WO2023066403A1 - Utilisation d'un hétéropolyacide et d'un sel d'hétéropolyacide comme catalyseur dans la préparation catalytique d'une résine phénolique d'o-crésol - Google Patents

Utilisation d'un hétéropolyacide et d'un sel d'hétéropolyacide comme catalyseur dans la préparation catalytique d'une résine phénolique d'o-crésol Download PDF

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WO2023066403A1
WO2023066403A1 PCT/CN2022/129224 CN2022129224W WO2023066403A1 WO 2023066403 A1 WO2023066403 A1 WO 2023066403A1 CN 2022129224 W CN2022129224 W CN 2022129224W WO 2023066403 A1 WO2023066403 A1 WO 2023066403A1
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acid
cresol
solution
heteropoly
salt
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PCT/CN2022/129224
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English (en)
Chinese (zh)
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张聪
张善如
何海波
黄帅
赵立伟
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山东海科创新研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—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

Definitions

  • the application belongs to the technical field of phenolic resin preparation, and in particular relates to the application of heteropolyacids and heteropolyacid salts as catalysts in the catalytic preparation of o-cresol phenolic resins.
  • O-cresol novolac epoxy resin is a polyfunctional glycidyl ether type epoxy resin. It has both phenolic structure and epoxy group in its molecular structure. After the resin is cured, it is very easy to form a high-performance network cross-linked rigid structure. , has excellent thermal stability, electrical insulation, high mechanical strength, good bonding performance, small shrinkage, good moisture resistance and chemical corrosion resistance; another notable feature is that when the softening point changes, the epoxy value basically does not change. Moreover, the melt viscosity is quite low, which endows the resin with excellent process stability and processability.
  • o-cresol novolac epoxy resin is widely used in the packaging materials of high-tech and cutting-edge electronic industries, and the packaging of capacitors, resistors, transistors, diodes, potentiometers, etc. in semiconductor integrated circuits (ICs) and large-scale integrated circuits (LICs).
  • ICs semiconductor integrated circuits
  • LICs large-scale integrated circuits
  • the high-ortho-position phenolic resin Due to the generation of a large number of hydrogen bonds caused by the large number of ortho-position structures in the molecule of the high-ortho-position phenolic resin, it has a faster curing speed and better storage stability than ordinary phenolic resins. At the same time, the high-ortho-position phenolic resin is also It has a relatively low softening point, so it can be cured at a relatively low temperature.
  • the common preparation method of high-ortho-position phenolic resin is mainly to enhance the ortho-position activity and increase the ortho-position reaction rate under the condition of divalent metal oxide or its salt as a catalyst, and catalyze the synthesis of high-ortho-position phenolic resin with the assistance of an acidic catalyst. bit phenolic resin.
  • the catalytic efficiency of this type of divalent metal weak salt catalyst is relatively low, and the reaction process is unstable, and the resin is easy to gel during high-temperature dehydration.
  • the application provides heteropolyacids and heteropolyacids as catalysts in the catalytic preparation of o-cresol novolac resins, the prepared o-cresol novolac
  • the ortho-position content of the resin is 30-90%, the residual phenol ⁇ 1000ppm, and the Gardner chroma ⁇ 1.
  • the o-cresol phenolic resin is prepared by the following steps:
  • the steps 1) to 3) are all carried out under nitrogen atmosphere.
  • the molar ratio of o-cresol to formaldehyde is 1:(0.5-1.5).
  • the organic acid is added in batches in the 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 added amount of the organic acid is 0.1%-1.0% of the molar weight of o-cresol.
  • the heteropoly acid salt is added in batches in the step 2), and the heteropoly acid salt is 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1 bromide -Butyl-3-methylimidazolium phosphotungstate, 1-(3-sulfonate)propyl-3-methylimidazolium phosphotungstate, 1-(3-sulfonate)propane Pyridine phosphotungstic heteropoly salt, 1-butyl-3-methylimidazolium tungstic heteropolyate, 1-butyl-3-methylimidazolium bromide silicotungstic heteropolyate, 1-(3- Sulfonic acid) propyl-3-methylimidazolium silicotungstic heteropoly salt, 1-(3-sulfonic acid) propylpyridine silicotungstic heteropoly salt, 1-butyl-3-methylimidazolium phosphomolybdenum Heteropolyacids
  • the temperature of the stirring reaction in the step 2) is 80-100° C., and the time is 0.5-2 h.
  • the heteropolyacid is added in batches in the step 3), and the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid ;
  • the added amount of the heteropolyacid is 0.1%-1.0% of the molar weight of o-cresol.
  • the reaction temperature in step 3) is 100-140° C., and the reaction time is 0.5-5 hours.
  • the organic solvent in the step 4) is methyl isobutyl ketone, toluene, xylene or cyclohexanone; the volume of the organic solvent is the milky white viscous solution obtained in the step 3). 1 to 5 times of that.
  • step 4 alkaline solution is used for neutralization and water washing, and the pH of the solution after neutralization and water washing is 6-7.
  • the o-cresol novolac resin prepared in at least one embodiment of the present application has controllable o-para content, low residual phenol content, and low chroma.
  • the examples of the present application provide the application of heteropolyacids and heteropolyacid salts as catalysts in the catalytic preparation of o-cresol phenolic resins. ⁇ 1000ppm, Gardner color ⁇ 1.
  • the o-cresol phenolic resin is preferably prepared by the following steps:
  • the steps 1) to 3) are all carried out under nitrogen atmosphere.
  • o-cresol and formaldehyde were mixed to obtain a mixed solution.
  • the molar ratio of o-cresol to formaldehyde is 1:(0.5-1.5), optionally 1:(0.6-1.0), and further optionally 1:(0.7-0.9).
  • the formaldehyde is optionally formaldehyde or paraformaldehyde.
  • the mixed solution is mixed with an organic acid and a heteropolyacid salt, and stirred and reacted to obtain a milky white solution.
  • the added amount of the organic acid is 0.1%-1.0%, optionally 0.2%-0.6%, and further optionally 0.3%-0.5% of the molar weight of o-cresol.
  • the organic acid is one or more of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid, optionally one of oxalic acid, benzoic acid and oxalic acid or more, further optionally oxalic acid.
  • the organic acid is optionally added in portions.
  • the added amount of the heteropolyacid salt is 5%-20% of the molar weight of o-cresol, optionally 6%-15%, further optionally 8%-10%.
  • the heteropoly acid salt is 1-butyl-3-methylimidazolium phosphotungstic heteropolyate, 1-butyl-3-methylimidazolium bromide phosphotungstic heteropolyate, 1 -(3-sulfo)propyl-3-methylimidazolium phosphotungstopolyate, 1-(3-sulfo)propylpyridine phosphotungstopolyate, 1-butyl-3-methyl Imidazole silicotungstic heteropoly acid salt, 1-butyl-3-methylimidazolium bromide silicotungstic heteropoly acid salt, 1-(3-sulfonic acid) propyl-3-methylimidazolium silicotungstic heteropoly acid Salt, 1-(3-sulfonate) propylpyridine silicotungstic heteropoly acid
  • the temperature of the stirring reaction is 80-100° C., and the time is 0.5-2 hours.
  • the temperature is 95° C., and the time is 0.7-1.5 hours.
  • the milky white solution and the heteropoly acid are mixed and reacted to obtain a milky white viscous solution.
  • the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid, optionally phosphotungstic acid or silicotungstic acid, further optionally
  • the base is phosphotungstic acid.
  • the amount of the heteropolyacid added is 0.1%-1.0%, optionally 0.2%-0.6%, and further optionally 0.3%-0.5% of the molar weight of o-cresol.
  • the heteropolyacid is optionally added in portions.
  • the temperature of the reaction is 100-140°C, optionally 115-145°C; the time is 0.5-5h, optionally 0.8-1h.
  • the milky white viscous solution is mixed with an organic solvent, and the obtained solution is neutralized and washed to obtain o-cresol phenolic resin.
  • the organic solvent is methyl isobutyl ketone, toluene, xylene or cyclohexanone, optionally methyl isobutyl ketone, xylene, and further optionally methyl isobutyl base ketones.
  • the volume of the organic solvent is 1-5 times, optionally 3 times, that of the milky white viscous solution.
  • alkaline solution is used for neutralization and water washing, and the pH of the solution after neutralization and water washing is 6-7.
  • heteropoly acid salts and organic acids are used as catalysts in combination, under the action of heteroatoms with high activity and obvious positioning effect, through the polycondensation reaction of phenolic aldehydes, different amounts of ortho cresol aldehydes are prepared resin.
  • the combination of organic acid and heteropoly acid salt is used as the catalyst, which has weak catalytic ability and moderate reaction, which can avoid the resin crosslinking due to the intense heat release in the initial stage of the reaction.
  • heteropolyacid is selected as the catalyst, which has high hydrogen dissociation ability and strong catalytic ability, which can effectively further increase the polycondensation reaction rate and improve the conversion rate and yield of o-cresol. Shorten the reaction cycle and reduce the production cost.
  • the o-cresol novolac resin prepared by the method is a product with controllable o-para content, controllable softening point and low chroma.
  • the content of the ortho- and para-positions of the ortho-cresol phenolic resin is controlled by the type and amount of the heteropolyacid salt.
  • the reaction mechanism of the ortho-position controllable ortho-cresol phenolic resin is: Organic acid mixed catalytic system, heteropoly acid salt provides a weakly acidic reaction environment, highlighting the difference in the degree of electrophilic substitution of the hydroxyl group "OH" at the ortho and para positions on the o-cresol ring, and selecting an ortho-position guiding function during the synthesis process
  • the heteroatoms such as P, Si, Fe, Co, etc.
  • polyatoms such as Mo, W, V, Nb, Ta, etc.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.2% o-cresol and 1-butanol with a molar mass of o-cresol 6% in batches Base-3-methylimidazolium phosphotungstic heteropoly salt catalyst, after the addition is completed, stir and react for 1 hour to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add in batches 0.5% o-cresol molar mass of formic acid and o-cresol molar mass 8% bromide 1 -Butyl-3-methylimidazolium silicotungstic heteropoly salt catalyst, stirring and reacting for 2 hours after the addition is complete, to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, then add acetic acid with a molar mass of 0.4% o-cresol and 1-( 3-sulfonic acid group) propyl pyridinium phosphotungstic heteropoly salt catalyst, stirred and reacted for 2 hours after adding, and obtained a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.5% o-cresol and bromide 1 with a molar mass of o-cresol 5% in batches -Butyl-3-methylimidazole silicomomolybdenum heteropoly salt catalyst, stirring and reacting for 2 hours after adding, to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.2% o-cresol and 1-butanol with a molar mass of o-cresol 10% in batches Base-3-methylimidazolium phosphotungstic heteropoly salt catalyst, after the addition is completed, stir and react for 1 hour to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.2% o-cresol and 1-butanol with a molar mass of o-cresol 15% in batches Base-3-methylimidazolium phosphotungstic heteropoly salt catalyst, after the addition is completed, stir and react for 1 hour to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95°C. After stirring and dissolving completely, add an oxalic acid catalyst with a molar mass of o-cresol of 0.6% in batches. After the addition, stir and react for 2 hours to obtain milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add an oxalic acid catalyst with a molar mass of o-cresol of 0.4% in batches, and stir and react for 4 hours after the addition to obtain milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add an oxalic acid catalyst with a molar mass of o-cresol of 0.2% in batches, and stir and react for 4 hours after the addition to obtain milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add an oxalic acid catalyst with a molar mass of o-cresol of 0.8% in batches, and stir and react for 4 hours after the addition to obtain milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.2% o-cresol and 1-butanol with a molar mass of o-cresol 6% in batches Base-3-methylimidazolium phosphotungstic heteropoly salt catalyst, after the addition is completed, stir and react for 1 hour to obtain a milky white solution;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 95° C., stir and dissolve completely, add oxalic acid with a molar mass of 0.2% o-cresol and zinc acetate catalyst with a molar mass of o-cresol 6% in batches , stirred and reacted for 1 hour after the addition was completed, and a milky white solution was obtained;
  • o-cresol novolac resins prepared in Examples 1-6 and Comparative Examples 1-6 were tested for o-para content, residual phenol content and chromaticity according to corresponding testing standards and methods, and the specific testing results are shown in Table 1.
