CN110591033A - Preparation method of water-resistant phenolic resin adhesive - Google Patents
Preparation method of water-resistant phenolic resin adhesive Download PDFInfo
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- CN110591033A CN110591033A CN201910820045.6A CN201910820045A CN110591033A CN 110591033 A CN110591033 A CN 110591033A CN 201910820045 A CN201910820045 A CN 201910820045A CN 110591033 A CN110591033 A CN 110591033A
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- phenolic resin
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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
- C08G14/12—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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
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.
Description
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.
Example 1
68.11g of methyltrimethoxysilane and 94.11g of phenol are mixed uniformly, 1.88g of methanesulfonic acid is added, the temperature is increased in a gradient manner, and the reaction is carried out at 150 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 32.94g of xylene and 24.04g of paraformaldehyde, reacting with the alkylphenoxysilane intermediate at 85 ℃ until the end point, distilling under reduced pressure, and drying in vacuum to obtain the water-resistant phenolic resin adhesive.
Example 2
41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 94.11g of phenol are mixed uniformly, 1.41g of phosphoric acid is added, the temperature is increased in a gradient manner, and the reaction is carried out at 160 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 23.53g of xylene and 26.13g of paraformaldehyde, reacting with the intermediate of the alkylphenoxysilane at 85 ℃ until the end point, distilling under reduced pressure, and drying in vacuum to obtain the water-resistant phenolic resin adhesive.
Example 3
116.20g of methyltrimethoxysilane and 228.29g of bisphenol A are uniformly mixed, 3.44g of p-toluenesulfonic acid is added, the temperature is increased in a gradient manner, and the reaction is carried out at 175 ℃ to obtain an alkyl phenoxy silane intermediate; and then cooling, adding 68.49g of xylene and 70.61g of formaldehyde water solution, reacting with an alkyl phenoxy silane intermediate at 90 ℃ until the end point, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain the water-resistant phenolic resin adhesive.
Claims (7)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910820045.6A CN110591033A (en) | 2019-08-31 | 2019-08-31 | Preparation method of water-resistant phenolic resin adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910820045.6A CN110591033A (en) | 2019-08-31 | 2019-08-31 | Preparation method of water-resistant phenolic resin adhesive |
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| CN110591033A true CN110591033A (en) | 2019-12-20 |
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| CN201910820045.6A Pending CN110591033A (en) | 2019-08-31 | 2019-08-31 | Preparation method of water-resistant phenolic resin adhesive |
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- 2019-08-31 CN CN201910820045.6A patent/CN110591033A/en active Pending
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Application publication date: 20191220 |
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| WD01 | Invention patent application deemed withdrawn after publication |