WO2024011789A1 - Procédé de préparation d'une résine phénol phénolique et produit ainsi obtenu - Google Patents

Procédé de préparation d'une résine phénol phénolique et produit ainsi obtenu Download PDF

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WO2024011789A1
WO2024011789A1 PCT/CN2022/129223 CN2022129223W WO2024011789A1 WO 2024011789 A1 WO2024011789 A1 WO 2024011789A1 CN 2022129223 W CN2022129223 W CN 2022129223W WO 2024011789 A1 WO2024011789 A1 WO 2024011789A1
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phenol
acid
salt
heteropoly
heteropoly acid
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PCT/CN2022/129223
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English (en)
Chinese (zh)
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张聪
何海波
张善如
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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Publication of WO2024011789A1 publication Critical patent/WO2024011789A1/fr

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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
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present application belongs to the technical field of phenolic resin preparation, and in particular relates to a preparation method of phenol-novolac resin and the resulting product.
  • Phenol novolac epoxy resin is a light brown viscous liquid. It is produced by the polycondensation reaction of phenol and formaldehyde in an acidic medium to obtain a novolac resin, which is then polycondensed with excess propylene oxide in the presence of sodium hydroxide. Because the molecular structure contains many epoxy groups and aromatic nuclei, the cured product has a high cross-linking density and excellent heat resistance and chemical resistance. Therefore, it has gained a good reputation in electronic packaging, copper-clad laminates, rubber and other electronic and electrical fields. Wide range of applications.
  • the ideal injection molding compound should have good fluidity in the barrel and the ability to solidify quickly in the mold. Injection plastics with fast curing characteristics can reduce molding time and improve production efficiency.
  • Phenol novolac resin is used as a tackifier and reinforcing resin in rubber compound formulations, but the relatively slow curing speed and relatively high heat production of phenol novolac resin can affect the adhesion of tire cord to rubber.
  • the biggest feature of high-ortho-position phenolic resin is its fast polymerization speed, relatively low softening point, and curing at a lower temperature. Therefore, the characteristics of high ortho phenolic resin exactly meet this requirement.
  • the preparation of high ortho phenolic resin is mainly carried out in the presence of catalysts (such as divalent metal ions such as calcium, magnesium, zinc, strontium, cadmium, lead and barium oxides, hydroxides or organic acid salts).
  • catalysts such as divalent metal ions such as calcium, magnesium, zinc, strontium, cadmium, lead and barium oxides, hydroxides or organic acid salts.
  • the catalytic efficiency of this type of divalent metal weak acid salt catalyst is relatively low, and the reaction process is unstable. The resin is prone to gelation during high-temperature dehydration.
  • one aspect of the embodiments of the present application provides a method for preparing phenol novolac resin, including the following steps:
  • the steps 1) to 3) are all performed under nitrogen atmosphere.
  • the temperature during mixing in step 1) is 40-60°C; the molar ratio of formaldehyde to phenol is 1: (0.3-0.7); the molar ratio of water to phenol It is 1: (0.5 ⁇ 1.2).
  • the formaldehyde is paraformaldehyde or an aqueous formaldehyde solution.
  • the organic acid is added in batches 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 added amount of the organic acid is 0.1% to 1.0% of the molar amount of phenol.
  • the heteropoly acid salt is added in batches, and the heteropoly acid salt is 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1 bromide -Butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1-(3-sulfonate)propyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1-(3-sulfonate)propyl 1-Butyl-3-methylimidazole silicotungstic heteropoly acid salt, 1-butyl-3-methylimidazole silicotungstic heteropoly acid salt, 1-(3-methylimidazole silicotungsten heteropoly acid salt) Sulfonate)propyl-3-methylimidazole silicon tungsten heteropoly salt, 1-(3-sulfonate)propylpyridine silicon tungsten heteropoly salt, 1-butyl-3-methylimidazole phosphomolybden
  • the temperature of the stirring reaction in step 2) is 60-100°C, and the time is 1-3 hours.
  • the heteropoly acid is added in batches in step 3), and the heteropoly acid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid. ;
  • the addition amount of the heteropolyacid is 0.1% to 1.0% of the molar amount of phenol.
  • the reaction temperature in step 3) is 60-100°C, and the reaction time is 0.5-1.5h.
  • step 4 high temperature and high pressure are used to dehydrate and remove phenol; the pressure during dehydration is 10-20KPa, and the temperature is 100-140°C; The pressure is 0.1 ⁇ 10Kpa and the temperature is 150 ⁇ 200°C.
  • Another aspect of the embodiments of the present application also provides a phenol novolac resin prepared by any of the above methods, the ortho position content of the phenol novolac resin is 25% to 95%, and the residual phenol is ⁇ 1000ppm; Gadde Color absorption ⁇ 1.
  • the preparation method provided by at least one embodiment of the present application has stable reaction, is not easy to produce gel, has high production efficiency, and the prepared phenol novolac resin has low residual phenol and Gardner color and controllable ortho-position content.
  • the preparation method provided by at least one embodiment of the present application uses organic acids and heteropolyacid salts as catalysts in the early stage of the reaction.
  • the catalytic ability is weak, so that the reaction is moderated and the intense heat generation in the early stage of the reaction is avoided to cross-link the resin;
  • heteropoly acid is used as the catalyst, which has large hydrogen dissociation ability and strong catalytic ability, which can effectively further increase the polycondensation reaction rate, increase the conversion rate and yield of o-cresol, shorten the reaction cycle, and reduce production costs.
  • the preparation method provided by at least one embodiment of the present application uses a composite of catalyst heteropolyacid salt and organic acid, and under the action of heteroatoms with high activity and obvious positioning effect, through the polycondensation reaction of phenolic aldehyde, different products are prepared. Ortho content of phenol novolac resin.
  • the phenol novolac resin prepared in at least one embodiment of the present application has controllable ortho-para content, low residual phenol content, and low chroma.
  • the embodiments of the present application provide a method for preparing phenol novolac resin, which includes the following steps:
  • the steps 1) to 3) are all performed under nitrogen atmosphere.
  • phenol, formaldehyde and water are mixed to obtain a transparent solution.
  • the molar ratio of formaldehyde to phenol is 1:(0.3 ⁇ 0.7), optionally 1:(0.4 ⁇ 0.6), further optionally 1:0.5.
  • the molar ratio of water and phenol is 1:(0.5-1.2), optionally 1:1.1.
  • the mixing temperature is 40-60°C.
  • the formaldehyde is optionally formaldehyde or paraformaldehyde.
  • the embodiment of the present application mixes the transparent solution with an organic acid and a heteropolyacid salt, and performs a stirring reaction to obtain a first reaction liquid.
  • the added amount of the organic acid is 0.1% to 1.0% of the molar amount of phenol, optionally 0.2% to 0.6%, further optionally 0.3% to 0.5%.
  • 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 batches.
  • the addition amount of the heteropolyacid salt is 5% to 20% of the molar amount of phenol, optionally 6% to 15%, further optionally 8% to 10%.
  • the heteropoly acid salt is 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, bromide 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1 -(3-Sulfonate)propyl-3-methylimidazolium phosphorus tungsten heteropoly salt, 1-(3-sulfonate)propylpyridine phosphotungstic heteropoly salt, 1-butyl-3-methyl 1-butyl-3-methylimidazole silicotungstic heteropoly acid salt, 1-butyl-3-methylimidazole silicotungstic heteropoly acid salt, 1-(3-sulfonate)propyl-3-methylimidazole silicotungstic heteropoly acid Salt, 1-(3-sulfonate)
  • the temperature of the stirring reaction is 60-100°C, and the time is 1-3 hours.
  • the embodiment of the present application mixes the first reaction liquid and the heteropolyacid and performs a reaction to obtain a phenol-formaldehyde resin.
  • the heteropoly acid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid, optionally phosphotungstic acid or silicotungstic acid, further optionally The ground is phosphotungstic acid.
  • the addition amount of the heteropolyacid is 0.1% to 1.0% of the molar amount of phenol, optionally 0.2% to 0.6%, further optionally 0.3% to 0.5%.
  • the heteropoly acid is optionally added in portions.
  • the reaction temperature is 60-100°C, optionally 70-90°C; the reaction time is 0.5-1.5h, optionally 0.8-1h.
  • the phenol-formaldehyde resin is dehydrated and dephenolized to obtain a phenol-formaldehyde resin.
  • high temperature and high pressure are used to perform dehydration and phenol removal; the pressure during dehydration is optionally 10-20KPa, and further optionally 12-15KPa; the temperature during dehydration is optionally 100-15KPa. 140°C, further optionally 110 to 130°C.
  • the pressure during dephenolization is optionally 0.1-10KPa, further optionally 1-5Mpa; the temperature during dephenolization is optionally 150-200°C, further optionally 170-180°C.
  • heteropolyacid salts and organic acids are used as catalysts in combination, and under the action of heteroatoms with high activity and obvious positioning effects, ortho-ocresol aldehydes with different contents are prepared through the polycondensation reaction of phenolic aldehydes. resin.
  • a composite of organic acid and heteropolyacid salt is used as a catalyst, which has weak catalytic ability and moderate reaction, which can avoid the severe exotherm in the early stage of the reaction to cross-link the resin.
  • heteropoly acid is selected as a catalyst in the middle stage of the reaction, which has large hydrogen dissociation ability and strong catalytic ability, which can effectively further increase the polycondensation reaction rate and increase the conversion rate and yield of o-cresol. Shorten the reaction cycle and reduce production costs.
  • the phenolic phenolic resin prepared by this method has controllable ortho-para content, controllable softening point and low chroma.
  • the ortho-para position content of the phenol novolac resin is controlled through the type and addition amount of the heteropoly acid salt.
  • the reaction mechanism for synthesizing the ortho-controllable phenol novolac resin is as follows: by selecting mixed catalysis of the heteropolyacid acid salt and an organic acid.
  • the heteropoly acid salt provides a weakly acidic reaction environment, highlighting the difference in the degree of electrophilic substitution of the hydroxyl "OH" at the ortho and para positions on the phenol ring, and selecting heteroatoms with ortho-guiding functions during the synthesis process (such as P , Si, Fe, Co, etc.) and polyatoms (such as Mo, W, V, Nb, Ta, etc.), so that formaldehyde can react preferentially with the ortho position of phenol to form an unstable chelate.
  • the polycondensation reaction with phenol continues to form ortho-linked and highly active diphenolmethane.
  • the type and content of heteroatoms and polyatoms are controlled, and the reaction with formaldehyde continues to form Phenol novolac resins with different ortho positions.
  • the embodiments of the present application also provide a phenol novolac resin prepared by any of the above methods.
  • the ortho position content of the phenol novolac resin is 25% to 95%, the residual phenol is ⁇ 1000ppm; the Gardner color is ⁇ 1.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 75°C. After stirring and dissolving completely, add acetic acid with a molar mass of phenol 0.3% and 1-butyl-3 with a molar mass of phenol 5% in 4 batches. -Methylimidazole phosphotungstic heteropoly salt catalyst, stir and react for 2 hours after addition;
  • step 4 After dehydrating the solution obtained in step 3) at 110°C and a pressure of 20KPa, the temperature is raised to 180°C and the pressure is 1KPa to remove phenol to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolving completely, add oxalic acid with a molar mass of phenol 0.3% and 1-butyl-3 with a molar mass of phenol 8% in 5 batches. -Methylimidazole phosphotungstic heteropoly salt catalyst, stir and react for 3 hours after addition;
  • step 4 Dehydrate the solution obtained in step 3) at 120°C and a pressure of 15KPa, then raise the temperature to 190°C and remove phenol under a pressure of 10KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 80°C. After stirring and dissolution, add oxalic acid with a molar mass of 0.7% of phenol and 1-(3 with a molar mass of phenol of 10% in 5 batches. -Sulfonate)propylpyridinium phosphotungstic heteropoly salt catalyst, stir and react for 1 hour after addition;
  • step 4 After dehydrating the solution obtained in step 3) at 120°C and a pressure of 20KPa, the temperature is raised to 200°C and the pressure is 5KPa to remove phenol to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolving completely, add oxalic acid with a molar mass of phenol 0.6% and 1-butyl bromide with a molar mass of phenol 12% in 4 batches. -3-methylimidazole silicon molybdenum heteropoly salt catalyst, stir and react for 2 hours after adding;
  • step 4 After dehydrating the solution obtained in step 3) at 110°C and a pressure of 10KPa, the temperature is raised to 200°C and the phenol is removed under a pressure of 10KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 75°C. After stirring and dissolving completely, add acetic acid with a molar mass of phenol 0.3% and 1-butyl-3 with a molar mass of phenol 8% in 4 batches. -Methylimidazole phosphotungstic heteropoly salt catalyst, stir and react for 2 hours after addition;
  • step 4 After dehydrating the solution obtained in step 3) at 110°C and a pressure of 20KPa, the temperature is raised to 180°C and the pressure is 1KPa to remove phenol to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 75°C. After stirring and dissolution, add acetic acid with a molar mass of 0.3% of phenol and 1-butyl-3 with a molar mass of phenol of 12% in 4 batches. -Methylimidazole phosphotungstic heteropoly salt catalyst, stir and react for 2 hours after addition;
  • step 3 After the solution obtained in step 3) is dehydrated under reduced pressure at 110°C and a pressure of 20KPa, the temperature is raised to 180°C and the phenol is removed under reduced pressure at a pressure of 1KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolution, add 0.6% oxalic acid with phenol molar mass in 4 batches. After the addition is completed, stir and react for 3 hours;
  • step 3 After the solution obtained in step 3) is dehydrated under reduced pressure at 110°C and a pressure of 20KPa, the temperature is raised to 200°C and the phenol is removed under reduced pressure at a pressure of 1KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolution, add acetic acid with phenol molar mass 0.4% in 4 batches. After the addition is completed, stir and react for 5 hours;
  • step 3 After the solution obtained in step 3) is dehydrated under reduced pressure at 105°C and a pressure of 20KPa, the temperature is raised to 190°C and the phenol is removed under reduced pressure at a pressure of 1KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 75°C. After stirring and dissolving completely, add acetic acid with a molar mass of phenol 0.3% and 1-butyl-3 with a molar mass of phenol 5% in 4 batches. -Methylimidazole phosphotungstic heteropoly salt catalyst, stir and react for 2 hours after addition;
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolution, add acetic acid with 0.2% molar mass of phenol in 4 batches. After the addition is completed, stir and react for 5 hours;
  • step 3 After the solution obtained in step 3) is dehydrated under reduced pressure at 105°C and a pressure of 20KPa, the temperature is raised to 190°C and the phenol is removed under reduced pressure at a pressure of 1KPa to obtain a phenol novolac resin.
  • step 1) Under a nitrogen atmosphere, heat the solution in step 1) to 70°C. After stirring and dissolution, add acetic acid with phenol molar mass 0.8% in 4 batches. After the addition is completed, stir and react for 5 hours;
  • step 3 After the solution obtained in step 3) is dehydrated under reduced pressure at 105°C and a pressure of 20KPa, the temperature is raised to 190°C and the phenol is removed under reduced pressure at a pressure of 1KPa to obtain a phenol novolac resin.
  • the phenol novolac resin prepared in Examples 1 to 6 has an ortho ratio of 25-95%, residual phenol ⁇ 1000 ppm, chroma ⁇ 1, and the softening point meets the design requirements.
  • the specific method for controlling the ortho-para position is: using the technical solution provided by this application, first determine the specific reaction raw materials, heteropoly acid salts, heteropoly acids, raw material dosage, specific reaction conditions and processes before preparation, and first conduct a small Batch test, determine the ortho-para content in the obtained phenol phenolic resin, then adjust the amount of heteropoly acid salt according to the ortho-para content in the product, and test again to obtain the phenol phenolic resin with the target ortho-para content. , and then industrial production can be carried out.
  • test methods for ortho-para content, residual phenol, softening point and colorimetry of phenol phenolic resin are as follows:
  • the epoxy resin was tested according to GBT12007.1-1989 epoxy resin color determination method.
  • the epoxy resin was tested according to the GB/T 12007.6-1989 epoxy resin softening point determination method.

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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 un procédé de préparation de résine phénol phénolique et un produit ainsi obtenu, appartenant au domaine technique de la préparation de résine phénolique. Le procédé de préparation de résine phénol phénolique comprend les étapes suivantes, consistant à : 1) mélanger du phénol, du formaldéhyde et de l'eau pour obtenir une solution transparente ; 2) mélanger la solution transparente avec un acide organique et un sel d'hétéropolyacide et faire réagir sous agitation pour obtenir une première solution réactionnelle ; 3) mélanger la première solution réactionnelle avec un hétéropolyacide et faire réagir pour obtenir une résine phénol-formaldéhyde ; et 4) effectuer un traitement de déshydratation et de déphénolisation sur la résine phénol-formaldéhyde pour obtenir une résine phénol phénolique. Les étapes 1) -3) sont toutes effectuées sous une atmosphère d'azote.
PCT/CN2022/129223 2022-07-15 2022-11-02 Procédé de préparation d'une résine phénol phénolique et produit ainsi obtenu WO2024011789A1 (fr)

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Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
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

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297473A (en) * 1979-05-21 1981-10-27 Sumitomo Bakelite Company Limited Quick-curing phenolic resin and process for preparing same
EP0209020A2 (fr) * 1985-07-13 1987-01-21 BASF Aktiengesellschaft Procédé pour la préparation des résines phénoliques
JPH11302350A (ja) * 1998-04-24 1999-11-02 Sumitomo Bakelite Co Ltd フェノール樹脂の製造方法
US6015873A (en) * 1996-06-26 2000-01-18 Shell Oil Company Polyphenol composition and method of producing the same
US20020091224A1 (en) * 2000-12-12 2002-07-11 Sumitomo Chemical Company, Limited Method of producing novolak resin
JP2007100028A (ja) * 2005-10-07 2007-04-19 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
JP2008106219A (ja) * 2006-03-29 2008-05-08 Sumitomo Bakelite Co Ltd フェノール樹脂の製造方法
CN101619125A (zh) * 2009-07-28 2010-01-06 陕西师范大学 双催化体系热塑性酚醛树脂的制备方法及其在制备覆膜砂中的应用
CN102643170A (zh) * 2012-05-09 2012-08-22 河北工业大学 一种用含离子液体的混酸催化体系合成对叔丁基邻苯二酚的方法
CN102850496A (zh) * 2012-03-21 2013-01-02 山东圣泉化工股份有限公司 一种高邻位酚醛树脂及其制备方法
CN104140361A (zh) * 2014-06-30 2014-11-12 湘潭大学 一种磷钨酸咪唑盐催化合成双酚f的方法
CN107353377A (zh) * 2017-08-09 2017-11-17 山东圣泉新材料股份有限公司 一种酚醛树脂及其制备方法
CN107383294A (zh) * 2017-09-04 2017-11-24 江苏三吉利化工股份有限公司 一种双酸催化合成浅色邻甲酚醛树脂的制备方法
CN108440730A (zh) * 2018-04-13 2018-08-24 圣戈莱（北京）科技有限公司 一种铸造用高质量酚醛树脂的精制纯化方法
CN113121780A (zh) * 2020-01-15 2021-07-16 瀚森有限责任公司 包含酚醛清漆的组合物
CN115109212A (zh) * 2022-07-15 2022-09-27 山东海科创新研究院有限公司 杂多酸和杂多酸盐作为催化剂在催化制备邻甲酚酚醛树脂中的应用
CN115124671A (zh) * 2022-07-15 2022-09-30 山东海科创新研究院有限公司 一种苯酚酚醛树脂的制备方法及其所得产品

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103084213B (zh) * 2012-11-16 2015-02-25 湖南长岭石化科技开发有限公司 合成2,6-二甲基苯酚的催化剂及其制备方法和合成2,6-二甲基苯酚的方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297473A (en) * 1979-05-21 1981-10-27 Sumitomo Bakelite Company Limited Quick-curing phenolic resin and process for preparing same
EP0209020A2 (fr) * 1985-07-13 1987-01-21 BASF Aktiengesellschaft Procédé pour la préparation des résines phénoliques
US6015873A (en) * 1996-06-26 2000-01-18 Shell Oil Company Polyphenol composition and method of producing the same
JPH11302350A (ja) * 1998-04-24 1999-11-02 Sumitomo Bakelite Co Ltd フェノール樹脂の製造方法
US20020091224A1 (en) * 2000-12-12 2002-07-11 Sumitomo Chemical Company, Limited Method of producing novolak resin
JP2007100028A (ja) * 2005-10-07 2007-04-19 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
JP2008106219A (ja) * 2006-03-29 2008-05-08 Sumitomo Bakelite Co Ltd フェノール樹脂の製造方法
CN101619125A (zh) * 2009-07-28 2010-01-06 陕西师范大学 双催化体系热塑性酚醛树脂的制备方法及其在制备覆膜砂中的应用
CN102850496A (zh) * 2012-03-21 2013-01-02 山东圣泉化工股份有限公司 一种高邻位酚醛树脂及其制备方法
CN102643170A (zh) * 2012-05-09 2012-08-22 河北工业大学 一种用含离子液体的混酸催化体系合成对叔丁基邻苯二酚的方法
CN104140361A (zh) * 2014-06-30 2014-11-12 湘潭大学 一种磷钨酸咪唑盐催化合成双酚f的方法
CN107353377A (zh) * 2017-08-09 2017-11-17 山东圣泉新材料股份有限公司 一种酚醛树脂及其制备方法
CN107383294A (zh) * 2017-09-04 2017-11-24 江苏三吉利化工股份有限公司 一种双酸催化合成浅色邻甲酚醛树脂的制备方法
CN108440730A (zh) * 2018-04-13 2018-08-24 圣戈莱（北京）科技有限公司 一种铸造用高质量酚醛树脂的精制纯化方法
CN113121780A (zh) * 2020-01-15 2021-07-16 瀚森有限责任公司 包含酚醛清漆的组合物
CN115109212A (zh) * 2022-07-15 2022-09-27 山东海科创新研究院有限公司 杂多酸和杂多酸盐作为催化剂在催化制备邻甲酚酚醛树脂中的应用
CN115124671A (zh) * 2022-07-15 2022-09-30 山东海科创新研究院有限公司 一种苯酚酚醛树脂的制备方法及其所得产品

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