CN115124671B - Preparation method of phenol-formaldehyde resin and product obtained by preparation method - Google Patents
Preparation method of phenol-formaldehyde resin and product obtained by preparation method Download PDFInfo
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- CN115124671B CN115124671B CN202210830296.4A CN202210830296A CN115124671B CN 115124671 B CN115124671 B CN 115124671B CN 202210830296 A CN202210830296 A CN 202210830296A CN 115124671 B CN115124671 B CN 115124671B
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- phenol
- acid
- formaldehyde resin
- reaction
- methylimidazole
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 65
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000011964 heteropoly acid Chemical class 0.000 claims abstract description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 51
- 238000010438 heat treatment Methods 0.000 description 25
- 238000012360 testing method Methods 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- -1 organic acid salts Chemical class 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- OIALIKXMLIAOSN-UHFFFAOYSA-N 2-Propylpyridine Chemical compound CCCC1=CC=CC=N1 OIALIKXMLIAOSN-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- DECWYWSYTFTUAV-UHFFFAOYSA-N 1-methyl-2-propylimidazole Chemical compound CCCC1=NC=CN1C DECWYWSYTFTUAV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DTQZKOBDNLNBCU-UHFFFAOYSA-N 1-methylimidazole Chemical class CN1C=CN=C1.CN1C=CN=C1 DTQZKOBDNLNBCU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 244000088401 Pyrus pyrifolia Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C08G8/10—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
Abstract
The invention provides a preparation method of phenol-formaldehyde resin and a product obtained by the preparation method, which belongs to the technical field of preparation of phenol-formaldehyde resin, and the preparation method of the phenol-formaldehyde resin comprises the following steps: 1) Mixing phenol, formaldehyde and water to obtain a transparent solution; 2) Mixing the transparent solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a first reaction solution; 3) Mixing the first reaction solution with heteropoly acid, and reacting to obtain phenol formaldehyde resin; 4) Dehydrating and dephenolizing the phenol formaldehyde resin to obtain phenol formaldehyde resin; the steps 1) to 3) are all carried out under the nitrogen atmosphere. The preparation method provided by the invention has the advantages of stable reaction and high production efficiency, and the prepared phenol-formaldehyde resin has low residual phenol and gardner chromaticity and controllable ortho-position content.
Description
Technical Field
The invention belongs to the technical field of phenolic resin preparation, and particularly relates to a preparation method of phenol-formaldehyde resin and a product obtained by the preparation method.
Background
The phenol novolac epoxy resin is a light brown yellow viscous liquid, phenol and formaldehyde are subjected to polycondensation reaction in an acid medium to obtain novolac resin, and then the novolac resin and excessive propylene oxide are subjected to polycondensation reaction in the presence of sodium hydroxide to obtain the phenolic novolac epoxy resin. Because the molecular structure contains more epoxy groups and aromatic nuclei, the crosslinking density of the cured product is very high, and the heat resistance and chemical resistance of the product are very good, the cured product has wide application in the fields of electronic packaging, copper-clad plates, rubber and other electronic and electrical appliances.
In the aspect of phenolic resin injection molding process, the ideal injection molding material has the characteristics of good fluidity in a barrel and rapid solidification and molding in a mold. The injection molding material with the characteristic of rapid solidification can reduce the molding time and improve the production efficiency. Phenol-formaldehyde resins are used as tackifying and reinforcing resins in rubber compounding formulations, but the relatively slow cure speed and relatively high heat generation of phenol-formaldehyde resins can affect the adhesion of tire cord to rubber. The high ortho phenolic resin has the characteristics of high polymerization speed and lower softening point, and can be cured at a lower temperature. Thus, the properties of the high ortho phenolic resin meet this requirement exactly.
Currently, high ortho phenolic resins are prepared primarily by reaction in the presence of catalysts such as oxides, hydroxides or organic acid salts of divalent metal ions such as calcium, magnesium, zinc, strontium, cadmium, lead and barium. However, the divalent metal weak acid salt catalyst has lower catalytic efficiency, unstable reaction process and easy gelation after high-temperature dehydration Shi Shuzhi.
Disclosure of Invention
The invention provides a preparation method of phenol-formaldehyde resin, which has the advantages of stable reaction, difficult gel generation, high production efficiency, low residual phenol and gardner chromaticity of the prepared phenol-formaldehyde resin and controllable ortho-position content.
In order to achieve the above purpose, the invention provides a preparation method of phenol-formaldehyde resin, comprising the following steps:
1) Mixing phenol, formaldehyde and water to obtain a transparent solution;
2) Mixing the transparent solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a first reaction solution;
3) Mixing the first reaction solution with heteropoly acid, and reacting to obtain phenol formaldehyde resin;
4) Dehydrating and dephenolizing the phenol formaldehyde resin to obtain phenol formaldehyde resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere.
Preferably, the temperature during mixing in the step 1) is 40-60 ℃; the molar ratio of formaldehyde to phenol is 1:0.3-0.7; the molar ratio of the water to the phenol is 1:0.5-1.2.
Preferably, the formaldehyde is paraformaldehyde or an aqueous formaldehyde solution.
Preferably, the organic acid in the step 2) is added in batches, and the organic acid is one or more of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid; the addition amount of the organic acid is 0.1-1.0% of the molar amount of phenol.
Preferably, the heteropolyacid salt in the step 2) is added in batches, wherein the heteropolyacid salt is 1-butyl-3-methylimidazole phosphotungstenate, brominated 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propylpyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphotungstenate, brominated 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfonic group) propyl pyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphomolybdate, brominated 1- (3-sulfonic group) propyl-3-methylimidazole phosphomolybdenate, 1-butyl-3-methylimidazole phosphomolybdenate, brominated 1-methylimidazole-3-methylimidazole phosphomolybdate, 1- (3-sulfonic group) propyl-pyridine phosphomolybdenate, or one or more of 1- (3-sulfonic group) propylmolybdic acid groups; the addition amount of the heteropolyacid salt is 5-20% of the molar amount of phenol.
Preferably, the temperature of the stirring reaction in the step 2) is 60-100 ℃ and the time is 1-3 h.
Preferably, the heteropolyacid in the step 3) is added in batches, and the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1% -1.0% of the molar amount of phenol.
Preferably, the temperature of the reaction in the step 3) is 60-100 ℃ and the time is 0.5-1.5 h.
Preferably, the step 4) adopts a high-temperature and high-pressure mode to carry out dehydration and dephenolization; the pressure during dehydration is 10-20 KPa, and the temperature is 100-140 ℃; the pressure during dephenolization is 0.1-10 Kpa, and the temperature is 150-200 ℃.
The invention also provides the phenol-formaldehyde resin prepared by the method according to any one of the above, wherein the ortho-position content of the phenol-formaldehyde resin is 25-95%, and the residual phenol is less than or equal to 1000ppm; the gardner color is less than or equal to 1.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) According to the invention, the organic acid and the heteropolyacid salt are selected as catalysts in the initial stage of the reaction, so that the catalytic capability is weak, the reaction is eased, and the resin is prevented from being crosslinked by violent heat release in the initial stage of the reaction; the heteropolyacid is selected as a catalyst in the middle reaction period, so that the catalyst has high hydrogen dissociation capability and high catalytic capability, the polycondensation reaction rate can be further improved effectively, the conversion rate and the yield of o-cresol are improved, the reaction period is shortened, and the production cost is reduced.
(2) The catalyst heteropolyacid salt and the organic acid are used in a compound way, and phenol-formaldehyde resins with different ortho-position contents are prepared through the polycondensation reaction of phenol formaldehyde under the action of hetero atoms with higher activity and obvious positioning effect.
