluminums, hexane solution (concentration of CHMMS is 0.1mmol/mL), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A1 for preparing of 10mg of l milliliter Cyclohexyl Methyl Dimethoxysilane (CHMMS).Close autoclave, introduce the hydrogen of 4.5NL and the liquid propene of 2L; Temperature is risen to 60 ℃ under agitation 10 minutes., stop stirring after 1 hour 60 ℃ of lower polyreactions, remove unpolymerized propylene monomer, collect and obtain polymer P 2.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Embodiment 3
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The preparation of olefin polymerization catalyst components: get diethylene glycol monoethyl ether benzoic ether (electron donor a, R in formula (I) that diethoxy magnesium carrier 88mmol that preparation example 5 makes and toluene 940mmol, preparation example 2 make 1Be ethyl, R 2Be ethyl, R 3Be phenyl, n is 2) 8mmol, n-butyl phthalate (electron donor b) 2mmol, be mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 94.00mmol and titanium tetrachloride 819mmol, be warming up to 80 ℃, then the suspension for preparing is added in still, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.Then add the mixed solution of toluene 1128mmol and titanium tetrachloride 273mmol to be warming up to 110 ℃ of stir process 1 hour, so process 3 times, elimination liquid, the solid of gained washs 4 times with hexane 1148mmol, elimination liquid is also dry, namely gets olefin polymerization catalyst components A3 of the present invention.
Polyolefine preparation: in 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5 milliliters of triethyl aluminums, hexane solution (concentration of CHMMS is 0.1mmol/mL), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A1 for preparing of 10mg of l milliliter Cyclohexyl Methyl Dimethoxysilane (CHMMS).Close autoclave, introduce the hydrogen of 4.5NL and the liquid propene of 2L; Temperature is risen to 70 ℃ under agitation 10 minutes., stop stirring after 1 hour 70 ℃ of lower polyreactions, remove unpolymerized propylene monomer, collect and obtain polymer P 3.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Embodiment 4
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The diethylene glycol monomethyl ether benzoic ether (electron donor a, the R in formula (I) that make except electron donor a being changed into preparation example 1 1Be methyl, R 2Be ethyl, R 3Be phenyl, n is 2) in addition, prepare olefin polymerization catalyst components A4 and polymer P 4 according to the method for embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is as shown in table 2.
Embodiment 5
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The dipropylene glycol monomethyl ether benzoic ether (electron donor a, the R in formula (I) that make except electron donor a being changed into preparation example 3 1Be methyl, R 2Be propyl group, R 3Be phenyl, n is 2) in addition, prepare olefin polymerization catalyst components A5 and polymer P 5 according to the method for embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is as shown in table 2.
Embodiment 6
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalyst components and olefine polymerizing process.
The dipropylene glycol monomethyl ether acetic ester (electron donor a, the R in formula (I) that make except electron donor a being changed into preparation example 3 1Be methyl, R 2Be ethyl, R 3Be methyl, n is 2) in addition, prepare olefin polymerization catalysis A6 and polymer P 6 according to the method for embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is as shown in table 2.
Embodiment 7
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The triethylene glycol monomethyl ether benzoic ether (electron donor a, the R in formula (I) that make except electron donor a being changed into preparation example 4 1Be methyl, R 2Be ethyl, R 3Be phenyl, n is 3) in addition, prepare olefin polymerization catalyst components A6 and polymer P 6 according to the method for embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is as shown in table 2.
Embodiment 8
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
The preparation of olefin polymerization catalyst components: in the reactor that repeats to replace through high pure nitrogen, add successively 50mmol Magnesium Chloride Anhydrous, 880mmol toluene, 50mmol epoxy chloropropane, 46mmol tributyl phosphate.Be under the condition of 60 ℃ in mixing speed 450rpm, temperature, make reaction mixture reaction 2 hours.Add the 10mmol Tetra hydro Phthalic anhydride, and allow reaction mixture to continue reaction one hour, then be cooled to-28 ℃.Drip titanium tetrachloride 510mmol, be warming up to gradually 85 ℃, the diethylene glycol monoethyl ether benzoic ether (electron donor a, the R in formula (I) that add 3.0mmol preparation example 2 to make in the time of 80 ℃ 1Be ethyl, R 2Be ethyl, R 3Be phenyl, n is 2) and 3mmol dibutyl phthalate (electron donor b), 85 ℃ are arrived the rear constant temperature of temperature one hour.The elimination mother liquor, then the residual solid thing was processed 2 hours at 110 ℃ with 570mmol toluene and 360mmol titanium tetrachloride with 950mmol toluene wash twice.Repeat again this processing once after filtration.The solids that obtains is washed 5 times with hexane, then dry, obtain olefin polymerization catalysis A8 of the present invention.
Use olefin polymerization catalyst components A8 to replace olefin polymerization catalyst components A1, prepare polymer P 8 according to the polyacrylic method of preparation polyolefine in embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Comparative Examples 2
In the reactor that repeats to replace through high pure nitrogen, add successively 50mmol Magnesium Chloride Anhydrous, 880mmol toluene, 50mmol epoxy chloropropane, 46mmol tributyl phosphate.Be under the condition of 60 ℃ in mixing speed 450rpm, temperature, make reaction mixture reaction 2 hours.Add the 10mmol Tetra hydro Phthalic anhydride, and allow reaction mixture to continue reaction one hour, then be cooled to-28 ℃.Drip titanium tetrachloride 510mmol, be warming up to gradually 85 ℃, add 6mmol dibutyl phthalate (electron donor b) in the time of 80 ℃, 85 ℃ are arrived the rear constant temperature of temperature one hour.The elimination mother liquor, then the residual solid thing was processed 2 hours at 110 ℃ with 570mmol toluene and 360mmol titanium tetrachloride with 950mmol toluene wash twice.Repeat again this processing once after filtration.The solids that obtains is washed 5 times with hexane, then dry, obtain catalyst component B2.
Use above-mentioned catalyst component B2, prepare polymkeric substance D2 according to the polyacrylic method of preparation polyolefine in embodiment 1.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Embodiment 9
The present embodiment is used for illustrating olefin polymerization catalyst components of the present invention, olefin polymerization catalysis and olefine polymerizing process.
Method according to embodiment 1 prepares olefin polymerization catalyst components A9.
Polyolefine preparation: in 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add hexane solution (concentration of diisopropyl dimethoxy silane is 0.1mmol/mL), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A9 for preparing of 10mg of the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5 milliliters of triethyl aluminums, 1 milliliter of diisopropyl dimethoxy silane.Close autoclave, introduce the hydrogen of 4.5NL and the liquid propene of 2L; Temperature is risen to 70 ℃ under agitation 10 minutes., stop stirring after 1 hour 70 ℃ of lower polyreactions, remove unpolymerized propylene monomer, collect and obtain polymer P 9.
Result in the polymerization activity of the content of the content of the content of the titanium of titanium elements, internal electron donor a, internal electron donor b and catalyst component in catalyst component is as shown in table 1.The performance perameter of polymkeric substance is shown in Table 2.
Table 1
Figure GDA00002918786000261
Table 2
Figure GDA00002918786000262
Can find out from the data of table 1 and table 2, use the polymerization activity of the olefin polymerization catalyst components that ad hoc structure internal electron donor a of the present invention obtains higher, the stereotaxis ability is better, the molecular weight distribution of resulting polymers is wider, especially has high melting index, illustrate that olefin polymerization catalyst components of the present invention has good hydrogen response, is suitable for by general formula CH 2The preparation of the polymkeric substance of the polyreaction of the alkene that=CHR represents (wherein R is that hydrogen or carbonatoms are the alkyl of 1-6).

Claims (22)

1. olefin polymerization catalyst components, this catalyst component contains titanium, magnesium and internal electron donor, it is characterized in that, described internal electron donor comprises internal electron donor a and internal electron donor b, described internal electron donor a is the compound shown in formula (I), described internal electron donor b is at least a in the binary aliphatic alcohol carboxylicesters shown in the binary aromatic carboxylic acid's ester shown in formula (II) and formula (III)
Figure FDA00002918785900011
In formula (I), R 1And R 3Identical or different, a kind of in the replacement of the straight or branched alkyl of the carbonatoms 1-10 that respectively does for oneself, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20 or unsubstituting aromatic yl;
R 2For the replacement of the straight or branched alkylidene group of carbonatoms 1-6 and carbon atom 6-20 or do not replace a kind of in arylidene;
N is the integer of 2-10;
In formula (II), R 4And R 5Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-8, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl;
R 6, R 7, R 8And R 9Be all hydrogen, perhaps wherein three be hydrogen, another one is that halogen, carbonatoms are a kind of in the straight or branched alkyl of 1-4 and straight or branched alkoxyl group that carbonatoms is 1-4;
Figure FDA00002918785900021
R in formula (III) 10And R 11Identical or different, the carbonatoms of respectively doing for oneself is a kind of in the replacement that is 6-20 of the straight or branched alkyl of 1-10, cycloalkyl that carbonatoms is 3-10 and carbonatoms or unsubstituting aromatic yl; R 12And R 13Identical or different, the carbonatoms of respectively doing for oneself is the straight or branched alkyl of 1-10; R 14And R 15Identical or different, a kind of in the straight or branched alkyl of respectively do for oneself hydrogen and carbonatoms 1-10.
2. catalyst component according to claim 1, wherein, take the gross weight of catalyst component as benchmark, the content of described internal electron donor a is the 1-10 % by weight, the content of described internal electron donor b is the 1-10 % by weight.
3. catalyst component according to claim 2, wherein, take the gross weight of catalyst component as benchmark, the content of described internal electron donor a is the 2-7 % by weight, the content of described internal electron donor b is the 3-8 % by weight.
4. the described catalyst component of any one according to claim 1-3, wherein, the internal electron donor a in described internal electron donor and the mol ratio of internal electron donor b are 0.1-10:1.
5. catalyst component according to claim 4, wherein, the internal electron donor a in described internal electron donor and the mol ratio of internal electron donor b are 0.2-5:1.
6. catalyst component according to claim 4, wherein, in described formula (I), described R 1Be the straight or branched alkyl of carbonatoms 1-6, described R3 is phenyl or the substituted-phenyl of carbonatoms 6-10, described R 2Straight or branched alkylidene group for carbonatoms 2-4.
7. catalyst component according to claim 4, wherein, in described formula (I), described n is the integer of 2-6.
8. catalyst component according to claim 4, wherein, described internal electron donor a is the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monomethyl ether propionic ester, the diethylene glycol monomethyl ether benzoic ether, diethylene glycol monomethyl ether (Chlorodracylic acid) ester, diethylene glycol monomethyl ether (m-bromobenzoic acid) ester, diethylene glycol monomethyl ether (o-bromobenzoic acid) ester, diethylene glycol monomethyl ether (p-methylbenzoic acid) ester, diethylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, diethylene glycol monomethyl ether (to butylbenzoic acid) ester, diethylene glycol monomethyl ether (anisic acid) ester, diethylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the diethylene glycol monoethyl ether acetic ester, the diethylene glycol monoethyl ether propionic ester, the diethylene glycol monoethyl ether benzoic ether, diethylene glycol monoethyl ether (Chlorodracylic acid) ester, diethylene glycol monoethyl ether (m-bromobenzoic acid) ester, diethylene glycol monoethyl ether (o-bromobenzoic acid) ester, diethylene glycol monoethyl ether (p-methylbenzoic acid) ester, diethylene glycol monoethyl ether (p-tert-butyl benzoic acid) ester, diethylene glycol monoethyl ether (to butylbenzoic acid) ester, diethylene glycol monoethyl ether (anisic acid) ester, diethylene glycol monoethyl ether (o-methoxybenzoic acid) ester, the triethylene glycol monomethyl ether acetic ester, the triethylene glycol monomethyl ether propionic ester, the triethylene glycol monomethyl ether benzoic ether, triethylene glycol monomethyl ether (Chlorodracylic acid) ester, triethylene glycol monomethyl ether (m-bromobenzoic acid) ester, triethylene glycol monomethyl ether (o-bromobenzoic acid) ester, triethylene glycol monomethyl ether (p-methylbenzoic acid) ester, triethylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, triethylene glycol monomethyl ether (to butylbenzoic acid) ester, triethylene glycol monomethyl ether (anisic acid) ester, triethylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the triethylene glycol monoethyl ether acetic ester, the triethylene glycol monoethyl ether propionic ester, the triethylene glycol monoethyl ether benzoic ether, triethylene glycol monoethyl ether (Chlorodracylic acid) ester, triethylene glycol monoethyl ether (m-bromobenzoic acid) ester, triethylene glycol monoethyl ether (o-bromobenzoic acid) ester, triethylene glycol monoethyl ether (p-methylbenzoic acid) ester, triethylene glycol monoethyl ether (p-tert-butyl benzoic acid) ester, triethylene glycol monoethyl ether (to butylbenzoic acid) ester, triethylene glycol monoethyl ether (anisic acid) ester, triethylene glycol monoethyl ether (o-methoxybenzoic acid) ester, the dipropylene glycol monomethyl ether acetic ester, the dipropylene glycol monomethyl ether propionic ester, the dipropylene glycol monomethyl ether benzoic ether, dipropylene glycol monomethyl ether (Chlorodracylic acid) ester, dipropylene glycol monomethyl ether (m-chlorobenzoic acid) ester, dipropylene glycol monomethyl ether (parabromobenzoic acid) ester, dipropylene glycol monomethyl ether (m-bromobenzoic acid) ester, dipropylene glycol monomethyl ether (o-bromobenzoic acid) ester, dipropylene glycol monomethyl ether (p-methylbenzoic acid) ester, dipropylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, dipropylene glycol monomethyl ether (to butylbenzoic acid) ester, dipropylene glycol monomethyl ether (anisic acid) ester, dipropylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the DPE acetic ester, the DPE propionic ester, the DPE benzoic ether, DPE (Chlorodracylic acid) ester, DPE (m-bromobenzoic acid) ester, DPE (o-bromobenzoic acid) ester, DPE (p-methylbenzoic acid) ester, DPE (p-tert-butyl benzoic acid) ester, DPE (to butylbenzoic acid) ester, DPE (anisic acid) ester, DPE (o-methoxybenzoic acid) ester, the tripropylene glycol methyl ether acetate, tripropylene glycol monomethyl ether propionic ester, tripropylene glycol monomethyl ether benzoic ether, tripropylene glycol monomethyl ether (Chlorodracylic acid) ester, tripropylene glycol monomethyl ether (m-chlorobenzoic acid) ester, tripropylene glycol monomethyl ether (parabromobenzoic acid) ester, tripropylene glycol monomethyl ether (m-bromobenzoic acid) ester, tripropylene glycol monomethyl ether (o-bromobenzoic acid) ester, tripropylene glycol monomethyl ether (p-methylbenzoic acid) ester, tripropylene glycol monomethyl ether (p-tert-butyl benzoic acid) ester, tripropylene glycol monomethyl ether (to butylbenzoic acid) ester, tripropylene glycol monomethyl ether (anisic acid) ester, tripropylene glycol monomethyl ether (o-methoxybenzoic acid) ester, the tripropylene glycol monoethyl ether acetate, tripropylene glycol list ether propionate ester, tripropylene glycol list ether benzoic ether, tripropylene glycol list ether (Chlorodracylic acid) ester, tripropylene glycol list ether (m-chlorobenzoic acid) ester, tripropylene glycol list ether (parabromobenzoic acid) ester, tripropylene glycol list ether (m-bromobenzoic acid) ester, tripropylene glycol list ether (o-bromobenzoic acid) ester, tripropylene glycol list ether (p-methylbenzoic acid) ester, tripropylene glycol list ether (p-tert-butyl benzoic acid) ester, tripropylene glycol list ether (to butylbenzoic acid) ester, at least a in tripropylene glycol list ether (anisic acid) ester and tripropylene glycol list ether (o-methoxybenzoic acid) ester.
9. catalyst component according to claim 4, wherein, described internal electron donor b is diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, O-phthalic di-isooctyl, 2,4-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 3,5-heptanediol dibenzoate and 4-ethyl-3, at least a in 5-heptanediol dibenzoate.
According to claim 1-3 and 5-9 in the described catalyst component of any one, wherein, described catalyst component is the reaction product of titanium compound, magnesium compound and internal electron donor.
11. catalyst component according to claim 10, wherein, described magnesium compound is at least a in the alcohol adducts of the hydrate of the magnesium compound shown in the magnesium compound shown in formula (IV), formula (IV) and the magnesium compound shown in formula (IV),
MgR 16R 17 （IV）
In formula (IV), R 16And R 17Respectively do for oneself halogen, carbonatoms is a kind of in the straight or branched alkoxyl group of 1-5 and straight or branched alkyl that carbonatoms is 1-5.
12. catalyst component according to claim 11, wherein, described magnesium compound is dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, methoxyl group chlorination magnesium, the methoxyl group magnesium bromide, the methoxyl group magnesium iodide, the oxyethyl group magnesium chloride, the oxyethyl group magnesium bromide, the oxyethyl group magnesium iodide, the propoxy-magnesium chloride, the propoxy-magnesium bromide, the propoxy-magnesium iodide, the butoxy magnesium chloride, the butoxy magnesium bromide, the butoxy magnesium iodide, magnesium dichloride, dibrominated magnesium, two magnesium iodides, the alcohol adducts of magnesium dichloride, at least a in the alcohol adducts of the alcohol adducts of dibrominated magnesium and two magnesium iodides.
13. catalyst component according to claim 10, wherein, described titanium compound is the compound shown in formula V,
TiX m(OR 18) 4-m （V）
In formula V, X is halogen, R 18Be the alkyl of 1-20 for carbonatoms, m is the integer of 1-4.
14. catalyst component according to claim 13, wherein, described titanium compound is at least a in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.
15. an olefin polymerization catalysis, this catalyzer is used for by general formula CH 2The polyreaction of the alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6, described catalyzer comprises the reaction product of following material:
(1) the described olefin polymerization catalyst components of any one in claim 1-14;
(2) as the organo-aluminium compound of promotor;
(3) randomly, external donor compound.
16. catalyzer according to claim 15, wherein, described organo-aluminium compound is the compound shown in formula (VI),
AlR' n'X' 3-n' （VI）
In formula (VI), R' is that hydrogen, carbonatoms are that alkyl or the carbonatoms of 1-20 is the aryl of 6-20, and X' is halogen, and n' is the integer of 1-3.
17. catalyzer according to claim 16, wherein, described organo-aluminium compound is at least a in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum and ethyl aluminum dichloride.
18. catalyzer according to claim 15, wherein, described external electron donor component is the silicoorganic compound shown in formula (VII),
R'' m'Si(OR''') 4-m' （VII）
In formula (VII), R'' be halogen, hydrogen atom, carbonatoms are the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms be 1-20 haloalkyl in a kind of; R''' be carbonatoms is the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms be 1-20 haloalkyl in a kind of; M' is the integer of 1-3.
19. catalyzer according to claim 18, wherein, described silicoorganic compound are at least a in trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, two cyclohexyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, Cyclohexyl Methyl Dimethoxysilane and dicyclopentyl dimethoxyl silane.
20. an olefine polymerizing process, the method is included under the olefinic polymerization condition, and one or more alkene are contacted with the described catalyzer of any one in claim 15-19, and at least a in described alkene is by general formula CH 2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.
21. method according to claim 20 is wherein, described by general formula CH 2The alkene that=CHR represents is at least a in ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
22. method according to claim 21, wherein, described olefinic polymerization condition comprises: temperature is 0-150 ℃, and the time is 0.1-5 hour, and pressure is 0.5-5MPa.
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