Ether ester compound, method for preparing the same, and use thereof in olefin polymerization

Abstract

This invention relates to an ether ester compound, specifically disclosing an ether ester compound, its preparation method, and its application in olefin polymerization. The ether ester compound is shown in formula M, wherein R... 1 Selected from hydrogen or C1-C18 alkyl groups; R 2 R is selected from C1-C18 alkyl groups; R is selected from C1-C18 alkyl groups, C6-C30 aryl groups with or without substituents, C7-C30 aralkyl groups with or without substituents, and C5-C30 cycloalkyl groups with or without substituents. This ether ester compound can be used in olefin polymerization reactions, for example as an internal electron donor in olefin polymerization catalysts. The ether ester compound according to the invention can be prepared from inexpensive and readily available raw materials, and the preparation method is simple and mild. Catalysts using this ether ester compound exhibit high activity in propylene polymerization reactions, and the resulting polymers have high isotactic indexes.

Description

Technical Field

[0001] This invention relates to an ether ester compound, specifically to an ether ester compound, its preparation method, and its application in olefin polymerization. Background Technology

[0002] The development of the polyolefin industry hinges on the preparation technology of polymerization catalysts. In the 1950s, Professor Natta of Italy invented the Ziegler-Natta catalyst (ZN catalyst) for the production of isotactic polypropylene. Currently, the polypropylene catalysts used in industrial production are still mainly based on highly efficient ZN catalyst systems. During catalyst preparation and polymerization reactions, electron-rich Lewis base compounds, i.e., electron donor compounds, need to be added. The addition of electron donor compounds can improve the stereoselectivity and activity of the catalyst, control the relative molecular mass and distribution of the polymer, optimize various performance indicators of the catalyst, and ultimately achieve the effect of regulating polymer performance. Depending on the method of addition, electron donor compounds can be divided into internal electron donor compounds and external electron donor compounds. Internal electron donors are added during the preparation of the solid catalyst component, while external electron donors are added as one of the components of the catalyst system during olefin polymerization.

[0003] Since the discovery of Zn catalysts, polypropylene catalysts have evolved from the first generation to the fifth generation. The advancement and upgrading of catalyst technology is largely due to the use of novel electron-donating compounds. Therefore, finding ideal electron-donating compounds has always been a hot topic in polypropylene catalyst research. Among them, internal electron-donating compounds play a crucial role in improving catalyst performance and increasing polymer stereoregularity; it can be said that internal electron-donating compounds are the core of polypropylene catalysts. Currently, the fourth-generation catalysts are most widely used in polypropylene industrial production, with phthalic acid diesters as internal electron donors. Commonly used are di-n-butyl phthalate (DNBP) and diisobutyl phthalate (DIBP). Catalysts containing phthalic acid diesters have low activity, and the resulting polymers have a narrow molecular weight distribution. External electron donors are required during polymerization to achieve high catalytic activity and obtain polymers with high isotacticity.

[0004] In the 1990s, Himont disclosed a class of 1,3-diether electron-donating compounds in Chinese patent CN1041752A. Using catalysts containing 1,3-diether compounds, high-isotactic polypropylene can be obtained with high catalytic activity without the need for the addition of external electron donors during polymerization, thus reducing the complexity of the reaction system.

[0005] However, although catalysts using 1,3-diethers as electron donors exhibit high activity and good hydrogen sensitivity, the resulting polymers have a narrow relative molecular weight distribution, which is detrimental to polymer processing. Furthermore, 1,3-diether compounds are prepared by O-alkylation of the corresponding 1,3-diols. The synthesis of the intermediate 1,3-diol involved in the preparation process is complex and yields are low. The O-alkylation reaction conditions are harsh, requiring the use of strong bases such as potassium tert-butoxide or sodium hydride for dehydrogenation, and the O-alkylating agent iodomethane is a highly toxic chemical. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention provides an ether ester compound, which is used as an internal electron donor in olefin polymerization catalysts and further applied in olefin polymerization reactions. The preparation method of this ether ester compound is simple, the reaction conditions are mild, the operation is straightforward, and the raw materials are inexpensive and readily available.

[0007] The first objective of this invention is to provide an ether ester compound, the structural formula of which is shown in Formula M:

[0008]

[0009] Among them, R 1 Selected from hydrogen or C1-C18 alkyl groups; R 2 R is selected from C1-C18 alkyl groups; R is selected from C1-C18 alkyl groups, C6-C30 aryl groups with or without substituents, C7-C30 aralkyl groups with or without substituents, and C5-C30 cycloalkyl groups with or without substituents.

[0010] Preferably, R 1 Selected from hydrogen or C1-C6 alkyl groups; and / or, R 2 R is selected from C1-C6 alkyl groups; and / or, R is selected from C1-C6 alkyl groups, C6-C20 aryl groups with or without substituents, C7-C20 aralkyl groups with or without substituents, and C5-C20 cycloalkyl groups with or without substituents.

[0011] More preferably, R 1 Selected from hydrogen or C1-C4 alkyl groups; and / or, R 2 R is selected from C1-C4 alkyl groups; and / or, R is selected from C1-C4 alkyl groups, C6-C10 aryl groups with or without substituents, C7-C10 aralkyl groups with or without substituents, and C5-C10 cycloalkyl groups with or without substituents, that is, R is selected from one of C1-C4 alkyl groups, C6-C10 aryl groups with or without substituents, C7-C10 aralkyl groups with or without substituents, and C5-C10 cycloalkyl groups with or without substituents.

[0012] Even more preferably, R1 Selected from hydrogen, methyl, or ethyl; and / or,

[0013] R 2 Selected from methyl or ethyl; and / or, R is selected from C1-C3 alkyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents.

[0014] According to the present invention, in formula M, R 1 Selected from hydrogen or C1-C18 alkyl groups, preferably hydrogen or C1-C6 alkyl groups, more preferably hydrogen or C1-C4 alkyl groups, and most preferably hydrogen, methyl, or ethyl alkyl groups;

[0015] R 2 The alkyl group is selected from C1-C18, preferably C1-C6, more preferably C1-C4, and most preferably methyl or ethyl;

[0016] R is selected from C1-C18 alkyl, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents, and C5-C30 cycloalkyl with or without substituents, preferably C1-C6 alkyl, C6-C20 aryl with or without substituents, C7-C20 aralkyl with or without substituents, and C5-C20 cycloalkyl with or without substituents, more preferably C1-C4 alkyl, C6-C10 aryl with or without substituents, C7-C10 aralkyl with or without substituents, and C5-C10 cycloalkyl with or without substituents, most preferably C1-C3 alkyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents.

[0017] In this invention, the substituent is preferably selected from one or more of C1-C18 alkyl, C1-C18 alkoxy, and halogen; more preferably, the substituent is selected from one or more of C1-C6 alkyl, C1-C6 alkoxy, and halogen; more preferably, the substituent is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, chlorine, and bromine; even more preferably, the substituent is selected from one or more of methyl, ethyl, methoxy, ethoxy, and chlorine.

[0018] The ether ester compound according to the present invention is preferably selected from the following compounds: said ether ester compound is selected from the following compounds: 2-methoxyphenyl acetate, 2-methoxyphenyl propionate, 2-methoxyphenyl butyrate, 2-methoxyphenyl isobutyrate, 2-methoxyphenyl benzoate, 2-ethoxybenzoate, 2-methoxyphenyl benzoate, 2-ethylbenzoate, 2-methylbenzoate, 2-chlorobenzoate, 4-ethoxybenzoate, 4-methoxyphenyl benzoate, 4-ethylbenzoate, 4-methylbenzoate, 4-chlorobenzoate, 2,4,6 2-Methoxyphenyl trimethylbenzoate, 2-methoxyphenyl 1-naphthoic acid, 2-methoxyphenyl 2-phenylacetic acid, 2-(2-ethoxyphenyl)acetic acid, 2-(2-methoxyphenyl)acetic acid, 2-(2-ethylphenyl)acetic acid, 2-(2-methylphenyl)acetic acid, 2-methoxyphenyl 2-(chlorophenyl)acetic acid, 2-(4-ethoxyphenyl)acetic acid, 2-(4-methoxyphenyl)acetic acid, 2-(4-ethylphenyl)acetic acid, 2-(4-methylphenyl)acetic acid, 2-(4-chlorophenyl)acetic acid, 2-methoxyphenyl 2-(4-chlorophenyl)acetic acid, 3-phenyl 2-Methoxyphenyl propionate, 2-Methoxyphenyl 3-(2-ethoxyphenyl)propionate, 2-Methoxyphenyl 3-(2-methoxyphenyl)propionate, 2-Methoxyphenyl 3-(2-ethylphenyl)propionate, 2-Methoxyphenyl 3-(2-methylphenyl)propionate, 2-Methoxyphenyl 3-(2-chlorophenyl)propionate, 2-Methoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-Methoxyphenyl 3-(4-methoxyphenyl)propionate, 2-Methoxyphenyl 3-(4-ethylphenyl)propionate, 2-Methoxyphenyl 3-(4-methylphenyl)propionate, 2-Methoxyphenyl 3-(4-chlorophenyl)propionate, 2-Methoxyphenyl cyclohexanecarboxylate, 2-Ethoxyphenyl acetate, 2-Ethoxyphenyl propionate, 2-Butyric acid 2-Ethoxyphenyl ester, 2-Ethoxyphenyl isobutyrate, 2-Ethoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Methoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Methylbenzoate, 2-Ethoxyphenyl benzoate, 2-Chlorobenzoate, 2-Ethoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Methoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Ethoxyphenyl benzoate, 2-Methylbenzoate, 2-Ethoxyphenyl benzoate, 2-Chlorobenzoate, 2,4,6-Trimethylbenzoate, 2-Ethoxyphenyl 1-Naphthoic acid, 2-Ethoxyphenyl acetic acid, 2-(2-Ethoxyphenyl)acetic acid.2-(2-Methoxyphenyl)acetic acid 2-ethoxyphenyl ester, 2-(2-Ethylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(2-Methylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(2-Chlorophenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Ethoxyphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Methoxyphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Ethylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Methylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Chlorophenyl)acetic acid 2-ethoxyphenyl ester, 3-Phenylacetic acid 2-ethoxyphenyl ester, 3-(2-Ethoxyphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Methoxyphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Ethylphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Ethylphenyl)propionic acid 2-ethoxyphenyl ester 2-Ethoxyphenyl phenyl propionate, 2-Ethoxyphenyl 3-(2-methylphenyl)propionate, 2-Ethoxyphenyl 3-(2-chlorophenyl)propionate, 2-Ethoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-Ethoxyphenyl 3-(4-methoxyphenyl)propionate, 2-Ethoxyphenyl 3-(4-ethylphenyl)propionate, 2-Ethoxyphenyl 3-(4-methylphenyl)propionate, 2-Ethoxyphenyl 3-(4-chlorophenyl)propionate, 2-Ethoxyphenyl cyclohexanecarboxylate, 2-Methoxy-4-methylphenyl acetate, 2-Methoxy-4-methylphenyl propionate, 2-Methoxy-4-methylphenyl butyrate, 2-Methoxy-4-methylphenyl isobutyrate, 2-Methoxy-4-methylphenyl benzoate, 2- 2-Methoxy-4-methylphenyl ester of ethoxybenzoic acid, 2-methoxy-4-methylphenyl ester of 2-methoxybenzoic acid, 2-methoxy-4-methylphenyl ester of 2-ethylbenzoic acid, 2-methoxy-4-methylphenyl ester of 2-methylbenzoic acid, 2-methoxy-4-methylphenyl ester of 2-chlorobenzoic acid, 2-methoxy-4-methylphenyl ester of 4-ethoxybenzoic acid, 2-methoxy-4-methylphenyl ester of 4-methoxybenzoic acid, 2-methoxy-4-methylphenyl ester of 4-ethylbenzoic acid, 2-methoxy-4-methylphenyl ester of 4-methylbenzoic acid, 2-methoxy-4-methylphenyl ester of 4-chlorobenzoic acid, 2,4,6-trimethylbenzoic acid, 2-methoxy-4-methylphenyl ester of 1-naphthoic acid, 2- 2-Methoxy-4-methylphenyl acetic acid, 2-(2-ethoxyphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(2-methoxyphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(2-ethylphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(2-methylphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(2-chlorophenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(4-ethoxyphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(4-methoxyphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(4-ethylphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid, 2-(4-methylphenyl)acetic acid 2-methoxy-4-methylphenyl acetic acid2-(4-Chlorophenyl)acetic acid 2-methoxy-4-methylphenyl ester, 3-phenylpropionic acid 2-methoxy-4-methylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(2-methylphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(2-chlorophenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(4-ethoxyphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(4-methoxyphenyl)propionic acid 2-methoxy-4-methylphenyl ester, 3-(4-ethylphenyl)propionic acid 2-methoxy-4-methylphenyl Esters, 2-methoxy-4-methylphenyl 3-(4-methylphenyl)propionic acid, 2-methoxy-4-methylphenyl 3-(4-chlorophenyl)propionic acid, 2-methoxy-4-methylphenyl cyclohexanecarboxylic acid, 2-ethoxy-4-methylphenyl acetate, 2-ethoxy-4-methylphenyl propionate, 2-ethoxy-4-methylphenyl butyrate, 2-ethoxy-4-methylphenyl isobutyrate, 2-ethoxy-4-methylphenyl benzoate, 2-ethoxy-4-methylphenyl 2-ethoxybenzoic acid, 2-ethoxy-4-methylphenyl 2-methoxybenzoic acid, 2-ethoxy-4-methylphenyl 2-ethylbenzoic acid, 2-ethoxy-4-methylphenyl 2-methylbenzoic acid, 2-ethoxy-4-methylphenyl 2-chlorobenzoic acid Phenyl ester, 2-ethoxy-4-methylphenyl 4-ethoxybenzoic acid, 2-ethoxy-4-methylphenyl 4-methoxybenzoic acid, 2-ethoxy-4-methylphenyl 4-ethylbenzoic acid, 2-ethoxy-4-methylphenyl 4-methylbenzoic acid, 2-ethoxy-4-methylphenyl 4-chlorobenzoic acid, 2,4,6-trimethylbenzoic acid, 2-ethoxy-4-methylphenyl 1-naphthoic acid, 2-ethoxy-4-methylphenyl 2-phenylacetic acid, 2-ethoxy-4-methylphenyl 2-(2-ethoxyphenyl)acetic acid, 2-ethoxy-4-methylphenyl 2-(2-methoxyphenyl)acetic acid, 2-ethoxy-4-methylphenyl 2-(2-ethylphenyl)acetic acid, 2 2-(2-Methylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-methylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 3-phenylpropionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester2-Ethoxy-4-methylphenyl 3-(2-ethylphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(2-methylphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(2-chlorophenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(4-ethoxyphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(4-methoxyphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(4-ethylphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(4-methylphenyl)propionic acid, 2-ethoxy-4-methylphenyl 3-(4-chlorophenyl)propionic acid, 2-ethoxy-4-methylphenyl cyclohexanecarboxylate, 2-methoxy-4-ethylphenyl acetate, 2-methoxy-4-ethylpropionic acid Phenyl ester, 2-methoxy-4-ethylphenyl butyrate, 2-methoxy-4-ethylphenyl isobutyrate, 2-methoxy-4-ethylphenyl benzoate, 2-ethoxybenzoate, 2-methoxy-4-ethylphenyl benzoate, 2-methoxy-4-ethylphenyl benzoate, 2-ethylbenzoate, 2-methoxy-4-ethylphenyl benzoate, 2-methylbenzoate, 2-chlorobenzoate, 2-methoxy-4-ethylphenyl benzoate, 2-ethoxy-4-ethylphenyl benzoate, 2-methoxy-4-ethylphenyl benzoate, 2-methoxy-4-ethylphenyl benzoate, 2-methylbenzoate, 2-methoxy-4-ethylphenyl benzoate, 2-methylbenzoate, 2-methoxy-4-ethylphenyl benzoate, 2-chlorobenzoate 2-Ethylphenyl ester, 2,4,6-trimethylbenzoic acid 2-methoxy-4-ethylphenyl ester, 1-naphthoic acid 2-methoxy-4-ethylphenyl ester, 2-phenylacetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-methylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester 2-(4-Ethylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-methylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 3-phenylpropionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-methylphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-chlorophenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(4-ethoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester2-Methoxy-4-Ethylphenyl 3-(4-methoxyphenyl)propionic acid, 2-Methoxy-4-Ethylphenyl 3-(4-ethylphenyl)propionic acid, 2-Methoxy-4-Ethylphenyl 3-(4-methylphenyl)propionic acid, 2-Methoxy-4-Ethylphenyl 3-(4-chlorophenyl)propionic acid, 2-Methoxy-4-Ethylphenyl cyclohexanecarboxylate, 2-Ethoxy-4-Ethylphenyl acetate, 2-Ethoxy-4-Ethylphenyl propionic acid, 2-Ethoxy-4-Ethylphenyl butyrate, 2-Ethoxy-4-Ethylphenyl isobutyrate, 2-Ethoxy-4-Ethylphenyl benzoate, 2-Ethoxy-4-Ethylphenyl 2-ethoxybenzoate, 2-Methoxy-4-Ethylphenyl 2-ethoxybenzoate, 2-Ethoxy-4-Ethylphenyl 2-Ethoxy- 4-Ethylphenyl ester, 2-Methylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 2-Chlorobenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-ethoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-methoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-Ethylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-Methylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-Chlorobenzoic acid 2-ethoxy-4-ethylphenyl ester, 2,4,6-trimethylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 1-Naphthoic acid 2-ethoxy-4-ethylphenyl ester, 2-Phenylacetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2- Ethoxy-4-ethylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-methylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-methylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 3-phenylpropionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester 2-Ethylphenyl ester, 2-ethoxy-4-ethylphenyl ester of 3-(2-methoxyphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(2-ethylphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(2-methylphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(2-chlorophenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(4-ethoxyphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(4-methoxyphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(4-ethylphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(4-methylphenyl)propionate, 2-ethoxy-4-ethylphenyl ester of 3-(4-chlorophenyl)propionate, 2-ethoxy-4-ethylphenyl ester of cyclohexanecarboxylic acid.

[0019] A second object of the present invention is to provide a method for preparing the ether ester compound, comprising:

[0020] The para-substituted or unsubstituted o-alkoxyphenol shown in Formula N is esterified with the acyl halide shown in Formula S in a solvent under the action of an acid-binding agent to obtain an ether ester compound as shown in Formula M.

[0021] In formula S, X is a halogen.

[0022] As an example, the ether ester compounds according to the present invention can be obtained by the following preparation method:

[0023] An esterification reaction is carried out between para-substituted or unsubstituted o-alkoxyphenol (formula N) and acyl chloride (formula S) in a solvent (such as THF) under the action of an acid-binding agent (such as Et3N) to obtain an ether ester compound as shown in formula M:

[0024]

[0025] According to the present invention, X is a halogen, preferably X is Cl.

[0026] In this invention, the acid-binding agent includes, but is not limited to, triethylamine.

[0027] According to the present invention, the molar ratio of the acid-binding agent to the o-alkoxyphenol can be selected within a wide range. In a preferred embodiment of the present invention, the molar ratio of the acid-binding agent to the o-alkoxyphenol is (1.3-1.7):1.

[0028] According to the present invention, the solvent includes, but is not limited to, tetrahydrofuran.

[0029] According to the present invention, the amount of solvent can be selected within a wide range. In a preferred embodiment of the present invention, the amount of solvent is 1-5 ml relative to 1 mmol of o-alkoxyphenol.

[0030] According to the present invention, the molar ratio of the o-alkoxyphenol to the acyl halide can be selected within a wide range. In a preferred embodiment of the present invention, the molar ratio of the o-alkoxyphenol to the acyl halide is 1:(0.8-1.2).

[0031] In a preferred embodiment of the present invention, the esterification reaction conditions include: reacting at a temperature of 15-80°C (preferably the reflux temperature of the solvent) for 7-24 hours under a protective atmosphere; preferably, the preparation method includes:

[0032] Under a protective atmosphere (e.g., nitrogen and / or inert gas), the o-alkoxyphenol, the acid-binding agent, and the solvent are mixed, and a solution containing the acyl halide is added dropwise at 10-20°C, followed by reflux reaction at the solvent's reflux temperature for 7-24 hours.

[0033] A third objective of this invention is to provide an application of the product obtained by the preparation method of the ether ester compound or the ether ester compound described above in olefin polymerization reactions.

[0034] For example, in the aforementioned application, the ether ester compound is used as a component of an olefin polymerization catalyst. In this case, the ether ester compound acts as an internal electron donor in the solid component of the olefin polymerization catalyst. The olefin is preferably propylene; that is, the present invention provides the application of the ether ester compound according to the invention in propylene polymerization, for example, as an internal electron donor in a propylene polymerization catalyst, such as a Ziegler-Natta catalyst.

[0035] The ether ester compounds provided by this invention have a simple structure and can be obtained by esterification of inexpensive and readily available acyl chlorides with para-substituted or unsubstituted o-alkoxyphenols. The preparation process is mild, simple, and safe, avoiding the use of highly toxic chemicals.

[0036] The ether ester compounds according to the present invention can be used as novel internal electron donors in olefin polymerization catalysts, and further in the polymerization reactions of olefins, especially propylene. Propylene polymerization catalysts using the ether ester compounds of the present invention exhibit high catalytic activity, while the polymers obtained from the polymerization reactions have high isotacticity. Detailed Implementation

[0037] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0038] The present invention will be further described below through specific embodiments, but the scope of the present invention is not limited thereto.

[0039] Test methods

[0040] Nuclear magnetic resonance (NMR) measurements: Measured using a Bruke DMX300 NMR spectrometer. 1 H-NMR (300MHz, solvent CDCl3, TMS as internal standard, measurement temperature 300K).

[0041] Polymer isotactic index: determined by heptane extraction method (boiling heptane extraction for 6 hours): 2 g of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotactic index.

[0042] Example 1

[0043] Preparation of ether ester compound (1)

[0044] The structural formula of ether ester compound (1) is as follows:

[0045]

[0046] Structural formula of ether ester compound (1)

[0047] Under nitrogen protection, 20 mmol of 2-methoxyphenol, 30 mmol of triethylamine, and 20 ml of tetrahydrofuran (THF) were added to a 250 ml three-necked flask and stirred. The mixture was cooled to 10 °C in an ice bath, and 10 ml of 20 mmol of acetyl chloride in THF solution was added dropwise at 10-20 °C. After the addition was complete, the ice bath was removed, and the mixture was allowed to warm naturally to room temperature. The mixture was then heated to the reflux temperature of THF and refluxed for 7-24 hours, with the reaction monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature. The mixture was washed with 30 ml of water, separated, and the aqueous phase was extracted twice with 25 ml of diethyl ether. The organic phases were combined. The mixture was washed with 30 ml of 1N HCl, then with 50 ml of saturated NaHCO3 solution, and then with 50 ml of water. The organic phase was dried over 10 g of anhydrous Na2SO4, concentrated under vacuum to remove the solvent, and purified by column chromatography to obtain the target ether ester compound (1).

[0048] Then, using 1 ¹H NMR confirmed the structure of the synthesized ether ester compound (1) as follows:

[0049] 1 ¹H NMR (300MHz, CDCl₃, TMS as internal standard, δ / ppm): 6.91-7.22 (m, 4H), 3.82 (s, 3H), 2.31 (s, 3H).

[0050] Example 2

[0051] Preparation of ether ester compound (2)

[0052] Following the method of Example 1, 2-methoxyphenol was reacted with benzoyl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 (2) is an ether ester compound with methyl and R being phenyl, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0053] Example 3

[0054] Preparation of ether ester compound (3)

[0055] Following the method of Example 1, 2-methoxy-4-ethylphenol was reacted with 2-ethoxybenzoyl chloride to generate R as shown in Formula M. 1 Ethyl, R 2 (3) is an ether ester compound of methyl and R is 2-ethoxyphenyl, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0056] Example 4

[0057] Preparation of ether ester compound (4)

[0058] Following the method of Example 1, 2-methoxy-4-methylphenol was reacted with 2-methoxybenzoyl chloride to generate R as shown in Formula M. 1 Methyl, R 2 (4) is an ether ester compound of methyl and R is 2-methoxyphenyl, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0059] Example 5

[0060] Preparation of ether ester compound (5)

[0061] Following the method of Example 1, 2-methoxyphenol was reacted with 3-phenylpropionyl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 5) is an ether ester compound with methyl group and R being phenylethyl group, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0062] Example 6

[0063] Preparation of ether ester compound (6)

[0064] Following the method of Example 1, 2-ethoxy-4-methylphenol was reacted with 2,4,6-trimethylbenzoyl chloride to generate R as shown in Formula M. 1 Methyl, R 2 It is an ether ester compound of ethyl group and R is 2,4,6-trimethylphenyl (6), and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0065] Example 7

[0066] Preparation of ether ester compound (7)

[0067] Following the method of Example 1, 2-methoxy-4-ethylphenol was reacted with 1-naphthoyl chloride to generate R as shown in Formula M.1 Ethyl, R 2 It is an ether ester compound with methyl and R being 1-naphthyl (7), and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0068] Example 8

[0069] Preparation of ether ester compound (8)

[0070] Following the method of Example 1, 2-methoxyphenol was reacted with 2-chlorobenzoyl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 8) is an ether ester compound of methyl and R is 2-chlorophenyl, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0071] Example 9

[0072] Preparation of ether ester compound (9)

[0073] Following the method of Example 1, 2-methoxyphenol was reacted with isobutyryl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 9) are ether ester compounds with methyl and isopropyl groups (R), and are used with... 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0074] Example 10

[0075] Preparation of ether ester compound (10)

[0076] Following the method of Example 1, 2-methoxyphenol was reacted with cyclohexylformyl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 10 is an ether ester compound with methyl group and R being cyclohexyl group, and is used with... 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0077] Example 11

[0078] Preparation of ether ester compound (11)

[0079] Following the method of Example 1, 2-methoxyphenol was reacted with n-butyryl chloride to generate R as shown in Formula M. 1 For hydrogen, R 2 11 is an ether ester compound with methyl and R being n-propyl, and is used with 1 Its structure was confirmed by H NMR, as detailed in Table 1.

[0080] Table 1 Ethers and Esters

[0081]

[0082]

[0083] Example 12

[0084] Preparation of solid components of catalyst

[0085] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. 1.4 g of phthalic anhydride was then added, and the mixture was maintained for another 1 h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, during which solids gradually precipitated. 6 mmol of 2-methoxyphenyl benzoate (2), the ether ester compound prepared in Example 2, was added as an internal electron donor, and the temperature was maintained for 1 h. After filtration, the mixture was washed twice with 70 mL of toluene to obtain a solid precipitate. Then add 60 mL of toluene and 40 mL of TiCl4, heat to 110 °C, maintain for 2 h, drain the filtrate, repeat the same operation once, then wash three times with 70 mL of toluene at 110 °C for 10 min each time, then add 60 mL of hexane and wash twice to obtain the catalyst solid component.