(3) The phenol-formaldehyde resin prepared by the invention has controllable ortho-para position content, low residual phenol content and low chromaticity.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of phenol-formaldehyde resin, which comprises the following steps:
1) Mixing phenol, formaldehyde and water to obtain a transparent solution;
2) Mixing the transparent solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a first reaction solution;
3) Mixing the first reaction solution with heteropoly acid, and reacting to obtain phenol formaldehyde resin;
4) Dehydrating and dephenolizing the phenol formaldehyde resin to obtain phenol formaldehyde resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere.
The invention mixes phenol, formaldehyde and water to obtain transparent solution. In the present invention, the molar ratio of formaldehyde to phenol is 1:0.3 to 0.7, more preferably 1:0.4 to 0.6, most preferably 1:0.5. In the present invention, the molar ratio of water to phenol is preferably 1:0.5 to 1.2, more preferably 1:1.1. In the present invention, the temperature of the mixing is preferably 40 to 60 ℃. In the present invention, the formaldehyde is preferably formaldehyde or paraformaldehyde.
After obtaining a transparent solution, the invention mixes the transparent solution with organic acid and heteropolyacid salt, and carries out stirring reaction to obtain a first reaction solution. In the present invention, the amount of the organic acid added is preferably 0.1 to 1.0%, more preferably 0.2 to 0.6%, and most preferably 0.3 to 0.5% of the molar amount of phenol. 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 addition amount of the heteropolyacid salt is preferably 5 to 20% by mole of phenol, more preferably 6 to 15% by mole, and most preferably 8 to 10% by mole. In the present invention, the heteropolyacid salt is preferably 1-butyl-3-methylimidazole phosphotungstic acid salt, brominated 1-butyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propylpyridinium phosphotungstic acid salt, 1-butyl-3-methylimidazole phosphomolybdic acid salt, brominated 1-butyl-3-methylimidazole phosphotungstic acid salt, 1- (3-sulfonate) propyl pyridinium phosphomolybdic acid salt, 1-butyl-3-methylimidazole phosphomolybdic acid salt, brominated 1-butyl-3-methylimidazole phosphomolybdic acid salt, 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylsulfolyimidazololytungstic acid salt, 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylimidazole base-3-methyl) and 1-3-methylimidazole phosphotungstic acid salt, 1-3-methylimidazole base-3-methyl phosphotungstic acid salt, or more preferably 1-3-methylimidazole phosphotungstic acid salt 1- (3-sulfonate) propyl-3-methylimidazole phosphotungstic heteropolyacid salt, 1- (3-sulfonate) propyl pyridine phosphotungstic heteropolyacid salt, most preferably 1-butyl-3-methylimidazole phosphotungstic heteropolyacid salt. The heteropolyacid salt is preferably added in portions.
In the present invention, the temperature of the stirring reaction is preferably 60 to 100℃and the time is preferably 1 to 3 hours.
After the first reaction liquid is obtained, the first reaction liquid and the heteropoly acid are mixed for reaction to obtain the phenol formaldehyde resin. 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, most preferably phosphotungstic acid. In the present invention, the addition amount of the heteropoly acid is preferably 0.1 to 1.0%, more preferably 0.2 to 0.6%, most preferably 0.3 to 0.5% of the molar amount of phenol. The heteropolyacid is preferably added in portions. In the present invention, the temperature of the reaction is preferably 60 to 100 ℃, more preferably 70 to 90 ℃; the time is preferably 0.5 to 1.5 hours, more preferably 0.8 to 1 hour.
After obtaining phenol formaldehyde resin, the invention carries out dehydration and dephenolization treatment on the phenol formaldehyde resin to obtain phenol formaldehyde resin. In the present invention, dehydration and dephenolization are preferably carried out by means of high temperature and high pressure; the pressure during dehydration is preferably 10 to 20KPa, more preferably 12 to 15KPa; the temperature at the time of dehydration is preferably 100 to 140 ℃, more preferably 110 to 130 ℃. The pressure during the dephenolization is preferably 0.1 to 10KPa, more preferably 1 to 5MPa; the temperature at the time of dephenolization is preferably 150 to 200℃and more preferably 170 to 180 ℃.
