阅读说明：本技术 一种可快速固化的固化剂及使用该固化剂的环氧树脂系统 (Curing agent capable of being rapidly cured and epoxy resin system using same ) 是由 吴梦雨 陈翠萍 吉明磊 于 2020-07-14 设计创作，主要内容包括：本发明涉及胶粘剂技术领域,更具体地,本发明涉及一种可快速固化的固化剂及使用该固化剂的环氧树脂系统。所述可快速固化的固化剂包括组分A,按重量份计,所述组分A包括50～90份杂环胺类化合物和10～20份金属盐催化剂。本发明提供的固化剂能够缩短环氧树脂的固化时间,耐湿热性能优异,在温度为85℃,湿度为85％老化1000h后拉伸剪切性能无降低,反而因长期受热,致使拉伸剪切强度略有提升。(The invention relates to the technical field of adhesives, in particular to a curing agent capable of being cured quickly and an epoxy resin system using the curing agent. The rapidly-curable curing agent comprises a component A, and the component A comprises 50-90 parts by weight of heterocyclic amine compounds and 10-20 parts by weight of metal salt catalysts. The curing agent provided by the invention can shorten the curing time of epoxy resin, has excellent humidity resistance, does not reduce the tensile shear performance after aging for 1000 hours at the temperature of 85 ℃ and the humidity of 85%, and slightly improves the tensile shear strength due to long-term heating.)

1. The curing agent capable of being rapidly cured is characterized by comprising a component A, wherein the component A comprises 50-90 parts by weight of heterocyclic amine compounds and 10-20 parts by weight of metal salt catalysts.

2. The fast-curing agent according to claim 1, wherein the heterocyclic amine compound is a nitrogen-containing heterocyclic amine compound.

3. The fast-curing hardener of claim 2, wherein the nitrogen-containing heterocyclic amine compound is selected from one or more of marine diamine, aminoethylpiperazine, aminocyclophosphazene, and phthalazinone.

4. The rapidly curable curing agent according to any one of claims 1 to 3, wherein the metal salt catalyst is a fluorine-containing metal salt catalyst.

5. The fast curing hardener of claim 4 wherein the fluorine-containing metal salt catalyst is a fluorine-containing metal sulfonate catalyst.

6. The rapidly curable curing agent according to claim 5, wherein the metal element in the fluorine-containing metal sulfonate catalyst is selected from any one of group I metal elements, group II metal elements and lanthanoid elements.

7. The rapidly curable curing agent according to any one of claims 1 to 6, further comprising 5 to 25 parts by weight of component B; the component B is selected from one or more of block copolymer, core-shell particles, nitrile rubber and polyether polyol.

8. The fast curable curing agent according to claim 7, wherein the component B comprises core shell particles.

9. An epoxy resin system obtained by using the rapidly curable curing agent according to any one of claims 1 to 8.

10. Epoxy resin system according to claim 9, having a cure time of 10min or less, preferably 15s or less, measured according to ASTM D5028-2009.

Technical Field

The invention relates to the technical field of adhesives, in particular to a curing agent capable of being cured quickly and an epoxy resin system using the curing agent.

Background

The epoxy resin adhesive is a liquid or solid adhesive consisting of epoxy resin, a curing agent, an accelerator, a modifier, a diluent, a filler and the like, and has excellent adhesive property on various metal materials (steel, iron, copper, aluminum and the like), non-metal materials (wood, glass, concrete and the like), thermosetting materials (phenolic plastics, aminoplasts, unsaturated polyesters and the like). The curing speed of the adhesive is basically determined by the structure and characteristics of the curing agent. Common basic curing agents such as amines, anhydrides and imidazoles have different curing times after being mixed with epoxy resin without adding an accelerator, and the curing time is from thirty minutes to dozens of days. Even so, in some low temperature areas, the curing speed still cannot meet the process requirements of specific construction environments.

Most epoxy resin curing agents currently in use on the market are thiol or salicylic acid system curing agents. The curing agents of the two systems have the characteristics of high curing speed and low curing temperature, can be used in a low-temperature environment, and can accelerate the construction efficiency. However, the two curing agent systems have the defects that the two curing agent systems are easy to slowly decompose in an extreme environment, especially in a high-temperature and high-humidity environment, and finally the performance of the materials is disabled, so that the application of the two curing agent systems is limited.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a rapidly-curable curing agent in a first aspect, which comprises a component A, wherein the component A comprises 50-90 parts by weight of heterocyclic amine compounds and 10-20 parts by weight of metal salt catalysts.

As a preferable technical solution of the present invention, the heterocyclic amine compound is a nitrogen-containing heterocyclic amine compound.

As a preferable technical scheme, the nitrogen-containing heterocyclic amine compound is selected from one or more of marine diamine, aminoethylpiperazine, amino cyclotriphosphazene and phthalazinone.

As a preferable embodiment of the present invention, the metal salt catalyst is a fluorine-containing metal salt catalyst.

As a preferable technical solution of the present invention, the fluorine-containing metal salt catalyst is a fluorine-containing metal sulfonate catalyst.

In a preferred embodiment of the present invention, the metal element in the fluorine-containing metal sulfonate catalyst is selected from any one of group I metal elements, group II metal elements, and lanthanoid elements.

As a preferable technical scheme of the invention, the rapidly curable curing agent further comprises 5-25 parts by weight of a component B; the component B is selected from one or more of block copolymer, core-shell particles, nitrile rubber and polyether polyol.

As a preferable technical solution of the present invention, the component B includes core-shell particles.

In a second aspect, the present invention provides an epoxy resin system obtained using the rapidly curable curing agent.

As a preferable technical scheme of the invention, the curing time of the epoxy resin system is less than or equal to 10min, preferably less than or equal to 15s, which is obtained by testing according to ASTM D5028-2009.

Compared with the prior art, the invention has the following beneficial effects:

(1) the curing agent provided by the invention can obviously shorten the curing time of the epoxy resin, and the curing time is as low as 15 s;

(2) the cured product of the epoxy resin system obtained by the invention has excellent humidity and heat resistance, and the tensile shear strength after 1000h aging is improved.

Detailed Description

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

The invention provides a curing agent capable of being rapidly cured, which comprises a component A, wherein the component A comprises 50-90 parts by weight of heterocyclic amine compounds and 10-20 parts by weight of metal salt catalysts.

In one embodiment, the curing agent further comprises 5 to 25 parts by weight of component B.

In a preferred embodiment, the component a comprises 70 parts of heterocyclic amine compound and 15 parts of metal salt catalyst by weight.

In a preferred embodiment, the component B is 10 parts by weight.

Component A

< heterocyclic amine Compound >

In one embodiment, the heterocyclic amine compound is a nitrogen-containing heterocyclic amine compound.

Preferably, the nitrogen-containing heterocyclic amine compound is selected from one or more of marine diamine, aminoethylpiperazine, aminocyclophosphazene and phthalazinone; more preferably, the nitrogen-containing heterocyclic amine compound is aminoethylpiperazine.

< Metal salt catalyst >

In one embodiment, the metal salt catalyst is a fluorine-containing metal salt catalyst.

Preferably, the fluorine-containing metal salt catalyst is a fluorine-containing metal sulfonate catalyst; further preferably, the metal element in the fluorine-containing metal sulfonate catalyst is selected from any one of group I metal elements, group II metal elements and lanthanoid elements; further preferably, the fluorine-containing metal sulfonate catalyst is selected from one or more of calcium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium trifluoromethanesulfonate and lanthanum trifluoromethanesulfonate; more preferably, the fluorosulfonate salt catalyst is calcium trifluoromethanesulfonate.

In one embodiment, the component A further comprises 10 to 30 parts by weight of an aromatic amine compound.

Preferably, the component a further includes 20 parts by weight of an aromatic amine compound.

The aromatic amine compound of the present invention is not particularly limited.

In one embodiment, when component a does not include aromatic amine compounds, the method for preparing component a comprises: and (3) uniformly mixing the heterocyclic amine compound and the metal salt catalyst to obtain the component A.

Preferably, when the component a does not include aromatic amine compounds, the preparation method of the component a includes: and stirring and mixing the heterocyclic amine compound and the metal salt catalyst at the rotating speed of 2000r/min for 1-10 min to obtain the component A.

More preferably, when the component a does not include aromatic amine compounds, the preparation method of the component a includes: and stirring and mixing the heterocyclic amine compound and the metal salt catalyst at the rotating speed of 2000r/min for 2min to obtain the component A.

In one embodiment, when the component a includes an aromatic amine compound, the preparation method of the component a includes: and (3) uniformly mixing the heterocyclic amine compound and the metal salt catalyst, adding the aromatic amine compound, and uniformly mixing to obtain the component A.

Preferably, when the component a includes an aromatic amine compound, the preparation method of the component a includes: and stirring and mixing the heterocyclic amine compound and the metal salt catalyst at the rotating speed of 2000r/min for 1-10 min, and then adding the aromatic amine compound at the rotating speed of 2000r/min, stirring and mixing for 1-10 min to obtain the component A.

More preferably, when the component a includes an aromatic amine-based compound, the preparation method of the component a includes: and stirring and mixing the heterocyclic amine compound and the metal salt catalyst at the rotating speed of 2000r/min for 2min, and then adding the aromatic amine compound at the rotating speed of 2000r/min, stirring and mixing for 2min to obtain the component A.

Component B

In one embodiment, the component B is selected from one or more of block copolymers, core shell particles, nitrile rubbers, polyether polyols.

Preferably, the component B comprises core-shell particles, more preferably, the core-shell particles are methyl methacrylate-butadiene-styrene core-shell particles.

The methyl methacrylate-butadiene-styrene core-shell particles are purchased from Japanese Korea under the brand name of M-210.

The component A and the component B in the curing agent are stored separately.

The applicant has unexpectedly found that when the curing agent comprises nitrogen-containing heterocyclic amine compounds and metal salts, especially nitrogen-containing heterocyclic amine compounds and fluorine-containing metal sulfonates, the wet heat strength of the epoxy resin can be ensured in a short curing time, and the tensile shear performance of the epoxy resin is not reduced after the epoxy resin is aged for 1000 hours at 85 ℃ and 85% humidity. The applicant believes that the possible reason is that the nitrogen-containing heterocyclic amine compound has a rich nitrogen atom skeleton and a stable chemical structure, and the crosslinking between the epoxy resin and the nitrogen-containing heterocyclic amine compound is promoted under the catalysis of a metal salt, particularly a fluorine-containing metal sulfonate, and further, the applicant unexpectedly found that the moisture and heat resistance performance is further improved, the curing time is further shortened, and the curing time is as low as 15s when the component B is a core-shell particle, particularly a core-shell particle, is a Japanese Brillouin M-210, and the applicant speculates that the core-shell particle can be uniformly dispersed in a system, and has a difference in the compatibility with the soft and hard segments of the epoxy resin, so that the crosslinking and chain growth between active centers are increased, the curing time is shortened, and the moisture and heat resistance performance is improved.

In a second aspect, the present invention provides an epoxy resin system obtained using the rapidly curable curing agent.

In one embodiment, the epoxy resin system comprises 65-135 parts by weight of a curing agent, 70-120 parts by weight of an epoxy resin and 5-30 parts by weight of an auxiliary agent.

Preferably, the epoxy resin system comprises 75-125 parts by weight of curing agent, 80-100 parts by weight of epoxy resin and 10-30 parts by weight of auxiliary agent.

More preferably, the epoxy resin system includes 95 parts curing agent, 85 parts epoxy resin, and 15 parts coagent.

Epoxy resin

The epoxy resin of the present invention is not particularly limited, and examples thereof include aromatic epoxy resins, aliphatic epoxy resins, and alicyclic epoxy resins.

The aromatic epoxy resin is bisphenol A epoxy resin which is purchased from Nantong star and is NPEL 127E.

Auxiliary agent

The additives of the present invention include, but are not limited to, epoxy diluents, inorganic fillers, and color pastes.

The auxiliary agent of the present invention is not particularly limited, and those skilled in the art can select it as desired.

The epoxy diluent is purchased from Anhui Xinyuan and has the model number XY 622A.

The weight parts in the invention are all the same.

The curing time of the epoxy resin system is less than or equal to 10 min; preferably, the curing time of the epoxy resin system is 15s or less.

The cure times of the present invention were tested according to the methods in the Performance evaluation section.

The third aspect of the present invention provides a method for preparing an epoxy resin system, comprising the steps of:

(1) fully mixing the epoxy resin and the auxiliary agent, adding the component B in the curing agent, uniformly mixing, preserving heat at 75-100 ℃, and grinding to obtain a first component;

(2) and uniformly mixing the component A and the first component in the curing agent.

In one embodiment, a method of making the epoxy resin system includes the steps of:

(1) stirring epoxy resin and an auxiliary agent at a rotating speed of 1000r/min for 5-120 min, adding a component B in a curing agent, uniformly mixing, keeping the temperature at 75-100 ℃ for 0.5-6 h, uniformly stirring at a rotating speed of 2000r/min, and grinding when the temperature is reduced to 40 ℃ until the particle size reaches within 20 micrometers to obtain a first component;

(2) and uniformly mixing the component A and the first component in the curing agent.

In a preferred embodiment, the method of preparing the epoxy resin system comprises the steps of:

(1) stirring the epoxy resin and the auxiliary agent at the rotating speed of 1000r/min for 60min, adding the component B in the curing agent, uniformly mixing, keeping the temperature at 85 ℃ for 3h, uniformly stirring at the rotating speed of 2000r/min, and grinding when the temperature is reduced to 40 ℃ until the particle size reaches within 20 microns to obtain a first component;

(2) and uniformly mixing the component A and the first component in the curing agent.