CN113372522B - Modified phenolic resin and preparation method thereof - Google Patents
Modified phenolic resin and preparation method thereof Download PDFInfo
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- CN113372522B CN113372522B CN202110870677.0A CN202110870677A CN113372522B CN 113372522 B CN113372522 B CN 113372522B CN 202110870677 A CN202110870677 A CN 202110870677A CN 113372522 B CN113372522 B CN 113372522B
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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
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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Abstract
The application relates to the technical field of phenolic resin, and particularly discloses modified phenolic resin and a preparation method thereof. The phenolic resin is prepared from the following raw materials in parts by weight: 50-60 parts of phenol; 35-45 parts of formaldehyde solution; 0.8-1.2 parts of oxalic acid; 2.7-4.8 parts of cashew nut shell oil mixed polymer; the cashew nut shell oil mixed polymer is a composition comprising modified cashew nut shell oil and cashew nut shell oil; the preparation method comprises the following steps: s1, adding the total amount of phenol and the total amount of cashew nut shell oil mixed polymer into a reaction vessel, uniformly mixing, adding the total amount of oxalic acid, heating to 90-95 ℃, and keeping the temperature for 1 h; s2, dropwise adding the formaldehyde solution into a reaction container, controlling the dropwise adding temperature to be 90-95 ℃, after the dropwise adding is finished, heating to 100 +/-0.5 ℃, and then preserving heat for 1h, wherein the content of free aldehyde is detected to be less than 0.1%; s3, heating the reaction container to 160 +/-1 ℃, distilling at normal pressure for 2-3h, filtering and discharging to obtain the modified phenolic resin. The phenolic resin with better strength and toughness is obtained.
Description
Technical Field
The application relates to the technical field of phenolic resin, in particular to modified phenolic resin and a preparation method thereof.
Background
The phenolic resin is a common industrial material obtained by condensation polymerization of phenolic compounds and aldehyde compounds under the action of a catalyst, and has comprehensive properties such as good heat resistance and flame retardance and the like due to the fact that the phenolic resin has a phenol unit and a regular molecular chain structure, so that the phenolic resin becomes one of important industrial resin varieties in recent century.
The phenolic resin is divided into thermosetting phenolic resin and thermoplastic phenolic resin according to a curing mode, wherein the thermosetting phenolic resin is obtained by firstly generating hydroxyalkyl phenol from excessive aldehyde compounds and phenolic compounds under an alkaline condition and then continuously carrying out polycondensation under an acidic environment; the thermoplastic phenolic resin is obtained by polycondensation of excessive phenolic compounds and aldehyde compounds under acidic conditions.
The thermoplastic phenolic resin needs to be cured when in use, has high hardness, high temperature resistance and chemical corrosion resistance after being cured, but has insufficient toughness, and greatly restricts the use and development of the phenolic resin in the industries of buildings, decorations, automobiles and the like.
Disclosure of Invention
In order to improve the toughness of the cured phenolic resin, the application provides a modified phenolic resin and a preparation method thereof.
In a first aspect, the present application provides a modified phenolic resin, which adopts the following technical scheme:
the modified phenolic resin is prepared from the following raw materials in parts by weight:
50-60 parts of phenol;
35-45 parts of formaldehyde solution;
0.8-1.2 parts of oxalic acid;
2.7-4.8 parts of cashew nut shell oil mixed polymer;
the cashew nut shell oil mixed polymer is a composition comprising modified cashew nut shell oil and cashew nut shell oil.
By adopting the technical scheme, phenol and formaldehyde react under the catalytic action of oxalic acid to generate thermoplastic phenolic resin, and the cashew nut shell oil mixed polymer is dispersed in the phenolic resin to modify the phenolic resin; because the cashew nut shell oil mixed polymer comprises cashew nut shell oil and modified cashew nut shell oil, when the cashew nut shell oil mixed polymer is heated, cashew phenol in the cashew nut shell oil can replace part of phenol to perform polycondensation reaction with formaldehyde, so that the toughness of the phenolic resin is improved, and after the modified cashew nut shell oil is modified and performs polycondensation reaction with formaldehyde, the strength of the phenolic resin can be improved.
Preferably, the formaldehyde solution has a formaldehyde content of 37%.
Preferably, the mixing ratio of the modified cashew nut shell oil to the cashew nut shell oil in parts by weight is (1.2-2.3): (1.5-2.5).
Preferably, after heating the cashew nut shell oil to 55 ℃, dropwise adding a sodium carbonate solution, carrying out reflux reaction for 30min, naturally cooling to room temperature, dropwise adding isopropyl-2-bromoethyl ether, controlling the reaction temperature to be 25-30 ℃, and carrying out reflux reaction for 30min after dropwise adding. Cooling to room temperature to obtain the modified cashew nut shell oil.
By adopting the technical scheme, the cashew shell oil is heated and then is dropwise added with a sodium carbonate solution, the system is adjusted to be alkalescent, the cashew shell oil is activated, after the cashew shell oil is cooled to room temperature, isopropyl-2-bromoethyl ether is dropwise added, and the isopropyl-2-bromoethyl ether and the cashew phenol are subjected to an addition reaction, so that the modification of the cashew shell oil is completed.
Preferably, heating the cashew nut shell oil to 35 ℃, dropwise adding the modified cashew nut shell oil, controlling the dropwise adding time to be 10min, after the dropwise adding is finished, heating to 40 ℃, and preserving the heat for 30min to obtain the cashew nut shell oil polymer.
In a second aspect, the present application provides a method for preparing a modified phenolic resin, which adopts the following technical scheme:
a method of preparing a modified phenolic resin, the method comprising the steps of:
s1, adding the total amount of phenol and the total amount of cashew nut shell oil mixed polymer into a reaction vessel, uniformly mixing, adding the total amount of oxalic acid, heating to 90-95 ℃, and keeping the temperature for 1 h;
s2, dropwise adding the formaldehyde solution into a reaction container, controlling the dropwise adding temperature to be 90-95 ℃, after the dropwise adding is finished, heating to 100 +/-0.5 ℃, and then preserving heat for 1h, wherein the content of free aldehyde is detected to be less than 0.1%;
s3, heating the reaction container to 160 +/-1 ℃, distilling at normal pressure for 2-3h, filtering and discharging to obtain the modified phenolic resin.
By adopting the technical scheme, in S1, after the phenol and the cashew nut shell oil mixed polymer are mixed, oxalic acid is added, and then the temperature is raised and maintained, so that the phenol and the cashew nut shell oil mixed polymer can be uniformly mixed; in S2, dropwise adding a formaldehyde solution into the reaction container, and carrying out polycondensation reaction on formaldehyde, phenol and cashew nut shell oil mixed polymer to form phenolic resin; in S3, the solvent was distilled off under normal pressure to obtain a modified phenol resin.
Preferably, in S1, the temperature rise time is controlled to 45 min.
Preferably, in S2, the temperature rise time is controlled for 30 min.
In summary, the present application has at least the following beneficial effects:
1. adopt cashew shell oil conjuncted polymer to modify phenolic resin in this application, because cashew shell oil conjuncted polymer includes cashew shell oil and modified cashew shell oil, when mixing and being heated, cashew in the cashew shell oil can replace partial phenol, takes place polycondensation reaction with formaldehyde, has improved phenolic resin's toughness, and modified cashew shell oil is modified the back, takes place polycondensation reaction back with formaldehyde, can improve phenolic resin's intensity.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Examples
Examples 1 to 5
The weight parts of the modified phenolic resin in examples 1-5 are shown in Table 1.
TABLE 1 modified phenolic resin in examples 1-5 parts by weight
Please refer to other documentations for details
The preparation method of the modified phenolic resin in the embodiments 1 to 5 comprises the following steps:
s1, adding the total amount of phenol and the total amount of cashew nut shell oil mixed polymer into a reflux reaction kettle, uniformly mixing, adding the total amount of oxalic acid, controlling the temperature rise time to be 45min, raising the temperature to 90-95 ℃, and then preserving the heat for 1 h;
s2, dropwise adding the formaldehyde solution into a reflux reaction kettle, controlling the dropwise adding temperature to be 90-95 ℃, controlling the temperature rise time to be 30min after the dropwise adding is finished, raising the temperature to 100 +/-0.5 ℃, preserving the heat for 1h, and detecting that the content of free aldehyde is less than 0.1%;
s3, heating the reflux reaction kettle to 160 +/-1 ℃, distilling at normal pressure for 2-3h until no solvent is separated out, filtering and discharging to obtain the modified phenolic resin.
Comparative example
Comparative examples 1 to 3
The weight parts of the modified phenolic resin in comparative examples 1-3 are shown in Table 2.
Please refer to other documentations for details
The preparation method of the modified phenolic resin in comparative example 3 comprises the following steps:
s1, adding the total amount of phenol into a reflux reaction kettle, uniformly mixing, adding the total amount of oxalic acid, controlling the temperature rise time to be 45min, raising the temperature to 90-95 ℃, and then preserving the heat for 1 h;
s2, dropwise adding the formaldehyde solution into a reflux reaction kettle, controlling the dropwise adding temperature to be 90-95 ℃, controlling the temperature rise time to be 30min after the dropwise adding is finished, raising the temperature to 100 +/-0.5 ℃, preserving the heat for 1h, and detecting that the content of free aldehyde is less than 0.1%;
s3, heating the reflux reaction kettle to 160 +/-1 ℃, distilling at normal pressure for 2-3h until no solvent is separated out, filtering and discharging to obtain the modified phenolic resin.
Performance test
Detection method/test method
Preparing test blocks with the length of 10cm, the width of 2cm and the thickness of 2cm from the modified phenolic resins prepared in examples 1-5 and comparative examples 1-3, applying 3N pressure by using the same fine needle, and measuring the depth of the fine needle penetrating into the test blocks; the middle part of the test block along the length thereof is used as a rod, 5N tensile force is applied to the two ends of the test block, the bending degree of the test block is measured, the included angle between the two ends of the test block and the initial position is calculated, and the detection result is shown in Table 3.
TABLE 3 Properties of modified phenolic resins in examples 1-5 and comparative examples 1-3
Please refer to other documentations for details
As can be seen by combining examples 1 to 5 and comparative examples 1 to 3, and by combining Table 3, the phenolic resin in the present application is superior in both hardness and toughness.
When the mixing ratio of the modified cashew nut shell oil and cashew nut shell oil in parts by weight is (1.2-2.3), as can be seen by combining examples 1-3 and examples 4-5, and combining Table 3: (1.5-2.5) out of this range, the hardness and toughness of the modified phenolic resin may be adversely affected.
Combining example 3 and comparative examples 1-3, and combining table 3, it can be seen that the hardness and toughness of the phenolic resin are greatly negatively affected when no modified cashew nut shell oil or cashew nut shell oil is added.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (5)
1. The modified phenolic resin is characterized by comprising the following raw materials in parts by weight:
50-60 parts of phenol;
35-45 parts of formaldehyde solution;
0.8-1.2 parts of oxalic acid;
2.7-4.8 parts of cashew nut shell oil mixed polymer;
the cashew nut shell oil mixed polymer is a composition comprising modified cashew nut shell oil and cashew nut shell oil;
the weight part mixing ratio of the modified cashew nut shell oil to the cashew nut shell oil is (1.2-2.3): (1.5-2.5);
the modified cashew nut shell oil is prepared by the following steps: heating cashew shell oil to 55 ℃, dropwise adding a sodium carbonate solution, performing reflux reaction for 30min, naturally cooling to room temperature, dropwise adding isopropyl-2-bromoethyl ether, controlling the reaction temperature to be 25-30 ℃, performing reflux reaction for 30min after the dropwise adding is finished, and cooling to room temperature to obtain modified cashew shell oil;
the preparation method of the modified phenolic resin comprises the following steps:
s1, adding the total amount of phenol and the total amount of cashew nut shell oil mixed polymer into a reaction vessel, uniformly mixing, adding the total amount of oxalic acid, heating to 90-95 ℃, and keeping the temperature for 1 h;
s2, dropwise adding the formaldehyde solution into a reaction container, controlling the dropwise adding temperature to be 90-95 ℃, after the dropwise adding is finished, heating to 100 +/-0.5 ℃, and then preserving heat for 1h, wherein the content of free aldehyde is detected to be less than 0.1%;
s3, heating the reaction container to 160 +/-1 ℃, distilling at normal pressure for 2-3h, filtering and discharging to obtain the modified phenolic resin.
2. The modified phenolic resin of claim 1, wherein: the formaldehyde solution contained 37% formaldehyde.
3. The modified phenolic resin of claim 1, wherein the cashew nut shell oil polymer is prepared by the steps of: heating cashew shell oil to 35 ℃, dropwise adding the modified cashew shell oil, controlling the dropwise adding time to be 10min, after the dropwise adding is finished, heating to 40 ℃, and preserving the temperature for 30min to obtain the cashew shell oil copolymer.
4. The modified phenolic resin as claimed in claim 1, wherein: in S1, the temperature rise time is controlled to 45 min.
5. The modified phenolic resin of claim 1, wherein: in S2, the temperature rise time is controlled for 30 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110870677.0A CN113372522B (en) | 2021-07-30 | 2021-07-30 | Modified phenolic resin and preparation method thereof |
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| CN202110870677.0A CN113372522B (en) | 2021-07-30 | 2021-07-30 | Modified phenolic resin and preparation method thereof |
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| CN113372522A CN113372522A (en) | 2021-09-10 |
| CN113372522B true CN113372522B (en) | 2022-05-24 |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246689A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Bakelite Co Ltd | Phenolic resin composition for friction material, and friction material |
| CN101143917A (en) * | 2006-09-14 | 2008-03-19 | 浙江南方塑胶制造有限公司 | Cashew shell modified alkyd resin and preparation method thereof |
| CN103073690B (en) * | 2013-01-21 | 2015-04-29 | 卡德莱化工(珠海)有限公司 | Cashew nut shell oil-modified phenolic resin as well as preparation method and application thereof |
| CN105622872B (en) * | 2014-12-15 | 2018-07-24 | 彤程化学（中国）有限公司 | A kind of cashew nut oil modified novolac resin and its preparation method and application |
| CN107082859A (en) * | 2017-05-12 | 2017-08-22 | 浙江杭摩合成材料股份有限公司 | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing |
| CN111100258A (en) * | 2019-12-04 | 2020-05-05 | 沈阳化工大学 | Method for synthesizing phenolic resin by pre-modifying phenol with 2-bromoethyl ether |
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