CN110563901A - Preparation method of diphenyl ether/organic silicon double-modified phenolic resin adhesive - Google Patents
Preparation method of diphenyl ether/organic silicon double-modified phenolic resin adhesive Download PDFInfo
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- CN110563901A CN110563901A CN201910820058.3A CN201910820058A CN110563901A CN 110563901 A CN110563901 A CN 110563901A CN 201910820058 A CN201910820058 A CN 201910820058A CN 110563901 A CN110563901 A CN 110563901A
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- diphenyl ether
- phenolic resin
- modified phenolic
- resin adhesive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of a diphenyl ether/organosilicon double-modified phenolic resin adhesive, and belongs to the technical field of adhesive preparation. Firstly, siloxane monomers and phenolic compounds react under the catalysis of an acid catalyst to generate an alkyl phenoxy silane intermediate; and then cooling, adding a certain amount of diphenyl ether and aldehyde compounds, reacting with the alkyl phenoxy silane intermediate to the end point, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive. According to the invention, a Si-O bond (460kJ/mol) with higher bond energy is introduced into the phenolic resin structure, so that weak link phenolic hydroxyl-OH in the structure is partially blocked, and the heat resistance of the resin is improved; and diphenyl ether is introduced into the resin structure, the density of benzene rings is indirectly increased, the crosslinking density is increased after curing, the heat resistance of the resin is further improved, and the resin has good insulation property and wide application prospect.
Description
Technical Field
The invention discloses a preparation method of a diphenyl ether/organosilicon double-modified phenolic resin adhesive, and belongs to the technical field of adhesive preparation.
Background
The phenolic resin is also called bakelite powder, and is widely applied to the fields of electronics, machinery, buildings, refractory materials, bonding and the like due to the advantages of simple synthesis process, low cost, high bonding strength and the like. 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 heat resistance of the prepared novel silicon phenolic resin is still insufficient, and a large number of applications in the high-temperature field are not yet satisfied, and the heat resistance needs to be further improved.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
The invention mainly solves the technical problem of the prior traditional phenolic resin adhesive due to phenolic hydroxyl-OH and methylene-CH on the structure2The diphenyl ether/organosilicon double-modified phenolic resin adhesive is easy to oxidize, so that the high-temperature resistance of the adhesive is poor.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: (1) adding siloxane monomers, phenolic compounds and an acidic catalyst into a reaction kettle, stirring until a uniform solution is formed, heating in a gradient manner, and reacting to obtain an alkyl phenoxy silane intermediate; (2) and then cooling, adding a certain amount of diphenyl ether and aldehyde compounds, reacting with the alkyl phenoxy silane intermediate to the end point, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive. Wherein the reaction temperature in the step (1) is 110-200 ℃; the reaction temperature in the step (2) is 70-95 ℃.
The preparation method of the diphenyl ether/organic silicon double-modified phenolic resin adhesive comprises the following steps of: the mass ratio of the siloxane monomer, the phenolic compound, the acidic catalyst and the diphenyl ether is 0.1-1.0: 1: 0.05-4% and 0.1-0.7; in addition, the dosage of the aldehyde compound and the phenolic compound is 0.5-1.0: 1 of molar ratio.
The siloxane monomer is 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-dodecylpropyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-dodecyltrimethoxysilane, n-, One or more of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
The phenolic compound is 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 acidic catalyst is 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 is 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.
According to the invention, a Si-O bond (460kJ/mol) with higher bond energy is introduced into the phenolic resin structure, so that weak link phenolic hydroxyl-OH in the structure is partially blocked, and the heat resistance of the resin is improved; and diphenyl ether is introduced into the resin structure, the density of benzene rings is indirectly increased, the crosslinking density is increased after curing, the heat resistance of the resin is further improved, and the resin has good insulation property and wide application prospect.
Taking methyltrimethoxysilane, phenol, diphenyl ether and formaldehyde as examples, the reaction generated in the preparation process of the diphenyl ether/organosilicon double-modified phenolic resin adhesive is as follows:
The structural formula of the diphenyl ether/organic silicon double-modified 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 diphenyl ether/organic silicon double-modified phenolic resin adhesive and the traditional thermoplastic phenolic resin adhesive are prepared under the same curing conditions to obtain a cured product sample, 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.
Example 1
Adding 116.20g of methyltrimethoxysilane, 228.29g of bisphenol A and 3.44g of p-toluenesulfonic acid into a reaction kettle, stirring until a uniform solution is formed, heating in a gradient manner, and reacting at 175 +/-5 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 62.68g of diphenyl ether and 70.61g of formaldehyde aqueous solution, reacting with the alkyl phenoxy silane intermediate at 90 ℃ until the end point, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive.
Example 2
41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 94.11g of phenol and 1.41g of phosphoric acid are added into a reaction kettle, stirred until a uniform solution is formed, and subjected to gradient temperature rise at 160 +/-5 ℃ for reaction to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 25.58g of diphenyl ether and 26.13g of paraformaldehyde, reacting with the alkyl phenoxy silane intermediate at 85 ℃ until the end, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive.
Example 3
Adding 68.11g of methyltrimethoxysilane, 94.11g of phenol and 1.88g of methanesulfonic acid into a reaction kettle, stirring until a uniform solution is formed, heating in a gradient manner, and reacting at 150 +/-5 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 31.27g of diphenyl ether and 24.04g of paraformaldehyde, reacting with the alkyl phenoxy silane intermediate at 85 ℃ until the end, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive.
Claims (8)
1. A preparation method of a diphenyl ether/organic silicon double-modified phenolic resin adhesive is characterized by comprising the following specific preparation steps: (1) adding siloxane monomers, phenolic compounds and an acidic catalyst into a reaction kettle, stirring until a uniform solution is formed, heating in a gradient manner, and reacting to obtain an alkyl phenoxy silane intermediate; (2) and then cooling, adding a certain amount of diphenyl ether and aldehyde compounds, reacting with the alkyl phenoxy silane intermediate to the end point, distilling under reduced pressure, and drying in vacuum to obtain the diphenyl ether modified phenolic resin adhesive.
2. the preparation method of the diphenyl ether/organosilicon double ~ modified phenolic resin adhesive according to claim 1, wherein the reaction temperature in the step (1) is 110 ~ 200 ℃, and the reaction temperature in the step (2) is 70 ~ 95 ℃.
3. the preparation method of the diphenyl ether/organosilicon double ~ modified phenolic resin adhesive according to claim 1, wherein the mass ratio of the siloxane monomer, the phenolic compound, the acidic catalyst and the diphenyl ether is 0.1 ~ 1.0:1:0.05 ~ 4: 0.1 ~ 0.7, and the molar ratio of the aldehyde compound to the phenolic compound is 0.5 ~ 1.0: 1.
4. The method as claimed in claim 1, wherein the siloxane monomer is 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- (meth) acryloyloxy) propyltrimethoxysilane, One or more of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
5. The method for preparing diphenyl ether/organosilicon double modified phenolic resin adhesive according to claim 1, wherein the phenolic compound is one or more of phenol, methyl (or ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) phenol, xylenol, naphthol, catechol, cardanol, bisphenol a, bisphenol F, and bisphenol S.
6. The preparation method of the diphenyl ether/organosilicon double-modified phenolic resin adhesive according to claim 1, wherein the acidic catalyst is one or more of hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzene sulfonic acid, glacial acetic acid, boric acid, formic acid and propionic acid.
7. The method for preparing diphenyl ether/organosilicon double-modified phenolic resin adhesive according to claim 1, wherein the aldehyde compound is one or more of formaldehyde (or ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty) aldehyde, paraformaldehyde, trioxymethylene, paraldehyde, and furfural.
8. A preparation method of diphenyl ether/organic silicon double modified phenolic resin adhesive is characterized in that the modified phenolic resin is prepared by the preparation method of any one of claims 1 to 7.
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| CN201910820058.3A CN110563901A (en) | 2019-08-31 | 2019-08-31 | Preparation method of diphenyl ether/organic silicon double-modified phenolic resin adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335651A (en) * | 2020-11-05 | 2021-02-09 | 辽宁蓝水化学品制造有限公司 | Preparation method of chlorine dioxide disinfection slow-release gel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335651A (en) * | 2020-11-05 | 2021-02-09 | 辽宁蓝水化学品制造有限公司 | Preparation method of chlorine dioxide disinfection slow-release gel |
| CN112335651B (en) * | 2020-11-05 | 2022-09-06 | 辽宁蓝水化学品制造有限公司 | Preparation method of chlorine dioxide disinfection slow-release gel |
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Application publication date: 20191213 |