[0086] Example 13

[0087] propylene polymerization reaction

[0088] A dry 250 mL three-necked flask was thoroughly purged with nitrogen and propylene, respectively. 100 mL of heptane was added, and the mixture was heated to 70 °C. Then, 2.0 mmol of AlEt3 and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS) were added under normal pressure to achieve an Al / Si molar ratio of 20. At this temperature, 10 mg of the catalyst solid component prepared in Example 12 (containing 3 wt% Ti) was added, and the reaction was allowed to proceed for 2 h. The reaction was then terminated with ethanol. The resulting polymer was washed with anhydrous ethanol and dried under vacuum. The catalyst activity was calculated to be 198 gPP / (gCat·2h), and the isotactic index of the polymer was 97.6%. It is evident that using the ether ester compound of this invention as the catalyst component for propylene polymerization results in a propylene polymerization catalyst with high catalytic activity and a polymer with high isotacticity.

[0089] It has been verified that using the ether ester compounds in Examples 1 and 3-11 of this invention as catalyst components for propylene polymerization results in propylene polymerization catalysts with high catalytic activity and high isotacticity of the polymer obtained from the polymerization reaction.

[0090] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0091] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0092] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0093] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0094] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

[0095] Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

Claims

1. Use of an ether ester compound in an olefin polymerization reaction, characterized in that, In the application, the ether ester compound is used as a component of an olefin polymerization catalyst; The ether ester compound has a structural formula as shown in formula M: Formula M; wherein R is selected from hydrogen or Ci-C6alkyl; 1 selected from hydrogen or Ci-C6alkyl; R 2 selected from C1-C6alkyl; R is selected from C1-C6 alkyl, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent, C5-C20 cycloalkyl with or without substituent.

2. The application according to claim 1, wherein R is selected from C1-C4 alkyl, C6-C10 aryl with or without substituent, C7-C10 aralkyl with or without substituent, C5-C10 cycloalkyl with or without substituent. R 1 selected from hydrogen or C1-C4alkyl; and / or, R 2 selected from the group consisting of C1-C4alkyl; and / or, 3. The application according to claim 1, wherein R is selected from C1-C3 alkyl, phenyl with or without substituent, naphthyl with or without substituent, benzyl with or without substituent, phenethyl with or without substituent, cyclohexyl with or without substituent.

4. The application according to claim 1, wherein the substituent is selected from one or more of C1-C18 alkyl, C1-C18 alkoxy, halogen. R 1 selected from hydrogen or methyl or ethyl; and / or, R 2 is selected from methyl or ethyl; and / or, 5. The application according to claim 1, wherein the substituent is selected from one or more of C1-C6 alkyl, C1-C6 alkoxy, halogen.

6. The application according to claim 1, wherein the substituent is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine.

7. The application according to claim 1, wherein the substituent is selected from one or more of methyl, ethyl, methoxy, ethoxy, chlorine.

8. The application according to claim 1, wherein the ether ester compound is prepared by a method comprising:

9. The application according to any one of claims 1-8, wherein the ether ester compound is prepared by a method comprising: carrying out esterification reaction of para-substituted or unsubstituted ortho-alkyloxy phenol shown in formula N with acyl halide shown in formula S in a solvent under the action of an acid binding agent to obtain the ether ester compound shown in formula M; 10. The application according to claim 9, wherein X is Cl; and / or, the molar ratio of the acid binding agent to the ortho-alkyloxy phenol is (1.3-1.7):1; and / or, the amount of the solvent is 1-5 ml relative to 1 mmol of the ortho-alkyloxy phenol; and / or, the molar ratio of the ortho-alkyloxy phenol to the acyl halide is 1:(0.8-1.2).

11. The application according to claim 9, wherein the conditions of the esterification reaction include: under a protective atmosphere, reacting at a temperature of 15-80℃ for 7-24 hours.

12. The application according to claim 9, wherein the method for preparing the ether ester compound comprises: mixing the ortho-alkyloxy phenol, the acid binding agent and the solvent under a protective atmosphere, adding a solution containing the acyl halide dropwise at 10-20℃, and then refluxing at the refluxing temperature of the solvent for 7-24 hours. The ether ester compound is selected from the group consisting of 2-methoxyphenyl acetate, 2-methoxyphenyl propionate, 2-methoxyphenyl n-butyrate, 2-methoxyphenyl isobutyrate, 2-methoxyphenyl benzoate, 2-methoxyphenyl 2-ethoxybenzoate, 2-methoxyphenyl 2-methoxybenzoate, 2-methoxyphenyl 2-ethylbenzoate, 2-methoxyphenyl 2-methylbenzoate, 2-methoxyphenyl 2-chlorobenzoate, 2-methoxyphenyl 4-ethoxybenzoate, 2-methoxyphenyl 4-methoxybenzoate, 2-methoxyphenyl 4-ethylbenzoate, 2-methoxyphenyl 4-methylbenzoate, 2-methoxyphenyl 4-chlorobenzoate, 2-methoxyphenyl 2,4,6-trimethylbenzoate, 2-methoxyphenyl 1-naphthoate, 2-methoxyphenyl 2-phenylacetate, 2-methoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(2-methoxyphenyl)acetate, 2-methoxyphenyl 2-(2-ethylphenyl)acetate, 2-methoxyphenyl 2-(2-methylphenyl)acetate, 2-methoxyphenyl 2-(2-chlorophenyl)acetate, 2-methoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(4-methoxyphenyl)acetate, 2-methoxyphenyl 2-(4-ethylphenyl)acetate, 2-methoxyphenyl 2-(4-methylphenyl)acetate, 2-methoxyphenyl 2-(4-chlorophenyl)acetate, 2-methoxyphenyl 3-phenylpropionate, 2-methoxyphenyl 3-(2-ethoxyphenyl)propionate, 2-methoxyphenyl 3-(2-methoxyphenyl)propionate, 2-methoxyphenyl 3-(2-ethylphenyl)propionate, 2-methoxyphenyl 3-(2-methylphenyl)propionate, 2-methoxyphenyl 3-(2-chlorophenyl)propionate, 2-methoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxyphenyl 3-(4-methoxyphenyl)propionate, 2-methoxyphenyl 3-(4-ethylphenyl)propionate, 2-methoxyphenyl 3-(4-methylphenyl)propionate, 2-methoxyphenyl 3-(4-chlorophenyl)propionate, 2-methoxyphenyl cyclohexanecarboxylate, 2-ethoxyphenyl acetate, 2-ethoxyphenyl propionate, 2-ethoxyphenyl butyrate, 2-ethoxyphenyl isobutyrate, 2-ethoxyphenyl benzoate, 2-ethoxyphenyl 2-ethoxybenzoate, 2-ethoxyphenyl 2-methoxybenzoate, 2-ethoxyphenyl 2-ethylbenzoate, 2-ethoxyphenyl 2-methylbenzoate, 2-ethoxyphenyl 2-chlorobenzoate, 2-ethoxyphenyl 4-ethoxybenzoate, 2-ethoxyphenyl 4-methoxybenzoate, 2-ethoxyphenyl 4-ethylbenzoate, 2-ethoxyphenyl 4-methylbenzoate, 2-ethoxyphenyl 4-chlorobenzoate, 2-ethoxyphenyl 2,4,6-trimethylbenzoate, 2-ethoxyphenyl 1-naphthoate, 2-ethoxyphenyl 2-phenylacetate, 2-ethoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(2-methoxyphenyl)acetate, 2-ethoxyphenyl 2-(2-ethylphenyl)acetate, 2-ethoxyphenyl 2-(2-methylphenyl)acetate, 2-ethoxyphenyl 2-(2-chlorophenyl)acetate, 2-ethoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-methoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-ethylphenyl)acetate, 2-ethoxyphenyl 2-(4-methylphenyl)acetate, 2-ethoxyphenyl 2-(4-chlorophenyl)acetate, 2-ethoxyphenyl 3-phenylpropionate, 2-ethoxyphenyl 3-(2-ethoxyphenyl)propionate, 2-ethoxyphenyl 3-(2-methoxyphenyl)propionate, 2-ethoxyphenyl 3-(2-ethylphenyl)propionate, 2-ethoxyphenyl 3-(2-methylphenyl)propionate, 2-ethoxyphenyl 3-(2-chlorophenyl)propionate, 2-ethoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-ethoxyphenyl 3-(4-methoxyphenyl)propionate, 2-ethoxyphenyl 3-(4-ethylphenyl)propionate, 2-ethoxyphenyl 3-(4-methylphenyl)propionate, 2-ethoxyphenyl 3-(4-chlorophenyl)propionate, 2-ethoxyphenyl cyclohexanecarboxylate, and mixtures thereof.2-(2-Ethylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(2-Methylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(2-Chlorophenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Ethoxyphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Methoxyphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Ethylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Methylphenyl)acetic acid 2-ethoxyphenyl ester, 2-(4-Chlorophenyl)acetic acid 2-ethoxyphenyl ester, 3-Phenylacetic acid 2-ethoxyphenyl ester, 3-(2-Ethoxyphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Methoxyphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Ethylphenyl)propionic acid 2-ethoxyphenyl ester, 3-(2-Methylphenyl)propionic acid 2- Ethoxyphenyl ester, 2-ethoxyphenyl 3-(2-chlorophenyl)propionic acid, 2-ethoxyphenyl 3-(4-ethoxyphenyl)propionic acid, 2-ethoxyphenyl 3-(4-methoxyphenyl)propionic acid, 2-ethoxyphenyl 3-(4-ethylphenyl)propionic acid, 2-ethoxyphenyl 3-(4-methylphenyl)propionic acid, 2-ethoxyphenyl 3-(4-chlorophenyl)propionic acid, 2-ethoxyphenyl cyclohexanecarboxylic acid, 2-methoxy-4-methylphenyl acetate, 2-methoxy-4-methylphenyl propionate, 2-methoxy-4-methylphenyl butyrate, 2-methoxy-4-methylphenyl isobutyrate, 2-methoxy-4-methylphenyl benzoate, 2-methoxy-4-methylphenyl 2-ethoxybenzoic acid, 2-methoxybenzoic acid 4-Methylphenyl ester, 2-ethylbenzoic acid 2-methoxy-4-methylphenyl ester, 2-methylbenzoic acid 2-methoxy-4-methylphenyl ester, 2-chlorobenzoic acid 2-methoxy-4-methylphenyl ester, 4-ethoxybenzoic acid 2-methoxy-4-methylphenyl ester, 4-methoxybenzoic acid 2-methoxy-4-methylphenyl ester, 4-ethylbenzoic acid 2-methoxy-4-methylphenyl ester, 4-methylbenzoic acid 2-methoxy-4-methylphenyl ester, 4-chlorobenzoic acid 2-methoxy-4-methylphenyl ester, 2,4,6-trimethylbenzoic acid 2-methoxy-4-methylphenyl ester, 1-naphthoic acid 2-methoxy-4-methylphenyl ester, 2-phenylacetic acid 2-methoxy-4-methylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-methoxy-4- 2-Methylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(2-methylphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(4-methylphenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-methoxy-4-methylphenyl ester, 2-phenylpropionic acid 2-methoxy-4-methylphenyl ester3-(2-ethoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-methylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-chlorophenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4-ethoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4-methoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4-ethylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4-methylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4-chlorophenyl)propionic acid 2-ethoxy-4-methylphenyl ester, cyclohexanecarboxylic acid 2-ethoxy-4-methylphenyl ester, acetic acid 2-ethoxy-4-methylphenyl ester, propionic acid 2-ethoxy-4-methylphenyl ester, butyric acid 2-ethoxy-4-methylphenyl ester, isobutyric acid 2-ethoxy-4-methylphenyl ester, benzoic acid 2-ethoxy-4-methylphenyl ester, 2-ethoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 2-methoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 2-ethylbenzoic acid 2-ethoxy-4-methylphenyl ester, 2-methylbenzoic acid 2-ethoxy-4-methylphenyl ester, 2-chlorobenzoic acid 2-ethoxy-4-methylphenyl ester, 4-ethoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 4-methoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 4-ethylbenzoic acid 2-ethoxy-4-methylphenyl ester, 4-methylbenzoic acid 2-ethoxy-4-methylphenyl ester, 4-chlorobenzoic acid 2-ethoxy-4-methylphenyl ester, 2,4,6-trimethylbenzoic acid 2-ethoxy-4-methylphenyl ester, 1-naphthoic acid 2-ethoxy-4-methylphenyl ester, 2-phenylacetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-methylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-methylphenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-ethoxy-4-methylphenyl ester, 3-phenylpropionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(2-methylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester,3-(2-chlorophenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4- ethoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4- methoxyphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4- ethylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4- methylphenyl)propionic acid 2-ethoxy-4-methylphenyl ester, 3-(4- chlorophenyl)propionic acid 2-ethoxy-4-methylphenyl ester, cyclohexanecarboxylic acid 2-ethoxy-4-methylphenyl ester, acetic acid 2-methoxy-4- ethylphenyl ester, propionic acid 2-methoxy-4-ethylphenyl ester, butyric acid 2-methoxy-4-ethylphenyl ester, isobutyric acid 2-methoxy-4- ethylphenyl ester, benzoic acid 2-methoxy-4-ethylphenyl ester, 2- ethoxybenzoic acid 2-methoxy-4-ethylphenyl ester, 2-methoxybenzoic acid 2-methoxy-4-ethylphenyl ester, 2-ethylbenzoic acid 2-methoxy-4- ethylphenyl ester, 2-methylbenzoic acid 2-methoxy-4-ethylphenyl ester, 2-chlorobenzoic acid 2-methoxy-4-ethylphenyl ester, 4-ethoxybenzoic acid 2-methoxy-4-ethylphenyl ester, 4-methoxybenzoic acid 2-methoxy-4- ethylphenyl ester, 4-ethylbenzoic acid 2-methoxy-4-ethylphenyl ester, 4-methylbenzoic acid 2-methoxy-4-ethylphenyl ester, 4-chlorobenzoic acid 2-methoxy-4-ethylphenyl ester, 2,4,6-trimethylbenzoic acid 2-methoxy-4- ethylphenyl ester, 1-naphthoic acid 2-methoxy-4-ethylphenyl ester, 2- phenylacetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-methylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-methylphenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-methoxy-4-ethylphenyl ester, 3- phenylpropionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-methylphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(2-chlorophenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(4-ethoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(4-methoxyphenyl)propionic acid 2-methoxy-4-ethylphenyl ester, 3-(4-ethylphenyl)propionic acid 2-methoxy-4-ethylphenyl ester,3-(4-methylphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-chlorophenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, cyclohexanecarboxylic acid 2-ethoxy-4-ethylphenyl ester, acetic acid 2-ethoxy-4-ethylphenyl ester, propionic acid 2-ethoxy-4-ethylphenyl ester, butyric acid 2-ethoxy-4-ethylphenyl ester, isobutyric acid 2-ethoxy-4-ethylphenyl ester, benzoic acid 2-ethoxy-4-ethylphenyl ester, 2-ethoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 2-methoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 2-ethylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 2-methylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 2-chlorobenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-ethoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-methoxybenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-ethylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-methylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 4-chlorobenzoic acid 2-ethoxy-4-ethylphenyl ester, 2,4,6-trimethylbenzoic acid 2-ethoxy-4-ethylphenyl ester, 1-naphthoic acid 2-ethoxy-4-ethylphenyl ester, 2-phenylacetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-ethoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-methoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-ethylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-methylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(2-chlorophenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-ethoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-methoxyphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-ethylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-methylphenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 2-(4-chlorophenyl)acetic acid 2-ethoxy-4-ethylphenyl ester, 3-phenylpropionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-ethoxyphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-methoxyphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-ethylphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-methylphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(2-chlorophenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-ethoxyphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-methoxyphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-ethylphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-methylphenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, 3-(4-chlorophenyl)propionic acid 2-ethoxy-4-ethylphenyl ester, cyclohexanecarboxylic acid 2-ethoxy-4-ethylphenyl ester. The olefin is propylene. ​ ​ Formula N; Formula S; in Formula S, X is halogen. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 13. The use according to any one of claims 1 to 8, characterized in that, ​

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