阅读说明：本技术 一种预浸料用快速固化环氧树脂基体及其制备方法 (A kind of prepreg fast-curing epoxy resin matrix and preparation method thereof ) 是由 王耀宗 刘晓丽 鹿海军 邢丽英 于 2019-09-19 设计创作，主要内容包括：本发明是一种预浸料用快速固化环氧树脂基体及其制备方法,本发明以双氰胺和改性胺作为混合固化剂,由两种固化剂协同调节环氧树脂快速固化特性。双氰胺在促进剂作用下能够和树脂进行快速固化反应,反应过程中迅速积聚的能量能够激发改性胺和树脂的固化反应。通过两种不同活性固化剂的搭配使用,能够有效减缓反应放热,同时实现树脂的快速固化。此外,改性胺的使用提升了树脂固化后的玻璃化转变温度,增加耐热性能。所得快速固化环氧树脂基体具有较好的储存稳定性。(The present invention is a kind of prepreg fast-curing epoxy resin matrix and preparation method thereof, and the present invention is using dicyandiamide and modified amine as mixed curing agent, by two kinds of curing agent synergic adjustment fast epoxy resin curing characteristics.Dicyandiamide can carry out rapid curing reaction under promotor effect with resin, and the energy gathered rapidly in reaction process can excite the curing reaction of modified amine and resin.It is used by the collocation of two kinds of different activities curing agent, can effectively slow down exothermic heat of reaction, while realizing the rapid curing of resin.In addition, the use of modified amine improves the glass transition temperature after resin solidification, increase heat resistance.Gained fast-curing epoxy resin matrix has preferable storage stability.)

1. a kind of prepreg fast-curing epoxy resin matrix, it is characterised in that: the chemical constituent of the epoxy resin-base and Mass fraction are as follows:

The curing agent is the mixture of dicyandiamide and modified amine, and the mass parts ratio of modified amine and dicyandiamide is 1~20: 1.

2. prepreg according to claim 1 fast-curing epoxy resin matrix, it is characterised in that: the epoxy resin For in tetraglycidel ether epoxy resin, glycidyl amine epoxy resin, ethylene oxidic ester epoxy resin, cycloaliphatic epoxy resin One or more of mixtures.

3. prepreg according to claim 1 fast-curing epoxy resin matrix, it is characterised in that: the promotor is Carbamide derivative or imidazole derivative.

4. prepreg according to claim 1 fast-curing epoxy resin matrix, it is characterised in that: the toughener is Thermoplastic, modified epoxy, caoutchouc elasticity particle, core-shell particles polymer, super high molecular weight epoxy resin or inorganic Rigid nanoparticle.

5. prepreg according to claim 1 fast-curing epoxy resin matrix, it is characterised in that: the epoxy resin-matrix The chemical constituent and mass fraction of body are as follows:

6. prepreg according to claim 1 fast-curing epoxy resin matrix, it is characterised in that: the epoxy resin-matrix The chemical constituent and mass fraction of body are as follows:

7. the method for preparing prepreg fast-curing epoxy resin matrix described in claim 1, it is characterised in that: this method It is to be heated to 150 DEG C~180 DEG C after mixing epoxy resin and toughener, is cooled to 70 DEG C~100 DEG C after mixing evenly Between, the modified amine in curing agent is added, stirring to modified amine is dissolved, and the dicyandiamide in curing agent is added, and continues to stir to equal Continue to be cooled between 60 DEG C~70 DEG C after even, promotor is added, continues after being stirred until homogeneous, obtains fast-curing epoxy resin base Body.

8. the prepreg according to claim 7 method of fast-curing epoxy resin matrix, it is characterised in that: described fast Fast cured epoxy resin matrix is less than or equal to 20 minutes in the curing time in 110 DEG C~160 DEG C sections.

9. the prepreg according to claim 7 method of fast-curing epoxy resin matrix, it is characterised in that: described fast Fast cured epoxy resin matrix is less than or equal to 15 minutes in the curing time in 130 DEG C~150 DEG C sections.

Technical field

The present invention is a kind of prepreg fast-curing epoxy resin matrix and preparation method thereof, this kind of epoxy resin-base Have the advantages that curing time is short, heat release is gentle, heat-resist, belongs to Epoxy Resin Technology field.

Background technique

Polymer matrix composites are due to Gao Bimo, Gao Biqiang, endurance, corrosion-resistant, integrally formed and can design The advantages that property is strong, is all with a wide range of applications in fields such as aerospace, automobile manufacture, sports goods.Wherein resin base Key components of the body as composite material, performance largely influence composite material process planning and molding matter Amount.Common resins system includes epoxy, phenolic aldehyde, span and cyanate ester resin etc..Epoxy resin is due to excellent resultant force Performance and processing performance are learned, is all one of research and the hot spot of application all the time.Epoxy resin for prepreg matrix majority is adopted Use latent curing agent.Usually there is certain stability under condition of storage, by external condition, such as heat, light, moisture excitation Afterwards, that is, start curing reaction.However, conventional epoxies matrix reactivity is low, curing time is longer, not only reduces production effect Rate also increases production economy cost.While guaranteeing composite molding quality, shorten consolidating for epoxy resin-base as far as possible Change the time, is the necessary condition for realizing the production of composite material high efficiency, low cost.

Existing prepreg generally uses high activity curing system with fast-curing epoxy resin matrix, can be realized resin and exists Rapid curing under specific temperature.But the reaction of such resin matrix is more violent, and curing exotherm is concentrated, and be easy to cause implode, shadow Ring material property.It part resin matrix the problems such as there is also poor storage stabilities, needs ready-to-use.In addition, most quickly solid Glass transition temperature is lower after changing epoxy resin-base solidification, and poor heat resistance restricts the further genralrlization application of material.

Summary of the invention

The present invention exactly designs in view of the above-mentioned deficiencies in the prior art and provides a kind of prepreg with quickly solid Change epoxy resin-base and preparation method thereof, is 130~150 DEG C the purpose is to obtain solidification temperature range, curing time is less than Equal to 20 minutes, glass transition temperature was more than or equal to 150 DEG C of epoxy resin for prepreg, to meet modern industrial production pair The manufacture demand of polymer matrix composites high efficiency, low cost.

The purpose of the present invention is achieved through the following technical solutions:

Technical solution of the present invention provides a kind of prepreg fast-curing epoxy resin matrix, it is characterised in that: the ring The chemical constituent and mass fraction of epoxy resin-based body are as follows:

The curing agent is the mixture of dicyandiamide and modified amine, and the mass parts ratio of modified amine and dicyandiamide is 1~20: 1。

In a kind of implementation, the epoxy resin is tetraglycidel ether epoxy resin, glycidyl amine epoxy resin, shrink The mixture of one or more of glycerol ester epoxy resin, cycloaliphatic epoxy resin.

In a kind of implementation, the promotor is carbamide derivative or imidazole derivative.

In a kind of implementation, the toughener is thermoplastic, modified epoxy, caoutchouc elasticity particle, nucleocapsid grain Sub- polymer, super high molecular weight epoxy resin or inorganic rigid nanoparticle.

In a kind of implementation, the chemical constituent and mass fraction of the epoxy resin-base are as follows:

In a kind of implementation, the chemical constituent and mass fraction of the epoxy resin-base are as follows:

Technical solution of the present invention additionally provides a kind of method for preparing above-mentioned prepreg fast-curing epoxy resin matrix, It is characterized by: this method is to be heated to 150 DEG C~180 DEG C after mixing epoxy resin and toughener, after mixing evenly It is cooled between 70 DEG C~100 DEG C, the modified amine in curing agent is added, stirring to modified amine is dissolved, and is added double in curing agent Cyanamide continues to continue to be cooled to after being stirred until homogeneous between 60 DEG C~70 DEG C, and promotor is added, continues after being stirred until homogeneous, obtains Fast-curing epoxy resin matrix.

The fast-curing epoxy resin matrix is less than or equal to 20 points in the curing time in 110 DEG C~160 DEG C sections Clock.Further, the fast-curing epoxy resin matrix is less than or equal to 15 in the curing time in 130 DEG C~150 DEG C sections Minute.

Traditional fast-curing epoxy resin generally is suitable for the curing molding of 3-5mm laminate structure, since there are heat release concentrations Problem, it is more difficult to realize that thickness is more than the product preparation of 10mm.To guarantee that resin implode does not occur in large scale product forming process, Often expendable material heat resistance reduces resin matrix glass transition temperature.Traditional fast-curing epoxy resin vitrifying turns Temperature is usually no more than 140 DEG C.The prepreg that the present invention is proposed in view of the above problems fast-curing epoxy resin matrix, Curing time is obtained less than or equal to 20 minutes, glass transition temperature is more than or equal to 150 DEG C of effect, and it is raw to meet modern industry Produce the manufacture demand to polymer matrix composites high efficiency, low cost.The characteristics of technical solution of the present invention and beneficial effect illustrate It is as follows:

1, using dicyandiamide and modified amine as mixed curing agent.Dicyandiamide can carry out fast under promotor effect with resin Fast curing reaction, the energy gathered rapidly in reaction process can excite the curing reaction of modified amine and resin.Not by two kinds With the front and back concerted reaction of active curing agent, it can effectively slow down exothermic heat of reaction.Curing exotherm section is more than or equal to 60 DEG C, resin Curing exotherm is gentle, is not susceptible to implode；

2, epoxy resin cure characteristic is adjusted by adjusting the ratio of dicyandiamide and modified amine in mixed curing agent.Double cyanogen The increase of amine content can greatly shorten epoxy cure time, promote quick setting capabilities.The increase of modified amine content, can have Effect improves the glass transition temperature after resin solidification, increases heat resistance.When gained epoxy resin-base solidifies at 130 DEG C Between be less than or equal to 20 minutes, glass transition temperature be more than or equal to 150 DEG C.

3, curing agent and promotor used are high activity resting form curing system, are guaranteeing the same of resin fast curing properties When, storage stability is taken into account, resin matrix room temperature storage stability is more than or equal to 20 days.

Specific embodiment

Technical solution of the present invention is further described below with reference to embodiment: