CN110950832B - Cyclic compound and preparation method and application thereof - Google Patents

Cyclic compound and preparation method and application thereof Download PDF

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CN110950832B
CN110950832B CN201811123235.4A CN201811123235A CN110950832B CN 110950832 B CN110950832 B CN 110950832B CN 201811123235 A CN201811123235 A CN 201811123235A CN 110950832 B CN110950832 B CN 110950832B
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dione
naphtho
dioxol
methyl
ethyl
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CN110950832A (en
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王军
高明智
刘海涛
马晶
马吉星
何世雄
刘文蕊
李昌秀
胡建军
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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention relates to a cyclic compound shown as 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 catalyst has good hydrogen regulation sensitivity, the isotactic index of the obtained polymer can be regulated, 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 and a preparation method and application thereof.
Background
Olefin polymerization catalysts can be divided into three broad categories, namely, traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For traditional Ziegler-Natta catalysts, polyolefin catalysts are constantly being updated with the development of electron donor compounds in the catalyst. Development of the catalyst from the first TiCl 3 AlCl 3 /AlEt 2 Cl system and second generation of TiCl 3 /AlEt 2 Cl 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 donor 4 ·ED·MgCl 2 /AlR 3 The catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved by an ED system. 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. Various electron-donor compounds have been disclosed, such as mono-or polycarboxylic esters, anhydrides, ketone 12/monoethers or polyethers, alcohols, amines, etc. and derivatives thereof, among which aromatic dicarboxylic esters are more commonly used (e.g. di-n-butyl phthalate or diisobutyl phthalate, etc., see US 4784983). Due to the limited use of phthalate compounds in the EU and other countries, new electron donor compounds have been developed for environmental protection, such as 1,3-diether compounds containing two ether groups [ e.g. 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane and 9,9-bis (methoxymethyl) fluorene ] containing two ether groups, as described in U.S. Pat. No. 4,4971937 and European patent EP0728769]And dicarboxylic acid ester compounds (such as succinate, malonate, glutarate, etc.,see patents WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO 00/55215), glycol ester compounds (see patents CN1436766A, CN1453298A, etc.). In recent years, many novel internal electron donor compounds containing nitrogen atom structures, such as maleic amide internal electron donor compounds (CN 102268109), hydrazide internal electron donor compounds (CN 103539874), diamide internal electron donor compounds (US 2017/0240667), carbamate internal electron donor compounds (WO 2014/048861), and amide ester internal electron donor compounds of dow ring ball technology ltd (US 2012322962), have emerged, but the overall effect of the obtained catalyst is not outstanding.
The present inventors have found and synthesized a novel organic compound having a cyclic structure, and have found that when the novel compound having a cyclic structure is added to prepare a catalyst for olefin polymerization, a catalyst having excellent overall properties can be obtained, and when the catalyst is used for propylene polymerization, a polymer having a high molecular weight distribution and a high melt index can be obtained.
Disclosure of Invention
The invention relates to 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 cyclic structure compound shown in the following general formula I is added in the preparation process of the catalyst to form a novel catalytic polymerization reaction system. When the catalyst and the system thereof are used in olefin polymerization reaction, the orientation capability of the catalyst can be adjusted, 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,
Figure BDA0001811711830000021
wherein R is 1 And R 2 Same or different, independently selected from hydrogen, C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radical、C 4 -C 30 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 30 Alkoxy radical, said C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl radical, C 4 -C 30 Heterocyclyl and C 1 -C 30 The hydrogen on carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group;
a is (CR) 3 R 4 ) m -G n -(CR 5 R 6 ) p Wherein G is selected from NR 7 、PR 8 O, S and SiR 9 R 10 ，R 3 To R 10 The same or different, are independently selected from hydrogen and C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 3 -C 30 And aliphatic cyclic hydrocarbon group of 6 -C 30 An aromatic group, said C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 3 -C 30 And aliphatic cyclic hydrocarbon group of 6 -C 30 The hydrogen on carbon of the aromatic group being optionally selected from halogen atoms, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 Alkyl, m, n and p are independently selected from integers of 0-6 such as 0, 1, 2,3,4, 5, 6, or R 3 And R 4 Linked to form a ring, and/or R 5 And R 6 Connecting to form a ring;
ar is C 6 -C 30 Arylene radicals or C 4 -C 30 Heteroarylene radical, C 6 -C 30 Arylene group and/or C 4 -C 30 The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C 1 -C 10 Alkyl, aryl, heteroaryl, and heteroaryl,C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group;
x and Y are the same or different and are selected from the group consisting of O, S and NR 11 ，R 11 Selected from hydrogen and C 1 -C 30 An alkyl group.
According to a preferred embodiment of the invention, R 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Alkynyl, C 6 -C 20 Aryl radical, C 4 -C 20 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 20 Alkoxy, preferably selected from hydrogen, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 20 Alkynyl, C 6 -C 15 Aryl radical, C 4 -C 10 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 10 Alkoxy, more preferably selected from hydrogen, C 1 -C 8 Alkyl radical, C 2 -C 8 Alkenyl radical, C 6 -C 10 Aryl radical, C 2 -C 8 Alkynyl, C 4 -C 8 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 8 An alkoxy group. According to some embodiments, R 1 And R 2 A group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, benzyl, phenyl, halophenyl, naphthyl, biphenyl, or a heterocyclic compound, and the like. The heterocyclic compound-containing group is preferably an azole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group, or the like.
According to a preferred embodiment of the invention, R 3 To R 10 Same or different, independently selected from hydrogen, C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Alkynyl, C 3 -C 20 And C is an aliphatic cyclic hydrocarbon 6 -C 20 Aromatic radicals, preferably selected from hydrogen, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Alkynyl, C 3 -C 10 And C is an aliphatic cyclic hydrocarbon 6 -C 15 An aromatic group.
According to a preferred embodiment of the invention, ar is C 6 -C 20 Arylene radicals or C 4 -C 20 Heteroarylene group, preferably Ar is C 6 -C 15 Arylene radicals or C 4 -C 15 A heteroarylene group. In some embodiments, ar is substituted or unsubstituted naphthylene. In some embodiments, the Ar is selected from,
Figure BDA0001811711830000031
Figure BDA0001811711830000041
wherein each R is 1 Independently selected from hydrogen, halogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group.
In the present invention, C 1 -C 10 Examples of alkyl groups include C 1 -C 6 Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-dimethylpropyl, 2-methylbutyl, n-hexyl and the like. 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 An alkyl group.
Examples of cyclic compounds of formula I described herein include, but are not limited to, the following: 7,9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 3-diethyl-7, 9-naphtho [1',10', 8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',gh, 8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 4-dibutyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-ethyl-4-propyl-7, 9-naphtho [1',10 ',8'-gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2,3, 4-trimethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-diethyl-3-methyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dipropyl-3-methyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dibutyl-3-methyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2,3, 4-triethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dibutyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 7, 8-benzo [ g ] -1, 5-dioxetane-6, 9-dione, 3-methyl-7, 8-benzo [ g ] -1, 5-dioxetane-6, 9-dione, 3-ethyl-7, 8-benzo [ g ] -1, 5-dioxetane-6, 9-dione, 3-propyl-7, 8-benzo [ g ] -1, 5-dioxetane-6, 9-dione -diketone, 3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecane-6, 10-dione, 3-methyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-ethyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 3-butyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-pentyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-cyclopentyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-cyclohexyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',10 ] -, 8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecan-6, 10-dione, 3-isopropyl-3-isopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-methyl-3-isopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, a 3-isopropyl-3-cyclopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-cyclohexyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-cyclopropyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclohexyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclopropyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 3-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 3-diethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione 2-Ethyl-3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-Ethyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2,3, 4-trimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-3-methyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-3-methyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-3-methyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-3-nonane-6, 9-dione 2,3, 4-triethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (2 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (2' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (2 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (2' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (2 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (3' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (3 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione 2, 4-dipropyl-7, 8- (3' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (3 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (3' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 '-ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione 2, 4-dipropyl-7, 8- (4' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 '-ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 '-propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 '-propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4 '-propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 '-butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione 2, 4-dipropyl-7, 8- (4' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 '-butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 '-chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, and 2, 4-dipentyl-7, 9-dione.
