CN109553709A - A kind of catalytic component and its catalyst for olefinic polymerization - Google Patents
A kind of catalytic component and its catalyst for olefinic polymerization Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The invention discloses a kind of catalytic components of olefin polymerization, prepare by the inclusion of the method for following steps: 1) mixing magnesium compound with organic alcohol compound and atent solvent, and the processing of general structure I compound represented is added, obtains alcohol adduct；2) alcohol adduct is contacted at low temperature with titanium compound, interior Donor compound reaction is then added, isolates the first solid particle；3) the first solid particle in step 2) is added in compound titanium solution, stirred and reacted, isolate the second solid particle；4) use atent solvent washing step 3) obtained in the second solid particle, obtain the catalytic component；
Description
Technical field
The catalytic component and preparation method thereof that the present invention relates to a kind of for olefinic polymerization, a kind of olefin polymerization catalysis
Agent system, the catalytic component and caltalyst tie up to application and olefine polymerizing process in olefin polymerization, belong to alkene
Polymerized hydrocarbon field.
Background technique
It is well known that being with magnesium chloride, oxygen using magnesium, titanium, halogen and electron donor as the polyolefin catalyst of basic component
The inorganic matters such as SiClx are carrier, and carrying transition metal compound is made.The early stage method of multi-purpose grinding prepares magnesium chloride support, but
The disadvantage is that catalyst granules poor morphology, therefore the morphology that catalysis obtains is bad, fine powder is more, and apparent density is low.Mesh
Before, people more use chemical method, i.e., first magnesium compound are dissolved in solvent and are prepared into homogeneous solution, then pass through knot again
Partial crystallization goes out.During solution modeling, even-grained solids usually only can be just obtained in the presence of precipitation additive
Matter.Wherein precipitation additive generallys use the compounds such as organic acid anhydride, organic ketone, ether.The precipitation additive reported in the prior art can
To be a plurality of types of compounds.Such as use alkane (CN200810223088.8 and CN03123950.1) or having without active hydrogen
Report of the organic silicon compound as precipitation additive (CN201110269970.8).With special construction in CN101643519A
Glycol ester compounds are precipitation additive, and at the same time a kind of glycol ester compounds or binary carboxylic with special construction of fit applications
Acid esters compound is as electron donor, at least one coating material in load, catalyst table when being used for olefinic polymerization
Reveal very high stereoselectivity, resulting polymers have wider molecular weight distribution and fine powder is less.CN1955195A is disclosed
A kind of catalyst system for olefinic polymerization or combined polymerization, is compounded with multi-carboxylate using aromatic monocarboxylate's ester,
Middle aromatic single-carboxy acid's ester is both precipitation additive and electron donor, and the particle shape of this catalyst and anti-impurity ability are preferable,
Resulting polymers have wider molecular weight distribution and fine powder is less.
It generally, is the classes compound such as organic acid anhydride, organic acid, ketone, ether using most precipitation additives in report, such as
(CN200910091115.5、CN201010204493.2、CN201010294618.5、CN85100997、
CN200910083987.7、CN200910209546.7、CN201110335576.X、CN201010283061.5、
CN98101108.X、CN98126383.6、CN200810117895.6、CN98126385.2、CN98126383.6、
CN98111780.5、CN98101108.X、CN201110335576.X、CN201010294618.5、CN201010283061.5、
CN201010204493.2、CN200910209546.7、CN200910177286.X、CN200910091115.5、
CN200910086590.3、CN200910084912.1、CN200810117895.1、CN200510114544.1、
CN200410062290.9、CN99102813.9、CN98126385.2、CN98126383.6、CN98111780.5、
CN98101108.X, CN98101108.X) etc..Precipitation additive in each patent mainly includes acetic anhydride, phthalic anhydride, fourth
Dicarboxylic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, first and second
One of ketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether or their mixture.Chinese patent
The preparation method of a kind of titanium-containing catalyst component is disclosed in CN101864009B, is used diol-lipid compound and is substituted phthalic anhydride
Class compound is precipitation additive, has obtained the catalytic component of high activity, high directionality.
In conclusion the effect for being used to prepare olefin polymerization catalysis reported in patent document at present preferably helps precipitation
Agent is phthalic anhydride, and the compound there are phthalate compounds easy to form, be unfavorable for current ring
Guaranteed request, it is therefore desirable to carry out innovative works on the basis of the prior art, it is good to obtain comprehensive performance, it is real with more industry
With the polyolefin catalyst of property.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of catalyst component for olefin and its system
Preparation Method introduces a kind of compound with special construction as precipitation additive in the preparation process of catalytic component, saves
Or reduce the use of phthalic anhydride compound, and then provide a kind of catalyst for olefines polymerizing, the catalytic component and catalyst
When system is applied to olefinic polymerization, high comprehensive performance, active and adjustable capacity of orientation with higher, the hydrogen tune of catalyst
Sensibility is good, the polymer molecular weight wider distribution of preparation.
According to an aspect of the present invention, a kind of catalytic component of olefin polymerization is provided, by the inclusion of following step
Rapid method preparation:
1) magnesium compound is mixed with organic alcohol compound and atent solvent, is added at general structure I compound represented
Reason, obtains alcohol adduct；
2) alcohol adduct is contacted at low temperature with titanium compound, it is anti-that internal electron donor compound is then added
It answers, isolates the first solid particle；
3) the first solid particle in step 2) is added in compound titanium solution, stirred and reacted, isolate second
Solid particle；
4) use atent solvent washing step 3) obtained in the second solid particle, obtain the catalytic component；
In formula, A is selected from-(XR1R2)nAnd-(YR5)m, Q is selected from-(XR3R4)aOr-(YR6)b, wherein X be carbon atom or
Silicon atom, Y are nitrogen-atoms or phosphorus atoms, and m, n, a, b are respectively 1~6 integer；R1~R6It may be the same or different, each independently
Selected from hydrogen, substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C2~C30Heterocycle, halogen, hydroxyl and take
Generation or unsubstituted C1~C30Alkoxy, be preferably selected from hydrogen, substituted or unsubstituted C1~C30Straight chained alkyl, replace or not
Substituted C3~C30Branched alkyl or naphthenic base, substituted or unsubstituted C2~C30Straight-chain alkenyl, substituted or unsubstituted
C3~C30Branched-chain alkenyl or cycloalkenyl, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C7~C30Alkane
Aryl or aralkyl, substituted or unsubstituted C2~C30Alicyclic heterocyclic base, substituted or unsubstituted C4~C30Aromatic heterocyclic, halogen
Element, hydroxyl and substituted or unsubstituted C1~C30Alkoxy；And R1~R6It is not simultaneously hydrogen.
