阅读说明：本技术 一种羟基化石墨烯导热酚醛树脂的制备方法 (Preparation method of hydroxylated graphene heat-conducting phenolic resin ) 是由 敖善世 秦存琪 叶鹏 于 2019-11-01 设计创作，主要内容包括：发明名称一种羟基化石墨烯导热酚醛树脂的制备方法摘要本发明提供了一种羟基化石墨烯导热酚醛树脂的制备方法,包括下列步骤：将羟基化石墨烯与酚类混合,再将酚类和醛类反应4-6h反应制得所述复合材料；所述羟基化石墨烯物质的用量为所述酚类化合物和醛类化合物的总重量的0.1-5％,优选0.1-1％,优选1-2％,优选2-5％。本发明的羟基化石墨烯酚醛树脂有效克服了纯酚醛树脂导热性能差,从原来的0.2(W·m<Sup>-1</Sup>·k<Sup>-1</Sup>)提高到0.6-0.9(W·m<Sup>-1</Sup>·k<Sup>-1</Sup>),极大的增强了酚醛树脂的导热性能,且绝缘性能、硬度黏度等性能均良好,在使在需要散热的器件上有老更广泛的应用。(The invention discloses a preparation method of hydroxylated graphene heat-conducting phenolic resin, and provides a preparation method of hydroxylated graphene heat-conducting phenolic resin, which comprises the following steps: mixing hydroxylated graphene with phenols, and then mixing the phenols and aldehydeCarrying out quasi-reaction for 4-6h to obtain the composite material; the amount of the hydroxylated graphene substance is 0.1-5%, preferably 0.1-1%, preferably 1-2%, preferably 2-5% of the total weight of the phenolic compound and the aldehyde compound. The hydroxylated graphene phenolic resin effectively overcomes the defect that pure phenolic resin has poor heat conductivity which is 0.2 (W.m) from the original value ‑1 ·k ‑1 ) Increased to 0.6-0.9 (W.m) ‑1 ·k ‑1 ) The heat-conducting property of the phenolic resin is greatly enhanced, and the insulating property, the hardness, the viscosity and other properties are good, so that the phenolic resin has old and wider application in devices needing heat dissipation.)

1. A preparation method of hydroxylated graphene heat-conducting phenolic resin is characterized by comprising the following steps:

s1, stirring a proper amount of graphene powder in hydrogen peroxide, vanadium pentoxide and a water solution with the pH of 3-5, carrying out ultrasonic treatment to obtain a hydroxylated graphene solution, washing, filtering, freezing and drying to obtain hydroxylated graphene powder;

mixing S2 hydroxylated graphene with phenols;

and (3) preparing S3 hydroxylated graphene phenolic resin.

2. The method for preparing the hydroxylated graphene heat-conducting phenolic resin according to claim 1, wherein the phenolic raw materials for preparing the phenolic resin comprise: phenol, xylenol, di-tert-butylphenol, resorcinol, polyhydric phenol, and the like; the aldehyde raw materials comprise: formaldehyde, acetaldehyde, furfural, etc.; the catalysts include: hydrochloric acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia water, magnesium hydroxide, zinc acetate and the like.

3. The preparation method of the hydroxylated graphene heat-conducting phenolic resin according to claim 1, wherein the method for preparing the hydroxylated graphene phenolic resin comprises the following specific steps:

(1) treating a proper amount of graphene powder with hydrogen peroxide, vanadium pentoxide and the like to prepare hydroxylated graphene;

(2) dissolving and dispersing hydroxylated graphene and phenols in hot water, and preparing a uniformly dispersed hydroxylated graphene phenol solution;

(3) condensing and refluxing the hydroxylated graphene phenol solution, water and sodium hydroxide for 20-30min at 40-60 ℃;

(4) heating to 60-65 deg.C, and adding aldehyde solution 3-4 times every 10-15 min;

(5) after the addition of the aldehydes is finished, keeping the temperature and reacting for 4-5h, then heating to 70-80 ℃, and continuing to react for 4-4.5 h;

(6) and cooling to 50-60 ℃, and adjusting the p H value to 7-8 to obtain the hydroxylated graphene phenolic resin suspension.

Technical Field

The invention relates to the technical field of composite materials, in particular to a preparation method of hydroxylated graphene heat-conducting phenolic resin.

Background

Phenolic resin has been used as one of three synthetic resins for more than 100 years, and has excellent adhesion performance, excellent heat resistance, good flame retardance and excellent mechanical properties; can be widely applied to the fields of coatings, adhesives, composite material resin matrixes, electronic and electronic engineering flame-retardant original parts, machinery, aerospace and the like. Due to the wide application of the phenolic resin and the development of high and new technologies, higher requirements are also put forward on the phenolic resin, and the defects of relatively high brittleness, high shrinkage rate, poor heat and electricity conductivity and the like of the phenolic resin limit the application of the pure phenolic resin, so that various modified phenolic resins are more and more concerned.

The graphene is used as a novel universal material, and most of the application modes are that the graphene is added as a functional filler, but the graphene surface has no any group and is easy to agglomerate. Therefore, the graphene cannot be well dispersed in the polymer composite material, and the dispersibility of the graphene is an important factor influencing the performance of the material. In order to further improve the dispersibility of graphene in phenolic resin, the hydroxylated graphene is obtained by hydroxylating and modifying the graphene, the hydroxylated graphene can be well dispersed in the phenolic resin, and the heat-conducting property of the phenolic resin is greatly improved by adding a small amount of hydroxylated graphene.

Disclosure of Invention

In view of the above technical problems, the present invention provides a hydroxylated graphene having a strong affinity with a phenolic resin adhesive. The heat-conducting property of the phenolic resin is improved by adding a small amount of hydroxylated graphene.

In order to achieve the purpose, the invention provides the following technical scheme:

the preparation method of the hydroxylated graphene reinforced phenolic resin adhesive heat-conducting performance material specifically comprises the following steps:

(1) treating a proper amount of graphene powder with hydrogen peroxide, vanadium pentoxide and the like to prepare hydroxylated graphene;

(2) dissolving and dispersing 1-5 parts of hydroxylated graphene and 90-100 parts of phenols in hot water, and preparing a uniformly dispersed hydroxylated graphene phenol solution;

(3) condensing and refluxing the hydroxylated graphene phenol solution, 5-10 parts of water and 5-10 parts of catalyst for 20-30min at 40-60 ℃;

(4) then heating to 60-65 ℃, and adding 120 parts of 100-120 parts of aldehyde solution every 10-15 min for 3-4 times;

(5) after the addition of the aldehydes is finished, keeping the temperature and reacting for 4-5h, then heating to 70-80 ℃, and continuing to react for 4-4.5 h; and (6) cooling to 50-60 ℃, and adjusting the p H value to 7-8 to obtain the hydroxylated graphene phenolic resin suspension.

(7) And (3) coating and drying the hydroxylated graphene phenolic resin suspension, and testing the performances such as heat conduction.

Preferably, the method comprises the following steps: in the reaction step (2), the phenols are one or more of phenol, xylenol, bis-tert-butylphenol and resorcinol;

preferably, the method comprises the following steps: in the reaction step (4), the aldehyde is one or more of formaldehyde, acetaldehyde and furfural;

preferably, the method comprises the following steps: the catalyst is one or more of hydrochloric acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia water, magnesium hydroxide and zinc acetate;

according to the preparation method for enhancing the thermal conductivity of the phenolic resin by using the hydroxylated graphene, the test result shows that the thermal conductivity of the phenolic resin added with 0.5-5% of the hydroxylated graphene is 0.2 (W.m) from the original thermal conductivity^-1·k^-1) Is directly increased to 0.6-0.9 (W.m)^-1·k^-1) Greatly enhances the heat conductivity of the phenolic resin, and has the resistivity of 10¹⁴Omega cm, good insulating property and wide application in devices requiring heat dissipation.

Detailed Description

The invention is further described with reference to specific examples.