CN115109212A - Application of heteropoly acid and heteropoly acid salt as catalyst in catalytic preparation of o-cresol novolac resin - Google Patents
Application of heteropoly acid and heteropoly acid salt as catalyst in catalytic preparation of o-cresol novolac resin Download PDFInfo
- Publication number
- CN115109212A CN115109212A CN202210830591.XA CN202210830591A CN115109212A CN 115109212 A CN115109212 A CN 115109212A CN 202210830591 A CN202210830591 A CN 202210830591A CN 115109212 A CN115109212 A CN 115109212A
- Authority
- CN
- China
- Prior art keywords
- acid
- salt
- solution
- cresol
- heteropoly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G8/04—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 invention provides application of heteropoly acid and heteropoly acid salt as a catalyst in catalytic preparation of o-cresol novolac resin, belonging to the technical field of phenolic resin preparation. The invention provides an application of heteropoly acid and heteropoly acid salt as a catalyst in catalytic preparation of o-cresol novolac resin, wherein the ortho content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the Gardner chroma is less than or equal to 1. The o-cresol novolac resin prepared by the method provided by the invention has low residual phenol and Gardner chroma and controllable ortho content.
Description
Technical Field
The invention belongs to the technical field of phenolic resin preparation, and particularly relates to application of heteropoly acid and heteropoly acid salt as catalysts in catalytic preparation of o-cresol novolac resin.
Background
The o-cresol novolac epoxy resin is a multifunctional glycidyl ether type epoxy resin, has a phenolic structure and an epoxy group in a molecular structure, is easy to form a high-performance net-shaped cross-linked rigid structure after the resin is cured, and has excellent thermal stability, electrical insulation property, high mechanical strength, good bonding property, small shrinkage, good moisture resistance and chemical corrosion resistance; the other remarkable characteristic is that when the softening point is changed, the epoxy value is basically unchanged, the melt viscosity is quite low, and the resin is endowed with excellent process stability and processing manufacturability. Therefore, the o-cresol novolac epoxy resin is widely applied to packaging materials in the advanced electronic industry, and packaging capacitors, resistors, triodes, diodes, potentiometers and the like of semiconductor Integrated Circuits (ICs), large-scale integrated circuits (LICs) and the like.
With the development of the human industrial technology to improve the production efficiency, a rapid curing type phenol resin has been developed. The high ortho phenolic resin has the characteristics of higher curing speed and better storage stability compared with 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 simultaneously has the characteristic of lower softening point, so that the high ortho phenolic resin can be cured at lower temperature.
At present, the common preparation method of the high-ortho phenolic resin is mainly to enhance the ortho-position activity and improve the ortho-position reaction rate under the condition that divalent metal oxide or salt thereof is used as a catalyst, and the high-ortho phenolic resin is synthesized through catalysis with the aid of an acid catalyst. However, the divalent metal weak acid salt catalysts have low catalytic efficiency, the reaction process is unstable, and the resin is easy to gel during high-temperature dehydration.
Disclosure of Invention
The invention provides application of heteropoly acid and heteropoly acid salt as catalysts in catalytic preparation of o-cresol novolac resin, the reaction process is stable, the resin is not easy to gel, the prepared o-cresol novolac resin has low residual phenol and Gardner chroma, and the content of ortho-position is controllable.
In order to achieve the purpose, the invention provides application of heteropoly acid and heteropoly acid salt as catalysts in catalytic preparation of o-cresol novolac resin, wherein the ortho content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the Gardner chroma 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 heteropoly acid salt, and stirring for reaction to obtain a milky white solution;
3) mixing the milky white solution with heteropoly acid, and reacting to obtain milky white viscous solution;
4) mixing the milky viscous solution with an organic solvent, and performing neutralization and water washing on the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out in a nitrogen atmosphere.
Preferably, the molar ratio of the o-cresol to the formaldehyde is 1: 0.5-1.5.
Preferably, in the step 2), the organic acid 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 to 1.0 percent of the molar amount of the o-cresol.
Preferably, the heteropolyacid salt is added in portions in step 2), and the heteropolyacid salt is 1-butyl-3-methylimidazole phosphotungstic heteropolyacid salt, brominated 1-butyl-3-methylimidazole phosphotungstic heteropolyacid salt, 1- (3-sulfonic acid group) propyl pyridine phosphotungstic heteropolyacid salt, 1-butyl-3-methylimidazole silicotungstic heteropolyacid salt, brominated 1-butyl-3-methylimidazole silicotungstic heteropolyacid salt, 1- (3-sulfonic acid group) propyl pyridine silicotungstic heteropolyacid salt, 1-butyl-3-methylimidazole phosphomolybdic heteropolyacid salt, 1- (3-sulfonic acid group) propyl pyridine silicotungstic heteropolyacid salt, 1-butyl-3-methylimidazole phosphomolybdic heteropolyacid salt, One or more of brominated 1-butyl-3-methylimidazole phosphomolybdic heteropolyacid salt, 1- (3-sulfonic acid group) propyl pyridine phosphomolybdic heteropolyacid salt, 1-butyl-3-methylimidazole silicon molybdic heteropolyacid salt, brominated 1-butyl-3-methylimidazole silicon molybdic heteropolyacid salt, 1- (3-sulfonic acid group) propyl-3-methylimidazole silicon molybdic heteropolyacid salt and 1- (3-sulfonic acid group) propyl pyridine silicon molybdic heteropolyacid salt; the addition amount of the heteropoly acid salt is 5 to 20 percent of the mol amount of o-cresol.
Preferably, the stirring reaction in the step 2) is carried out at the temperature of 80-100 ℃ for 0.5-2 h.
Preferably, the heteropoly acid in the step 3) is added in batches, and the heteropoly acid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1 to 1.0 percent of the molar amount of 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 step 4) is methyl isobutyl ketone, toluene, xylene or cyclohexanone; the volume of the organic solvent is 1-5 times of the milky viscous solution obtained in the step 3).
Preferably, in the step 4), an alkali solution is adopted for neutralization and water washing, and the pH value of the solution after the neutralization and water washing is 6-7.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) according to the invention, organic acid and heteropoly acid salt are selected as catalysts in the initial stage of reaction, so that the catalytic capability is weak, the reaction is mild, and the resin is prevented from crosslinking due to violent heat release in the initial stage of reaction; the heteropoly acid is selected as the catalyst in the middle reaction period, so that the hydrogen dissociation capability is high, the catalytic capability is strong, the polycondensation reaction rate can be effectively further improved, the conversion rate and the yield of o-cresol are improved, the reaction period is shortened, and the production cost is reduced.
(2) The invention uses catalyst heteropoly acid salt and organic acid in a composite way, and prepares the o-cresol formaldehyde resin with different content of ortho-position by the condensation polymerization of the phenol formaldehyde under the action of heteroatom with higher activity and obvious positioning effect.
(3) The o-cresol formaldehyde resin prepared by the method has controllable o-para content, low residual phenol content and low chroma.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides application of heteropoly acid and heteropoly acid salt as catalysts in catalytic preparation of o-cresol novolac resin, wherein the ortho content of the prepared o-cresol novolac resin is 30-90%, the residual phenol is less than or equal to 1000ppm, and the Gardner chroma is less than or equal to 1.
In the invention, 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 heteropoly acid salt, and stirring for reaction to obtain a milky white solution;
3) mixing the milky white solution with heteropoly acid, and reacting to obtain milky white viscous solution;
4) mixing the milky viscous solution with an organic solvent, and performing neutralization and water washing on the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out in a nitrogen atmosphere.
The invention mixes o-cresol and formaldehyde to obtain mixed liquid. In the present invention, the molar ratio of the o-cresol to the 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 invention, the formaldehyde is preferably formaldehyde or paraformaldehyde.
