阅读说明：本技术 一种耐水性酚醛树脂胶黏剂的制备方法 (Preparation method of water-resistant phenolic resin adhesive ) 是由 袁天顺 简亚溜 邹文俊 彭进 刘鹏展 赵硕 于 2019-08-31 设计创作，主要内容包括：本发明公开了一种耐水性酚醛树脂胶黏剂的制备方法,所述耐水性酚醛树脂胶黏剂是由二甲苯、硅氧烷单体、酚类化合物、酸性催化剂和醛类化合物组成。该耐水性酚醛树脂胶黏剂的制备方法,通过酚醛树脂结构中引入疏水性结构二甲苯环和键能较高的Si-O键(460 kJ/mol),酚羟基-OH中的氢原子H部分会被硅原子Si取代,因此改性酚醛树脂的耐水性和耐热性均得到较大提升。(The invention discloses a preparation method of a water-resistant phenolic resin adhesive, which consists of xylene, siloxane monomers, phenolic compounds, acidic catalysts and aldehyde compounds. According to the preparation method of the water-resistant phenolic resin adhesive, a hydrophobic structure dimethylbenzene ring and a Si-O bond (460kJ/mol) with high bond energy are introduced into a phenolic resin structure, and a hydrogen atom H part in a phenolic hydroxyl group-OH can be replaced by a silicon atom Si, so that the water resistance and the heat resistance of the modified phenolic resin are greatly improved.)

1. A preparation method of a water-resistant phenolic resin adhesive is characterized by comprising the following steps of uniformly mixing a siloxane monomer and a phenolic compound, carrying out gradient heating in the presence of an acid catalyst, carrying out reaction at 110 ~ 200 ℃ to obtain an alkyl phenoxy silane intermediate, cooling, adding a certain amount of xylene and the aldehyde compound, carrying out reaction with the alkyl phenoxy silane intermediate at 70 ~ 95 ℃ to reach a terminal point, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain the water-resistant phenolic resin adhesive.

2. The preparation method of the water-resistant phenolic resin adhesive according to claim 1, wherein the preparation method comprises the following steps: the siloxane monomer may be methyl (or phenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) trimethoxysilane, methyl (or phenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) triethoxysilane, ethyl orthosilicate, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, n-dodecyltrimethoxysilane, One or more of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.

3. The preparation method of the water-resistant phenolic resin adhesive according to claim 1, wherein the preparation method comprises the following steps: the phenolic compound can be one or more of phenol, methyl (or ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl) phenol, xylenol, naphthol, catechol, cardanol, bisphenol A, bisphenol F and bisphenol S.

4. The preparation method of the water-resistant phenolic resin adhesive according to claim 1, wherein the preparation method comprises the following steps: the acid catalyst can be one or more of hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, glacial acetic acid, boric acid, formic acid and propionic acid.

5. The preparation method of the water-resistant phenolic resin adhesive according to claim 1, wherein the preparation method comprises the following steps: the aldehyde compound can be one or more of formaldehyde (or ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen and twenty) aldehyde, paraformaldehyde, trioxymethylene, paraldehyde and furfural.

6. The preparation method of the water-resistant phenolic resin adhesive is characterized in that the mass ratio of the siloxane monomer to the phenolic compound to the acidic catalyst to the xylene is 0.1 ~ 1.0.0: 1: 0.05% to ~ 4% to 0.1 ~ 0.4.4, and the molar ratio of the aldehyde compound to the phenolic compound is 0.5 ~ 1.0.0: 1.

7. A preparation method of a water-resistant phenolic resin adhesive, which is characterized in that the water-resistant phenolic resin adhesive is prepared by the preparation method of any one of claims 1 to 6.

Technical Field

The invention relates to the technical field of industrial production, in particular to a preparation method of a water-resistant phenolic resin adhesive.

Background

The phenolic resin is also called bakelite, is colorless or tawny transparent solid, and is widely and largely applied to the fields of buildings, machinery, electronics, aerospace, bonding and the like due to low production cost, mature preparation process and excellent comprehensive performance. However, the phenolic hydroxyl and methylene in the molecular structure of the traditional phenolic resin are easy to oxidize, so that the heat resistance of the traditional phenolic resin is influenced, and the application of the traditional phenolic resin in certain fields, particularly in the high-temperature field, is limited.

In order to improve the thermal stability of the phenolic resin, silicon atoms are introduced into a macromolecular structure of the phenolic resin to partially block phenolic hydroxyl groups, and Si-O bonds (460kJ/mol) with higher bond energy than C-O bonds (326kJ/mol) are formed at the same time, so that the method is an effective way for improving the thermal stability of the phenolic resin. However, the traditional silicon phenolic resin preparation process is complex, hydrolysis self-polymerization of organic silicon monomers, phenol self-polymerization, copolymerization of monomers and phenol and the like exist, and the degree of reaction polymerization is difficult to control.

In earlier researches, the inventor prepares novel silicon phenolic resin (SPF) by synthesis through an ester exchange method, and solves the problem that the reaction process is difficult to control in the preparation process of the silicon phenolic resin; however, the prepared novel silicon phenolic resin has poor water resistance, and the industrial production is not yet satisfied, so that the water resistance needs to be further improved.

The present invention has been made in view of the above circumstances.

Disclosure of Invention

Aiming at the current situation, the invention provides a preparation method of a water-resistant phenolic resin adhesive, which aims to solve the problem of insufficient water resistance of phenolic resin.

In order to achieve the purpose, the invention provides the following technical scheme: uniformly mixing siloxane monomers and phenolic compounds, carrying out gradient temperature rise in the presence of an acid catalyst, and carrying out reaction at 110-200 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding a certain amount of xylene and aldehyde compounds, reacting with an alkyl phenoxy silane intermediate at 70-95 ℃ until the end point, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain the water-resistant phenolic resin adhesive.

The siloxane monomer may be methyl (or phenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) trimethoxysilane, methyl (or phenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) triethoxysilane, ethyl orthosilicate, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, n-dodecyltrimethoxysilane, One or more of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.

The phenolic compound can be one or more of phenol, methyl (or ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl) phenol, xylenol, naphthol, catechol, cardanol, bisphenol A, bisphenol F and bisphenol S.

The acid catalyst can be one or more of hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, glacial acetic acid, boric acid, formic acid and propionic acid.

The aldehyde compound can be one or more of formaldehyde (or ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen and twenty) aldehyde, paraformaldehyde, trioxymethylene, paraldehyde and furfural.

The preparation method of the water-resistant phenolic resin adhesive comprises the following raw materials in parts by weight: the mass ratio of the siloxane monomer, the phenolic compound, the acidic catalyst and the dimethylbenzene is 0.1-1.0: 1: 0.05-4% and 0.1-0.4; the molar ratio of the aldehyde compound to the phenolic compound is 0.5-1.0: 1.

According to the invention, a hydrophobic structure dimethylbenzene ring and a Si-O bond (460kJ/mol) with high bond energy are introduced into the phenolic resin structure, and the hydrogen atom H in phenolic hydroxyl-OH can be partially replaced by silicon atom Si, so that the water resistance and heat resistance of the modified phenolic resin are greatly improved.

Taking methyltrimethoxysilane, phenol, xylene and formaldehyde as examples, the reactions occurring in the preparation process of the water-resistant phenolic resin adhesive are as follows:

the structural formula of the water-resistant phenolic resin adhesive prepared by the invention is as follows:

detailed description of the invention

The embodiments in the following examples can be further combined or replaced, and the examples are only for describing the preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and those skilled in the art can make various changes and modifications to the technical solution of the present invention without departing from the design concept of the present invention, and all fall within the protection scope of the present invention.

Curing conditions of the cured product: the water-resistant phenolic resin and the traditional thermoplastic phenolic resin are prepared into a cured product sample under the same curing conditions, and the curing procedure of the sample is as follows: heating at 1-10 deg.C/min, respectively maintaining at 80 deg.C, 100 deg.C, 120 deg.C, 140 deg.C and 160 deg.C for 2h, heating to 180 deg.C, maintaining for 4h, and naturally cooling.