阅读说明：本技术 新型亚胺酯类化合物及其制备方法 (Novel imidate compound and preparation method thereof ) 是由 王军 高明智 马晶 刘海涛 马吉星 蔡晓霞 何世雄 刘文蕊 李昌秀 胡建军 许景 于 2019-10-21 设计创作，主要内容包括：本发明公开一种式I所示的亚胺酯类化合物及其制备方法。所述亚胺酯类化合物可以作为烯烃聚合反应催化剂的内给电子体化合物使用,并且催化剂的氢调敏感性好,所得聚丙烯树脂分子量分布宽。(The invention discloses an imine ester compound shown in a formula I and a preparation method thereof. The imine ester compound can be used as an internal electron donor compound of an olefin polymerization catalyst, the hydrogen regulation sensitivity of the catalyst is good, and the molecular weight distribution of the obtained polypropylene resin is wide.)

1. An imidate compound having a structure represented by formula I:

in the formula I, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₃₀Alkoxy, and R₁And R₂Not hydrogen at the same time; or R₁And R₂Linking to form a ring;

r is selected from C containing or not containing substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀A heterocyclic group of (A), a halogen atom, a hydroxyl group, C with or without a substituent₁-C₃₀Alkoxy, C with or without substituents₁-C₃₀Acyloxy groups and amino groups with or without substituents; r is selected from C containing or not containing substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent₁-C₃₀Alkoxy and amino with or without substituents;

a is C with or without substituents₁-C₃₀Alkylene or hetero atoms, preferably C with or without substituents₁-C₃₀Alkylene, C with or without substituents₆-C₃₀Arylene, C with or without substituents₄-C₃₀A heteroarylene group, or a combination thereof.

2. The compound of claim 1, wherein said substituent is selected from the group consisting of halogen, hydroxy, amino, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl radical, C₇-C₂₀Alkylaryl group, C₁-C₁₀Alkyl and C₁-C₂₀Alkoxy, preferably selected from halogen, hydroxy, amino, phenyl, naphthyl, benzyl, phenethyl, C₁-C₆Alkyl-substituted phenyl, C₁-C₁₀Alkyl and C₁-C₂₀Alkoxy, more preferably selected from fluorine, chlorine, bromine, iodine, hydroxyl, amino, phenyl, naphthyl, benzyl, phenethyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and n-hexoxy.

3. A compound according to claim 1 or 2, wherein R is₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₂₀Alkyl, C with or without substituents₂-C₂₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₄-C₂₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₂₀An alkoxy group;

preferably, R₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₁₀Alkyl, C with or without substituents₂-C₁₀Alkenyl, C with or without substituents₆-C₁₅Aryl, C with or without substituents₄-C₅₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₁₀An alkoxy group;

more preferably, R₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₁₀Alkyl and C with or without substituents₆-C₁₅An aryl group;

further preferably, R₁And R₂Each independently is C with or without substituent₁-C₁₀Straight-chain alkyl, C with or without substituents₃-C₁₀Branched alkyl, C with or without substituents₃-C₁₀Cycloalkyl or phenyl with or without substituents.

4. A compound according to any one of claims 1 to 3, wherein R is selected from C with or without substituents₁-C₁₀Alkyl and C with or without substituents₆-C₁₅An aryl group; preferably, R is C with or without substituents₁-C₁₀Straight-chain alkyl, C with or without substituents₃-C₁₀Branched alkyl, C with or without substituents₃-C₁₀Cycloalkyl or phenyl with or without substituents.

5. The compound of any one of claims 1-4, wherein A is C with or without substituents₁-C₂₀Alkylene radical, C₆-C₂₀Arylene radical, C₄-C₂₀A heteroarylene group, a heteroatom, or a combination thereof;

preferably, A is C with or without substituents₁-C₁₀Alkylene radical, C₆-C₁₀Arylene radical, C₄-C₁₀A heteroarylene group or a combination thereof; more preferably, A is C with or without substituents₁-C₈Alkylene, further preferably A is C₁-C₈Alkylene (e.g. methylene, ethylene, propylene, butylene, pentylene or hexylene), C₁-C₆Alkyl substituted C₁-C₈Alkylene or C₁-C₆Alkoxy-substituted C₁-C₈An alkylene group.

6. The compound according to any one of claims 1 to 5, wherein the imido ester compound is selected from the group consisting of (2-phenyliminoethyl) benzoate, [2- (2-methyl) phenyliminoethyl benzoate, [2- (3-methyl) phenyliminoethyl benzoate ], [2- (4-methyl) phenyliminoethyl benzoate, [2- (2-ethyl) phenyliminoethyl benzoate ], [2- (3-ethyl) phenyliminoethyl benzoate ], [2- (4-ethyl) phenyliminoethyl benzoate ], [2- (2-propyl) phenyliminoethyl benzoate ], [2- (3-propyl) phenyliminoethyl benzoate ], [2- (2-butyl) phenyliminoethyl benzoate ], [, Benzoic acid [2- (3-butyl) phenyliminoethyl ester ], benzoic acid [2- (3-methoxy) phenyliminoethyl ester ], benzoic acid [2- (4-methoxy) phenyliminoethyl ester ], benzoic acid [2- (3-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (4-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (2-hydroxy) phenyliminoethyl ester ], benzoic acid [2- (2, 4-dimethyl) phenyliminoethyl ester ], [2- (2, 6-dimethyl) phenyliminoethyl ester ], benzoic acid [2- (2,4, 6-trimethyl) phenyliminoethyl ester ], benzoic acid [2- (2, 6-diisopropyl) phenyliminoethyl ester ], [2- (2, 6-diisopropyl) phenyliminoethyl ester ], [2- (3, 5-di-tert-butyl) phenyliminoethyl benzoate ], [ 2-ethyliminoethyl benzoate ], [ 2-propyliminoethyl benzoate ], [ 2-butyliminoethyl benzoate ], [ 2-pentyliminoethyl benzoate ], [ 2-hexyliminoethyl benzoate ], 3-phenyliminopropyl benzoate, [3- (2-methyl) phenyliminopropyl benzoate ], 3- (3-methyl) phenyliminopropyl benzoate, [3- (4-methyl) phenyliminopropyl benzoate ], 3- (2-ethyl) phenyliminopropyl benzoate, 3- (3-ethyl) phenyliminopropyl benzoate, 3- (4-ethyl) phenyliminopropyl benzoate, [3- (2-propyl) phenyliminopropyl benzoate ], [3- (3-propyl) phenyliminopropyl benzoate ], [3- (2-butyl) phenyliminopropyl benzoate ], [3- (3-butyl) phenyliminopropyl benzoate ], [3- (4-butyl) phenyliminopropyl benzoate ], [3- (3-methoxy) phenyliminopropyl benzoate ], [3- (4-methoxy) phenyliminopropyl benzoate ], [3- (3-ethoxy) phenyliminopropyl benzoate ], [3- (4-ethoxy) phenyliminopropyl benzoate ], [3- (2-hydroxy) phenyliminopropyl benzoate ], [3- (3-hydroxy) phenyliminopropyl benzoate ], [, [3- (4-hydroxy) phenyliminopropyl benzoate ], [3- (2, 4-dimethyl) phenyliminopropyl benzoate ], [3- (2,4, 6-trimethyl) phenyliminopropyl benzoate ], [3- (3, 5-di-tert-butyl) phenyliminopropyl benzoate ], [3- (2, 6-dimethyl) phenyliminopropyl benzoate ], [3- (2, 6-diisopropyl) phenyliminopropyl benzoate ], [ 3-ethyliminopropyl benzoate ], [ 3-propyliminopropyl benzoate ], [ 3-butyliminopropyl benzoate ], [ 3-pentyliminopropyl benzoate ], [ 3-hexyliminopropyl benzoate ], 4-phenylimino-2-pentyl benzoate-, Benzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], (benzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], Benzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], (benzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], Benzoic acid [4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], benzoic acid [ 4-ethylimino-2-propyl ester ], benzoic acid [ 4-propylimino-2-pentyl ester ], benzoic acid [ 4-butylimino-2-pentyl ester ], benzoic acid [ 4-pentylimino-2-pentyl ester ], benzoic acid [ 4-hexylimino-2-pentyl ester ], benzoic acid [ 4-heptylimino-2-pentyl ester ], benzoic acid [ 4-octylimino-2-pentyl ester ], benzoic acid (3-methyl-4-phenylimino-2-pentyl ester), Benzoic acid [ 3-ethyl-4- (2-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-propyl-4- (2-propyl) phenylimino-2-pentyl ester ], [ 3-propyl-4- (2-propyl) phenylimino-2-pentyl ester ], Benzoic acid [ 3-butyl-4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (2-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethoxy) phenylimino-2-pentyl ester ], [ 3-methyl-4- (4-ethoxy) phenylimino-2-pentyl ester ], Benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], benzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], [ 3-methyl-4-propylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-methylbenzoic acid (4-phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], (methyl-4-phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], (methyl-benzoic acid-4- (4-propyl) phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], (methyl-benzoic acid-4- (2, 4-dimethyl) phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester, 4-methylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-methylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ] 4-butylbenzoic acid (4-phenylimino-2-pentyl ester), 4-butylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ] 4-butylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], (a salt thereof, a base, a, 4-butylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], (a salt thereof, a solvate thereof, a salt thereof, a hydrate thereof, and a pharmaceutically acceptable salt thereof, 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-butylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], (a-ethyl-4-hexylimino-2-pentyl ester), 4-butylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-propylbenzoic acid (4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ] 4-propylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], (methyl) ethyl-4-propylbenzoic acid, methyl-4-phenylimino-2-pentyl ester, and mixtures thereof, 4-propylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester, 4-propylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-propylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-pentaimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], propionic acid (4-phenylimino-2-pentyl ester), propionic acid [4- (2-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (3-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (4-methyl) phenylimino-2-pentyl ester ], (4-methyl) phenylimino-2-pentyl ester), [4- (2-ethyl) phenylimino-2-pentyl propionate ], [4- (3-ethyl) phenylimino-2-pentyl propionate ], [4- (4-ethyl) phenylimino-2-pentyl propionate ], [4- (2-propyl) phenylimino-2-pentyl propionate ], [4- (3-propyl) phenylimino-2-pentyl propionate ], [4- (4-propyl) phenylimino-2-pentyl propionate ], [4- (2-butyl) phenylimino-2-pentyl propionate ], [4- (4-butyl) phenylimino-2-pentyl propionate ], and [4- (3-methoxy) phenylimino-2-pentyl propionate ], Propionic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], propionic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], propionic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], propionic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) benzimido-2-pentyl propionate, [ 3-methyl-4- (2, 6-dimethyl) benzimido-2-pentyl propionate ], [ 3-methyl-4- (2, 6-diisopropyl) benzimido-2-pentyl propionate ], [ 3-methyl-4-ethylimido-2-propyl propionate ], [ 3-methyl-4-propimido-2-pentyl propionate ], [ 3-ethyl-4-butylimino-2-pentyl propionate ], [ 3-ethyl-4-pentylimino-2-pentyl propionate ], [ 3-ethyl-4-hexylimino-2-pentyl propionate ], 3-ethyl-4-heptylimino-2-pentyl propionate, [ 3-methyl-4-octylimino-2-pentyl propionate ], valeric acid (4-phenylimino-2-pentyl ester), valeric acid [4- (2-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethyl) phenylimino-2-pentyl ester ], [4- (4-ethyl) phenylimino-2-pentyl ester ], Valeric acid [4- (2-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-butyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-butyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], [4- (4-ethoxy) phenylimino-2-pentyl ester ], Valeric acid [4- (2, 4-dimethyl) phthalimido-2-pentyl ester ], valeric acid [4- (2,4, 6-trimethyl) phthalimido-2-pentyl ester ], valeric acid [4- (3, 5-di-tert-butyl) phthalimido-2-pentyl ester ], valeric acid [ 3-methyl-4- (2,4, 6-trimethyl) phthalimido-2-pentyl ester ], valeric acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phthalimido-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-dimethyl) phthalimido-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-diisopropyl) phthalimido-2-pentyl ester ], [ 3-methyl-4-ethylimino-2-propyl valerate ], [ 3-methyl-4-propylimino-2-pentyl valerate ], [ 3-ethyl-4-butylimino-2-pentyl valerate ], [ 3-ethyl-4-pentylimino-2-pentyl valerate ], [ 3-ethyl-4-hexylimino-2-pentyl valerate ], [ 3-ethyl-4-heptylimino-2-pentyl valerate ], [ 3-methyl-4-octylimino-2-pentyl valerate ], 4-methylbenzoic acid (3-phenylimino-pentyl ester), 4-methylbenzoic acid [ 3-phenylimino-pentyl ester ], [, 4-methylbenzoic acid [3- (3-methyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-methyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-ethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-ethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-ethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminopentyl ester ], (N-methyl-benzoic acid [3- (2-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2, 4-dimethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopentyl ester ], benzoic acid (4-phenyliminobutyl ester), benzoic acid [4- (2-methyl) phenyliminobutyl ester ], benzoic acid [4- (3-methyl) phenyliminobutyl ester ], benzoic acid [4- (4-methyl) phenyliminobutyl ester ], benzoic acid [4- (2-ethyl) phenyliminobutyl ester ], benzoic acid [4- (3-ethyl) phenyliminobutyl ester ], benzoic acid [4- (4-ethyl) phenyliminobutyl ester ], benzoic acid [4- (2-propyl) phenyliminobutyl ester ], benzoic acid [4- (3-propyl) phenyliminobutyl ester ], benzoic acid [4- (4-propyl) phenyliminobutyl ester ], benzoic acid [4- (2-butyl) phenyliminobutyl ester ], (benzoic acid [4- (2-butyl) phenyliminobutyl ester ]), Benzoic acid [4- (3-butyl) phenyliminobutyl ester ], benzoic acid [4- (3-methoxy) phenyliminobutyl ester ], benzoic acid [4- (4-methoxy) phenyliminobutyl ester ], benzoic acid [4- (3-ethoxy) phenyliminobutyl ester ], benzoic acid [4- (4-ethoxy) phenyliminobutyl ester ], benzoic acid [4- (2-hydroxy) iminobutyl ester ], benzoic acid [4- (3-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (4-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ester, ] benzoic acid [4- (2,4, 6-trimethyl) phenyliminobutyl, benzoic acid [4- (3, 5-di-tert-butyl) phenyliminobutyl ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ], benzoic acid [ 4-ethyliminobutyl ], benzoic acid [ 4-propyliminobutyl ], benzoic acid [ 4-butyliminobutyl ], benzoic acid [ 4-pentyliminobutyl ], benzoic acid [ 4-hexyliminobutyl ], benzoic acid [ 4-heptiminobutyl ], benzoic acid [ 4-octyliminobutyl ], benzoic acid (3-phenyliminobutyl), benzoic acid [3- (2-methyl) phenyliminobutyl ], benzoic acid [3- (3-methyl) phenyliminobutyl ], (N-methyl) phenyliminobutyl) benzoate, Benzoic acid [3- (4-methyl) phenyliminobutyl ester ], benzoic acid [3- (2-ethyl) phenyliminobutyl ester ], benzoic acid [3- (3-ethyl) phenyliminobutyl ester ], benzoic acid [3- (4-ethyl) phenyliminobutyl ester ], benzoic acid [3- (2-propyl) phenyliminobutyl ester ], benzoic acid [3- (3-propyl) phenyliminobutyl ester ], benzoic acid [3- (4-propyl) phenyliminobutyl ester ], benzoic acid [3- (2-butyl) phenyliminobutyl ester ], benzoic acid [3- (3-methoxy) phenyliminobutyl ester ], benzoic acid [3- (4-methoxy) phenyliminobutyl ester ] (I), Benzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], benzoic acid [3- (2-hydroxy) phenyliminobutyl ester ], benzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], benzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ester ], benzoic acid [ 3-ethyliminobutyl ester ], benzoic acid [ 3-propyliminobutyl ester ], benzoic acid [ 3-butyliminobutyl ester ], benzoic acid [ 3-pentyliminobutyl ester ], benzoic acid [ 3-hexyliminobutyl ester ], (a) benzoic acid, Benzoic acid [ 3-heptyliminobutyl ] benzoate [ 4-nonyliminobutyl ] benzoate, 4-methylbenzoic acid (3-phenyliminobutyl) 4-methylbenzoic acid [3- (2-methyl) phenyliminobutyl ] benzoate, 4-methylbenzoic acid [3- (3-methyl) phenyliminobutyl ] 4-methylbenzoic acid [3- (4-methyl) phenyliminobutyl ] 4-methylbenzoic acid [3- (2-ethyl) phenyliminobutyl ] 4-methylbenzoic acid [3- (3-ethyl) phenyliminobutyl ] 4-methylbenzoic acid [3- (4-ethyl) phenyliminobutyl ] 4-methylbenzoic acid [3- (2-propyl) phenyliminobutyl ] 4-methylbenzoic acid, 4-methylbenzoic acid [3- (3-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], (N-methyl-benzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], (N-methyl-benzoic acid [3- (4-, 4-methylbenzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ester ], 4-methylbenzoic acid [ 3-ethyliminobutyl ester ], 4-methylbenzoic acid [ 3-propyliminobutyl ester ], benzoic acid [ 3-butyliminobutyl ester ], 4-methylbenzoic acid [ 3-pentyliminobutyl ester ], 4-methylbenzoic acid [ 3-hexyliminobutyl ester ], 4-methylbenzoic acid [ 4-nonyiminobutyl ] 4-methylbenzoic acid [ 3-sunflower iminobutyl ] 4-methylbenzoic acid [ 3-phenyliminopropyl ] 4-propylbenzoic acid [3- (2-methyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (3-methyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (4-methyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (2-ethyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (3-ethyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (4-ethyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (2-propyl) phenyliminopropyl ] 4-propylbenzoic acid, 4-propylbenzoic acid [3- (3-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], (N-propylbenzoic acid, N-propyl, 4-butylbenzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl ester ], 4-propylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ester ], 4-propylbenzoic acid [ 3-ethyliminobutyl ester ], 4-propylbenzoic acid [ 3-propyliminobutyl ester ], 4-butylbenzoic acid [ 3-butyliminobutyl ester ], 4-propylbenzoic acid [ 3-pentyliminobutyl ester ], 4-butylbenzoic acid [ 3-hexyliminobutyl ester ], 4-butylbenzoic acid [ 4-nonyliminobutyl ester ], 4-butylbenzoic acid [ 3-decyliminylbutyl ester ], 4-methoxybenzoic acid (3-phenyliminopropyl ester), 4-methoxybenzoic acid [3- (2-methyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (3-methyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (4-methyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2-ethyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (3-ethyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (4-ethyl) phenyliminopropyl ester ], (methyl-4-ethylmethyl) phenyliminopropyl ester), 4-methoxybenzoic acid [3- (2-propyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-propyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (4-propyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (2-butyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-butyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (4-butyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-methoxy) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-ethoxy) phenylimino-propyl ester ], (methyl-ethyl-propyl ester) and (methyl-ethyl-propyl) phenyl-imino-propyl ester) 4-methoxybenzoic acid, 4-methoxybenzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [ 3-ethyliminobutyl ester ], 4-methoxybenzoic acid [ 3-propyliminobutyl ester ], 4-methoxybenzoic acid [ 3-butyliminobutyl ester ], 4-methoxybenzoic acid [ 3-pentyliminobutyl ] ester, 4-methoxybenzoic acid [ 3-hexyliminobutyl ] ester, 4-nonyiiminobutyl ] 4-methoxybenzoate [ 3-decyliminobutyl ] 4-methoxybenzoate, 3-phenyliminopropyl acetate [3- (2-methyl) phenyliminopropyl ] acetate [3- (3-methyl) phenyliminopropyl ] acetate [3- (4-methyl) phenyliminopropyl ] acetate [3- (2-ethyl) phenyliminopropyl ] acetate [3- (3-ethyl) phenyliminopropyl ] acetate [3- (4-ethyl) phenyliminopropyl ] acetate [3- (2-propyl) phenyliminopropyl ] acetate, Acetic acid [3- (3-propyl) phenylimino-propyl ester ], acetic acid [3- (4-propyl) phenylimino-propyl ester ], acetic acid [3- (2-butyl) phenylimino-propyl ester ], acetic acid [3- (3-butyl) phenylimino-propyl ester ], acetic acid [3- (4-butyl) phenylimino-propyl ester ], acetic acid [3- (3-methoxy) phenylimino-propyl ester ], acetic acid [3- (4-methoxy) phenylimino-propyl ester ], acetic acid [3- (3-ethoxy) phenylimino-propyl ester ], acetic acid [3- (4-ethoxy) phenylimino-propyl ester ], acetic acid [3- (2, 4-dimethyl) phenylimino-propyl ester ], acetic acid [3- (2,4, 6-trimethyl) phenylimino-propyl ester ], [3- (3, 5-di-tert-butyl) phenyliminopropyl acetate ], [3- (2, 6-dimethyl) phenyliminopropyl acetate ], [3- (2, 6-diisopropyl) phenyliminopropyl acetate ], [ 3-ethyliminopropyl acetate ], [ 3-propyliminopropyl acetate ], [ 3-butyliminopropyl acetate ], [ 3-pentyliminopropyl acetate ], [ 3-hexyliminopropyl acetate ], [ 3-heptiminopropyl acetate ], [ 4-noniminopropyl acetate ], 3-phenyliminopropyl propionate, 3- (2-methyl) phenyliminopropyl propionate ], 3- (2-methyl) phenyliminopropyl propionate, 3- (2-methyl) phenyliminopropyl butyrate ], 3- (2-methyl) phenyliminopropyl butyrate, Butyric acid [3- (4-methyl) phenyliminopropyl ester, valeric acid [3- (2-methyl) phenyliminopropyl ester ], valeric acid [3- (4-methyl) phenyliminopropyl ester ], caproic acid [3- (4-methyl) phenyliminopropyl ester, heptanoic acid [3- (2-methyl) phenyliminopropyl ester ], caprylic acid [3- (4-methyl) phenyliminopropyl ester ], propionic acid [3- (2-ethyl) phenyliminopropyl ester ], propionic acid [3- (3-ethyl) phenyliminopropyl ester ], propionic acid [3- (4-ethyl) phenyliminopropyl ester ], propionic acid [3- (2-propyl) phenyliminopropyl ester ], propionic acid [3- (3-propyl) phenyliminopropyl ester ], propionic acid [3- (4-propyl) phenyliminopropyl ester ], (a) propionic acid [3- (4-propyl) phenyliminopropyl ester ], (a salt thereof, 3- (2-butyl) phenyliminopropyl propionate, 3- (3-butyl) phenyliminopropyl propionate, 3- (4-butyl) phenyliminopropyl propionate, 3- (3-methoxy) phenyliminopropyl propionate, 3- (4-methoxy) phenyliminopropyl propionate, 3- (3-ethoxy) phenyliminopropyl propionate, 3- (4-ethoxy) phenyliminopropyl propionate, 3- (2, 4-dimethyl) phenyliminopropyl propionate, 3- (2,4, 6-trimethyl) phenyliminopropyl propionate, 3- (3, 5-di-tert-butyl) phenyliminopropyl propionate, One or more of cyclohexanoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 2-naphthoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], propionic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], propionic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], propionic acid [ 3-ethyliminopropyl ester ], propionic acid [ 3-propyliminopropyl ester ], acetic acid [ 3-butyliminopropyl ester ], propionic acid [ 3-pentyliminopropyl ester ], propionic acid [ 3-hexyliminopropyl ester ], propionic acid [ 3-heptiminopropyl ester ], and propionic acid [ 4-noniminopropyl ester ].

7. A method for producing the imidate compound according to any one of claims 1 to 6, comprising:

reacting a compound of formula IIA with RCOX or (RCO)₂O reacts to generate the imine ester compound shown in the formula I,

wherein R in the formula IIA₁、R₂And A is as defined for formula I, RCOX or (RCO)₂R in O is as defined for formula I, and X is selected from halogen, preferably from chlorine, bromine and iodine.

8. The preparation method according to claim 7, characterized in that the reaction is carried out in the presence of an acid or a base, the acid being 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, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid; the base is selected from inorganic or organic bases, preferably from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, diethylamine, ethylenediamine, 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.

9. The process according to claim 7 or 8, characterized in that the reaction is carried out in a solvent selected from ethers and hydrocarbons, preferably from diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether and diglycidyl ether.

10. Use of a compound according to any one of claims 1 to 6 in the polymerisation of olefins.

Technical Field

The invention relates to a novel imine ester compound and a preparation method thereof.

Background

For the conventional Ziegler-Natta catalyst, the polyolefin catalyst is continuously updated with the development of electron donor compounds in the catalyst, and the process technology of polypropylene is improved. Catalyst development from first/second generation of TiCl₃The magnesium chloride from the alkyl aluminum system to the third generation is used as a carrier, TiCl₄Adding TiCl taking monoester or aromatic dibasic acid ester as internal electron donor and silane as external electron donor as active center₄·ED·MgCl₂/AlR₃The ED system, the catalytic activity of the catalyst for olefin polymerization and the high isotacticity of the obtained polypropylene are greatly improved. In the prior art, a 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 essential components in the catalyst component. Various electron donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyethers, alcohols, amines and derivatives thereof, among which aromatic dicarboxylic acid esters (such as di-n-butyl phthalate or o-butyl phthalate) are more commonly usedDiisobutyl phthalate, etc., see US 4784983).

Recently, many novel internal electron donor compounds containing nitrogen atom structure have appeared, such as maleic amide internal electron donor compound (CN102268109) and hydrazide structure electron donor compounds (CN103539874 and CN103694385), diamide structure internal electron donor compound (US2020/0240667), diamine internal electron donor compound (CN1087918), imine internal electron donor compounds (CN105085733 and CN105085746), amino ester compounds (CN101104589, CN101125896 and CN101172965) and amide ester internal electron donor compound (US2012322962), but the obtained catalyst effect is not outstanding.

Therefore, there is still a need in the art to develop new internal electron donor compounds useful for olefin polymerization.

Disclosure of Invention

The present inventors have studied and synthesized a novel organic compound having an imidate structure, and have found that it can be used as an internal electron donor for an olefin polymerization catalyst, and thus the present invention widens the selection range of the internal electron donor. Furthermore, when the imine ester compound shown in the formula I is used as an internal electron donor compound of the olefin polymerization catalyst, not only the hydrogen regulation sensitivity of the catalyst is good, but also the molecular weight of the obtained polymer is relatively wide.

In a first aspect, the present invention provides an imidate compound of formula I,

in the formula I, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀Of (2)Cyclic group, halogen atom, hydroxyl group and C with or without substituent₁-C₃₀Alkoxy, and R₁And R₂Not hydrogen at the same time; or R₁And R₂Linking to form a ring;

r is selected from C containing or not containing substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent₁-C₃₀Alkoxy and amino with or without substituents;

a is C with or without substituents₁-C₃₀Alkylene, hetero atom or combination thereof, preferably C with or without substituent₁-C₃₀Alkylene, C with or without substituents₆-C₃₀Arylene, C with or without substituents₄-C₃₀A heteroarylene group, or a combination thereof.

The second aspect of the present invention also provides a method for preparing the above-mentioned imidate compound, comprising:

reacting a compound of formula IIA with RCOX or (RCO)₂O reacts to generate the imine ester compound shown in the formula I,

in formula IIA, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₃₀Alkoxy, and R₁And R₂Not hydrogen at the same time; or R₁And R₂Are linked intoRing, A is C with or without substituents₁-C₃₀Alkylene, hetero atom or combination thereof, preferably C with or without substituent₁-C₃₀Alkylene, C with or without substituents₆-C₃₀Arylene, C with or without substituents₄-C₃₀A heteroarylene group or a combination thereof;

RCOX or (RCO)₂In O, R is selected from C with or without substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent₁-C₃₀Alkoxy and amino with or without substituents,

in RCOX, X is selected from halogen, preferably from chlorine, bromine and iodine,

in a third aspect, the present invention also provides the use of the imidate compounds as described above in olefin polymerization, in particular as internal electron donor components for olefin polymerization catalysts.

Detailed Description

In a first aspect, the present invention provides an imidate compound of formula I.

In the formula I, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, with or withoutC of a substituent₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₃₀Alkoxy, and R₁And R₂Not hydrogen at the same time; or R₁And R₂Linking to form a ring;

r is selected from C containing or not containing substituent₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₃₀Aryl, C with or without substituents₆-C₃₀Heteroaryl, C with or without substituents₄-C₃₀Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent₁-C₃₀Alkoxy and amino with or without substituents;

a is C with or without substituents₁-C₃₀Alkylene, hetero atom or combination thereof, preferably C with or without substituent₁-C₃₀Alkylene, C with or without substituents₆-C₃₀Arylene, C with or without substituents₄-C₃₀A heteroarylene group, or a combination thereof.

In the context of the present application, the term "substituent" refers to substituents common in the art, which may be selected from halogen, hydroxy, amino, C₆-C₂₀Aryl (including but not limited to phenyl, naphthyl, etc.), C₇-C₂₀Aralkyl (e.g., benzyl, phenethyl, etc.), C₇-C₂₀Alkylaryl (C)₁-C₆Alkyl-substituted phenyl), C₁-C₁₀Alkyl (including C)₁-C₆Alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.), C₁-C₂₀Alkoxy (including C)₁-C₆Alkoxy, e.g. methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxyAlkyl, n-pentyloxy, isopentyloxy, n-hexyloxy, etc.), and the like. In the context of this application, halogen means fluorine, chlorine, bromine or iodine. In the context of the present application, the term "alkyl" includes straight chain alkyl, branched chain alkyl and cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

According to some embodiments of the invention, the substituent is selected from halogen, hydroxy, amino, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl radical, C₇-C₂₀Alkylaryl group, C₁-C₁₀Alkyl and C₁-C₂₀Alkoxy, preferably selected from halogen, hydroxy, amino, phenyl, naphthyl, benzyl, phenethyl, C₁-C₆Alkyl-substituted phenyl, C₁-C₁₀Alkyl and C₁-C₂₀Alkoxy, more preferably selected from fluorine, chlorine, bromine, iodine, hydroxyl, amino, phenyl, naphthyl, benzyl, phenethyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and n-hexoxy.

According to some embodiments of the invention, R₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₂₀Alkyl, C with or without substituents₂-C₂₀Alkenyl, C with or without substituents₂-C₃₀Alkynyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₄-C₂₀Heterocyclic group, halogen atom, hydroxyl group and C with or without substituent₁-C₂₀An alkoxy group.

According to some embodiments of the invention, R₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₁₀Alkyl, C with or without substituents₂-C₁₀Alkenyl, C with or without substituents₆-C₁₅Aryl, with or withoutC of a substituent₄-C₅₀A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent₁-C₁₀An alkoxy group.

According to some embodiments, R₁And R₂Each independently selected from hydrogen, C with or without substituents₁-C₁₀Alkyl and C with or without substituents₆-C₁₅An aromatic group. According to some embodiments, R₁And R₂Is C with or without substituents₁-C₁₀Straight-chain alkyl, C with or without substituents₃-C₁₀Branched alkyl, C with or without substituents₃-C₁₀Cycloalkyl or substituted phenyl or unsubstituted phenyl. Preferably, said substituted phenyl, said substituted C₁-C₁₀Alkyl, substituted C₃-C₁₀Branched alkyl and substituted C₃-C₁₀The substituents on the cycloalkyl being selected from C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, halogen, hydroxy and amino.

According to some embodiments, R₁And R₂Each independently 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-containing group, etc.; the heterocyclic compound-containing group is preferably an azole-containing group, a pyridine-containing group, a pyrimidine-containing group, and a quinoline-containing group.

In some embodiments, R₁Is hydrogen, R₂Is C₁-C₁₀Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, etc.), phenyl, C₁-C₆Alkyl-substituted phenyl, hydroxy-substituted phenyl, halogen-substituted phenyl or C₁-C₆Phenyl substituted by at least two of alkyl, halogen and hydroxyl.

According to some embodiments, R is selected from C with or without substituents₁-C₁₀Alkyl and C with or without substituents₆-C₁₅An aromatic group. According to some embodiments, R is C with or without substituents₁-C₁₀Straight-chain alkyl, C with or without substituents₃-C₁₀Branched alkyl, C with or without substituents₃-C₁₀Cycloalkyl or phenyl with or without substituents. Preferably, the substituents are selected from C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy, halogen, hydroxy and amino.

According to some embodiments of the invention, A is C with or without substituents₁-C₂₀Alkylene, C with or without substituents₆-C₂₀Arylene, C with or without substituents₄-C₂₀A heteroarylene group, or a combination thereof.

According to some embodiments of the invention, A is C with or without substituents₁-C₁₀Alkylene, C with or without substituents₆-C₁₀Arylene, C with or without substituents₄-C₁₀A heteroarylene group, or a combination thereof.

According to some embodiments of the invention, A is C with or without substituents₁-C₈An alkylene group. According to some embodiments, a is unsubstituted C₁-C₈Alkylene (e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene) or C₁-C₆Alkyl or C₁-C₆Alkoxy-substituted C₁-C₈An alkylene group.

According to some embodiments of the invention, A is- (CR)^IR^II)_n-, wherein R^I、R^IIMay be the same or different and is selected from hydrogen, C with or without substituents₁-C₃₀Alkyl, C with or without substituents₂-C₃₀Alkenyl, C with or without substituents₃-C₃₀And C with or without substituents₆-C₃₀An aromatic group; n is 1-6; or said R is^IAnd R^IIThe links form a ring.

According to some embodiments, A is- (CR)^IR^II)_n-，Wherein R is^I、R^IISame or different and selected from hydrogen, C with or without substituents₁-C₂₀Alkyl, C with or without substituents₂-C₂₀Alkenyl, C with or without substituents₃-C₁₀And C with or without substituents₆-C₂₀An aromatic group; n is 1, 2, 3, 4, 5 or 6.

According to some embodiments, A is- (CR)^IR^II)_n-, wherein R^I、R^IISame or different and selected from hydrogen, C with or without substituents₁-C₁₀Alkyl, C with or without substituents₂-C₁₀Alkenyl, C with or without substituents₃-C₁₀Cycloalkane of (2) and C with or without substituents₆-C₁₀An aromatic group; n is 1, 2, 3, 4, 5 or 6.

According to some embodiments, A is- (CR)^IR^II)_n-, wherein R^I、R^IISame or different and selected from hydrogen, C with or without substituents₁-C₁₀Alkyl, C with or without substituents₂-C₁₀Alkenyl, C with or without substituents₃-C₁₀Cycloalkane of (2) and C with or without substituents₆-C₁₀An aromatic group; n is 1, 2, 3, 4, 5 or 6.

According to some embodiments, A is- (CR)^IR^II)_n-, wherein R^I、R^IISame or different and selected from hydrogen, C with or without substituents₁-C₈Alkyl, C with or without substituents₂-C₈Alkenyl, C with or without substituents₃-C₈Cycloalkane of (2) and C with or without substituents₆-C₁₀An aromatic group; n is 1, 2, 3, 4, 5 or 6.

According to some embodiments of the invention, a is a heteroatom selected from the group consisting of nitrogen, phosphorus and silicon atoms.