In the invention, heteropolyacid salt and organic acid are used as catalysts in a compound way, and under the action of hetero atoms with higher activity and obvious positioning effect, the ortho-o-cresol formaldehyde resin with different contents is prepared through the polycondensation reaction of phenolic aldehyde. Meanwhile, the organic acid and the heteropolyacid salt are compounded to be used as a catalyst, so that the catalytic capability is weak, the reaction is mild, and the resin is prevented from being crosslinked by violent heat release in the initial stage of the reaction. And then, heteropolyacid is selected as a catalyst in the middle reaction period, so that the catalyst has high hydrogen dissociation capability and high catalytic capability, the polycondensation reaction rate can be effectively further improved, and the conversion rate and the yield of o-cresol are improved. Shortens the reaction period and reduces the production cost. Meanwhile, the phenol-formaldehyde resin prepared by the method has the advantages of controllable ortho-para content, controllable softening point and low chromaticity.
The invention controls the content of ortho-para position of phenol-formaldehyde resin by the type and the addition amount of heteropolyacid salt, and the reaction mechanism for synthesizing the ortho-controllable phenol-formaldehyde resin is as follows: the mixed catalysis system of heteropolyacid salt and organic acid is selected, the heteropolyacid salt provides weak acid reaction environment, the difference of electrophilic substitution degree of hydroxyl (OH) at ortho position and para position on phenol ring is highlighted, hetero atoms (such as P, si, fe, co and the like) and multi-atoms (such as Mo, W, V, nb, ta and the like) with ortho position guiding function are selected in the synthesis process, formaldehyde can be subjected to addition reaction with ortho position of phenol preferentially to form an unstable chelate, one hydroxyl group and hetero atom are removed, the multi-atoms continue to be subjected to polycondensation reaction with phenol to form bisphenol-based methane with ortho position connection and high activity, and simultaneously the types and the content of the hetero atoms are controlled, so that phenol-formaldehyde resin with different ortho position contents is formed after the reaction with formaldehyde.
The invention also provides the phenol-formaldehyde resin prepared by the method according to any one of the above, wherein the ortho-position content of the phenol-formaldehyde resin is 25-95%, and the residual phenol is less than or equal to 1000ppm; the gardner color is less than or equal to 1.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
S1, under the nitrogen atmosphere, the molar ratio is 0.5:1:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 75 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.3% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the phenol molar mass of 5% into 4 batches, and stirring and reacting for 2 hours after the addition is finished;
s3, adding 0.2% of phosphotungstic acid in phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 1 hour at 95 ℃;
s4, dehydrating the solution obtained in the step 3) at 110 ℃ and under the pressure of 20KPa, heating to 180 ℃, and removing phenol at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Example 2
S1, under the nitrogen atmosphere, the molar ratio is 1.2:1.8:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 40 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the phenol molar mass of 0.3% and a 1-butyl-3-methylimidazole phosphotungstic acid salt catalyst with the phenol molar mass of 8% into 5 batches, and stirring and reacting for 3 hours after the addition is finished;
s3, adding 0.1% phosphomolybdic acid in phenol molar mass into the reaction solution in the step 2) in a nitrogen atmosphere, and reacting for 1.5 hours at 85 ℃;
s4, dehydrating the solution obtained in the step 3) at 120 ℃ under the pressure of 15KPa, heating to 190 ℃, and removing phenol under the pressure of 10KPa to obtain the phenol-formaldehyde resin.
Example 3
S1, under the nitrogen atmosphere, the molar ratio is 0.65:2:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 40 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 80 ℃ in a nitrogen atmosphere, stirring and dissolving completely, and adding oxalic acid with 0.7% of phenol molar mass and 1- (3-sulfonic) propyl phosphotungstic acid salt catalyst with 10% of phenol molar mass into 5 batches, and stirring and reacting for 1 hour after the addition is finished;
s3, adding 0.3% of phosphotungstic acid with phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and then reacting for 0.5 hours at 100 ℃;
s4, dehydrating the solution obtained in the step 3) at 120 ℃ and under the pressure of 20KPa, heating to 200 ℃, and removing phenol at the pressure of 5KPa to obtain the phenol-formaldehyde resin.
Example 4
S1, under the nitrogen atmosphere, the molar ratio is 0.6:0.90:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 40 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the phenol molar mass of 0.6% and a brominated 1-butyl-3-methylimidazole silicon molybdenum heteropolyacid salt catalyst with the phenol molar mass of 12% into 4 batches, and stirring and reacting for 2 hours after the addition is finished;
s3, adding 0.3% of silicotungstic acid with phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 1 hour at 90 ℃;
s4, dehydrating the solution obtained in the step 3) at 110 ℃ under the pressure of 10KPa, heating to 200 ℃, and removing phenol under the pressure of 10KPa to obtain the phenol-formaldehyde resin.
Example 5
S1, under the nitrogen atmosphere, the molar ratio is 0.5:1:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 75 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.3% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the phenol molar mass of 8% into 4 batches, and stirring and reacting for 2 hours after the addition is finished;
s3, adding 0.2% of phosphotungstic acid in phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 1 hour at 95 ℃;
s4, dehydrating the solution obtained in the step 3) at 110 ℃ and under the pressure of 20KPa, heating to 180 ℃, and removing phenol at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Example 6
S1, under the nitrogen atmosphere, the molar ratio is 0.5:1:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 75 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.3% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the phenol molar mass of 12% into 4 batches, and stirring and reacting for 2 hours after the addition is finished;
s3, adding 0.2% of phosphotungstic acid in phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 1 hour at 95 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 110 ℃ and the pressure of 20KPa, heating to 180 ℃, and carrying out reduced pressure dephenolization at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Comparative example 1
S1, under the nitrogen atmosphere, the molar ratio is 0.55:0.80:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 40 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding oxalic acid with the phenol molar mass of 0.6% in 4 batches, and stirring and reacting for 3 hours after the adding is completed;
s3, adding 0.5% of phosphotungstic acid in phenol molar mass into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 2 hours at 90 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 110 ℃ and the pressure of 20KPa, heating to 200 ℃, and carrying out reduced pressure dephenolization at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Comparative example 2
S1, under the nitrogen atmosphere, the molar ratio is 0.60:0.90:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with 0.4% of phenol molar mass in 4 batches, and stirring and reacting for 5 hours after the addition is completed;
s3, adding oxalic acid with the molar mass of 0.8% of phenol into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 4 hours at the temperature of 85 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 105 ℃ and the pressure of 20KPa, then heating to 190 ℃, and carrying out reduced pressure dephenolization at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Comparative example 3
S1, under the nitrogen atmosphere, the molar ratio is 0.45:0.76:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 75 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.3% and a 1-butyl-3-methylimidazole phosphotungstic heteropoly acid salt catalyst with the phenol molar mass of 5% into 4 batches, and stirring and reacting for 2 hours after the addition is finished;
s3, adding oxalic acid with the molar mass of 0.2% of phenol into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 1 hour at 95 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 110 ℃ and the pressure of 20KPa, then heating to 180 ℃, and carrying out reduced pressure dephenolization at the pressure of 10KPa to obtain phenolic resins with different ortho-position contents.
Comparative example 4
S1, under the nitrogen atmosphere, the molar ratio is 0.60:0.90:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.2% in 4 batches, and stirring and reacting for 5 hours after the addition is finished;
s3, adding oxalic acid with the molar mass of 0.8% of phenol into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 4 hours at the temperature of 85 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 105 ℃ and the pressure of 20KPa, then heating to 190 ℃, and carrying out reduced pressure dephenolization at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
Comparative example 5
S1, under the nitrogen atmosphere, the molar ratio is 0.60:0.90:1, adding phenol, paraformaldehyde and pure water into a reaction kettle in proportion, and stirring for 60min at 50 ℃ to obtain a transparent solution;
s2, heating the solution obtained in the step 1) to 70 ℃ in a nitrogen atmosphere, stirring and dissolving completely, adding acetic acid with the phenol molar mass of 0.8% in 4 batches, and stirring and reacting for 5 hours after the addition is finished;
s3, adding oxalic acid with the molar mass of 0.8% of phenol into the reaction liquid in the step 2) in a nitrogen atmosphere, and reacting for 4 hours at the temperature of 85 ℃;
s4, carrying out reduced pressure dehydration on the solution obtained in the step 3) at 105 ℃ and the pressure of 20KPa, then heating to 190 ℃, and carrying out reduced pressure dephenolization at the pressure of 1KPa to obtain the phenol-formaldehyde resin.
The phenol-formaldehyde resins prepared in examples 1 to 6 and comparative examples 1 to 5 were tested for softening point, ortho-para content, residual phenol and chromaticity according to the corresponding test standards and methods, and the specific test results are shown in table 1.
TABLE 1 detection results of phenol novolac resins
As can be seen from Table 1, the ortho-position ratio of the phenol-formaldehyde resins prepared in examples 1 to 6 is 25-95%, the residual phenol is less than or equal to 1000ppm, the chromaticity is less than or equal to 1, and the softening point meets the design requirements.
The operations of examples 1, 5 to 6 and comparative examples 2, 4 to 5 were repeated 3 times, and the specific detection results are shown in Table 2.
TABLE 2 detection of phenol novolac resins
As can be seen from Table 2, the method provided by the invention has stable reaction products, and the ortho-para content in each batch of phenol-formaldehyde resin is almost unchanged. Meanwhile, as can be seen from comparison of examples 1 and 5 to 6, the ortho-position content in the phenol-formaldehyde resin gradually increases with the increase of the use amount of the heteropolyacid salt, and the regular change is shown, while the regular change is not shown in comparative examples 2 and 4 to 5. According to the technical scheme provided by the application, the content of the ortho-para position in the phenol-formaldehyde resin can be controlled according to the dosage of heteropolyacid salt, and further production can be carried out according to the performance requirements of actual products. The specific method for controlling the adjacent position is as follows: by adopting the technical scheme provided by the application, the specific reaction raw materials, heteropolyacid salt, heteropolyacid and raw material dosage are determined before preparation, specific reaction conditions and processes are carried out, small batch tests are carried out firstly, the ortho-para content in the obtained phenol-formaldehyde resin is determined, then the dosage of heteropolyacid salt is adjusted according to the ortho-para content in the product, the tests are carried out again, so that the phenol-formaldehyde resin with the target ortho-para content is obtained, and industrial production can be carried out.
Wherein: the ortho-para content, residual phenol, softening point and chromaticity of the phenol-formaldehyde resin were tested as follows:
1. checking of ortho-para content
1.1 test device
Agilent gas chromatography
1.2 sample
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the acetonitrile, covering a cover, shaking uniformly, and measuring.
1.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D.x 250mm x 5um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, UV detector (wavelength 275 nm), column temperature of 30deg.C, and sample injection amount of 20ul;
2) After the liquid chromatography baseline is stable, sampling is performed for detection;
3) And calculating according to the peak area in the spectrogram, and recording the test result into a test report.
2. Examination of phenol content
2.1 test device
Agilent gas chromatography
2.2 sample
Weighing 0.1-1mg of resin, adding about 20g of acetonitrile, recording the accurate mass of the acetonitrile, covering a cover, shaking uniformly, and measuring.
2.3 test procedure and test results
1) Setting liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D.x 250mm x 5um), flow rate of 0.7mL/min, mobile phase of water and acetonitrile, UV detector (wavelength 275 nm), column temperature of 30deg.C, and sample injection amount of 20ul;
2) After the liquid chromatography baseline is stable, sampling is performed for detection;
3) And calculating the peak area of the residual phenol, and recording the test result into a test report after comparing the peak area with an internal standard curve.
3. Chromaticity of
3.1 according to the standard
The epoxy resin was tested according to GBT12007.1-1989 epoxy resin color measurement method.
3.2 test instruments
1) Nashi cuvette 25ml
2) Analytical balance
3) Volumetric flask 25ml, 100ml
4) Pipette with a pipette tip
3.3 test procedure
1) Preparing a gardner color code solution 1-16 according to the standard;
2) 4 parts by mass of epoxy resin are dissolved in 6 parts by mass of acetone;
3) And (3) introducing the prepared solution into a colorimetric tube, and comparing the prepared solution with the prepared gardner color code, wherein the color is close to the chromaticity.
4) And completing the test report according to the test result.
4. Softening Point test
4.1 according to the standard
The epoxy resin was tested according to GB/T12007.6-1989 method for determining the softening point of epoxy resin.
4.2 test instruments
1) Asphalt softening point tester
4.3 test procedure
1) Introducing the molten resin into a sample ring to make the liquid level of the resin higher than that of the ring, cooling, and then scraping by a heating knife;
2) And (3) placing the sample ring into an asphalt softening point instrument, wherein a heating medium is glycerin, and the heating rate is set to be 5 ℃/min until the temperature of the steel ball falling to a lower bottom plate after resin softening is the softening point.
3) And completing the test report according to the test result.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The preparation method of the phenol-formaldehyde resin is characterized by comprising the following steps:
1) Mixing phenol, formaldehyde and water to obtain a transparent solution;
2) Mixing the transparent solution with organic acid and heteropolyacid salt, and stirring for reaction to obtain a first reaction solution;
3) Mixing the first reaction solution with heteropoly acid, and reacting to obtain phenol formaldehyde resin;
4) Dehydrating and dephenolizing the phenol formaldehyde resin to obtain phenol formaldehyde resin;
the steps 1) to 3) are all carried out under the nitrogen atmosphere;
the temperature in the mixing in the step 1) is 40-60 ℃; the molar ratio of formaldehyde to phenol is 1:0.3-0.7; the molar ratio of the water to the phenol is 1:0.5-1.2;
the heteropolyacid salt in the step 2) is added in batches, and the heteropolyacid salt is one or more of 1-butyl-3-methylimidazole phosphotungstenate, 1- (3-sulfo) propyl-3-methylimidazole phosphotungstenate, 1- (3-sulfo) propylpyridine phosphotungstenate, 1-butyl-3-methylimidazole phosphomolybdate, 1- (3-sulfo) propyl-3-methylimidazole phosphomolybdate, 1- (3-sulfo) propylpyridine phosphomolybdenate, 1-butyl-3-methylimidazole phosphomolybdenate, 1- (3-sulfo) propyl-3-methylimidazole phosphomolybdenate and 1- (3-sulfo) propylpyridine phosphomolybdenate; the addition amount of the heteropolyacid salt is 5% -20% of the molar amount of phenol;
the temperature of the stirring reaction in the step 2) is 60-100 ℃ and the time is 1-3 h;
the heteropolyacid in the step 3) is added in batches, and the heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid; the addition amount of the heteropoly acid is 0.1% -1.0% of the molar amount of phenol;
the reaction temperature in the step 3) is 60-100 ℃ and the reaction time is 0.5-1.5 h.
2. The method according to claim 1, wherein the formaldehyde is paraformaldehyde or an aqueous formaldehyde solution.
3. The method according to claim 1, wherein the organic acid in step 2) is added in portions, and the organic acid is one or more of formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid; the addition amount of the organic acid is 0.1% -1.0% of the molar amount of phenol.
4. The method according to claim 1, wherein the dehydration and dephenolization are performed in step 4) at high temperature and high pressure; the pressure during dehydration is 10-20 KPa, and the temperature is 100-140 ℃; the pressure during dephenolization is 0.1-10 KPa, and the temperature is 150-200 ℃.
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| JPS55155013A (en) * | 1979-05-21 | 1980-12-03 | Sumitomo Bakelite Co Ltd | Preparation of quick-curing phenol resin |
| DE3525072A1 (en) * | 1985-07-13 | 1987-01-22 | Basf Ag | METHOD FOR THE PRODUCTION OF O, O'-METHYLENETHER LINKED PHENOLIC RESIN AND THE USE THEREOF |
| JP3808542B2 (en) * | 1996-06-26 | 2006-08-16 | ジャパンエポキシレジン株式会社 | NOVEL POLYPHENOL COMPOUND AND PROCESS FOR PRODUCING THE SAME |
| JPH11302350A (en) * | 1998-04-24 | 1999-11-02 | Sumitomo Bakelite Co Ltd | Production of phenolic resin |
| US6936680B2 (en) * | 2000-12-12 | 2005-08-30 | Chang Chun Plastics Co., Ltd. | Method of producing novolak resin |
| JP2007100028A (en) * | 2005-10-07 | 2007-04-19 | Sumitomo Bakelite Co Ltd | Method for producing novolak-type phenol resin |
| JP2008106219A (en) * | 2006-03-29 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
| CN101619125A (en) * | 2009-07-28 | 2010-01-06 | 陕西师范大学 | Dual catalyst system thermoplastic phenolic resin preparation method and application for preparing coated sand thereof |
| CN102850496B (en) * | 2012-03-21 | 2015-03-11 | 山东圣泉化工股份有限公司 | High-ortho phenolic resin and preparation method thereof |
| CN102643170A (en) * | 2012-05-09 | 2012-08-22 | 河北工业大学 | Method for synthesizing para-tert-butylcatechol by using acid-mixed mixed system containing ionic liquid |
| CN103084213B (en) * | 2012-11-16 | 2015-02-25 | 湖南长岭石化科技开发有限公司 | Catalyst for synthesizing 2,6-xylenol as well as preparation method of catalyst and method for synthesizing 2,6-xylenol |
| CN104140361B (en) * | 2014-06-30 | 2015-09-23 | 湘潭大学 | A kind of phospho-wolframic acid imidazole salts catalyzes and synthesizes the method for Bisphenol F |
| CN107353377A (en) * | 2017-08-09 | 2017-11-17 | 山东圣泉新材料股份有限公司 | A kind of phenolic resin and preparation method thereof |
| CN107383294B (en) * | 2017-09-04 | 2019-05-07 | 江苏三吉利化工股份有限公司 | A kind of two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin |
| CN108440730A (en) * | 2018-04-13 | 2018-08-24 | 圣戈莱（北京）科技有限公司 | A kind of polishing purification method of casting high quality phenolic resin |
| EP3851493A1 (en) * | 2020-01-15 | 2021-07-21 | Hexion GmbH | Composition comprising a novolak |
| CN115124671B (en) * | 2022-07-15 | 2023-04-25 | 东营市赫邦化工有限公司 | Preparation method of phenol-formaldehyde resin and product obtained by preparation method |
| CN115109212B (en) * | 2022-07-15 | 2023-10-13 | 东营市赫邦化工有限公司 | Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin |
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Denomination of invention: A preparation method of phenol formaldehyde resin and its resulting product Effective date of registration: 20231204 Granted publication date: 20230425 Pledgee: Yantai Bank Co.,Ltd. Dongying Branch Pledgor: DONGYING HEBANG CHEMICAL CO.,LTD. Registration number: Y2023980069282 |