In a second aspect, the present invention provides a process for the preparation of a cyclic compound of formula I, comprising: reacting a compound represented by formula II with at least one compound selected from an acid 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,
Figure BDA0001811711830000071
wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl radical, C 4 -C 30 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 30 Alkoxy radical, said C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl radical, C 4 -C 30 Heterocyclyl and C 1 -C 30 The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group;
a is (CR) 3 R 4 ) m -G n -(CR 5 R 6 ) p Wherein G is selected from NR 7 、PR 8 O, S and SiR 9 R 10 ，R 3 To R 10 The same or different, are independently selected from hydrogen and C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 3 -C 30 And aliphatic cyclic hydrocarbon group of 6 -C 30 An aromatic group, said C 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 3 -C 30 And aliphatic cyclic hydrocarbon group of 6 -C 30 The hydrogen on carbon of the aromatic radical being optionally selected fromHalogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 Alkyl, m, n and p are independently selected from integers from 0 to 6, or R 3 And R 4 Linked to form a ring, and/or R 5 And R 6 Connecting to form a ring;
ar is C 6 -C 30 Arylene radicals or C 4 -C 30 Heteroarylene radical, C 6 -C 30 Arylene group and/or C 4 -C 30 The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C 1 -C 10 An alkyl group;
x and Y are the same or different and are selected from the group consisting of O, S and NR 11 ，R 11 Selected from hydrogen and C 1 -C 30 An alkyl group;
e 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 process, R 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Alkynyl, C 6 -C 20 Aryl radical, C 4 -C 20 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 20 Alkoxy, preferably selected from hydrogen, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 20 Alkynyl, C 6 -C 15 Aryl radical, C 4 -C 10 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 10 Alkoxy, more preferably selected from hydrogen, C 1 -C 8 Alkyl radical, C 2 -C 8 Alkenyl radical, C 6 -C 10 Aryl radical, C 2 -C 8 Alkynyl, C 4 -C 8 Heterocyclic group, halogen atom, hydroxyl group and C 1 -C 8 An alkoxy group.
According to a preferred embodiment of the above preparation process, R 3 To R 10 The same or different, are independently selected from hydrogen and C 1 -C 20 Alkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Alkynyl, C 3 -C 20 And C is an aliphatic cyclic hydrocarbon 6 -C 20 Aromatic radicals, preferably selected from hydrogen, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Alkynyl, C 3 -C 10 And aliphatic cyclic hydrocarbons of (C) 6 -C 15 An aromatic group.
According to a preferred embodiment of the above preparation process, ar is C 6 -C 20 Arylene radicals or C 4 -C 20 A heteroarylene group, preferably Ar is C 6 -C 15 Arylene radicals or C 4 -C 15 A heteroarylene group. In some embodiments, ar is substituted or unsubstituted naphthylene. In some embodiments, ar is selected from
Figure BDA0001811711830000081
Wherein each R is 1 Independently selected from hydrogen, halogen atom, OH, OR, SR, C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, 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, R 11 Selected from hydrogen and C 1 -C 20 Alkyl, preferably hydrogen and 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 and optionally an inorganic salt.
According to a preferred embodiment of the above preparation process, 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 process, 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 aminyl, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, hexahydropyridine, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazabicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclono-5-ene) and pyrazole.
According to a preferred embodiment of the above production process, the solvent is selected from the group consisting of alcohols, ethers and hydrocarbon solvents, preferably from the group consisting of 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 dioxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, more preferably from the group consisting of diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF and acetone.
According to a preferred embodiment of the above production 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 hydrogen carbonate, 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 a catalyst for the polymerisation of olefins or in the polymerisation of olefins. 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 olefin polymerization, comprising said 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 can be selected for preparing the catalyst component for olefin polymerization of the present invention, and several methods for preparing the catalyst are listed below without being limited thereto.
The method comprises the following steps: the magnesium halide is dissolved in a homogeneous solution of an organic epoxy compound and an organic phosphorus compound, and an inert diluent may also be added. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation assistant exists in the reaction system, a solid is precipitated. The compound with the structure I is carried on a solid and then treated by titanium tetrahalide or inert diluent to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 2 comprises the following steps: suspending the alkoxy magnesium or alkoxy magnesium chloride or magnesium chloride alcoholate spherical carrier in an inert solvent to form a suspension, and mixing and contacting the suspension solution with titanium tetrahalide or derivatives thereof to obtain a solid. And then contacting the compound with the structure I with a solid to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 3 comprises the following steps: fully mixing and stirring magnesium halide or an organic magnesium compound, an alcohol compound and a titanate or titanium halide compound in an inert solvent, heating and cooling to obtain a spherical carrier or adding the spherical carrier into the inert solvent to obtain a uniform alcohol compound solution. Mixing the carrier or the uniform solution with titanium tetrahalide or derivatives thereof, maintaining at a low temperature for a period of time, heating, adding the compound with 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 containing titanium, magnesium, halogen, electron donor and other components.
The catalyst may be prepared by adding a magnesium compound, an electron donor compound having the above structure, and the like to a diluent to form an emulsion, adding a titanium compound to fix the emulsion to obtain a spherical solid, and treating the spherical solid to obtain a solid catalyst.
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 comprises 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 compound of the general structural formula (I) according to the present invention may be added at any step during the preparation of the above catalyst.
The magnesium compound is selected from one of magnesium dihalide, hydrate or alcoholate of magnesium dihalide, and derivatives of magnesium dihalide in which one halogen atom is replaced by hydrocarbyloxy or halohydrocarbyloxy, or their mixture. Preference is given to magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
The titanium compound can be selected from the general formula of TiX m (OR 1 ) 4-m A compound of (1), wherein R 1 Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and m =1 to 4. For example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, 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 oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes with 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 organophosphorus compounds include hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and trityl phosphite.
In addition to the compounds described by the above general formula (I), the other internal electron donor compounds include compounds selected from or described by the above general formula ketones, ethers, amines, esters (aromatic esters or aliphatic diesters), alcohol esters, and the like.
It is another object of the present invention to provide a method for CH 2 Catalyst system for the polymerization of CHR olefins, where R is hydrogen or C 1 -C 6 Comprising the reaction product of:
component a, one of the above-mentioned solid catalyst components comprising magnesium, titanium, halogen and a compound selected from the compounds of the general formula (I);
component b, an alkyl aluminum compound;
component c, optionally, an external electron donor component.
Wherein the alkyl aluminum compound has the general formula of AlR I n X 3-n A compound of (1), wherein R I Is hydrogen, alkyl with 1-20 carbon atoms, X is halogen, n is a number which is more than 1 and less than or equal to 3; specifically, the aluminum chloride can be selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, and preferably triethylaluminum and triisobutylaluminum are selected.
For the application of olefin polymers with high stereoregularity, an external electron donor compound is added, for example, the general formula R II k Si(OR III ) 4-k Wherein k is not less than 0 and not more than 3 II And R III Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R II And may be a halogen or hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-tert-butyldimethoxysilane, preferably cyclohexylmethyldimethylsilaneOxysilane, diphenyldimethoxysilane.
Wherein the ratio of the component a to the component b to the component c is 1 (5-1000) to (0-500) in terms of the molar ratio of titanium to aluminum to silicon; preferably 1 (25-100) to 25-100.
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out by a combination of liquid phase and gas phase polymerization stages. The homopolymerization of propylene and/or the copolymerization of other olefins of propylene is carried out by conventional techniques such as slurry process, bulk process, gas-phase fluidized bed, bulk-gas phase process, etc., wherein the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. The following reaction conditions are preferably employed: the polymerization temperature is from 0 to 150 ℃ and preferably from 60 to 90 ℃.
The catalyst of the invention can be added directly to the reactor for use in the polymerization process or the catalyst can be prepolymerized before being added to the first polymerization reactor. In the present invention, "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a relatively low degree of conversion. According to the present invention, the prepolymerized catalyst comprises a prepolymer obtained by prepolymerizing the above solid catalyst component with an olefin, the prepolymerization ratio being 0.1 to 1000g of the olefin polymer per g of the solid catalyst component.
The prepolymerization can be carried out using the same α -olefin as the aforementioned olefin, wherein the olefin to be subjected to the prepolymerization is preferably ethylene or propylene. In particular, it is particularly preferred to carry out the prepolymerization with a mixture of ethylene or one or more alpha-olefins in a balance of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is about 0.2 to 500 g polymer/g solid catalyst component.
The prepolymerization step can be carried out at a temperature of-20 to 80 c, preferably 0 to 50 c, in liquid or gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers in amounts of from 0.5 to 20g per g of catalyst component, the batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01-10 MPa.
The catalysts of the invention are also suitable for the production of 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 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. Particularly when the catalyst is used for propylene polymerization, the catalyst has high activity and good hydrogen regulation sensitivity, the isotactic index of the obtained polymer can be regulated, and the molecular weight distribution of the obtained polypropylene resin is wide.
Detailed Description
The compound shown as the general formula I is used for preparing an olefin polymerization reaction catalyst to form a novel catalytic polymerization reaction system, and the catalytic behavior of the novel catalytic polymerization reaction system in the propylene polymerization reaction is researched, and the results are shown in Table 1.
Examples
Synthesis of Compound (I)
Example 1 Synthesis of 2, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-1)
In a 250 ml three-necked flask, after nitrogen purging, 2.08 g of 2, 4-pentanediol, 100ml of acetonitrile, 2.15 ml of triethylamine, and 0.15 g of potassium chloride were added, and 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed for 8 hours at elevated temperature. After concentration under reduced pressure, recrystallization from a mixed solution of ether/petroleum ether (1. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.33-8.32(2H,m,ArH),7.98-7.97(2H,m,ArH),7.47-7.46(2H,m,ArH),4.15-4.13(2H,m,OCH),2.25-2.24(1H,m,CH 2 ),2.02-2.01(1H,m,CH 2 ),1.44-1.42(6H,m,CH 3 )。
Example 2 Synthesis of 2, 4-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-2)
In a 250 ml three-neck flask, 2.08 g of 2 are added after nitrogen purging4.02 g of phthaloyl chloride was added dropwise to 4-pentanediol, 100ml of THF, 2.15 ml of triethylamine and 0.15 g of potassium chloride at room temperature, and the mixture was stirred uniformly. After stirring the mixture for reaction for 2 hours, the mixture is heated and refluxed for reaction for 8 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.12-8.10(2H,m,＝CH),7.58-7.56(2H,m,ArH),4.15-4.13(2H,m,OCH),2.25-2.24(1H,m,CH 2 ),2.01-2.00(1H,m,CH 2 ),1.44-1.42(6H,m,CH 3 )。
Example 3 Synthesis of 2,3, 4-trimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-3)
In a 250 ml three-necked flask, after nitrogen gas was purged, 2.36 g of 3-methyl-2, 4-pentanediol, 100ml of THF, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 4.02 g of phthaloyl chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed for 8 hours at an elevated temperature. After concentration under reduced pressure, recrystallization from a mixed solution of ether/petroleum ether (1. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.12-8.11(2H,m,＝CH),7.57-7.56(2H,m,ArH),4.13-4.12(2H,m,OCH),2.84-2.83(1H,m,CH),2.01-2.00(1H,m,CH),1.44-1.42(6H,m,CH 3 ),1.05-1.03(3H,d,CH 3 )。
Example 4 Synthesis of 2, 4-diethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-4)
In a 250 ml three-necked flask, after nitrogen purging, 2.64 g of 3, 5-heptanediol, 120 ml of THF, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 4.02 g of phthaloyl chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 10 hours. After concentration under reduced pressure, concentration under reduced pressure and column chromatography separation, 1.67 g of a colorless viscous liquid was obtained (yield: 32%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.12-8.10(2H,m,＝CH),7.57-7.56(2H,m,ArH),3.96-3.96(2H,m,OCH),2.27-2.25(1H,m,CH 2 ),2.01-2.00(1H,m,CH 2 ),1.75-1.73(4H,m,CH 2 ),0.97-0.95(6H,m,CH 3 )。
Example 5 Synthesis of 2, 4-dimethyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-5)
In a 250 ml three-necked flask, after nitrogen purging, 2.64 g of 3-ethyl-2, 4-pentanediol, 50ml of acetonitrile, 70 ml of THF, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 4.02 g of phthaloyl chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 10 hours. After concentration under reduced pressure, the product was isolated by column chromatography to give 1.60 g (30% yield) of a colorless viscous liquid. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.12-8.10(2H,m,＝CH),7.57-7.56(2H,m,ArH),4.13-4.11(2H,m,OCH),2.66-2.65(1H,m,CH),1.40-1.37(6H,m,CH 3 ),1.28-1.26(2H,m,CH 2 ),0.97-0.95(3H,m,CH 3 )。
Example 6 Synthesis of 2, 4-dimethyl-7, 8- (2' -methylbenzo) [ g ] -1, 5-Dioxononane-6, 9-dione (FE-6)
In a 250 ml three-necked flask, after nitrogen purging, 2.08 g of 2, 4-pentanediol, 100ml of acetonitrile, 2.15 ml of triethylamine, and 0.35 g of potassium carbonate were added, and 4.25 g of 2-methylphthaloyl chloride was added dropwise at room temperature and stirred uniformly. After stirring the mixture for reaction for 2 hours, the mixture is heated and refluxed for reaction for 12 hours. After concentration under reduced pressure, the product was isolated by column chromatography to give 1.59 g (yield: 32%) of a colorless viscous liquid. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):7.93-7.92(1H,m,＝CH),7.46-7.45(1H,m,ArH),7.38-7.37(1H,m,ArH),4.13-4.11(2H,m,OCH),2.36-2.35(3H,m,CH 3 ),2.27-2.26(1H,m,CH 2 ),2.02-2.01(1H,m,CH 2 ),1.42-1.40(6H,m,CH 3 )。
Example Synthesis of 7, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-7)
In a 250 ml three-necked flask, after nitrogen purging, 2.64 g of 3, 5-heptanediol, 120 ml of THF, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 10 hours. After concentration under reduced pressure, the mixture is recrystallized by using an ether/petroleum ether (1Yellow crystals, dried in vacuo to yield 2.18 g of product (35% yield). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.34-8.33(2H,m,ArH),7.98-7.97(2H,m,ArH),7.45-7.44(2H,m,ArH),3.96-3.94(2H,m,OCH),2.26-2.25(1H,m,CH 2 ),2.02-2.01(1H,m,CH 2 ),1.75-1.73(4H,m,CH 2 ),0.98-0.96(6H,m,CH 3 )。
Example 8 Synthesis of 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-8)
In a 250 ml three-necked flask, after nitrogen purging, 2.64 g of 3-ethyl-2, 4-pentanediol, 120 ml of THF, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed for 10 hours at an elevated temperature. After concentration under reduced pressure, recrystallization from a mixed solution of ether/petroleum ether (1. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.35-8.34(2H,m,ArH),7.98-7.96(2H,m,ArH),7.47-7.46(2H,m,ArH),4.13-4.11(2H,m,OCH),2.66-2.65(1H,m,CH),1.40-1.37(6H,m,CH 3 ),1.29-1.27(2H,m,CH 2 ),0.97-0.95(3H,m,CH 3 )。
Example 9 Synthesis of 3-isopropyl-3-isopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-9)
In a 250 ml three-necked flask, after nitrogen gas was purged, 3.78 g of 2-isopropyl-2-isoamyl-1, 3-propanediol, 100ml of acetonitrile, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, 4.02 g of phthaloyl chloride was added dropwise at room temperature, and the mixture was stirred uniformly. After stirring for 6 hours, the reaction was refluxed for 16 hours at an elevated temperature. After concentration under reduced pressure and column chromatography, 1.96 g of a colorless viscous liquid was obtained (yield 31%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.10-8.09(2H,m,＝CH),7.57-7.55(2H,m,ArH),4.30-4.28(2H,m,OCH 2 ),4.06-4.04(2H,m,OCH 2 ),1.84-1.83(1H,m,CH),1.79-1.78(1H,m,CH),1.25-1.23(2H,m,CH 2 ),1.21-1.20(2H,m,CH 2 ),1.02-1.0 0(6H,m,CH 3 ),0.97-0.95(6H,m,CH 3 )。
Example 10 Synthesis of 3-isopropyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-10)
In a 250 ml three-necked flask, after nitrogen gas was purged, 3.78 g of 2-isopropyl-2-isoamyl-1, 3-propanediol, 100ml of acetonitrile, 2.15 ml of triethylamine and 0.35 g of potassium carbonate were added, and 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 18 hours. After concentration under reduced pressure and column chromatography, 2.20 g of a colorless viscous liquid was obtained (yield 30%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.33-8.32(2H,m,＝CH),7.97-7.95(2H,m,ArH),7.45-7.43(2H,m,ArH),4.31-4.29(2H,m,OCH 2 ),4.06-4.05(2H,m,OCH 2 ),1.84-1.83(1H,m,CH),1.80-1.79(1H,m,CH),1.25-1.23(2H,m,CH 2 ),1.21-1.20(2H,m,CH 2 ),1.03-1.0 0(6H,m,CH 3 ),0.96-0.93(6H,m,CH 3 )。
Preparation of solid component in catalyst and propylene polymerization
Example 11
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, the solution is cooled to below minus 25 ℃, and TiCl is dropwise added within 1 hour 4 60mL, slowly heating to 80 ℃, gradually precipitating a solid, adding 6mmol of the electron donor compound FE-1 with the structure, and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. 100mL of toluene was added, the temperature was raised to 110 ℃ and three washes were carried out for 10 minutes each. And adding 60mL of hexane, washing for three times, and drying in vacuum to obtain a catalyst solid 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 added 3 2.5mL of methylcyclohexyldimethoxysilane (CHMMS) 5mL of Al/Si (mol) =25 was added to the solid group prepared in the above exampleIntroducing 2.5L liquid propylene in 10mg and 1.2NL hydrogen, heating to 70 deg.C, maintaining the temperature for 1 hr, cooling, releasing pressure, and discharging to obtain PP resin, the results are shown in attached Table 1.
Example 12
In the same manner as in example 11, only the electron donor compound FE-1 was replaced with FE-2.
Example 13
In the same manner as in example 11, only the electron donor compound FE-1 was replaced with FE-3.
Example 14
In the same manner as in example 11, only the electron donor compound FE-1 was replaced with FE-4.
Example 15
In the same manner as in example 11, only the electron donor compound FE-1 was replaced with FE-5.
Example 16
In the same manner as in example 11, only the electron donor compound FE-1 was replaced with FE-6.
TABLE 1
Figure BDA0001811711830000161
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (23)

1. A cyclic compound of the formula I,
Figure FDA0003990958700000011
wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 30 An alkyl group;
a is CR 3 R 4 Wherein R is 3 And R 4 Same or different, independently selected from hydrogen, C 1 -C 30 An alkyl group;
ar is selected from
Figure FDA0003990958700000012
Wherein each R is 1 Independently selected from hydrogen, C 1 -C 10 An alkyl group;
x and Y are O.
2. A compound of claim 1, wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 20 An alkyl group.
3. A compound of claim 2, wherein R is 1 And R 2 Same or different, independently selected from hydrogen, C 1 -C 10 An alkyl group.
4. A compound of claim 3, wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 8 An alkyl group.
5. A compound according to any one of claims 1 to 4, wherein R is 3 And R 4 Same or different, independently selected from hydrogen, C 1 -C 20 An alkyl group.
6. A compound of claim 5, wherein R is 3 And R 4 Is the same as orDifferent from, independently selected from hydrogen, C 1 -C 10 An alkyl group.
7. The compound of any one of claims 1 to 4, wherein the compound is selected from the group consisting of 7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-dioxosunflower ring-6, 10-dione, 1, 5-dioxosunflower ring-6, 10-dione, 2, 3-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',10-dione, a mixture of these two or a mixture of two 8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dibutyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2,3, 4-trimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2, 4-diethyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2, 4-dipropyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 2, 4-dibutyl-3-methyl-7, 9-naphtho [1',9, 8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2,3, 4-triethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dipropyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dibutyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',10-dione, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-methyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-ethyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-butyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-pentyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-cyclopentyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-cyclohexyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione.
8. A process for the preparation of a compound according to any one of claims 1 to 7, comprising: reacting a compound represented by formula II with at least one compound selected from an acid halide compound represented by formula III, an acid anhydride compound represented by formula IV, a diacid compound represented by formula V, and an ester compound represented by formula VI to produce the cyclic compound represented by formula I,
Figure FDA0003990958700000031
wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 30 An alkyl group;
a is CR 3 R 4 Wherein R is 3 And R 4 Same or different, independently selected from hydrogen, C 1 -C 30 An alkyl group;
ar is selected from
Figure FDA0003990958700000041
Wherein each R is 1 Independently selected from hydrogen, C 1 -C 10 An alkyl group;
x and Y are O;
e is a halogen atom;
r is C 1 -C 20 An alkyl group.
9. The method of claim 8, wherein E is selected from the group consisting of fluorine, chlorine, bromine, and iodine; r is C 1 -C 10 An alkyl group.
10. The method of claim 9, wherein R is C 1 -C 5 An alkyl group.
11. The method of any one of claims 8-10, wherein R is 1 And R 2 Same or different, independently selected from hydrogen, C 1 -C 20 An alkyl group;
and/or, R 3 And R 4 The same or different, are independently selected from hydrogen and C 1 -C 20 An alkyl group.
12. The method of claim 11, wherein R is 1 And R 2 The same or different, are independently selected from hydrogen and C 1 -C 10 An alkyl group;
and/or, R 3 And R 4 The same or different, are independently selected from hydrogen and C 1 -C 10 An alkyl group.
13. The method of claim 12, wherein R is 1 And R 2 Same or different, independently selected from hydrogen, C 1 -C 8 An alkyl group.
14. The method of claim 13, wherein the cyclic compound of formula I is selected from the group consisting of 7,9-naphtho [1',8' -gh ] -1, 5-dioleyl ring-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioleyl ring-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioleyl ring-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioleyl ring-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane ring-6, 10-dione, 2, 3-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',10-dione, a mixture of these two or a mixture of two 8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dibutyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2,3, 4-trimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-diethyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dibutyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxetane-6, 10-dione, 2,3, 4-triethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxetane-6, 10-dione, 2, 4-dipropyl-3-ethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxetane-6, 10-dione, 2, 4-dibutyl-3-ethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxetane-6, 10-dione, 2-methyl-3, 4-diethyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxetane-6, 10-dione, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',10-dione 8'-gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxol-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-isoamyl-7, 9-naphtho [1',8'-gh ] -1, 5-dioxol-6, 10-dione, 3-methyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-ethyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-butyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-pentyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-cyclopentyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-cyclohexyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione.
15. A process according to any one of claims 8 to 10, characterised in that the reaction is carried out in a solvent in the presence of an acid or base and optionally an inorganic salt.
16. The method according to claim 15, wherein the acid is selected from inorganic or organic acids; the base is selected from inorganic or organic bases; the solvent is selected from the group consisting of alcohols, ethers, and hydrocarbon solvents; 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.
17. The method of claim 15, 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 the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, butyllithium, sodium aminyl, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, 1, 8-diazabicyclo [5,4,0] undec-7-ene, 1, 5-diazabicyclono-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, dichloromethane, chloroform, ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.
18. The method of claim 15, wherein the solvent is selected from the group consisting of diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF, and acetone.
19. Use of a cyclic compound of formula I according to any one of claims 1 to 7 in the preparation of an olefin polymerization catalyst.
20. Use of a cyclic compound of formula I according to any one of claims 1-7 in the polymerization of olefins.
21. Use according to claim 19 or claim 20, wherein the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
22. A catalyst component for the polymerization of olefins comprising a cyclic compound of formula I according to any of claims 1 to 7.
23. The catalyst component according to claim 22 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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