CN100513432C - Catalyst component for olefinic polymerization and its catalyst - Google Patents
Catalyst component for olefinic polymerization and its catalyst Download PDFInfo
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- CN100513432C CN100513432C CNB200510066038XA CN200510066038A CN100513432C CN 100513432 C CN100513432 C CN 100513432C CN B200510066038X A CNB200510066038X A CN B200510066038XA CN 200510066038 A CN200510066038 A CN 200510066038A CN 100513432 C CN100513432 C CN 100513432C
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Abstract
The invention supplies a catalyst constituent used in alkene polyreaction. It includes magnesium, titanium, halogen and electron supplying identity. The electron supplying identity contains at least one of acetal or ketal compounds. When using in olefinic polymerization, the polymerizing yield could be satisfied. And the stereospecificity of the polymer is high.
Description
Technical field
The present invention relates to a kind of acetal of special construction or ingredient of solid catalyst of ketal compounds of containing, 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 that yield is higher, isotactic is higher and the polymkeric substance of molecular weight distribution broad, and catalyzer has good hydrogen response.
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 U.S. Pat 4784983.
In recent years, the electron donor that people attempt to adopt the compound of other kinds to be used as in the olefin polymerization catalyst components again uses, for example at CN1042547A, CN1143651A and CN1298887A disclose a series of catalyst component that is used for olefinic polyreaction, it adopts a kind of diether compound as internal electron donor, when being used for third rare polymerization, can improve activity of such catalysts and hydrogen response, but in order to improve the polymkeric substance taxis, when being used with external electron donor such as organosilicon compound, the hydrogen response of catalyzer then significantly reduces, and the molecular weight distribution of the polymkeric substance that is obtained by such catalyzer is also narrower in addition.
The inventor comes in and goes out and has found a kind of acetal or ketal compounds that contains special construction with expecting, when it uses as the electron donor in the olefin polymerization catalysis, can obtain the catalyzer of high comprehensive performance, during especially for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, and the susceptibility that catalyzer is transferred hydrogen when using external electron donor simultaneously is still fine, and also broad of the molecular weight distribution of resulting polymers.
Summary of the invention
One of purpose of the present invention is to provide a kind of catalyst component that is used for olefinic polyreaction, and this catalyst component comprises magnesium, titanium, halogen and electron donor, and described electron donor is selected from least a acetal or the ketal compounds in the following general formula (I):
R wherein
1-8Be selected from hydrogen, contain or do not contain heteroatomic replacement or unsubstituted C
1-C
10The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
20Alkylene, C
7-C
20Alkaryl or aralkyl, fused ring aryl or ester group, and R
1To R
8In can be keyed to ring between any two groups.
According to preferred version of the present invention, wherein said electron donor is selected from least a acetal or the ketal compounds in the following general formula (II):
Wherein:
A, B, C are carbon atoms or are selected from N, Si heteroatoms that D is carbon atom or is selected from N, Si, O, S heteroatoms that y equals 0,1 or 3;
And working as A, B or C is the N atomic time, corresponding R
a, R
bOr R
cGroup is empty;
D is O or S atomic time, corresponding R
dGroup is empty;
R
1-R
6Be selected from hydrogen, or C
1-C
10The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
20Alkylene, C
7-C
20Alkaryl or aralkyl;
R
a-R
dAnd R
xBe hydrogen identical or inequality, C
1-C
20Alkyl, C
6-C
20Aryl or C
2-C
20Alkylene;
R
1And R
2, R
3And R
4, R
5And R
6, R
aAnd R
x, R
bAnd R
c, R
dAnd R
d(y=2) can connect into saturated or unsaturated ring-type between the group.
The preferred scheme of the present invention is that wherein said electron donor is selected from least a acetal or the ketal compound in the following general formula (III):
Wherein, R
1-R
6Definition as general formula (II); R is hydrogen identical or inequality, contains heteroatoms or do not contain heteroatomic C
1-C
20Alkyl, aryl or alkylene, and can connect into ring-type between two close each other R groups, especially that replace or unsubstituted phenyl ring.
The preferred scheme of the present invention is that wherein said electron donor is selected from least a acetal or the ketal compound in the following general formula (IV):
Wherein, R
1-R
6And the R in R group and the general formula (II)
1-R
6Identical etc. group definition, cannot connect into ring between the R group.Be preferably R or R
1-
6Be C
1-C
8Alkyl or C
6-C
10Aryl; More preferably methyl, ethyl, propyl group, sec.-propyl, butyl, phenyl or benzyl.
Concrete acetal or ketal compound comprise:
1,3-dibenzo-7,9-dioxo spiro [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methylspiro [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4,5] decane;
1,3-dibenzo-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1,3-dibenzo-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1,3-diene-7,9-dioxo spiro [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methylspiro [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two-oxa--8-methyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4.5] decane;
5,13-two oxa-s-8,10-diene two spiral shells [3.2.4.2] tridecane;
1,3-diene-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1,3-diene-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
2,3-two cyclopentyl-1,3-diene-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1-benzo-7,9-dioxo spiro [4.5] decane;
1-benzo-7,9-two oxa-s-8-methylspiro [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4.5] decane;
5,13-two oxa-s-8-benzo two spiral shells [3.2.4.2] tridecane;
1-benzo-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1-benzo-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane.
Above-mentioned acetal or ketal compound can pass through corresponding aldehydes or ketones and 1, and the 3-glycol reacts and prepares, and its synthetic method can be referring to monograph (Greene, T.W.; Wuts, P.G.M.Protective Groups in OrganicSynthesis, 2
NdEd.; John Wiley ﹠amp; Sons, Inc.:New York, 199l; 185-188).
The ingredient of solid catalyst that is used for olefinic polymerization of the present invention preferably comprises titanium compound, magnesium compound and is selected from acetal with above-mentioned general formula (I) or the reaction product of ketal compound.
Wherein used magnesium compound is selected from a kind of by in-oxyl or the halo-oxyl institute metathetical derivative of one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula, 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 halogenated aliphatic 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, can prepare with reference to disclosed method among the Chinese patent CN85100997, wherein disclosed associated viscera is incorporated herein the present invention as a reference.
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 be selected from general formula (I) shown in acetal or ketal compounds handle, it is attached on the solids, in case of necessity, with titanium tetrahalide and inert diluent solids is handled again, wherein precipitation additive can be selected a kind of in organic acid anhydride, organic acid, ether, the ketone or their mixture for use.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 compound, 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 acetal of general formula (I) or ketal compounds are 0.02～0.4 mole.
Also can prepare ingredient of solid catalyst of the present invention according to another kind of method, it is with described titanium compound, 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 above-mentioned general formula cyano group ketone compound of 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
2=CHR
1The catalyzer of olefinic polyreaction, wherein R
1Be hydrogen or C
1-C
6Alkyl or aryl, comprise the reaction product of following component:
(1) a kind of above-mentioned acetal or ketal compounds 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 is of the same race or different alkyl, cycloalkyl, aryl, haloalkyls with R, R also can be halogen or hydrogen atom.For example: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane.
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 (V), 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
1, R
II, R
V, and R
VIBe hydrogen.For example: 9,9-two (methoxymethyl) fluorenes.
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.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 α-alkene, 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 acetal or ketal compounds, 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 higher, the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
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 down at 150 ℃ with the trichlorobenzene, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300 x 7.5nm).
4, the polymkeric substance degree of isotacticity adopts the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
5, melting index is to measure according to ASTM D1238-99.
