CN115109212B - Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin - Google Patents
Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin Download PDFInfo
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- CN115109212B CN115109212B CN202210830591.XA CN202210830591A CN115109212B CN 115109212 B CN115109212 B CN 115109212B CN 202210830591 A CN202210830591 A CN 202210830591A CN 115109212 B CN115109212 B CN 115109212B
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- 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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- 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
Abstract
The application provides an application of heteropolyacid and heteropolyacid salt as a catalyst in preparing o-cresol novolac resin by catalysis, belonging to the technical field of novolac resin preparation. The application provides an application of heteropoly acid and heteropoly acid salt as catalysts in preparing o-cresol novolac resin by catalysis, wherein the ortho-position content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the gardner color is less than or equal to 1. The prepared o-cresol novolac resin has low gardner chromaticity and controllable ortho-position content.
Description
Technical Field
The application belongs to the technical field of phenolic resin preparation, and particularly relates to application of heteropolyacid and heteropolyacid salt as catalysts in catalytic preparation of o-cresol phenolic resin.
Background
The o-cresol novolac epoxy resin is a multifunctional glycidyl ether epoxy resin, has a phenolic structure and an epoxy group in a molecular structure, is extremely easy to form a high-performance reticular crosslinked rigid structure after being cured, and has the advantages of excellent thermal stability, electrical insulation, high mechanical strength, good adhesive property, small shrinkage, good moisture resistance and good chemical corrosion resistance; another remarkable characteristic is that the epoxy value is basically unchanged when the softening point is changed, and the melt viscosity is quite low, so that the resin is endowed with excellent process stability and processing manufacturability. Therefore, o-cresol novolac epoxy is widely used as a packaging material in high and new electronic industries, and for packaging capacitors, resistors, triodes, diodes, potentiometers, etc. of semiconductor Integrated Circuits (ICs), large-scale integrated circuits (LIC), etc.
With the development of the human industrial technology to improve the production efficiency, fast curing type phenolic resins have been developed. The high ortho phenolic resin has the characteristics of higher curing speed and better storage stability than the common phenolic resin due to the generation of a large number of hydrogen bonds caused by a large number of ortho structures existing in the molecules of the high ortho phenolic resin, and meanwhile, the high ortho phenolic resin also has the characteristic of lower softening point, so that the curing can be realized at a lower temperature.
At present, the common preparation method of the high ortho-position phenolic resin mainly comprises the steps of enhancing ortho-position activity under the condition that divalent metal oxide or salts thereof are used as catalysts, improving ortho-position reaction rate, and catalyzing and synthesizing the high ortho-position phenolic resin with the assistance of an acid catalyst. However, the divalent metal weak acid salt catalyst has lower catalytic efficiency, unstable reaction process and easy gelation after high-temperature dehydration Shi Shuzhi.
Disclosure of Invention
The application provides an application of heteropoly acid and heteropoly acid salt as catalysts in preparing o-cresol novolac resin in a catalysis way, wherein the reaction process is stable, the resin is not easy to gel, and the prepared o-cresol novolac resin has low residual phenol and gardner chromaticity and controllable ortho-position content.
In order to achieve the aim, the application provides application of heteropolyacid and heteropolyacid salt as catalysts in catalysis preparation of o-cresol novolac resin, wherein the ortho-position content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the gardner color is less than or equal to 1.
Preferably, the o-cresol novolac resin is prepared by the following steps:
1) Mixing o-cresol and formaldehyde to obtain a mixed solution;
2) Mixing the mixed solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a milky solution;
3) Mixing the milky white solution with heteropoly acid, and reacting to obtain a milky white viscous solution;
4) Mixing the milky viscous solution with an organic solvent, and neutralizing and washing the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere.
Preferably, the molar ratio of the o-cresol to the formaldehyde is 1:0.5-1.5.
Preferably, the organic acid in the step 2) is added in batches, and the organic acid is one or more of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid; the addition amount of the organic acid is 0.1-1.0% of the molar amount of the o-cresol.
Preferably, the heteropolyacid salt in the step 2) is added in batches, wherein the heteropolyacid salt is 1-butyl-3-methylimidazole phosphotungstenate, brominated 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propylpyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphotungstenate, brominated 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propyl pyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphomolybdate, brominated 1-butyl-3-methylimidazole phosphomolybdate, 1- (3-sulfonic group) propyl-3-methylimidazole phosphomolybdate, 1-butyl-3-methylimidazole phosphomolybdenate, brominated 1-3-methylimidazole phosphomolybdate, 1- (3-sulfonic group) propyl-pyridine phosphomolybdenate, 1-butyl-3-methylimidazole phosphomolybdenate, or one or more of 1- (3-sulfonic group) propylmolybdic acid groups; the addition amount of the heteropolyacid salt is 5-20% of the molar amount of the o-cresol.
Preferably, the temperature of the stirring reaction in the step 2) is 80-100 ℃ and the time is 0.5-2 h.
Preferably, the heteropolyacid in the step 3) is added in batches, and the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1-1.0% of the molar amount of the o-cresol.
Preferably, the reaction temperature in the step 3) is 100-140 ℃ and the reaction time is 0.5-5 h.
Preferably, the organic solvent in the step 4) is methyl isobutyl ketone, toluene, xylene or cyclohexanone; the volume of the organic solvent is 1-5 times of that of the milky viscous solution obtained in the step 3).
Preferably, in the step 4), the neutralization and water washing are performed by using an alkali solution, and the pH of the solution after the neutralization and water washing is 6-7.
Compared with the prior art, the application has the advantages and positive effects that:
(1) According to the application, the organic acid and the heteropolyacid salt are selected as catalysts in the initial stage of the reaction, so that the catalytic capability is weak, the reaction is eased, and the resin is prevented from being crosslinked by violent heat release in the initial stage of the reaction; the heteropolyacid is selected as a catalyst in the middle reaction period, so that the catalyst has high hydrogen dissociation capability and high catalytic capability, the polycondensation reaction rate can be further improved effectively, the conversion rate and the yield of o-cresol are improved, the reaction period is shortened, and the production cost is reduced.
(2) The catalyst heteropolyacid salt and the organic acid are used in a compound way, and o-cresol formaldehyde resins with different ortho-positions are prepared through the polycondensation reaction of phenolic aldehyde under the action of hetero atoms with higher activity and obvious positioning effect.
(3) The o-cresol formaldehyde resin prepared by the application has controllable o-para content, low residual phenol content and low chromaticity.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application provides an application of heteropoly acid and heteropoly acid salt as catalysts in preparing o-cresol novolac resin by catalysis, wherein the ortho-position content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the gardner color is less than or equal to 1.
In the application, the o-cresol novolac resin is preferably prepared by the following steps:
1) Mixing o-cresol and formaldehyde to obtain a mixed solution;
2) Mixing the mixed solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a milky solution;
3) Mixing the milky white solution with heteropoly acid, and reacting to obtain a milky white viscous solution;
4) Mixing the milky viscous solution with an organic solvent, and neutralizing and washing the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere.
The application mixes o-cresol and formaldehyde to obtain mixed solution. In the present application, the molar ratio of the o-cresol to formaldehyde is preferably 1:0.5 to 1.5, more preferably 1:0.6 to 1.0, and most preferably 1:0.7 to 0.9. In the present application, the formaldehyde is preferably formaldehyde or paraformaldehyde.
After the mixed solution is obtained, the mixed solution is mixed with organic acid and heteropolyacid salt, and stirred for reaction to obtain milky solution. In the present application, the amount of the organic acid added is preferably 0.1 to 1.0%, more preferably 0.2 to 0.6%, and most preferably 0.3 to 0.5% of the molar amount of o-cresol. In the present application, the organic acid is preferably one or more of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid, more preferably one or more of oxalic acid, benzoic acid and oxalic acid, and most preferably oxalic acid. The organic acid is preferably added in portions.
In the present application, the addition amount of the heteropolyacid salt is preferably 5% to 20%, more preferably 6% to 15%, and most preferably 8% to 10% of the molar amount of o-cresol. In the present application, the heteropolyacid salt is preferably 1-butyl-3-methylimidazole phosphotungstic acid salt, brominated 1-butyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propylpyridinium phosphotungstic acid salt, 1-butyl-3-methylimidazole phosphomolybdic acid salt, brominated 1-butyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propyl pyridinium phosphomolybdic acid salt, 1-butyl-3-methylimidazole phosphomolybdic acid salt, brominated 1-butyl-3-methylimidazole phosphomolybdic acid salt, 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylsulfolyimidazololytungstic acid salt, 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylimidazole base-3-methyl) and 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylimidazole base-3-methyl phosphotungstic acid salt, or more preferably 1-3-methylimidazole phosphotungstic acid salt 1- (3-sulfonate) propyl-3-methylimidazole phosphotungstic heteropolyacid salt, 1- (3-sulfonate) propyl pyridine phosphotungstic heteropolyacid salt, most preferably 1-butyl-3-methylimidazole phosphotungstic heteropolyacid salt. The heteropolyacid salt is preferably added in portions.
In the present application, the temperature of the stirring reaction is preferably 80 to 100 ℃, and the time is preferably 0.5 to 2 hours, more preferably 95 ℃, and the time is 0.7 to 1.5 hours.
After the milky white solution is obtained, the milky white solution and the heteropoly acid are mixed and reacted to obtain the milky white viscous solution. In the present application, the heteropolyacid is preferably one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid, more preferably phosphotungstic acid or silicotungstic acid, most preferably phosphotungstic acid. In the present application, the addition amount of the heteropoly acid is preferably 0.1 to 1.0%, more preferably 0.2 to 0.6%, and most preferably 0.3 to 0.5% of the molar amount of o-cresol. The heteropolyacid is preferably added in portions. In the present application, the temperature of the reaction is preferably 100 to 140 ℃, more preferably 115 to 145 ℃; the time is preferably 0.5 to 5 hours, more preferably 0.8 to 1 hour.
After obtaining a milky viscous solution, the application mixes the milky viscous solution with an organic solvent, and performs neutralization and water washing on the obtained solution to obtain the o-cresol novolac resin. In the present application, the organic solvent is preferably methyl isobutyl ketone, toluene, xylene or cyclohexanone, more preferably methyl isobutyl ketone, xylene, and most preferably methyl isobutyl ketone. In the present application, the volume of the organic solvent is preferably 1 to 5 times, more preferably 3 times, that of the milky white viscous solution. In the present application, it is preferable to use an alkali solution for neutralization and water washing, and the pH of the solution after neutralization and water washing is 6 to 7.
In the application, heteropolyacid salt and organic acid are used as catalysts in a compound way, and under the action of hetero atoms with higher activity and obvious positioning effect, the ortho-o-cresol formaldehyde resin with different contents is prepared through the polycondensation reaction of phenolic aldehyde. Meanwhile, the organic acid and the heteropolyacid salt are compounded to be used as a catalyst, so that the catalytic capability is weak, the reaction is mild, and the resin is prevented from being crosslinked by violent heat release in the initial stage of the reaction. And then, heteropolyacid is selected as a catalyst in the middle reaction period, so that the catalyst has high hydrogen dissociation capability and high catalytic capability, the polycondensation reaction rate can be effectively further improved, and the conversion rate and the yield of o-cresol are improved. Shortens the reaction period and reduces the production cost. Meanwhile, the o-cresol formaldehyde resin prepared by the method has the advantages of controllable o-para content, controllable softening point and low chromaticity.
The application controls the ortho-para content of the ortho-cresol novolac resin by the type and the addition amount of heteropolyacid salt, and the reaction mechanism for synthesizing the ortho-controllable ortho-cresol novolac resin is as follows: the mixed catalysis system of heteropolyacid salt and organic acid is selected, the heteropolyacid salt provides weak acid reaction environment, the difference of electrophilic substitution degree of hydroxyl (OH) at ortho position and para position on o-cresol ring is highlighted, hetero atoms (such as P, si, fe, co and the like) and multi-atoms (such as Mo, W, V, nb, ta and the like) with ortho position guiding function are selected in the synthesis process, formaldehyde can be subjected to addition reaction with ortho position of o-cresol preferentially to form an unstable chelate, and the mixed catalysis system continuously performs polycondensation reaction with o-cresol by removing one hydroxyl group, hetero atoms and multi-atoms to form bisphenol-based methane with ortho position connection and high activity, and simultaneously, the types and the content of the hetero atoms are controlled, so that the mixed catalysis system continuously reacts with formaldehyde to form o-cresol phenolic resin with different ortho positions.
The technical solutions provided by the present application are described in detail below in conjunction with examples for further illustrating the present application, but they should not be construed as limiting the scope of the present application.
Example 1
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the molar mass of o-cresol of 0.2% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the molar mass of o-cresol of 6% in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.5% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 2
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.834, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding formic acid with the o-cresol molar mass of 0.5% and a brominated 1-butyl-3-methylimidazole tungsten silicate heteropolyacid salt catalyst with the o-cresol molar mass of 8% in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.4% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 0.5 hour at 135 ℃ to obtain a milky viscous solution;
s4, adding cyclohexanone with the resin volume being three times that of the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the cyclohexanone, washing the cyclohexanone with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Example 3
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.903, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding acetic acid with the o-cresol molar mass of 0.4% and a 1- (3-sulfonic) propyl phosphotungstic heteropolyacid salt catalyst with the o-cresol molar mass of 10% in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky solution;
s3, adding phosphomolybdic acid with 0.8% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 1 hour at 115 ℃ to obtain a milky viscous solution;
s4, adding methyl isobutyl ketone with the volume of three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the viscous solution, adding sodium hydroxide to neutralize the viscous solution, washing the viscous solution with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Example 4
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.707, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the molar mass of o-cresol of 0.5% and a brominated 1-butyl-3-methylimidazole silicon molybdenum heteropolyacid salt catalyst with the molar mass of o-cresol of 5% in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky solution;
s3, under the nitrogen atmosphere, adding silicomolybdic acid with the molar mass of 1.0% of o-cresol into the reaction liquid in the step 2) in batches, and carrying out reflux dehydration reaction at 140 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding xylene with the volume of three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the xylene, adding sodium hydroxide to neutralize the xylene, washing the xylene with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Example 5
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the molar mass of o-cresol of 0.2% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the molar mass of o-cresol of 10% in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.5% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 6
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the o-cresol molar mass of 0.2% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the o-cresol molar mass of 15% in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.5% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 1
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid catalyst with 0.6% of o-cresol molar mass in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.5% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 0.5 hour at 135 ℃ to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 2
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.903, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid catalyst with 0.4% of o-cresol molar mass in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky solution;
s3, adding oxalic acid with 0.1% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 3 hours at 135 ℃ to obtain a milky viscous solution;
s4, adding cyclohexanone with the resin volume being three times that of the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the cyclohexanone, washing the cyclohexanone with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Comparative example 3
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.903, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid catalyst with 0.2% of o-cresol molar mass in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky solution;
s3, adding oxalic acid with 0.1% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 3 hours at 135 ℃ to obtain a milky viscous solution;
s4, adding cyclohexanone with the resin volume being three times that of the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the cyclohexanone, washing the cyclohexanone with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Comparative example 4
S1, under the nitrogen atmosphere, o-cresol and formaldehyde are added into a reaction kettle according to a molar ratio of 1:0.903, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid catalyst with 0.8% of o-cresol molar mass in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky solution;
s3, adding oxalic acid with 0.1% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction for 3 hours at 135 ℃ to obtain a milky viscous solution;
s4, adding cyclohexanone with the resin volume being three times that of the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the cyclohexanone, washing the cyclohexanone with water to enable the pH value of the solution to be 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Comparative example 5
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the molar mass of o-cresol of 0.2% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the molar mass of o-cresol of 6% in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky solution;
s3, under the nitrogen atmosphere, adding grass with the molar mass of 0.1% of o-cresol into the reaction liquid in the step 2) in batches, and carrying out reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 6
S1, under the nitrogen atmosphere, o-cresol and paraformaldehyde are added into a reaction kettle according to a molar ratio of 1:0.784, and the mixture is stirred for 60 minutes at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and then adding oxalic acid with the molar mass of o-cresol of 0.2% and zinc acetate catalyst with the molar mass of o-cresol of 6% in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky solution;
s3, adding phosphotungstic acid with 0.5% of o-cresol molar mass into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and carrying out reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume three times of that of the resin into the viscous solution obtained in the step 3) to dissolve the resin, adding sodium hydroxide to neutralize the solution, washing the solution with water to enable the pH value of the solution to be 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
The o-cresol formaldehyde resins prepared in examples 1 to 6 and comparative examples 1 to 6 were tested for o-para content, residual phenol content and chromaticity according to the corresponding detection standards and methods, and the specific detection results are shown in table 1.
TABLE 1 detection results of o-cresol formaldehyde resin
As can be seen from Table 1, the ortho-position ratio of the o-cresol formaldehyde resins prepared in examples 1 to 6 is 30 to 90%, the residual phenol is less than or equal to 1000ppm, the chromaticity is less than or equal to 1, and the softening point meets the design requirements.
The operations of examples 1, 5 to 6 and comparative examples 2 to 4 were repeated 3 times, and specific test results are shown in Table 2.
TABLE 2 detection of o-cresol formaldehyde resins
As can be seen from Table 2, the method provided by the application has stable reaction products, and the ortho-para content in each batch of o-cresol novolac resin is almost unchanged. Meanwhile, as can be seen from comparison of examples 1 and 5 to 6, the ortho-position content in the o-cresol novolac resin gradually increases with increasing use amount of the heteropolyacid salt, and the ortho-position content shows regular change, while the ortho-position content in comparative examples 2 to 4 does not show regular change. According to the technical scheme provided by the application, the content of ortho-para position in the o-cresol novolac resin can be controlled according to the dosage of heteropolyacid salt, so that the o-cresol novolac resin can be produced according to the performance requirement of actual products. The specific method for controlling the adjacent position is as follows: by adopting the technical scheme provided by the application, the specific reaction raw materials, heteropolyacid salt, heteropolyacid and raw material dosage are determined before preparation, specific reaction conditions and processes are carried out, small batch tests are carried out firstly, the ortho-para content in the obtained o-cresol novolac resin is determined, then the dosage of heteropolyacid salt is adjusted according to the ortho-para content in the product, the tests are carried out again, so that the o-cresol novolac resin with the target ortho-para content is obtained, and industrial production can be carried out.
Wherein: the o-para content, the residual phenol content and the chromaticity of the o-cresol formaldehyde resin were tested as follows:
1. checking of ortho-para content
1.1 test device
Agilent gas chromatography
1.2 sample
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the acetonitrile, covering a cover, shaking uniformly, and measuring.
1.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D.x 250mm x 5um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, UV detector (wavelength 275 nm), column temperature of 30deg.C, and sample injection amount of 20ul;
2) After the liquid chromatography baseline is stable, sampling is performed for detection;
3) And calculating according to the peak area in the spectrogram, and recording the test result into a test report.
2. Examination of the o-cresol content
2.1 test device
Agilent gas chromatography
2.2 sample
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the acetonitrile, covering a cover, shaking uniformly, and measuring.
2.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D.x 250mm x 5um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, UV detector (wavelength 275 nm), column temperature of 30deg.C, and sample injection amount of 20ul;
2) After the liquid chromatography baseline is stable, sampling is performed for detection;
3) And calculating the peak area of the residual phenol, and recording the test result into a test report after comparing the peak area with an internal standard curve.
3. Chromaticity of
3.1 according to the standard
The epoxy resin was tested according to GBT12007.1-1989 epoxy resin color measurement method.
3.2 test instruments
1) Nashi cuvette 25ml
2) Analytical balance
3) Volumetric flask 25ml, 100ml
4) Pipette with a pipette tip
3.3 test procedure
1) Preparing a gardner color code solution 1-16 according to the standard;
2) 4 parts by mass of epoxy resin are dissolved in 6 parts by mass of acetone;
3) And (3) introducing the prepared solution into a colorimetric tube, and comparing the prepared solution with the prepared gardner color code, wherein the color is close to the chromaticity.
4) And completing the test report according to the test result.
4. Softening Point test
4.1 according to the standard
The epoxy resin was tested according to GB/T12007.6-1989 method for determining the softening point of epoxy resin.
4.2 test instruments
1) Asphalt softening point tester
4.3 test procedure
1) Introducing the molten resin into a sample ring to make the liquid level of the resin higher than that of the ring, cooling, and then scraping by a heating knife;
2) And (3) placing the sample ring into an asphalt softening point instrument, wherein a heating medium is glycerin, and the heating rate is set to be 5 ℃/min until the temperature of the steel ball falling to a lower bottom plate after resin softening is the softening point.
3) And completing the test report according to the test result.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (3)
1. The application of heteropoly acid and heteropoly acid salt as catalysts in the catalytic preparation of o-cresol novolac resin is characterized in that the ortho-position content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the gardner color is less than or equal to 1;
the o-cresol novolac resin is prepared by the following steps:
1) Mixing o-cresol and formaldehyde to obtain a mixed solution;
2) Mixing the mixed solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a milky solution;
3) Mixing the milky white solution with heteropoly acid, and reacting to obtain a milky white viscous solution;
4) Mixing the milky viscous solution with an organic solvent, and neutralizing and washing the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere;
the molar ratio of the o-cresol to the formaldehyde is 1:0.5-1.5;
the organic acid in the step 2) is added in batches, and the organic acid is one or more of formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid; the addition amount of the organic acid is 0.1% -1.0% of the molar amount of the o-cresol;
the heteropolyacid salt in the step 2) is added in batches, and the heteropolyacid salt is one or more of 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfo) propyl-3-methylimidazole phosphotungstenate, 1- (3-sulfo) propylpyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphomolybdate, 1- (3-sulfo) propyl-3-methylimidazole phosphomolybdate, 1- (3-sulfo) propylpyridine phosphomolybdenate, 1-butyl-3-methylimidazole phosphomolybdenate, 1- (3-sulfo) propyl-3-methylimidazole phosphomolybdenate and 1- (3-sulfo) propylpyridine phosphomolybdenate; the addition amount of the heteropolyacid salt is 5% -20% of the molar amount of the o-cresol;
the temperature of the stirring reaction in the step 2) is 80-100 ℃ and the time is 0.5-2 h;
the heteropolyacid in the step 3) is added in batches, and the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1% -1.0% of the molar amount of the o-cresol;
the reaction temperature in the step 3) is 100-140 ℃ and the reaction time is 0.5-5 h.
2. The use according to claim 1, wherein the organic solvent in step 4) is methyl isobutyl ketone, toluene, xylene or cyclohexanone; the volume of the organic solvent is 1-5 times of that of the milky viscous solution obtained in the step 3).
3. The use according to claim 1, wherein in the step 4), the neutralization and the water washing are performed by using an alkali solution, and the pH of the solution after the neutralization and the water washing is 6 to 7.
Priority Applications (2)
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| CN202210830591.XA CN115109212B (en) | 2022-07-15 | 2022-07-15 | Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin |
| PCT/CN2022/129224 WO2023066403A1 (en) | 2022-07-15 | 2022-11-02 | Use of heteropoly acid and heteropoly acid salt as catalyst in catalytic preparation of o-cresol phenolic resin |
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| CN202210830591.XA CN115109212B (en) | 2022-07-15 | 2022-07-15 | Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin |
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| CN115894466B (en) * | 2023-03-08 | 2023-05-05 | 东营市赫邦化工有限公司 | Preparation method of epoxy resin |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302350A (en) * | 1998-04-24 | 1999-11-02 | Sumitomo Bakelite Co Ltd | Production of phenolic resin |
| JP2003064142A (en) * | 2001-08-23 | 2003-03-05 | Japan Epoxy Resin Kk | Polyhydric phenol compound, curing agent for epoxy resin using the same compound and epoxy resin composition |
| JP2004209469A (en) * | 2002-12-20 | 2004-07-29 | Showa Denko Kk | Heteropoly acid and/or heteropoly acid salt-supported type catalyst, method for producing the catalyst, and method for producing compound obtained by using the catalyst |
| JP2004244526A (en) * | 2003-02-14 | 2004-09-02 | Japan Epoxy Resin Kk | Novel phenol resin, curing agent for epoxy resin, and epoxy resin composition |
| JP2008106219A (en) * | 2006-03-29 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
| CN101508761A (en) * | 2009-03-13 | 2009-08-19 | 江苏文昌电子化工有限公司 | Process for preparing phenolic resin containing nitrogen |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN103435844A (en) * | 2013-07-23 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Flame retardation catalyst and supported flame retardation catalyst composed of same |
| TW201434886A (en) * | 2012-11-27 | 2014-09-16 | Polyplastics Co | Production method for polyacetal copolymer |
| CN107383294A (en) * | 2017-09-04 | 2017-11-24 | 江苏三吉利化工股份有限公司 | A kind of preparation method of the two acid catalyzed light o-cresol-formaldehyde resin of synthesis |
-
2022
- 2022-07-15 CN CN202210830591.XA patent/CN115109212B/en active Active
- 2022-11-02 WO PCT/CN2022/129224 patent/WO2023066403A1/en unknown
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11302350A (en) * | 1998-04-24 | 1999-11-02 | Sumitomo Bakelite Co Ltd | Production of phenolic resin |
| JP2003064142A (en) * | 2001-08-23 | 2003-03-05 | Japan Epoxy Resin Kk | Polyhydric phenol compound, curing agent for epoxy resin using the same compound and epoxy resin composition |
| JP2004209469A (en) * | 2002-12-20 | 2004-07-29 | Showa Denko Kk | Heteropoly acid and/or heteropoly acid salt-supported type catalyst, method for producing the catalyst, and method for producing compound obtained by using the catalyst |
| JP2004244526A (en) * | 2003-02-14 | 2004-09-02 | Japan Epoxy Resin Kk | Novel phenol resin, curing agent for epoxy resin, and epoxy resin composition |
| JP2008106219A (en) * | 2006-03-29 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
| CN101508761A (en) * | 2009-03-13 | 2009-08-19 | 江苏文昌电子化工有限公司 | Process for preparing phenolic resin containing nitrogen |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| TW201434886A (en) * | 2012-11-27 | 2014-09-16 | Polyplastics Co | Production method for polyacetal copolymer |
| CN103435844A (en) * | 2013-07-23 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Flame retardation catalyst and supported flame retardation catalyst composed of same |
| CN107383294A (en) * | 2017-09-04 | 2017-11-24 | 江苏三吉利化工股份有限公司 | A kind of preparation method of the two acid catalyzed light o-cresol-formaldehyde resin of synthesis |
Non-Patent Citations (3)
| Title |
|---|
| Acid catalysis of silica-included heteropolyacid in polar reaction media;Yusuke Izumi et al.;Applied Catalysis A: General;第277-282页 * |
| Keggin 结构型硅钨酸催化β-萘酚与醛的缩合反应;韩波等;有机化学;第1121-1125页 * |
| 合成条件对邻甲酚系线形酚醛树脂的影响;杨金瑞等;热固性树脂;第11-14页 * |
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