阅读说明：本技术 含磷三氮唑有机胺盐阻燃固化剂及其在环氧树脂中的应用 (Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin ) 是由 简荣坤 刘鑫铎 艾远芳 庞付渠 郑贤庭 于 2020-06-18 设计创作，主要内容包括：本发明公开了含磷三氮唑有机胺盐阻燃固化剂及其在环氧树脂中的应用。本发明利用三氮唑含显酸性的仲胺基团,采用含磷三氮唑与有机胺为原料通过酸碱反应制得含磷三氮唑有机胺盐阻燃固化剂。本发明提供的含磷三氮唑有机胺盐不仅具有阻燃活性的磷杂菲基团和三氮唑基团,还具有固化环氧树脂的功能基团,集阻燃、固化功能于一体,将其应用于阻燃固化环氧树脂,所得环氧树脂具有优异的阻燃性能和力学性能。本发明所制备的环氧树脂阻燃材料易于工业化生产、不含卤素,符合绿色环保理念。(The invention discloses a phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin. The invention utilizes triazole containing secondary amine groups which show acidity, and adopts phosphorus-containing triazole and organic amine as raw materials to prepare the flame-retardant curing agent of the organic amine salt of the phosphorus-containing triazole through acid-base reaction. The organic amine salt containing the triazole not only has the phosphaphenanthrene group and the triazole group with flame retardant activity, but also has the functional group for curing the epoxy resin, integrates flame retardant and curing functions, is applied to the flame retardant cured epoxy resin, and the obtained epoxy resin has excellent flame retardant property and mechanical property. The epoxy resin flame-retardant material prepared by the invention is easy for industrial production, does not contain halogen, and accords with the concept of environmental protection.)

1. The flame-retardant curing agent containing the phosphorus triazole organic amine salt is characterized in that: the structural formula is any one of the following fifteen structural formulas:

2. the preparation method of the flame retardant curing agent containing the organic amine salt of triazole as claimed in claim 1, which is characterized in that: adding a phosphorus-containing triazole compound and organic amine into a three-neck flask provided with a thermometer and a mechanical stirrer, adding a solvent, uniformly mixing, carrying out a heating reaction, carrying out rotary evaporation on the obtained solution to remove the solvent, and drying to obtain a phosphorus-containing triazole organic amine salt flame-retardant curing agent;

the structural formula of the phosphorus-containing triazole compound is as follows:

3. the preparation method of the phosphorus-containing triazole organic amine salt flame-retardant curing agent according to claim 2, which is characterized in that: the organic amine is aliphatic amine or aromatic amine.

4. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole of claim 3, which is characterized in that: the aliphatic amine comprises ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethyleneimine.

5. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole of claim 3, which is characterized in that: the aromatic amine comprises imidazole, 2-methylimidazole, diaminodiphenylmethane or m-phenylenediamine.

6. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole as claimed in claim 2, which is characterized in that: the molar ratio of the phosphorus-containing triazole compound to the organic amine is 1-2: 1.

7. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole as claimed in claim 2, which is characterized in that: the molar ratio of the phosphorus-containing triazole compound to the solvent is 1: 15-25.

8. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole as claimed in claim 2, which is characterized in that: the solvent is one of methanol, ethanol and water.

9. The preparation method of the flame retardant curing agent containing the organic amine salt of triazole as claimed in claim 2, which is characterized in that: the reaction temperature is 60-90 ℃, and the reaction time is 1-9 hours.

10. The use of the organic amine salt flame retardant curing agent containing phosphorus triazole of claim 1 in flame retardant curing epoxy resin.

Technical Field

The invention relates to the technical field of flame-retardant curing agents, in particular to a phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin.

Background

Epoxy resin (EP) is an important high polymer material, and plays an important role in the industrial fields of coatings, laminated plates, electronic devices, adhesives, aerospace and the like due to excellent adhesive property, mechanical property, chemical resistance and insulating property of the epoxy resin. However, since epoxy resin has strong flammability, a large amount of smoke is generated and toxic gases are released during combustion, and thus, the application of epoxy resin in the fields of electronic devices, buildings, aerospace and the like with high requirements for flame retardancy is limited to a certain extent. Therefore, it is of great importance to develop flame retardants that reduce the flammability of epoxy resins.

The phosphorus flame retardant is a research hotspot of the current flame-retardant epoxy resin material due to the green and environment-friendly characteristics of excellent char forming capability, low smoke, low toxicity and the like in the combustion process. The phosphorus-containing triazole contains phosphorus-nitrogen flame retardant elements and has a synergistic flame retardant effect, so that the phosphorus-containing triazole is a high-efficiency flame retardant. In addition, the phosphorus-containing triazole contains hydrogen bonds and pi-pi bonds, so that the mechanical property of the epoxy resin can be enhanced. However, when the epoxy resin is modified, the epoxy resin is required to be mixed with a curing agent for use, and the flame-retardant curing is not realized.

Disclosure of Invention

The invention aims to provide an organic amine modified phosphorus-containing triazole organic amine salt flame-retardant curing agent and a preparation method thereof, and aims to solve the problem that the flame retardance and the mechanical property of epoxy resin are difficult to balance.

The structural formula of the flame-retardant curing agent containing the phosphorus triazole organic amine salt is any one of the following:

the preparation method of the flame-retardant curing agent containing the phosphorus triazole organic amine salt comprises the following steps: adding a certain amount of phosphorus-containing triazole compound and organic amine into a three-neck flask provided with a thermometer and a mechanical stirrer, adding a certain amount of solvent, uniformly mixing, heating for reaction for a period of time, performing rotary evaporation on the obtained solution to remove the solvent, and drying to obtain the phosphorus-containing triazole organic amine salt flame-retardant curing agent.

The structural formula of the phosphorus-containing triazole compound is as follows:

the organic amine is aliphatic amine or aromatic amine. The aliphatic amine comprises ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and polyethyleneimine; the aromatic amine comprises imidazole, 2-methylimidazole, diaminodiphenylmethane and m-phenylenediamine.

The molar ratio of the phosphorus-containing triazole compound to the organic amine is 1-2: 1.

The molar ratio of the phosphorus-containing triazole compound to the solvent is 1: 15-25.

The solvent is one of methanol, ethanol and water.

The reaction temperature is 60-90 ℃, and the reaction time is 1-9 hours.

The flame-retardant curing agent containing the phosphorus-containing triazole organic amine salt can be used for preparing flame-retardant cured epoxy resin.

By adopting the technical scheme, the invention provides the organic amine salt of the phosphorus-containing triazole obtained by modifying the phosphorus-containing triazole by using organic amine, and the organic amine salt of the phosphorus-containing triazole has the following advantages:

1. the flame-retardant curing agent containing the organic amine salt of the phosphorus-containing triazole contains amino groups and imidazole groups with curing activity, so that the phosphorus-containing triazole is not only a flame retardant but also a curing agent for curing epoxy resin.

2. The process for preparing the phosphorus-containing triazole organic amine salt flame-retardant curing agent is simple and easy to operate, and is green, environment-friendly and pollution-free.

3. The phosphorus-containing triazole organic amine salt flame-retardant curing agent prepared by the invention is applied to epoxy resin, and the obtained epoxy resin material has excellent flame-retardant property and mechanical property.

Detailed Description

The synthetic example of the flame retardant curing agent containing the organic amine salt of triazole comprises the following components: