WO2023077910A1 - Curing agent, curing agent composition and preparation method therefor - Google Patents

Curing agent, curing agent composition and preparation method therefor Download PDF

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Publication number
WO2023077910A1
WO2023077910A1 PCT/CN2022/113416 CN2022113416W WO2023077910A1 WO 2023077910 A1 WO2023077910 A1 WO 2023077910A1 CN 2022113416 W CN2022113416 W CN 2022113416W WO 2023077910 A1 WO2023077910 A1 WO 2023077910A1
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Prior art keywords
curing agent
epoxy resin
agent composition
preparation
acid anhydride
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PCT/CN2022/113416
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French (fr)
Chinese (zh)
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骆万兴
吉明磊
陈翠萍
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道生天合材料科技(上海)股份有限公司
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Publication of WO2023077910A1 publication Critical patent/WO2023077910A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides

Definitions

  • the invention relates to the technical field of curing agents, in particular to a curing agent, a curing agent composition and a preparation method thereof.
  • the two-component epoxy curing system due to the adjustable mixing ratio, easy mixing, and balanced product performance after curing, is a type of adhesive application that is widely used.
  • the two-component epoxy curing system uses basic amine curing agents or Due to the molecular structure of the modified curing agent, the high temperature resistance of the cured product is defective. Even if the product of the two-component room temperature curing system is cured at room temperature, the Tg of the product can only reach about 70°C , it is difficult to meet the higher temperature resistance requirements.
  • Acid anhydride curing agent has a high Tg point after curing and good temperature resistance, which is very suitable for occasions that require high temperature resistance.
  • the heating temperature is as high as 170 ° C, so the curing of the acid anhydride is limited. The scope of application of the agent.
  • the object of the present invention is to provide a method for preparing a curing agent composition, which solves the problem that the product cured by the basic amine curing agent has poor high temperature resistance, and the acid anhydride curing agent needs to be heated and cured at high temperature.
  • a method for preparing a curing agent composition comprising the following steps: providing a first component and a second component; mixing the first component and the second component, raising the temperature and stirring to start a reaction, so as to prepare the Curing agent composition;
  • the first component is a basic amine curing agent;
  • the second component is an acid anhydride curing agent, wherein the acid anhydride curing agent is selected from 3,3',4,4'- One of benzophenone tetracarboxylic dianhydride curing agent, trimellitic anhydride curing agent, and pyromellitic dianhydride curing agent.
  • the beneficial effect of the preparation method of the curing agent composition of the present invention is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, At the same time, the room temperature curing ability of the obtained curing agent composition is realized, and the epoxy resin can be cured at room temperature. At the same time, it has good high temperature resistance. Instead of physical mixing, a curing agent composition is obtained by using the reactivity of the two, which solves the problems of poor high temperature resistance of products cured by basic amine curing agents and the need for high temperature heating and curing of acid anhydride curing agents.
  • the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.6-0.9:0.1-0.4.
  • the beneficial effect is that: the acid anhydride curing agent reacts completely, the basic amine curing agent partially reacts, and the curing agent composition can reflect the advantages of both.
  • the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.7-0.8:0.2-0.3.
  • the beneficial effect is that: the acid anhydride curing agent reacts completely, the basic amine curing agent partially reacts, and the curing agent composition can better reflect the advantages of both.
  • the acid anhydride curing agent is selected from 3,3',4,4'-benzophenonetetraacid dianhydride curing agents.
  • the basic amine curing agent is selected from m-xylylenediamine, aminoethylpiperazine, 2-methylpentamethylenediamine, trimethylhexamethylenediamine, 1,3 cyclohexanedimethylamine, isofor Alone diamine, diaminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, methylcyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 1,2-cyclohexane One of hexamethylenediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and diethyltoluenediamine.
  • the beneficial effect is that the effect of the curing agent composition obtained by reacting the basic amine curing agent and the acid anhydride curing agent is better.
  • the basic amine curing agent is selected from the group consisting of aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine and 3,3'-dimethyl-4,4-diaminobicyclic One of the hexylmethane.
  • the temperature range of the reaction is 80-150°C, and the reaction time is 2h-8h. Its beneficial effect is that: at the reaction temperature and the reaction time, the acid anhydride curing agent can completely react, and the curing agent composition can better reflect the acid anhydride curing agent and the base Advantages of amine curing agents.
  • Another object of the present invention is to provide a curing agent composition prepared by the preparation method of the curing agent composition. Its beneficial effect is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the obtained combination of the curing agent
  • the normal temperature curing ability of epoxy resin can be cured under normal temperature conditions, and at the same time, it has good high temperature resistance. Reactivity, a curing agent composition is obtained, which solves the problem of poor high temperature resistance of products cured by basic amine curing agents and the need for high temperature heating and curing of acid anhydride curing agents.
  • Another object of the present invention is to provide a curing agent, comprising the curing agent composition and an epoxy resin.
  • the beneficial effect is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the advantages of the obtained curing agent composition. Curing ability at room temperature, epoxy resin can be cured at room temperature, and at the same time has good high temperature resistance.
  • the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin and novolak type epoxy resin A sort of.
  • the preparation method of the curing agent composition includes the following steps: providing a first component and a second component; mixing the first component and the second component and raising the temperature and stirring reaction to prepare the curing agent composition;
  • the first component is a basic amine curing agent;
  • the second component is an acid anhydride curing agent, wherein the acid anhydride curing agent is selected from 3,3' , One of 4,4'-benzophenone tetracarboxylic dianhydride curing agent, trimellitic anhydride curing agent, and pyromellitic dianhydride curing agent.
  • the curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the normal temperature curing ability of the obtained curing agent composition, which can
  • the epoxy resin can be cured under normal temperature conditions, and at the same time it has good high temperature resistance. It is not a simple physical mixing of acid anhydride curing agent and basic amine curing agent, but using the reactivity of the two to obtain a kind of
  • the curing agent composition solves the problems that the products cured by the basic amine curing agent have poor high temperature resistance and the acid anhydride curing agent needs to be heated and cured at high temperature.
