CN110591027A - Preparation method of polyurethane modified silicon phenolic resin - Google Patents
Preparation method of polyurethane modified silicon phenolic resin Download PDFInfo
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- CN110591027A CN110591027A CN201910838816.4A CN201910838816A CN110591027A CN 110591027 A CN110591027 A CN 110591027A CN 201910838816 A CN201910838816 A CN 201910838816A CN 110591027 A CN110591027 A CN 110591027A
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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
The invention discloses a preparation method of modified phenolic resin, in particular to a preparation method of polyurethane modified silicon phenolic resin, which is characterized by comprising the following steps of firstly adding polyurethane, siloxane monomer, phenolic compound and acid catalyst into a reaction kettle, uniformly stirring, slowly heating, reacting at 110 ~ 200 ℃ to generate an intermediate containing carbamate or silicon atom, slowly cooling, adding a certain amount of aldehyde compound, and further reacting with the intermediate containing carbamate or silicon atom at 70 ~ 95 ℃ to obtain the polyurethane modified silicon phenolic resin.
Description
Technical Field
The invention relates to toughening modification of phenolic resin, in particular to a preparation method of polyurethane modified silicon phenolic resin.
Background
The phenolic resin is widely applied to the related fields of buildings, machinery, electronics, flame-retardant materials, adhesion and the like due to the characteristics of good acid resistance, mechanical property, insulating property 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 toughness performance and is not satisfactory for industrial production, and the prepared novel silicon phenolic resin needs to be toughened and modified.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of polyurethane modified silicon phenolic resin.
The technical scheme of the invention is as follows:
firstly, adding polyurethane, 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 intermediate containing a carbamate group or a silicon atom; and slowly cooling, adding a certain amount of aldehyde compounds, and further reacting with an intermediate containing urethane groups or silicon atoms at the temperature of 70-95 ℃ to obtain the polyurethane modified silicon phenolic resin. .
A preparation method of polyurethane modified silicon phenolic resin comprises the following raw materials: the mass ratio of the polyurethane to the siloxane monomer to the phenolic compound to the acidic catalyst is 0.05-0.30: 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 technical effects that: according to the invention, flexible long molecular chains are introduced into the molecular structure of the phenolic resin in a chemical copolymerization manner, and the polyurethane modified silicon phenolic resin with different toughness degrees can be prepared by controlling different introduction ratios of the flexible long molecular chains, namely the addition amount of polyurethane, so as to meet the requirements of related fields.
Taking methyltrimethoxysilane, phenol, and diphenylmethane diisocyanate/1, 4-butanediol-type polyurethane as examples, the reaction occurring during the preparation of the urethane group-containing or silicon atom-containing intermediate of the present invention is as follows:
taking formaldehyde as an example, the reaction between the intermediate containing carbamate groups or silicon atoms and the aldehyde compound in the preparation process of the resin is as follows:
the structural formula of the polyurethane modified silicon 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 polyurethane modified silicon 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
Firstly, adding 57.24g of polyurethane, 116.20g of methyltrimethoxysilane, 228.29g of bisphenol A and 3.44g of p-toluenesulfonic acid into a reaction kettle, uniformly stirring, slowly heating, and reacting at 175 ℃ to generate an intermediate containing carbamate groups or silicon atoms; then slowly cooling, adding 70.61g of formaldehyde aqueous solution, and further reacting with the intermediate containing urethane groups or silicon atoms at the temperature of 90 ℃ to prepare the polyurethane modified silicon phenolic resin.
Example 2
Firstly, adding 26.94g of polyurethane, 68.11g of methyltrimethoxysilane, 94.11g of phenol and 1.88g of methanesulfonic acid into a reaction kettle, uniformly stirring, slowly heating, and reacting at 150 ℃ to generate an intermediate containing a carbamate group or a silicon atom; then slowly cooling, adding 24.04g of paraformaldehyde, and further reacting with an intermediate containing urethane groups or silicon atoms at the temperature of 85 ℃ to prepare the polyurethane modified silicon phenolic resin.
Example 3
Firstly, 18.55g of polyurethane, 41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 94.11g of phenol and 1.41g of phosphoric acid are added into a reaction kettle, uniformly stirred, slowly heated and reacted at 160 ℃ to generate an intermediate containing a carbamate group or a silicon atom; then slowly cooling, adding 26.13g of paraformaldehyde, and further reacting with an intermediate containing urethane groups or silicon atoms at the temperature of 85 ℃ to obtain the polyurethane modified silicon phenolic resin.
Claims (7)
1. A preparation method of polyurethane modified silicon phenolic resin is characterized by comprising the following steps of firstly adding polyurethane, siloxane monomers, phenolic compounds and an acid catalyst into a reaction kettle, uniformly stirring, slowly heating, reacting at 110 ~ 200 ℃ to generate an intermediate containing carbamate groups or silicon atoms, then slowly cooling, adding a certain amount of aldehyde compounds, and further reacting with the intermediate containing carbamate groups or silicon atoms at 70 ~ 95 ℃ to obtain the polyurethane modified silicon phenolic resin.
2. The method for preparing the polyurethane modified silicon phenolic resin according to claim 1, wherein the mass ratio of the four raw materials of the polyurethane, the siloxane monomer, the phenolic compound and the acidic catalyst is 0.05 ~ 0.30:0.1 ~ 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 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, methyl (or phenyl), ethyl (ethyl, propyl, hexyl, heptyl, octyl, nonyl, decyl), dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl) triethoxysilane, or mixtures thereof, One or more of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
4. The method of 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 of claim 1, wherein the acidic catalyst is one or more selected from 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 of claim 1, wherein the aldehyde compound is 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 polyurethane modified silicon phenolic resin 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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| CN201910838816.4A CN110591027A (en) | 2019-09-05 | 2019-09-05 | Preparation method of polyurethane modified silicon phenolic resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
| CN110484176B (en) * | 2019-09-30 | 2021-09-03 | 河南工业大学 | Preparation method of modified silicon phenolic resin adhesive |
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Application publication date: 20191220 |