  • Example 1 95 51.4 0.012 0.5 99.5 no Example 2 105 65.4 0.015 0.6 99.6 no Example 3 122 83.7 0.015 0.5 99.5 no Example 4 86 32.8 0.013 0.4 99.7 no Example 5 95 79.3 0.008 0.3 99.4 no Example 6 95 86.8 0.011 0.5 99.5 no Comparative example 1 97 49.5 0.023 0.6 99.4 yes Comparative example 2 123 51.6 0.251 0.5 87.7 yes Comparative example 3 122 52.1 0.264 0.4 87.5 yes Comparative example 4 122 50.7 0.158 0.5 89.4 yes Comparative example 5 94 51.8 0.124 0.4 88.6 no Comparative example 6 94 48.4 0.020 0.5 98.9 yes
  • the o-cresol resin prepared in Examples 1-6 has an ortho-position ratio of 30-90%, residual phenol ⁇ 1000ppm, chroma ⁇ 1, and the softening point meets the design requirements.
  • the specific method for controlling the ortho-para position is: adopt the technical scheme provided by the application, determine the specific reaction raw materials, heteropoly acid salts, heteropoly acids, raw material consumption, specific reaction conditions and processes before the preparation, and first carry out a small Batch test, determine the ortho-para content in the obtained o-cresol phenolic resin, then adjust the amount of heteropolyacid salt according to the ortho-para content in the product, test again, so as to obtain the ortho-para content of the target
  • the cresol phenolic resin can be industrialized afterwards.
  • Epoxy resin was tested according to GBT12007.1-1989 Epoxy Resin Color Determination Method.
  • Epoxy resin was tested according to GB/T 12007.6-1989 Determination of softening point of epoxy resin.
  • the heating medium is glycerin, and the heating rate is set at 5°C/min, until the temperature at which the steel ball falls to the lower bottom plate after the resin is softened is the softening point.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne l'utilisation d'un hétéropolyacide et d'un sel d'hétéropolyacide comme catalyseur dans la préparation catalytique d'une résine phénolique d'o-crésol, qui appartient au domaine technique de la préparation d'une résine phénolique. Dans l'utilisation d'un hétéropolyacide et d'un sel d'hétéropolyacide comme catalyseur dans la préparation catalytique d'une résine phénolique d'o-crésol, la teneur en positions ortho dans la résine phénolique d'o-crésol préparée est de 30 à 90 %, la teneur en phénol résiduel est inférieure ou égale à 1000 ppm, et l'échelle de couleur Gardner est inférieure ou égale à 1.
PCT/CN2022/129224 2022-07-15 2022-11-02 Utilisation d'un hétéropolyacide et d'un sel d'hétéropolyacide comme catalyseur dans la préparation catalytique d'une résine phénolique d'o-crésol WO2023066403A1 (fr)

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CN115124671B (zh) * 2022-07-15 2023-04-25 东营市赫邦化工有限公司 一种苯酚酚醛树脂的制备方法及其所得产品
CN115894466B (zh) * 2023-03-08 2023-05-05 东营市赫邦化工有限公司 一种环氧树脂的制备方法

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