CN110950832A - Cyclic compound and preparation method and application thereof - Google Patents

Cyclic compound and preparation method and application thereof Download PDF

Info

Publication number
CN110950832A
CN110950832A CN201811123235.4A CN201811123235A CN110950832A CN 110950832 A CN110950832 A CN 110950832A CN 201811123235 A CN201811123235 A CN 201811123235A CN 110950832 A CN110950832 A CN 110950832A
Authority
CN
China
Prior art keywords
dione
benzo
dioxononane
naphtho
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811123235.4A
Other languages
Chinese (zh)
Other versions
CN110950832B (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201811123235.4A priority Critical patent/CN110950832B/en
Publication of CN110950832A publication Critical patent/CN110950832A/en
Application granted granted Critical
Publication of CN110950832B publication Critical patent/CN110950832B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • 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 hydrogen regulation sensitivity of the catalyst is good, the isotacticity 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 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 the conventional Ziegler-Natta catalysts, polyolefin catalysts are continuously updated with the development of electron donor compounds in the catalysts. Development of the catalyst from the first TiCl3AlCl3/AlEt2Cl system and second generation of TiCl3/AlEt2Cl system, magnesium chloride of the third generation as a carrier, monoester or aromatic dibasic acid ester as an internal electron donor, and TiCl with silane as an external electron donor4·ED·MgCl2/AlR3The 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). Phthalate ester compounds in European Union and other countriesDue to the environmental protection requirements, new electron donor compounds have been developed, such as 1, 3-diethers containing two ether groups [ e.g. 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene ], see U.S. Pat. No. 4,497,1937 and European patent EP0728769]And dibasic aliphatic carboxylic acid ester compounds (e.g. succinate, malonate, glutarate, etc., see patents WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), and 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 (CN102268109), hydrazide internal electron donor compounds (CN103539874), diamide internal electron donor compounds (US2017/0240667), carbamate internal electron donor compounds (WO2014/048861) and amide ester internal electron donor compounds of dow ring ball technology ltd (US2012322962), 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 is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic group being optionally selected from halogen atoms, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers of 0 to 6 such as 0, 1, 2,3,4, 5, 6, orR3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group.
According to a preferred embodiment of the invention, R1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group. According to some embodiments, R1And R2A 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, and a quinoline-containing groupAnd the like.
According to a preferred embodiment of the invention, R3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
According to a preferred embodiment of the invention, Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A 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 is1Independently selected from hydrogen, halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
In the present invention, C1-C10Examples of alkyl groups include C1-C6Alkyl 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, R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10An 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-dioxocanin-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocanin-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocanin-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocanin-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocanin-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-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-dioxosunflower ring-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',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-dioxol-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-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-dioxol-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-dioxoanecyclo-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 7, 8-benzo [ g ] -1, 5-dioxoanecyclo-6, 9-dione, 3-methyl-7, 8-benzo [ g ] -1, 5-dioxoanecyclo-6, 9-dione, 3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecane-6, 10-dione, 3-methyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecane-6, 10-dione, 3-ethyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-butyl-3-isopentyl-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',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-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, 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, a salt thereof, a hydrate thereof, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof, 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, a salt thereof, a hydrate thereof, a salt thereof, and a salt, 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, 2,3, 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-diamyl-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-dipentyl-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-dipentyl-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, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 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 is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic group being optionally selected from halogen atoms, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers from 0 to 6, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group;
e is a halogen atom, preferably fluorine, chlorine, bromine and iodine;
r is C1-C20Alkyl, preferably C1-C10Alkyl, more preferably C1-C5An alkyl group.
According to a preferred embodiment of the above preparation process, R1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group.
According to a preferred embodiment of the above preparation process, R3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
According to a preferred embodiment of the above preparation process, Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A heteroarylene group. In some embodiments, Ar is substituted or unsubstituted naphthylene. In some embodiments, Ar is selected from
Figure BDA0001811711830000081
Wherein each R is1Independently selected from hydrogen, halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
According to a preferred embodiment of the above preparation process, R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10An 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 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 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 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 can be selected for preparing the catalyst component for olefin polymerization of the present invention, and several methods for preparing the catalyst are exemplified 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 is present 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-mentioned catalyst.
The magnesium compound is selected from one of magnesium dihalide, hydrate or alcoholate of magnesium dihalide and derivative of magnesium dihalide whose 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 TiXm(OR1)4-mA compound of (1), wherein R1Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and m is 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 an oxide, a glycidyl ether and an internal ether of aliphatic olefin with 2-8 carbon atoms, diene or halogenated aliphatic olefin or diene. 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 CH2Catalyst system for the polymerization of olefins, where R is hydrogen or C1-C6Comprising 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 AlRI nX3-nA compound of (1), wherein RIIs hydrogen, alkyl with 1-20 carbon atoms, X is halogen, and 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 RII kSi(ORIII)4-kIn the formula, k is more than or equal to 0 and less than or equal to 3, RIIAnd RIIIIs the same or different alkyl, cycloalkyl, aryl, haloalkyl, RIIAnd may be a halogen or hydrogen atom. For example: trimethyl methoxysilane, trimethyl ethylOxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-tert-butyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, 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 in an operation combining 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 0-150 ℃, preferably 60-90 ℃.
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 invention, the pre-polymerization catalyst comprises a pre-polymer obtained by pre-polymerizing the solid catalyst component and olefin, and the pre-polymerization multiple is 0.1-1000 g of olefin polymer/g of the solid catalyst component.
The same α -olefin as previously described can be used for the prepolymerization, wherein the olefin to be prepolymerized is preferably ethylene or propylene, in particular it is particularly preferred to prepolymerize with ethylene or a mixture of one or more α -olefins in a balance of up to 20 mol% preferably the prepolymerized catalyst component has a degree of conversion of 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 ℃, preferably 0 to 50 ℃, in a liquid or in a 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 0.5 to 20g/g of catalyst component, batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01 to 10 MPa.
The catalysts of the invention are also suitable for the production of polyethylene and copolymers of ethylene with α -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 Synthesis of 12, 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, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 2.04 g of a product (yield 36%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH2),2.02-2.01(1H,m,CH2),1.44-1.42(6H,m,CH3)。
Example Synthesis of 22, 4-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione (FE-2)
In a 250 ml three-necked flask, after nitrogen purging, 2.08 g of 2, 4-pentanediol, 100ml of THF, 2.15 ml of triethylamine, and 0.15 g of potassium chloride were added, and 4.02 g of phthaloyl 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 8 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 1.74 g of a product (yield: 37%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH2),2.01-2.00(1H,m,CH2),1.44-1.42(6H,m,CH3)。
Example Synthesis of 32, 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 elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 1.70 g of a product (yield: 34%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH3),1.05-1.03(3H,d,CH3)。
Example Synthesis of 42, 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. Concentrating under reduced pressureAfter concentration under reduced pressure, the mixture was subjected to column chromatography to obtain 1.67 g of a colorless viscous liquid (yield: 32%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH2),2.01-2.00(1H,m,CH2),1.75-1.73(4H,m,CH2),0.97-0.95(6H,m,CH3)。
Example Synthesis of 52, 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 and column chromatography, 1.60 g of a colorless viscous liquid was obtained (yield 30%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH3),1.28-1.26(2H,m,CH2),0.97-0.95(3H,m,CH3)。
Example Synthesis of 62, 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 and column chromatography, 1.59 g of a colorless viscous liquid was obtained (yield: 32%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH3),2.27-2.26(1H,m,CH2),2.02-2.01(1H,m,CH2),1.42-1.40(6H,m,CH3)。
Example Synthesis of 72, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-7)
At one 250 mmIn a three-necked flask, 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 after purging with nitrogen, 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature, and the mixture was stirred uniformly. After stirring for 4 hours, the reaction was refluxed at elevated temperature for 10 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 2.18 g of a product (yield: 35%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH2),2.02-2.01(1H,m,CH2),1.75-1.73(4H,m,CH2),0.98-0.96(6H,m,CH3)。
Example Synthesis of 82, 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 at elevated temperature for 10 hours. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 2.18 g of a product (yield: 35%).1H-NMR(δ,ppm,TMS,CDCl3):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,CH3),1.29-1.27(2H,m,CH2),0.97-0.95(3H,m,CH3)。
Example Synthesis of 93-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%).1H-NMR(δ,ppm,TMS,CDCl3):8.10-8.09(2H,m,＝CH),7.57-7.55(2H,m,ArH),4.30-4.28(2H,m,OCH2),4.06-4.04(2H,m,OCH2),1.84-1.83(1H,m,CH),1.79-1.78(1H,m,CH),1.25-1.23(2H,m,CH2),1.21-1.20(2H,m,CH2),1.02-1.00(6H,m,CH3),0.97-0.95(6H,m,CH3)。
Example 103 Synthesis of isopropyl-3-isopentyl-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, 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature, and the mixture was 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%).1H-NMR(δ,ppm,TMS,CDCl3):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,OCH2),4.06-4.05(2H,m,OCH2),1.84-1.83(1H,m,CH),1.80-1.79(1H,m,CH),1.25-1.23(2H,m,CH2),1.21-1.20(2H,m,CH2),1.03-1.0 0(6H,m,CH3),0.96-0.93(6H,m,CH3)。
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 the temperature below minus 25 ℃, and TiCl is dropwise added within 1 hour460mL, slowly heating to 80 ℃, gradually precipitating the 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. Adding 60mL of hexane, washing for three times, and drying in vacuum to obtain the productTo the solid component of the catalyst.
(2) Polymerization of propylene
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of methylcyclohexyldimethoxysilane (CHMMS)5mL of Al/Si (mol): 25, 10mg of the solid fraction prepared in the above example and 1.2NL of hydrogen gas were added thereto, and 2.5L of liquid propylene was introduced, and the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, followed by cooling, pressure release and discharge to obtain a PP resin, the results of which are shown in 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 with reference to exemplary embodiments, but 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 (10)

1. A cyclic compound of the formula I,
Figure FDA0001811711820000011
wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR 8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic group being optionally selected from halogen atoms, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers of 0 to 6, such as 0, 1, 2,3,4, 5 or 6, and m, n and p are not simultaneously 0, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group.
2. A compound of claim 1, wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group.
3. A compound according to claim 1 or 2, wherein R is3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
4. A compound according to any one of claims 1 to 3 wherein Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A heteroarylene group; and/or R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10An alkyl group; more preferably, Ar is selected from
Figure FDA0001811711820000021
Wherein each R is1Independently selected from hydrogen, halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
5. 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-dioxoanecyclo-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoanecyclo-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-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-dioxosunflower ring-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',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-dioxol-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-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-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',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-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',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxorane-6, 10-dione, 7, 8-benzo [ g ] -1, 5-dioxorane-6, 9-dione, 3-methyl-7, 8-benzo [ g ] -1, 5-dioxorane-6, 9-dione, 2-methyl-7, 8-dioxorane-6, 9-dione, and mixtures thereof, 3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecane-6, 10-dione, 3-methyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecane-6, 10-dione, a salt thereof, and a pharmaceutically acceptable carrier, 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-dioxol-6, 10-dione, 3-cyclohexyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoleno-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoleno-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoleno [ 6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxoleno-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, 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, a salt thereof, a hydrate thereof, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof, 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, a salt thereof, a hydrate thereof, a salt thereof, and a salt, 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, 2,3, 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-diamyl-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-dipentyl-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-dipentyl-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, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione.
6. A process for the preparation of a compound according to any one of claims 1 to 5, 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 FDA0001811711820000051
wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30Hydrogen on carbon of aromatic radical optionallyIs selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers of 0 to 6, such as 0, 1, 2,3,4, 5 or 6, and m, n and p are not simultaneously 0, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group;
e is a halogen atom, preferably fluorine, chlorine, bromine and iodine;
r is C1-C20Alkyl, preferably C1-C10Alkyl, more preferably C1-C5An alkyl group.
7. The process according to claim 6, characterized in that the reaction is carried out in a solvent in the presence of an acid or a base and optionally an inorganic salt.
8. The process according to claim 7, characterized in that 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; 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 aminide, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazabicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclono-5-ene) and pyrazole; 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 double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, more preferably from the group consisting of diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF and acetone; 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.
9. Use of a cyclic compound of formula I according to any one of claims 1 to 5 in the preparation of a catalyst for the polymerization of olefins or in the polymerization of olefins, preferably the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
10. A catalyst component for the polymerization of olefins comprising a cyclic compound of formula I according to any of claims 1 to 5, preferably the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
CN201811123235.4A 2018-09-26 2018-09-26 Cyclic compound and preparation method and application thereof Active CN110950832B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811123235.4A CN110950832B (en) 2018-09-26 2018-09-26 Cyclic compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811123235.4A CN110950832B (en) 2018-09-26 2018-09-26 Cyclic compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110950832A true CN110950832A (en) 2020-04-03
CN110950832B CN110950832B (en) 2023-03-28

Family

ID=69964468

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811123235.4A Active CN110950832B (en) 2018-09-26 2018-09-26 Cyclic compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110950832B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1278837A (en) * 1997-09-15 2001-01-03 伊斯曼化学公司 Monoesters and macrocyclic diester of phthalic acid and synthesis thereof
US20050239636A1 (en) * 2002-02-07 2005-10-27 Mingzhi Gao Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1278837A (en) * 1997-09-15 2001-01-03 伊斯曼化学公司 Monoesters and macrocyclic diester of phthalic acid and synthesis thereof
US20050239636A1 (en) * 2002-02-07 2005-10-27 Mingzhi Gao Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ACS: "RN号：1089921-45-8等", 《STN数据库结构检索》 *
EHRHART, WENDELL A.: "Synthesis of macrocyclic o-phthalate esters from the corresponding polyesters", 《JOURNAL OF ORGANIC CHEMISTRY》 *
LE LIU, ET AL.: "Silver carboxylate promoted lactonization: a general method applicable to prepare medium and large-sized lactones without high dilution or slow addition", 《TETRAHEDRON》 *

Also Published As

Publication number Publication date
CN110950832B (en) 2023-03-28

Similar Documents

Publication Publication Date Title
JP4769246B2 (en) Olefin polymerization catalyst component and catalyst containing the same
CN107868152B (en) Catalyst component for olefin polymerization, catalyst and application thereof
WO2014187323A1 (en) Catalyst component for use in olefin polymerization reaction, catalyst, and application
CN101165073A (en) Catalyst component used for olefin polymerization reaction and catalyst thereof
CN107868153B (en) Catalyst component for olefin polymerization, catalyst and application thereof
CN105085726B (en) A kind of catalytic component and catalyst for olefinic polymerization
CN107129549A (en) Ingredient of solid catalyst, catalyst and application for olefinic polymerization
CN110950985B (en) Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN110950832B (en) Cyclic compound and preparation method and application thereof
CN110950986B (en) Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN110950982B (en) Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN110950984B (en) Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN110950983B (en) Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN113929797B (en) Solid catalyst component and catalyst system for producing polymers
CN110950831B (en) Cyclic compound and preparation method and application thereof
CN110950830B (en) Cyclic compound and preparation method and application thereof
CN109553704B (en) Catalyst component for olefin polymerization, catalyst and application
CN109553706B (en) Catalyst component for olefin polymerization, catalyst and application
CN109553707B (en) Catalyst component for olefin polymerization, catalyst and application
CN105085729B (en) A kind of catalytic component and catalyst for olefinic polymerization
CN105085730B (en) It is a kind of for the catalytic component of olefinic polymerization, preparation method and its catalyst
CN112759674B (en) Catalyst component for olefin polymerization, catalyst and application thereof
CN109553703B (en) Catalyst component for olefin polymerization and preparation method thereof
CN110903417B (en) Solid catalyst component for olefin polymerization, catalyst and application thereof
CN101172965B (en) Piperidine ester compounds for producing catalyst for polymerization of olefins and catalyst thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant