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CN-120987965-B - Cyclic anhydride compound and preparation method and application thereof

CN120987965BCN 120987965 BCN120987965 BCN 120987965BCN-120987965-B

Abstract

The invention belongs to the field of organic synthesis, and particularly relates to a cyclic anhydride compound, and a preparation method and application thereof. The cyclic anhydride compound has a structure represented by formula (1'). The preparation method of the cyclic anhydride compound provided by the invention is characterized in that the cyclic anhydride compound can be constructed by three steps of reaction of Michael addition, cyano hydrolysis and intramolecular condensation from the polyhydroxy aromatic compound, the complex protecting group operation is not needed, the reaction temperature is lower than 70 ℃, the high temperature and the high pressure are avoided, the preparation method is suitable for industrial amplified production, and meanwhile, the yield of the target product is stabilized at 60% -80%. In addition, when the cyclic anhydride compound is used as a curing agent of the epoxy resin composition, the epoxy resin composition has high-temperature-resistant adhesive strength and high Tg, and can meet the requirements of underfill in the field of semiconductor packaging. Equation (1 `)

Inventors

  • Li sanliang
  • CHEN CHANGJING

Assignees

  • 韦尔通科技股份有限公司

Dates

Publication Date
20260508
Application Date
20250928

Claims (19)

  1. 1. A cyclic anhydride compound, characterized in that the cyclic anhydride compound has a structure represented by formula (1'): (1'), ,R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 And R 14 in the formula (1') are each independently H or C1-C6 alkyl.
  2. 2. The cyclic anhydride compound according to claim 1, wherein the cyclic anhydride compound has a symmetrical structure.
  3. 3. The cyclic anhydride compound according to claim 1, wherein ,R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 and R 14 in formula (1) are each H.
  4. 4. A method for producing a cyclic anhydride compound according to any one of claims 1 to 3, comprising the steps of: s1 ', michael addition, namely performing cyanoethylation reaction on a polyhydroxy aromatic compound shown in a formula (2') and acrylonitrile to obtain a polycyanoaromatic compound; s2', cyano group hydrolysis, namely, hydrolyzing the polycyanoaromatic compound to convert cyano groups into carboxyl groups so as to obtain the polycyanoaromatic compound; S3', intramolecular condensation, namely carrying out intramolecular anhydride reaction on the polycarboxylic aromatic compound to obtain a cyclic anhydride compound; (2'), In the formula (2'), R 3 、R 4 、R 5 、R 10 、R 11 and R 12 are independently H or C1-C6 alkyl.
  5. 5. The method for producing a cyclic anhydride compound according to claim 4, wherein the polyhydroxy aromatic compound has a symmetrical structure.
  6. 6. The process for producing a cyclic anhydride compound according to claim 4, wherein R 3 、R 4 、R 5 、R 10 、R 11 and R 12 are each H in the formula (2).
  7. 7. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in step S1', the cyanoethylation reaction is performed in the presence of a base and an organic solvent.
  8. 8. The method for producing a cyclic anhydride compound according to claim 7, wherein the molar ratio of the base to the polyhydroxy aromatic compound is 5:1 to 12:1.
  9. 9. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in step S1', the amount of acrylonitrile is 5 to 12 times the molar amount of the polyhydroxy aromatic compound.
  10. 10. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in the step S1', the conditions for cyanoethylation reaction include a temperature of 20 to 50 ℃ for 8 to 24 hours.
  11. 11. The method for producing a cyclic anhydride compound according to claim 7, wherein the base is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate.
  12. 12. The method for producing a cyclic anhydride compound according to claim 7, wherein the organic solvent is methanol and/or ethanol.
  13. 13. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in step S2', the hydrolysis reaction comprises reflux reaction of a polycyanoaromatic compound in a concentrated hydrochloric acid/methanol system.
  14. 14. The method for producing a cyclic anhydride compound according to claim 13, wherein the volume ratio of the concentrated hydrochloric acid to methanol is 1:3 to 1:5.
  15. 15. The method for producing a cyclic anhydride compound according to claim 13, wherein the reflux reaction is carried out for 6 to 24 hours.
  16. 16. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in step S3', the intramolecular anhydrization reaction is performed in the presence of dicyclohexylcarbodiimide.
  17. 17. The method for producing a cyclic anhydride compound according to claim 16, wherein the molar ratio of dicyclohexylcarbodiimide to the polycarboxylic aromatic compound is 2:1 to 3:1.
  18. 18. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein in step S3', the intramolecular anhydration reaction conditions include a temperature of 0 to 30 ℃ and a time of 10 to 36 hours.
  19. 19. The use of the cyclic anhydride compound according to any one of claims 1 to 3 in adhesives.

Description

Cyclic anhydride compound and preparation method and application thereof Technical Field The invention belongs to the field of organic synthesis, and particularly relates to a cyclic anhydride compound, and a preparation method and application thereof. Background The cyclic anhydride compound is an important organic chemical intermediate, can be subjected to ring-opening polymerization reaction with an epoxy compound to generate polyester, and can be widely applied to the fields of adhesives, biodegradable materials, drug carriers, coatings and the like. However, the prior art for synthesizing the cyclic anhydride compound has the remarkable limitations that (1) the protection group-dependent strategy needs to perform stepwise protection and deprotection on active groups such as hydroxyl groups and the like, so that the reaction steps are increased by 3-5 steps, (2) the reaction conditions are harsh, a part of the method depends on strong corrosive reagents such as concentrated sulfuric acid, trifluoroacetic acid and the like, or a high-temperature and high-pressure reaction kettle with the temperature of more than 150 ℃ is needed, the equipment cost is increased, side reactions are easily initiated, the purity of a target product is low, and (3) the substrate applicability is narrow, the traditional method is mostly suitable for simple chain anhydride synthesis, the construction efficiency of a symmetrical cyclic structure is low, and the yield is generally low. Therefore, the development of the synthesis method of the cyclic anhydride compound, which has the advantages of simple steps, mild conditions and stable yield, has important practical value. The Underfill adhesive is a resin adhesive used in the electronic packaging process, penetrates the micron-sized gap through capillary action, and is mainly applied to the field of semiconductor packaging, and besides being filled between a common PCB and a chip, the Underfill adhesive is also filled between a flexible soft board and the chip. Compared with the adhesive filled in the chip and the PCB, the adhesive filled between the chip and the flexible soft board has more formulation design difficulty. The adhesive needs to have stronger bond strength and toughness in addition to the basic properties of conventional underfill adhesives. Curing agents commonly include amine-type curing agents and anhydride-type curing agents. However, after the epoxy underfill using the existing anhydride compound as a curing agent is aged for 120 hours at 85 ℃ and 85%, the bonding strength can only reach 11MPa, i.e. the high-temperature-resistant bonding strength is lower. In addition, in order to ensure the operation stability of the electronic product, the glass transition temperature (Tg) of the epoxy underfill must be higher than the use temperature, and if the use temperature approaches or exceeds Tg, the epoxy underfill is rapidly softened due to the increase of molecular chain movement, so that the strength is reduced, and the performance of the electronic product is affected. Disclosure of Invention The first object of the present invention is to provide a cyclic anhydride compound which can improve the high-temperature-resistant adhesive strength and Tg of an epoxy adhesive when used as a curing agent for the epoxy adhesive. The second object of the present invention is to provide a process for producing the above cyclic anhydride compound. A third object of the present invention is to provide an application of the above cyclic anhydride compound in an adhesive. The cyclic anhydride compound provided by the invention has a structure shown in a formula (1'): (1'), ,R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13 And R 14 in the formula (1') are each independently H or C1-C6 alkyl. The preparation method of the cyclic anhydride compound provided by the invention comprises the following steps: s1 ', michael addition, namely performing cyanoethylation reaction on a polyhydroxy aromatic compound shown in a formula (2') and acrylonitrile to obtain a polycyanoaromatic compound; s2', cyano group hydrolysis, namely, hydrolyzing the polycyanoaromatic compound to convert cyano groups into carboxyl groups so as to obtain the polycyanoaromatic compound; S3', intramolecular condensation, namely carrying out intramolecular anhydride reaction on the polycarboxylic aromatic compound to obtain a cyclic anhydride compound; (2'), In the formula (2'), R 3、R4、R5、R10、R11 and R 12 are independently H or C1-C6 alkyl. The preparation method of the cyclic anhydride compound provided by the invention is characterized in that the cyclic anhydride compound can be constructed by three steps of reaction of Michael addition, cyano hydrolysis and intramolecular condensation from the polyhydroxy aromatic compound, the complex protecting group operation is not needed, the reaction temperature is lower than 70 ℃, the high temperature and the high pressure are avoided, the method is suitable for industrial a