CN110563902A - Preparation method of nylon modified thermoplastic silicon phenolic resin - Google Patents
Preparation method of nylon modified thermoplastic silicon phenolic resin Download PDFInfo
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- CN110563902A CN110563902A CN201910856624.6A CN201910856624A CN110563902A CN 110563902 A CN110563902 A CN 110563902A CN 201910856624 A CN201910856624 A CN 201910856624A CN 110563902 A CN110563902 A CN 110563902A
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- nylon
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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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- Phenolic Resins Or Amino Resins (AREA)
Abstract
A preparation method of nylon modified thermoplastic silicon phenolic resin comprises the steps of mixing nylon, siloxane monomers and phenolic compounds, uniformly stirring, adding an acidic catalyst, adjusting pH to acidity, heating, reacting to obtain an intermediate containing silicon atoms or amide groups, and reacting with aldehyde compounds to obtain the nylon modified thermoplastic silicon phenolic resin. The method has the advantages of wide raw material sources and low cost, and reduces the relative content of phenolic hydroxyl and water in the process of preparing the nylon modified thermoplastic silicon phenolic resin, so that the thermal stability and the mechanical property of the modified phenolic resin are improved to a certain extent, and the high-performance phenolic resin with uniform molecular weight distribution, small particle size and small volatile matter is prepared.
Description
Technical Field
The invention belongs to a preparation method of modified thermoplastic silicon phenolic resin; in particular to a method for preparing modified thermoplastic silicon phenolic resin by nylon.
background
The phenolic resin is one of engineering resins with the largest dosage, is the resin which is firstly discovered and industrially synthesized in the world, has the characteristics of easily available production raw materials, low cost, simple and convenient synthesis process and equipment, excellent mechanical strength, difficult combustion, low toxicity, low smoke generation and the like, and is widely applied to a plurality of fields of buildings, chemical industry, machinery, refractory materials, bonding 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, and the industrial production is not yet satisfied, so that the toughness needs to be further improved.
The present invention has been made in view of the above circumstances.
disclosure of Invention
The invention aims to provide a preparation method of nylon modified thermoplastic silicon phenolic resin, which comprises the following steps: the method has the advantages of wide raw material sources and low cost, and reduces the relative content of phenolic hydroxyl and water in the process of preparing the nylon modified thermoplastic silicon phenolic resin, so that the thermal stability and the mechanical property of the modified phenolic resin are improved to a certain extent, and the high-performance phenolic resin with uniform molecular weight distribution, small particle size and small volatile matter is prepared.
The technical scheme adopted by the invention is as follows: firstly, uniformly stirring nylon, siloxane monomers and phenolic compounds according to the mass ratio of 0.05-0.5: 0.1-1.0: 1, adding an acid catalyst, adjusting the pH to 1-5, heating and raising the temperature, and reacting to obtain an intermediate containing silicon atoms or amide groups; then reacting the compound with an aldehyde compound, wherein the molar ratio of the aldehyde compound to the phenolic compound is 0.5-1.0: 1; and drying the product in a vacuum drier to obtain the nylon modified thermoplastic silicon phenolic resin.
The nylon is one or more of nylon-6, nylon-66, nylon-1010, nylon-610, nylon-612, nylon-11, nylon-12, nylon-46, nylon-6T and nylon-9T.
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.
By adopting the technical scheme, the invention has the following advantages:
(1) Raw materials such as nylon, siloxane monomers, phenolic compounds and the like are easily available in the market and are low in price;
(2) The modified thermoplastic silicon phenolic resin prepared by adjusting different proportions of the raw materials and controlling the preparation process conditions in the provided proportion range can reach the following indexes: the water content is less than or equal to 1.5 percent, the free phenol is less than or equal to 2.0 percent, the fluidity is 30-60 mm, the curing temperature is 140-160 ℃, the curing speed (150 ℃) is 60-90 s, the volatile matter is less than or equal to 6 percent, the softening point is 90-105 ℃, and the particle size is at least 95 percent under 200 meshes;
(3) the prepared modified silicon phenolic resin has lower high-temperature weight loss than that of the common phenolic resin through differential thermal analysis;
(4) The modified thermoplastic silicon phenolic resin is applied to organic grinding tools to improve the bending and impact properties of products.
Taking nylon-6, methyltrimethoxysilane and phenol as examples, the reaction occurring during the preparation of the intermediate containing silicon atom or amide group in the present invention is as follows:
taking formaldehyde as an example, the reaction between the intermediate containing a silicon atom or an amide group and the aldehyde compound in the preparation process of the resin is as follows:
The structural formula of the nylon modified thermoplastic 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 nylon 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
Adding 22.83g of nylon-1010, 116.20g of methyltrimethoxysilane and 228.29g of bisphenol A into a reaction kettle, uniformly stirring, adding 3.44g of p-toluenesulfonic acid, adjusting the pH to about 2, heating and raising the temperature, and reacting to obtain an intermediate containing silicon atoms or amide groups; then cooling, adding 70.61g of formaldehyde water solution, and reacting to the end point; and drying the product in a vacuum drier to obtain the nylon modified thermoplastic silicon phenolic resin.
example 2
Adding 14.12g of nylon-6, 68.11g of methyltrimethoxysilane and 94.11g of phenol into a reaction kettle, stirring uniformly, adding 1.88g of boric acid, adjusting the pH to about 2, heating and raising the temperature, and reacting to obtain an intermediate containing silicon atoms or amide groups; then cooling, adding 24.04g of paraformaldehyde, and reacting to the end point; and drying the product in a vacuum drier to obtain the nylon modified thermoplastic silicon phenolic resin.
Example 3
adding 9.41g of nylon-610, 41.27g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 94.11g of phenol into a reaction kettle, uniformly stirring, adding 1.41g of phosphoric acid, adjusting the pH to about 3, heating and raising the temperature, and reacting to obtain an intermediate containing a silicon atom or an amide group; then cooling, adding 26.13g of paraformaldehyde, and reacting to the end point; and drying the product in a vacuum drier to obtain the nylon modified thermoplastic silicon phenolic resin.
Claims (7)
1. A preparation method of nylon modified thermoplastic silicon phenolic resin is characterized by comprising the following steps of uniformly stirring nylon, siloxane monomers and phenolic compounds according to a mass ratio of 0.05 ~ 0.5:0.1 ~ 1.0:1, adding an acid catalyst, adjusting the pH value to 1 ~ 5, heating and raising the temperature to react to obtain an intermediate containing a silicon atom or an amide group, reacting the intermediate with an aldehyde compound according to a molar ratio of 0.5 ~ 1.0:1, and drying the product in a vacuum dryer to obtain the nylon modified thermoplastic silicon phenolic resin.
2. The method for preparing nylon modified thermoplastic silicone phenolic resin according to claim 1, wherein: the nylon is one or more of nylon-6, nylon-66, nylon-1010, nylon-610, nylon-612, nylon-11, nylon-12, nylon-46, nylon-6T and nylon-9T.
3. The method for preparing nylon modified thermoplastic silicone phenolic resin according to 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-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.
4. The method for preparing nylon modified thermoplastic silicone phenolic resin 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 and octadecyl) phenol, xylenol, naphthol, catechol, cardanol, bisphenol A, bisphenol F and bisphenol S.
5. The method for preparing nylon modified thermoplastic silicone phenolic resin 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, dodecylbenzenesulfonic acid, glacial acetic acid, boric acid, formic acid and propionic acid.
6. The method for preparing nylon modified thermoplastic silicone phenolic resin 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 and twenty) aldehyde, paraformaldehyde, trioxymethylene, paraldehyde and furfural.
7. A nylon modified thermoplastic silicon phenolic resin, characterized in that the nylon modified thermoplastic silicon phenolic resin is prepared by the preparation method of any one of claims 1 to 6.
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| CN201910856624.6A CN110563902A (en) | 2019-09-11 | 2019-09-11 | Preparation method of nylon modified thermoplastic silicon phenolic resin |
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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 |
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
-
2019
- 2019-09-11 CN CN201910856624.6A patent/CN110563902A/en active Pending
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 |
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
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