CN109553705B - Catalyst component for olefin polymerization and preparation method thereof - Google Patents

Catalyst component for olefin polymerization and preparation method thereof Download PDF

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CN109553705B
CN109553705B CN201710887345.7A CN201710887345A CN109553705B CN 109553705 B CN109553705 B CN 109553705B CN 201710887345 A CN201710887345 A CN 201710887345A CN 109553705 B CN109553705 B CN 109553705B
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phenyl
acetate
ethyl
butyl
ester
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CN109553705A (en
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王军
高明智
马晶
刘海涛
陈建华
马吉星
蔡晓霞
李昌秀
胡建军
何世雄
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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Abstract

The invention discloses a catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown as a general formula I is added in the preparation process of the catalyst component as a precipitation aid;
Figure DDA0001420308190000011
wherein A is- (CR)1R2)nOr- (XR)1R2)n(YR3)m-, wherein X is a carbon atom or a silicon atom, Y is a nitrogen atom or a phosphorus atom, n is 1 to 5, and m is 0 to 5; r1～R3Independently selected from hydrogen, substituted or unsubstituted C1～C30A substituted or unsubstituted C2～C30Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Alkoxy of R1And R2Can be linked to form a ring; r and R' may be the same or different and are selected from substituted or unsubstituted C1～C30And substituted or unsubstituted C2～C30The heterocyclic group of (1). The catalyst component and the catalyst prepared by the catalyst component are used for olefin polymerization, and have high activity and adjustable orientation capability, good hydrogen regulation sensitivity of the catalyst, and wide molecular weight distribution of the prepared polymer.

Description

Catalyst component for olefin polymerization and preparation method thereof
Technical Field
The invention relates to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst system for olefin polymerization, application of the catalyst component and the catalyst system in olefin polymerization reaction and an olefin polymerization method, and belongs to the field of olefin polymerization.
Background
Olefin polymerization catalysts can be divided into three broad categories, namely, traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For the conventional Ziegler-Natta catalysts for propylene polymerization, polyolefin catalysts are continuously updated with the development of electron donor compounds in the catalysts. Development of the catalyst from the first TiCl3AlCl3/AlEt2Cl system and second generation of TiCl3/AlEt2Cl system, magnesium chloride of the third generation as a carrier, monoester or aromatic dibasic acid ester as an internal electron donor, and TiCl with silane as an external electron donor4·ED·MgCl2/AlR3An ED system, the catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved, and a catalyst system taking diethers and diesters as internal electron donors is newly developed. In the prior art, a titanium catalyst system for propylene polymerization mostly uses magnesium, titanium, halogen and an electron donor as basic components, wherein the electron donor compound is one of the essential components in the catalyst component. At present, various electron-donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyethers, alcohols, amines, etc., andderivatives thereof, among which aromatic dicarboxylic acid esters such as di-n-butyl phthalate or diisobutyl phthalate are more commonly used, can be found in US 4784983. In the components disclosed in US4971937 and EP0728769 for olefin polymerization catalysts, specific 1, 3-diether compounds containing two ether groups are used as electron donors, such as 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene, etc. Thereafter, a special class of aliphatic dicarboxylic acid ester compounds such as succinate, malonate, glutarate and the like is disclosed (see WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), and the use of the electron donor compound can not only improve the activity of the catalyst, but also obviously widen the molecular weight distribution of the obtained propylene polymer.
The preparation method of the traditional solid particle type Ziegler-Natta titanium catalyst loaded with magnesium halide generally comprises the steps of preparing homogeneous solution by halogenation, crystallizing and precipitating, and then loading the titanium-containing active component on the magnesium halide. In the process of dissolution, solid substances with uniform particle size can be obtained only in the presence of the precipitation aid. The auxiliary precipitation agent is usually a compound such as an organic acid anhydride, an organic ketone, an ether, or the like. Such as CN85100997, CN98101108.x, CN98126383.6, CN98126385.2, CN98111780.5, cn98101108.x, CN99102813.9, CN98111780.5, CN201110335576.x, CN201010204493.2, CN201010294618.5, CN201010283061.5, CN200910209546.7, CN200910177286.x, CN200910091115.5, CN200910086590.3, CN200910084912.1, CN200910083987.7, CN200810117895.6, CN200810117895.1, CN200510114544.1, CN200410062290.9, etc. The precipitation assistant in each patent mainly comprises one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and amyl ether, or a mixture of the acetic anhydride, the phthalic anhydride, the succinic anhydride, the maleic anhydride, the pyromellitic anhydride, the acetic acid, the propionic acid, the butyric acid, the acrylic acid, the methacrylic acid, the acetone, the methyl. The precipitation aids reported in the patent literature to be effective for the preparation of olefin polymerization catalysts generally employ compounds of phthalic anhydride structure.
In the preparation method of the titanium-containing catalyst component disclosed in chinese patent CN1931885A, after magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound, a class of organic alcohol electron donors is added to form a uniform solution, and an alcohol or alkane is used as a coprecipitator to replace a conventional benzoic anhydride precipitation aid, so as to obtain a catalyst solid. In the chinese patent CN101864009B, after magnesium halide is dissolved in organic epoxy compound and organic phosphorus compound, polyol ester compound is used to replace the traditional benzoic anhydride precipitation aid, and the catalyst solid is obtained.
In summary, the precipitation assistant with good effect for preparing the olefin polymerization catalyst reported in the patent literature is phthalic anhydride, and the presence of the compound is likely to form phthalate compounds, which is not good for the current environmental protection requirement, so that innovative work needs to be carried out on the basis of the prior art to obtain a polyolefin catalyst with good comprehensive performance and industrial practicability.
Disclosure of Invention
The invention aims to provide a catalyst component for olefin polymerization and a preparation method thereof aiming at the defects of the prior art, a compound with a special structure is introduced as a precipitation aid in the preparation process of the catalyst component, the use of a phthalic anhydride compound is omitted or reduced, and further the catalyst for olefin polymerization is provided.
According to one aspect of the invention, a catalyst component for olefin polymerization is provided, which comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown as a general formula I is added into the catalyst component in the preparation process;
Figure BDA0001420308180000031
wherein A is- (CR)1R2)nOr- (XR)1R2)n(YR3)m-, wherein X is a carbon atom or a silicon atom, Y is a nitrogen atom or a phosphorus atom, n is 1 to 5, and m is 0 to 5; r1～R3Independently selected from hydrogen, substituted or unsubstituted C1～C30A substituted or unsubstituted C2～C30Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Preferably selected from hydrogen, substituted or unsubstituted C1～C30Linear alkyl, substituted or unsubstituted C of3～C30Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C30Linear alkenyl of (A), substituted or unsubstituted C3～C30Substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C7～C30Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C30A substituted or unsubstituted C4～C30Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C30Alkoxy group of (a); r1And R2Can be linked to form a ring;
r and R' may be the same or different and are selected from substituted or unsubstituted C1～C30And substituted or unsubstituted C2～C30Preferably selected from substituted or unsubstituted C1～C30Linear alkyl, substituted or unsubstituted C of3～C30Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C30Linear alkenyl of (A), substituted or unsubstituted C3～C30Substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C7～C30Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C30And substituted or unsubstituted C4～C30The aromatic heterocyclic group of (1).
According to some embodiments of the invention, the R is1～R3Selected from hydrogen, substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl, substituted or unsubstituted C7～C20Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C20A substituted or unsubstituted C4～C20Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C1～C20Preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, propoxy, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group, chloro, bromo, iodo, hydroxy and hydroxyalkyl; r1And R2Optionally linked to form a ring, preferably R on each X1And R2Optionally linked to substituted or unsubstituted C3～C10Cycloalkyl, substituted or unsubstituted C3～C10Or is substituted or unsubstituted C2～C10And heterocyclic groups such as cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl and cyclopentadienyl.
According to a preferred embodiment of the invention, said R and R', which may be identical or different, are chosen from substituted or unsubstituted C1～C10And substituted or unsubstituted C2～C10Preferably selected from substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C10And substituted or unsubstituted C4～C10The aromatic heterocyclic group of (a) is preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group and hydroxyalkyl.
According to the invention, said substitution means R1～R3The hydrogen atom bonded to a carbon atom in the alkyl, cycloalkyl, aryl, alkaryl or aralkyl group in R and R' may be optionally substituted with a heteroatom, an alkyl group or an alkoxy group, and the carbon atom on the main chain may be optionally substituted with a heteroatom. The hetero atom includes a halogen atom and the like.
According to some embodiments of the invention, the compound of formula I is selected from the group consisting of ethyl 2-phenyl-2-benzoyloxyacetate, propyl 2-phenyl-2-benzoyloxyacetate, butyl 2-phenyl-2-benzoyloxyacetate, pentyl 2-phenyl-2-benzoyloxyacetate, ethyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, butyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-methylbenzoyloxy, Propyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, pentyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, butyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, Butyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, 2-phenyl-2- (4-propylbenzoyloxy) acetate (2-furylmethyl), 2-phenyl-2- (4-propylbenzoyloxy) acetate (2-pyranyl methyl), ethyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, propyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, methyl ethyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, methyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, methyl (, Amyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, butyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, amyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, propyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, amyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, Ethyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, propyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, butyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, amyl 2-phenyl-2- (3-chlorobenzoyloxy) acetate, ethyl 2-phenyl-2- (3-chlorobenzoyloxy) acetate, propyl 2-phenyl-2- (3-chlorobenzoyloxy) acetate, ethyl 2-phenyl-2- (2-chlorobenzoyloxy) acetate, propyl 2-phenyl-2- (2-chlorobenzoyloxy) acetate, butyl 2-phenyl-2- (2-chlorobenzoyloxy) acetate, methyl ethyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, methyl ethyl 2-phenyl-2- (3-chlorobenzoyloxy) acetate, methyl ethyl 2-, 2-phenyl-2- (2-chlorobenzoyloxy) acetic acid pentyl ester, 2-phenyl-2- (3-bromobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (3-bromobenzoyloxy) acetic acid propyl ester, 2-phenyl-2- (2-bromobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (2-bromobenzoyloxy) acetic acid propyl ester, 2-phenyl-2- (2-bromobenzoyloxy) acetic acid butyl ester, 2-phenyl-2- (2-bromobenzoyloxy) acetic acid pentyl ester, 2-phenyl-2- (4-bromobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (4-bromobenzoyloxy) acetic acid propyl ester, Butyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, pentyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, ethyl 2-phenyl-2-cyclohexylformyloxy acetate, propyl 2-phenyl-2-cyclohexylformyloxy acetate, butyl 2-phenyl-2-cyclohexylformyloxy acetate, pentyl 2-phenyl-2-cyclohexylformyloxy acetate, methyl 2-phenyl-2-cyclopentylcarboxoyloxy acetate, ethyl 2-phenyl-2-cyclopentylcarboxoyloxy acetate, propyl 2-phenyl-2-cyclopentylcarboxoyloxy acetate, butyl 2-phenyl-2-cyclopentylcarboxoyloxy acetate, methyl 2-phenyl-2-cyclopentylc, Amyl 2-phenyl-2-cyclopentylcarboxyloxyacetate, ethyl 2-phenyl-2-propionyloxyacetate, propyl 2-phenyl-2-propionyloxyacetate, butyl 2-phenyl-2-propionyloxyacetate, amyl 2-phenyl-2-propionyloxyacetate, octyl 2-phenyl-2-propionyloxyacetate, ethyl 2-phenyl-2-phenylacetyloxyacetate, propyl 2-phenyl-2-phenylacetyloxyacetate, butyl 2-phenyl-2-phenylacetyloxyacetate, amyl 2-phenyl-2-phenylacetyloxyacetate, methyl 2-phenyl-2-furoyloxyacetate, ethyl 2-propionyloxyacetate, ethyl 2-phenyl-2-propionyloxyacetate, propyl 2-phenyl-2-, Propyl 2-phenyl-2-furoyloxyacetate, butyl 2-phenyl-2-furoyloxyacetate, pentyl 2-phenyl-2-furoyloxyacetate, ethyl 2-phenyl-2-pyranoyloxyacetate, propyl 2-phenyl-2-pyranoyloxyacetate, butyl 2-phenyl-2-pyranoyloxyacetate, methyl 2-benzoyloxybutyrate, ethyl 2-benzoyloxybutyrate, butyl 2-benzoyloxybutyrate, pentyl 2-benzoyloxybutyrate, benzyl 2-benzoyloxybutyrate, cyclohexyl 2-benzoyloxybutyrate, phenol 2-benzoyloxybutyrate, naphthyl 2-benzoyloxybutyrate, Ethyl 3-benzoyloxybutyrate, pentyl 3-benzoyloxybutyrate, butyl 3-benzoyloxybutyrate, benzyl 3-benzoyloxybutyrate, cyclohexyl 3-benzoyloxybutyrate, phenol 3-benzoyloxybutyrate, naphthol 3-benzoyloxybutyrate, ethyl 2-benzoyloxypentanoate, butyl 2-benzoyloxypentanoate, pentyl 2-benzoyloxypentanoate, benzyl 2-benzoyloxypentanoate, cyclohexyl 2-benzoyloxypentanoate, phenol 2-benzoyloxypentanoate, naphthol 2-benzoyloxypentanoate, ethyl 3-benzoyloxypentanoate, butyl 3-benzoyloxypentanoate, pentyl 3-benzoyloxypentanoate, benzyl 3-benzoyloxypentanoate, Cyclohexanol 3-benzoyloxypentanoate, phenol 3-benzoyloxypentanoate, naphthol 3-benzoyloxypentanoate, ethyl 4-benzoyloxypentanoate, butyl 4-benzoyloxypentanoate, pentyl 4-benzoyloxypentanoate, benzyl 4-benzoyloxypentanoate, cyclohexanol 4-benzoyloxypentanoate, phenol 4-benzoyloxypentanoate, naphthol 4-benzoyloxypentanoate, ethyl 1-benzoyloxycyclohexoate, propyl 1-benzoyloxycyclohexanoate, butyl 1-benzoyloxycyclohexanoate, pentyl 1-benzoyloxycyclohexanoate, butyl 1- (2, 4-dimethylbenzoyloxy) cyclohexanoate, butyl 1- (2,4, 6-trimethylbenzoyloxy) cyclohexanoate, 1- (4-Propylbenzoyloxy) butyl cyclohexanecarboxylate, 1- (4-butylbenzoyloxy) butyl cyclohexanecarboxylate, ethyl 2-benzoyloxycyclohexanecarboxylate, propyl 2-benzoyloxycyclohexanecarboxylate, butyl 2-benzoyloxycyclohexanecarboxylate, pentyl 2-benzoyloxycyclohexanecarboxylate, butyl 2- (2,4, 6-trimethylbenzoyloxy) cyclohexanecarboxylate, butyl 2- (4-propylbenzoyloxy) cyclohexanecarboxylate, ethyl 3-benzoyloxycyclohexanecarboxylate, propyl 3-benzoyloxycyclohexanecarboxylate, butyl 3-benzoyloxycyclohexanecarboxylate, pentyl 3-benzoyloxycyclohexanecarboxylate, ethyl 4-benzoyloxycyclohexanecarboxylate, propyl 4-benzoyloxycyclohexanecarboxylate, pentyl 2-benzoyloxybenzoate, hexyl benzoate, pentyl 2-benzoyloxybenzoate, pentyl, 4-benzoyloxycyclohexanecarboxylic acid butyl ester, 4-benzoyloxycyclohexanecarboxylic acid pentyl ester, 1-benzoyloxycyclohexanedienoic acid ethyl ester, 1-benzoyloxycyclohexanedienoic acid propyl ester, 1-benzoyloxycyclohexanedienoic acid butyl ester, 2-benzoyloxycyclohexanedienoic acid ethyl ester, 2-benzoyloxycyclohexanedienoic acid butyl ester, 1-benzoyloxycyclopentanoic acid ethyl ester, 1-benzoyloxycyclopentanoic acid propyl ester, 1-benzoyloxycyclopentanoic acid butyl ester, 1-benzoyloxycyclopentanoic acid pentyl ester, 2-benzoyloxycyclopentanoic acid ethyl ester, 2-benzoyloxycyclopentanoic acid propyl ester, 2-benzoyloxycyclopentanoic acid butyl ester, 2-benzoyloxycyclopentanoic acid pentyl ester, 1-benzoyloxycyclopentadienoic acid ethyl ester, 1-benzoyloxy cyclopentadienylcarboxylic acid butyl ester, 2-benzoyloxy cyclopentadienylcarboxylic acid pentyl ester, benzoyloxy methylaminoacetic acid ethyl ester, benzoyloxy methylaminoacetic acid butyl ester, benzoyloxy methylaminoacetic acid phenol ester, benzoyloxy methylaminoacetic acid naphthol ester, 2-benzoyloxy ethylaminoacetic acid ethyl ester, 2-benzoyloxy ethylaminoacetic acid butyl ester, 2-benzoyloxy ethylaminoacetic acid phenol ester, 2-benzoyloxy ethylaminoacetic acid naphthol ester, 2-benzoyloxy propylaminoacetic acid ethyl ester, 2-benzoyloxy propylaminoacetic acid butyl ester, 2-benzoyloxy propylaminoacetic acid phenol ester, 2-benzoyloxy propylaminoacetic acid naphthol ester, 3-benzoyloxy propylaminoacetic acid ethyl ester, One or more of 3-benzoyloxy propylamino butyl acetate, 3-benzoyloxy propylamino phenol acetate and 3-benzoyloxy propylamino naphthol acetate.
Among the above compounds, the fact that a normal or abnormal compound is not indicated means that the normal or abnormal group is included.
According to a preferred embodiment of the present invention, the compound of formula I is added as a precipitation aid during the preparation of the catalyst component.
According to some embodiments of the invention, the catalyst component is prepared by a process comprising the steps of:
1) dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a homogeneous solution;
2) mixing the uniform solution with a titanium compound to obtain a mixture;
3) adding an internal electron donor compound into the mixture obtained in the step 2), and then treating the mixture with a titanium compound or an inert diluent to obtain the catalyst component;
wherein, the compound shown in the structural general formula I is added in the step 1) and/or the step 2).
According to a preferred embodiment of the present invention, the compound of formula I is used in an amount of 0.01 to 6 moles, preferably 0.01 to 2 moles, more preferably 0.02 to 1 mole per mole of magnesium.
According to a preferred embodiment of the present invention, the internal electron donor compound is used in an amount of 0.001 to 15 moles, preferably 0.005 to 10 moles, more preferably 0.05 to 5 moles, per mole of magnesium.
According to some embodiments of the present invention, the magnesium compound comprises at least one of magnesium dihalide, a hydrate of magnesium dihalide, a water or alcohol complex of magnesium dihalide, alkyl magnesium halide, alkoxy magnesium and alkoxy magnesium halide, the halogen being selected from at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine. In some specific embodiments, the magnesium compound preferably includes at least one of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, ethoxymagnesium, and ethoxymagnesium chloride.
According to a preferred embodiment of the invention, the organic epoxide comprises C2-C10At least one of an oxide of an aliphatic olefin, a diene, a halogenated aliphatic olefin, a glycidyl ether and an internal ether. In some specific embodiments, the organic epoxide comprises at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, and diglycidyl ether, preferably epichlorohydrin.
According to one embodiment of the invention, the organophosphorus compound comprises a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid. In some specific embodiments, the organophosphorus compound comprises at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, tributyl phosphite, and triphenyl phosphite, preferably trimethyl orthophosphate.
According to some preferred embodiments of the present invention, the inert diluent is not particularly limited, as long as it does not react with the other components; inert diluents suitable for use in the present invention include at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
According to a preferred embodiment of the invention, the titanium compound comprises a compound of formula Ti (OR)4)aM4-aAnd/or derivatives thereof, wherein R4Is C1-C20Is preferably C1-C10Alkyl groups of (a); m is halogen, preferably chlorine, bromine or iodine; a is 1 to 4. In some specific embodiments, the titanium compound preferably comprises at least one of a titanium tetrahalide, an alkoxy titanium trihalide, a dialkoxy titanium trihalide, and a trialkoxy titanium halide; more excellentOne or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxide, titanium tetrabutoxide, titanium monochlorotriethoxyide, titanium dichlorodiethoxylate and titanium trichloroethoxylate are selected. According to one embodiment of the invention, the titanium compound is preferably titanium tetrachloride.
According to some preferred embodiments of the present invention, the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines, preferably from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds, and more preferably comprises one or more of benzoate compounds, phthalate compounds, malonate compounds, succinate compounds and glutarate compounds. In some specific embodiments, the second internal electron donor compound comprises di-n-butyl phthalate, diisobutyl phthalate, 2, 4-diphenylmethylcarboxylpentane, 2, 4-di (methylbenzocarboxyl) pentane, 2, 4-di (ethylbenzylcarboxyl) pentane, 2, 4-di (n-propylbenzylcarboxyl) pentane, 2, 4-di (isopropylbenzylcarboxyl) pentane, 2, 4-di (n-butylbenzylcarboxyl) pentane, 2, 4-di (isobutylbenzylcarboxyl) pentane, 2, 4-di (tert-butylbenzylcarboxyl) pentane, 9-dimethoxymethylfluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxyfluorene, 1, 8-diphenylcarboxynaphthol, 3-tert-butyl-1, one or more of 2-dibenzyl carboxyl phenol and 2, 3-diisopropyl diethyl succinate.
According to a preferred embodiment of the present invention, the organic epoxy compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 5 moles, per mole of magnesium; the amount of the organic phosphorus compound is 0.1 to 3 mol, preferably 0.2 to 2 mol; the titanium compound is used in an amount of 0.5 to 50 mol, preferably 1 to 40 mol.
According to an embodiment of the present invention, the precipitation-aiding agent further comprises a second precipitation-aiding agent, i.e., the compound represented by the general formula I is used in combination with the second precipitation-aiding agent.
According to a preferred embodiment of the invention, the second precipitation aid comprises phthalic anhydride. In some specific embodiments, the second precipitation aid is used in an amount of 0 to 0.5 mol, preferably 0.01 to 0.1mol, per mol of magnesium.
According to a preferred embodiment of the present invention, said step 1) is preferably carried out by dissolving the magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent, and maintaining at-30 to 150 ℃ for 0.5 to 10 hours until the magnesium compound is completely dissolved to form a homogeneous solution.
According to a preferred embodiment of the present invention, the mixing temperature of the titanium compound in the step (2) and the homogeneous solution obtained in the step (1) is-40 ℃ to 60 ℃, preferably-30 ℃ to 10 ℃.
According to a preferred embodiment of the present invention, in the step 3), the temperature of the mixture in the step 2) is preferably raised to 50 to 150 ℃, then the internal electron donor compound is added to react at a temperature of 20 to 120 ℃ for 0.5 to 6 hours, and solid particles are separated by filtration; and treating the solid particles with a titanium compound and/or an inert diluent, and drying to obtain the catalyst component.
According to some embodiments of the present invention, the compound of the general structural formula I may be added in step 1) and/or 2), preferably before the homogeneous solution of step 2) is mixed with the titanium compound.
The catalyst component for olefin polymerization obtained according to the present invention can be used for preparing an olefin polymerization catalyst system.
According to another aspect of the present invention, there is provided a catalyst system for the polymerization of olefins comprising the reaction product of:
a. the above catalyst component for olefin polymerization;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
According to a preferred embodiment of the invention, the molar ratio of component b to component a, calculated as aluminium/titanium, is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500):1, preferably (0.01-100): 1.
According to some embodiments of the present invention, the alkylaluminum compound is not particularly limited, and an alkylaluminum compound that can be used in a ziegler-natta type catalyst, which is commonly used in the art, may be selected.
Suitable alkylaluminum compounds for use in the present invention are preferably of the formula AlR "n'X'3-n'The alkyl aluminum compound is shown in the specification, wherein R' is selected from hydrogen and C1-C20Alkyl and C6-C20Aryl of (a); x 'is halogen, and n' is an integer of 1 to 3.
In some specific embodiments, as a specific example of the alkylaluminum compound, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride can be selected.
According to a particular embodiment of the invention, said component c being optionally an organosilicon compound means that the catalyst system for the polymerization of olefins may or may not contain organosilicon compounds. According to a preferred embodiment of the present invention, the external electron donor compound is not particularly limited, and an external electron donor compound that can be used in a ziegler-natta type catalyst, which is generally used in the art, may be selected.
The external electron donor compounds suitable for use in the present invention are preferably of the formula R'm'Si(OR””)4-m'The organic silicon compound is shown in the specification, wherein R' is selected from hydrogen, halogen and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20A haloalkyl group of (a); m' is an integer of 1 to 3.
In some specific examples, as specific examples of the organosilicon compound, at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, etc., preferably at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane and diphenyldimethoxysilane.
According to another aspect of the present invention there is provided the use of a catalyst system as described above in the polymerisation of olefins.
According to another aspect of the present invention, there is provided an olefin polymerization process comprising carrying out an olefin polymerization reaction using one or more olefins in the presence of the above catalyst component or the above catalyst system.
According to a preferred embodiment of the invention, at least one of said olefins is of formula CH2Olefins represented by ═ CHR, where R is hydrogen or C1-C7Alkyl group of (1).
The olefin polymerization process of the invention can be used for the polymerization of olefins of the general formula CH2Homopolymerization of olefins represented by ═ CHR, can also be used for the preparation of the compound of formula CH2Olefins represented by ═ CHR are copolymerized with various olefins. R is hydrogen or C1-C7Alkyl group of (1). Said general formula is CH2Specific examples of olefins represented by ═ CHR include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
According to the olefin polymerization process of the present invention, the olefin polymerization conditions are not particularly limited, and the conditions conventional in the art may be selected; the amount of the catalyst to be used is not particularly limited, and the amount of each catalyst to be used in the olefin polymerization of the prior art can be selected.
According to the invention, a compound with a special structure is introduced in the preparation process of the catalyst component as a precipitation aid, so that the use of a phthalic anhydride compound is omitted or reduced, the obtained catalyst component has high catalytic activity and slow activity decay, and the obtained polymer has high melt index, wide molecular weight distribution and high isotacticity. The catalyst provided by the invention has the advantages of excellent comprehensive catalytic activity performance, higher activity, adjustable orientation capability, good hydrogen regulation sensitivity, adjustable isotactic index of the prepared polymer and wider molecular weight distribution.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the following examples, the evaluation and testing methods involved are as follows:
1. polymer isotacticity (%): determination by heptane extraction: a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours and the residue was dried to constant weight, the ratio of the weight of the polymer (g) to 2g being the isotacticity.
2. Polymer melt index (g/10 min): measured according to ASTM D1238-99.
3. Polymer molecular weight distribution (Mw/Mn): measuring with gel permeation chromatograph manufactured by Waters company, and using 1,2, 4-trichlorobenzene and styrene as standard sample as solvent; nuclear magnetic analysis of the Compounds the 1H-NMR of the polymer was determined with a Bruke dmx 300MHz NMR spectrometer, solvent: deuterated chloroform with TMS as internal standard and temperature 275K. Synthesis of Compound (I)
EXAMPLE 1 Synthesis of Compound ethyl 2-phenyl-2-benzoyloxyacetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.02 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.40 g of benzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.04 g of a product (yield 72%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):8.06～8.04(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.22～4.20(2H,q,CH2),1.30～1.27(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 284.
EXAMPLE 2 Synthesis of the Compound Ethyl 2-phenyl-2- (4-n-butylbenzoyloxy) acetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of tetrahydrofuran and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.96 g of 4-n-butylbenzoyl chloride dissolved in 40ml of tetrahydrofuran solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 12 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.27 g of a product (yield: 67%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.94～7.92(2H,m,ArH),7.35～7.33(5H,m,ArH),7.23～7.21(2H,m,ArH),6.10～6.08(1H,m,CH),4.22～4.20(2H,q,CH2),2.55～2.53(2H,m,CH2),1.66～1.64((2H,m,CH2),1.38～1.36(2H,m,CH2),1.30～1.28(3H,m,CH3),1.25～1.22(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 3 Synthesis of ethyl 2-phenyl-2- (4-isobutylbenzoyloxy) acetate, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. 1.96 g of 4-isobutylbenzoyl chloride dissolved in 40ml of toluene solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then heated under reflux for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.15 g of a product (yield 63%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.95～7.93(2H,m,ArH),7.39～7.36((5H,m,ArH),7.24～7.21(2H,m,ArH),6.10～6.08(1H,m,CH),4.20～4.18(2H,q,CH2),2.53～2.51(2H,m,CH2),2.25～2.22(1H,m,CH3),1.30～1.27(3H,t,CH3),1.25～1.22(6H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 4 Synthesis of ethyl 2-phenyl-2- (4-tert-butylbenzoyloxy) acetate, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.96 g of 4-tert-butylbenzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.97～7.95(2H,m,ArH),7.43～7.40(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.20～4.18(2H,q,CH2),1.36～1.32(9H,m,CH3),1.28～1.25(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 340.
EXAMPLE 5 Synthesis of Compound 2-phenyl-2-benzoyloxyacetic acid cyclohexyl ester
In a 250 ml three-necked flask, after nitrogen purging, 2.34 g of cyclohexyl mandelate, 100 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.40 g of benzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to 85 ℃ for reflux reaction for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted three times with anhydrous ether. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.20 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):8.07～8.05(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.36(5H,m,ArH),6.08～6.06(1H,s,CH),3.93～3.91(1H,m,CH),1.80～1.78(2H,m,CH2),1.56～1.53(4H,m,CH2),1.49～1.47(2H,m,CH2),1.43～1.41(2H,m,CH2) (ii) a Mass Spectrometry, FD-mass spectrometry: 338.
EXAMPLE 6 Synthesis of the Compound Ethyl 2-phenyl-2- (3-methylbutanoyloxy) acetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of tetrahydrofuran and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropping 1.20 g of 3-methylbutyryl chloride dissolved in 40ml of tetrahydrofuran solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating and refluxing for reaction for 14 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 1.58 g of a product (yield 60%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.38～7.35(5H,m,ArH),6.07～6.05(1H,s,CH),4.21～4.19(2H,q,CH),2.40～2.38(1H,m,CH),2.16～2.14(2H,m,CH2),1.30～1.28(3H,t,CH3),0.94～0.92(6H,d,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 264.
EXAMPLE 7 Synthesis of the Compound Ethyl 2-phenyl-2- (4-n-propylbenzoyloxy) acetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. 1.82 g of 4-n-propylbenzoyl chloride dissolved in 40ml of toluene solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.99～7.97(2H,m,ArH),7.38～7.35(5H,m,ArH),6.95～7.93(2H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),2.65～2.63(2H,q,CH2),1.65～1.62(2H,m,CH2),1.28～1.25(3H,t,CH3),0.94～0.92(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry: 326.
EXAMPLE 8 Synthesis of ethyl 2-phenyl-2- (4-isopropylbenzoyloxy) acetate, Compound
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.82 g of 4-isopropylbenzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.21 g of a product (yield 65%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.96～7.95(2H,m,ArH),7.42～7.40(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),2.88～2.86(1H,m,CH),1.29～1.26(3H,t,CH3),1.23～1.21(3H,m,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry:326。
EXAMPLE 9 Synthesis of the Compound ethyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.74 g of 4-chlorobenzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.13 g of a product (yield: 67%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.89～7.87(2H,m,ArH),7.62～7.60(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.21～4.19(2H,q,CH2),1.27～1.25(3H,t,CH3) (ii) a Mass Spectrometry, FD-massspectrometry: 318.
EXAMPLE 10 Synthesis of the Compound ethyl 2-phenyl-2- (3-chlorobenzoyloxy) acetate
In a 250 ml three-necked flask, after nitrogen purging, 1.80 g of ethyl mandelate, 80 ml of toluene and 1.05 g of triethylamine were added and stirred at room temperature. Slowly dropwise adding 1.74 g of 3-chlorobenzoyl chloride dissolved in 40ml of toluene solution at low temperature, stirring at room temperature for reaction for 4 hours, and then heating to reflux for reaction for 12 hours. The reaction solution was cooled to room temperature, and low boiling point substances were removed by evaporation under reduced pressure. Extracted three times with anhydrous ether, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow viscous liquid, which was dried under vacuum to give 2.10 g of a product (yield 66%).
The product is detected, and the test method and the result are as follows:1H-NMR(δ,ppm,TMS,CDCl3):7.98～7.97(1H,m,ArH),7.93～7.91(1H,m,ArH),7.70～7.68(1H,m,ArH),7.50～7.48(1H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),4.22～4.20(2H,q,CH2),1.29～1.27(3H,t,CH3) (ii) a Mass Spectrometry, FD-mass spectrometry 318.
Preparation of component in catalyst and propylene polymerization
Example 11
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 97ml of toluene, 4ml of epichlorohydrin and 12.5ml of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, and the temperature is raised to 50 ℃ under stirring and maintained for 2.5 hours. After the solid was completely dissolved, the compound ethyl 2-phenyl-2-benzoyloxyacetate (8mmol) was added and the reaction was continued for 1 hour, the solution was cooled to below-25 ℃ and TiCl was added dropwise over 1 hour4Slowly heating to 80 ℃, adding 6mmol of electron donor compound 2, 4-dibenzyl carboxyl pentane, and maintaining at 80 ℃ for 1 hour. After filtration, 70ml of toluene was added, and the mixture was washed twice. 60ml of toluene and TiCl were added440ml, heated to 110 ℃ and maintained for 2 hours. After filtration, 60ml of toluene was added and the mixture was washed at boiling temperature for 5 minutes. 60ml of hexane were added and the mixture was washed twice at boiling temperature for 5 minutes each time. Then 60ml of hexane was added, and the mixture was washed twice at normal temperature for 5 minutes each time and dried to obtain a solid catalyst component.
(2) Polymerization of propylene
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of methylcyclohexyldimethoxysilane (CHMMS) was added in an amount of 0.1mol, 10mg of the solid component prepared in the above example and 1.2NL of hydrogen gas were added, 2.3L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, and then the temperature was lowered and the pressure was released to obtain PP powder, and the results are shown in Table 1.
Example 12
In the same manner as in example 11, only ethyl 2-phenyl-2-benzoyloxy acetate, which is the compound, was replaced with ethyl 2-phenyl-2- (4-n-butylbenzoyloxy) acetate.
Example 13
In the same manner as in example 11, only ethyl 2-phenyl-2-benzoyloxyacetate, which was a compound thereof, was replaced with ethyl 2-phenyl-2- (4-isobutylbenzoyloxy) acetate.
Example 14
In the same manner as in example 11, only ethyl 2-phenyl-2-benzoyloxyacetate, which was the compound, was replaced with ethyl 2-phenyl-2- (4-n-propylbenzoyloxy) acetate.
Example 15
In the same manner as in example 11, only the compound ethyl 2-phenyl-2-benzoyloxy acetate was replaced with ethyl 2-phenyl-2- (4-isopropylbenzoyloxy) acetate.
Example 16
In the same manner as in example 11, only ethyl 2-phenyl-2-benzoyloxyacetate, which was a compound thereof, was replaced with cyclohexyl 2-phenyl-2-benzoyloxyacetate.
Example 17
In example 11, only the compound 2, 4-diphenylmethylcarboxypentane was replaced by DNBP (di-n-butyl phthalate).
Example 18
In example 11, only the compound 2, 4-diphenylmethylcarboxypentane was replaced by DIBP (diisobutylphthalate).
Example 19
In example 11, only the compound 2, 4-dibenzylcarboxypentane was replaced with 2, 4-bis (n-propylbenzoyloxy) pentane.
Example 20
In the same manner as in example 11, only the compound 2, 4-diphenylcarboxypentane therein was replaced by 9, 9-dimethoxymethylfluorene.
Example 21
In the same manner as in example 11, only the compound 2, 4-dibenzylcarboxypentane therein was replaced by 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
Example 22
As in example 11, only ethyl 2-phenyl-2-benzoyloxyacetate (8mmol) was changed to ethyl 2-phenyl-2-benzoyloxyacetate (4mmol) and phthalic anhydride (0.7 g).
Example 23
The same as example 17 except that the amount of hydrogenation in example was changed to 7.2NL, the results are shown in Table 1.
Comparative example 1
In the same manner as in example 17, only ethyl 2-phenyl-2-benzoyloxyacetate (8mmol) was replaced with phthalic anhydride (1.4 g).
Comparative example 2
The same as in comparative example 1, except that the amount of hydrogen added at the time of polymerization was changed to 7.2 NL. The polymerization data are shown in Table 1.
TABLE 1
Figure BDA0001420308180000181
As can be seen from Table 1, under the same reaction conditions, compared with the method of using phthalic anhydride as the separation aid, the catalyst component prepared by using the separation aid and the catalyst prepared by using the catalyst have isotacticity and melt index which reach or even exceed the level of the prior art, and the catalyst has higher catalytic activity and wider molecular weight distribution of the obtained polymer. Under the condition of high hydrogen, the catalyst component and the catalyst prepared by the precipitation aid have better catalytic activity, and the obtained polymer has higher melt index, which shows that the catalyst has better hydrogen regulation sensitivity.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.

Claims (18)

1. A catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein a compound shown as a general formula I is added in the preparation process of the catalyst component;
Figure FDA0002876422890000011
wherein A is- (CR)1R2)n，n＝1～5；R1～R2Same or different, selected from hydrogen, substituted or unsubstituted C1～C30And substituted or unsubstituted C1～C30Alkoxy of R1And R2Can be linked to form a ring; r and R' are the same or different and are selected from substituted or unsubstituted C1～C30A hydrocarbon group of (1).
2. The catalyst component according to claim 1 in which R is1～R2Same or different, selected from hydrogen, substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl, substituted or unsubstituted C7～C20And substituted or unsubstituted C1～C20Alkoxy group of (a); r1And R2Optionally linked to substituted or unsubstituted C3～C10Cycloalkyl, substituted or unsubstituted C3～C10Or is substituted or unsubstituted C2～C10The heterocyclic group of (1).
3. The catalyst component according to claim 2 in which R is1～R2Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylPhenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, and propoxy; r1And R2Optionally linked to one or more of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl, and cyclopentadienyl.
4. The catalyst component according to claim 1 in which R and R', equal to or different from each other, are chosen from substituted or unsubstituted C1～C20A hydrocarbon group of (1).
5. The catalyst component according to claim 4 in which R and R' are chosen from substituted or unsubstituted C1～C20Linear alkyl, substituted or unsubstituted C of3～C20Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C20Linear alkenyl of (A), substituted or unsubstituted C3～C20Substituted or unsubstituted C6～C20Aryl and substituted or unsubstituted C7～C20Or an alkylaryl or arylalkyl group.
6. The catalyst component according to claim 5 wherein R and R' are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, and biphenyl.
7. The catalyst component according to claim 1, wherein the compound of formula I is selected from the group consisting of ethyl 2-phenyl-2-benzoyloxyacetate, propyl 2-phenyl-2-benzoyloxyacetate, butyl 2-phenyl-2-benzoyloxyacetate, pentyl 2-phenyl-2-benzoyloxyacetate, ethyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, butyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-methylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, and, Propyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, pentyl 2-phenyl-2- (2-methylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, butyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-ethylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, Butyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-propylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, propyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, pentyl 2-phenyl-2- (2-propylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, propyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, isopropyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, Butyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, pentyl 2-phenyl-2- (4-butylbenzoyloxy) acetate, ethyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, propyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, butyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, pentyl 2-phenyl-2- (2-butylbenzoyloxy) acetate, ethyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, propyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, butyl 2-phenyl-2- (4-chlorobenzoyloxy) acetate, 2-phenyl-2- (3-chlorobenzoyloxy) acetic acid pentyl ester, 2-phenyl-2- (3-chlorobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (3-chlorobenzoyloxy) acetic acid propyl ester, 2-phenyl-2- (2-chlorobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (2-chlorobenzoyloxy) acetic acid propyl ester, 2-phenyl-2- (2-chlorobenzoyloxy) acetic acid butyl ester, 2-phenyl-2- (2-chlorobenzoyloxy) acetic acid pentyl ester, 2-phenyl-2- (3-bromobenzoyloxy) acetic acid ethyl ester, 2-phenyl-2- (3-bromobenzoyloxy) acetic acid propyl ester, Ethyl 2-phenyl-2- (2-bromobenzoyloxy) acetate, propyl 2-phenyl-2- (2-bromobenzoyloxy) acetate, butyl 2-phenyl-2- (2-bromobenzoyloxy) acetate, pentyl 2-phenyl-2- (2-bromobenzoyloxy) acetate, ethyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, propyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, butyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, pentyl 2-phenyl-2- (4-bromobenzoyloxy) acetate, ethyl 2-phenyl-2- (4-cyclohexylformyloxy) acetate, ethyl 2-phenyl-2-benzoyloxy acetate, ethyl 2-phenyl-2-cyclohexylformyloxy acetate, ethyl 2-phenyl-2-benzoyloxy acetate, methyl ethyl 2-phenyl-2-benzoyloxy acetate, 2-phenyl-2-cyclohexylformyloxyacetic acid propyl ester, 2-phenyl-2-cyclohexylformyloxyacetic acid butyl ester, 2-phenyl-2-cyclohexylformyloxyacetic acid pentyl ester, 2-phenyl-2-cyclopentylcarboxoyloxyacetic acid methyl ester, 2-phenyl-2-cyclopentylcarboxoyloxyacetic acid ethyl ester, 2-phenyl-2-cyclopentylcarboxoyloxyacetic acid propyl ester, 2-phenyl-2-cyclopentylcarboxoyloxyacetic acid butyl ester, 2-phenyl-2-cyclopentyloxyacetic acid pentyl ester, 2-phenyl-2-propionyloxyacetic acid ethyl ester, 2-phenyl-2-propionyloxyacetic acid propyl ester, 2-phenyl-2-propionyloxyacetic acid butyl ester, Amyl 2-phenyl-2-propionyloxyacetate, octyl 2-phenyl-2-propionyloxyacetate, ethyl 2-phenyl-2-phenylacetyloxyacetate, propyl 2-phenyl-2-phenylacetyloxyacetate, butyl 2-phenyl-2-phenylacetyloxyacetate, amyl 2-phenyl-2-phenylacetyloxyacetate, methyl 2-benzoyloxybutyrate, ethyl 2-benzoyloxybutyrate, butyl 2-benzoyloxybutyrate, amyl 2-benzoyloxybutyrate, benzyl 2-benzoyloxybutyrate, cyclohexyl 2-benzoyloxybutyrate, phenol 2-benzoyloxybutyrate, naphthyl 2-benzoyloxybutyrate, or the like, Ethyl 3-benzoyloxybutyrate, pentyl 3-benzoyloxybutyrate, butyl 3-benzoyloxybutyrate, benzyl 3-benzoyloxybutyrate, cyclohexyl 3-benzoyloxybutyrate, phenol 3-benzoyloxybutyrate, naphthol 3-benzoyloxybutyrate, ethyl 2-benzoyloxypentanoate, butyl 2-benzoyloxypentanoate, pentyl 2-benzoyloxypentanoate, benzyl 2-benzoyloxypentanoate, cyclohexyl 2-benzoyloxypentanoate, phenol 2-benzoyloxypentanoate, naphthol 2-benzoyloxypentanoate, ethyl 3-benzoyloxypentanoate, butyl 3-benzoyloxypentanoate, pentyl 3-benzoyloxypentanoate, benzyl 3-benzoyloxypentanoate, Cyclohexanol 3-benzoyloxypentanoate, phenol 3-benzoyloxypentanoate, naphthol 3-benzoyloxypentanoate, ethyl 4-benzoyloxypentanoate, butyl 4-benzoyloxypentanoate, pentyl 4-benzoyloxypentanoate, benzyl 4-benzoyloxypentanoate, cyclohexanol 4-benzoyloxypentanoate, phenol 4-benzoyloxypentanoate, naphthol 4-benzoyloxypentanoate, ethyl 1-benzoyloxycyclohexoate, propyl 1-benzoyloxycyclohexanoate, butyl 1-benzoyloxycyclohexanoate, pentyl 1-benzoyloxycyclohexanoate, butyl 1- (2, 4-dimethylbenzoyloxy) cyclohexanoate, butyl 1- (2,4, 6-trimethylbenzoyloxy) cyclohexanoate, 1- (4-Propylbenzoyloxy) butyl cyclohexanecarboxylate, 1- (4-butylbenzoyloxy) butyl cyclohexanecarboxylate, ethyl 2-benzoyloxycyclohexanecarboxylate, propyl 2-benzoyloxycyclohexanecarboxylate, butyl 2-benzoyloxycyclohexanecarboxylate, pentyl 2-benzoyloxycyclohexanecarboxylate, butyl 2- (2,4, 6-trimethylbenzoyloxy) cyclohexanecarboxylate, butyl 2- (4-propylbenzoyloxy) cyclohexanecarboxylate, ethyl 3-benzoyloxycyclohexanecarboxylate, propyl 3-benzoyloxycyclohexanecarboxylate, butyl 3-benzoyloxycyclohexanecarboxylate, pentyl 3-benzoyloxycyclohexanecarboxylate, ethyl 4-benzoyloxycyclohexanecarboxylate, propyl 4-benzoyloxycyclohexanecarboxylate, pentyl 2-benzoyloxybenzoate, hexyl benzoate, pentyl 2-benzoyloxybenzoate, pentyl, 4-benzoyloxycyclohexanecarboxylic acid butyl ester, 4-benzoyloxycyclohexanecarboxylic acid pentyl ester, 1-benzoyloxycyclohexanedienoic acid ethyl ester, 1-benzoyloxycyclohexanedienoic acid propyl ester, 1-benzoyloxycyclohexanedienoic acid butyl ester, 2-benzoyloxycyclohexanedienoic acid ethyl ester, 2-benzoyloxycyclohexanedienoic acid butyl ester, 1-benzoyloxycyclopentanoic acid ethyl ester, 1-benzoyloxycyclopentanoic acid propyl ester, 1-benzoyloxycyclopentanoic acid butyl ester, 1-benzoyloxycyclopentanoic acid pentyl ester, 2-benzoyloxycyclopentanoic acid ethyl ester, 2-benzoyloxycyclopentanoic acid propyl ester, 2-benzoyloxycyclopentanoic acid butyl ester, 2-benzoyloxycyclopentanoic acid pentyl ester, 1-benzoyloxycyclopentadienoic acid ethyl ester, One or more of 1-benzoyloxy cyclopentadien carboxylic acid butyl ester, 2-benzoyloxy cyclopentadien carboxylic acid butyl ester and 2-benzoyloxy cyclopentadien carboxylic acid amyl ester.
8. The catalyst component according to any of claims 1 to 7, characterized in that it is prepared by a process comprising the following steps:
1) dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a homogeneous solution;
2) mixing the uniform solution with a titanium compound to obtain a mixture;
3) adding an internal electron donor compound into the mixture obtained in the step 2), and then treating the mixture with a titanium compound or an inert diluent to obtain the catalyst component;
wherein, the compound shown in the structural general formula I is added in the step 1) and/or the step 2).
9. The catalyst component according to claim 8, wherein the magnesium compound comprises at least one of a magnesium dihalide, a hydrate of a magnesium dihalide, a water or alcohol complex of a magnesium dihalide, an alkyl magnesium halide, an alkoxy magnesium and an alkoxy magnesium halide, and the halogen is selected from at least one of fluorine, chlorine, bromine and iodine.
10. The catalyst component according to claim 9, characterized in that the halogen is chlorine and/or bromine.
11. The catalyst component according to any of claims 1 to 7 wherein the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines.
12. The catalyst component according to claim 11, wherein the internal electron donor compound is selected from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds.
13. The catalyst component according to any of claims 1 to 7 in which the compound of formula I is used in an amount of 0.01 to 6 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.001-15 mol.
14. The catalyst component according to any of claims 1 to 7 in which the compound of formula I is used in an amount of 0.01 to 2 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.005 to 10 mol.
15. The catalyst component according to any of claims 1 to 7 in which the compound of formula I is used in an amount of 0.02 to 1 mole per mole of magnesium; and/or the amount of the internal electron donor compound is 0.05-5 mol.
16. A catalyst system for olefin polymerization comprising the reaction product of:
a. the catalyst component of any one of claims 1 to 15;
b. an organoaluminum compound;
c. optionally, an organosilicon compound.
17. The catalyst system of claim 16 wherein the molar ratio of component b to component a is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500): 1.
18. A process for the polymerization of olefins comprising the polymerization of olefins using one or more olefins in the presence of a catalyst component as claimed in any of claims 1 to 15 or a catalyst system as claimed in claim 16 or 17.
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CN1436796A (en) * 2002-02-07 2003-08-20 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
CN102372797A (en) * 2010-08-12 2012-03-14 中国石油化工股份有限公司 Catalyst components for olefin polymerization and catalyst thereof
CN102712704A (en) * 2009-12-02 2012-10-03 陶氏环球技术有限责任公司 Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture

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CN1436796A (en) * 2002-02-07 2003-08-20 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
CN102712704A (en) * 2009-12-02 2012-10-03 陶氏环球技术有限责任公司 Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture
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