  • the basic amine curing agent is a simple amine curing agent, that is, a single polyamine curing agent
  • the single polyamine curing agent is an aliphatic amine curing agent, an aromatic amine curing agent Agents, alicyclic amine curing agents and polyamide curing agents, excluding mixed amine curing agents and modified amine curing agents.
  • using the curing agent composition to cure epoxy resin can achieve complete curing at room temperature, and the curing time is related to the type of basic amine curing agent.
  • the selected basic amine curing agent is different, and the reaction rate will vary.
  • the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.6-0.9:0.1-0.4, the acid anhydride curing agent reacts completely, and the basic amine curing agent will partial reaction, the curing agent composition can reflect the advantages of both.
  • the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.7-0.8:0.2-0.3, the acid anhydride curing agent has completely reacted, and the basic amine curing agent partial reaction, the curing agent composition can better reflect the advantages of both.
  • the acid anhydride curing agent is selected from 3,3',4,4'-benzophenonetetraacid dianhydride curing agents.
  • the basic amine curing agent is selected from the group consisting of m-xylylenediamine, aminoethylpiperazine, 2-methylpentamethylenediamine, trimethylhexamethylenediamine, 1,3cyclohexanediamine Methylamine, isophoronediamine, diaminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, methylcyclohexanediamine, 4,4'-diaminodicyclohexylmethane, One of 1,2-cyclohexanediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and diethyltoluenediamine, the basic amine curing agent and the The effect achieved by the curing agent composition obtained by reacting the acid anhydride curing agent is better.
  • the basic amine curing agent is not limited to the single polyamine curing agent listed above.
  • the basic amine curing agent is selected from aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine and 3,3'-dimethyl-4,4 - one of diaminodicyclohexylmethane.
  • the temperature range of the reaction is 80-150°C, and the reaction time is 2h-8h.
  • the acid anhydride curing agent can complete reaction, the curing agent composition can better reflect the advantages of the acid anhydride curing agent and the basic amine curing agent.
  • the curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent, and utilizes the acid anhydride curing agent high temperature resistance characteristics, and at the same time realize the normal temperature curing ability of the obtained curing agent composition, and can cure the epoxy resin under normal temperature conditions, and at the same time have good high temperature resistance performance, it is not simply an acid anhydride curing agent Physical mixing with the basic amine curing agent, but using the reactivity of the two to obtain a curing agent composition, which solves the problem of poor high temperature resistance of the product cured by the basic amine curing agent and the problem of acid anhydride curing The problem that the agent needs high temperature heating and curing.
  • the curing agent includes the curing agent composition and epoxy resin.
  • the curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent.
  • the high temperature resistance characteristics of the curing agent and at the same time realize the room temperature curing ability of the obtained curing agent composition, which can cure the epoxy resin at room temperature, and at the same time have good high temperature resistance performance, not simply an acid anhydride curing agent Physical mixing with the basic amine curing agent, but using the reactivity of the two to obtain a curing agent composition, which solves the poor high temperature resistance of the product cured by the basic amine curing agent and the need for an anhydride curing agent High temperature heat curing problem.
  • the epoxy resins include glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and epoxidized olefin epoxy resins; wherein the Glycidyl ether epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, brominated ring Oxygen resin, the glycidyl ether epoxy resin does not include aliphatic glycidyl ether epoxy resin.
  • the epoxy resin also includes novel epoxy resins, such as hydantoin epoxy resin; the epoxy resin does not include cycloaliphatic epoxy resin, which is one of epoxy resins.
  • a branch is a compound having the general properties of an aliphatic compound and a carbocyclic structure.
  • the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin and phenolic type epoxy resin
  • the epoxy resins is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin and phenolic type epoxy resin
  • the epoxy resin used in the embodiment is bisphenol A type epoxy resin NPEL128E.
  • Preparation of curing agent composition 1 Accurately weigh 80g of aminoethylpiperazine and place it in a 1000ml container; then add 80g of 3,3',4,4'-benzophenonetetraacid dianhydride to the 1000ml container; Stir at a temperature of °C and start to react, and the reaction time is 2 hours; the product obtained after the reaction, that is, the curing agent composition 1, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 100g of curing agent composition 1 at room temperature, vacuum stirring by speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 5 hours to obtain an epoxy resin cured material.
  • Preparation of curing agent composition 2 Accurately weigh 60g of aminoethylpiperazine and place it in a 1000ml container; then add 80g of 3,3',4,4'-benzophenonetetraacid dianhydride to the 1000ml container; Stir at a temperature of °C and start to react, and the reaction time is 3 hours; the product obtained after the reaction, that is, the curing agent composition 2, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 120g of curing agent composition 2 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
  • Preparation of curing agent composition 3 Accurately weigh 120g of isophoronediamine and place it in a 1000ml container; then add 80g of trimellitic anhydride to the 1000ml container; stir at a temperature of 100°C and start to react, and the reaction time is 4h; The product obtained after the reaction, that is, the curing agent composition 3, is cooled and placed for later use.
  • the preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 45g of curing agent composition 3 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 7 hours to obtain an epoxy resin cured material.
  • Preparation of curing agent composition 4 Accurately weigh 100g of isophoronediamine and place it in a 1000ml container; then add 80g of trimellitic anhydride to the 1000ml container; stir at a temperature of 110°C and start to react, and the reaction time is 5h; The product obtained after the reaction, that is, the curing agent composition 4, is cooled and placed for later use.
  • the preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 60g of curing agent composition 4 at room temperature, vacuum stirring by speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 8 hours to obtain an epoxy resin cured material.
  • Preparation of curing agent composition 5 Accurately weigh 140g of methylcyclohexanediamine and place it in a 1000ml container; then add 80g of pyromellitic dianhydride into the 1000ml container; stir at a temperature of 120°C and start the reaction, the reaction The time is 6 hours; the product obtained after the reaction, that is, the curing agent composition 5, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 30g of curing agent composition 5 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
  • Preparation of curing agent composition 6 Accurately weigh 120g of methylcyclohexanediamine and place it in a 1000ml container; then add 80g of pyromellitic dianhydride into the 1000ml container; stir at a temperature of 130°C and start the reaction, the reaction The time is 7 hours; the product obtained after the reaction, that is, the curing agent composition 6, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 40g of curing agent composition 6 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 7 hours to obtain an epoxy resin cured material.
  • curing agent composition 7 Preparation of curing agent composition 7: Accurately weigh 140g of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and place it in a 1000ml container; then add 80g of 3,3',4 , 4'-benzophenonetetraacid dianhydride; Stir at a temperature of 140°C and start the reaction, the reaction time is 8h; The product obtained after the reaction, that is, the curing agent composition 7, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 55g of curing agent composition 7 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 5 hours to obtain an epoxy resin cured material.
  • curing agent composition 8 Preparation of curing agent composition 8: Accurately weigh 120g of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and place it in a 1000ml container; then add 80g of 3,3',4 , 4'-benzophenonetetraacid dianhydride; Stir at a temperature of 150°C and start to react, the reaction time is 5h; The product obtained after the reaction, that is, the curing agent composition 8, is cooled and placed for use.
  • the preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 65g of curing agent composition 8 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
  • TMA of TA Company was used to test the glass transition temperature of the high-temperature-resistant epoxy resins of Examples 1 to 8 and Comparative Examples 1 to 4 of the present invention, and the results are shown in Table 1.
  • the TMA test procedure is: 0-190°C, heating at a rate of 10°C/min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a preparation method for a curing agent composition, comprising the following steps: providing a first component and a second component; and mixing the first component and the second component, heating the mixture, and stirring same to start a reaction so as to prepare the curing agent composition, wherein the first component is a basic amine curing agent; the second component is an anhydride curing agent; the anhydride curing agent is selected from one of a 3,3',4,4'-benzophenonetetracarboxylic dianhydride curing agent, a trimellitic anhydride curing agent, and a pyromellitic dianhydride curing agent. The preparation method for the curing agent composition provided by the present invention is simple and easy to operate, the obtained curing agent composition is used to cure an epoxy resin at normal temperature, and the obtained curing agent is relatively highly temperature resistant.

Description

固化剂、固化剂组合物及其制备方法Curing agent, curing agent composition and preparation method thereof
交叉引用cross reference
本申请要求2021年11月4日提交的申请号为2021112996189的中国专利申请的优先权。上述申请的内容以引用方式被包含于此。This application claims the priority of Chinese patent application number 2021112996189 filed on November 4, 2021. The content of the above application is incorporated herein by reference.
技术领域technical field
本发明涉及固化剂技术领域，尤其涉及一种固化剂、固化剂组合物及其制备方法。The invention relates to the technical field of curing agents, in particular to a curing agent, a curing agent composition and a preparation method thereof.
背景技术Background technique
双组分环氧固化体系，由于混合比例可调，混合方便，固化后产品性能均衡，是一类应用非常广泛的胶粘剂应用，但是双组分环氧固化体系，使用的基础胺类固化剂或者改性后的固化剂，由于分子结构的关系，造成了固化后产物的耐高温性能有缺陷，即使对双组分常温固化体系的产品进行常温固化处理，产品的Tg也只能达到70℃左右，难以满足更高的耐温需求。The two-component epoxy curing system, due to the adjustable mixing ratio, easy mixing, and balanced product performance after curing, is a type of adhesive application that is widely used. However, the two-component epoxy curing system uses basic amine curing agents or Due to the molecular structure of the modified curing agent, the high temperature resistance of the cured product is defective. Even if the product of the two-component room temperature curing system is cured at room temperature, the Tg of the product can only reach about 70°C , it is difficult to meet the higher temperature resistance requirements.
酸酐类固化剂，固化后Tg点高，耐温性好，非常适合耐高温需求的场合，但是实际应用当中，由于酸酐类固化剂需要加热固化，加热温度高达170℃，因此限制了酸酐类固化剂的应用范围。Acid anhydride curing agent has a high Tg point after curing and good temperature resistance, which is very suitable for occasions that require high temperature resistance. However, in practical applications, because the acid anhydride curing agent needs to be heated and cured, the heating temperature is as high as 170 ° C, so the curing of the acid anhydride is limited. The scope of application of the agent.
因此，有必要开发一种固化剂组合物，以避免现有技术中存在的上述问题。Therefore, it is necessary to develop a curing agent composition to avoid the above-mentioned problems in the prior art.
发明内容Contents of the invention
本发明的目的在于提供一种固化剂组合物的制备方法，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。The object of the present invention is to provide a method for preparing a curing agent composition, which solves the problem that the product cured by the basic amine curing agent has poor high temperature resistance, and the acid anhydride curing agent needs to be heated and cured at high temperature.
一种固化剂组合物的制备方法，包括以下步骤：提供第一组分和第二组分；将所述第一组分和所述第二组分混合并升温搅拌开始反应，以制备所述固化剂 组合物；所述第一组份为基础胺类固化剂；所述第二组分为酸酐类固化剂，其中，所述酸酐类固化剂选自3,3’,4,4’-二苯酮四酸二酐固化剂、偏苯三酸酐固化剂、均苯四甲酸二酐固化剂中的一种。A method for preparing a curing agent composition, comprising the following steps: providing a first component and a second component; mixing the first component and the second component, raising the temperature and stirring to start a reaction, so as to prepare the Curing agent composition; the first component is a basic amine curing agent; the second component is an acid anhydride curing agent, wherein the acid anhydride curing agent is selected from 3,3',4,4'- One of benzophenone tetracarboxylic dianhydride curing agent, trimellitic anhydride curing agent, and pyromellitic dianhydride curing agent.
本发明所述固化剂组合物的制备方法的有益效果在于：所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的固化剂组合物的常温固化能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。The beneficial effect of the preparation method of the curing agent composition of the present invention is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, At the same time, the room temperature curing ability of the obtained curing agent composition is realized, and the epoxy resin can be cured at room temperature. At the same time, it has good high temperature resistance. Instead of physical mixing, a curing agent composition is obtained by using the reactivity of the two, which solves the problems of poor high temperature resistance of products cured by basic amine curing agents and the need for high temperature heating and curing of acid anhydride curing agents.
优选的，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比为0.6～0.9：0.1～0.4。其有益效果在于：所述酸酐类固化剂反应完全，所述基础胺类固化剂会部分反应，所述固化剂组合物能够体现出两者的优点。Preferably, the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.6-0.9:0.1-0.4. The beneficial effect is that: the acid anhydride curing agent reacts completely, the basic amine curing agent partially reacts, and the curing agent composition can reflect the advantages of both.
进一步优选的，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比为0.7～0.8：0.2～0.3。其有益效果在于：所述酸酐类固化剂反应完全，所述基础胺类固化剂会部分反应，所述固化剂组合物能够更好地体现出两者的优点。Further preferably, the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.7-0.8:0.2-0.3. The beneficial effect is that: the acid anhydride curing agent reacts completely, the basic amine curing agent partially reacts, and the curing agent composition can better reflect the advantages of both.
进一步优选的，所述酸酐类固化剂选自3,3’,4,4’-二苯酮四酸二酐固化剂。Further preferably, the acid anhydride curing agent is selected from 3,3',4,4'-benzophenonetetraacid dianhydride curing agents.
优选的，所述基础胺类固化剂选自间苯二甲胺、氨乙基哌嗪、2-甲基戊二胺、三甲基己二胺、1,3环己二甲胺、异佛尔酮二胺、二氨基二环己基甲烷、乙二胺、二乙烯三胺、三乙烯四胺、甲基环己二胺、4,4'-二氨基二环己基甲烷、1,2-环己二胺、3,3'-二甲基-4,4-二氨基二环己基甲烷和二乙基甲苯二胺中的一种。其有益效果在于：提供的基础胺类固化剂与酸酐类固化剂反应得到的固化剂组合物所达到的效果更佳。Preferably, the basic amine curing agent is selected from m-xylylenediamine, aminoethylpiperazine, 2-methylpentamethylenediamine, trimethylhexamethylenediamine, 1,3 cyclohexanedimethylamine, isofor Alone diamine, diaminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, methylcyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 1,2-cyclohexane One of hexamethylenediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and diethyltoluenediamine. The beneficial effect is that the effect of the curing agent composition obtained by reacting the basic amine curing agent and the acid anhydride curing agent is better.
进一步优选的，所述基础胺类固化剂选自氨乙基哌嗪、异佛尔酮二胺、甲基环己二胺和3,3'-二甲基-4,4-二氨基二环己基甲烷中的一种。Further preferably, the basic amine curing agent is selected from the group consisting of aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine and 3,3'-dimethyl-4,4-diaminobicyclic One of the hexylmethane.
优选的，所述反应的温度范围为80～150℃，所述反应的时间为2h～8h。其有益效果在于：在所述反应的温度和所述反应的时间下，所述酸酐类固化剂能够完全反应，所述固化剂组合物能够更好地体现所述酸酐类固化剂和所述基础胺类固化剂的优点。Preferably, the temperature range of the reaction is 80-150°C, and the reaction time is 2h-8h. Its beneficial effect is that: at the reaction temperature and the reaction time, the acid anhydride curing agent can completely react, and the curing agent composition can better reflect the acid anhydride curing agent and the base Advantages of amine curing agents.
本发明的另一目的在于提供一种固化剂组合物，通过所述固化剂组合物的制备方法制备而成。其有益效果在于：所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的所述固化剂组合物的常温固化能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种所述固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。Another object of the present invention is to provide a curing agent composition prepared by the preparation method of the curing agent composition. Its beneficial effect is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the obtained combination of the curing agent The normal temperature curing ability of epoxy resin can be cured under normal temperature conditions, and at the same time, it has good high temperature resistance. Reactivity, a curing agent composition is obtained, which solves the problem of poor high temperature resistance of products cured by basic amine curing agents and the need for high temperature heating and curing of acid anhydride curing agents.
本发明的另一目的在于提供一种固化剂，包括所述固化剂组合物和环氧树脂。其有益效果在于：所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的固化剂组合物的常温固化能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。Another object of the present invention is to provide a curing agent, comprising the curing agent composition and an epoxy resin. The beneficial effect is that: the curing agent composition organically combines the acid anhydride curing agent and the basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the advantages of the obtained curing agent composition. Curing ability at room temperature, epoxy resin can be cured at room temperature, and at the same time has good high temperature resistance. It is not a simple physical mixing of anhydride curing agent and basic amine curing agent, but the reactivity of the two , A curing agent composition is obtained, which solves the problem that the product cured by the basic amine curing agent has poor high temperature resistance and the acid anhydride curing agent needs to be heated and cured at high temperature.
优选的，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂和酚醛型环氧树脂中的一种。Preferably, the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin and novolak type epoxy resin A sort of.
附图说明Description of drawings 具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实 施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。除非另外定义，此处使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。本文中使用的“包括”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. the embodiment. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein shall have the usual meanings understood by those skilled in the art to which the present invention belongs. As used herein, "comprising" and similar words mean that the elements or items appearing before the word include the elements or items listed after the word and their equivalents, without excluding other elements or items.
本发明一些实施例中，所述固化剂组合物的制备方法包括以下步骤：提供第一组分和第二组分；将所述第一组分和所述第二组分混合并升温搅拌开始反应，以制备所述固化剂组合物；所述第一组份为基础胺类固化剂；所述第二组分为酸酐类固化剂，其中，所述酸酐类固化剂选自3,3’,4,4’-二苯酮四酸二酐固化剂、偏苯三酸酐固化剂、均苯四甲酸二酐固化剂中的一种。所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的固化剂组合物的常温固化能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。In some embodiments of the present invention, the preparation method of the curing agent composition includes the following steps: providing a first component and a second component; mixing the first component and the second component and raising the temperature and stirring reaction to prepare the curing agent composition; the first component is a basic amine curing agent; the second component is an acid anhydride curing agent, wherein the acid anhydride curing agent is selected from 3,3' , One of 4,4'-benzophenone tetracarboxylic dianhydride curing agent, trimellitic anhydride curing agent, and pyromellitic dianhydride curing agent. The curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent, utilizes the high temperature resistance characteristics of the acid anhydride curing agent, and at the same time realizes the normal temperature curing ability of the obtained curing agent composition, which can The epoxy resin can be cured under normal temperature conditions, and at the same time it has good high temperature resistance. It is not a simple physical mixing of acid anhydride curing agent and basic amine curing agent, but using the reactivity of the two to obtain a kind of The curing agent composition solves the problems that the products cured by the basic amine curing agent have poor high temperature resistance and the acid anhydride curing agent needs to be heated and cured at high temperature.
本发明一些实施例中，所述基础胺类固化剂为单纯胺类固化剂即单一多胺类固化剂，所述单一多胺类固化剂为脂肪族胺类固化剂、芳香胺类固化剂、脂环胺类固化剂和聚酰胺类固化剂，不包括混合胺类固化剂和改性胺类固化剂。In some embodiments of the present invention, the basic amine curing agent is a simple amine curing agent, that is, a single polyamine curing agent, and the single polyamine curing agent is an aliphatic amine curing agent, an aromatic amine curing agent Agents, alicyclic amine curing agents and polyamide curing agents, excluding mixed amine curing agents and modified amine curing agents.
本发明一些实施例中，使用所述固化剂组合物固化环氧树脂，可以在常温下实现完全固化，固化时间与基础胺类固化剂的种类相关，选择的基础胺类固化剂不同，反应速率会有所差异。In some embodiments of the present invention, using the curing agent composition to cure epoxy resin can achieve complete curing at room temperature, and the curing time is related to the type of basic amine curing agent. The selected basic amine curing agent is different, and the reaction rate will vary.
本发明一些实施例中，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比 为0.6～0.9：0.1～0.4，所述酸酐类固化剂反应完全，所述基础胺类固化剂会部分反应，所述固化剂组合物能够体现出两者的优点。In some embodiments of the present invention, the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.6-0.9:0.1-0.4, the acid anhydride curing agent reacts completely, and the basic amine curing agent will partial reaction, the curing agent composition can reflect the advantages of both.
本发明又一些实施例中，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比为0.7～0.8：0.2～0.3，所述酸酐类固化剂反应完全，所述基础胺类固化剂会部分反应，所述固化剂组合物能够更好地体现出两者的优点。In some other embodiments of the present invention, the molar ratio of the basic amine curing agent to the acid anhydride curing agent is 0.7-0.8:0.2-0.3, the acid anhydride curing agent has completely reacted, and the basic amine curing agent partial reaction, the curing agent composition can better reflect the advantages of both.
本发明一些具体实施例中，所述酸酐类固化剂选自3,3’,4,4’-二苯酮四酸二酐固化剂。In some specific embodiments of the present invention, the acid anhydride curing agent is selected from 3,3',4,4'-benzophenonetetraacid dianhydride curing agents.
本发明一些具体实施例中，所述基础胺类固化剂选自间苯二甲胺、氨乙基哌嗪、2-甲基戊二胺、三甲基己二胺、1,3环己二甲胺、异佛尔酮二胺、二氨基二环己基甲烷、乙二胺、二乙烯三胺、三乙烯四胺、甲基环己二胺、4,4'-二氨基二环己基甲烷、1,2-环己二胺、3,3'-二甲基-4,4-二氨基二环己基甲烷和二乙基甲苯二胺中的一种，所述基础胺类固化剂与所述酸酐类固化剂反应得到的所述固化剂组合物所达到的效果更佳。In some specific embodiments of the present invention, the basic amine curing agent is selected from the group consisting of m-xylylenediamine, aminoethylpiperazine, 2-methylpentamethylenediamine, trimethylhexamethylenediamine, 1,3cyclohexanediamine Methylamine, isophoronediamine, diaminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, methylcyclohexanediamine, 4,4'-diaminodicyclohexylmethane, One of 1,2-cyclohexanediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and diethyltoluenediamine, the basic amine curing agent and the The effect achieved by the curing agent composition obtained by reacting the acid anhydride curing agent is better.
本发明一些实施例中，所述基础胺类固化剂不限于上述所列举的单一多胺类固化剂。In some embodiments of the present invention, the basic amine curing agent is not limited to the single polyamine curing agent listed above.
本发明一些更具体实施例中，所述基础胺类固化剂选自氨乙基哌嗪、异佛尔酮二胺、甲基环己二胺和3,3'-二甲基-4,4-二氨基二环己基甲烷中的一种。In some more specific embodiments of the present invention, the basic amine curing agent is selected from aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine and 3,3'-dimethyl-4,4 - one of diaminodicyclohexylmethane.
本发明一些实施例中，所述反应的温度范围为80～150℃，所述反应的时间为2h～8h，在所述反应的温度和所述的反应时间下，所述酸酐类固化剂能够完全反应，所述固化剂组合物能够更好地体现所述酸酐类固化剂和所述基础胺类固化剂的优点。In some embodiments of the present invention, the temperature range of the reaction is 80-150°C, and the reaction time is 2h-8h. Under the reaction temperature and the reaction time, the acid anhydride curing agent can complete reaction, the curing agent composition can better reflect the advantages of the acid anhydride curing agent and the basic amine curing agent.
本发明一些实施例中，通过所述固化剂组合物的制备方法制备而成，所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的所述固化剂组合物的常温固化 能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种所述固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。In some embodiments of the present invention, it is prepared through the preparation method of the curing agent composition. The curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent, and utilizes the acid anhydride curing agent high temperature resistance characteristics, and at the same time realize the normal temperature curing ability of the obtained curing agent composition, and can cure the epoxy resin under normal temperature conditions, and at the same time have good high temperature resistance performance, it is not simply an acid anhydride curing agent Physical mixing with the basic amine curing agent, but using the reactivity of the two to obtain a curing agent composition, which solves the problem of poor high temperature resistance of the product cured by the basic amine curing agent and the problem of acid anhydride curing The problem that the agent needs high temperature heating and curing.
本发明一些实施例中，所述固化剂包括所述固化剂组合物和环氧树脂，所述固化剂组合物是将酸酐类固化剂和基础胺类固化剂有机的结合起来，利用了酸酐类固化剂的耐高温特点，同时实现了所获得的固化剂组合物的常温固化能力，可以对环氧树脂实现常温条件下固化，同时拥有了良好的耐高温性能，不是简单的将酸酐类固化剂和基础胺类固化剂的物理混合，而是利用两者的反应性，获得了一种固化剂组合物，解决了基础胺类固化剂固化后的产物耐高温性能差，以及酸酐类固化剂需要高温加热固化的问题。In some embodiments of the present invention, the curing agent includes the curing agent composition and epoxy resin. The curing agent composition is an organic combination of an acid anhydride curing agent and a basic amine curing agent. The high temperature resistance characteristics of the curing agent, and at the same time realize the room temperature curing ability of the obtained curing agent composition, which can cure the epoxy resin at room temperature, and at the same time have good high temperature resistance performance, not simply an acid anhydride curing agent Physical mixing with the basic amine curing agent, but using the reactivity of the two to obtain a curing agent composition, which solves the poor high temperature resistance of the product cured by the basic amine curing agent and the need for an anhydride curing agent High temperature heat curing problem.
本发明一些具体实施例中，所述环氧树脂包括缩水甘油醚类环氧树脂，缩水甘油脂类环氧树脂，缩水甘油胺类环氧树脂，环氧化烯烃类环氧树脂；其中所述缩水甘油醚类环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂、酚醛型环氧树脂、溴代环氧树脂，所述缩水甘油醚类环氧树脂不包括脂肪族缩水甘油醚环氧树脂。In some specific embodiments of the present invention, the epoxy resins include glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and epoxidized olefin epoxy resins; wherein the Glycidyl ether epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, brominated ring Oxygen resin, the glycidyl ether epoxy resin does not include aliphatic glycidyl ether epoxy resin.
具体的，所述环氧树脂还包括新型环氧树脂，例如海因环氧树脂；所述环氧树脂不包括脂环族环氧树脂，所述脂环族环氧树脂是环氧树脂的一个分支，是具有脂肪族化合物的一般性质和碳环的结构的化合物。Specifically, the epoxy resin also includes novel epoxy resins, such as hydantoin epoxy resin; the epoxy resin does not include cycloaliphatic epoxy resin, which is one of epoxy resins. A branch is a compound having the general properties of an aliphatic compound and a carbocyclic structure.
本发明一些具体实施例中，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂和酚醛型环氧树脂中的一种，In some specific embodiments of the present invention, the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin and phenolic type epoxy resin One of the epoxy resins,
实施例中使用的环氧树脂均为双酚A型环氧树脂NPEL128E。The epoxy resin used in the embodiment is bisphenol A type epoxy resin NPEL128E.
实施例1Example 1
制备固化剂组合物1：准确称量80g氨乙基哌嗪并放置于1000ml容器中；然后向1000ml容器中加入80g 3,3’,4,4’-二苯酮四酸二酐；在80℃的温度下搅拌并开始反应，反应时间为2h；将反应得到后的产品即固化剂组合物1冷却后放置备用。Preparation of curing agent composition 1: Accurately weigh 80g of aminoethylpiperazine and place it in a 1000ml container; then add 80g of 3,3',4,4'-benzophenonetetraacid dianhydride to the 1000ml container; Stir at a temperature of °C and start to react, and the reaction time is 2 hours; the product obtained after the reaction, that is, the curing agent composition 1, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和100g固化剂组合物1在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置5h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 100g of curing agent composition 1 at room temperature, vacuum stirring by speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 5 hours to obtain an epoxy resin cured material.
实施例2Example 2
制备固化剂组合物2：准确称量60g氨乙基哌嗪并放置于1000ml容器中；然后向1000ml容器中加入80g 3,3’,4,4’-二苯酮四酸二酐；在90℃的温度下搅拌并开始反应，反应时间为3h；将反应得到后的产品即固化剂组合物2冷却后放置备用。Preparation of curing agent composition 2: Accurately weigh 60g of aminoethylpiperazine and place it in a 1000ml container; then add 80g of 3,3',4,4'-benzophenonetetraacid dianhydride to the 1000ml container; Stir at a temperature of °C and start to react, and the reaction time is 3 hours; the product obtained after the reaction, that is, the curing agent composition 2, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和120g固化剂组合物2在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/s min h的转速下搅拌2min，将搅拌后的混合品在室温下放置6h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 120g of curing agent composition 2 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
实施例3Example 3
制备固化剂组合物3：准确称量120g异佛尔酮二胺并放置于1000ml容器中；然后向1000ml容器中加入80g偏苯三酸酐；在100℃的温度下搅拌并开始反应，反应时间为4h；将反应得到后的产品即固化剂组合物3冷却后放置备用。Preparation of curing agent composition 3: Accurately weigh 120g of isophoronediamine and place it in a 1000ml container; then add 80g of trimellitic anhydride to the 1000ml container; stir at a temperature of 100°C and start to react, and the reaction time is 4h; The product obtained after the reaction, that is, the curing agent composition 3, is cooled and placed for later use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和45g固化剂组合物3在室温下混合后，经speedmixer浆料搅拌机 真空搅拌，在2000rpm/s min h的转速下搅拌2min，将搅拌后的混合品在室温下放置7h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 45g of curing agent composition 3 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 7 hours to obtain an epoxy resin cured material.
实施例4Example 4
制备固化剂组合物4：准确称量100g异佛尔酮二胺并放置于1000ml容器中；然后向1000ml容器中加入80g偏苯三酸酐；在110℃的温度下搅拌并开始反应，反应时间为5h；将反应得到后的产品即固化剂组合物4冷却后放置备用。Preparation of curing agent composition 4: Accurately weigh 100g of isophoronediamine and place it in a 1000ml container; then add 80g of trimellitic anhydride to the 1000ml container; stir at a temperature of 110°C and start to react, and the reaction time is 5h; The product obtained after the reaction, that is, the curing agent composition 4, is cooled and placed for later use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和60g固化剂组合物4在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/s min h的转速下搅拌2min，将搅拌后的混合品在室温下放置8h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of this embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 60g of curing agent composition 4 at room temperature, vacuum stirring by speedmixer slurry mixer, at 2000rpm/s min Stir at a speed of h for 2 minutes, and place the stirred mixture at room temperature for 8 hours to obtain an epoxy resin cured material.
实施例5Example 5
制备固化剂组合物5：准确称量140g甲基环己二胺并放置于1000ml容器中；然后向1000ml容器中加入80g均苯四甲酸二酐；在120℃的温度下搅拌并开始反应，反应时间为6h；将反应得到后的产品即固化剂组合物5冷却后放置备用。Preparation of curing agent composition 5: Accurately weigh 140g of methylcyclohexanediamine and place it in a 1000ml container; then add 80g of pyromellitic dianhydride into the 1000ml container; stir at a temperature of 120°C and start the reaction, the reaction The time is 6 hours; the product obtained after the reaction, that is, the curing agent composition 5, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和30g固化剂组合物5在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置6h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 30g of curing agent composition 5 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
实施例6Example 6
制备固化剂组合物6：准确称量120g甲基环己二胺并放置于1000ml容器中；然后向1000ml容器中加入80g均苯四甲酸二酐；在130℃的温度下搅拌并开始反应，反应时间为7h；将反应得到后的产品即固化剂组合物6冷却后放置 备用。Preparation of curing agent composition 6: Accurately weigh 120g of methylcyclohexanediamine and place it in a 1000ml container; then add 80g of pyromellitic dianhydride into the 1000ml container; stir at a temperature of 130°C and start the reaction, the reaction The time is 7 hours; the product obtained after the reaction, that is, the curing agent composition 6, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和40g固化剂组合物6在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置7h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 40g of curing agent composition 6 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 7 hours to obtain an epoxy resin cured material.
实施例7Example 7
制备固化剂组合物7：准确称量140g 3,3'-二甲基-4,4-二氨基二环己基甲烷并放置于1000ml容器中；然后向1000ml容器中加入80g 3,3’,4,4’-二苯酮四酸二酐；在140℃的温度下搅拌并开始反应，反应时间为8h；将反应得到后的产品即固化剂组合物7冷却后放置备用。Preparation of curing agent composition 7: Accurately weigh 140g of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and place it in a 1000ml container; then add 80g of 3,3',4 , 4'-benzophenonetetraacid dianhydride; Stir at a temperature of 140°C and start the reaction, the reaction time is 8h; The product obtained after the reaction, that is, the curing agent composition 7, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和55g固化剂组合物7在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置5h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 55g of curing agent composition 7 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 5 hours to obtain an epoxy resin cured material.
实施例8Example 8
制备固化剂组合物8：准确称量120g 3,3'-二甲基-4,4-二氨基二环己基甲烷并放置于1000ml容器中；然后向1000ml容器中加入80g 3,3’,4,4’-二苯酮四酸二酐；在150℃的温度下搅拌并开始反应，反应时间为5h；将反应得到后的产品即固化剂组合物8冷却后放置备用。Preparation of curing agent composition 8: Accurately weigh 120g of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and place it in a 1000ml container; then add 80g of 3,3',4 , 4'-benzophenonetetraacid dianhydride; Stir at a temperature of 150°C and start to react, the reaction time is 5h; The product obtained after the reaction, that is, the curing agent composition 8, is cooled and placed for use.
本实施例的耐高温环氧树脂的制备方法为：将100g双酚A型环氧树脂NPEL128E和65g固化剂组合物8在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置6h即可得到环氧树脂固化材料。The preparation method of the high temperature resistant epoxy resin of the present embodiment is: after mixing 100g of bisphenol A type epoxy resin NPEL128E and 65g of curing agent composition 8 at room temperature, vacuum stirring by a speedmixer slurry mixer, at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 6 hours to obtain an epoxy resin cured material.
对比例1Comparative example 1
将100g双酚A型环氧树脂NPEL128E和23g氨乙基哌嗪在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置6h即可得到环氧树脂固化材料。After mixing 100g of bisphenol A epoxy resin NPEL128E and 23g of aminoethylpiperazine at room temperature, the speedmixer slurry mixer was vacuum stirred at a speed of 2000rpm/min for 2min, and the stirred mixture was placed at room temperature The epoxy resin cured material can be obtained after standing for 6 hours.
对比例2Comparative example 2
将100g双酚A型环氧树脂NPEL128E和22g异佛尔酮二胺在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置7h即可得到环氧树脂固化材料。After mixing 100g of bisphenol A epoxy resin NPEL128E and 22g of isophorone diamine at room temperature, the speedmixer slurry mixer vacuum stirred, stirred at a speed of 2000rpm/min for 2min, and the stirred mixture was placed at room temperature Put it down for 7 hours to get the epoxy resin cured material.
对比例3Comparative example 3
将100g双酚A型环氧树脂NPEL128E和17g甲基环己二胺在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置8h即可得到环氧树脂固化材料。After mixing 100g of bisphenol A epoxy resin NPEL128E and 17g of methylcyclohexanediamine at room temperature, the speedmixer slurry mixer vacuum stirred, stirred at a speed of 2000rpm/min for 2min, and the stirred mixture was placed at room temperature Put it down for 8 hours to get the epoxy resin cured material.
对比例4Comparative example 4
将100g双酚A型环氧树脂NPEL128E和32g 3,3'-二甲基-4,4-二氨基二环己基甲烷在室温下混合后，经speedmixer浆料搅拌机真空搅拌，在2000rpm/min的转速下搅拌2min，将搅拌后的混合品在室温下放置7h即可得到环氧树脂固化材料。After mixing 100g of bisphenol A type epoxy resin NPEL128E and 32g of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane at room temperature, it was vacuum stirred by a speedmixer slurry mixer at 2000rpm/min Stir at a rotating speed for 2 minutes, and place the stirred mixture at room temperature for 7 hours to obtain an epoxy resin cured material.
采用TA公司的TMA测试本发明实施例1至实施例8以及对比例1至对比例4的耐高温环氧树脂的玻璃化转变温度，结果见表1。TMA of TA Company was used to test the glass transition temperature of the high-temperature-resistant epoxy resins of Examples 1 to 8 and Comparative Examples 1 to 4 of the present invention, and the results are shown in Table 1.
TMA测试程序为：0～190℃，以10℃/min的速率升温。The TMA test procedure is: 0-190°C, heating at a rate of 10°C/min.
表1 制备得到的耐高温环氧树脂的性能参数Table 1 The performance parameters of the prepared high temperature resistant epoxy resin
Figure PCTCN2022113416-appb-000001
Figure PCTCN2022113416-appb-000001
根据表1可知，随着所述固化剂组合物中所述酸酐类固化剂的含量的增多，玻璃化温度Tg也随之增高。According to Table 1, it can be seen that as the content of the acid anhydride curing agent in the curing agent composition increases, the glass transition temperature Tg also increases.
虽然在上文中详细说明了本发明的实施方式，但是对于本领域的技术人员来说显而易见的是，能够对这些实施方式进行各种修改和变化。但是，应理解，这种修改和变化都属于权利要求书中所述的本发明的范围和精神之内。而且，在此说明的本发明可有其它的实施方式，并且可通过多种方式实施或实现。Although the embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and changes can be made to the embodiments. However, it should be understood that such modifications and changes are within the scope and spirit of the present invention described in the claims. Furthermore, the invention described herein is capable of other embodiments and of being practiced or carried out in various ways.

Claims (10)

  1. 一种固化剂组合物的制备方法，其特征在于，包括以下步骤：A preparation method of curing agent composition, is characterized in that, comprises the following steps:
    提供第一组分和第二组分；providing a first component and a second component;
    将所述第一组分和所述第二组分混合并升温搅拌开始反应，以制备所述固化剂组合物；mixing the first component and the second component, raising the temperature and stirring to start the reaction, so as to prepare the curing agent composition;
    所述第一组份为基础胺类固化剂；所述第二组分为酸酐类固化剂，The first component is a basic amine curing agent; the second component is an acid anhydride curing agent,
    其中，所述酸酐类固化剂选自3,3’,4,4’-二苯酮四酸二酐固化剂、偏苯三酸酐固化剂、均苯四甲酸二酐固化剂中的一种。Wherein, the acid anhydride curing agent is selected from one of 3,3',4,4'-benzophenonetetracarboxylic dianhydride curing agent, trimellitic anhydride curing agent, and pyromellitic dianhydride curing agent.
  2. 根据权利要求1所述的固化剂组合物的制备方法，其特征在于，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比为(0.6～0.9)：(0.1～0.4)。The preparation method of the curing agent composition according to claim 1, characterized in that the molar ratio of the basic amine curing agent to the acid anhydride curing agent is (0.6-0.9): (0.1-0.4).
  3. 根据权利要求2所述的固化剂组合物的制备方法，其特征在于，所述基础胺类固化剂与所述酸酐类固化剂的摩尔比为(0.7～0.8)：(0.2～0.3)。The preparation method of the curing agent composition according to claim 2, characterized in that, the molar ratio of the basic amine curing agent to the acid anhydride curing agent is (0.7-0.8): (0.2-0.3).
  4. 根据权利要求1所述的固化剂组合物的制备方法，其特征在于，所述酸酐类固化剂为3,3’,4,4’-二苯酮四酸二酐。The preparation method of the curing agent composition according to claim 1, wherein the acid anhydride curing agent is 3,3',4,4'-benzophenonetetraacid dianhydride.
  5. 根据权利要求1所述的固化剂组合物的制备方法，其特征在于，所述基础胺类固化剂选自间苯二甲胺、氨乙基哌嗪、2-甲基戊二胺、三甲基己二胺、1,3环己二甲胺、异佛尔酮二胺、二氨基二环己基甲烷、乙二胺、二乙烯三胺、三乙烯四胺、甲基环己二胺、4,4'-二氨基二环己基甲烷、1,2-环己二胺、3,3'-二甲基-4,4-二氨基二环己基甲烷和二乙基甲苯二胺中的一种。The preparation method of the curing agent composition according to claim 1, wherein the basic amine curing agent is selected from the group consisting of m-xylylenediamine, aminoethylpiperazine, 2-methylpentamethylenediamine, trimethyl Hexamethylenediamine, 1,3 cyclohexanedimethylamine, isophoronediamine, diaminodicyclohexylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, methylcyclohexanediamine, 4 , one of 4'-diaminodicyclohexylmethane, 1,2-cyclohexanediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane and diethyltoluenediamine .
  6. 根据权利要求5所述的固化剂组合物的制备方法，其特征在于，所述基础胺类固化剂选自氨乙基哌嗪、异佛尔酮二胺、甲基环己二胺和3,3'-二甲基-4,4-二氨基二环己基甲烷中的一种。The preparation method of curing agent composition according to claim 5, is characterized in that, described basic amine curing agent is selected from the group consisting of aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine and 3, One of 3'-dimethyl-4,4-diaminodicyclohexylmethane.
  7. 根据权利要求1所述的固化剂组合物的制备方法，其特征在于，所述反应的 温度为80～150℃，所述反应的时间为2h～8h。The preparation method of curing agent composition according to claim 1, is characterized in that, the temperature of described reaction is 80～150 ℃, and the time of described reaction is 2h～8h.
  8. 一种固化剂组合物，其特征在于，通过权利要求1所述的固化剂组合物的制备方法制备而成。A curing agent composition, characterized in that it is prepared by the preparation method of the curing agent composition according to claim 1.
  9. 一种固化剂，其特征在于，包括权利要求8所述的固化剂组合物和环氧树脂。A curing agent, characterized in that it comprises the curing agent composition and epoxy resin according to claim 8.
  10. 根据权利要求9所述的固化剂，其特征在于，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂和酚醛型环氧树脂中的一种。The curing agent according to claim 9, wherein the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type One of epoxy resin and novolac epoxy resin.
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