CN114957617A - Epoxy curing agent and preparation method and application thereof - Google Patents
Epoxy curing agent and preparation method and application thereof Download PDFInfo
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- CN114957617A CN114957617A CN202210554627.6A CN202210554627A CN114957617A CN 114957617 A CN114957617 A CN 114957617A CN 202210554627 A CN202210554627 A CN 202210554627A CN 114957617 A CN114957617 A CN 114957617A
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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
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention provides an epoxy curing agent and a preparation method and application thereof. The curing agent comprises the structure
Description
Technical Field
The invention belongs to the field of epoxy resin, and particularly relates to an epoxy curing agent, and a preparation method and application thereof.
Background
Epoxy resins are widely used in the field of composite material manufacture and the like due to their excellent properties such as heat resistance, mechanical properties, adhesion, electrical insulation, chemical resistance and the like. Epoxy resin is generally liquid or solid micromolecule or oligomer at room temperature, and forms a three-dimensional cross-linked network structure after reacting with a curing agent, wherein common curing agents comprise amines, anhydrides, thiols, phenols, phenolic compounds, imidazoles and the like.
When the epoxy resin is used for a large composite material system, the resin needs to be capable of flowing fully in a mould before curing, at the moment, a mixed system needs to have a longer pot life and even does not react at normal temperature, and after the temperature of the mould is raised, the curing agent and the epoxy resin are subjected to crosslinking curing, so that the curing agent needs to have lower reactivity, and the currently commonly used low-activity curing agent is mainly a latent curing agent.
The commonly used latent curing agents for the large-scale composite materials mainly comprise ketimine, dicyandiamide, organic acid anhydride and microcapsules, wherein the ketimine is easy to absorb moisture in air to decompose and has higher requirements on construction environment; dicyandiamide is solid at normal temperature and has poor compatibility with epoxy resin; the organic acid anhydride is easy to hydrolyze and has poor moisture resistance, chemical modification is not easy to carry out, and the post-curing temperature is higher; the microcapsule preparation process has strict requirements, the thickness of the microcapsule membrane can bring different degrees of influence on storage, transportation and use, and the industrial application is difficult.
US4335228 proposes that acyl group substituted modified imidazole is adopted, the electron donating ability of imine is weakened due to the strong electron withdrawing effect of acyl group, the energy barrier of imine reacting with epoxy resin is improved, and curing activity is lost at normal temperature, so that the imidazole modified imidazole has good latency, and when the temperature is raised enough to overcome the energy barrier of imine reacting with epoxy resin, the curing activity can be recovered by acyl group substituted imidazole curing agent, but the modified imidazole is generally solid and has poor compatibility with epoxy resin;
CN101885832A proposes that imine compounds of secondary amine prepared by reacting polyamine and carbonyl compounds are used for end capping, the imine structure in a curing agent is hydrolyzed to generate hydrophilic amino in water environment, and the carbonyl compounds generated during the hydrolysis of the latent curing agent exist as a toughening agent in the system, so that the mechanical property of the material is reduced;
CN105837798A proposes that mono-thiocarboxylic acid and epoxy resin are subjected to ring-opening addition to seal mercaptan, the curing agent can automatically convert mercaptan groups in the presence or absence of a catalyst to react with the epoxy resin, but the acetylation reaction dissociation temperature of the mercaptan group dissociation is higher, and the curing agent does not meet the use requirements of a large-scale composite material perfusion process.
In view of the above problems, a new epoxy resin curing agent needs to be found, which has a long pot life after being matched with epoxy resin at normal temperature, can dissociate active groups after being heated, and can rapidly react with epoxy resin.
Disclosure of Invention
The invention aims to provide an epoxy resin curing agent which is a low-viscosity liquid at normal temperature, has good workability after being matched with epoxy resin, has a long working life at room temperature, has no obvious viscosity rise after being stored for 6 months at 25 ℃, can react to generate primary amine groups under the heating condition after construction is finished, and can quickly cure the epoxy resin by primary amine.
Another object of the present invention is to provide an epoxy resin composition comprising the above epoxy curing agent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an epoxy resin curing agent, which comprises a compound with a structure shown in a formula (I) and an amino metal compound,
wherein R is 1 Is composed of
One of (1), R 2 Is composed of
The amino metal compound is selected from group I amino metal compounds, preferably sodium amide and/or potassium amide, more preferably sodium amide.
Another object of the present invention is to provide a method for preparing an epoxy resin curing agent.
A preparation method for preparing an epoxy resin curing agent, the preparation method comprising the steps of:
s1: reacting picolinic acid with aromatic diamine to obtain picolinamide;
s2: and stirring and mixing the pyridine amide and the amino metal compound to obtain the epoxy curing agent.
In the present invention, the picolinic acid in S1 is selected from 3-picolinic acid and/or 4-picolinic acid, preferably 4-picolinic acid.
In the present invention, the aromatic diamine in S1 is selected from one or more of diphenylmethane diamine, p-phenylenediamine, m-phenylenediamine and toluene diamine, preferably diphenylmethane diamine; preferably, the molar ratio of picolinic acid to aromatic diamine is 2 (0.9-1.1), preferably 2 (0.95-1.05).
In the invention, the reaction temperature of S1 is 170-260 ℃, preferably 180-230 ℃, and the reaction time is 3-5 h, preferably 2-3.5 h.
In the present invention, the reaction of S1 is carried out under an inert gas atmosphere.
In the invention, the mixing temperature of S2 is 25-90 ℃, preferably 35-80 ℃.
In one embodiment, 4-picolinic acid and diphenylmethane diamine are used as raw materials, and the preparation reaction process for preparing the compound shown in the formula (I) in the curing agent is as follows:
in the invention, the compound shown in the formula (I) is used as a curing agent, is low-viscosity liquid at normal temperature, has a long working life after being matched with epoxy resin, and can react with the epoxy resin quickly under the action of an accelerator by virtue of the formation of primary amino at alpha position of pyridine by virtue of the Ziziphus reaction of sodium amide and the pyridine after the temperature is raised. Schematically, the action principle is as follows:
the invention also aims to provide application of the epoxy resin curing agent.
The use of an epoxy resin curing agent, which is the epoxy resin curing agent described above, or the epoxy resin curing agent prepared by the preparation method described above, for the curing of epoxy resins, preferably for the curing of epoxy resins requiring long open time, more preferably for the curing of electronic potting epoxy resins requiring long open time.
It is still another object of the present invention to provide an epoxy resin composition.
An epoxy resin composition, characterized in that the composition comprises the following components:
the component A comprises the following components in percentage by weight based on the component A:
55-80 wt%, preferably 65-75 wt% of epoxy resin,
2 to 23 wt%, preferably 7 to 14 wt% of a diluent,
1-22 wt% of defoaming agent, preferably 11-21 wt%;
the component B comprises the following components in percentage by weight based on the component B:
75-95 wt% of epoxy curing agent,
5-25 wt% of an accelerator;
wherein the epoxy resin curing agent is the epoxy resin curing agent of claim 1 or the epoxy resin curing agent prepared by the preparation method of any one of claims 2 to 4; preferably, the mass ratio of the component A to the component B is (1-6): 1, preferably (2-3): 1.
In the invention, the epoxy resin is one or more of bisphenol A type epoxy resin which is liquid at room temperature and bisphenol F type epoxy resin which is liquid at room temperature; selecting bisphenol A type epoxy resin with an epoxy value of 0.1-0.65 and liquid at room temperature.
In the invention, the diluent is selected from one or more of butyl glycidyl ether, benzyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, benzyl alcohol, nonylphenol, diisopropanol methyl ether, toluene and xylene, and is preferably 1, 4-butanediol diglycidyl ether.
In the invention, the defoaming agent is one or more of polyacrylate and modified organosilicon, preferably one or more of BYK066N, BYKA530, BYK6800, BYK141 and BYK 354.
In the present invention, the accelerator is selected from one or more of phenol, nonylphenol, salicylic acid and N, N' -dimethylcyclohexylamine, preferably phenol.
In the invention, the component A is obtained by uniformly mixing the epoxy resin, the diluent and the defoaming agent and then standing.
In the invention, the component B is obtained by uniformly mixing the epoxy resin curing agent and the accelerator and then standing.
In the invention, when the composition is used, the component A and the component B are uniformly mixed, defoamed and cured; preferably, the component A and the component B are uniformly mixed and then stand for 15-60 min, preferably 20-45 min; the curing temperature is 80-170 ℃, and preferably 90-160 ℃; the curing time is 3-6 h, preferably 4-5 h.
The invention also aims to provide the application of the epoxy resin composition.
The epoxy resin composition is used for building enclosures, acid storage tanks, acid-proof pumps, wind power blades, chemical pipelines, reaction tanks, containers, automobile shells, yachts, mineboats, submarine components, buoys, yachts, electric poles, motor retaining rings, radar covers and floating bridges.
The invention has the beneficial effects that:
(1) the epoxy curing agent provided by the invention is a low-viscosity liquid at normal temperature, and has good compatibility with epoxy resin.
(2) The curing agent of the invention does not react with epoxy group at normal temperature, and has longer pot life when being matched with epoxy resin.
(3) The curing agent can react with an amino metal compound to generate a primary amino group after the temperature is raised, and can quickly react with epoxy resin under the action of an accelerator.
Detailed Description
TABLE 1 raw materials and sources
The main performance and index testing method comprises the following steps:
| test items | Test standard | Instrument manufacturer and model |
| Viscosity of the oil | GB/T22314 | Brookfield DV-II + PRO |
| Exothermic reaction | GB/T22314 | Mettler-tollidods DSC-600 |
| Tensile strength | GB/T 2567 | Youhong measurement and control technology Limited company UH6503Y |
| Glass transition temperature | GB/T 22567-2008 | Mettler-tollidods DSC-600 |
Example 1
Preparation of epoxy curing agent:
s1: in N 2 Under protection, 2mol of 3-picolinic acid reacts with 0.9mol of diphenylmethane diamine at 180 ℃ for 3.5h to obtain 3-picolinic acid amide.
S2: and (3) fully and uniformly stirring 1mol of the obtained 3-picolinic acid amide and 2mol of sodium amide at 35 ℃ to obtain the epoxy resin curing agent.
Preparation of epoxy resin composition:
preparation of the component A: 150g of bisphenol F diglycidyl ether (epoxy value of 0.51), 20g of 1, 4-butanediol diglycidyl ether and 30g of BYK354 defoaming agent were mixed uniformly and then left to stand.
Preparation of the component B: 95g of the curing agent prepared in the example and 5g of phenol were added to a reaction kettle, mixed uniformly and then allowed to stand.
Uniformly mixing the 200g A component and the 100g B component, standing for 45min, heating to 90 ℃ for curing for 5 h.
The viscosity of the curing agent prepared by the invention at 25 ℃ is 1135mpa & s, the highest exothermic peak time is 452min, and the highest exothermic peak temperature is 51 ℃; the tensile strength of a cured product is 112MPa, and the glass transition temperature is 147 ℃.
The epoxy resin composition can be used in the fields of wind power blades and the like.
Example 2
Preparation of epoxy curing agent:
s1: at N 2 Under protection, 2mol of 4-picolinic acid reacts with 1.1mol of p-phenylenediamine at 230 ℃ for 2h to obtain 4-picolinic acid amide.
S2: and (3) fully and uniformly stirring 1mol of the obtained 4-picolinic acid amide and 2mol of amino potassium at the temperature of 80 ℃ to obtain the epoxy resin curing agent.
Preparation of epoxy resin composition:
preparation of component A: 195g of bisphenol A glycidyl ether E-51(DOW brand is DER331, epoxy value is 0.51), 42g of 1, 6-hexanediol diglycidyl ether and 63g of BYK066N defoamer were mixed uniformly and then left to stand.
Preparation of the component B: 75g of the curing agent prepared in the embodiment and 25g of salicylic acid are added into a reaction kettle and are uniformly mixed and then are stood.
Uniformly mixing the 300g A component and the 100g B component, standing for 45min, heating to 160 ℃ and curing for 4 h.
The viscosity of the curing agent prepared by the invention at 25 ℃ is 1275mpa & s, the highest exothermic peak time is 475min, and the highest exothermic peak temperature is 59.3 ℃; the tensile strength of the cured product was 103MPa, and the glass transition temperature was 163 ℃.
The epoxy resin composition can be used in the fields of electronic potting and the like.
Example 3
Preparation of epoxy curing agent:
s1: in N 2 Under protection, 2mol of 4-picolinic acid and 1mol of toluenediamine react for 3 hours at 200 ℃ to obtain 4-picolinic acid amide.
S2: and (3) fully and uniformly stirring 1mol of the obtained 4-picolinic acid amide and 2mol of amino potassium at 70 ℃ to obtain the epoxy resin curing agent.
Preparation of epoxy resin composition:
preparation of component A: 175g of bisphenol A glycidyl ether E-51(DOW brand DER331, epoxy value of 0.51) was mixed uniformly with 25g of butyl glycidyl ether and 50g of BYK6800 as an antifoaming agent and then left to stand.
Preparation of the component B: 80g of the curing agent prepared in the embodiment and 20g N, N' -dimethylcyclohexylamine are added into a reaction kettle, mixed uniformly and then kept stand.
Uniformly mixing the 250g A component and the 100g B component, standing for 30min, heating to 120 ℃ for curing for 4.5 h.
The viscosity of the curing agent prepared by the invention at 25 ℃ is 1083mpa & s, the highest exothermic peak time is 529min, and the highest exothermic peak temperature is 47.5 ℃; the tensile strength of the cured product is 122MPa, and the glass transition temperature is 149 ℃.
The epoxy resin composition can be used in the fields of prepregs and the like.
Comparative example 1
The difference compared to example 3 is that toluene diamine was used instead of the curing agent according to the invention.
Preparation of the component A: 175g of bisphenol A glycidyl ether E-51(DOW brand DER331, epoxy value of 0.51) was mixed uniformly with 25g of butyl glycidyl ether and 50g of BYK6800 as an antifoaming agent and then left to stand.
Preparation of the component B: 80g of toluenediamine and 20g N, N' -dimethylcyclohexylamine are added into a reaction kettle, mixed evenly and then kept stand.
Uniformly mixing the 250g A component and the 100g B component, standing for 30min, and heating to 100 ℃ for curing, wherein the curing time is 4.5 h.
The viscosity of the comparative example curing agent at 25 ℃ is 2784mpa & s, the maximum exothermic peak time is 248min, and the maximum exothermic peak temperature is 74 ℃; the tensile strength of the cured product is 49.5MPa, and the glass transition temperature is 89 ℃.
Comparative example 2
In contrast to example 1, reference is made to the latent macromolecular polythiol curing agent prepared in CN 112500554A.
1) 89.6g of polyether polyol (molecular weight 1000) using triethylene glycol as a starting material and 0.46g of AlCl are taken 3 Heating to completely dissolve the catalyst, dropwise adding 67.2g of Epichlorohydrin (EPCH) into the reaction solution, controlling the reaction temperature at 80 ℃ in the dropwise adding process, and reacting for 6 hours to obtain an intermediate product of chlorinated Polyether (PCE) after the reaction is finished;
2) adding the generated chlorinated polyether into 400g of 10 wt% NaOH solution, reacting for 3h at 20 ℃, and filtering generated salt after the reaction is finished to obtain a polyether polyol epoxy compound;
3) and (3) reacting the polyether polybasic epoxy compound obtained in the last step with 60.7g of thioacetic acid at the temperature of 30 ℃ for 4 hours, and after the reaction is finished, evaporating and removing excessive thioacetic acid at 0.01MPaA to obtain the polythiol curing agent.
Preparation of epoxy resin composition:
preparation of component A: 195g of bisphenol A glycidyl ether E-51(DOW brand DER331, epoxy value of 0.51), 42g of 1, 6-hexanediol diglycidyl ether and 63g of BYK066N defoamer were mixed uniformly and then left to stand.
Preparation of the component B: 75g of the curing agent prepared in the embodiment and 25g of salicylic acid are added into a reaction kettle and are uniformly mixed and then are stood.
Uniformly mixing the 300g A component and the 100g B component, standing for 45min, heating to 160 ℃ and curing for 4 h.
The viscosity of the comparative example curing agent at 25 ℃ is 3732mpa & s, the maximum exothermic peak time is 433min, and the maximum exothermic peak temperature is 67.3 ℃; the tensile strength of the cured product is 84MPa, and the glass transition temperature is 157 ℃.
As can be seen from the above examples and comparative examples, the epoxy curing agent of the present invention has low viscosity, is favorable for the uniform mixing of two components, has lower temperature of the highest exothermic peak, and has longer time of the highest exothermic peak, which indicates that the curing agent of the present invention has more excellent construction performance, and the cured product has better heat resistance and mechanical performance, and can meet the use requirements of structural members.
Claims (10)
1. An epoxy resin curing agent is characterized in that the curing agent comprises a compound with a structure shown as a formula (I) and an amino metal compound,
wherein R is 1 Is composed of
One of (1), R 2 Is composed of
And/or
The amino metal compound is selected from group I amino metal compounds, preferably sodium amide and/or potassium amide, more preferably sodium amide.
2. A method for preparing the epoxy resin curing agent of claim 1, comprising the steps of:
s1: reacting picolinic acid with aromatic diamine to obtain picolinamide;
s2: and stirring and mixing the pyridine amide and the amino metal compound to obtain the epoxy curing agent.
3. The process according to claim 2, wherein the picolinic acid in S1 is selected from 3-picolinic acid and/or 4-picolinic acid, preferably 4-picolinic acid;
and/or, the aromatic diamine in S1 is selected from one or more of diphenylmethane diamine, p-phenylenediamine, m-phenylenediamine and toluene diamine, preferably diphenylmethane diamine;
preferably, the molar ratio of the picolinic acid to the aromatic diamine is 2 (0.9-1.1), preferably 2 (0.95-1.05);
and/or the reaction temperature of S1 is 170-260 ℃, preferably 180-230 ℃, and the reaction time is 3-5 h, preferably 2-3.5 h;
and/or, the reaction of S1 is carried out under the protection of inert gas.
4. The method according to claim 2, wherein the mixing temperature of S2 is 25-90 ℃, preferably 35-80 ℃.
5. Use of an epoxy resin curing agent according to claim 1 or prepared by the preparation method according to any one of claims 2 to 4 for curing epoxy resins, preferably epoxy resins requiring long open time, more preferably electronic potting epoxy resins requiring long open time.
6. An epoxy resin composition, characterized in that the composition comprises the following components:
the component A comprises the following components in percentage by weight based on the component A:
55-80 wt%, preferably 65-75 wt% of epoxy resin,
2 to 23 wt%, preferably 7 to 14 wt% of a diluent,
1-22 wt% of defoaming agent, preferably 11-21 wt%;
the component B comprises the following components in percentage by weight based on the component B:
75-95 wt% of epoxy curing agent,
5-25 wt% of an accelerator;
wherein the epoxy resin curing agent is the epoxy resin curing agent of claim 1 or the epoxy resin curing agent prepared by the preparation method of any one of claims 2 to 4;
preferably, the mass ratio of the component A to the component B is (1-6): 1, preferably (2-3): 1.
7. The composition of claim 6, wherein the epoxy resin is one or more of a bisphenol A type epoxy resin that is liquid at room temperature and a bisphenol F type epoxy resin that is liquid at room temperature; selecting bisphenol A type epoxy resin with an epoxy value of 0.1-0.65 and liquid at room temperature;
and/or the diluent is selected from one or more of butyl glycidyl ether, benzyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, benzyl alcohol, nonylphenol, diisopropanol methyl ether, toluene and xylene, preferably 1, 4-butanediol diglycidyl ether;
and/or the defoaming agent is one or more of polyacrylate and modified silicone, preferably one or more of BYK066N, BYKA530, BYK6800, BYK141 and BYK 354;
and/or the accelerator is selected from one or more of phenol, nonyl phenol, salicylic acid and N, N' -dimethyl cyclohexylamine, and is preferably phenol.
8. The composition as claimed in claim 6 or 7, wherein the component A is obtained by uniformly mixing the epoxy resin, the diluent and the defoaming agent and then standing;
and/or the component B is obtained by uniformly mixing the epoxy resin curing agent and the accelerator and then standing.
9. The composition according to any one of claims 6 to 8, wherein the composition is used by uniformly mixing the A component and the B component, defoaming, and curing;
preferably, the component A and the component B are uniformly mixed and then stand for 15-60 min, preferably 20-45 min; the curing temperature is 80-170 ℃, and preferably 90-160 ℃; the curing time is 3-6 h, preferably 4-5 h.
10. Use of an epoxy resin composition according to any one of claims 6 to 9 for building envelopes, acid storage tanks, acid pumps, wind blades, chemical pipelines, reaction tanks, containers, car housings, yachts, mineswervers, submarine components, pontoons, yachts, electric poles, motor grommets, radomes, pontoons.
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