Embodiment 11,3-dibenzo-7,9-dioxo spiro [4.5] decane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), Paraformaldehyde 96 1.00g (0.033mol) joins in the 120ml benzene, heating reflux reaction 4h.Reaction mixture is cooled to room temperature, transfers in the separating funnel, successively with sodium bicarbonate aqueous solution, common salt aqueous solution washing, anhydrous magnesium sulfate drying, filter, desolventizing gets yellow thickness oily matter, uses ethyl alcohol recrystallization, get white crystal 3.21g, yield 45.0%, m.p.92-93 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：3.98(s，4H，2OCH
2)，5.22(s，2H，OCH
2O)，7.25～7.80(m，8H，ArH)。
Embodiment 21,3-dibenzo-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), acetone 3.48g (0.06mol) joins in the 75ml benzene, heating reflux reaction 4h.Reaction mixture is cooled to room temperature, transfers in the separating funnel, successively with sodium bicarbonate aqueous solution, common salt aqueous solution washing, anhydrous sodium sulfate drying, filter, desolventizing gets yellow thickness oily matter, uses ethyl alcohol recrystallization, get white crystal 4.04g, yield 54.7%, m.p.96-98 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：1.72(s，6H，2CH
3)，4.02(s，4H，2OCH
2)，7.24～7.80(m，8H，ArH)。
Embodiment 31,3-dibenzo-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), pimelinketone 3.15g (0.032mol) joins in the 75ml benzene, heating reflux reaction 4h.Reaction mixture is cooled to room temperature, transfers in the separating funnel, successively with sodium bicarbonate aqueous solution, common salt aqueous solution washing, anhydrous sodium sulfate drying, filter, desolventizing gets thickness oily matter, uses ethyl alcohol recrystallization, get white crystal 4.42g, yield 48.1%, m.p.168-169 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：1.48-2.10(m，10H，5CH
2)，4.00(s，4H，2OCH
2)，7.32～7.80(m，8H，ArH)。
Embodiment 41,3-dibenzo-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4,5] decane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), benzophenone 5.46g (0.03mol) joins in the 120ml benzene, heating reflux reaction 4h.Reaction mixture is cooled to room temperature, has a large amount of white solids to separate out, filter, collect white solid.Filtrate is transferred in the separating funnel, successively with the washing of sodium bicarbonate aqueous solution, common salt aqueous solution, the desolventizing part solid of getting back.Merge the gained solid, water, absolute ethanol washing successively, drying, white crystal 8.49g, yield 72.6%, m.p.〉220 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：4.13(s，4H，2OCH
2)，7.21～7.74(m，18H，ArH)。
Embodiment 51,3-dibenzo-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4,5] decane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), methyl phenyl ketone 3.60g (0.03mol) joins in the 90ml benzene, heating reflux reaction 4h.Reaction mixture is cooled to room temperature, transfers in the separating funnel, successively with sodium bicarbonate aqueous solution, common salt aqueous solution washing, anhydrous sodium sulfate drying, filter, desolventizing gets white solid 9.87g, uses ethyl alcohol recrystallization, get white crystal 4.00g, yield 40.7%, m.p.166-167 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：1.81(s，3H，CH
3)，3.54?&?4.32(dd，4H，2OCH
2)，6.95～7.70(m，13H，ArH)。
Embodiment 61,3-dibenzo-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane synthetic
With 9,9-dihydroxymethyl fluorenes 6.78g (0.03mol), p-methyl benzenesulfonic acid 0.57g (0.003mol), O-methoxy phenyl aldehyde 4.20g (0,03mol) join in the 75ml benzene heating reflux reaction 4h.Reaction mixture is cooled to room temperature, transfers in the separating funnel, successively with sodium bicarbonate aqueous solution, common salt aqueous solution washing, anhydrous sodium sulfate drying, filter, desolventizing gets thickness oily matter, uses ethyl alcohol recrystallization, get light yellow crystal 7.34g, yield 71.1%, m.p.158-160 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：3.88&4.55(dd，4H，2OCH
2)，3.91(s，3H，OCH
3)，6.22(s，1H，OC(Ar)HO)，6.95～7.77(m，12H，ArH)。
Embodiment 7
(1) preparation of olefins polymerizing solid catalyst component
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml is warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1 hour.Solution is cooled to below-25 ℃, drips titanium tetrachloride 56ml in 1 hour, slowly be warming up to 80 ℃, in temperature-rise period, separate out solids gradually, add the compound 6mmol of embodiment 1, holding temperature 1 hour is after the filtration, add toluene 70ml, washed twice obtains solid sediment.Add toluene 60ml then, titanium tetrachloride 40ml 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 ingredient of solid catalyst.
(2) propylene polymerization experiment
Volume is the stainless steel cauldron of 5L, after propylene is fully replaced, add triethyl aluminum 2.5mmol, methylcyclohexyl dimethoxy silane 0.1mmol, add above-mentioned ingredient of solid catalyst 10mg and 1.2NL hydrogen again, feed liquid propene 2.3L, be warming up to 70 ℃, kept this temperature 1 hour, cooling, pressure release obtains polymer powders, the results are shown in following table.
Embodiment 8-12
With embodiment 7, just the compound with embodiment 1 preparation substitutes with the compound of embodiment 2-6 preparation respectively.
Comparative example 1
With embodiment 7, just the compound with embodiment 1 preparation changes 9,9-dimethyl methoxy base fluorenes into.
| Catalyzer | Active kgPP/gcat | Degree of isotacticity % | Melting index g/10min | Molecular weight distribution mw/mn |
| Embodiment 7 | 21.6 | 95.2 | 5.6 | 6.7 |
| Embodiment 8 | 32.6 | 94.8 | 8.6 | 7.1 |
| Embodiment 9 | 28.2 | 95.7 | 9.8 | 6.3 |
| Embodiment 10 | 29.0 | 96.0 | 8.3 | 6.5 |
| Embodiment 11 | 26.4 | 97.2 | 5.0 | 6.2 |
| Embodiment 12 | 26.5 | 98.0 | 6.1 | 5.6 |
| Comparative example 1 | 51.6 | 98.5 | 3.8 | 4.5 |
Claims (14)
1, the catalyst component that is used for olefinic polymerization, it comprises magnesium, titanium, halogen and electron donor, and described electron donor is selected from least a in acetal shown in the following general formula (I) or the ketal compounds:
R wherein
1-8Be selected from hydrogen, contain or do not contain heteroatomic replacement or unsubstituted C
1-C
10The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
20Alkylene, C
7-C
20Alkaryl or aralkyl, fused ring aryl or ester group, and R
1To R
8In can be keyed to ring between any two groups, described heteroatoms is selected from O, S, N, P, Si and halogen atom.
2, the catalyst component that is used for olefinic polymerization according to claim 1, wherein said electron donor is selected from least a acetal or the ketal compounds in the following general formula (II):
Wherein:
A, B, C be carbon atom or be selected from N, Si heteroatoms, and D is carbon atom or the heteroatoms that is selected from N, Si, O, S, and y equals 0,1 or 3;
And working as A, B or C is the N atomic time, corresponding R
a, R
bOr R
cGroup is empty;
D is O or S atomic time, corresponding R
dGroup is empty;
R
1-R
6Be selected from hydrogen, or C
1-C
10The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
2-C
20Alkylene, C
7-C
20Alkaryl or aralkyl;
R
a-R
dAnd R
xBe hydrogen identical or inequality, C
1-C
20Alkyl, C
6-C
20Aryl or C
2-C
20Alkylene;
R
1And R
2, R
3And R
4, R
5And R
6, R
aAnd R
x, R
bAnd R
cCan connect into saturated or unsaturated ring-type between the group.
3, the catalyst component that is used for olefinic polymerization according to claim 2, wherein said electron donor is selected from least a acetal or the ketal compound in the following general formula (III):
Wherein, R
1-R
6As the definition in the claim 2; R is hydrogen identical or inequality, contains heteroatoms or do not contain heteroatomic C
1-C
20Alkyl, C
6-C
20Aryl or C
2-C
20Alkylene, and can connect into ring-type between two close each other R groups.
4, the catalyst component that is used for olefinic polymerization according to claim 3, wherein said electron donor is selected from least a acetal or the ketal compound in the following general formula (IV):
Wherein, R
1-R
6And the definition in R group such as the claim 3, and cannot connect into ring between the R group.
5, the catalyst component that is used for olefinic polymerization according to claim 4, in the wherein said general formula (IV), R or R
1-
6Be C
1-C
8Alkyl or C
6-C
10Aryl.
6, the catalyst component that is used for olefinic polymerization according to claim 1, wherein said electron donor are selected from least a in the following compound:
1,3-dibenzo-7,9-dioxo spiro [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methylspiro [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1,3-dibenzo-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4,5] decane;
1,3-dibenzo-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1,3-dibenzo-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1,3-diene-7,9-dioxo spiro [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methylspiro [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1,3-diene-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4.5] decane;
5,13-two oxa-s-8,10-diene two spiral shells [3.2.4.2] tridecane;
1,3-diene-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1,3-diene-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetramethyl--1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetraphenyl-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1,2,3,4-tetrafluoro-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
2,3-two cyclopentyl-1,3-diene-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
2,3-two cyclopentyl-1,3-diene-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
1-benzo-7,9-dioxo spiro [4.5] decane;
1-benzo-7,9-two oxa-s-8-methylspiro [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-dimethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-ethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-butyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isobutyl-spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-tertiary butyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-diethyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-amyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isopentyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-neo-pentyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-sec.-propyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-dipropyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-di-isopropyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-diisobutyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-guaiacyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-m-methoxyphenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-p-methoxyphenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-p-nitrophenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-propyl group spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-methyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-ethyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-propyl group-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-sec.-propyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-butyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isobutyl--8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8-isopentyl-8-phenyl spiral shell [4.5] decane;
1-benzo-7,9-two oxa-s-8,8-phenylbenzene spiral shell [4.5] decane;
5,13-two oxa-s-8-benzo two spiral shells [3.2.4.2] tridecane;
1-benzo-7,13-two oxa-s, two spiral shells [4.2.4.2] tetradecane;
1-benzo-7,14-two oxa-s, two spiral shells [4.2.5.2] pentadecane;
7, the catalyst component that is used for olefinic polymerization according to claim 1, it comprises titanium compound, magnesium compound and is selected from the acetal of general formula (I) or the reaction product of ketal compound,
Described 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;
Described titanium compound is that general formula is TiXn (OR)
4-n, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.
8, the catalyst component that is used for olefinic polymerization according to claim 7, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
9, the catalyst component that is used for olefinic polymerization according to claim 8, its organic epoxy compounds comprise at least a in the oxide compound of 2～8 aliphatics alkene or halogenated aliphatic alkene or diolefine, inner ether of carbonatoms.
10, the catalyst component that is used for olefinic polymerization according to claim 8, its organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
11, the catalyst component that is used for olefinic polymerization according to claim 7, the magnesium compound that it adopted is the alcohol adduct of magnesium dihalide.
12, a kind of CH that is used for
2=CHR
1The catalyzer of olefinic polymerization, wherein R
1Be hydrogen or C
1-C
6Alkyl or aryl, comprise the reaction product of following component:
(1) the described catalyst component of one of claim 11;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
13, a kind of alkene CH that is used for
2=CHR
1Polymeric pre-polymerized catalyst, wherein R
1Be hydrogen or C
1-C
12Alkyl group, described pre-polymerized catalyst comprises a kind of prepolymer that carries out the prepolymerization gained according to each described ingredient of solid catalyst and alkene among the claim 1-11, or the described catalyzer of claim 12 and alkene carries out the prepolymer of prepolymerization gained, and the pre-polymerization multiple is 0.1-1000g olefin polymer/g ingredient of solid catalyst.
14, be used for alkene CH
2=CHR
1Polymeric method, wherein R
1Be the hydrocarbyl group of hydrogen or 1-6 carbon atom, in the presence of described catalyzer of claim 12 or 13 described pre-polymerized catalysts, carry out.
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| CN101735346B (en) | 2008-11-07 | 2012-05-30 | 中国石油天然气股份有限公司 | Catalyst for propylene homopolymerization and copolymerization, and preparation method and application thereof |
| CN103665210B (en) * | 2012-09-18 | 2016-05-11 | 中国石油天然气股份有限公司 | Polypropylene catalyst and preparation method thereof |
| CN105482002B (en) * | 2014-10-10 | 2018-03-02 | 中国石油化工股份有限公司 | Catalytic component, catalyst for vinyl polymerization and preparation method thereof |
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