After the mixed solution is obtained, the mixed solution is mixed with the organic acid and the heteropoly acid salt, and stirring reaction is carried out to obtain a milky white solution. In the present invention, the organic acid is preferably added in an amount of 0.1 to 1.0% by mole, more preferably 0.2 to 0.6% by mole, and most preferably 0.3 to 0.5% by mole, based on the o-cresol. In the present invention, 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 invention, the amount of the heteropolyacid salt added is preferably 5% to 20%, more preferably 6% to 15%, and most preferably 8% to 10% of the molar amount of the o-cresol. In the present invention, the heteropolyacid salt is preferably 1-butyl-3-methylimidazolium phosphotungstate, brominated 1-butyl-3-methylimidazolium phosphotungstate, 1- (3-sulfonic) propyl pyridinium phosphotungstate, 1-butyl-3-methylimidazolium silicotungstate, brominated 1-butyl-3-methylimidazolium silicotungstate, 1- (3-sulfonic) propyl pyridinium silicotungstate, 1-butyl-3-methylimidazolium phosphomolybdic heteropolyacid salt, brominated 1-butyl-3-methylimidazolium phosphomolybdic heteropolyacid salt, brominated 1-butyl-3-methylimidazolium phosphomolybdic heteropolyacid salt, 1- (3-sulfonic group) propyl-3-methylimidazole phosphomolybdic acid heteropoly salt, 1- (3-sulfonic group) propyl pyridine phosphomolybdic acid heteropoly salt, 1-butyl-3-methylimidazole silicomolybdic acid heteropoly salt, brominated 1-butyl-3-methylimidazole silicomolybdic acid heteropoly salt, one or more of 1- (3-sulfonic group) propyl-3-methylimidazole silicomolybdic acid heteropoly salt and 1- (3-sulfonic group) propyl pyridine silicomolybdic acid heteropoly salt, more preferably 1-butyl-3-methylimidazole phosphotungstic acid heteropoly salt, brominated 1-butyl-3-methylimidazole phosphotungstic acid heteropoly salt, 1- (3-sulfonic group) propyl-3-methylimidazole phosphotungstic acid heteropoly salt, a salt of a compound of formula (I, 1- (3-sulfo) propylpyridylphosphatid, most preferably 1-butyl-3-methylimidazolium phosphotungstate. The heteropolyacid salt is preferably added in portions.
In the invention, the stirring reaction is preferably carried out at the temperature of 80-100 ℃ for 0.5-2 h, more preferably at the temperature of 95 ℃ for 0.7-1.5 h.
After a milky white solution is obtained, the milky white solution and heteropoly acid are mixed and react to obtain a milky white viscous solution. In the present invention, the heteropolyacid is preferably one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid, more preferably phosphotungstic acid or silicotungstic acid, and most preferably phosphotungstic acid. In the present invention, the amount of the heteropoly acid added is preferably 0.1 to 1.0% of the molar amount of o-cresol, more preferably 0.2 to 0.6%, and most preferably 0.3 to 0.5%. The heteropolyacid is preferably added batchwise. In the invention, the reaction temperature is preferably 100-140 ℃, and more preferably 115-145 ℃; the time is preferably 0.5 to 5 hours, and more preferably 0.8 to 1 hour.
After the milky viscous solution is obtained, the milky viscous solution is mixed with an organic solvent, and the obtained solution is neutralized and washed to obtain the o-cresol novolac resin. In the present invention, 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 invention, the volume of the organic solvent is preferably 1 to 5 times, and more preferably 3 times that of the milky viscous solution. In the invention, preferably, the neutralization and water washing is carried out by using an alkali solution, and the pH of the solution after the neutralization and water washing is 6-7.
In the invention, heteropolyacid salt and organic acid are used as catalysts in a composite way, and under the action of heteroatoms with higher activity and obvious positioning effect, ortho-cresol formaldehyde resin with different contents is prepared through the condensation polymerization of phenolic aldehyde. Meanwhile, the organic acid and the heteropoly acid salt are compounded to be used as a catalyst, so that the catalytic capability is weak, the reaction is mild, and the resin can be prevented from being crosslinked due to 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 hydrogen dissociation capability is high, the catalytic capability is strong, the polycondensation reaction rate can be effectively further improved, and the conversion rate and the yield of o-cresol are improved. The reaction period is shortened, and the production cost is reduced. Meanwhile, the o-cresol formaldehyde resin prepared by the method has controllable ortho-para content, controllable softening point and low chroma.
The invention controls the ortho-para content of the o-cresol novolac resin by the type and the addition of the heteropolyacid salt, and the reaction mechanism for synthesizing the ortho-cresol novolac resin with controllable ortho-position is as follows: by selecting a mixed catalytic system of heteropoly acid salt and organic acid, the heteropoly acid salt provides a weak acidic reaction environment, highlights the difference of electrophilic substitution degree of hydroxyl groups 'OH' at the ortho-position and the para-position on an o-cresol ring, and selects heteroatoms (such as P, Si, Fe, Co and the like) and polyatomic groups (such as Mo, W, V, Nb, Ta and the like) with an ortho-position guide function in the synthetic process, so that formaldehyde can preferentially perform an addition reaction with the ortho-position of o-cresol to form an unstable chelate, the chelate can continuously perform a polycondensation reaction with the o-cresol by removing one hydroxyl group, heteroatom and polyatomic group to form diphenol methane with ortho-position connection and high activity, and simultaneously controls the types and the contents of the heteroatom and the polyatomic group, and continuously reacts with the formaldehyde to form the o-cresol formaldehyde resin with different ortho-position contents.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to the molar ratio of 1:0.784 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the molar mass of 0.2% of o-cresol and a 1-butyl-3-methylimidazolium phosphotungstate heteropoly acid salt catalyst with the molar mass of 6% of o-cresol in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.5% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 2
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to a molar ratio of 1:0.834 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding formic acid with the molar mass of 0.5% of o-cresol and a brominated 1-butyl-3-methylimidazolium silicotungstophosphate catalyst with the molar mass of 8% of o-cresol in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.4% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 135 ℃ for 0.5 hour to obtain a milky viscous solution;
s4, adding cyclohexanone with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 3
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.903 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the molar mass of 0.4% of o-cresol and a 1- (3-sulfonic group) propyl pyridine phosphotungstic heteropoly acid salt catalyst with the molar mass of 10% of o-cresol in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky white solution;
s3, adding phosphomolybdic acid with the molar mass of 0.8% o-cresol into the reaction liquid obtained in the step 2) in batches under the nitrogen atmosphere, and performing reflux dehydration reaction at 115 ℃ for 1 hour to obtain a milky viscous solution;
s4, adding methyl isobutyl ketone with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the methyl isobutyl ketone, adding sodium hydroxide to neutralize the viscous solution, washing the viscous solution with water to ensure that the pH value of the solution is 6-7, and removing the solvent to obtain the o-cresol novolac resin.
Example 4
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.707 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid accounting for 0.5% of the molar mass of o-cresol and a brominated 1-butyl-3-methylimidazolidosilmolybdic heteropolyacid catalyst accounting for 5% of the molar mass of o-cresol in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky white solution;
s3, adding silicomolybdic acid with the molar mass of 1.0% o-cresol into the reaction liquid in the step 2) in batches under the nitrogen atmosphere, and performing reflux dehydration reaction at 140 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding xylene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the xylene, adding sodium hydroxide to neutralize the mixture, then washing the mixture with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 5
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to the molar ratio of 1:0.784 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid accounting for 0.2% of the molar mass of o-cresol and a 1-butyl-3-methylimidazolium phosphotungstate heteropoly acid salt catalyst accounting for 10% of the molar mass of o-cresol in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.5% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Example 6
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to the molar ratio of 1:0.784 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid accounting for 0.2% of the molar mass of o-cresol and a 1-butyl-3-methylimidazolium phosphotungstate heteropoly acid salt catalyst accounting for 15% of the molar mass of o-cresol in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.5% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 1
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.784 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding an oxalic acid catalyst with the molar mass of 0.6% of o-cresol in batches, and stirring and reacting for 2 hours after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.5% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 135 ℃ for 0.5 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 2
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.903 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding an oxalic acid catalyst with the molar mass of 0.4% of o-cresol in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky white solution;
s3, under the nitrogen atmosphere, adding oxalic acid with the molar mass of 0.1% o-cresol into the reaction liquid in the step 2) in batches, and performing reflux dehydration reaction at 135 ℃ for 3 hours to obtain milky viscous solution;
s4, adding cyclohexanone with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 3
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.903 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding an oxalic acid catalyst with the molar mass of 0.2% of o-cresol in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky solution;
s3, under the nitrogen atmosphere, adding oxalic acid with the molar mass of 0.1% o-cresol into the reaction liquid in the step 2) in batches, and performing reflux dehydration reaction at 135 ℃ for 3 hours to obtain milky viscous solution;
s4, adding cyclohexanone with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 4
S1, putting o-cresol and formaldehyde into a reaction kettle according to the molar ratio of 1:0.903 in the nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding an oxalic acid catalyst with the molar mass of 0.8% of o-cresol in batches, and stirring and reacting for 4 hours after the addition is finished to obtain a milky solution;
s3, under the nitrogen atmosphere, adding oxalic acid with the molar mass of 0.1% o-cresol into the reaction liquid in the step 2) in batches, and performing reflux dehydration reaction at 135 ℃ for 3 hours to obtain milky viscous solution;
s4, adding cyclohexanone with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the cyclohexanone, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 5
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to the molar ratio of 1:0.784 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the molar mass of 0.2% of o-cresol and a 1-butyl-3-methylimidazolium phosphotungstate heteropoly acid salt catalyst with the molar mass of 6% of o-cresol in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky white solution;
s3, under the nitrogen atmosphere, adding grass with the molar mass of 0.1% o-cresol into the reaction liquid obtained in the step 2) in batches, and performing reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 6-7, and then removing the solvent to obtain the o-cresol novolac resin.
Comparative example 6
S1, putting o-cresol and paraformaldehyde into a reaction kettle according to a molar ratio of 1:0.784 in a nitrogen atmosphere, and stirring at 50 ℃ for 60min to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 95 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the molar mass of 0.2% of o-cresol and a zinc acetate catalyst with the molar mass of 6% of o-cresol in batches, and stirring and reacting for 1 hour after the addition is finished to obtain a milky white solution;
s3, adding phosphotungstic acid with the molar mass of 0.5% o-cresol into the reaction liquid obtained in the step 2) in batches in a nitrogen atmosphere, and performing reflux dehydration reaction at 125 ℃ for 0.8 hour to obtain a milky viscous solution;
s4, adding toluene with the volume being three times that of the resin into the viscous solution obtained in the step 3) to dissolve the toluene, adding sodium hydroxide to neutralize the solution, then washing the solution with water to ensure that the pH value of the solution is 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 chroma according to the corresponding test standards and methods, and the specific test 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 proportion of the o-cresol formaldehyde resin prepared in the examples 1 to 6 is 30 to 90 percent, the residual phenol is less than or equal to 1000ppm, the chroma 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 the specific test results are shown in table 2.
TABLE 2 detection of o-cresol formaldehyde resin
As can be seen from Table 2, the method provided by the invention has stable reaction products and almost no difference of the ortho-para content in each batch of the ortho-cresol novolac resin. Meanwhile, as can be seen from comparison of examples 1 and 5 to 6, the content of ortho-position in the o-cresol novolac resin gradually increases with the increase of the amount of the heteropolyacid salt, and shows regular change, while the content of ortho-position in the o-cresol novolac resin does not show regular change in comparative examples 2 to 4. According to the technical scheme provided by the application, the content of the ortho-para position in the ortho-cresol novolac resin can be controlled according to the using amount of the heteropolyacid salt, and further the production can be carried out according to the actual product performance requirement. The method for specifically controlling the adjacent alignment comprises the following steps: by adopting the technical scheme provided by the application, the specific reaction raw materials, heteropolyacid salt, heteropolyacid and raw material dosage, specific reaction conditions and processes are determined before preparation, a small batch of test is firstly carried out, the content of ortho-para position in the obtained o-cresol novolac resin is determined, then the dosage of the heteropolyacid salt is adjusted according to the content of ortho-para position in the product, the test is carried out again, so that the o-cresol novolac resin with the target content of ortho-para position is obtained, and then the industrial production can be carried out.
Wherein: the o-para content, residual phenol content and chroma test method of the o-cresol formaldehyde resin comprises the following steps:
1. examination of ortho-para content
1.1 test device
Agilent gas chromatography
1.2 test specimens
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the added acetonitrile, covering a cover, shaking up, and detecting.
1.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mm I.D. X250 mm X5 um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, detector of UV (wavelength of 275nm), column temperature of 30 deg.C, and sample amount of 20 ul;
2) after the liquid chromatogram baseline is stable, sampling for detection;
3) and (4) calculating according to the peak area in the spectrogram, and recording the test result into an inspection report.
2. Examination of the o-cresol content
2.1 test device
Agilent gas chromatography
2.2 samples
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the added acetonitrile, covering a cover, shaking up, and detecting.
2.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mm I.D. X250 mm X5 um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, detector of UV (wavelength of 275nm), column temperature of 30 deg.C, and sample amount of 20 ul;
2) after the liquid chromatogram baseline is stable, sampling for detection;
3) and calculating the peak area of the residual phenol, and after comparing the peak area with an internal standard curve, recording the test result into a test report.
3. Color intensity
3.1 compliance Standard
Epoxy resins were tested according to GBT12007.1-1989 epoxy color determination method.
3.2 test Instrument
1) Nashi color comparison tube 25ml
2) Analytical balance
3) Volumetric flask 25ml, 100ml
4) Liquid transfer tube
3.3 test procedure
1) Preparing a Gardner color code solution No. 1-16 according to the standard;
2) dissolving 4 parts by mass of epoxy resin in 6 parts by mass of acetone;
3) and (3) introducing the prepared solution into a colorimetric tube, and comparing the solution with the prepared Gardner color code to obtain the chromaticity, wherein the chromaticity is obtained when the color is close to the color.
4) And finishing a test report according to the test result.
4. Testing of softening Point
4.1 compliance Standard
The epoxy resin was tested according to GB/T12007.6-1989 epoxy resin softening point determination.
4.2 test Instrument
1) Asphalt softening point tester
4.3 test procedure
1) Melting the resin, introducing the melted resin into a sample ring to enable the liquid level of the resin to be higher than that of the ring, and cooling and scraping the resin by using a heating knife;
2) and (3) putting the sample ring into an asphalt softening point instrument, wherein the heating medium is glycerol, the heating rate is set to be 5 ℃/min, and the temperature of the steel ball falling to the lower bottom plate after the resin is softened is the softening point.
3) And finishing a test report according to the test result.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The application of heteropoly acid and heteropoly acid salt as catalysts in catalytic preparation of o-cresol novolac resin is characterized in that the o-position content of the prepared o-cresol novolac resin is 30-90%, the residual phenol content is less than or equal to 1000ppm, and the Gardner color is less than or equal to 1.
2. The use according to claim 1, wherein 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 heteropoly acid salt, and stirring for reaction to obtain a milky white solution;
3) mixing the milky white solution with heteropoly acid, and reacting to obtain milky white viscous solution;
4) mixing the milky viscous solution with an organic solvent, and performing neutralization and water washing on the obtained solution to obtain o-cresol novolac resin;
the steps 1) to 3) are all carried out in a nitrogen atmosphere.
3. The use according to claim 2, wherein the molar ratio of o-cresol to formaldehyde is from 1:0.5 to 1.5.
4. The use according to claim 2, wherein the organic acid is added in portions in step 2), and the organic acid is one or more of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid; the adding amount of the organic acid is 0.1 to 1.0 percent of the molar amount of the o-cresol.
5. The use according to claim 2, wherein in step 2) the heteropolyacid salt is added in portions, the heteropolyacid salt being 1-butyl-3-methylimidazolium phosphotungstate heteropolyacid salt, brominated 1-butyl-3-methylimidazolium phosphotungstate heteropolyacid salt, 1- (3-sulfo) propyl pyridine phosphotungstate heteropolyacid salt, 1-butyl-3-methylimidazolium silicotungstic heteropolyacid salt, brominated 1-butyl-3-methylimidazolium silicotungstic heteropolyacid salt, 1- (3-sulfo) propyl pyridine silicotungstic heteropolyacid salt, a salt thereof, One or more of 1-butyl-3-methylimidazole phosphomolybdic acid heteropoly salt, brominated 1-butyl-3-methylimidazole phosphomolybdic acid heteropoly salt, 1- (3-sulfonic acid group) propyl pyridine phosphomolybdic acid heteropoly salt, 1-butyl-3-methylimidazole silicomolybdic acid heteropoly salt, brominated 1-butyl-3-methylimidazole silicomolybdic acid heteropoly salt, 1- (3-sulfonic acid group) propyl-3-methylimidazole silicomolybdic acid heteropoly salt and 1- (3-sulfonic acid group) propyl pyridine silicomolybdic acid heteropoly salt; the addition amount of the heteropoly acid salt is 5 to 20 percent of the mol amount of o-cresol.
6. The application of claim 2, wherein the stirring reaction in the step 2) is carried out at a temperature of 80-100 ℃ for 0.5-2 h.
7. The use according to claim 2, wherein the heteropoly acid in step 3) is added in portions, and the heteropoly acid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1 to 1.0 percent of the molar amount of o-cresol.
8. The use of claim 2, wherein the reaction temperature in step 3) is 100-140 ℃ and the reaction time is 0.5-5 h.
9. The use according to claim 2, 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 the milky viscous solution obtained in the step 3).
