CN111087562A - Preparation method of blending modified phenolic resin - Google Patents
Preparation method of blending modified phenolic resin Download PDFInfo
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- CN111087562A CN111087562A CN201911254728.6A CN201911254728A CN111087562A CN 111087562 A CN111087562 A CN 111087562A CN 201911254728 A CN201911254728 A CN 201911254728A CN 111087562 A CN111087562 A CN 111087562A
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- phenolic resin
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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
Abstract
The invention discloses a preparation method of a blending modified phenolic resin, and relates to a preparation method of a phenolic resin. The product prepared by the invention is mainly used for carrying out a modification experiment of the phenolic resin by using the organic silicon with the epoxy group, a certain amount of octa-n-propyl glycidyl ether is added into the organic silicon as a cross-linking agent, and the organic silicon is introduced into a reaction system through the reaction between the epoxy group and the hydrocarbon group, so that the organic silicon is stably combined with the phenolic resin. And with the increase of the amount of the cross-linking agent, the heat resistance of the modified thermosetting phenolic resin can be obviously improved, and the surface performance of the modified thermosetting phenolic resin is enhanced.
Description
Technical Field
The invention relates to a preparation method of phenolic resin, in particular to a preparation method of blending modified phenolic resin.
Background
The phenolic resin is prepared by condensation polymerization of phenol formaldehyde or derivatives thereof, has excellent performances of high bonding strength, high carbon residue rate, low smoke, low toxicity, various processing forms and the like, is an indispensable raw material in the modern industry, and has wide application in the fields of electronics, buildings, printing, aerospace and aviation. However, the traditional phenolic resin still has the defects of insufficient heat resistance, poor toughness, easy water absorption and moisture absorption and the like.
Chinese patent CN 102675572A discloses an application of an organic silicon modifier in modifying thermosetting phenolic resin, the organic silicon modifier is easy to prepare, the phenolic resin system modified by the organic silicon modifier has good uniformity and stable product quality, phenol, formaldehyde solution and the organic silicon modifier are used as raw materials, and a class of thermosetting phenolic resin can be prepared by alkali catalytic condensation. However, the compatibility of the two components of the phenolic resin obtained by the method is poor. Therefore, how to introduce the silicone in a large amount and maintain strong two-phase interaction is a key problem of the silicone modified phenolic resin. The present invention has been made in view of the above circumstances.
Disclosure of Invention
The invention aims to provide a preparation method of a blending modified phenolic resin, which introduces a phenolic resin blended and modified by epoxy-terminated organosilicon and octa-n-propyl glycidyl ether. And with the increase of the amount of the cross-linking agent, the heat resistance of the modified thermosetting phenolic resin can be obviously improved, and the surface performance of the modified thermosetting phenolic resin is enhanced.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a blending modified phenolic resin is a preparation method of a phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, and comprises the following preparation processes:
preparing the following components in parts by weight: 100 parts of phenolic compound, 40-60 parts of aldehyde compound, 2-8 parts of cross-linking agent, 8-20 parts of modifier and 1-6 parts of catalyst; setting the temperature of a water bath kettle at 60 ℃, adding a melted phenolic compound solution into a three-necked bottle provided with a stirring paddle according to a ratio, adding a certain amount of catalyst and cross-linking agent, stirring for 5min to be uniform, then reacting for half an hour to activate the phenolic compound, simultaneously adding aldehyde compounds in batches, controlling the temperature to be added within half an hour at 60 ℃, keeping the temperature for half an hour after all the aldehyde compounds are added, fully reacting the aldehyde compounds, adding a modifier, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at a heating speed of 3 ℃/min, reacting for half an hour at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
In the preparation method of the blended modified phenolic resin, the phenolic compound is one or more of phenol, cresol, dimethylphenol, nonylphenol, bisphenol A, resorcinol, propyl phenol and ethyl phenol, and is preferably phenol.
In the preparation method of the blended modified phenolic resin, the aldehyde compound is one of formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene, and paraformaldehyde is preferred.
In the preparation method of the blending modified phenolic resin, the catalyst is one of sodium hydroxide, potassium hydroxide or ammonia water, and preferably sodium hydroxide.
According to the preparation method of the blending modified phenolic resin, the cross-linking agent is octa-n-propyl glycidyl ether.
The preparation method of the blended modified phenolic resin is characterized in that the modifier is epoxy-terminated organosilicon with the average relative molecular mass of 3666.9.
The invention has the advantages and effects that:
the invention has the main purposes that: the heat resistance of the modified phenolic resin can be obviously improved, and the surface performance of the modified phenolic resin is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes organosilicon with epoxy groups to carry out a modification experiment of phenolic resin, a certain amount of octa-n-propyl glycidyl ether is added to the organosilicon as a cross-linking agent, and the organosilicon is introduced into a reaction system through the reaction between the epoxy groups and hydrocarbon groups, so that the organosilicon and the phenolic resin are stably combined. And with the increase of the amount of the cross-linking agent, the heat resistance of the modified phenolic resin can be remarkably improved and can reach 200-260 ℃, and the surface performance of the modified phenolic resin is enhanced.
2. The preparation method has the advantages of simple preparation process, short reaction period and easily obtained raw materials.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting the scope of protection. Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The raw materials used in the examples were as follows:
phenol and its preparation
Paraformaldehyde
Sodium hydroxide
Octa-n-propyl glycidyl ether
Epoxy-terminated silicones
Acetic acid
Example 1
The invention relates to phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, which comprises the following steps:
setting the temperature of a water bath kettle at 60 ℃, adding 65g of phenol solution into a three-necked bottle provided with a stirring paddle, adding 0.65g of sodium hydroxide and 0.89g of octan-propyl glycidyl ether, stirring for 5min to be uniform, then reacting for half an hour to activate phenol, simultaneously adding 35g of paraformaldehyde in batches, controlling the temperature to be finished within half an hour at 60 ℃, keeping the temperature for half an hour after all the materials are added to ensure that the paraformaldehyde is fully reacted, adding 5.2g of epoxy group-terminated organic silicon, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at the heating rate of 3 ℃/min, reacting for about one and half hours at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
Example 2
The invention relates to phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, which comprises the following steps:
setting the temperature of a water bath kettle at 60 ℃, adding 65g of phenol solution into a three-necked bottle provided with a stirring paddle, adding 0.65g of sodium hydroxide and 0.89g of octan-propyl glycidyl ether, stirring for 5min to be uniform, then reacting for half an hour to activate phenol, simultaneously adding 35g of paraformaldehyde in batches, controlling the temperature to be finished within half an hour at 60 ℃, keeping the temperature for half an hour to fully react the paraformaldehyde after all the materials are added, adding 6.5g of epoxy group-terminated organic silicon, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at the heating speed of 3 ℃/min, reacting for about one and half hours at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
Example 3
The invention relates to phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, which comprises the following steps:
setting the temperature of a water bath kettle at 60 ℃, adding 65g of phenol solution into a three-necked bottle provided with a stirring paddle, adding 0.65g of sodium hydroxide and 0.89g of octan-propyl glycidyl ether, stirring for 5min to be uniform, then reacting for half an hour to activate phenol, simultaneously adding 35g of paraformaldehyde in batches, controlling the temperature to be finished within half an hour at 60 ℃, keeping the temperature for half an hour to fully react the paraformaldehyde after all the materials are added, adding 9.75g of epoxy group-terminated organic silicon, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at the heating speed of 3 ℃/min, reacting for about one and half hours at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
Example 4
The invention relates to phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, which comprises the following steps:
setting the temperature of a water bath kettle at 60 ℃, adding 65g of phenol solution into a three-necked bottle provided with a stirring paddle, adding 0.65g of sodium hydroxide and 0.89g of octan-propyl glycidyl ether, stirring for 5min until the mixture is uniform, then reacting for half an hour to activate phenol, simultaneously adding 35g of paraformaldehyde in batches, controlling the temperature to be completely added within half an hour at 60 ℃, keeping the temperature for half an hour after all the materials are completely added to ensure that the paraformaldehyde fully reacts, adding 13g of epoxy group-terminated organic silicon, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at the heating speed of 3 ℃/min, reacting at constant temperature for about one and half hours, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
Comparative example
Setting the temperature of a water bath kettle at 60 ℃, adding 65g of phenol solution into a three-necked bottle provided with stirring paddles, adding 0.65g of sodium hydroxide and 0.89g of octan-propyl glycidyl ether, stirring for 5min to be uniform, then reacting for half an hour to activate phenol, simultaneously adding 35g of paraformaldehyde in batches, controlling the temperature to be completely added within half an hour at 60 ℃, keeping the temperature for half an hour after all the paraformaldehyde are completely added to fully react, slowly heating to 90 ℃ at the heating speed of 3 ℃/min, reacting for about one and a half hours at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 with acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
The modification experiment of the phenolic resin is carried out by utilizing organosilicon with epoxy groups, a certain amount of octa-n-propyl glycidyl ether is added to the organosilicon as a cross-linking agent, and the organosilicon is introduced into a reaction system through the reaction between the epoxy groups and hydrocarbon groups, so that the organosilicon and the phenolic resin are stably combined. And with the increase of the amount of the cross-linking agent, the heat resistance of the modified phenolic resin can be remarkably improved and can reach 200-260 ℃, and the surface performance of the modified phenolic resin is enhanced.
The present invention has been described in connection with the specific embodiments, and it is to be understood that the invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of a blending modified phenolic resin is a preparation method of a phenolic resin modified by blending epoxy-terminated organosilicon and octa-n-propyl glycidyl ether, and is characterized by comprising the following preparation processes:
preparing the following components in parts by weight: 100 parts of phenolic compound, 40-60 parts of aldehyde compound, 2-8 parts of cross-linking agent, 8-20 parts of modifier and 1-6 parts of catalyst; setting the temperature of a water bath kettle at 60 ℃, adding a melted phenolic compound solution into a three-necked bottle provided with a stirring paddle according to a ratio, adding a certain amount of catalyst and cross-linking agent, stirring for 5min to be uniform, then reacting for half an hour to activate the phenolic compound, simultaneously adding aldehyde compounds in batches, controlling the temperature to be added within half an hour at 60 ℃, keeping the temperature for half an hour after all the aldehyde compounds are added, fully reacting the aldehyde compounds, adding a modifier, stirring for 10min by magnetic force, introducing N2 for protection, slowly heating to 90 ℃ at a heating speed of 3 ℃/min, reacting for half an hour at constant temperature, cooling to 75 ℃, adjusting the pH to 7-8 by using acetic acid, dehydrating, and cooling the synthesized phenolic resin for 24h to obtain the modified target phenolic resin.
2. The preparation method of the blended modified phenolic resin as claimed in claim 1, wherein the phenolic compound is one or more of phenol, cresol, dimethylphenol, nonylphenol, bisphenol A, resorcinol, propylphenol and ethylphenol, and is preferably phenol.
3. The preparation method of the blending modified phenolic resin as claimed in claim 1, wherein the aldehyde compound is one of formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene, and is preferably paraformaldehyde.
4. The preparation method of the blended modified phenolic resin as claimed in claim 1, wherein the catalyst is one of sodium hydroxide, potassium hydroxide or ammonia water, preferably sodium hydroxide.
5. The preparation method of the blended modified phenolic resin as claimed in claim 1, wherein the cross-linking agent is octa-n-propyl glycidyl ether.
6. The method for preparing the blended modified phenolic resin as claimed in claim 1, wherein the modifier is epoxy-terminated silicone with average relative molecular mass of 3666.9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911254728.6A CN111087562A (en) | 2019-12-10 | 2019-12-10 | Preparation method of blending modified phenolic resin |
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| CN201911254728.6A CN111087562A (en) | 2019-12-10 | 2019-12-10 | Preparation method of blending modified phenolic resin |
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| CN111087562A true CN111087562A (en) | 2020-05-01 |
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| CN201911254728.6A Withdrawn CN111087562A (en) | 2019-12-10 | 2019-12-10 | Preparation method of blending modified phenolic resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112848603A (en) * | 2021-01-07 | 2021-05-28 | 广东中晨电子科技有限公司 | Pressure-sensitive backing plate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015162022A1 (en) * | 2014-04-24 | 2015-10-29 | Nexans | Self-healing materials and cables |
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2019
- 2019-12-10 CN CN201911254728.6A patent/CN111087562A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015162022A1 (en) * | 2014-04-24 | 2015-10-29 | Nexans | Self-healing materials and cables |
Non-Patent Citations (2)
| Title |
|---|
| 刘成林等: "有机硅改性酚醛树脂的研究进展" * |
| 张蔓青: "有机硅改性酚醛树脂的研究" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112848603A (en) * | 2021-01-07 | 2021-05-28 | 广东中晨电子科技有限公司 | Pressure-sensitive backing plate and preparation method thereof |
| CN112848603B (en) * | 2021-01-07 | 2023-02-17 | 广东中晨电子科技有限公司 | Pressure-sensitive backing plate and preparation method thereof |
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