CN110591620A - Preparation method of aniline/organic silicon double-modified phenolic resin adhesive - Google Patents
Preparation method of aniline/organic silicon double-modified phenolic resin adhesive Download PDFInfo
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- CN110591620A CN110591620A CN201910838793.7A CN201910838793A CN110591620A CN 110591620 A CN110591620 A CN 110591620A CN 201910838793 A CN201910838793 A CN 201910838793A CN 110591620 A CN110591620 A CN 110591620A
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- phenolic resin
- aniline
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
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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
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of phenolic resin adhesive preparation, and particularly relates to a preparation method of an aniline/organic silicon double-modified phenolic resin adhesive. Firstly, siloxane monomers and phenolic compounds react under the action of an acid catalyst to generate an alkyl phenoxy silane intermediate; and further reacting with aniline and aldehyde compounds to obtain the aniline/organic silicon double-modified phenolic resin adhesive. According to the invention, a high-bond-energy Si-O bond (460kJ/mol) is introduced into a phenolic resin structure in a chemical copolymerization manner, and thermolabile groups, namely phenolic hydroxyl-OH, in the structure are partially blocked, so that the heat resistance of the resin is improved; the introduction of aniline increases the percentage of heat-resistant groups, namely benzene rings, in the resin structure, so that the heat resistance of the resin is further improved; the heat resistance of the modified phenolic resin is obviously improved compared with that of the unmodified phenolic resin by the comprehensive action of the two phenolic resin modifiers.
Description
Technical Field
The invention belongs to the technical field of phenolic resin adhesive preparation, and particularly relates to a preparation method of an aniline/organic silicon double-modified phenolic resin adhesive.
Background
Phenolic resin is a kind of resin formed by condensation polymerization of phenolic compounds and aldehyde compounds under the action of acidic or basic catalysts, and is widely applied to the fields of buildings, machinery, electronics, aerospace, bonding and the like due to the characteristics of excellent mechanical property, dimensional stability, electrical insulation 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 prepared novel silicon phenolic resin has poor heat resistance performance, and industrial production is not yet satisfied, and heat resistance modification needs to be carried out on the novel silicon phenolic resin.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the technical defects, the invention provides a preparation method of an aniline/organosilicon double-modified phenolic resin adhesive.
The preparation method of the aniline/organic silicon double-modified phenolic resin adhesive comprises the following steps:
uniformly mixing siloxane monomers, phenolic compounds and an acid catalyst, heating by a program, and reacting at 110-200 ℃ to generate an alkyl phenoxy silane intermediate; and then cooling, adding a certain amount of aniline and aldehyde compounds, and further reacting with an alkyl phenoxy silane intermediate at the temperature of 70-95 ℃ to obtain the aniline/organosilicon double-modified phenolic resin adhesive.
A preparation method of aniline/organic silicon double-modified phenolic resin adhesive comprises the following raw materials: the mass ratio of the siloxane monomer to the phenolic compound to the aniline to the acidic catalyst is 0.1-1.0: 1: 0.05-0.50: 0.05-4%; the use amount of the aldehyde compound and the phenolic compound is 0.5-1.0: 1 in molar ratio.
The siloxane monomer can 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-dodecylpropyl, n-butylpropyl, n-butylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) triethoxysilane, or mixtures thereof, 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 acidic 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, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane and icosane), paraformaldehyde, trioxymethylene, paraldehyde and furfural.
According to the invention, a high-bond-energy Si-O bond (460kJ/mol) is introduced into a phenolic resin structure in a chemical copolymerization manner, and thermolabile groups, namely phenolic hydroxyl-OH, in the structure are partially blocked, so that the heat resistance of the resin is improved; the introduction of aniline increases the percentage of heat-resistant groups, namely benzene rings, in the resin structure, so that the heat resistance of the resin is further improved; the heat resistance of the modified phenolic resin is obviously improved compared with that of the unmodified phenolic resin by the comprehensive action of the two phenolic resin modifiers.
Taking phenol and methyltrimethoxysilane as an example, the reactions occurring during the preparation of the alkylphenoxysilane intermediate of the present invention are as follows:
taking formaldehyde as an example, the reaction of the alkyl phenoxysilane intermediate and the aldehyde compound in the preparation process of the resin is as follows:
the structural formula of the aniline/organic silicon double-modified phenolic resin 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 aniline/organic silicon double-modified phenolic resin and the traditional thermoplastic phenolic resin are prepared under the same curing conditions to obtain a cured substance 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
41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 94.11g of phenol and 1.41g of phosphoric acid are mixed uniformly, temperature programming is carried out, and an alkyl phenoxy silane intermediate is generated by reaction at 160 ℃; and then cooling, adding 25.39g of aniline and 26.13g of paraformaldehyde, and further reacting with the alkyl phenoxy silane intermediate at the temperature of 85 ℃ to obtain the aniline/organosilicon double-modified phenolic resin adhesive.
Example 2
68.11g of methyltrimethoxysilane, 94.11g of phenol and 1.88g of methanesulfonic acid are uniformly mixed, the temperature is programmed to rise, and an alkyl phenoxy silane intermediate is generated by reaction at 150 ℃; and then cooling, adding 30.03g of aniline and 24.04g of paraformaldehyde, and further reacting with an alkyl phenoxy silane intermediate at the temperature of 85 ℃ to obtain the aniline/organosilicon double-modified phenolic resin adhesive.
Example 3
116.20g of methyltrimethoxysilane, 228.29g of bisphenol A and 3.44g of p-toluenesulfonic acid are uniformly mixed, the temperature is programmed to rise, and the mixture reacts at 175 ℃ to generate an alkyl phenoxy silane intermediate; and then cooling, adding 62.98g of aniline and 70.61g of formaldehyde aqueous solution, and further reacting with an alkyl phenoxy silane intermediate at the temperature of 90 ℃ to obtain the aniline/organosilicon double-modified phenolic resin adhesive.
Claims (7)
1. A preparation method of an aniline/organosilicon double-modified phenolic resin adhesive is characterized by comprising the following preparation steps of uniformly mixing a siloxane monomer, a phenolic compound and an acid catalyst, carrying out temperature programming, reacting at 110 ~ 200 ℃ to generate an alkyl phenoxy silane intermediate, cooling, adding a certain amount of aniline and aldehyde compounds, and further reacting with the alkyl phenoxy silane intermediate at 70 ~ 95 ℃ to obtain the aniline/organosilicon double-modified phenolic resin adhesive.
2. The preparation method of the aniline/organosilicon double-modified phenolic resin adhesive according to claim 1, wherein the mass ratio of the siloxane monomer, the phenolic compound, the aniline and the acidic catalyst is 0.1 ~ 1.0.0: 1:0.05 ~ 0.50.50: 0.05% ~ 4%, and the molar ratio of the aldehyde compound to the phenolic compound is 0.5 ~ 1.0.0: 1.
3. The method of 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, One or more of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
4. The method for preparing the aniline/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.
5. The method for preparing the aniline/organosilicon double-modified phenolic resin adhesive according to claim 1, wherein the acidic catalyst can be 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.
6. The method for preparing the aniline/organosilicon double-modified phenolic resin adhesive according to claim 1, wherein 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, twenty) aldehyde, paraformaldehyde, trioxymethylene, paraldehyde, and furfural.
7. A preparation method of aniline/organosilicon 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 6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910838793.7A CN110591620A (en) | 2019-09-05 | 2019-09-05 | Preparation method of aniline/organic silicon double-modified phenolic resin adhesive |
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| CN201910838793.7A CN110591620A (en) | 2019-09-05 | 2019-09-05 | Preparation method of aniline/organic silicon double-modified phenolic resin adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573773A (en) * | 2022-03-09 | 2022-06-03 | 常州大学 | Method for preparing modified high-ortho-o-cresol formaldehyde resin by condensation of amines and aldehydes |
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2019
- 2019-09-05 CN CN201910838793.7A patent/CN110591620A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573773A (en) * | 2022-03-09 | 2022-06-03 | 常州大学 | Method for preparing modified high-ortho-o-cresol formaldehyde resin by condensation of amines and aldehydes |
| CN114573773B (en) * | 2022-03-09 | 2023-08-22 | 常州大学 | Method for preparing modified high-ortho-cresol formaldehyde resin by adopting condensation of amines and aldehydes |
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Application publication date: 20191220 |