CN110950831B - Cyclic compound and preparation method and application thereof - Google Patents

Cyclic compound and preparation method and application thereof Download PDF

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CN110950831B
CN110950831B CN201811123228.4A CN201811123228A CN110950831B CN 110950831 B CN110950831 B CN 110950831B CN 201811123228 A CN201811123228 A CN 201811123228A CN 110950831 B CN110950831 B CN 110950831B
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sodium
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CN110950831A (en
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王军
高明智
马晶
马吉星
何世雄
刘文蕊
刘海涛
胡建军
李昌秀
蔡晓霞
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a cyclic compound shown in a formula I, and a preparation method and application thereof. The cyclic compound is used as an internal electron donor compound, and an olefin polymerization catalyst with excellent comprehensive performance can be obtained. Particularly when the catalyst is used for propylene polymerization, the hydrogen regulation sensitivity of the catalyst is good, the isotactic index of the obtained polymer is adjustable, and the molecular weight distribution of the obtained polypropylene resin is wide.

Description

Cyclic compound and preparation method and application thereof
Technical Field
The invention relates to a cyclic compound, a preparation method and application thereof.
Background
Olefin polymerization catalystThree broad categories, conventional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts, can be distinguished. For traditional Ziegler-Natta catalysts, polyolefin catalysts are continually updated as electron donor compounds in the catalysts develop. Catalyst development was carried out from the first generation TiCl 3 AlCl 3 /AlEt 2 Cl system and TiCl of the second generation 3 /AlEt 2 Cl system, tiCl with third generation magnesium chloride as carrier, monoester or aromatic dibasic acid ester as internal electron donor and silane as external electron donor 4 ·ED·MgCl 2 /AlR 3 The ED system, the catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved. In the prior art, titanium catalyst systems for propylene polymerization are mostly based on magnesium, titanium, halogen and electron donors, wherein the electron donor compound is one of the indispensable components in the catalyst component. Currently, various electron donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketone 12/. Times.mono-or polyether, alcohols, amines, etc. and derivatives thereof, among which aromatic dicarboxylic acid esters are more commonly used (such as di-n-butyl phthalate or di-isobutyl phthalate, etc. see US 4784983). Due to the limited use of phthalate compounds by European Union, new electron donor compounds, such as 1, 3-diether compounds containing two ether groups (e.g. 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene, have been developed for environmental protection, see U.S. Pat. No. 5, 4971937 and European patent EP0728769]Aliphatic dibasic carboxylic acid ester compounds (e.g., succinic acid ester, malonic acid ester, glutaric acid ester, etc., see patent WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO 00/55215), glycol ester compounds (see patent CN1436766A, CN1453298A, etc.). In recent years, various novel nitrogen atom-containing internal electron donor compounds have been developed, such as maleimide internal electron donor compounds (CN 102268109) and hydrazide internal electron donor compounds (CN 103539874), diamide internal electron donor compounds (US 2017/024067), amine groupsFormate internal electron donor compounds (WO 2014/048861) and amide ester internal electron donor compounds (US 2012322962) of the dow ring technology limited liability company, but the overall effect of the resulting catalyst is not outstanding.
The inventor discovers and synthesizes a novel organic compound with a cyclic structure through research, and discovers that when the novel compound with the cyclic structure is added in the preparation of an olefin polymerization catalyst, the catalyst with excellent comprehensive performance can be obtained, and when the catalyst is used for propylene polymerization, a polymer with high molecular weight distribution and high melt index can be obtained.
Disclosure of Invention
The invention aims at a compound with a special cyclic structure, a preparation method and application thereof, in particular to the preparation of a catalyst for olefin polymerization. A novel catalytic polymerization reaction system is formed by adding a cyclic structure compound shown in the following general formula I in the preparation process of the catalyst. When the catalyst and the system thereof are used for olefin polymerization reaction, the orientation capability of the catalyst is adjustable, the hydrogen regulation sensitivity of the catalyst is obviously improved, and the obtained polymer has higher melt index and wider molecular weight distribution.
In a first aspect, the present invention provides a cyclic compound of formula I,
wherein R is 1 -R 4 The same or different are independently selected from hydrogen, C 1 -C 30 Alkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 4 -C 30 Heterocyclyl, halogen atom, hydroxy and C 1 -C 30 Alkoxy, R 1 -R 4 Optionally interconnected in a ring, said C 1 -C 30 Alkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 4 -C 30 Heterocyclyl and C 1 -C 30 On carbon of alkoxy radicalsIs optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group;
ar is C 6 -C 30 Arylene group or C 4 -C 30 Heteroarylene group, C 6 -C 30 Arylene groups and/or C 4 -C 30 The heteroarylene group is optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group.
According to a preferred embodiment of the invention, R 1 -R 4 The same or different are independently selected from hydrogen, C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl, C 2 -C 20 Alkynyl, C 6 -C 20 Aromatic radicals, C 4 -C 20 Heterocyclyl, halogen atom, hydroxy and C 1 -C 20 Alkoxy groups, preferably selected from hydrogen, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 20 Alkynyl, C 6 -C 15 Aromatic radicals, C 4 -C 10 Heterocyclyl, halogen atom, hydroxy and C 1 -C 10 Alkoxy groups, more preferably selected from hydrogen, C 1 -C 8 Alkyl, C 2 -C 8 Alkenyl, C 6 -C 10 Aromatic radicals, C 2 -C 8 Alkynyl, C 4 -C 8 Heterocyclyl, halogen atom, hydroxy and C 1 -C 8 An alkoxy group. According to some embodiments of the invention, R 1 -R 4 Independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, alkoxy, benzyl, phenyl, naphthyl, indenyl, fluorenyl, biphenyl, or a heterocyclic compound-containing group; the heterocyclic compound-containing group is preferably selected from the group consisting of a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, and a quinoline-containing group.
According to some embodiments, the cyclic compound of formula I has a structure of formula IA, preferably the cyclic compound of formula I has a structure of formula IB,
wherein each R 1 Independently selected from hydrogen, halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
According to a preferred embodiment of the invention Ar is C 6 -C 20 Arylene group or C 4 -C 20 Heteroarylene group, preferably Ar is C 6 -C 15 Arylene group or C 4 -C 15 Heteroarylene groups. More preferably, the Ar is selected from
Wherein each R 1 Independently selected from hydrogen, halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
According to a preferred embodiment of the invention, R 11 Selected from hydrogen and C 1 -C 20 Alkyl, preferably hydrogen and C 1 -C 10 Alkyl, more preferably hydrogen and C 1 -C 6 An alkyl group.
In the invention, C 1 -C 10 Examples of alkyl groups include C 1 -C 6 Alkyl groups, e.g. methyl, ethyl, n-propyl, isopropyl, n-butylRadical, isobutyl, tertiary butyl, n-pentyl, isopentyl, 2-dimethylpropyl, 2-methylbutyl, n-hexyl, and the like.
Examples of the cyclic compound represented by formula I according to the present invention include, but are not limited to, the following compounds: 8, 9-benzo [ h ] -2, 6-dioxa-4, 1'- (2', 4 '-cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 1' - (2 ',4' -cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1'- (2', 4 '-cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-ethyl-4, 1' - (2 ',4' -cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1'- (2', 3',4',5 '-tetraphenyl-2', 4 '-cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 1' - (2 ',3',4',5' -tetraphenyl-2 ',4' -cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1'- (2', 3',4',5 '-tetraphenyl-2', 4 '-cyclopentadienyl) -1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3-ethyl-4, 1' - (2 ',3',4',5' -tetraphenyl-2 ',4' -cyclopentadienyl) -1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1'- (2', 3',4',5 '-tetramethyl-2', 4 '-cyclopentadienyl) -1, 7-cyclononyldione, 8, 9-benzo [ h ] -2, 6-dioxa-4, 1' - (2 ',3',4',5' -tetramethyl-2 ',4' -cyclopentadienyl) -1, 7-cyclononyldione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 1'- (2', 3',4',5 '-tetramethyl-2', 4 '-cyclopentadienyl) -1, 7-cyclononyldione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1' - (2 ',3',4',5' -tetramethyl-2 ',4' -cyclopentadienyl) -1, 7-cyclononyldione, 8, 9-benzo [ h ] -2, 6-dioxa-3-ethyl-4, 1'- (2', 3',4',5 '-tetramethyl-2', 4 '-cyclopentadienyl) -1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-4, 1' -indenyl-1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 1 '-indenyl-1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3-ethyl-4, 1' -indenyl-1, 7-cyclonondione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 1 '-indenyl-1, 7-cyclonondione 8, 9-benzo [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-4, 9 '-fluorenyl-1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3-ethyl-4, 9' -fluorenyl-1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 9 '-fluorenyl-1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3, 5-diethyl-4, 9' -fluorenyl-1, 7-cyclononanedione, 8, 9-benzo [ h ] -2, 6-dioxa-3-methyl-5-ethyl-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (- (2 ' -methylbenzo) [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (3 ' -methylbenzo) [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (- (2 ' -ethylbenzo) [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (3 ' -propylbenzo) [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8, 9' -butylbenzo [ h ] -2, 9' -dioxa-4, 9' -cyclononanedione, 8- (2 ' -ethylbenzo) [ h ] -2, 9' -dioxa-4, 9' -cyclononanedione, 8,9- (- (2 ' -ethylbenzo) [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (- (2 ' -ethylbenzo) [ h ] -2,6 ' -dioxa-4, 9' -cyclononanedione, 8,9- (3, 9' -propylbenzo) [ h ] -2, 6-dioxa-1, 7-cyclononanedione, 9-1, 9-2, 9-3-and 9-cyclononanedione, 8,9- (- (2 ',3' -naphtho) [ h ] -2, 6-dioxa-3-ethyl-4, 9 '-fluorenyl-1, 7-cyclononanedione, 8,9- (- (2', 3 '-naphtho) [ h ] -2, 6-dioxa-3, 5-dimethyl-4, 9' -fluorenyl-1, 7-cyclononanedione, 8,9- (- (2 ',3' -naphtho) [ h ] -2, 6-dioxa-4, 1'- (2', 3',4',5 '-tetramethyl-2', 4 '-cyclopentadienyl) -1, 7-cyclononanedione, 8,9- (- (2' -butylbenzo) [ h ] -2, 6-dioxa-4, 9 '-fluorenyl-1, 7-cyclononanedione, 8,9, 10-naphtho [1',8'-hi ] -2, 6-dioxa-4, 9' -fluorenyl 1, 7-cyclosunflower dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-3-methyl-4, 9 '-fluorenyl 1, 7-cyclosunflower dione, 8,9, 10-naphtho [1',8'-hi ] -2, 6-dioxa-3-ethyl-4, 9' -fluorenyl 1, 7-cyclosunflower dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-3, 5-dimethyl-4, 9 '-fluorenyl 1, 7-cyclosunflower dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-3, 5-diethyl-4, 9' -fluorenyl-1, 7-cyclosunflower-dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-4, 1' - (2 ',3',4',5' -tetraphenyl-2 ',4' -cyclopentadienyl) -1, 7-cyclosunflower-dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-4, 1' - (2 ',3',4',5' -tetramethyl-2 ',4' -cyclopentadienyl) -1, 7-cyclosunflower-dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-4, 1' - (2 ',4' -cyclopentadienyl) -1, 7-cyclosunflower dione, 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-4, 1' -indenyl-1, 7-cyclosunflower dione, 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-4, 9' -fluorenylundecyclo-1, 7-dione, 8,9,8,9,10,11-dibenzo [ hj ] -2, 6-dioxa-3-methyl-4, 9' -fluorenylundecyclo-1, 7-dione, 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-3-ethyl-4, 9' -fluorenylundecyclo-1, 7-cyclodione, 10, 11-dibenzo [ hj ] -2, 6-dioxa-3, 5-dimethyl-4, 9' -fluorenyl undecyl-1, 7-dione, 10, 11-dibenzo [ hj ] -2, 6-dioxa-3, 5-diethyl-4, 9' -fluorenyl undecyl-1, 7-dione, 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-4, 1' - (2 ',3',4',5' -tetraphenyl-2 ',4' -cyclopentadienyl) undecyl-1, 7-dione, 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-4, 1' - (2 ',3',4',5' -tetramethyl-2 ',4' -cyclopentadienyl) undecyl-1, 7-dione, and 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-4, 1' - (2 ',4' -cyclopentadienyl) undecyl-1, 7-dione.
In a second aspect, the present invention also provides a method for preparing a cyclic compound of formula I according to the first aspect of the present invention, comprising: reacting a diol compound represented by formula II with at least one compound selected from the group consisting of an acyl halide compound represented by formula III, an acid anhydride compound represented by formula IV and an ester compound represented by formula V to produce the cyclic compound represented by formula I,
wherein R is 1 -R 4 The same or different are independently selected from hydrogen, C 1 -C 30 Alkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 4 -C 30 Heterocyclyl, halogen atom, hydroxy and C 1 -C 30 Alkoxy, R 1 -R 4 Optionally interconnected in a ring, said C 1 -C 30 Alkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 4 -C 30 Heterocyclyl and C 1 -C 30 The hydrogen on the carbon of the alkoxy group being optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group;
ar is C 6 -C 30 Arylene group or C 4 -C 30 Heteroarylene group, C 6 -C 30 Arylene groups and/or C 4 -C 30 The heteroarylene group is optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group;
x is a halogen atom, preferably fluorine, chlorine, bromine and iodine;
r is C 1 -C 20 Alkyl, preferably C 1 -C 10 Alkyl, more preferably C 1 -C 5 An alkyl group.
According to a preferred embodiment of the above preparation method, R 1 -R 4 The same or different are independently selected from hydrogen, C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl, C 2 -C 20 Alkynyl, C 6 -C 20 Aromatic radicals, C 4 -C 20 Heterocyclyl, halogen atom, hydroxy and C 1 -C 20 Alkoxy groups, preferably selected from hydrogen, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 20 Alkynyl, C 6 -C 15 Aromatic radicals, C 4 -C 10 Heterocyclyl, halogen atom, hydroxy and C 1 -C 10 Alkoxy groups, more preferably selected from hydrogen, C 1 -C 8 Alkyl, C 2 -C 8 Alkenyl, C 6 -C 10 Aromatic radicals, C 2 -C 8 Alkynyl, C 4 -C 8 Heterocyclic radicalHalogen atom, hydroxy group and C 1 -C 8 An alkoxy group. According to some embodiments of the invention, R 1 -R 4 Independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, alkoxy, benzyl, phenyl, naphthyl, indenyl, fluorenyl, biphenyl, or a heterocyclic compound-containing group; the heterocyclic compound-containing group is preferably selected from the group consisting of a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, and a quinoline-containing group.
According to a preferred embodiment of the above preparation method, ar is C 6 -C 20 Arylene group or C 4 -C 20 Heteroarylene group, preferably Ar is C 6 -C 15 Arylene group or C 4 -C 15 Heteroarylene groups. In some embodiments, ar is a substituted or unsubstituted naphthylene. In some embodiments, the Ar is selected from
Wherein each R 1 Independently selected from hydrogen, halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
According to some embodiments, the cyclic compound has a structure represented by formula IA, preferably, the compound has a structure represented by formula IB,
wherein each R 1 Independently selected from hydrogen, halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
According to a preferred embodiment of the above preparation process, the reaction is carried out in a solvent in the presence of an acid or a base, optionally an inorganic salt.
According to a preferred embodiment of the above preparation method, the acid is selected from inorganic or organic acids, preferably from hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid and oxalic acid.
According to a preferred embodiment of the above preparation method, the base is selected from inorganic or organic bases, preferably from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, butyllithium, sodium amide, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazobicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclon-5-ene) and pyrazole.
According to a preferred embodiment of the above preparation method, the solvent is selected from alcohols, ethers and hydrocarbon solvents, preferably from methanol, ethanol, propanol, butanol, ethylene glycol, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, white oil, silicone oil, paraffin, methylene chloride, chloroform, ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, more preferably from diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF and acetone.
According to a preferred embodiment of the above preparation method, the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, cesium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate and cesium sulfate.
In a third aspect, the present invention provides the use of a cyclic compound of formula I as described above in the preparation of an olefin polymerization catalyst or in olefin polymerization. Preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
In a fourth aspect, the present invention provides a catalyst component for the polymerization of olefins comprising the cyclic compound of formula I. Preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
Different methods may be selected to prepare the catalyst component for olefin polymerization of the present invention, and the following are illustrative of several methods for preparing the catalyst and are not limited thereto.
Method 1: an inert diluent may be added to a homogeneous solution of magnesium halide in the organic epoxy compound and the organic phosphorus compound. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation-assisting agent is present in the reaction system, a solid is precipitated. And (3) carrying the compound with the structure I on a solid object, and treating the solid object by using titanium tetrahalide or an inert diluent to obtain the solid catalyst comprising components such as titanium, magnesium, halogen, electron donor and the like.
Method 2: suspending alkoxy magnesium or alkoxy magnesium chloride or magnesium chloride alkoxide spherical carrier in inert solvent to form suspension, and mixing the suspension solution with titanium tetrahalide or its derivative to obtain solid. And then contacting the compound with the structure I with a solid substance to obtain the solid catalyst comprising titanium, magnesium, halogen, electron donor and other components.
Method 3: fully mixing and stirring magnesium halide or an organic magnesium compound, an alcohol compound and titanate or a titanium halide compound in an inert solvent, heating and cooling to obtain a spherical carrier or adding the inert solvent to obtain a uniform alkoxide solution. Mixing the carrier or the uniform solution with titanium tetrahalide or a derivative thereof, maintaining at a low temperature for a period of time, heating, adding the compound of the structure I, treating with titanium tetrahalide or an inert diluent, treating with the compound, and finally filtering, washing and drying to obtain the solid catalyst comprising components such as titanium, magnesium, halogen, electron donor and the like.
The method for preparing the catalyst may be a method in which, for example, a magnesium compound, an electron donor compound having the above-mentioned structure, or the like is formed into an emulsion in a diluent, a titanium compound is added to fix the emulsion to obtain a spherical solid, and the solid catalyst is obtained by treatment.
The solid catalyst component for olefin polymerization according to the present invention preferably comprises a titanium compound, a magnesium compound and a corresponding internal electron donor compound. The internal electron donor compound includes a compound selected from the compounds described by the general formula I or the compounds described by the general formula I and other internal electron donor compounds. The compounds of the general structural formula I according to the invention can be added in any step of the preparation process of the catalysts described above.
The magnesium compound is selected from one of magnesium dihalide, hydrate or alkoxide of magnesium dihalide, and derivative of magnesium dihalide in which one halogen atom is replaced by hydrocarbyloxy or halohydrocarbonoxy, or mixture thereof. Preference is given to magnesium dihalide or to magnesium dihalide alkoxides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and also to their alkoxides.
The titanium compound can be TiX m (OR 1 ) 4-m Wherein R is 1 Is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, and m=1 to 4. For example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide, preferably titanium tetrachloride.
The magnesium compound may be dissolved in a solvent system containing an organic epoxy compound and an organic phosphorus compound, or may be dissolved in a 1, 3-diol ester compound. Wherein the organic epoxy compound comprises at least one of an aliphatic olefin, a diene or a halogenated aliphatic olefin or an oxide of a diene, a glycidyl ether and an internal ether having 2 to 8 carbon atoms. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
The organic phosphorus compound comprises hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite.
In addition to the compounds of formula I described above, the other internal electron donor compounds include those selected from or of the formula ketones, ethers, amines, esters (aromatic or aliphatic diesters), alcohol esters, and the like.
Another object of the present invention is to provide a method for CH 2 Catalyst system for CHR olefin polymerization, in which R is hydrogen or C 1 -C 6 An alkyl group comprising the reaction product of:
component a, a solid catalyst component comprising magnesium, titanium, halogen and a cyclic compound selected from the group consisting of compounds of formula I;
component b, an alkylaluminum compound;
component c, optionally, an external electron donor component.
Wherein the alkyl aluminum compound has a general formula of AlR I n X 3-n Wherein R is I Is hydrogen, hydrocarbon radical with 1-20 carbon atoms, X is halogen, n is a number of 1 < n < 3; specifically selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, preferably triethylaluminum, triisobutylaluminum.
For applications where highly stereoregular olefin polymers are desired, it is desirable to add external electron donor compounds, e.g. of the formula R II k Si(OR III ) 4-k Wherein k is 0.ltoreq.3, R II And R is III Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R II Or may be a halogen or a hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilaneMethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane.
Wherein the mol ratio of the component a, the component b and the component c is 1 (5-1000) to 0-500; preferably 1 (25-100): 25-100.
The olefin polymerization of the present invention can be carried out according to a known polymerization method, in a liquid phase or a gas phase, or in a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, bulk processes, gas-phase fluidised beds, bulk-gas phase processes and the like are employed wherein the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, in particular the homo-polymerisation of propylene and or the co-polymerisation of other olefins of propylene. The following reaction conditions are preferably employed: the polymerization temperature is 0 to 150℃and preferably 60 to 90 ℃.
The catalyst of the present invention may be directly fed into the reactor for use in the polymerization process or the catalyst may be pre-polymerized prior to being fed into the first polymerization reactor. In the present invention, "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a low degree of conversion. According to the present invention, the prepolymerization catalyst comprises the prepolymer obtained by prepolymerizing the above solid catalyst component with an olefin, the prepolymerization multiple being 0.1 to 1000g of olefin polymer per g of solid catalyst component.
The same alpha-olefins as the previously described olefins may be used for the prepolymerization, wherein the olefin to be prepolymerized is preferably ethylene or propylene. In particular, it is particularly preferred to carry out the prepolymerization with ethylene or a mixture of one or more alpha-olefins in a remaining amount of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is from about 0.2 to 500 g polymer per g solid catalyst component.
The prepolymerization step can be carried out in liquid or in gas phase at a temperature of from-20 to 80 ℃, preferably from 0 to 50 ℃. The prepolymerization step can be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers having a catalyst component content of from 0.5 to 20g/g, the batch prepolymerization of the catalyst according to the invention with ethylene is particularly preferred. The polymerization pressure is 0.01-10 MPa.
The catalysts of the invention are also suitable for producing polyethylene and copolymers of ethylene with alpha-olefins such as propylene, butene, pentene, hexene, 4-methyl-1-pentene.
The invention has the following characteristics:
1. the cyclic structure compound shown in the formula I is a novel cyclic compound, and is not reported in the literature.
2. The novel cyclic compound is used as an internal electron donor, so that the catalyst with excellent comprehensive performance can be obtained. In particular to the polypropylene resin with high activity, good hydrogen regulation sensitivity, adjustable isotactic index of the obtained polymer and wide molecular weight distribution.
Detailed Description
The cyclic compound shown in the general formula I is used for preparing an olefin polymerization catalyst to form a novel catalytic polymerization system, and the catalytic behavior of the novel catalytic polymerization system in propylene polymerization is researched, and the results are shown in Table 1.
Examples
Synthesis of (one) Compounds
EXAMPLE 1 Compound 8, 9-benzo [ h ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclononanedione (FC-1)
In a 250 ml three-necked flask, after nitrogen purging, 4.52 g of 9, 9-dimethylolfluorene, 120 ml of acetonitrile, 2.15 ml of triethylamine and 0.32 g of potassium chloride were added, 4.02 g of phthaloyl chloride was added dropwise at room temperature, and the mixture was stirred uniformly. After stirring and reacting for 4 hours, heating and refluxing for reacting for 8 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 2.42 g of the product (yield 34%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.10～8.08(2H,m,ArH),7.85～7.83(2H,m,ArH),7.58～7.55(4H,m,ArH),7.37～7.36(2H,m,ArH),7.26～7.24(2H,m,ArH),4.83～4.81(4H,m,O CH 2 )。
EXAMPLE 2 Compound 8,9, 10-naphtho [1',8' -hi ] -2, 6-dioxa-4, 9' -fluorenyl-1, 7-cyclosunflower dione (FC-2)
In a 250 ml three-necked flask, after nitrogen purging, 4.52 g of 9, 9-dimethylolfluorene, 120 ml of acetonitrile, 2.15 ml of triethylamine and 0.32 g of potassium chloride were added, 5.00 g of 1, 8-naphthalene dicarboxylic acid chloride was added dropwise at room temperature and stirred well. After stirring and reacting for 4 hours, heating and refluxing for reacting for 10 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave yellow crystals, which were dried under vacuum to give 2.43 g of the product (yield 30%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.35～8.32(2H,m,ArH),7.98～7.96(2H,m,ArH),7.85～7.83(2H,m,ArH),7.56～7.54(2H,m,ArH),7.47～7.45(2H,m,ArH),7.38～7.36(2H,m,ArH),7.28～7.26(2H,m,ArH),4.83～4.81(4H,m,O CH 2 )。
EXAMPLE 3 Compound 8,9,10, 11-dibenzo [ hj ] -2, 6-dioxa-4, 9' -fluorenylundecylenic ring-1, 7-dione (FC-3)
In a 250 ml three-necked flask, after nitrogen purging, 4.52 g of 9, 9-dimethylolfluorene, 130 ml of acetonitrile, 2.15 ml of triethylamine and 0.32 g of potassium chloride were added, and 5.54 g of 1,1' -biphenyl dicarboxylic acid chloride was added dropwise at room temperature and stirred well. After stirring and reacting for 4 hours, heating and refluxing for 14 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave yellow crystals, which were dried under vacuum to give 2.59 g of the product (yield 30%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.05～8.03(2H,m,ArH),7.85～7.83(2H,m,ArH),7.59～7.58(2H,m,ArH),7.55～7.53(4H,m,ArH),7.38～7.36(2H,m,ArH),7.33～7.31(2H,m,ArH),7.28～7.26(2H,m,ArH),4.84～4.81(4H,m,O CH 2 )。
Preparation of solid component in catalyst and propylene polymerization
Example 4
(1) Preparation of catalyst solid component
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were added in this order, and the temperature was raised to 50℃with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the mixture is kept for 1 hour, and the solution is cooled to below-25 ℃ for 1 hourTiCl is added dropwise in time 4 60mL was slowly warmed to 80℃and the solid was gradually precipitated, and 6mmol of the electron donor compound FC-1 was added thereto and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to give a solid. 100mL of toluene was added, the temperature was raised to 110℃and three washes were performed for 10 minutes each. And adding 60mL of hexane for three times, and vacuum drying to obtain the catalyst solid component.
(2) Propylene polymerization
The stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mL, methylcyclohexyldimethoxy silane (CHMMS) 5mL, al/Si (mol) =25, 10mg of the solid component prepared in the above example and 1.2NL of hydrogen were added, 2.5L of liquid propylene was introduced, the temperature was raised to 70℃and maintained for 1 hour, the temperature was lowered, the pressure was released, and the PP resin was obtained by discharging, and the results are shown in Table 1.
Example 5
As in example 4, only the electron donor compound FC-1 was replaced with FC-2, and the results are shown in Table 1.
Example 6
As in example 4, only the electron donor compound FC-1 was replaced with FC-3, and the results are shown in Table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (16)

1. A cyclic compound represented by the formula IB,
wherein R is 1 Selected from hydrogen;
ar is C 6 -C 30 Arylene group or C 4 -C 30 Heteroarylene group, C 6 -C 30 Arylene groups and/or C 4 -C 30 The heteroarylene group is optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group.
2. A compound according to claim 1, wherein Ar is C 6 -C 20 Arylene group or C 4 -C 20 Heteroarylene groups.
3. A compound according to claim 2, wherein Ar is C 6 -C 15 Arylene group or C 4 -C 15 Heteroarylene groups.
4. A compound according to claim 3, wherein Ar is selected from
Wherein each R 1 Independently selected from hydrogen, halogen atoms,OH、OR、SR、C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
5. The method for producing a cyclic compound according to any one of claims 1 to 4, comprising: reacting 9, 9-dimethylolfluorene with at least one compound selected from the group consisting of an acyl halide compound represented by formula III, an acid anhydride compound represented by formula IV, a dibasic acid compound represented by formula V and an ester compound represented by formula VI to produce the cyclic compound represented by formula IB,
wherein Ar is C 6 -C 30 Arylene group or C 4 -C 30 Heteroarylene group, C 6 -C 30 Arylene groups and/or C 4 -C 30 The heteroarylene group is optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, nitro and cyano groups, wherein R is C 1 -C 10 An alkyl group;
x is a halogen atom;
r is C 1 -C 20 An alkyl group.
6. The process according to claim 5, wherein X is selected from fluorine, chlorine, bromine and iodine, and/or R is C 1 -C 10 An alkyl group.
7. The method of claim 6, wherein R is C 1 -C 5 An alkyl group.
8. The process according to any one of claims 5 to 7, wherein the reaction is carried out in a solvent in the presence of an acid or a base and optionally an inorganic salt.
9. The method of claim 8, wherein the acid is selected from inorganic or organic acids; the base is selected from inorganic or organic bases; the solvent is selected from alcohols, ethers and hydrocarbon solvents; the inorganic salt is selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, cesium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, and cesium sulfate.
10. The method of claim 8, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, and oxalic acid; the base is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, butyllithium, sodium amide, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, DBN (1, 5-diazabicyclon-5-ene) and pyrazole; the solvent is selected from methanol, ethanol, propanol, butanol, ethylene glycol, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, white oil, silicone oil, paraffin, methylene chloride, chloroform, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.
11. The method of claim 8, wherein the solvent is selected from the group consisting of diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF, and acetone.
12. Use of a cyclic compound of formula IB according to any one of claims 1-4 in the preparation of an olefin polymerization catalyst.
13. Use of a cyclic compound of formula IB according to any one of claims 1-4 in olefin polymerization.
14. The use according to claim 12 or 13, characterized in that the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
15. A catalyst component for the polymerization of olefins comprising a cyclic compound of formula IB according to any of claims 1-4.
16. The catalyst component according to claim 15 in which the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000230011A (en) * 1999-02-10 2000-08-22 Tosoh Corp Transition metal compound, olefin polymerization catalyst, and production of polyolefin using the catalyst
CN1765941A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Catalyst for olefin polymerization and its uses
CN101724102A (en) * 2008-10-24 2010-06-09 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
CN103923238A (en) * 2013-10-31 2014-07-16 北京利和知信科技有限公司 Catalyst component for olefin polymerization and catalyst
CN108059689A (en) * 2016-11-09 2018-05-22 中国石油天然气股份有限公司 Olefin polymerization procatalyst compositions and preparation method thereof, olefin Polymerization catalyst compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000230011A (en) * 1999-02-10 2000-08-22 Tosoh Corp Transition metal compound, olefin polymerization catalyst, and production of polyolefin using the catalyst
CN1765941A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Catalyst for olefin polymerization and its uses
CN101724102A (en) * 2008-10-24 2010-06-09 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
CN103923238A (en) * 2013-10-31 2014-07-16 北京利和知信科技有限公司 Catalyst component for olefin polymerization and catalyst
CN108059689A (en) * 2016-11-09 2018-05-22 中国石油天然气股份有限公司 Olefin polymerization procatalyst compositions and preparation method thereof, olefin Polymerization catalyst compositions

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