CN109251288B - Preparation method of bio-based phenolic resin for laminated friction brake material - Google Patents
Preparation method of bio-based phenolic resin for laminated friction brake material Download PDFInfo
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- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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Abstract
The invention discloses a preparation method of bio-based phenolic resin for a laminated friction brake material, which comprises the following steps: (1) distilling cashew nut shell oil under reduced pressure, collecting distillate obtained by distillation to obtain cashew nut shell phenol; (2) mixing the cashew nutshell phenol obtained in the step (1) with paraformaldehyde or a formaldehyde water solution, heating a reaction system, and then carrying out heat preservation reaction; (3) adding an alkaline catalyst after the heat preservation reaction, heating and then carrying out the heat preservation reaction to generate the bio-based phenolic resin; (4) and dissolving the bio-based phenolic resin in methanol or ethanol, and adjusting the solid content to 20-75% to obtain a finished product of the bio-based phenolic resin. The preparation method provided by the invention solves the problems of insufficient raw material continuity and poor environmental protection in the prior art of phenolic resin prepared from phenol and formaldehyde, and is simple to operate, environment-friendly and low in production cost; the heat resistance of the prepared bio-based phenolic resin is obviously improved.
Description
Technical Field
The invention belongs to a preparation method of phenolic resin, and particularly relates to a preparation method of bio-based phenolic resin for a laminated friction brake material.
Background
The main raw materials of the traditional phenolic resin mainly use phenol and formaldehyde derived from petrochemical resources, and along with the gradual reduction of the petrochemical resources, the traditional phenolic resin has the defect of insufficient persistence of raw material sources. In addition, the use of petrochemical resources has also created an increasing environmental problem, and the free phenol in conventional phenolic resins can also pose additional hazards to the environment and users. Therefore, the search of biomass raw materials capable of replacing phenol to prepare the bio-based phenolic resin has great significance for solving the problems of insufficient sustainability of the traditional phenolic resin raw material sources and the damage of free phenol to the environment and users.
The Chinese patent document with the publication number of 103319670A relates to a bio-based phenolic resin and a preparation method thereof, wherein the bio-based phenolic resin is obtained by polymerizing diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester and furfural, the oxygen content of the bio-based phenolic resin is 19.7-28.8 wt%, and the molecular weight of the bio-based phenolic resin is 3000-4000. Chinese patent publication No. 102817336A discloses a method for preparing biomass-based phenolic resin, which comprises using biomass-based monomer 2, 5-diformylfuran and phenol as raw materials, carrying out addition and condensation reaction for 1-10h under the action of alkali catalysis at 30-200 ℃ under the protection of nitrogen, and removing water and other impurities in the reaction system by vacuum distillation to obtain a novel high-quality phenolic resin product with 2, 5-diformylfuran replacing formaldehyde.
The cashew nut shell phenol is extracted from natural cashew nut shell oil, is waste in the production process of cashew nuts, and has the characteristics of low price and easiness in obtaining. In addition, as a natural product, it is less harmful to the environment.
Disclosure of Invention
The invention aims to provide a preparation method of bio-based phenolic resin for a laminated friction brake material, which solves the problems of insufficient raw material continuity and poor environmental protection property in the prior art of phenolic resin prepared from phenol and formaldehyde, and has the advantages of simple operation, environmental friendliness and low production cost.
The purpose of the invention is realized by the following technical scheme:
a preparation method of bio-based phenolic resin for a laminated friction brake material comprises the following steps:
(1) mixing cashew nutshell phenol with paraformaldehyde or a formaldehyde aqueous solution, heating a reaction system, and carrying out heat preservation reaction;
(2) adding an alkaline catalyst after the heat preservation reaction, heating and then carrying out the heat preservation reaction to generate the bio-based phenolic resin;
(3) and dissolving the bio-based phenolic resin in methanol or ethanol, and adjusting the solid content to 20-75% to obtain a finished product of the bio-based phenolic resin.
The reaction equation of cashew nutshell phenol and formaldehyde is:
wherein R ═ C15H31-X(X ═ 0, 2, 4, or 6).
R is (CH)2)14CH3、(CH2)7CHCH(CH2)5CH3、(CH2)7CHCHCH2CHCH(CH2)2CH3Or (CH)2)7CHCHCH2CHCHCH2CHCH3。
The preparation method further comprises the step of distilling the cashew nut shell oil under reduced pressure, and collecting distillate obtained by distillation at the pressure of 0-14 kPa and the temperature of 90-200 ℃ to obtain the cashew nut shell phenol.
In the step (1), the molar ratio of the cashew nutshell phenol to the paraformaldehyde or the formaldehyde aqueous solution is 1: 1.1-3.0.
The preparation of thermosetting phenolic resin refers to reaction under the condition of alkaline catalyst and excessive formaldehyde, but formaldehyde can not be excessive because the active site for formaldehyde reaction is a hydrogen atom on 3 benzene rings positioned adjacent to and para to the phenolic hydroxyl.
In the step (1), the reaction temperature is 55-75 ℃, and the reaction time is 0.5-2 h.
Preferably, in the step (1), the molar ratio of the cashew nutshell phenol to the paraformaldehyde or the formaldehyde aqueous solution is 1:2.0-2.5, the reaction temperature is 65-70 ℃, and the reaction time is 1-1.5 h. The reaction under the above reaction conditions is more sufficient.
In the step (2), the dosage of the alkaline catalyst accounts for 0.1-1.5% of the total mass of the reactants, and the reactants are the sum of the mass of the cashew nutshell phenol and the mass of the paraformaldehyde or the aqueous solution of formaldehyde.
The alkaline catalyst is selected from NaOH aqueous solution with the concentration of 30-50 percent and Ba (OH) with the concentration of 30-50 percent2An aqueous solution or an aqueous solution of ammonium hydroxide with a concentration of 10 to 25%.
In the step (2), the reaction temperature is 80-95 ℃ and the reaction time is 1.5-5 h.
Preferably, in the step (2), the reaction temperature is 85-90 ℃, and the reaction time is 3-4 h.
The preparation method also comprises the step of purifying the bio-based phenolic resin generated in the step (2), wherein the purification method comprises the following steps:
(2-1) decompressing the bio-based phenolic resin obtained in the step (2) in a rotary evaporator to remove the solvent to obtain a bio-based phenolic resin crude product;
(2-2) dissolving the crude product of the bio-based phenolic resin obtained in the step (2-1) in dichloromethane or trichloromethane, repeatedly washing with water with the same volume, taking an organic phase, and drying with anhydrous magnesium sulfate;
(2-3) filtering the system obtained in the step (2-2), and removing the solvent from the obtained filtrate in a rotary evaporator under reduced pressure to obtain the bio-based phenolic resin;
in the step (2-1), the solvent is removed under reduced pressure under the conditions that the gauge pressure is less than or equal to-0.085 MPa and the temperature is 50-65 ℃.
In the step (2-2), the mass of the dichloromethane or the trichloromethane is 5-10 times of that of the crude product of the bio-based phenolic resin, the washing is repeated for 3-5 times, and the mass of the anhydrous magnesium sulfate is 0.5-3 times of that of the dichloromethane or the trichloromethane.
In the step (2-2), drying is carried out for 12-24 h by using anhydrous magnesium sulfate.
In the step (2-3), the solvent is removed under reduced pressure under the conditions that the gauge pressure is less than or equal to-0.085 MPa and the temperature is 35-60 ℃.
The bio-based phenolic resin prepared by the preparation method provided by the invention is applied to laminated friction braking materials.
The chemical structure of the cashew nutshell phenol contains a benzene ring structure and a phenolic hydroxyl group, and the meta position of the phenolic hydroxyl group contains a carbon 15 straight chain of an unsaturated double bond. The chemical structure of the phenolic resin contains phenolic hydroxyl, so that the cashew nutshell phenol can replace phenol to prepare the bio-based phenolic resin. The cashew nut shell phenol comes from waste in the production process of cashew nuts, so that the defect that the raw material sustainability of the existing phenol is insufficient due to the fact that the phenol comes from petrochemical resources is overcome; the preparation method provided by the invention is simple to operate, environment-friendly and low in production cost; the heat resistance of the prepared bio-based phenolic resin is obviously improved.
Drawings
FIG. 1 is a FT-IR plot of a bio-based phenolic resin prepared in example 1;
FIG. 2 is a DSC of the curing process of the bio-based phenolic resin prepared in example 1;
FIG. 3 is a DTG chart of cured bio-based phenolic resin obtained in example 1 under an inert atmosphere;
FIG. 4 is a DSC of the curing process of the phenolic resin obtained in comparative example 1;
FIG. 5 is a DTG chart of a cured phenolic resin obtained in comparative example 1 under an inert atmosphere;
FIG. 6 is a gas mass spectrum of cashew nutshell phenol in example 1.
Detailed Description
The present invention will be described in detail with reference to the following examples, but is not limited thereto.
Example 1
Putting 1000g cashew nut shell oil into a vacuum distillation device with zeolite, collecting the fraction with temperature of 110 deg.C under pressure of 500Pa to obtain light yellow transparent cashew nut shell phenol, and gas chromatography-mass spectrometry spectrum is shown in FIG. 6.
30.4g (1.0mol) of cashew nutshell phenol is put into a three-neck flask with an electric stirring, a condensing reflux pipe and a thermometer, 60.0g (2.0mol) of paraformaldehyde is added into the three-neck flask, the temperature of the system is slowly raised to 65 ℃, the temperature is kept for reaction for 1h, then 4.5g of 20 percent ammonium hydroxide aqueous solution is added, the temperature is raised to 85 ℃, and the temperature is kept for reaction for 3 h.
And after the reaction is finished, transferring the system to a rotary evaporator, and decompressing and removing the solvent under the conditions of gauge pressure of-0.085 MPa and temperature of 60 ℃ to obtain a crude product of the bio-based phenolic resin. 10.0g of the crude product are taken and subsequently dissolved in 50.0g of dichloromethane and washed with 3X 50.0ml of deionized water, the organic phase is taken and dried over 25.0g of anhydrous magnesium sulfate for 12 h. Filtering, decompressing the filtrate under the conditions of gauge pressure of-0.085 MPa and temperature of 50 ℃ to remove the solvent, and dissolving the rotary evaporation product in 10.0g of absolute ethyl alcohol to obtain the bio-based phenolic resin with the solid content of 50 percent.
The FT-IR diagram of the prepared bio-based phenolic resin is shown in FIG. 1, wherein the FT-IR diagram is at 2830-2950cm-1A very clear CH stretching vibration peak appears, which is because a long alkyl chain with 15 carbon atoms is arranged between phenolic hydroxyl groups in the cashew nutshell phenol, and the fact shows thatCorresponding bio-based phenolic resin is synthesized; the DSC chart of the curing process is shown in FIG. 2, and the peak of the curing exotherm occurs at 250 ℃; the DTG graph of the cured product of the bio-based phenolic resin in the inert atmosphere is shown in FIG. 3, the initial temperature of the thermal weight loss is higher than 400 ℃, the peak temperature is higher than 450 ℃, and the thermal weight loss hardly occurs at 380 ℃, and it is noted that the weight loss of the resin at the temperature of about 100 ℃ is caused by the volatilization of the resin solvent, so the bio-based phenolic resin shows good heat resistance.
Example 2
Putting 1500g of cashew nut shell oil into a vacuum distillation device with zeolite, and collecting the fraction with the temperature of 105 ℃ under the pressure condition of 300Pa to obtain light yellow transparent cashew nut shell phenol.
60.8g (2.0mol) of cashew nutshell phenol is put into a three-neck flask with an electric stirring, a condensing reflux pipe and a thermometer, 120.0g (4.0mol) of paraformaldehyde is added into the three-neck flask, the temperature of the system is slowly raised to 70 ℃, the temperature is kept for reaction for 1.5h, then 9.0g of NaOH aqueous solution with the concentration of 30 percent is added, the temperature is raised to 85 ℃, and the temperature is kept for reaction for 4 h.
And after the reaction is finished, transferring the system to a rotary evaporator, and removing the solvent under reduced pressure at the gauge pressure of-0.085 MPa and the temperature of 55 ℃ to obtain a crude product of the bio-based phenolic resin. 20.0g of the crude product are taken and subsequently dissolved in 200.0g of dichloromethane and washed with 5X 200.0ml of deionized water, the organic phase is taken and dried over 100.0g of anhydrous magnesium sulfate for 12 h. Filtering, decompressing the filtrate under the conditions of gauge pressure of-0.085 MPa and temperature of 40 ℃ to remove the solvent, and dissolving the rotary evaporation product in 80.0g of anhydrous methanol to obtain the bio-based phenolic resin with the solid content of 20 percent.
The peak of the curing exotherm of the bio-based phenolic resin prepared in example 2 occurred at 250 ℃ in the DSC test, the onset temperature at which the thermal weight loss occurred in the DTG test was higher than 400 ℃, the peak temperature was higher than 450 ℃, and almost no thermal weight loss occurred at 380 ℃.
Example 3
Putting 2000g of cashew nut shell oil into a vacuum distillation device with zeolite, and collecting the fraction with the temperature of 115 ℃ under the pressure condition of 1000Pa to obtain light yellow transparent cashew nut shell phenol.
45.6g (1.5mol) of cashew nutshell phenol was charged in a three-necked flask equipped with an electric stirrer, a reflux condenser and a thermometer, 364.8g (4.5mol) of 37% by weight aqueous formaldehyde was added thereto, the temperature of the system was slowly raised to 55 ℃ and the reaction was maintained for 0.5 hour, followed by 9.0g of 50% Ba (OH)2The temperature is raised to 80 ℃ and the reaction is kept for 1.5 h.
And after the reaction is finished, transferring the system to a rotary evaporator, and removing the solvent under reduced pressure at the gauge pressure of-0.085 MPa and the temperature of 65 ℃ to obtain a crude product of the bio-based phenolic resin. 30.0g of the crude product are taken and subsequently dissolved in 150.0g of dichloromethane and washed with 3X 150.0ml of deionized water, the organic phase is taken and dried over 60.0g of anhydrous magnesium sulfate for 24 h. Filtering, decompressing the filtrate under the conditions of gauge pressure of-0.085 MPa and temperature of 50 ℃ to remove the solvent, and dissolving the rotary evaporation product in 10.0g of absolute ethyl alcohol to obtain the bio-based phenolic resin with the solid content of 75 percent.
The peak of the curing exotherm of the bio-based phenolic resin prepared in example 3 occurred at 250 ℃ in the DSC test, the onset temperature at which the thermal weight loss occurred in the DTG test was higher than 400 ℃, the peak temperature was higher than 450 ℃, and almost no thermal weight loss occurred at 380 ℃.
Example 4
1000g of cashew nut shell oil is put into a vacuum distillation device with zeolite, and the fraction with the temperature of 90 ℃ is collected under the pressure condition of 5Pa, so that the light yellow transparent cashew nut shell phenol is obtained.
30.4g (1.0mol) of cashew nutshell phenol is put into a three-neck flask with an electric stirring, a condensing reflux pipe and a thermometer, 60.0g (2.0mol) of paraformaldehyde is added into the three-neck flask, the temperature of the system is slowly raised to 70 ℃, the temperature is kept for reaction for 1.5h, then 4.5g of 25 percent ammonium hydroxide aqueous solution is added, the temperature is raised to 90 ℃, and the temperature is kept for reaction for 3.5 h.
And after the reaction is finished, transferring the system to a rotary evaporator, and decompressing and removing the solvent under the conditions of gauge pressure of-0.085 MPa and temperature of 50 ℃ to obtain a crude product of the bio-based phenolic resin. 10.0g of the crude product are taken and subsequently dissolved in 50.0g of dichloromethane and washed with 3X 50.0ml of deionized water, the organic phase is taken and dried over 25.0g of anhydrous magnesium sulfate for 12 h. Filtering, decompressing the filtrate under the conditions of gauge pressure of-0.085 MPa and temperature of 35 ℃ to remove the solvent, and dissolving the rotary evaporation product in 10.0g of absolute ethyl alcohol to obtain the bio-based phenolic resin with the solid content of 50 percent.
The peak of the curing exotherm of the bio-based phenolic resin prepared in example 4 occurred at 250 ℃ in the DSC test, the onset temperature at which the thermal weight loss occurred in the DTG test was higher than 400 ℃, the peak temperature was higher than 450 ℃, and almost no thermal weight loss occurred at 380 ℃.
Example 5
1000g of cashew nut shell oil is put into a vacuum distillation device with zeolite, and the distillate with the temperature of 200 ℃ is collected under the pressure condition of 14000Pa to obtain the light yellow transparent cashew nut shell phenol.
30.4g (1.0mol) of cashew nutshell phenol is put into a three-neck flask with an electric stirring, a condensing reflux pipe and a thermometer, 33.0g (1.1mol) of paraformaldehyde is added into the three-neck flask, the temperature of the system is slowly raised to 55 ℃, the temperature is kept for reaction for 2 hours, then 7g of 10 percent ammonium hydroxide aqueous solution is added, the temperature is raised to 95 ℃, and the temperature is kept for reaction for 5 hours.
And after the reaction is finished, transferring the system to a rotary evaporator, and decompressing and removing the solvent under the conditions of gauge pressure of-0.085 MPa and temperature of 60 ℃ to obtain a crude product of the bio-based phenolic resin. 10.0g of the crude product are taken and subsequently dissolved in 50.0g of dichloromethane and washed with 3X 50.0ml of deionized water, the organic phase is taken and dried over 25.0g of anhydrous magnesium sulfate for 12 h. Filtering, decompressing the filtrate under the conditions of gauge pressure of-0.085 MPa and temperature of 60 ℃ to remove the solvent, and dissolving the rotary evaporation product in 10.0g of absolute ethyl alcohol to obtain the bio-based phenolic resin with the solid content of 50 percent.
The peak of the curing exotherm of the bio-based phenolic resin prepared in example 5 occurred at 250 ℃ in the DSC test, the onset temperature at which the thermal weight loss occurred in the DTG test was higher than 400 ℃, the peak temperature was higher than 450 ℃, and almost no thermal weight loss occurred at 380 ℃.
Example 6
The bio-based phenolic resin prepared as in example 1 had a molar ratio of cashew nutshell phenol to paraformaldehyde of 1: 2.5.
The peak of the curing exotherm of the bio-based phenolic resin prepared in example 6 occurred at 250 ℃ in the DSC test, the onset temperature at which the thermal weight loss occurred in the DTG test was higher than 400 ℃, the peak temperature was higher than 450 ℃, and almost no thermal weight loss occurred at 380 ℃.
Comparative example 1
94.0g (1.0mol) of phenol was charged into a three-necked flask equipped with an electric stirring, reflux condenser and thermometer, 60.0g (2.0mol) of paraformaldehyde was added thereto, the temperature of the system was slowly raised to 55 ℃ and the reaction was maintained for 1 hour, followed by addition of 4.5g of a 20% aqueous ammonium hydroxide solution and raising the temperature to 85 ℃ and the reaction was maintained for 3 hours. After the reaction is finished, transferring the system to a rotary evaporator, and decompressing and removing the solvent under the conditions of gauge pressure of-0.085 MPa and temperature of 60 ℃ to obtain a crude product of the phenolic resin. 10.0g of the crude product are taken and subsequently dissolved in 50.0g of dichloromethane and washed with 3X 50.0ml of deionized water, the organic phase is taken and dried over 25.0g of anhydrous magnesium sulfate for 12 h. Filtering, removing the solvent from the filtrate under reduced pressure at a gauge pressure of-0.085 MPa and a temperature of 50 ℃, and dissolving the rotary evaporation product in 10.0g of absolute ethyl alcohol to obtain the phenolic resin with a solid content of 50%.
The IR spectrum of the phenolic resin prepared in comparative example 1 is shown in FIG. 4, and the differential thermogravimetric curve thereof is shown in FIG. 5. As can be seen from FIG. 4, since the conventional phenol resin does not contain a long alkyl chain, it is found at 2850-2900cm-1Without a distinct characteristic absorption peak. As can be seen from FIG. 5, the ordinary phenol resin is decomposed drastically at 400 ℃ or lower regardless of the rate of temperature rise, and almost no weight loss occurs after the temperature exceeds 400 ℃, indicating that the ordinary phenol resin is decomposed completely almost at 400 ℃ and loses its value for further use.
Claims (7)
1. A preparation method of bio-based phenolic resin for a laminated friction brake material comprises the following steps:
(1) mixing cashew nutshell phenol with paraformaldehyde or a formaldehyde aqueous solution, heating a reaction system, and carrying out heat preservation reaction;
(2) adding an alkaline catalyst after the heat preservation reaction, heating and then carrying out the heat preservation reaction to generate the bio-based phenolic resin;
(3) dissolving the bio-based phenolic resin in methanol or ethanol, and adjusting the solid content to 20-75% to obtain a finished product of the bio-based phenolic resin
In the step (1), the reaction temperature is 55-75 ℃, and the reaction time is 0.5-2 h;
wherein, the method comprises the steps of distilling cashew nut shell oil under reduced pressure, collecting distillate obtained by distillation under the pressure of 500Pa, the temperature of 110 ℃, or the pressure of 300Pa, the temperature of 105 ℃, or the pressure of 1000Pa, the temperature of 115 ℃, or the pressure of 5Pa, the temperature of 90 ℃, or the pressure of 14000Pa and the temperature of 200 ℃, and obtaining cashew nut shell phenol.
2. A method of preparing a bio-based phenolic resin for a laminated friction brake material as claimed in claim 1, wherein in step (1), the molar ratio of the cashew nutshell phenol to paraformaldehyde or aqueous formaldehyde solution is 1: 1.1-3.0.
3. A method of preparing a bio-based phenolic resin for a laminated friction brake material as claimed in claim 1, wherein in step (1), the molar ratio of the cashew nutshell phenol to paraformaldehyde or aqueous formaldehyde solution is 1: 2.0-2.5.
4. The preparation method of the bio-based phenolic resin for the laminated friction brake material as claimed in claim 1, wherein in the step (2), the amount of the alkaline catalyst is 0.1% to 1.5% of the total mass of the reactants, and the reactants are the sum of the mass of the cashew nutshell phenol and the mass of the paraformaldehyde or the aqueous solution of formaldehyde.
5. The preparation method of the bio-based phenolic resin for the laminated friction brake material as claimed in claim 4, wherein the alkaline catalyst is selected from NaOH aqueous solution with concentration of 30-50%, Ba (OH) with concentration of 30-50%2An aqueous solution or an aqueous solution of ammonium hydroxide with a concentration of 10 to 25%.
6. The preparation method of the bio-based phenolic resin for the laminated friction brake material as claimed in claim 4, wherein in the step (2), the reaction temperature is 80-95 ℃ and the reaction time is 1.5-5 h.
7. The method for preparing a bio-based phenolic resin for a laminated friction brake material as claimed in claim 1, wherein the method further comprises the step of purifying the bio-based phenolic resin generated in step (2) by:
(2-1) decompressing the bio-based phenolic resin obtained in the step (2) in a rotary evaporator to remove the solvent to obtain a bio-based phenolic resin crude product;
(2-2) dissolving the crude product of the bio-based phenolic resin obtained in the step (2-1) in dichloromethane or trichloromethane, repeatedly washing with water with the same volume, taking an organic phase, and drying with anhydrous magnesium sulfate;
and (2-3) filtering the system obtained in the step (2-2), and removing the solvent from the obtained filtrate in a rotary evaporator under reduced pressure to obtain the bio-based phenolic resin.
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| US4385682A (en) * | 1979-10-26 | 1983-05-31 | Aisin Seiki Company, Limited | Motor vehicle clutch facing and friction property modifier therefor |
| CN102558467A (en) * | 2012-02-24 | 2012-07-11 | 山东圣泉化工股份有限公司 | Modified phenolic resin and preparation method thereof |
| CN103122054A (en) * | 2013-02-19 | 2013-05-29 | 中国西电集团公司 | Method for modifying phenolic resin by using cardanol |
| CN104762062A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing natural plant resource composite modified phenolic resin-based friction material |
| CN105461872A (en) * | 2015-12-07 | 2016-04-06 | 中华全国供销合作总社西安生漆涂料研究所 | Light-colored cardanol resin and preparation method thereof |
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