CN110551264A - Preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin - Google Patents
Preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin Download PDFInfo
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- CN110551264A CN110551264A CN201910838818.3A CN201910838818A CN110551264A CN 110551264 A CN110551264 A CN 110551264A CN 201910838818 A CN201910838818 A CN 201910838818A CN 110551264 A CN110551264 A CN 110551264A
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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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Abstract
2The invention discloses a preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin, which belongs to the technical field of phenolic resin.A siloxane monomer and a phenolic compound react under the action of an acid catalyst to generate an alkyl phenoxy silane intermediate, and then the alkyl phenoxy silane intermediate reacts with an aldehyde compound and furfuryl alcohol to prepare the furfuryl alcohol/organic silicon double-modified phenolic resin.
Description
Technical Field
The invention relates to the technical field of phenolic resin preparation, and particularly relates to a preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin.
Background
Phenolic resin, also called bakelite, is a kind of resin prepared by polycondensation of phenolic compounds and aldehyde compounds under the condition of catalyst, neutralization and water washing, is the earliest artificially synthesized resin in the world, and is still an important kind of high molecular material. 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
The invention mainly solves the technical problem and provides a preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin aiming at the defect of poor high-temperature resistance of a phenolic resin adhesive.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
A preparation method of furfuryl alcohol/organic silicon double-modified phenolic resin is characterized by comprising the following specific preparation steps:
adding a siloxane monomer, a phenolic compound and an acid catalyst into a reaction kettle, uniformly stirring, slowly heating, and reacting at 110-200 ℃ to generate an alkyl phenoxy silane intermediate; and slowly cooling, adding a certain amount of furfuryl alcohol and aldehyde compounds, and further reacting with the alkyl phenoxy silane intermediate at the temperature of 70-95 ℃ to prepare the furfuryl alcohol/organic silicon double-modified phenolic resin.
A method for preparing furfuryl alcohol/organosilicon double-modified phenolic resin comprises the following raw materials: the mass ratio of the furfuryl alcohol to the siloxane monomer to the phenolic compound to the acid catalyst is 0.05-0.50: 0.1-1.0: 1: 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.
The invention has the beneficial effects that: from the perspective of molecular structure, the invention introduces high bond energy Si-O bond (460kJ/mol) into the phenolic resin structure by ester exchange, blocks phenolic hydroxyl-OH, and improves the heat resistance of the resin; the addition of furfuryl alcohol plays a role in protecting-CH 2, the heat resistance of the resin is further improved, and the furfuryl alcohol and the organic silicon act synergistically, so that the aim of resisting high temperature is fulfilled.
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 furfuryl alcohol/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 furfuryl alcohol/organic silicon double-modified phenolic resin and the traditional thermoplastic phenolic resin are prepared into a cured substance 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
41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 94.11g of phenol and 1.41g of phosphoric acid are added into a reaction kettle, evenly stirred, slowly heated and reacted at 160 ℃ to generate an alkyl phenoxy silane intermediate; then slowly cooling, adding 20.33g of furfuryl alcohol and 26.13g of paraformaldehyde, and further reacting with the alkyl phenoxy silane intermediate at the temperature of 85 ℃ to prepare the furfuryl alcohol/organic silicon double-modified phenolic resin.
example 2
68.11g of methyltrimethoxysilane, 94.11g of phenol and 1.88g of methanesulfonic acid are added into a reaction kettle, stirred uniformly, slowly heated and reacted at 150 ℃ to generate an alkyl phenoxy silane intermediate; then slowly cooling, adding 27.25g of furfuryl alcohol and 24.04g of paraformaldehyde, and further reacting with the alkyl phenoxy silane intermediate at the temperature of 85 ℃ to prepare the furfuryl alcohol/organic silicon double-modified phenolic resin.
example 3
Adding 116.20g of methyltrimethoxysilane, 228.29g of bisphenol A and 3.44g of p-toluenesulfonic acid into a reaction kettle, stirring uniformly, slowly heating, and reacting at 175 ℃ to generate an alkyl phenoxy silane intermediate; then slowly cooling, adding 64.92g of furfuryl alcohol and 70.61g of formaldehyde aqueous solution, and further reacting with the alkyl phenoxy silane intermediate at the temperature of 90 ℃ to prepare the furfuryl alcohol/organic silicon double-modified phenolic resin.
Claims (7)
1. A method for preparing furfuryl alcohol/organosilicon double modified phenolic resin is characterized by comprising the specific steps of adding siloxane monomers, phenolic compounds and an acid catalyst into a reaction kettle, uniformly stirring, slowly heating, reacting at 110 ~ 200 ℃ to generate alkyl phenoxy silane intermediates, slowly cooling, adding a certain amount of furfuryl alcohol and aldehyde compounds, and further reacting with the alkyl phenoxy silane intermediates at 70 ~ 95 ℃ to obtain the furfuryl alcohol/organosilicon double modified phenolic resin.
2. The method for preparing furfuryl alcohol/silicone double-modified phenolic resin as claimed in claim 1, wherein the mass ratio of the furfuryl alcohol, the siloxane monomer, the phenolic compound and the acidic catalyst is 0.05 ~ 0.50:0.1 ~ 1.0.0: 1: 0.05% ~ 4%, and the usage amount of the aldehyde compound and the phenolic compound is 0.5 ~ 1.0.0: 1.
3. 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.
4. The method for preparing furfuryl alcohol/silicone double modified phenolic resin as claimed in 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 furfuryl alcohol/organosilicon double modified phenolic resin as claimed in 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, dodecylbenzenesulfonic acid, glacial acetic acid, boric acid, formic acid and propionic acid.
6. The method for preparing furfuryl alcohol/organosilicon double-modified phenolic resin 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, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane and icosane), paraformaldehyde, trioxymethylene, paraldehyde and furfural.
7. a preparation method of furfuryl alcohol/organosilicon double modified phenolic resin, which 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 publication date: 20191210 |