CN109553707A - A kind of catalytic component, catalyst and application for olefinic polymerization - Google Patents

A kind of catalytic component, catalyst and application for olefinic polymerization Download PDF

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CN109553707A
CN109553707A CN201710887474.6A CN201710887474A CN109553707A CN 109553707 A CN109553707 A CN 109553707A CN 201710887474 A CN201710887474 A CN 201710887474A CN 109553707 A CN109553707 A CN 109553707A
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diketone
dioxane
bis
compound
silicon
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CN109553707B (en
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王军
高明智
马晶
刘海涛
陈建华
马吉星
蔡晓霞
胡建军
李昌秀
张天
张天一
何世雄
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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

Abstract

The invention discloses a kind of catalytic component of olefin polymerization, including magnesium, titanium, halogen and internal electron donor compound, the internal electron donor includes general formula I compound represented,In formula, A is selected from-(XR1R2)nAnd-(YR5)m, Q is selected from-(XR3R4)aOr-(YR6)b, wherein X is carbon atom or silicon atom, and Y is nitrogen-atoms or phosphorus atoms, m, n, a, b=1~6；R1~R6It may be the same or different, be selected from hydrogen, substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C2~C30Heterocycle, halogen, hydroxyl and substituted or unsubstituted C1~C30Alkoxy.Catalytic component of the invention and catalyst prepared therefrom are used for olefinic polymerization, activity with higher and adjustable capacity of orientation, and the hydrogen response of catalyst is good, the polymer molecular weight wider distribution of preparation.

Description

A kind of catalytic component, catalyst and application for olefinic polymerization
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
Olefin polymerization catalysis can be divided into three categories, i.e., traditional Ziegler-Natta catalyst, metallocene catalyst with And non-metallocene catalyst.For traditional Ziegler-Natta catalyst, with the electron donor chemical combination in catalyst The development of object, polyolefin catalyst are also continuously updated the replacement.TiCl of the research and development of catalyst from the first generation3AlCl3/AlEt2Cl The TiCl of system and the second generation3/AlEt2Cl system, the magnesium chloride to the third generation are in carrier, monoesters or aromatic dibasic acid ester are Electron donor, the TiCl that silane is external electron donor4·ED·MgCl2/AlR3ED system, the catalytic polymerization of catalyst Activity and gained polypropylene isotacticity height are all greatly improved.
In the prior art, for the titanium catalyst system of propylene polymerization mostly using magnesium, titanium, halogen and electron donor as base This ingredient, wherein electron donor compound is one of essential component in catalytic component.At present, it has been disclosed that a variety of to give Electron compound, such as monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine and its derivative, In more the most commonly used is aromatic dicarboxylic acids' esters (such as n-butyl phthalate or diisobutyl phthalate, ginseng See United States Patent (USP) US4784983).
Since the states such as European Union use the limitation of phthalate compound, for the requirement of environmentally protective aspect, Novel electron donor compound is had developed, such as containing there are two 1,3- diether compound [such as 2- isopropyls-of ether group 2- isopentyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy propane and 9,9- bis- (methoxyl methyl) fluorenes, See United States Patent (USP) US4971937 and European patent EP 0728769], dibasic aliphatic carboxylic acid ester compound (such as succinate, Malonate, glutarate etc., referring to patent WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), diol-lipid compound (referring to patent CN1436766A, CN1453298A etc.).In recent years, it and emerges Many is used for the new structural electron donor compound of olefin polymerization catalysis, as again ethers group existing in molecular structure has The ether alcohol esters internal electron donor compound (WO2012175425, US20100974322, US20100974667) of ester groups, Phenylacetate (WO2013/174759) and benzenpropanoic acid esters electron donor compound (WO2013057026).It is reported in Chinese patent A kind of tricarboxylic acids ester type compound (CN102399329) in road and a kind of disubstituted succinic acid compound anhydride (CN102286117) catalyst as internal electron donor synthesis is used for olefinic polymerization, but the overall effect of gained catalyst is not It is prominent.
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 cyclic carboxylic acids lactone compound in catalytic component, and then provides a kind of catalyst for olefines polymerizing, institute When stating catalytic component and catalyst system applied to olefinic polymerization, high comprehensive performance is with higher active and adjustable The hydrogen response of capacity of orientation, catalyst 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, including magnesium, titanium, halogen and Internal electron donor compound, the internal electron donor include general formula I compound represented,
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- two Isobutyl group -1,4- dioxane -2,5- diketone, two n-pentyl -1,4- dioxane -2,5- diketone of 3,6- dimethyl -3,6-, 3, 6- dimethyl -3,6- diisoamyl -1,4- dioxane -2,5- diketone, 2,2,5,5- tetramethyl -1,4- dioxane -2,5- Two silicon -3,6- diketone, two silicon -3,6- diketone of 2,2,5,5- tetraethyl -1,4- dioxane -2,5-, tetrapropyl -1 2,2,5,5-, Two silicon -3,6- diketone of 4- dioxane -2,5-, two silicon -3,6- diketone of the 2,2,5,5- tetrabutyl -1,4- dioxane -2,5-, 2, Two silicon -3,6- diketone of 2- dimethyl -5,5- diethyl -1,4- dioxane -2,5-, 2,2- dimethyl -5,5- dipropyl -1,4- Two silicon -3,6- diketone of dioxane -2,5-, two silicon -3,6- two of 2,2- dimethyl -5,5- dipropyl -1,4- dioxane -2,5- Ketone, two silicon -3,6- diketone of 2,2- dimethyl -5,5- dibutyl -1,4- dioxane -2,5-, 2,2- diethyl -5,5- diethyl Two silicon -3,6- diketone of base -1,4- dioxane -2,5-, 2,2- diethyl -5,5- dipropyl -1,4- dioxane -2,5- two Silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- diethyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- diethyl - Two silicon -3,6- diketone of 5,5- dibutyl -1,4- dioxane -2,5-, 2,2- dipropyl -5,5- diethyl -1,4- dioxane - Bis- silicon -3,6- diketone of 2,5-, two silicon -3,6- diketone of 2,2- dipropyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- bis- Two silicon -3,6- diketone of propyl -5,5- dipropyl -1,4- dioxane -2,5-, 2,2- dipropyl -5,5- dibutyl -1,4- dioxy Six ring -2,5-, two silicon -3,6- diketone, two silicon -3,6- diketone of 2,2- dibutyl -5,5- diethyl -1,4- dioxane -2,5-, Two silicon -3,6- diketone of 2,2- dibutyl -5,5- dipropyl -1,4- dioxane -2,5-, dipropyl -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- dibutyl -1,4- dioxane -2,5- Diketone, 2,5- dimethyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diethyl -1,4- dioxane -2,5- two Nitrogen -3,6- diketone, 2,5- dipropyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- dibutyl -1,4- dioxy six Base -1 ring -2,5- phenodiazine -3,6- diketone, 2,5- diamyl -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- bis-, 4- dioxane -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- dioxane -2,5- phenodiazine -3,6- diketone, 2,5- diethyl oxygen propyl group -1,4- dioxane -2,5- phenodiazine -3,6- diketone, 2, Two phosphorus -3,6- diketone of 5- dimethyl -1,4- dioxane -2,5-, two phosphorus -3,6- of 2,5- diethyl -1,4- dioxane -2,5- Diketone, two phosphorus -3,6- diketone of 2,5- dipropyl -1,4- dioxane -2,5-, 2,5- dibutyl -1,4- dioxane -2,5- two Phosphorus -3,6- diketone, two phosphorus -3,6- diketone of 2,5- diamyl -1,4- dioxane -2,5-, 2,5- bis- base -1,4- dioxy six Two phosphorus -3,6- diketone of ring -2,5-, 2,5- dimethoxy methyl-1, two phosphorus -3,6- diketone of 4- dioxane -2,5-, 2,5- dimethoxy Two phosphorus -3,6- diketone of ethyl -1,4- dioxane -2,5-, two phosphorus -3,6- of 2,5- dimethoxypropyl -1,4- dioxane -2,5- Diketone, 2,5- diethoxy methyl-1, two phosphorus -3,6- diketone of 4- dioxane -2,5-, 2,5- diethoxy ethyl -1,4- dioxy six One of two phosphorus -3,6- diketone of two phosphorus -3,6- diketone of ring -2,5- and 2,5- diethyl oxygen propyl group -1,4- dioxane -2,5- or It 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.
Some preferred embodiments according to the present invention further include the second internal electron donor chemical combination in the catalytic component General formula I compound represented and the second internal electron donor compound are used in compounding by object.
Wherein, second internal electron donor compound is selected from one of ester, ether, carboxylic acid, ketone and amine or a variety of, preferably Selected from Polycarboxylic acids, polybasic carboxylic acid esters compound, diol-lipid compound, dihydric phenol ester type compound and diether One of class compound is a variety of, more preferably includes benzoates, phthalate, malonic acid esters, succinic acid One of esters and glutaric acid ester type compound are a variety of.In some specific embodiments, second internal electron donor Compound includes n-butyl phthalate, diisobutyl phthalate, bis- benzoyloxy pentane of 2,4-, bis- (first of 2,4- Base benzoyloxy) pentane, 2,4- bis- (ethylamino benzonitrile carboxyl) pentane, 2,4- bis- (n-propylbenzene carboxyphenyl) pentane, 2,4- bis- be (different Propyl benzoyloxy) pentane, 2,4- bis- (n-butylbenzene carboxyphenyl) pentane, 2,4- bis- (isobutyl-benzene carboxyphenyl) pentane, 2,4- Two (tert-butyl benzene carboxyphenyl) pentanes, 9,9- dimethoxy-methyl fluorenes, 2- isopropyl -2- isopentyl -1,3- dimethoxy fluorenes, 1, One kind of bis- benzoyloxy naphthols of 8-, 3- tert-butyl -1,2- two benzoyloxy phenol and 2,3- diisopropyl diethyl succinate Or it is a variety of.
Preferred embodiment in accordance with the present invention, weight percent of the general formula I compound represented in the catalytic component Content is 0.05-20%, preferably 0.5-15%, more preferably 2-10%；And/or second internal electron donor compound exists Weight percentage in the catalytic component is 0-20%, preferably 0.01-15%, more preferably 1-10%.
According to some embodiments of the present invention, the catalytic component includes magnesium compound, titanium compound and interior electron The reaction product of body compound；The internal electron donor includes general formula I compound represented.
According to the preferred embodiment of the present invention, the catalytic component by the inclusion of the method for following steps preparation:
Magnesium compound and organic solvent are mixed to form solution by S1, are optionally added into titanium compound processing；
S2 is handled the mixture of step S1 using internal electron donor compound, then optionally with titanium compound and/ Or inert diluent processing, obtain the catalytic component；The internal electron donor includes general formula I compound represented.
According to certain embodiments of the present invention, it can be optionally added or be added without at titanium compound in the step S1 Reason.
Preferred embodiment in accordance with the present invention, the internal electron donor further include the second internal electron donor compound, i.e., will General formula I compound represented is used in compounding with the second internal electron donor compound.
According to the preferred embodiment of the present invention, second 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.In some specific embodiments, in described second Electron donor compound includes n-butyl phthalate, diisobutyl phthalate, bis- benzoyloxy pentane of 2,4-, 2, 4- bis- (methyl benzoyloxy) pentane, 2,4- bis- (ethylamino benzonitrile carboxyl) pentane, 2,4- bis- (n-propylbenzene carboxyphenyl) pentane, 2, 4- bis- (cumene carboxyphenyl) pentane, 2,4- bis- (n-butylbenzene carboxyphenyl) pentane, 2,4- bis- (isobutyl-benzene carboxyphenyl) penta Alkane, 2,4- bis- (tert-butyl benzene carboxyphenyl) pentane, 9,9- dimethoxy-methyl fluorenes, 2- isopropyl -2- isopentyl -1,3- dimethoxy Base fluorenes, bis- benzoyloxy naphthols of 1,8-, two benzoyloxy phenol of 3- tert-butyl -1,2- and 2,3- diisopropyl 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 0.01-10 moles, preferably 0.01-5 moles, more preferably 0.2-5 moles；And/or the second internal electron donor chemical combination The dosage of object is 0-10 moles, preferably 0-5 moles, more preferably 0.01-5 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.
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.
Some preferred embodiments according to the present invention, for the inert diluent, there is no particular limitation, guarantees it It does not react with the other compositions；Be suitable for the invention inert diluent include hexane, heptane, octane, decane, At least one of benzene, toluene and dimethylbenzene.
According to certain embodiments of the present invention, described " optionally being handled with titanium compound and/or inert diluent " is Finger can be as needed, is used with or without titanium compound and/or inert diluent handles solids.
A preferred embodiment according to the present invention, the preparation method of above-mentioned catalyst group may include following specific step It is rapid:
1) by magnesium halide be dissolved in by organic epoxy compound object, organic phosphorus compound and optionally inert diluent form it is molten Homogeneous solution is formed in agent system, is then mixed with titanium compound, and in the presence of precipitation additive, solids is precipitated；
2) solids is handled using internal electron donor compound, is carried on it on solids, then optionally Ground titanium compound and/or inert diluent processing, finally to obtain after being filtered, washed, drying include titanium, magnesium, halogen, interior The catalytic component of the ingredients such as electron donor.
According to the preferred embodiment of the present invention, the organic epoxide includes C2-C10Fatty alkene, alkadienes, The oxide of halogenated aliphatic alkene, at least one of glycidol ether and inner ether.It is described in some specific embodiments Organic epoxide includes epoxy ether, propylene oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxy chlorine At least one of propane, methyl glycidyl ether and diglycidyl ether, preferably epoxychloropropane.
According to one embodiment of present invention, the organic phosphorus compound includes the hydrocarbyl carbonate or halogen of orthophosphoric acid or phosphorous acid For hydrocarbyl carbonate.In some specific embodiments, the organic phosphorus compound include orthophosphoric acid trimethyl, orthophosphoric acid triethyl, At least one in orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, tributyl phosphite and triphenyl phosphite Kind, preferably orthophosphoric acid trimethyl.
According to the preferred embodiment of the present invention, in terms of every mole of magnesium, the dosage of the organic epoxy compound object is 0.2- 10 moles, preferably 0.5-5 moles；The dosage of the organic phosphorus compound is 0.1-3 moles, preferably 0.2-2 moles；It is described The dosage of titanium compound is 0.5-50 moles, preferably 1-40 moles；
A preferred embodiment according to the present invention, the preparation method of above-mentioned catalyst group may include following specific step It is rapid:
1) alkoxyl magnesium or alkoxy-magnesium chloride are suspended in atent solvent and form suspension, it is then mixed with titanium compound Splice grafting touches to obtain solids；
2) solids is handled using internal electron donor compound, is carried on it on solids, then optionally Ground titanium compound and/or inert diluent processing, finally to obtain after being filtered, washed, drying include titanium, magnesium, halogen, interior The catalytic component of the ingredients such as electron donor.
According to some embodiments of the present invention, the atent solvent include hexane, heptane, octane, decane, benzene, toluene and At least one of dimethylbenzene.
According to the preferred embodiment of the present invention, in terms of every mole of magnesium, the dosage of the titanium compound is 0.5-50 moles, Preferably 1-40 moles；
A preferred embodiment according to the present invention, the preparation method of above-mentioned catalyst group may include following specific step It is rapid:
1) magnesium compound, organic alcohol compound and titanium compound are mixed to form in atent solvent homogeneous solution, heated Cooling obtains ball type carrier after the homogeneous solution；
2) ball type carrier is mixed with titanium compound, heat temperature raising after a period of time is maintained under low temperature, then with interior Electron donor compound, then optionally handled with titanium compound and/or inert diluent, finally after being filtered, washed, drying Obtain include the ingredients such as titanium, magnesium, halogen, internal electron donor catalytic component.
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.
A preferred embodiment according to the present invention, the preparation method of above-mentioned catalyst group may include following specific step It is rapid:
1) magnesium compound, organic alcohol compound and titanium compound are mixed to form alcohol adduct solution in atent solvent；
2) the alcohol adduct solution is mixed with titanium compound, under low temperature maintain a period of time after heat temperature raising, then plus Enter internal electron donor compound to be handled, then optionally handled with titanium compound and/or inert diluent, was finally passed through Filter, washing, it is dry after obtain include the ingredients such as titanium, magnesium, halogen, internal electron donor catalytic component.
A preferred embodiment according to the present invention, the preparation method of above-mentioned catalyst group may include following specific step It is rapid:
Magnesium halide is dissolved in by organic epoxy compound object, organic phosphorus compound and the optionally solvent that forms of inert diluent Homogeneous solution is formed in system, general formula I compound represented is added, then mixes with titanium compound, when maintaining one section under low temperature Between after heat temperature raising, then with titanium compound and/or inert diluent processing, then handled with internal electron donor compound, Finally obtained after being filtered, washed, drying include the ingredients such as titanium, magnesium, halogen, internal electron donor catalytic component.
The catalyst component for olefin that method produced according to the present invention obtains can be used in preparing olefinic polymerization catalysis Agent 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 (5-800) with aluminium/titanium: 1； And/or the molar ratio of the component c and component a is calculated as (0-500) with silicon/titanium: 1, preferably (0.01-500): 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 can be with or without organo-silicon compound in the catalyst system of conjunction.According to a preferred embodiment of the present invention, for described outer There is no particular limitation for electron 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, olefinic polymerization, catalysis are used for as internal electron donor compound using general formula I compound represented Active height, decay of activity are slow, and high melt index, the molecular weight distribution of resulting polymer are wide, isotacticity is high.It mentions according to the present invention The catalyst of confession, is catalyzed high comprehensive performance living, activity with higher and adjustable capacity of orientation, and the hydrogen tune of catalyst is sensitive Property is good, and the polymer isotactic index of preparation 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
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added Alkane 4ml, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring.After solid is completely dissolved, Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour460mL slowly rises Gradually solids is precipitated to 80 DEG C for temperature, addition compound 3,6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (6mmol), It maintains temperature 1 hour.After heat filtering, toluene 150mL is added, washing is secondary, obtains solid.Toluene 100mL is added, is warming up to It 110 DEG C, is washed three times, the time is respectively 10 minutes.It adds hexane 60mL washing three times, catalyst is obtained after vacuum drying Solid component.
(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) 5ml makes Al/Si (mol)=25, add solid component 10mg prepared in the above embodiments and 1.2NL hydrogen is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling is bled off pressure, and discharge to obtain PP resin, It 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- n-propyl phenyl) -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- isopropyl 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- Diisobutyl -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- benzene Base -6- (4- isopropyl phenyl) -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 3,6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (3mmol) and DNBP (n-butyl phthalate, 3mmol).
Embodiment 17
With embodiment 16, compound DNBP therein is only changed to 2,4-, bis- benzoyloxy pentane.
Embodiment 18
With embodiment 16, compound DNBP therein is only replaced with into 2,4- bis- (n-butylbenzene carboxyphenyl) pentane.
Embodiment 19
With embodiment 16, compound DNBP therein is only changed to DIBP (diisobutyl phthalate).
Embodiment 20
With embodiment 16, compound DNBP therein is only replaced with into 9,9- dimethoxy-methyl fluorenes.
Embodiment 21
With embodiment 16, compound DNBP therein is only replaced with into 2- isopropyl -2- isopentyl -1,3- dimethoxy third Alkane.
Embodiment 22
With embodiment 16, compound DNBP therein is only changed to 1,8-, bis- benzoyloxy naphthols.
Embodiment 23
With embodiment 16, wherein bis- benzoyloxy phenol of 3- tert-butyl -1,2- only will be changed to by compound DNBP.
Embodiment 24
With embodiment 16, the compound DNBP in embodiment is only replaced with into 2,3- diisopropyl diethyl succinate.
Embodiment 25
(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.Phthalic anhydride 1.4g is added, continues It maintains 130 DEG C of reactions to obtain alcohol adduct in 1 hour, alcohol adduct is cooled to room temperature.Under nitrogen protection, above-mentioned alcohol adduct is added dropwise Into the 120ml titanium tetrachloride solution for being cooled to -22 DEG C in advance, 100 DEG C are to slowly warm up to, compound 3,6- diphenyl-Isosorbide-5-Nitrae-is added Dioxane -2,5- diketone (6mmol) is warming up to 110 DEG C and maintains 2 hours.It filters while hot, adds 120 milliliters of titanium tetrachloride, be raised to 110 DEG C are reacted 2 hours, filtering.With anhydrous hexane solid particle 4 times, catalyst solid constituent is obtained after vacuum drying.
(2) propylene polymerization
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt is added32.5mL, CHMMS5ml make Al/Si (mol)=25 adds solid component 10mg and 1.2NL hydrogen prepared in the above embodiments, is passed through liquid propene 2.5L is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling is bled off pressure, discharge to obtain PP resin, the results are shown in Table 1.
Embodiment 26
(1) preparation of catalyst solid constituent
In the reactor being sufficiently displaced from by high pure nitrogen, 300mLTiCl is added4, -20 DEG C are cooled to, chlorination is added When being warming up to 40 DEG C under stirring stage by stage, 2,4- hexichol first carboxylic is added in magnesium alcoholate carrier 7.0g (see patent CN1330086A) Base pentane (3mmol) and compound 3,6- diphenyl-Isosorbide-5-Nitrae-dioxane -2,5- diketone (3mmol) maintain temperature 2 hours, mistake After filter.Add TiCl4100mL is warming up to 110 DEG C, is handled three times.Add hexane 60mL washing three times, vacuum is dry Catalyst solid constituent 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, CHMMS5ml make Al/Si (mol)=25 adds solid component 10mg and 1.2NL hydrogen prepared in the above embodiments, is passed through liquid propene 2.5L is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling is bled off pressure, discharge to obtain PP resin, the results are shown in Table 1.
Embodiment 27
(1) preparation of catalyst solid constituent
In the reactor being sufficiently displaced from by high pure nitrogen, add 300mLTiCl4, -20 DEG C are cooled to, ethyoxyl is added When being warming up to 40 DEG C under stirring stage by stage, 2,4-, bis- benzoyloxy pentane (3mmol) and compound 3,6- hexichol is added in magnesium 7.0g Base-Isosorbide-5-Nitrae-dioxane -2,5- diketone (3mmol) maintains temperature 3 hours, after filtering.TiCl is added4100mL is warming up to 110 DEG C, it is handled three times.It adds hexane 60mL washing three times, obtains catalyst solid constituent 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, CHMMS5ml make Al/Si (mol)=25 adds solid component 10mg and 1.2NL hydrogen prepared in the above embodiments, is passed through liquid propene 2.5L is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling is bled off pressure, discharge to obtain PP resin, the results are shown in Table 1.
Embodiment 28
With embodiment 16, in embodiment plus hydrogen amount is only become into 7.2NL, concrete outcome is shown in Table 1.
Comparative example 1
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added Alkane 4ml, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring.After solid is completely dissolved, Phthalic anhydride 1.4g is added, continues to 1 hour.Solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour4, it is to slowly warm up to 80 DEG C, gradually solids is precipitated, is added DNBP (6mmol), maintained temperature 1 hour.After heat filtering, toluene 150mL is added, washes It washs secondary, obtains solid.Toluene 100mL is added, is warming up to 110 DEG C, is washed three times, the time is respectively 10 minutes.It adds Hexane 60mL is washed three times, obtains catalyst solid constituent after dry.
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt is added32.5mL, CHMMS5ml make Al/Si (mol)=25 adds solid component 10mg and the 1.2NL hydrogen of above-mentioned preparation, is passed through liquid propene 2.5L, rises Temperature maintains this temperature 1 hour to 70 DEG C, and cooling is bled off pressure, discharge to obtain PP resin, the results are shown in Table 1.
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
As can be seen from Table 1, using compound described in the application structural formula I separately as internal electron donor or and other The catalyst that internal electron donor is used in compounding preparation is used to be catalyzed isotacticity and the melting of polymer prepared by propylene polymerization Index has met or exceeded the level of the prior art.In terms of from the result of embodiment 28 and comparative example 2, added hydrogen compared with Under conditions of height, the catalyst hydrogen with higher of other internal electron donors preparation is compounded using compound described in structural formula I It adjusts sensitive property (molecular weight distribution of resulting polymers is wider).
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 (12)

1. a kind of catalytic component for olefinic polymerization, including magnesium, titanium, halogen and internal electron donor, the internal electron donor Including general formula I compound represented,
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 1~6 integer；R1~R6It may be the same or different, be each independently selected 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, substituted or unsubstituted 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~C30Alkaryl Or aralkyl, substituted or unsubstituted C2~C30Alicyclic heterocyclic base, substituted or unsubstituted C4~C30Aromatic heterocyclic, halogen, 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 in the catalytic component also Including the second internal electron donor compound, second internal electron donor compound in ester, ether, carboxylic acid, ketone and amine one Kind is a variety of, is preferably selected from Polycarboxylic acids, polybasic carboxylic acid esters compound, diol-lipid compound, binary phenolic ester One of class compound and diether compound are a variety of.
5. catalytic component described in any one of -4 according to claim 1, which is characterized in that general formula I compound represented Weight percentage in the catalytic component is 0.05-20%, preferably 0.5-15%, more preferably 2-10%；With/ Or weight percentage of second external donor compound in the catalytic component is 0-20%, preferably 0.01-15%, more preferably 1-10%.
6. catalytic component described in any one of claim 1-5, which is characterized in that the catalytic component includes magnesium Close the reaction product of object, titanium compound and internal electron donor compound；The internal electron donor includes chemical combination shown in general formula I Object.
7. catalytic component described in any one of -6 according to claim 1, which is characterized in that by the inclusion of following steps Method preparation:
Magnesium compound and organic solvent are mixed to form solution by S1, are optionally added into titanium compound processing；
S2 is handled the mixture of step S1 using internal electron donor compound, then optionally with titanium compound and/or lazy Property diluent treatment, obtains the catalytic component；The internal electron donor includes general formula I compound represented.
8. catalytic component according to any one of claims 1-7, which is characterized in that the internal electron donor also wraps The second internal electron donor compound is included, second internal electron donor compound is selected from one of ester, ether, carboxylic acid, ketone and amine Or it is a variety of, it is preferably selected from Polycarboxylic acids, polybasic carboxylic acid esters compound, diol-lipid compound, dihydric phenol esters One of compound and diether compound are a variety of.
9. catalytic component described in any one of -8 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 0.01-10 moles, preferably 0.01-5 moles, more preferably 0.2-5 moles；And/or The dosage of second internal electron donor compound is 0-10 moles, preferably 0-5 moles, more preferably 0.01-5 moles.
10. a kind of catalyst system for olefinic polymerization comprising the reaction product of following components:
A. catalytic component described in any one of claim 1-9；
B. organo-aluminum compound；
C. optionally, organo-silicon compound.
11. catalyst system according to claim 10, 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.
12. a kind of olefine polymerizing process, including using one or more alkene urging described in any one of claim 1-9 Olefin polymerization is carried out in the presence of catalyst system described in agent component or claim 10 or 11.
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