Preferred embodiment in accordance with the present invention, m be 1-6 integer, preferably 1~4；N be 1-6 integer, preferably 1~
4；A be 1-6 integer, preferably 1~4；B be 1-6 integer, preferably 1~4；The R1~R6It may be the same or different, respectively
Independently selected from hydrogen, substituted or unsubstituted C1~C10Straight chained alkyl, substituted or unsubstituted C3~C10Branched alkyl or
Naphthenic base, substituted or unsubstituted C2~C10Straight-chain alkenyl, substituted or unsubstituted C3~C10Branched-chain alkenyl or cycloalkenyl,
Substituted or unsubstituted C6~C10Aryl, substituted or unsubstituted C7~C10Alkaryl or aralkyl, substituted or unsubstituted
C2~C10Alicyclic heterocyclic base, substituted or unsubstituted C4~C10Aromatic heterocyclic, halogen, hydroxyl and substituted or unsubstituted C1
~C10Alkoxy, preferably be selected from methyl, ethyl, propyl, butyl, amyl, hexyl, cyclopenta, cyclohexyl, vinyl, acrylic,
Cyclobutenyl, phenyl, aminomethyl phenyl, ethylphenyl, propyl phenyl, butyl phenyl, amyl phenyl, halogenophenyl, benzyl, benzene second
Base, phenylpropyl, benzene butyl, naphthalene, xenyl, methoxyl group, ethyoxyl, propoxyl group, the group containing pyrroles, the group containing pyridine
Base, the group containing pyrimidine, the group containing quinoline, chlorine, bromine, iodine, hydroxyl and hydroxyalkyl.
According to the present invention, the substitution refers to R1~R6In alkyl, naphthenic base, aryl, in alkaryl or aralkyl with carbon
The connected hydrogen atom of atom is optionally replaced by hetero atom, alkyl or alkoxy, and the carbon atom on main chain is optionally miscellaneous
Atom replaces.The hetero atom includes halogen atom etc..
According to some embodiments of the present invention, the general formula I compound represented is selected from 3,6- diphenyl-Isosorbide-5-Nitrae-dioxy six
Ring -2,5- diketone, 3,6- bis- (4- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (2- aminomethyl phenyl) -1,4-
Dioxane -2,5- diketone, 3,6- bis- (3- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, (the 4- ethylo benzene of 3,6- bis-
Base) -1,4- dioxane -2,5- diketone, 3,6- bis- (2- ethylphenyl) -1,4- dioxane -2,5- diketone, bis- (3- of 3,6-
Ethylphenyl) -1,4- dioxane -2,5- diketone, (4- n-propyl the phenyl) -1,4- dioxane -2,5- of 3,6- bis- diketone, 3,
(2- n-propyl the phenyl)-1,4- dioxane-2,5- of 6- bis- diketone, 3,6- bis- (3- n-propyl phenyl) dioxane-2-1,4-,
5- diketone, 3,6- bis- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (2- isopropyl phenyl) -1,4- two
Six ring -2,5- diketone of oxygen, 3,6- bis- (4- n-butylphenyl) -1,4- dioxane -2,5- diketone, (the 2- n-butylbenzene of 3,6- bis-
Base) -1,4- dioxane -2,5- diketone, 3,6- bis- (3- n-butylphenyl) -1,4- dioxane -2,5- diketone, 3,-two (2,
4- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, (2,4,6- the trimethylphenyl) -1,4- dioxane of 3,6- bis- -2,5-
Diketone, 3- phenyl -6- (4- n-propyl phenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (4- isopropyl phenyl) -1,
4- dioxane -2,5- diketone, 3- phenyl -6- (2,4- 3,5-dimethylphenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6-
(2,4,6- trimethylphenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (2- aminomethyl phenyl) -1,4- dioxane -
2,5- diketone, 3- phenyl -6- (2- chlorphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (4- chlorphenyl) -1,4- dioxy
Six ring -2,5- diketone, 3,6- bis- (2- chlorphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (3- chlorphenyl) -1,4- two
Six ring -2,5- diketone of oxygen, 3,6- dimethyl -3,6- diphenyl -1,4- dioxane -2,5- diketone, 3,6- dimethyl -1,4- two
Six ring -2,5- diketone of oxygen, 3,6- diethyl -1,4- dioxane -2,5- diketone, dioxane -2 3,6- diη-propyl -1,4-,
5- diketone, 3,6- diisopropyl -1,4- dioxane -2,5- diketone, 3,6- di-n-butyl -1,4- dioxane -2,5- diketone,
3,6- diisobutyl -1,4- dioxane -2,5- diketone, 3,6- bis- (1- methyl-propyl) -1,4- dioxane -2,5- diketone,
3,6- bis- (1- methyl butyl) -1,4- dioxane -2,5- diketone, (1- the methyl amyl) -1,4- dioxane of 3,6- bis- -2,5-
Diketone, bis- n-pentyl -1,4- dioxane -2,5- diketone of 3,6-, 3,6- diisoamyl -1,4- dioxane -2,5- diketone, 3,
6- dimethyl -3,6- diη-propyl -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- diisopropyl -1,4- dioxy
Six ring -2,5- diketone, 3,6- dimethyl -3,6- di-n-butyl -1,4- dioxane -2,5- diketone,
3,6- dimethyl -3,6- diisobutyl -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- two positive penta
Base -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- diisoamyl -1,4- dioxane -2,5- diketone, 2,2,5,
Two silicon -3,6- diketone of 5- tetramethyl -1,4- dioxane -2,5-, two silicon of 2,2,5,5- tetraethyl -1,4- dioxane -2,5- -
3,6- diketone, two silicon -3,6- diketone of 2,2,5,5- tetrapropyl -1,4- dioxane -2,5-, the 2,2,5,5- tetrabutyl -1,4- two
Six ring -2,5- of oxygen, two silicon -3,6- diketone, two silicon -3,6- two of 2,2- dimethyl -5,5- diethyl -1,4- dioxane -2,5-
Ketone, two silicon -3,6- diketone of 2,2- dimethyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- dimethyl -5,5- dipropyl
Two silicon -3,6- diketone of base -1,4- dioxane -2,5-, 2,2- dimethyl -5,5- dibutyl -1,4- dioxane -2,5- two
Silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- diethyl -5,5- diethyl -1,4- dioxane -2,5-, 2,2- diethyl -
Two silicon -3,6- diketone of 5,5- dipropyl -1,4- dioxane -2,5-, 2,2- diethyl -5,5- dipropyl -1,4- dioxane -
Bis- silicon -3,6- diketone of 2,5-, two silicon -3,6- diketone of 2,2- diethyl -5,5- dibutyl -1,4- dioxane -2,5-, 2,2- bis-
Two silicon -3,6- diketone of propyl -5,5- diethyl -1,4- dioxane -2,5-, 2,2- dipropyl -5,5- dipropyl -1,4- dioxy
Six ring -2,5-, two silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- dipropyl -5,5- dipropyl -1,4- dioxane -2,5-,
Two silicon -3,6- diketone of 2,2- dipropyl -5,5- dibutyl -1,4- dioxane -2,5-, diethyl -1 2,2- dibutyl -5,5-,
Two silicon -3,6- diketone of 4- dioxane -2,5-, two silicon -3,6- of 2,2- dibutyl -5,5- dipropyl -1,4- dioxane -2,5-
Diketone, two silicon -3,6- diketone of 2,2- dibutyl -5,5- dipropyl -1,4- dioxane -2,5-, two fourth of 2,2- dibutyl -5,5-
Two silicon -3,6- diketone of base -1,4- dioxane -2,5-, 2,5- dimethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone,
2,5- diethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, phenodiazine -3 2,5- dipropyl -1,4- dioxane -2,5-,
6- diketone, 2,5- dibutyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diamyl -1,4- dioxane -2,5-
Phenodiazine -3,6- diketone, 2,5- bis- base -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- dimethoxy methyl-1,4- bis-
Six ring -2,5- phenodiazine -3,6- diketone of oxygen, 2,5- dimethoxy ethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- bis-
Methoxycarbonyl propyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diethoxy methyl-1,4- dioxane -2,5- phenodiazine -
3,6- diketone, 2,5- diethoxy ethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diethyl oxygen propyl group -1,4- two
Six ring -2,5- phenodiazine -3,6- diketone of oxygen, two phosphorus -3,6- diketone of 2,5- dimethyl -1,4- dioxane -2,5-, 2,5- diethyl
Two phosphorus -3,6- diketone of base -1,4- dioxane -2,5-, two phosphorus -3,6- diketone of 2,5- dipropyl -1,4- dioxane -2,5-,
Two phosphorus -3,6- diketone of 2,5- dibutyl -1,4- dioxane -2,5-, two phosphorus -3 2,5- diamyl -1,4- dioxane -2,5-,
6- diketone, 2,5- bis- two phosphorus -3,6- diketone of base -1,4- dioxane -2,5-, 2,5- dimethoxy methyl-1,4- dioxane -
Bis- phosphorus -3,6- diketone of 2,5-, two phosphorus -3,6- diketone of 2,5- dimethoxy ethyl -1,4- dioxane -2,5-, 2,5- dimethoxy third
Two phosphorus -3,6- diketone of base -1,4- dioxane -2,5-, 2,5- diethoxy methyl-1, two phosphorus -3,6- two of 4- dioxane -2,5-
Ketone, two phosphorus -3,6- diketone of 2,5- diethoxy ethyl -1,4- dioxane -2,5- and 2,5- diethyl oxygen propyl group -1,4- dioxy six
One of two phosphorus -3,6- diketone of ring -2,5- is a variety of.
In above compound, do not indicate compound just, different it is meant that it comprises just, the situation of different group.
In some specific embodiments, the compound represented of general structure I described in step 1) in mixed process or
It is added later.
Some preferred embodiments according to the present invention, the internal electron donor compound be selected from ester, ether, carboxylic acid, ketone and
One of amine is a variety of, be preferably selected from Polycarboxylic acids, polybasic carboxylic acid esters compound, diol-lipid compound,
One of dihydric phenol ester type compound and diether compound are a variety of, more preferably include benzoates, phthalic acid
One of esters, malonic acid esters, succinate compound and glutaric acid ester type compound are a variety of.In some specific embodiments
In, second internal electron donor compound includes n-butyl phthalate, diisobutyl phthalate, 2,4- hexichol
Carboxyphenyl pentane, 2,4- bis- (methyl benzoyloxy) pentane, 2,4- bis- (ethylamino benzonitrile carboxyl) pentane, bis- (n-propylbenzene of 2,4-
Carboxyphenyl) pentane, 2,4- bis- (cumene carboxyphenyl) pentane, 2,4- bis- (n-butylbenzene carboxyphenyl) pentane, bis- (isobutyl of 2,4-
Base benzoyloxy) pentane, 2,4- bis- (tert-butyl benzene carboxyphenyl) pentane, 9,9- dimethoxy-methyl fluorenes, 2- isopropyl -2- isoamyl
Base -1,3- dimethoxy fluorenes, bis- benzoyloxy naphthols of 1,8-, two benzoyloxy phenol of 3- tert-butyl -1,2- and 2,3- diisopropyl
Base diethyl succinate it is one or more.
A preferred embodiment according to the present invention, in terms of every mole of magnesium, the dosage of the general formula I compound represented
It is 0.01-6 moles, preferably 0.01-2 moles, more preferably 0.02-1 moles.
Preferred embodiment in accordance with the present invention, in terms of every mole of magnesium, the dosage of the internal electron donor compound is
0.001-15 moles, preferably 0.005-10 moles, more preferably 0.05-5 moles.
According to some embodiments of the present invention, the magnesium compound includes magnesium dihalide, the hydrate of magnesium dihalide, dihalo-
Change at least one of water or complex compound, alkyl magnesium halide, alkoxyl magnesium and the Alkoxymagnesium halides of alcohol of magnesium, the halogen choosing
From at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine.In some specific embodiments, the magnesium compound
Preferably include magnesium dichloride, magnesium dibromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium, magnesium ethylate and
At least one of ethyoxyl magnesium chloride.
According to certain embodiments of the present invention, for the organic alcohol compound, there is no particular limitation, selects ability
Domain common are machine alcohol compound；Preferred embodiment in accordance with the present invention, the organic alcohols compound include fat
At least one of alcohol, alicyclic ring alcohol and aromatic alcohol.Wherein, the fatty alcohol is preferably C1-C10Straight-chain fatty alcohol or C3-C10's
Branched fatty alcohol.The alicyclic ring alcohol is preferably C3-C12Fatty alcohol.The aromatic alcohol is preferably C6-C20Aryl alcohol or C7-C20
Alkyl aromatic alcohol.In some specific embodiments, be suitable for the invention alcohol compound preferably comprises ethyl alcohol, third
At least one of alcohol, butanol, 2-Ethylhexyl Alcohol, isooctanol, benzyl alcohol and benzyl carbinol.
Preferred embodiment in accordance with the present invention, the titanium compound include that general formula is Ti (OR7)xM4-xCompound and/or
Its derivative, R in formula7For for C1-C20Alkyl, preferably C1-C10Alkyl；M is halogen, preferably chlorine, bromine or iodine；X=1
~4.In some specific embodiments, the titanium compound preferably includes titanium tetrahalide, three halogenated titanium of alkoxy, dialkoxy
At least one of three halogenated titaniums and tri-alkoxy halogenated titanium；It more preferably include titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four
In ethoxylation titanium, four butoxylated titaniums, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium and tri-chloroethoxy base titanium
It is one or more.According to one embodiment of present invention, the titanium compound is preferably titanium tetrachloride.
A preferred embodiment according to the present invention, preferably by magnesium compound and organic alcohol compound in the step 1)
0.5-10h is mixed at 30 to 150 DEG C with atent solvent, until magnesium compound is completely dissolved；Then it is added shown in general structure I
Compound, the 0.5-3h that maintains at 30 to 150 DEG C that the reaction was continued obtain alcohol adduct.
In some specific embodiments, in terms of every mole of magnesium, the dosage of the organic alcohol compound is 0.2-10 moles,
Preferably 0.5-5 moles.
According to a preferred embodiment of the present invention, the alcohol adduct is preferably cooled to room temperature in the step 2), added
Enter in -40 to 0 DEG C of titanium compound and contact 0.5-5h, then heat to 50-150 DEG C, internal electron donor compound is added and exists
It is reacted 0.5-6 hours at a temperature of 20-120 DEG C, filters to isolate the first solid particle.
According to a preferred embodiment of the present invention, preferably the first solid particle in step 2) is added in the step 3)
Enter into compound titanium solution, 50-150 DEG C at a temperature of react 1-6 hours, after filter to isolate the second solid
Grain.
According to a preferred embodiment of the present invention, preferably with atent solvent washing step 3 in the step 4)) in obtain
The second solid particle, obtain the catalytic component after dry.
The catalyst component for olefin obtained according to the present invention can be used in preparing olefin polymerization catalyst system.
According to another aspect of the present invention, a kind of catalyst system for olefinic polymerization is provided comprising following
The reaction product of component:
A. the above-mentioned catalytic component for olefinic polymerization；
B. organo-aluminum compound；
C. optionally, organo-silicon compound.
The molar ratio of preferred embodiment in accordance with the present invention, the component b and component a are calculated as (5-1000) with aluminium/titanium ratio:
1；And/or the molar ratio of the component c and component a is calculated as (0-500) with silicon/titanium ratio: 1, preferably (0.01-50): 1.
According to certain embodiments of the present invention, for the alkyl aluminum compound, there is no particular limitation, selects ability
The common alkyl aluminum compound that can be used in Ziegler-natta catalyst in domain.
It is suitable for the invention alkyl aluminum compound, preferably general formula AlR'n'X'3-n'Shown in alkyl aluminum compound,
In, R' is selected from hydrogen, C1-C20Alkyl and C6-C20Aryl；X' is halogen, and n' is the integer of 1-3.
In some specific embodiments, the specific example as alkyl aluminum compound be can choose such as trimethyl aluminium, three
Aluminium ethide, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine two are different
At least one of butyl aluminium, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.
Specific embodiment according to the present invention, the component c refer to poly- for alkene for optionally organo-silicon compound
It may or may not contain organic silicon compound in the catalyst system of conjunction.According to a preferred embodiment of the present invention, for described
There is no particular limitation for external donor compound, and this field is common can be used in Ziegler-natta catalyst for selection
External donor compound.
It is suitable for the invention external donor compound, preferably general formula R "m'Si(OR”')4-m'Shown in it is siliconated
Close object, wherein R " is selected from hydrogen, halogen, C1-C20Alkyl, C3-C20Naphthenic base, C6-C20Aryl and C1-C20Alkyl halide
Base；M' is the integer of 1-3.
In some specific embodiments, the specific example as organo-silicon compound be can choose such as trimethyl methoxy
Silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane,
Methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, two cyclohexyl dimethoxys
Silane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyl trimethoxy silicon
Alkane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- tert-butyl dimethoxy
Silane, (the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- propyl of 1,1,1- tri-)-methyl two
At least one of methoxy silane etc., preferably Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane and
At least one of dimethoxydiphenylsilane.
According to another aspect of the present invention, the application that above-mentioned caltalyst ties up in olefin polymerization is provided.
According to another aspect of the present invention, a kind of olefine polymerizing process is provided, including one or more alkene is used to exist
Olefin polymerization is carried out in the presence of above-mentioned catalytic component or above-mentioned catalyst system.
According to the preferred embodiment of the present invention, at least one of described alkene is by general formula CH2The alkene that=CHR is indicated
Hydrocarbon, wherein R is hydrogen or C1-C7Alkyl.
Olefine polymerizing process of the invention can be used for by general formula CH2The homopolymerization for the alkene that=CHR is indicated, can also use
In will be by general formula CH2The alkene and a variety of alkene that=CHR is indicated carry out combined polymerization.R is hydrogen or C1-C7Alkyl.It is described by general formula
CH2The specific example for the alkene that=CHR is indicated includes ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene and 4- first
One of base -1- amylene is a variety of.
Olefine polymerizing process according to the present invention, for the olefin polymerization conditions, there is no particular limitation, can choose
The normal condition of this field；For the dosage of catalyst, there is no particular limitation, can choose each in prior art olefinic polymerization
The dosage of kind catalyst.
According to the present invention, a kind of compound with special construction is introduced in the preparation process of catalytic component as helping
Precipitation agent saves or reduces the use of phthalic anhydride compound, and gained catalytic component catalytic activity is high, decay of activity is slow, gained
Polymer high melt index, molecular weight distribution be wide, isotacticity is high.The catalyst provided according to the present invention is catalyzed synthesis living
Function admirable, activity with higher and adjustable capacity of orientation, the hydrogen response of catalyst is good, the polymer isotactic of preparation
Index is adjustable, and molecular weight distribution is wider.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but does not constitute any limitation of the invention.
In following embodiment, the evaluation and test method being related to are as follows:
1. polymer isotacticity (%): measured using heptane extraction process: 2g dry polymer samples are placed in extractor
After being extracted 6 hours with boiling heptane, residue is dry to constant weight, and resulting polymers weight (g) and the ratio of 2g are isotactic
Degree.
2. melt index (g/10min): being measured according to ASTMD1238-99.
3. polymer molecular weight distribution (Mw/Mn): being measured with the gel permeation chromatograph that Waters company manufactures, solvent is used
1,2,4- trichloro-benzenes, styrene are standard specimen；The nmr analysis of compound is poly- with Bruke dmx 300MHz nmr determination
The 1H-NMR of object is closed, solvent: deuterated chloroform, TMS are internal standard, temperature 275K.
(1) synthesis of compound
The synthesis of 1 compound 3,6- diphenyl -1,4- dioxane -2,5- diketone of embodiment
In one 250 milliliters of there-necked flask, nitrogen blow row after be added 3.04 grams of mandelic acid, 80 milliliters of toluene and
0.3 milliliter of the concentrated sulfuric acid, stirs evenly at room temperature.Temperature rising reflux reacts 6 hours after being stirred to react 4 hours.After being concentrated under reduced pressure
It is recrystallized to give light yellow crystal with ether/ethanol (1:20) mixed solution, vacuum drying obtains 1.07 grams of product (yields
40%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.40~7.38
(6H, m, ArH), 7.36~7.34 (4H, m, ArH), 6.10~6.08 (2H, m, CH)；Mass spectrum, FD-mass
spectrometry:268。
The synthesis of embodiment 2 compound 3,6- bis- (4- ethylphenyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, nitrogen blow row after be added 3.60 grams 4- ethyl mandelic acid, 80 milliliters of first
Benzene and 0.3 milliliter of the concentrated sulfuric acid, stir evenly at room temperature.Temperature rising reflux reacts 8 hours after being stirred to react 1 hour.It is dense through depressurizing
It is recrystallized to give light yellow crystal with ether/ethanol (1:20) mixed solution after contracting, vacuum drying obtains 1.23 grams of product (yields
38%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.32~7.30
(4H, m, ArH), 7.05~7.03 (4H, m, ArH), 6.10~6.08 (2H, m, CH), 2.58~2.56 (4H, m, CH2),1.25
~1.22 (6H, m, CH3)；Mass spectrum, FD-mass spectrometry:324.
The synthesis of embodiment 3 compound 3,6- bis- (4- n-propyl phenyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, 3.88 grams of 4- n-propyl mandelic acids, 80 milliliters of toluene are added after blowing row in nitrogen
With 0.3 milliliter of concentrated sulfuric acid, stir evenly at room temperature.Temperature rising reflux reacts 12 hours after being stirred to react 1 hour.After being concentrated under reduced pressure
It is recrystallized to give light yellow crystal with ether/ethanol (1:20) mixed solution, vacuum drying obtains 1.33 grams of product (yields
38%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.32~7.29
(4H, m, ArH), 7.05~7.03 (4H, m, ArH), 6.10~6.08 (2H, m, CH), 2.63~2.61 (4H, m, CH2),1.64
~1.62 (4H, m, CH2), 0.95~0.92 (6H, m, CH3)；Mass spectrum, FD-mass spectrometry:352.
The synthesis of embodiment 4 compound 3,6- bis- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone
With embodiment 3, the difference is that 4- n-propyl mandelic acid is replaced with 4- isopropyl mandelic acid, 1.40 grams of products are obtained
(yield 40%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.28~7.26
(4H, m, ArH), 7.23~7.21 (4H, m, ArH), 6.08~6.06 (2H, m, CH), 2.88~2.86 (2H, m, CH2),1.23
~1.20 (6H, m, CH3), 1.18~1.15 (6H, m, CH3)；Mass spectrum, FD-mass spectrometry:352.
The synthesis of embodiment 5 compound 3- phenyl -6- (4- ethylphenyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, 3.10 grams of mandelic acids, 100 milliliters of toluene, 3.60 grams are added after blowing row in nitrogen
4- ethyl mandelic acid and 0.3 milliliter of the concentrated sulfuric acid, temperature rising reflux reacts 10 hours after being stirred to react at room temperature 8 hours.Through depressurizing
It is recrystallized to give light yellow crystal with ether/ethanol (1:20) mixed solution after concentration, vacuum drying obtains 0.97 gram of product and (produces
Rate 33%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.38~7.36
(5H, m, ArH), 7.33~7.31 (2H, m, ArH), 7.03~7.01 (2H, m, ArH), 6.10~6.08 (2H, m, CH), 2.59
~2.57 (2H, m, CH2), 1.26~1.24 (3H, m, CH3)；Mass spectrum, FD-mass spectrometry:296.
The synthesis of embodiment 6 compound 3- phenyl -6- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, 3.10 grams of mandelic acids, 3.88 grams of 4- isopropyl almonds are added after blowing row in nitrogen
Acid, 100 milliliters of toluene and 0.4 milliliter of the concentrated sulfuric acid, stir evenly at room temperature.Temperature rising reflux reacts after being stirred to react 8 hours
10 hours.It is recrystallized to give light yellow crystal with ether/ethanol (1:20) mixed solution after being concentrated under reduced pressure, vacuum drying obtains
0.96 gram of product (yield 31%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.38~7.36
(5H, m, ArH), 7.28~7.26 (2H, m, ArH), 7.23~7.21 (2H, m, ArH), 6.10~6.08 (2H, m, CH), 2.87
~2.85 (1H, m, CH), 1.25~1.22 (6H, m, CH3)；Mass spectrum, FD-mass spectrometry:310.
The synthesis of embodiment 7 compound 3,6- bis- (4- chlorphenyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, nitrogen blow row after be added 3.72 grams of 4- chloro mandelic acids, 80 millis toluene and
0.3 milliliter of concentrated sulfuric acid, stirs evenly at room temperature.Temperature rising reflux reacts 12 hours after being stirred to react 6 hours.It is used after being concentrated under reduced pressure
Ether/ethanol (1:20) mixed solution is recrystallized to give light yellow crystal, and vacuum drying obtains 1.41 grams of products (yield 42%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 7.42~7.40
(4H, m, ArH), 7.31~7.28 (4H, m, ArH), 6.08~6.06 (2H, m, CH)；Mass spectrum, FD-mass
spectrometry:336。
The synthesis of 8 compound 3,6- diisobutyl -1,4- dioxane -2,5- diketone of embodiment
In one 250 milliliters of there-necked flask, 5.28 grams of 2- hydroxy-4-methyl valeric acids, 80 milliliters are added after blowing row in nitrogen
Toluene and 0.3 milliliter of concentrated sulfuric acid, stir evenly at room temperature.Temperature rising reflux reacts 8 hours after being stirred to react 8 hours, dense through depressurizing
Column is crossed after contracting to chromatograph to obtain 1.45 grams of colourless liquids (yield 32%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 4.80~4.78
(2H, m, CH), 1.89~1.86 (4H, m, CH2), 1.63~1.61 (2H, m, CH), 0.95~0.92 (6H, m, CH3)；Mass spectrum,
FD-mass spectrometry:228。
The synthesis of 9 compound 3,6- diη-propyl -1,4- dioxane -2,5- diketone of embodiment
In one 250 milliliters of there-necked flask, nitrogen blow row after be added 4.73 grams of 2- hydroxypentanoic acids, 100 milliliters of toluene and
0.3 milliliter of concentrated sulfuric acid, stirs evenly at room temperature.Temperature rising reflux reacts 10 hours after being stirred to react 4 hours.The mistake after being concentrated under reduced pressure
Column chromatographs to obtain 1.20 grams of colourless liquids (yield 30%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 4.80~4.78
(2H, m, CH), 1.95~1.92 (4H, m, CH2), 1.33~1.30 (4H, m, CH2), 0.93~0.90 (6H, m, CH3)；Mass spectrum,
FD-mass spectrometry:200。
The synthesis of embodiment 10 compound 3,6- bis- (1- methyl-propyl) -1,4- dioxane -2,5- diketone
In one 250 milliliters of there-necked flask, nitrogen blow row after be added 5.28 grams of 2- hydroxy-3-methyl valeric acids, 100 milliliters
Toluene and 0.3 milliliter of the concentrated sulfuric acid, stir evenly at room temperature.Temperature rising reflux reacts 10 hours after being stirred to react 4 hours, through depressurizing
Column is crossed after concentration to chromatograph to obtain 1.36 grams of colourless liquids (yield 30%).
Nuclear-magnetism measurement, test method and result are carried out to product are as follows:1H-NMR(δ,ppm,TMS,CDCl3): 4.80~4.78
(2H, m, CH), 2.89~2.87 (2H, m, CH), 1.56~1.53 (4H, m, CH2), 0.99~0.97 (6H, m, CH3), 0.93~
0.90(6H,m,CH3)；Mass spectrum, FD-mass spectrometry:228.
(2) preparation of Components of Catalysts and propylene polymerization
Embodiment 11
(1) preparation of catalyst solid constituent
Under nitrogen protection, 4.8g anhydrous magnesium chloride, 19.5g isooctanol and 19.5g decane solvent are added to be equipped with and are stirred
It mixes in the 500ml reactor of device, is heated to 130 DEG C, reaction 1.5 hours to magnesium chloride is completely dissolved.The general structure I is added
Compound 3,6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (8mmol) continues to 130 DEG C of reactions and obtains alcohol in 1 hour
Close object.Alcohol adduct is cooled to room temperature.Under nitrogen protection, above-mentioned alcohol adduct is added drop-wise to the pre- 120ml tetrachloro for being cooled to -22 DEG C
Change in titanium solution, be to slowly warm up to 100 DEG C, object is closed in 2,4-, the bis- benzoyloxy pentanizing that 6mmol is added, and is warming up to 110 DEG C of dimensions
It holds 2 hours.It filters while hot, adds 120 milliliters of titanium tetrachloride, be raised to 110 DEG C and react 2 hours, filtering.With anhydrous hexane solid
Particle 4 times, solid catalyst is obtained after dry.
(2) propylene polymerization
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt is added32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 0.1mol adds solid component 8-10mg and 1.2NL hydrogen prepared in the above embodiments,
It is passed through liquid propene 2.3L, is warming up to 70 DEG C, maintains this temperature 1 hour, is cooled down, pressure release obtains PP powder, the results are shown in Table 1.
Embodiment 12
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone replaces with 3,6-
Two (4- ethylphenyl) -1,4- dioxane -2,5- diketone.
Embodiment 13
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone replaces with 3,6-
Two (4- n-propyl phenyl) -1,4- dioxane -2,5- diketone.
Embodiment 14
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone replaces with 3,6-
Two (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone.
Embodiment 15
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone replaces with 3,6-
Diisobutyl -1,4- dioxane -2,5- diketone.
Embodiment 16
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (6mmol) is replaced
It is changed to 3- phenyl -6- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone.
Embodiment 17
With embodiment 16, only by compound 2 therein, bis- benzoyloxy pentane of 4- replaces with DNBP (phthalic acid two
N-butyl).
Embodiment 18
With embodiment 16, only by compound 2 therein, bis- benzoyloxy pentane of 4- replaces with (the n-butylbenzene first of 2,4- bis-
Carboxyl) pentane.
Embodiment 19
With embodiment 16, only by compound 2 therein, bis- benzoyloxy pentane of 4- replaces with DIBP (phthalic acid two
Isobutyl ester).
Embodiment 20
With embodiment 16, only by compound 2 therein, bis- benzoyloxy pentane of 4- replaces with 9,9- dimethoxy-methyl
Fluorenes.
Embodiment 21
With embodiment 16, only by compound 2 therein, bis- benzoyloxy pentane of 4- replaces with 2- isopropyl -2- isopentyl -
1,3- dimethoxy propane.
Embodiment 22
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (8mmol) is replaced
It is changed to 3,6- diphenyl -1,4- dioxane -2,5- diketone (4mmol) and phthalic anhydride (0.7g).
Embodiment 23
With embodiment 11, in embodiment plus hydrogen amount is only become into 7.2NL, concrete outcome is shown in Table 1.
Comparative example 1
With embodiment 11, only by compound 3 therein, 6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (6mmol) is replaced
It is changed to phthalic anhydride (1.4g).
Comparative example 2
With comparative example 1, the difference is that the additional amount of hydrogen is changed to 7.2NL when polymerization.Aggregated data is shown in Table 1.
Table 1
By embodiment 11-16 it is found that the catalyst group prepared using the application precipitation additive compared with the data of comparative example 1
Point and catalyst activity, prepare polymer isotacticity and melt index met or exceeded the water of the prior art
It is flat, and at identical conditions, relative to use phthalic anhydride as precipitation additive, the catalysis prepared using the application precipitation additive
Agent component and catalyst, obtained polymer have broader molecular weight distribution.Under high hydrogen condition, precipitation is helped using the application
The catalytic component and catalyst of agent preparation, obtained melt index is higher, illustrates that catalyst of the invention has more
Good hydrogen response.
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two
The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if stating one kind
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of catalytic component for olefinic polymerization is prepared by the inclusion of the method for following steps:
1) magnesium compound is mixed with organic alcohol compound and atent solvent, the processing of general structure I compound represented is added, obtains
To alcohol adduct；
2) alcohol adduct is contacted at low temperature with titanium compound, internal electron donor compound is then added, isolated
First solid particle；
3) the first solid particle in step 2) is added in compound titanium solution, stirred and reacted, isolated second is solid
Body particle；
4) use atent solvent washing step 3) obtained in the second solid particle, obtain the catalytic component；
In formula, A is selected from-(XR1R2)nAnd-(YR5)m, Q is selected from-(XR3R4)aAnd-(YR6)b, wherein X is that carbon atom or silicon are former
Son, Y are nitrogen-atoms or phosphorus atoms, and m, n, a, b are respectively selected from 1~6 integer；R1~R6It may be the same or different, select each independently
From hydrogen, substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C2~C30Heterocycle, halogen, hydroxyl and substitution
Or unsubstituted C1~C30Alkoxy, be preferably selected from hydrogen, substituted or unsubstituted C1~C30Straight chained alkyl, replace or do not take
The C in generation3~C30Branched alkyl or naphthenic base, substituted or unsubstituted C2~C30Straight-chain alkenyl, substituted or unsubstituted C3
~C30Branched-chain alkenyl or cycloalkenyl, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C7~C30Alkane virtue
Base or aralkyl, substituted or unsubstituted C2~C30Alicyclic heterocyclic base, substituted or unsubstituted C4~C30Aromatic heterocyclic, halogen
Element, hydroxyl and substituted or unsubstituted C1~C30Alkoxy；And R1~R6It is not simultaneously hydrogen.
2. catalytic component according to claim 1, which is characterized in that the R1~R6It may be the same or different, it is respectively independent
Ground is selected from hydrogen, substituted or unsubstituted C1~C10Straight chained alkyl, substituted or unsubstituted C3~C10Branched alkyl or cycloalkanes
Base, substituted or unsubstituted C2~C10Straight-chain alkenyl, substituted or unsubstituted C3~C10Branched-chain alkenyl or cycloalkenyl, substitution
Or unsubstituted C6~C10Aryl, substituted or unsubstituted C7~C10Alkaryl or aralkyl, substituted or unsubstituted C2
~C10Alicyclic heterocyclic base, substituted or unsubstituted C4~C10Aromatic heterocyclic, halogen, hydroxyl and substituted or unsubstituted C1~C10
Alkoxy, preferably be selected from methyl, ethyl, propyl, butyl, amyl, hexyl, cyclopenta, cyclohexyl, vinyl, acrylic, butylene
Base, phenyl, aminomethyl phenyl, ethylphenyl, propyl phenyl, butyl phenyl, amyl phenyl, halogenophenyl, benzyl, phenethyl,
Phenylpropyl, naphthalene, xenyl, methoxyl group, ethyoxyl, propoxyl group, the group containing pyrroles, the group base containing pyridine, contains benzene butyl
The group of pyrimidine, the group containing quinoline, chlorine, bromine, iodine, hydroxyl and hydroxyalkyl.
3. catalytic component according to claim 1 or 2, which is characterized in that the general formula I compound represented is selected from 3,
6- diphenyl -1,4- dioxane -2,5- diketone, 3,6- bis- (4- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, 3,6-
Two (2- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, (3- the aminomethyl phenyl) -1,4- dioxane of 3,6- bis- -2,5- two
Ketone, 3,6- bis- (4- ethylphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (2- ethylphenyl) -1,4- dioxane -
2,5- diketone, 3,6- bis- (3- ethylphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (4- n-propyl phenyl) -1,4- two
Six ring -2,5- diketone of oxygen, (2- n-propyl the phenyl) -1,4- dioxane -2,5- of 3,6- bis- diketone, (the 3- n-propylbenzene of 3,6- bis-
Base) -1,4- dioxane -2,5- diketone, 3,6- bis- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone, 3,6- bis-
(2- isopropyl phenyl) -1,4- dioxane -2,5- diketone, (4- the n-butylphenyl) -1,4- dioxane of 3,6- bis- -2,5- two
Ketone, 3,6- bis- (2- n-butylphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (3- n-butylphenyl) -1,4- dioxy six
Ring -2,5- diketone, 3,-two (2,4- aminomethyl phenyl) -1,4- dioxane -2,5- diketone, (the 2,4,6- trimethylbenzene of 3,6- bis-
Base) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (4- n-propyl phenyl) -1,4- dioxane -2,5- diketone, 3- benzene
Base -6- (4- isopropyl phenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (2,4- 3,5-dimethylphenyl) -1,4- dioxy
Six ring -2,5- diketone, 3- phenyl -6- (2,4,6- trimethylphenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (2-
Aminomethyl phenyl) -1,4- dioxane -2,5- diketone, 3- phenyl -6- (2- chlorphenyl) -1,4- dioxane -2,5- diketone, 3,
6- bis- (4- chlorphenyl) -1,4- dioxane -2,5- diketone, 3,6- bis- (2- chlorphenyl) -1,4- dioxane -2,5- diketone,
3,6- bis- (3- chlorphenyl) -1,4- dioxane -2,5- diketone, dioxane -2 3,6- dimethyl -3,6- diphenyl -1,4-,
5- diketone, 3,6- dimethyl -1,4- dioxane -2,5- diketone, 3,6- diethyl -1,4- dioxane -2,5- diketone, 3,6-
Diη-propyl -1,4- dioxane -2,5- diketone, 3,6- diisopropyl -1,4- dioxane -2,5- diketone, the positive fourth of 3,6- bis-
Base -1,4- dioxane -2,5- diketone, 3,6- diisobutyl -1,4- dioxane -2,5- diketone, (the 1- methyl-prop of 3,6- bis-
Base) -1,4- dioxane -2,5- diketone, 3,6- bis- (1- methyl butyl) -1,4- dioxane -2,5- diketone, bis- (1- of 3,6-
Methyl amyl) -1,4- dioxane -2,5- diketone, bis- n-pentyl -1,4- dioxane -2,5- diketone of 3,6-, 3,6- diisoamyl
Base -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- diη-propyl -1,4- dioxane -2,5- diketone, 3,6- bis-
Methyl -3,6- diisopropyl -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- di-n-butyl -1,4- dioxane -
2,5- diketone, 3,6- dimethyl -3,6- diisobutyl -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- two positive penta
Base -1,4- dioxane -2,5- diketone, 3,6- dimethyl -3,6- diisoamyl -1,4- dioxane -2,5- diketone, 3,6- bis-
Ethyl -3,6- diη-propyl -1,4- dioxane -2,5- diketone, two silicon of 2,2,5,5- tetramethyl -1,4- dioxane -2,5- -
3,6- diketone, two silicon -3,6- diketone of 2,2,5,5- tetraethyl -1,4- dioxane -2,5-, 2,2,5,5- tetrapropyl -1,4- two
Six ring -2,5- of oxygen, two silicon -3,6- diketone, two silicon -3,6- diketone of the 2,2,5,5- tetrabutyl -1,4- dioxane -2,5-, 2,2- bis-
Two silicon -3,6- diketone of methyl -5,5- diethyl -1,4- dioxane -2,5-, 2,2- dimethyl -5,5- dipropyl -1,4- dioxy
Six ring -2,5-, two silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- dimethyl -5,5- dipropyl -1,4- dioxane -2,5-,
Two silicon -3,6- diketone of 2,2- dimethyl -5,5- dibutyl -1,4- dioxane -2,5-, diethyl -1 2,2- diethyl -5,5-,
Two silicon -3,6- diketone of 4- dioxane -2,5-, two silicon -3,6- of 2,2- diethyl -5,5- dipropyl -1,4- dioxane -2,5-
Diketone, two silicon -3,6- diketone of 2,2- diethyl -5,5- dipropyl -1,4- dioxane -2,5-, two fourth of 2,2- diethyl -5,5-
Two silicon -3,6- diketone of base -1,4- dioxane -2,5-, 2,2- dipropyl -5,5- diethyl -1,4- dioxane -2,5- two
Silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- dipropyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- dipropyl -
Two silicon -3,6- diketone of 5,5- dipropyl -1,4- dioxane -2,5-, 2,2- dipropyl -5,5- dibutyl -1,4- dioxane -
Bis- silicon -3,6- diketone of 2,5-, two silicon -3,6- diketone of 2,2- dibutyl -5,5- diethyl -1,4- dioxane -2,5-, 2,2- bis-
Two silicon -3,6- diketone of butyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- dibutyl -5,5- dipropyl -1,4- dioxy
Six ring -2,5-, two silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- dibutyl -5,5- dibutyl -1,4- dioxane -2,5-,
2,5- dimethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, phenodiazine -3 2,5- diethyl -1,4- dioxane -2,5-,
6- diketone, 2,5- dipropyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- dibutyl -1,4- dioxane -2,5-
Phenodiazine -3,6- diketone, 2,5- diamyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- bis- base -1,4- dioxy six
Ring -2,5- phenodiazine -3,6- diketone, 2,5- dimethoxy methyl-1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- dimethoxy
Ethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- dimethoxypropyl -1,4- dioxane -2,5- phenodiazine -3,6-
Diketone, 2,5- diethoxy methyl-1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diethoxy ethyl -1,4- dioxy six
Ring -2,5- phenodiazine -3,6- diketone, 2,5- diethyl oxygen propyl group -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diformazan
Two phosphorus -3,6- diketone of base -1,4- dioxane -2,5-, two phosphorus -3,6- diketone of 2,5- diethyl -1,4- dioxane -2,5-,
Two phosphorus -3,6- diketone of 2,5- dipropyl -1,4- dioxane -2,5-, two phosphorus -3 2,5- dibutyl -1,4- dioxane -2,5-,
6- diketone, two phosphorus -3,6- diketone of 2,5- diamyl -1,4- dioxane -2,5-, 2,5- bis- base -1,4- dioxane -2,5-
Two phosphorus -3,6- diketone, 2,5- dimethoxy methyl-1, two phosphorus -3,6- diketone of 4- dioxane -2,5-, dimethoxy ethyl -1 2,5-,
Two phosphorus -3,6- diketone of 4- dioxane -2,5-, two phosphorus -3,6- diketone of 2,5- dimethoxypropyl -1,4- dioxane -2,5-, 2,
5- diethoxy methyl-1, two phosphorus -3,6- diketone of 4- dioxane -2,5-, 2,5- diethoxy ethyl -1,4- dioxane -2,5-
One of two phosphorus -3,6- diketone of two phosphorus -3,6- diketone and 2,5- diethyl oxygen propyl group -1,4- dioxane -2,5- is a variety of.
4. catalytic component described in any one of -3 according to claim 1, which is characterized in that the magnesium compound includes two
Magnesium halide, the hydrate of magnesium dihalide, the water of magnesium dihalide or alcohol complex compound, alkyl magnesium halide, alkoxyl magnesium and alkoxy
At least one of magnesium halide, the halogen are selected from least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine.
5. catalytic component described in any one of -4 according to claim 1, which is characterized in that the internal electron donor chemical combination
Object is selected from one of ester, ether, carboxylic acid, ketone and amine or a variety of, is preferably selected from Polycarboxylic acids, polybasic carboxylic acid esters
Close one of object, diol-lipid compound, dihydric phenol ester type compound and diether compound or a variety of.
6. catalytic component described in any one of -5 according to claim 1, which is characterized in that described in terms of every mole of magnesium
The dosage of general formula I compound represented is 0.01-6 moles, preferably 0.01-2 moles, more preferably 0.02-1 moles.
7. catalytic component described in any one of -6 according to claim 1, which is characterized in that described in terms of every mole of magnesium
The dosage of internal electron donor compound is 0.001-15 moles, preferably 0.005-10 moles, more preferably 0.05-5 moles.
8. a kind of catalyst system for olefinic polymerization comprising the reaction product of following components:
A. catalytic component described in any one of claim 1-7；
B. organo-aluminum compound；
C. optionally, organo-silicon compound.
9. catalyst system according to claim 8, which is characterized in that the molar ratio of the component b and component a with aluminium/
Titanium is calculated as (5-1000): 1；And/or the molar ratio of the component c and component a is calculated as (0-500) with silicon/titanium: 1.
10. a kind of olefine polymerizing process, including using one or more alkene urging described in any one of claim 1-7
Olefin polymerization is carried out in the presence of catalyst system described in agent component or claim 8 or 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169845C (en) * | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| US20110130529A1 (en) * | 2009-12-02 | 2011-06-02 | Dow Global Technologies Inc. | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
| CN102146146A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| US20140212355A1 (en) * | 2013-01-28 | 2014-07-31 | Abbott Cardiovascular Systems Inc. | Trans-arterial drug delivery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169845C (en) * | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| US20110130529A1 (en) * | 2009-12-02 | 2011-06-02 | Dow Global Technologies Inc. | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
| CN102146146A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| US20140212355A1 (en) * | 2013-01-28 | 2014-07-31 | Abbott Cardiovascular Systems Inc. | Trans-arterial drug delivery |
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