阅读说明：本技术 一种制备4-(1-酮-2-炔苯丙烷)苯酐的方法 (Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride ) 是由 栗晓东 于 2021-06-15 设计创作，主要内容包括：本发明提供了一种制备4-(1-酮-2-炔苯丙烷)苯酐的方法,原料包括苯乙炔、1,2,4-偏苯三酸酐酰氯、催化剂、有机碱和有机溶剂,将苯乙炔、1,2,4-偏苯三酸酐酰氯、催化剂和有机碱加入到有机溶剂中,加热条件下反应制得,所述1,2,4-偏苯三酸酐酰氯、苯乙炔、催化剂、有机碱和有机溶剂的摩尔比为1:(1～1.1):(0.01～0.05):(1.05～1.5):(16～27)。本发明反应原料易得,成本低,液相纯度高,操作步骤简单,收率高,具有工业化应用前景。(The invention provides a method for preparing 4- (1-ketone-2-propargyl phenylpropane) phthalic anhydride, which comprises the following steps of adding phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, an organic base and an organic solvent into the organic solvent, and reacting under a heating condition to obtain the 4- (1-ketone-2-propargyl phenylpropane) phthalic anhydride, wherein the molar ratio of the phenylacetylene, the 1,2, 4-trimellitic anhydride acyl chloride, the catalyst and the organic base to the organic solvent is 1 (1-1.1) to (0.01-0.05) to (1.05-1.5) to (16-27). The method has the advantages of easily obtained reaction raw materials, low cost, high liquid phase purity, simple operation steps, high yield and industrial application prospect.)

1. A method for preparing 4- (1-ketone-2-alkyne phenylpropane) phthalic anhydride comprises the following raw materials of phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, organic base and an organic solvent, and is characterized in that: adding phenylacetylene, 1,2, 4-trimellitic anhydride chloride, a catalyst and organic base into an organic solvent, and reacting under a heating condition to obtain the compound; the molar ratio of the 1,2, 4-trimellitic anhydride acyl chloride to the phenylacetylene to the catalyst to the organic base to the organic solvent is 1 (1-1.1): 0.01-0.05): 1.05-1.5): 16-27;

the organic base is one or more of triethylamine, pyridine, diethylamine, propylamine, tetramethyldiethylamine, tetramethylguanidine or N-methylmorpholine;

the catalyst is one or a mixture of two of nickel bis (triphenylphosphine) chloride, copper tris (triphenylphosphine) iodide, copper tris (triphenylphosphine) bromide, cobalt bis (triphenylphosphine) chloride and ammonium bis (triphenylphosphine) chloride;

the organic solvent is one of trimethylbenzene, methylcyclohexane, dimethylacetamide and tetrahydrofuran.

2. The process for producing 4- (1-keto-2-alkynylpropane) phthalic anhydride according to claim 1, wherein: the method comprises the following reaction steps:

1) adding 1,2, 4-trimellitic anhydride chloride, an organic solvent and an organic base into a reaction bottle, adding a catalyst under mechanical stirring, and heating to 20-90 ℃;

2) dissolving phenylacetylene in an organic solvent, slowly dropwise adding the phenylacetylene into the mixed solution obtained in the step 1), and keeping the temperature for continuous reaction;

3) after the raw material 1,2, 4-trimellitic anhydride chloride completely reacts, cooling the reaction liquid to 10 ℃, filtering, and washing filter cakes with tetrahydrofuran and water respectively;

4) drying in a vacuum drying oven.

3. The process for producing 4- (1-keto-2-alkynylpropane) phthalic anhydride according to claim 2, wherein: the reflux reaction temperature was 50 ℃.

4. The process for producing 4- (1-keto-2-alkynylpropane) phthalic anhydride from tetrahydrofuran according to claim 3, wherein: the organic solvent is tetrahydrofuran.

5. The process for producing 4- (1-keto-2-alkynylpropane) phthalic anhydride according to claim 4, wherein: the organic base is tetramethyl diethylamine.

6. The method for preparing 4- (1-keto-2-alkynylpropane) phthalic anhydride according to claim 5, wherein the catalyst is copper triphenylphosphonium bromide.

7. The process for producing 4- (1-keto-2-alkynylpropane) phthalic anhydride according to any one of claims 1 to 6, wherein: the molar ratio of 1,2, 4-trimellitic anhydride chloride, phenylacetylene, copper triphenyl phosphonium bromide, tetramethyl diethylamine and tetrahydrofuran is 1:1.05:0.03:1.3: 22.

Technical Field

The invention relates to the technical field of polyimide dianhydride monomers, in particular to a method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride.

Background

4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride is used for preparing thermosetting polyimide due to the high temperature resistance, and the heat resistance, the mechanical property and the tensile strength of the material can be improved. The prior literature reports on the preparation of 4- (1-keto-2-alkynylpropane) phthalic anhydride include: chinese patent 201180024067.3, which is obtained by using trimellitic chloride and phenylacetylene as raw materials, toluene as a solvent, palladium acetate as a catalyst and triethylamine as a base, has a yield of only 39.64%.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for preparing high-yield 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride.

Based on the problems, the technical scheme provided by the invention is a method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride, the raw materials comprise phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, organic base and an organic solvent, the phenylacetylene, the 1,2, 4-trimellitic anhydride acyl chloride, the catalyst and the organic base are added into the organic solvent, and the acylation reaction is carried out under the heating condition to obtain the product. The reaction formula is as follows:

wherein the molar ratio of the 1,2, 4-trimellitic anhydride acyl chloride to the phenylacetylene to the catalyst to the organic base to the organic solvent is 1 (1-1.1): 0.01-0.05): 1.05-1.5): 16-27. When the raw material ratio is low, the reaction time is prolonged and a part of the raw material conversion is incomplete. When the proportion is too high, impurities are generated and the color of the product becomes dark.

The organic base is one or more of triethylamine, pyridine, diethylamine, propylamine, tetramethyldiethylamine, tetramethylguanidine or N-methylmorpholine.

The catalyst is one or a mixture of two of bis (triphenylphosphine) nickel chloride, tris (triphenylphosphine) copper iodide, tris (triphenylphosphine) copper bromide, bis (triphenylphosphine) cobalt chloride and bis (triphenylphosphine) ammonium chloride.

The organic solvent is one of trimethylbenzene, methylcyclohexane, dimethylacetamide and tetrahydrofuran.

Specifically, the method comprises the following reaction steps:

1) adding 1,2, 4-trimellitic anhydride chloride, an organic solvent and an organic base into a reaction bottle, adding a catalyst under mechanical stirring, and heating to 20-90 ℃;

2) dissolving phenylacetylene in an organic solvent, slowly dropwise adding the phenylacetylene into the mixed solution obtained in the step 1), and keeping the temperature for continuous reaction;

3) after the raw material 1,2, 4-trimellitic anhydride chloride completely reacts, cooling the reaction liquid to 10 ℃, filtering, and washing filter cakes with tetrahydrofuran and water respectively;

4) drying in a vacuum drying oven.

Preferably, the reflux reaction temperature is 50 deg.C

Preferably, the organic solvent is tetrahydrofuran.

Preferably, the organic base is tetramethyldiethylamine.

Preferably, the catalyst is copper triphenylphosphonium bromide.

Preferably, the molar ratio of 1,2, 4-trimellitic anhydride acid chloride, phenylacetylene, copper triphenylphosphonium bromide, tetramethyldiethylamine and tetrahydrofuran is 1:1.05:0.03:1.3: 22.

The invention has the advantages and beneficial effects that:

the invention provides a new method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride, which has the advantages of easily obtained reaction raw materials, low synthesis cost, high reaction conversion rate which can reach about 90 percent, high liquid phase purity, and liquid phase content which can reach 99.77 percent; the reaction steps are simple and easy to control, and the method has an industrial application prospect.

Drawings

FIG. 1 is a liquid chromatogram of the product prepared according to the present invention.

Detailed Description

The following describes in detail embodiments of the present invention with reference to specific examples.

Example 1 a reaction flask was charged with 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 70g of tetrahydrofuran, and 7.5g of tetramethylethylenediamine, and then 1.4g of triphenylphosphonium cupric bromide was added with mechanical stirring, the temperature was raised to 45 ℃, a 10g tetrahydrofuran solution of 5.3g phenylacetylene was slowly added dropwise, and then the reaction was maintained at this temperature, after the reaction of the raw material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 ℃ and filtered, and after the filter cake was washed with tetrahydrofuran and water, the filter cake was dried in a vacuum drying oven to obtain 4- (1-keto-2-alkynylphenylpropane) phthalic anhydride, 12.2g of a white solid, with a yield of 88.4%.

Example 2 a reaction flask was charged with 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 50g of tetrahydrofuran, and 7.5g of tetramethylethylenediamine, and then 0.8g of triphenylphosphonium cupric bromide was added with mechanical stirring, the temperature was raised to 40 ℃, a 10g tetrahydrofuran solution of 5.1g phenylacetylene was slowly added dropwise, and then the reaction was maintained at this temperature, after the reaction of the raw material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 ℃ and filtered, and after the filter cake was washed with tetrahydrofuran and water, the filter cake was dried in a vacuum drying oven to obtain 4- (1-keto-2-alkynylphenylpropane) phthalic anhydride, 8.3g of white solid, with a yield of 60.1%.

Example 3 a reaction flask was charged with 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 80g of tetrahydrofuran, and 7.5g of tetramethylethylenediamine, and then 2.3g of triphenylphosphonium cupric bromide was added with mechanical stirring, the temperature was raised to 50 ℃, a solution of 5.6g of phenylacetylene in 20g of tetrahydrofuran was slowly added dropwise, and then the reaction was carried out while maintaining the temperature, after the reaction of the raw material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 ℃ and filtered, and after the filter cake was washed with tetrahydrofuran and water, the filter cake was dried in a vacuum drying oven to obtain 4- (1-keto-2-alkynylphenylpropane) phthalic anhydride, 12.5g of white solid, with a yield of 90.6%.

The liquid chromatogram of the product is shown in FIG. 1, and the chromatographic peak conditions are shown in the following Table 1:

TABLE 1 chromatographic Peak area Condition Table

Peak number	Retention time	Area of	Height	Area%
					1	5.273	12008	1236	0.125
2	5.571	2629	305	0.027
					3	5.788	5080	411	0.053
4	6.119	9572024	994006	99.770
					5	9.362	2339	193	0.024
Total of		9594080	996151	100.000

The liquid phase content of the product prepared from table 1 was 99.77%.

Example 4 into a reaction flask were charged 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 60g of methylcyclohexane, and 7.5g of tetramethylethylenediamine, and then 1.5g of triphenylphosphonium cupric bromide was added with mechanical stirring, the temperature was raised to 40 ℃, a solution of 5.6g of phenylacetylene in 20g of methylcyclohexane was slowly dropped, and then the reaction was maintained at this temperature, after the reaction of the raw material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 ℃ and filtered, and after the filter cake was washed with tetrahydrofuran and water, the filter cake was dried in a vacuum drying oven to obtain 4- (1-keto-2-alkynylphenylpropane) phthalic anhydride, 10.8g of which was a white solid, with a yield of 78.3%.

Although the embodiments of the present invention have been described in detail, the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.