10. The use according to claim 2, wherein in the step 4), the solution is washed with neutralizing water by using an alkali solution, and the pH of the solution after the washing with neutralizing water is 6-7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115109212A true CN115109212A (en) | 2022-09-27 |
| CN115109212B CN115109212B (en) | 2023-10-13 |
Family
ID=83332638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210830591.XA Active CN115109212B (en) | 2022-07-15 | 2022-07-15 | Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115109212B (en) |
| WO (1) | WO2023066403A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894466A (en) * | 2023-03-08 | 2023-04-04 | 东营市赫邦化工有限公司 | Preparation method of epoxy resin |
| WO2024011789A1 (en) * | 2022-07-15 | 2024-01-18 | 山东海科创新研究院有限公司 | Preparation method for phenol phenolic resin and product obtained thereby |
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 |
|---|
| YUSUKE IZUMI ET AL.: "Acid catalysis of silica-included heteropolyacid in polar reaction media", APPLIED CATALYSIS A: GENERAL, pages 277 - 282 * |
| 杨金瑞等: "合成条件对邻甲酚系线形酚醛树脂的影响", 热固性树脂, pages 11 - 14 * |
| 韩波等: "Keggin 结构型硅钨酸催化β-萘酚与醛的缩合反应", 有机化学, pages 1121 - 1125 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024011789A1 (en) * | 2022-07-15 | 2024-01-18 | 山东海科创新研究院有限公司 | Preparation method for phenol phenolic resin and product obtained thereby |
| CN115894466A (en) * | 2023-03-08 | 2023-04-04 | 东营市赫邦化工有限公司 | Preparation method of epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023066403A1 (en) | 2023-04-27 |
| CN115109212B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115109212A (en) | Application of heteropoly acid and heteropoly acid salt as catalyst in catalytic preparation of o-cresol novolac resin | |
| JP4998271B2 (en) | Phenolic resin and resin composition | |
| JP5549107B2 (en) | Method for producing novolac resin | |
| CN115197173B (en) | Bio-based epoxy resin and preparation method thereof | |
| KR20140033313A (en) | Phenol-type oligomer and process for production thereof | |
| US4368299A (en) | Epoxy resin compositions | |
| CN102812060B (en) | Solid resol-type phenolic resin and method for producing same | |
| CN115124671B (en) | Preparation method of phenol-formaldehyde resin and product obtained by preparation method | |
| KR100656489B1 (en) | Epoxy resin and resin-sealed type semiconductor apparatus | |
| JP3633674B2 (en) | Liquid epoxy resin composition for sealing and cured product thereof | |
| JP5347678B2 (en) | Method for producing novolac resin | |
| CN105017714A (en) | Preparation method of bisphenol A modified phenolic resin | |
| JP4761417B2 (en) | Novel epoxy resin, curing agent and epoxy resin composition | |
| JPH06192361A (en) | Phenolic resin and epoxy resin composition and maleimide resin composition comprising the same | |
| CN115403774B (en) | Synthesis and reforming method of reworkable silicone resin containing dynamic covalent Si-O-Ph bond | |
| KR0137688B1 (en) | Phenolic resin composition | |
| JPH0533251B2 (en) | ||
| JPH0397710A (en) | Production of conjugated double bond-containing silicone-modified novolak resin | |
| JPH07173235A (en) | Allylnapththol cocondensate and epoxy resin composition | |
| JPH083257A (en) | Novolak phenolic resin and its preparation | |
| JP3704081B2 (en) | Epoxy resin, its production method and its use | |
| JPH045043B2 (en) | ||
| JPH0455422A (en) | Epoxy resin composition for semiconductor sealing | |
| Afrinaldi et al. | Effect of modified citric acid on the thermal properties of epoxy | |
| JP2008231374A (en) | Method of manufacturing phenol-modified aromatic hydrocarbon formaldehyde resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230320 Address after: 257200 West of Donggang Road and north of Gangbei 1st Road, Dongying Port Economic Development Zone, Dongying City, Shandong Province Applicant after: DONGYING HEBANG CHEMICAL CO.,LTD. Address before: 257000 ecological Valley future building, University Science Park, No. 38, Huanghe Road, Dongying District, Dongying City, Shandong Province Applicant before: Shandong Haike Innovation Research Institute Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |