Heterogeneous polymerization reaction catalyst and application of heterogeneous polymerization reaction catalyst to preparing homopolymer and copolymer

Abstract

The invention relates to a heterogeneous polymerization reaction catalyst and application of the heterogeneous polymerization reaction catalyst to preparing a homopolymer and a copolymer. The heterogeneous polymerization reaction catalyst mainly comprises a supported catalyst promoter A and a catalyst B, the structure of the catalyst B is shown in the formula (I) or the formula (II), R1-R5 are respectively independently chosen from hydrogen, alkyl group, substituendum of the alkyl group, alkoxy group, alkyl sulphanyl, halogen, nitryl, aryl group or substituendum of the aryl group in the formula, the adjacent groups in the R1-R5 form a ring and the number of the formed ring structures is less than 4, R6 is the alkyl group or the aryl group, and L is alkyl group substituted phosphine or allyl. The heterogeneous polymerization reaction catalyst can be used to prepare the homopolymer and the copolymer, the activity is relatively high, the tolerance of the polar functional group is relatively good, the molecular weight of the prepared polymer is relatively large, the distribution of the molecular weight is relatively narrow, the morphology is controllable, no subsequent processing is needed, and the phenomenon of adhesion on a kettle is effectively improved.

Description

technical field

[0001] The invention belongs to the field of polymerization catalysis, and relates to a heterogeneous polymerization reaction catalyst and its application in preparing homopolymers and copolymers. Background technique

[0002] At present, catalysts are divided into homogeneous catalysts and heterogeneous catalysts according to the phase state of the reaction system; homogeneous catalysis refers to the catalytic process in which the catalyst and reactants are in the same homogeneous phase, and the reactants, catalysts and products in homogeneous catalysis They are all in the same phase, the contact area is large, the amount of catalyst is small, and the catalytic efficiency is high. However, the product, catalyst and raw materials need to be separated after the reaction. The process is complicated. Often the catalysts are disposable and cannot be reused. Poor; heterogeneous catalysis refers to the catalytic process in which the reactants and the catalyst are n...

Examples

Embodiment 1

[0069] The preparation method of catalyst B, the steps are as follows:

[0070] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in n-heptane, add trifluoroacetic acid to react to obtain anilinonaphthoquinone ligands, the reaction temperature is 100°C, the time is 15h, the reaction Initially, the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline was 1:1.15, and the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone was 0.33:1,2-hydroxy- The concentration of 1,4-naphthoquinone in n-heptane is 0.125mol / L, and the structural formula of substituted aniline is as follows:

[0071]

[0072] In the formula, R 1 is methyl, R 2 is ethyl, R 3 is methyl, R 4 is ethyl, R 5 It is a methyl group, and after the reaction, the anilinaquinone ligands are purified by toluene recrystallization;

[0073] (2) Dissolving the anilino-naphthoquinone ligands in toluene, adding sodium hydride to react to obtain a ligand salt compound, the tempe...

Embodiment 2

[0079] The preparation method of catalyst B, the steps are as follows:

[0080] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in toluene, add trifluoroacetic acid to react to obtain aniline naphthoquinone ligands, the reaction temperature is 110°C, the time is 6h, when the reaction starts , the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline is 1:1, the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone is 0.32:1, 2-hydroxy-1, The concentration of 4-naphthoquinone in toluene is 0.1mol / L, and the structural formula of substituted aniline is as shown in embodiment 1, and in the formula, R 1 is ethyl, R 2 is methyl, R 3 is ethyl, R 4 is methyl, R 5 After the reaction, the anilinaquinone ligands are purified by n-hexane extraction;

[0081] (2) Dissolving the anilinaquinone ligands in tetrahydrofuran, adding potassium hydride to react to obtain a ligand salt compound, the reaction temperature is 40°C, and the time is 1h....

Embodiment 3

[0085] The preparation method of catalyst B, the steps are as follows:

[0086] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in chlorobenzene, add trifluoroacetic acid to react to obtain anilino-naphthoquinone ligands, the reaction temperature is 130°C, the time is 6h, and the reaction starts , the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline is 1:1.02, and the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone is 0.32:1,2-hydroxy-1 , the concentration of 4-naphthoquinone in chlorobenzene is 0.11mol / L, and the structural formula of substituted aniline is as shown in embodiment 1, and in the formula, R 1 is isopropyl, R 2 is tert-butyl, R 3 is tert-butyl, R 4 is isopropyl, R 5It is isopropyl, and after the reaction, the p-aniline ligands are purified by recrystallization from tetrahydrofuran;

[0087] (2) Aniline naphthoquinone ligands are dissolved in dichloromethane, and n-butyllithium is added to react to obtai...

technical field

[0001] The invention belongs to the field of polymerization catalysis, and relates to a heterogeneous polymerization reaction catalyst and its application in preparing homopolymers and copolymers. Background technique

[0002] At present, catalysts are divided into homogeneous catalysts and heterogeneous catalysts according to the phase state of the reaction system; homogeneous catalysis refers to the catalytic process in which the catalyst and reactants are in the same homogeneous phase, and the reactants, catalysts and products in homogeneous catalysis They are all in the same phase, the contact area is large, the amount of catalyst is small, and the catalytic efficiency is high. However, the product, catalyst and raw materials need to be separated after the reaction. The process is complicated. Often the catalysts are disposable and cannot be reused. Poor; heterogeneous catalysis refers to the catalytic process in which the reactants and the catalyst are n...

Examples

Embodiment 1

[0069] The preparation method of catalyst B, the steps are as follows:

[0070] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in n-heptane, add trifluoroacetic acid to react to obtain anilinonaphthoquinone ligands, the reaction temperature is 100°C, the time is 15h, the reaction Initially, the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline was 1:1.15, and the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone was 0.33:1,2-hydroxy- The concentration of 1,4-naphthoquinone in n-heptane is 0.125mol / L, and the structural formula of substituted aniline is as follows:

[0071]

[0072] In the formula, R 1 is methyl, R 2 is ethyl, R 3 is methyl, R 4 is ethyl, R 5 It is a methyl group, and after the reaction, the anilinaquinone ligands are purified by toluene recrystallization;

[0073] (2) Dissolving the anilino-naphthoquinone ligands in toluene, adding sodium hydride to react to obtain a ligand salt compound, the tempe...

Embodiment 2

[0079] The preparation method of catalyst B, the steps are as follows:

[0080] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in toluene, add trifluoroacetic acid to react to obtain aniline naphthoquinone ligands, the reaction temperature is 110°C, the time is 6h, when the reaction starts , the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline is 1:1, the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone is 0.32:1, 2-hydroxy-1, The concentration of 4-naphthoquinone in toluene is 0.1mol / L, and the structural formula of substituted aniline is as shown in embodiment 1, and in the formula, R 1 is ethyl, R 2 is methyl, R 3 is ethyl, R 4 is methyl, R 5 After the reaction, the anilinaquinone ligands are purified by n-hexane extraction;

[0081] (2) Dissolving the anilinaquinone ligands in tetrahydrofuran, adding potassium hydride to react to obtain a ligand salt compound, the reaction temperature is 40°C, and the time is 1h....

Embodiment 3

[0085] The preparation method of catalyst B, the steps are as follows:

[0086] (1) Dissolve 2-hydroxy-1,4-naphthoquinone and substituted aniline in chlorobenzene, add trifluoroacetic acid to react to obtain anilino-naphthoquinone ligands, the reaction temperature is 130°C, the time is 6h, and the reaction starts , the molar ratio of 2-hydroxy-1,4-naphthoquinone to substituted aniline is 1:1.02, and the molar ratio of trifluoroacetic acid to 2-hydroxy-1,4-naphthoquinone is 0.32:1,2-hydroxy-1 , the concentration of 4-naphthoquinone in chlorobenzene is 0.11mol / L, and the structural formula of substituted aniline is as shown in embodiment 1, and in the formula, R 1 is isopropyl, R 2 is tert-butyl, R 3 is tert-butyl, R 4 is isopropyl, R 5It is isopropyl, and after the reaction, the p-aniline ligands are purified by recrystallization from tetrahydrofuran;

[0087] (2) Aniline naphthoquinone ligands are dissolved in dichloromethane, and n-butyllithium is added to react to obtai...

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