The imidate compound of formula I according to the present invention can be selected from, but is not limited to, the following compounds:

(2-phenyliminoethyl) benzoate, [2- (2-methyl) phenyliminoethyl ] benzoate, [2- (3-methyl) phenyliminoethyl ] benzoate, [2- (4-methyl) phenyliminoethyl ] benzoate, [2- (2-ethyl) phenyliminoethyl ] benzoate, [2- (3-ethyl) phenyliminoethyl ] benzoate, [2- (4-ethyl) phenyliminoethyl ] benzoate, [2- (2-propyl) phenyliminoethyl ] benzoate, [2- (3-propyl) phenyliminoethyl ] benzoate, [2- (2-butyl) phenyliminoethyl ] benzoate, [2- (3-butyl) phenyliminoethyl ] benzoate, and [2- (3-methoxy) phenyliminoethyl ] benzoate, Benzoic acid [2- (4-methoxy) phenyliminoethyl ester ], benzoic acid [2- (3-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (4-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (2-hydroxy) phenyliminoethyl ester ], benzoic acid [2- (2, 4-dimethyl) phenyliminoethyl ester ], [2- (2, 6-dimethyl) phenyliminoethyl ester ], benzoic acid [2- (2,4, 6-trimethyl) phenyliminoethyl ester ], benzoic acid [2- (2, 6-diisopropyl) phenyliminoethyl ester ], benzoic acid [2- (3, 5-di-tert-butyl) phenyliminoethyl ester ], benzoic acid [ 2-ethyliminoethyl ester ], benzoic acid [ 2-propyliminoethyl ester ], [ 2-butyliminoethyl benzoate ], [ 2-pentyliminoethyl benzoate ], [ 2-hexyliminoethyl benzoate ], 3-phenyliminopropyl benzoate, 3- (2-methyl) phenyliminopropyl benzoate, 3- (3-methyl) phenyliminopropyl benzoate, 3- (4-methyl) phenyliminopropyl benzoate, 3- (2-ethyl) phenyliminopropyl benzoate, 3- (3-ethyl) phenyliminopropyl benzoate, 3- (4-ethyl) phenyliminopropyl benzoate, 3- (2-propyl) phenyliminopropyl benzoate, 3- (3-propyl) phenyliminopropyl benzoate, 3- (2-butyl) phenyliminopropyl benzoate, Benzoic acid [3- (3-butyl) phenyliminopropyl ester ], benzoic acid [3- (4-butyl) phenyliminopropyl ester ], benzoic acid [3- (3-methoxy) phenyliminopropyl ester ], benzoic acid [3- (4-methoxy) phenyliminopropyl ester ], benzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], benzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], benzoic acid [3- (2-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (3-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (4-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], benzoic acid [3- (2,4, 6-trimethyl) phenylimidopropyl ester, 3- (3, 5-di-tert-butyl) phenylimidopropyl benzoate, 3- (2, 6-dimethyl) phenylimidopropyl benzoate, 3- (2, 6-diisopropyl) phenylimidopropyl benzoate, 3-ethyliminopropyl benzoate, 3-propylimidopropyl benzoate, 3-butyliminopropyl benzoate, 3-pentyliminopropyl benzoate, 3-hexyliminopropyl benzoate, 4-phenylimido-2-pentyl benzoate, 4- (2-methyl) phenylimido-2-pentyl benzoate, 4- (3-methyl) phenylimido-2-pentyl benzoate, Benzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], (benzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], Benzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], [4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], Benzoic acid [ 4-ethylimino-2-propyl ester ], benzoic acid [ 4-propylimino-2-pentyl ester ], benzoic acid [ 4-butylimino-2-pentyl ester ], benzoic acid [ 4-pentylimino-2-pentyl ester ], benzoic acid [ 4-hexylimino-2-pentyl ester ], benzoic acid [ 4-heptylimino-2-pentyl ester ], benzoic acid [ 4-octylimino-2-pentyl ester ], benzoic acid (3-methyl-4-phenylimino-2-pentyl ester), benzoic acid [ 3-ethyl-4- (2-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methyl) phenylimino-2-pentyl ester ], [ 3-methyl-4- (3-methyl) phenylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-propyl-4- (2-propyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-butyl-4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (2-butyl) phenylimino-2-pentyl ester ], [ 3-ethyl-4- (2-butyl) phenylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester, benzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], benzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], [ 3-ethyl-4-pentylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-methylbenzoic acid (4-phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], and mixtures thereof, 4-methylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], (methyl-benzoic acid-4- (4-butyl) phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], and, 4-methylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-methylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], (methyl-4-propylimino-2-pentyl ester), 4-methylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-butylbenzoic acid (4-phenylimino-2-pentyl ester), 4-butylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ] Pentyl ester ], 4-butylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], (4-propyl) phenylimino-2-pentyl ester), 4-butylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], (methyl-ethyl-4-phenyl) imino-2-pentyl ester), 4-butylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester, 4-butylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-butylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ] 4-propylbenzoic acid (4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], (methyl-ethyl) phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], (methyl-4-propylbenzoic acid, methyl-4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], (methyl-ethyl-4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-propylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], (N-methyl-4-hexylimino-2-pentyl ester), 4-propylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], propionic acid (4-phenylimino-2-pentyl ester), propionic acid [4- (2-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (3-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (4-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], propionic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], propionic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], (4-ethyl) phenylimino-2-pentyl ester), [4- (2-propyl) phenylimino-2-pentyl propionate ], [4- (3-propyl) phenylimino-2-pentyl propionate ], [4- (4-propyl) phenylimino-2-pentyl propionate ], [4- (2-butyl) phenylimino-2-pentyl propionate ], [4- (4-butyl) phenylimino-2-pentyl propionate ], [4- (3-methoxy) phenylimino-2-pentyl propionate ], [4- (4-methoxy) phenylimino-2-pentyl propionate ], [4- (3-ethoxy) phenylimino-2-pentyl propionate ], and [4- (4-ethoxy) phenylimino-2-pentyl propionate ], Propionic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 3-methyl-4-ethylimino-2-propyl propionate, [ 3-methyl-4-propylimino-2-pentyl propionate ], [ 3-ethyl-4-butylimino-2-pentyl propionate ], [ 3-ethyl-4-pentylimino-2-pentyl propionate ], [ 3-ethyl-4-hexylimino-2-pentyl propionate ], [ 3-ethyl-4-heptylimino-2-pentyl propionate ], [ 3-methyl-4-octylimino-2-pentyl propionate ], [ 4-phenylimino-2-pentyl valerate ], [4- (2-methyl) phenylimino-2-pentyl valerate ], [ 3-methyl) phenylimino-2-pentyl valerate ], and mixtures thereof, Valeric acid [4- (3-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-butyl) phenylimino-2-pentyl ester ], "valeric acid [4- (2-butyl) phenylimino-2-pentyl ester ], Valeric acid [4- (4-butyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], valeric acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], valeric acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], valeric acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester, valeric acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4-ethylimino-2-propyl ester ], valeric acid [ 3-methyl-4-propylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-butylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], [ 3-ethyl-4-pentylimino-2-pentyl ester ], Valeric acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], valeric acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-methylbenzoic acid (3-phenylimino-pentyl ester), 4-methylbenzoic acid [ 3-phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (3-methyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (4-methyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (2-ethyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (3-ethyl) phenylimino-pentyl ester ], (methyl-o-pentyl ester), 4-methylbenzoic acid [3- (4-ethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminopentyl ester ], (4-methylbenzoic acid [3- (4-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (2, 4-dimethyl) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenylimidopentyl ester ], benzoic acid (4-phenylimidobutyl ester), benzoic acid [4- (2-methyl) phenylimidobutyl ester ], benzoic acid [4- (3-methyl) phenylimidobutyl ester ], benzoic acid [4- (4-methyl) phenylimidobutyl ester ], benzoic acid [4- (2-ethyl) phenylimidobutyl ester ], (a) a-methyl ester, a-ethyl, Benzoic acid [4- (3-ethyl) phenyliminobutyl ester ], benzoic acid [4- (4-ethyl) phenyliminobutyl ester ], benzoic acid [4- (2-propyl) phenyliminobutyl ester ], benzoic acid [4- (3-propyl) phenyliminobutyl ester ], benzoic acid [4- (4-propyl) phenyliminobutyl ester ], benzoic acid [4- (2-butyl) phenyliminobutyl ester ], benzoic acid [4- (3-methoxy) phenyliminobutyl ester ], benzoic acid [4- (4-methoxy) phenyliminobutyl ester ], benzoic acid [4- (3-ethoxy) phenyliminobutyl ester ], benzoic acid [4- (4-ethoxy) phenyliminobutyl ester ], [4- (4-ethoxy) phenyliminobutyl ester ] (B-methyl ester, Benzoic acid [4- (2-hydroxy) iminobutyl ester ], benzoic acid [4- (3-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (4-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ester, ] benzoic acid [4- (2,4, 6-trimethyl) phenyliminobutyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ester ], benzoic acid [ 4-ethyliminobutyl ester ], benzoic acid [ 4-propyliminobutyl ester ] (I), Benzoic acid [ 4-butyliminobutyl ] acid, benzoic acid [ 4-pentyliminobutyl ] acid, benzoic acid [ 4-hexyliminobutyl ] acid, benzoic acid [ 4-heptiminobutyl ] acid, benzoic acid [ 4-octyliminobutyl ] acid, benzoic acid (3-phenyliminobutyl) acid, benzoic acid [3- (2-methyl) phenyliminobutyl ] acid, benzoic acid [3- (3-methyl) phenyliminobutyl ] acid, benzoic acid [3- (4-methyl) phenyliminobutyl ] acid, benzoic acid [3- (2-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (3-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (4-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (2-propyl) phenyliminobutyl ] acid, Benzoic acid [3- (3-propyl) phenyliminobutyl ester ], benzoic acid [3- (4-propyl) phenyliminobutyl ester ], benzoic acid [3- (2-butyl) phenyliminobutyl ester ], benzoic acid [3- (3-methoxy) phenyliminobutyl ester ], benzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], benzoic acid [3- (2-hydroxy) phenyliminobutyl ester ], benzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], benzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ester ], benzoic acid [ 3-ethyliminobutyl ester ], benzoic acid [ 3-propyliminobutyl ester ], benzoic acid [ 3-butyliminobutyl ester ], benzoic acid [ 3-pentyliminobutyl ester ], benzoic acid [ 3-hexyliminobutyl ester ], benzoic acid [ 3-heptiminobutyl ester ], benzoic acid [ 4-noniminobutyl ester ], 4-methylbenzoic acid (3-phenyliminobutyl ester), 4-methylbenzoic acid [3- (2-methyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-methyl) phenyliminobutyl ester ], (methyl) phenylobuty, 4-methylbenzoic acid [3- (4-methyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminobutyl ester ], (methyl-4-methylbenzoic acid [3- (3-, 4-methylbenzoic acid [3- (4-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl 4-methylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ] 4-methylbenzoic acid [ 3-ethyliminobutyl ] 4-methylbenzoic acid [ 3-propyliminobutyl ] 4-methylbenzoic acid, 3-butyliminobutyl ] benzoic acid [ 3-pentyliminobutyl ] 4-methylbenzoic acid [ 3-hexyliminobutyl ] 4-methylbenzoic acid [ 4-nonyiiminobutyl ] 4-methylbenzoic acid [ 3-marinobutyl ] 4-methylbenzoic acid [ 3-phenyliminopropyl ] 4-propylbenzoic acid [3- (2-methyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (3-methyl) phenyliminopropyl ] 4-propylbenzoic acid, 4-propylbenzoic acid [3- (4-methyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-butyl) phenyliminopropyl ester ], (methyl) phenylthiopropionic acid, 4-propylbenzoic acid [3- (4-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl, 4-propylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ], 4-propylbenzoic acid [ 3-ethyliminobutyl ], 4-propylbenzoic acid [ 3-propyliminobutyl ], 4-butylbenzoic acid [ 3-butyliminobutyl ], 4-propylbenzoic acid [ 3-pentyliminobutyl ], 4-butylbenzoic acid [ 3-hexyliminobutyl ], 4-butylbenzoic acid [ 4-nonyliminobutyl ], 4-butylbenzoic acid [ 3-sunflower iminobutyl ], 4-methoxybenzoic acid (3-phenyliminopropyl), 4-methoxybenzoic acid [3- (2-methyl) phenyliminopropyl ], (methyl) phenyliminobutyl) and (methyl) phenylimino-butyl) ether, 4-methoxybenzoic acid [3- (3-methyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (4-methyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-ethyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-ethyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (4-ethyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (4-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-butyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-butyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (4-butyl) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-methoxy) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (4-methoxy) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (3-ethoxy) phenylimino-propyl ester ], 4-methoxybenzoic acid [3- (4-ethoxy) phenylimino-propyl ester ], 4-ethoxybenzoic acid [3- (2, 4-dimethyl) phenylimino-propyl ester ], 4-ethoxybenzoic acid [3- (2,4, 6-trimethyl) phenylimino-propyl ester ], 4-ethoxybenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [ 3-ethyliminobutyl ester ], 4-methoxybenzoic acid [ 3-propyliminobutyl ester ], 4-methoxybenzoic acid [ 3-butyliminobutyl ester ], 4-methoxybenzoic acid [ 3-pentyliminobutyl ester ], 4-methoxybenzoic acid [ 3-hexyliminobutyl ester ], 4-methoxybenzoic acid [ 4-noniminobutyl ester ], 4-methoxybenzoic acid [ 3-sunflower iminobutyl ester ] (methyl-ethyl-methyl-4-methoxybenzoic acid), (3-phenyliminopropyl) acetate, [3- (2-methyl) phenyliminopropyl ] acetate, [3- (3-methyl) phenyliminopropyl ] acetate, [3- (4-methyl) phenyliminopropyl ] acetate, [3- (2-ethyl) phenyliminopropyl ] acetate, [3- (3-ethyl) phenyliminopropyl ] acetate, [3- (4-ethyl) phenyliminopropyl ] acetate, [3- (2-propyl) phenyliminopropyl ] acetate, [3- (3-propyl) phenyliminopropyl ] acetate, [3- (4-propyl) phenyliminopropyl ] acetate, [3- (2-butyl) phenyliminopropyl ] acetate, [3- (3-butyl) phenyliminopropyl ] acetate, Acetic acid [3- (4-butyl) phenyliminopropyl ester ], acetic acid [3- (3-methoxy) phenyliminopropyl ester ], acetic acid [3- (4-methoxy) phenyliminopropyl ester ], acetic acid [3- (3-ethoxy) phenyliminopropyl ester ], acetic acid [3- (4-ethoxy) phenyliminopropyl ester ], acetic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], acetic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], acetic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], acetic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], acetic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], acetic acid [ 3-ethyliminopropyl ester ], (3-ethyliminopropyl ester), Acetic acid [ 3-propylimidoyl ester ], acetic acid [ 3-butylimidopropyl ester ], acetic acid [ 3-pentylimidoyl ester ], acetic acid [ 3-hexylimidoyl ester ], acetic acid [ 3-heptimidoyl ester ], acetic acid [ 4-nonimidoyl propyl ester ], propionic acid (3-phenylimidoyl propyl ester), propionic acid [3- (2-methyl) phenylimidoyl ester ], propionic acid [3- (2-methyl) phenylimidoyl propyl ester ], butyric acid [3- (4-methyl) phenylimidoyl propyl ester, valeric acid [3- (2-methyl) phenylimidoyl ester ], valeric acid [3- (4-methyl) phenylimidoyl propyl ester ], caproic acid [3- (4-methyl) phenylimidoyl propyl ester, acetic acid [3- (3-methyl) phenylimidoyl ester, [3- (2-methyl) phenyliminopropyl heptanoate ], [3- (4-methyl) phenyliminopropyl octanoate ], [3- (2-ethyl) phenyliminopropyl propionate ], [3- (3-ethyl) phenyliminopropyl propionate ], [3- (4-ethyl) phenyliminopropyl propionate ], [3- (2-propyl) phenyliminopropyl propionate ], [3- (3-propyl) phenyliminopropyl propionate ], [3- (4-propyl) phenyliminopropyl propionate ], [3- (2-butyl) phenyliminopropyl propionate ], [3- (3-butyl) phenyliminopropyl propionate ], [3- (4-butyl) phenyliminopropyl propionate ], [3- (3-methoxy) phenyliminopropyl propionate ], (a salt thereof, Propionic acid [3- (4-methoxy) phenyliminopropyl ester ], propionic acid [3- (3-ethoxy) phenyliminopropyl ester ], propionic acid [3- (4-ethoxy) phenyliminopropyl ester ], propionic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], propionic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], propionic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], cyclohexanoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 2-naphthoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], propionic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], (a) propionic acid, Propionic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], propionic acid [ 3-ethyliminopropyl ester ], propionic acid [ 3-propyliminopropyl ester ], acetic acid [ 3-butyliminopropyl ester ], propionic acid [ 3-pentyliminopropyl ester ], propionic acid [ 3-hexyliminopropyl ester ], propionic acid [ 3-heptiminopropyl ester ], propionic acid [ 4-noniminopropyl ester ], and the like.

The second aspect of the present invention also provides a preparation method of an imidate compound represented by formula I, comprising:

reacting a compound of formula IIA with RCOX or (RCO)₂O reacts to generate the imine ester compound shown in the formula I, and the reaction formula can be shown as follows

Wherein R in the formula IIA₁、R₂And A is as defined for formula I, RCOX or (RCO)₂R in O is as defined in formula I, X is selected from halogen, preferably from chlorine,Bromine and iodine.

According to an embodiment of the invention, said compound of formula IIA is reacted with RCOX or (RCO)₂The O reaction is carried out in the presence of an acid or a base. 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, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid; the base is selected from inorganic or organic bases, preferably from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, diethylamine, ethylenediamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazobicyclo [5,4,0] diazo-bicyclo]Undec-7-ene), DBN (1, 5-diazabicyclonon-5-ene), pyrazole, and the like.

According to an embodiment of the invention, said compound of formula IIA is reacted with RCOX or (RCO)₂The O reaction is carried out in a solvent. The solvent may be ether, hydrocarbon, etc., and specifically may be diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether, diglycidyl ether, etc.

According to some embodiments of the invention, the compound of formula IIA is reacted with RCOX or (RCO)₂The O reaction is carried out in the presence of an organic base, preferably triethylamine, and an ethereal solvent, preferably tetrahydrofuran.

The third aspect of the invention also provides the application of the imidate compound in olefin polymerization, in particular to the imidate compound serving as an internal electron donor component of an olefin polymerization catalyst.

The invention has the following characteristics:

1. the compound used in the invention and the application thereof in the preparation of olefin polymerization catalysts and olefin polymerization reactions are not reported in documents.

2. The novel internal electron donor compound can be used for obtaining a catalyst with excellent comprehensive performance, the hydrogen regulation sensitivity of the catalyst is good when the catalyst is used for propylene polymerization reaction, and the molecular weight distribution of the obtained polypropylene resin is wide.

The test method comprises the following steps:

1. polymer Melt Index (MI): measured according to GB/T3682-2000;

2. propylene polymer Isotacticity Index (II): determination by heptane extraction: 2g of dried polymer sample is put in an extractor and extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue is dried to constant weight, namely the isotacticity;

3. polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: polystyrene, flow rate: 1.0mL/min, column: 3X Plgel 10um MlxED-B300X 7.5 nm).

4. And (3) activity calculation: the catalyst activity (mass of polyolefin prepared)/(mass of catalyst solid component) g/g.

Examples

The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.

Synthesis of Compound (I)

EXAMPLE 1 Synthesis of benzoic acid (4-phenylimino-2-pentyl ester), a compound of

In a 250 ml three-necked flask, after nitrogen purging, 3.26 g of 4-phenylimino-2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. 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 3.37 g of a product (yield 60%).¹H-NMR(δ,ppm,TMS,CDCl₃):8.01～7.99(2H,m,ArH),7.78～7.75(2H,m,ArH),7.46～7.44(2H,m,ArH),7.36～7.34(2H,m,ArH),7.35～7.32(3H,m,ArH),7.26～7.24(2H,m,ArH),4.15～4.13(1H,t,OCH),1.95～1.93(1H,m,CH₂),1.58～1.56(1H,m,CH₂),1.38～1.35(3H,d,CH₃),0.99～0.95(3H,s,CH₃)。

EXAMPLE 2 Synthesis of the Compound benzoic acid [3- (3, 5-di-tert-butylphenylimino) propyl ester ]

In a 250 ml three-necked flask, after nitrogen purging, 5.22 g of 3- (3, 5-di-tert-butylphenylimino) propanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl 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 3.65 g of a product (yield 50%).¹H-NMR(δ,ppm,TMS,CDCl₃):7.98～7.95(2H,m,ArH),7.63～7.61(2H,m,ArH),7.50～7.48(1H,m,ArH),7.43～7.41(1H,m,ArH),7.32～7.30(1H,m,ArH),7.26～7.23(2H,m,ArH),4.25～4.23(2H,t,OCH₂),2.05～2.03(2H,t,CH₂),1.35～1.33(3H,s,CH₃),1.28～1.26(3H,s,CH₃)。

EXAMPLE 3 Synthesis of the Compound benzoic acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ]

In a 250 ml three-necked flask, after nitrogen purging, 6.10 g of 4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring for 12 hours, the reaction was refluxed at elevated temperature for 12 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 4.49 g of a product (yield: 55%).¹H-NMR(δ,ppm,TMS,CDCl₃):8.03～8.01(2H,m,ArH),7.46～7.44(1H,m,ArH),7.38～7.36(2H,m,ArH),7.12～7.10(1H,m,ArH),6.96～6.95(1H,m,ArH),4.50～4.46(1H,m,OH),4.13～4.10(1H,m,OCH),2.05～2.03(2H,t,CH₂),1.36～1.33(12H,m,CH₃),1.30～1.27(9H,m,CH₃),0.97～0.95(3H,s,CH₃)。

EXAMPLE 4 Synthesis of 4-n-propylbenzoic acid [4- (2-hydroxyphenylimino) -2-pentyl ester ] as a Compound

In a 250 ml three-necked flask, after nitrogen purging, 3.86 g of 4- (2-hydroxyphenylimino) -2-pentanol, 100 ml of THF and 2.15 ml of triethylamine were added, and 3.64 g of 4-n-propylbenzoyl chloride was added dropwise at room temperature and stirred well. 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 4.20 g of a product (yield 62%).¹H-NMR(δ,ppm,TMS,CDCl₃):7.96～7.94(2H,m,ArH),7.26～7.23(2H,m,ArH),7.16～7.13(2H,m,ArH),6.96～6.94(2H,m,ArH),4.56～4.52(1H,m,OH),4.12～4.10(1H,m,OCH),2.56～2.54(2H,t,CH₂),2.05～2.03(2H,m,CH₂),1.68～1.66(2H,m,CH₂),1.28～1.26(3H,s,CH₃),1.04～1.02(3H,t,CH₃),0.97～0.95(3H,s,CH₃)。

EXAMPLE 5 Synthesis of benzoic acid (4-butylimino-2-pentyl ester)

In a 250 ml three-necked flask, after nitrogen purging, 3.14 g of 4- (2-hydroxyphenylimino) -2-pentanol, 100 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring the reaction mixture for 3 hours, the reaction mixture was refluxed for 14 hours at an elevated temperature. After concentration under reduced pressure and separation by column chromatography, 2.50 g (yield 48%) of a pale yellow viscous liquid was obtained.¹H-NMR(δ,ppm,TMS,CDCl₃):7.98～7.96(2H,m,ArH),7.46～7.44(1H,m,ArH),7.39～7.37(2H,m,ArH),4.20～4.19(1H,m,OCH),2.85～2.83(2H,dt,CH₂),2.56～2.54(2H,t,CH₂),1.56～1.54(2H,m,CH₂),1.42～1.40(2H,m,CH₂),1.35～1.33(3H,m,CH₃),1.23～1.20(2H,m,CH₂),1.04～1.02(3H,t,CH₃),0.97～0.95(3H,s,CH₃)。

EXAMPLE 6 Synthesis of the Compound 4-n-propylbenzoic acid (4-butylimino-2-pentyl ester)

In a 250 ml three-necked flask, after nitrogen purging, 3.14 g of 4- (2-hydroxyphenylimino) -2-pentanol, 100 ml of THF and 2.15 ml of triethylamine were added, and 3.64 g of 4-n-propylbenzoyl chloride was added dropwise at room temperature and stirred well. After stirring for 4 hours, the reaction was refluxed for 16 hours at an elevated temperature. After concentration under reduced pressure, concentration under reduced pressure and column chromatography separation, 2.73 g of a light yellow viscous liquid is obtained (yield is 45%).¹H-NMR(δ,ppm,TMS,CDCl₃):7.94～7.92(2H,m,ArH),7.25～7.23(2H,m,ArH),4.22～4.20(1H,m,OCH),2.86～2.84(2H,dt,CH₂),2.57～2.55(2H,t,CH₂),1.67～1.65(2H,m,CH₂),1.56～1.54(2H,m,CH₂),1.42～1.40(2H,m,CH₂),1.35～1.33(3H,m,CH₃),1.23～1.20(2H,m,CH₂),1.04～1.02(3H,t,CH₃),0.98～0.95(6H,m,CH₃)。

EXAMPLE 7 Synthesis of the Compound butyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ]

In a 250 ml three-necked flask, after nitrogen purging, 6.10 g of 4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 2.12 g of butyryl chloride was added dropwise at room temperature and stirred well. After stirring for 6 hours, the reaction was refluxed for 12 hours at an elevated temperature. Concentration under reduced pressure and separation by column chromatography gave 3.20 g (42% yield) of a pale yellow viscous liquid.¹H-NMR(δ,ppm,TMS,CDCl₃):7.40～7.38(1H,m,ArH),6.98～6.96(1H,m,ArH),4.52～4.49(1H,m,OH),4.10～4.09(1H,m,OCH),2.26～2.24(2H,t,CH₂),1.74～1.72(2H,t,CH₂),1.43～1.41(1H,m,CH₂),1.36～1.32(12H,m,CH₃),1.30～1.27(9H,m,CH₃),1.18～1.17(1H,m,CH₂),0.98～0.96(6H,m,CH₃)。

EXAMPLE 8 Synthesis of 3-methylbutyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ] as a Compound

In a 250 ml three-necked flask, after nitrogen purging, 6.10 g of 4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 2.42 g of 3-methylbutyryl chloride was added dropwise at room temperature and stirred well. After stirring for 6 hours, the reaction was refluxed for 16 hours at an elevated temperature. Concentration under reduced pressure and separation by column chromatography gave 3.11 g (40% yield) of a pale yellow viscous liquid.¹H-NMR(δ,ppm,TMS,CDCl₃):7.40～7.38(1H,m,ArH),6.98～6.96(1H,m,ArH),4.54～4.51(1H,m,OH),4.12～4.10(1H,m,OCH),2.47～2.46(1H,m,CH),2.22～2.20(2H,d,CH₂),1.76～1.75(1H,t,CH₂),1.43～1.42(1H,m,CH₂),1.36～1.32(12H,m,CH₃),1.30～1.27(9H,m,CH₃),1.18～1.17(1H,m,CH₂),1.04～1.02(6H,m,CH₃),0.98～0.96(3H,s,CH₃)。

EXAMPLE 9 Synthesis of 4-propylbenzoic acid [4- (3-tert-butylbenzimido) -2-pentyl ester ] as Compound

In a 250 ml three-necked flask, after nitrogen purging, 4.92 g of 3-methyl-4- (3-tert-butylphenylimino) -2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, 3.64 g of 4-n-propylbenzoyl chloride was added dropwise at room temperature, and then stirredAnd (4) uniformly stirring. After stirring for 6 hours, the reaction was refluxed for 12 hours at an elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether and petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 3.93 g (50% yield).¹H-NMR(δ,ppm,TMS,CDCl₃):7.96～7.94(2H,m,ArH),7.26～7.23(2H,m,ArH),7.20～7.18(2H,m,ArH),6.97～6.95(2H,m,ArH),4.12～4.10(1H,m,OCH),2.56～2.54(2H,t,CH₂),2.23～2.21(2H,m,CH₂),1.68～1.66(2H,m,CH₂),1.34～1.31(12H,m,CH₃),1.04～1.02(3H,t,CH₃),0.98～0.95(6H,m,CH₃)。

EXAMPLE 10 Synthesis of 4-chlorobenzoic acid [4- (3-tert-butylphenylimino) -2-pentyl ester ] as a Compound

In a 250 ml three-necked flask, after nitrogen purging, 4.65 g of 4- (3-tert-butylphenylimino) -2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were added, and 3.58 g of 4-chlorobenzoyl chloride was added dropwise at room temperature and stirred uniformly. After stirring for 6 hours, the reaction was refluxed for 8 hours at an elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether and petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 3.41 g (yield: 46%).¹H-NMR(δ,ppm,TMS,CDCl₃):7.95～7.93(2H,m,ArH),7.35～7.33(2H,m,ArH),7.22～7.20(2H,m,ArH),6.96～6.94(2H,m,ArH),4.12～4.10(1H,m,OCH),2.04～2.02(1H,m,CH₂),1.48～1.47(1H,m,CH₂),1.34～1.31(12H,m,CH₃),0.97～0.95(3H,m,CH₃)。

EXAMPLE 11 Synthesis of the Compound benzoic acid [4- (8-quinolineimino) -2-pentyl ester ]

In a 250 ml three-necked flask, 4.56 g of 4- (8-quinolinimino) -2-pentanol, 100 ml of THF and 2.15 ml of THF are added after purging with nitrogenTriethylamine, 2.80 g benzoyl chloride is added dropwise at room temperature and stirred evenly. 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 and petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 3.32 g (50% yield) of a product.¹H-NMR(δ,ppm,TMS,CDCl₃):8.14～8.12(2H,m,ArH),7.97～7.95(2H,m,ArH),7.69～7.67(2H,m,ArH),7.48～7.46(2H,m,ArH),7.35～7.33(3H,m,ArH),4.12～4.10(1H,m,OCH),1.98～1.97(1H,m,CH₂),1.43～1.41(1H,m,CH₂),0.98～0.96(3H,m,CH₃)。

EXAMPLE 12 Synthesis of benzoic acid (4-cyclohexylimino-2-pentyl ester)

In a 250 ml three-necked flask, after nitrogen purging, 3.65 g of 4-cyclohexylimino-2-pentanol, 100 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring for 6 hours, the reaction was refluxed for 10 hours at an elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether and petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 2.42 g (yield: 42%).¹H-NMR(δ,ppm,TMS,CDCl₃):8.01～7.99(2H,m,ArH),7.47～7.46(1H,m,ArH),7.38～7.36(2H,m,ArH),4.08～4.07(1H,m,OCH),2.85～2.84(1H,m,CH₂),2.63～2.62(1H,m,CH₂),1.70～1.68(2H,m,CH₂),1.52～1.50(4H,m,CH₂),1.46～1.43(4H,m,CH₂),1.38～1.36(4H,m,CH₂),1.32～1.30(3H,m,CH₃),0.98～0.96(3H,m,CH₃)。

EXAMPLE 13 Synthesis of 4-propylbenzoic acid [3- (3-tert-butylphenylimino) -5-heptyl ester ] as a Compound

In a 250 ml three-neck flask, 5 is added after nitrogen is blown off32 g of 3- (3-tert-butylphenylimino) -5-heptanol, 100 ml of THF and 2.15 ml of triethylamine are added dropwise, while stirring at room temperature, 2.80 g of benzoyl chloride and stirred homogeneously. After stirring for 6 hours, the reaction was refluxed for 12 hours at an elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether and petroleum ether (1:50) to give yellow crystals, which were dried under vacuum to give 3.82 g (yield: 47%).¹H-NMR(δ,ppm,TMS,CDCl₃):7.95～7.93(2H,m,ArH),7.37～7.36(2H,m,ArH),7.23～7.21(2H,m,ArH),6.97～6.95(2H,m,ArH),4.16～4.15(1H,m,OCH),2.55～2.53(2H,m,CH₂),2.03～2.02(1H,m,CH₂),1.78～1.76(2H,m,CH₂),1.66～1.64(2H,m,CH₂),1.58～1.56(1H,m,CH₂),1.46～1.43(2H,m,CH₂),1.35～1.33(9H,m,CH₃),1.04～1.02(3H,m,CH₃),0.98～0.95(6H,m,CH₃)。

(II) preparation of solid component in catalyst and examples of propylene polymerization are as follows:

example 14

(1) Preparation of solid catalyst component

4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, and the temperature is raised to 50 ℃ under stirring and maintained for 2.5 hours. After the solid 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 hour₄56mL, slowly heating to 80 ℃, gradually separating out the solid, adding 6mmol of the structural compound benzoic acid (4-phenylimino-2-pentyl ester), and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. Then 60mL of toluene and TiCl were added₄40mL of the mixture was heated to 110 ℃ and maintained for 2 hours, the same operation was repeated once, and the mixture was washed with 70mL of toluene for 3 times each of 10min at 110 ℃ and then with 60mL of hexane for 2 times. Vacuum drying to obtain solid catalyst component.

(2) Polymerization of propylene

The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added₃2.5mL of methylcyclohexyldimethoxysilane(CHMMS)5ml Al/Si (mol) ═ 25, then 10mg of the solid component prepared in the above example and 1.2NL of hydrogen were added, 2.5L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, the temperature was lowered, the pressure was released, and PP resin was obtained by discharging, the results are shown in Table 1.

Example 15

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with [3- (3, 5-di-tert-butylphenylimino) propyl ] benzoate.

Example 16

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with benzoic acid [4- (3, 5-di-tert-butyl-2-hydroxybenzimido) -2-pentyl ester ].

Example 17

In the same manner as in example 14, only benzoic acid (4-benzimido-2-pentyl ester) was replaced by benzoic acid (4-butylimido-2-pentyl ester).

Example 18

In the same manner as in example 14, only the compound benzoic acid (4-benzimido-2-pentyl ester) was replaced with 4-n-propylbenzoic acid (4-butylimido-2-pentyl ester).

Example 19

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with butyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ].

Example 20

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 3-methylbutyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ].

Example 21

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 3-methylbutyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ].

Example 22

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 4-propylbenzoic acid [4- (3-tert-butylphenylimino) -2-pentyl ester ].

Example 23

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 4-chlorobenzoic acid [4- (3-tert-butylphenylimino) -2-pentyl ester ].

Example 24

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with benzoic acid [4- (8-quinolinimino) -2-pentyl ester ].

Example 25

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 4-propylbenzoic acid [3- (3-tert-butylphenylimino) -5-heptyl ester.

Example 26

In the same manner as in example 14, only the compound benzoic acid (4-phenylimino-2-pentyl ester) was replaced with 4-propylbenzoic acid [4- (2-hydroxyphenylimino) -5-pentyl ester.

TABLE 1

As can be seen from the examples, when the catalyst component of the invention is used in propylene polymerization reaction, the hydrogen regulation sensitivity of the catalyst is good, and the obtained polypropylene resin has wide molecular weight distribution.

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.