WO2024011789A1 - Preparation method for phenol phenolic resin and product obtained thereby - Google Patents
Preparation method for phenol phenolic resin and product obtained thereby Download PDFInfo
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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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- WIPO (PCT)
- Prior art keywords
- phenol
- acid
- salt
- heteropoly
- heteropoly acid
- Prior art date
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 257
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 30
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 title abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 86
- 239000011964 heteropoly acid Chemical class 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 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
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 64
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- 229920003986 novolac Polymers 0.000 claims description 37
- 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 17
- 238000000034 method Methods 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims description 14
- -1 poly salt bromide Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 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
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 8
- OIALIKXMLIAOSN-UHFFFAOYSA-N 2-Propylpyridine Chemical compound CCCC1=CC=CC=N1 OIALIKXMLIAOSN-UHFFFAOYSA-N 0.000 claims description 8
- 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
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical group CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 6
- 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
- HSNVNALJRSJDHT-UHFFFAOYSA-N P(=O)(=O)[Mo] Chemical compound P(=O)(=O)[Mo] HSNVNALJRSJDHT-UHFFFAOYSA-N 0.000 claims description 5
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 claims 1
- CRTKBIFIDSNKCN-UHFFFAOYSA-N 1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1 CRTKBIFIDSNKCN-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229940102396 methyl bromide Drugs 0.000 claims 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N methyl bromide Substances BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003197 catalytic effect 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
- 230000000694 effects Effects 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000005684 electric field Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000001879 gelation Methods 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
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004413 injection moulding compound Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 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
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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Abstract
A preparation method for phenol phenolic resin and a product obtained thereby, belonging to the technical field of preparation of phenolic resin. The preparation method for phenol phenolic resin comprises the following steps: 1) mixing phenol, formaldehyde and water to obtain a transparent solution; 2) mixing the transparent solution with an organic acid and a heteropoly acid salt, and carrying out a reaction with stirring to obtain a first reaction solution; 3) mixing the first reaction solution with a heteropoly acid, and carrying out a reaction to obtain phenol formaldehyde resin; and 4) carrying out dehydration and dephenolization treatment on the phenol formaldehyde resin to obtain phenol phenolic resin. The steps 1)-3) are all carried out in a nitrogen atmosphere.
Description
本申请要求在2022年07月15日提交中国专利局、申请号为202210830296.4、申请名称为“一种苯酚酚醛树脂的制备方法及其所得产品”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims priority to the Chinese patent application submitted to the China Patent Office on July 15, 2022, with the application number 202210830296.4 and the application title "A preparation method of phenol novolac resin and the resulting product", the entire content of which is incorporated by reference. incorporated in this application.
本申请属于酚醛树脂制备技术领域,尤其涉及一种苯酚酚醛树脂的制备方法及其所得产品。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.
苯酚酚醛环氧树脂是一种浅棕黄色黏稠液体,在酸性介质中苯酚与甲醛进行缩聚反应得到线型酚醛树脂,再与过量环氧丙烷在氢氧化钠存在下进行缩聚反应制得。由于分子结构中含有较多环氧基及芳香核,固化产物交联密度很高,产品的耐热性,耐化学药品性非常优良,因而在电子封装、覆铜板、橡胶等电子电器领域获得了广泛的应用。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.
在酚醛树脂注塑料工艺方面,理想的注塑料应该具有在机桶中具有较好的流动性,而在模具中又能快速固化成型的特点。具有快速固化特性的注塑料可减少成型时间,提高生产效率。苯酚酚醛树脂在橡胶复合配方中用作增粘和增强树脂,但是苯酚酚醛树脂相对慢的固化速度和相对高的产热会影响轮胎帘布与橡胶的粘合。高邻位酚醛树脂的最大特点就是聚合速度快,具有软化点比较低的特点,在较低温度下就可实现固化。因此,高邻位酚醛树脂的特性正好满足这一要求。In terms of the phenolic resin injection molding process, 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.
目前,高邻位酚醛树脂的制备主要是在催化剂(如二价金属离子如钙、镁、锌、锶、镉、铅和钡的氧化物、氢氧化物或有机酸盐)存在下进行反应 的。但是,该类二价金属弱酸盐催化剂的催化效率比较低,且反应过程不稳定,高温脱水时树脂易凝胶。At present, 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). . However, 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.
发明内容Contents of the invention
为了解决现有技术中存在的以上至少一个不足之处,本申请实施例的一方面提供了一种苯酚酚醛树脂的制备方法,包括如下步骤:In order to solve at least one of the above shortcomings in the prior art, one aspect of the embodiments of the present application provides a method for preparing phenol novolac resin, including the following steps:
1)将苯酚、甲醛和水混合,得到透明溶液;1) Mix phenol, formaldehyde and water to obtain a transparent solution;
2)将所述透明溶液与有机酸和杂多酸盐混合,进行搅拌反应,得到第一反应液;2) Mix the transparent solution with an organic acid and a heteropolyacid salt, and perform a stirring reaction to obtain a first reaction solution;
3)将第一反应液和杂多酸混合,进行反应,得到苯酚甲醛树脂;3) Mix the first reaction solution and the heteropoly acid to react to obtain a phenol formaldehyde resin;
4)将所述苯酚甲醛树脂进行脱水和脱苯酚处理,得到苯酚酚醛树脂;4) The phenol-formaldehyde resin is dehydrated and dephenolized to obtain a phenol-formaldehyde resin;
所述步骤1)~3)均在氮气氛围下进行。The steps 1) to 3) are all performed under nitrogen atmosphere.
在本申请的一些实施例中,所述步骤1)中混合时的温度为40~60℃;所述甲醛与苯酚的摩尔比为1:(0.3~0.7);所述水和苯酚的摩尔比为1:(0.5~1.2)。In some embodiments of the present application, 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).
在本申请的一些实施例中,所述甲醛为多聚甲醛或甲醛水溶液。In some embodiments of the present application, the formaldehyde is paraformaldehyde or an aqueous formaldehyde solution.
在本申请的一些实施例中,所述步骤2)中有机酸分批加入,所述有机酸为草酸、甲酸、乙酸、丁酸、苯甲酸和乙二酸中的一种或多种;所述有机酸的加入量为苯酚摩尔量的0.1%~1.0%。In some embodiments of the present application, 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.
在本申请的一些实施例中,所述步骤2)中杂多酸盐分批加入,所述杂多酸盐为1-丁基-3-甲基咪唑磷钨杂多酸盐、溴化1-丁基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基吡啶磷钨杂多酸盐、1-丁基-3-甲基咪唑硅钨杂多酸盐、溴化1-丁基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基吡啶硅钨杂多酸盐、1-丁基-3-甲基咪唑磷钼杂多酸盐、溴化1-丁基-3-甲基咪唑磷 钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钼杂多酸盐、1-(3-磺酸基)丙基吡啶磷钼杂多酸盐、1-丁基-3-甲基咪唑硅钼杂多酸盐、溴化1-丁基-3-甲基咪唑硅钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钼杂多酸盐、1-(3-磺酸基)丙基吡啶硅钼杂多酸盐中的一种或几种;所述杂多酸盐的加入量为苯酚摩尔量的5%~20%。In some embodiments of the present application, in step 2), 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 phosphomolybdenum Heteropoly acid salt, 1-butyl-3-methylimidazolium phosphomolybdenum heteropoly acid salt, bromide, 1-(3-sulfonate)propyl-3-methylimidazolium phosphomolybdenum heteropoly acid salt, 1- (3-Sulfonate)propylpyridinium phosphomolybdenum heteropoly acid salt, 1-butyl-3-methylimidazole silicomolybdenum heteropoly acid salt, 1-butyl-3-methylimidazole silicomolybdenum heteropoly acid bromide One of acid salt, 1-(3-sulfonate)propyl-3-methylimidazole silicomolybdate heteropoly acid salt, 1-(3-sulfonate)propylpyridine silicomolybdate heteropoly acid salt, or Several; the addition amount of the heteropolyacid salt is 5% to 20% of the molar amount of phenol.
在本申请的一些实施例中,所述步骤2)中搅拌反应的温度为60~100℃,时间为1~3h。In some embodiments of the present application, the temperature of the stirring reaction in step 2) is 60-100°C, and the time is 1-3 hours.
在本申请的一些实施例中,所述步骤3)中杂多酸分批加入,所述杂多酸为磷钨酸、硅钨酸、磷钼酸和硅钼酸中的一种或多种;所述杂多酸的加入量为苯酚摩尔量的0.1%~1.0%。In some embodiments of the present application, 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.
在本申请的一些实施例中,所述步骤3)中反应的温度为60~100℃,时间为0.5~1.5h。In some embodiments of the present application, the reaction temperature in step 3) is 60-100°C, and the reaction time is 0.5-1.5h.
在本申请的一些实施例中,所述步骤4)中采用高温高压的方式进行脱水和脱苯酚;所述脱水时的压力为10~20KPa,温度为100~140℃;所述脱苯酚时的压力为0.1~10Kpa,温度为150~200℃。In some embodiments of the present application, in 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℃.
本申请实施例的另一方面还提供了一种上述任意一项所述的方法制备得到的苯酚酚醛树脂,所述苯酚酚醛树脂的邻位含量为25~95%,残留酚≤1000ppm;加德纳色度≤1。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.
与现有技术相比,本申请的优点和积极效果在于:Compared with the existing technology, the advantages and positive effects of this application are:
(1)本申请至少一个实施例所提供的制备方法,反应稳定,不易产生凝胶,生产效率高,且制备得到的苯酚酚醛树脂残留酚及加德纳色度低,邻位含量可控。(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.
(2)本申请至少一个实施例所提供的制备方法,通过在反应初期选用有 机酸和杂多酸盐作为催化剂,催化能力较弱,使反应缓和,避免反应初期剧烈放热使树脂交联;在反应中期选用杂多酸做催化剂,氢离解能力大,催化能力较强,可有效进一步提高缩聚反应速率,提高邻甲酚的转化率以及产率,缩短反应周期,降低生产成本。(2) 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; In the middle stage of the reaction, 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.
(3)本申请至少一个实施例所提供的制备方法,将催化剂杂多酸盐和有机酸复合使用,在活性较高而且定位效果明显的杂原子作用下,通过酚醛的缩聚反应,制备出不同邻位含量的苯酚酚醛树脂。(3) 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.
(4)本申请至少一个实施例制备得到的苯酚酚醛树脂,邻对位含量可控、残留酚含量低、色度低。(4) 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.
下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.
本申请实施例提供了一种苯酚酚醛树脂的制备方法,包括如下步骤:The embodiments of the present application provide a method for preparing phenol novolac resin, which includes the following steps:
1)将苯酚、甲醛和水混合,得到透明溶液;1) Mix phenol, formaldehyde and water to obtain a transparent solution;
2)将所述透明溶液与有机酸和杂多酸盐混合,进行搅拌反应,得到第一反应液;2) Mix the transparent solution with an organic acid and a heteropolyacid salt, and perform a stirring reaction to obtain a first reaction solution;
3)将第一反应液和杂多酸混合,进行反应,得到苯酚甲醛树脂;3) Mix the first reaction solution and the heteropoly acid to react to obtain a phenol formaldehyde resin;
4)将所述苯酚甲醛树脂进行脱水和脱苯酚处理,得到苯酚酚醛树脂;4) The phenol-formaldehyde resin is dehydrated and dephenolized to obtain a phenol-formaldehyde resin;
所述步骤1)~3)均在氮气氛围下进行。The steps 1) to 3) are all performed under nitrogen atmosphere.
本申请实施例将苯酚、甲醛和水混合,得到透明溶液。在一些实施例中,所述甲醛与苯酚的摩尔比为1:(0.3~0.7),可选地为1:(0.4~0.6),进一步可选地为1:0.5。在一些实施例中,所述水和苯酚的摩尔比为1:(0.5~1.2),可选地为1:1.1。在一些实施例中,所述混合的温度为40~60℃。在一些实施例中, 所述甲醛可选地为甲醛或多聚甲醛。In the embodiment of this application, phenol, formaldehyde and water are mixed to obtain a transparent solution. In some embodiments, the molar ratio of formaldehyde to phenol is 1:(0.3~0.7), optionally 1:(0.4~0.6), further optionally 1:0.5. In some embodiments, the molar ratio of water and phenol is 1:(0.5-1.2), optionally 1:1.1. In some embodiments, the mixing temperature is 40-60°C. In some embodiments, the formaldehyde is optionally formaldehyde or paraformaldehyde.
得到透明溶液后,本申请实施例将所述透明溶液与有机酸和杂多酸盐混合,进行搅拌反应,得到第一反应液。在一些实施例中,所述有机酸的加入量为苯酚摩尔量的0.1%~1.0%,可选地为0.2%~0.6%,进一步可选地为0.3%~0.5%。在一些实施例中,所述有机酸为草酸、甲酸、乙酸、丁酸、苯甲酸和乙二酸中的一种或多种,可选地为草酸、苯甲酸和乙二酸中的一种或多种,进一步可选地为草酸。所述有机酸可选地为分批加入。After obtaining a transparent solution, 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. In some embodiments, 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%. In some embodiments, 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.
在一些实施例中,所述杂多酸盐的加入量为苯酚摩尔量的5%~20%,可选地为6%~15%,进一步可选地为8%~10%。在一些实施例中,所述杂多酸盐为1-丁基-3-甲基咪唑磷钨杂多酸盐、溴化1-丁基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基吡啶磷钨杂多酸盐、1-丁基-3-甲基咪唑硅钨杂多酸盐、溴化1-丁基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基吡啶硅钨杂多酸盐、1-丁基-3-甲基咪唑磷钼杂多酸盐、溴化1-丁基-3-甲基咪唑磷钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钼杂多酸盐、1-(3-磺酸基)丙基吡啶磷钼杂多酸盐、1-丁基-3-甲基咪唑硅钼杂多酸盐、溴化1-丁基-3-甲基咪唑硅钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钼杂多酸盐和1-(3-磺酸基)丙基吡啶硅钼杂多酸盐中的一种或几种,可选地为1-丁基-3-甲基咪唑磷钨杂多酸盐、溴化1-丁基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基吡啶磷钨杂多酸盐,进一步可选地为1-丁基-3-甲基咪唑磷钨杂多酸盐。所述杂多酸盐可选地分批加入。In some embodiments, 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%. In some embodiments, 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)propylpyridine silicon tungsten heteropoly salt, 1-butyl-3-methylimidazole phosphomolybdenum heteropoly salt, 1-butyl-3-methylimidazole bromide Phosphomolybdenum heteropoly acid salt, 1-(3-sulfonate)propyl-3-methylimidazole phosphomolybdenum heteropoly acid salt, 1-(3-sulfonate)propylpyridine phosphomolybdate heteropoly acid salt, 1-Butyl-3-methylimidazole silicomolybdenum heteropoly acid salt, 1-butyl-3-methylimidazole silicomolybdenum heteropoly acid salt, 1-(3-sulfonate)propyl-3- One or more of methylimidazole silicon molybdenum heteropoly acid salt and 1-(3-sulfonate)propylpyridine silicon molybdenum heteropoly acid salt, optionally 1-butyl-3-methylimidazole Phosphotungstic heteropoly acid salt, 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt, bromide, 1-(3-sulfonate)propyl-3-methylimidazolium phosphotungstic heteropoly acid salt, 1-(3-Sulfonate)propylpyridinium phosphotungstic heteropoly acid salt, further optionally 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid salt. The heteropolyacid salt is optionally added in portions.
在一些实施例中,所述搅拌反应的温度为60~100℃,时间为1~3h。In some embodiments, the temperature of the stirring reaction is 60-100°C, and the time is 1-3 hours.
得到第一反应液后,本申请实施例将所述第一反应液和杂多酸混合,进行反应,得到苯酚甲醛树脂。在一些实施例中,所述杂多酸为磷钨酸、硅钨酸、磷钼酸和硅钼酸中的一种或多种,可选地为磷钨酸或硅钨酸,进一步可选地为磷钨酸。在一些实施例中,所述杂多酸的加入量为苯酚摩尔量的 0.1%~1.0%,可选地为0.2%~0.6%,进一步可选地为0.3%~0.5%。所述杂多酸可选地分批加入。在一些实施例中,所述反应的温度为60~100℃,可选地为70~90℃;时间为0.5~1.5h,可选地为0.8~1h。After obtaining the first reaction liquid, the embodiment of the present application mixes the first reaction liquid and the heteropolyacid and performs a reaction to obtain a phenol-formaldehyde resin. In some embodiments, 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. In some embodiments, 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. In some embodiments, the reaction temperature is 60-100°C, optionally 70-90°C; the reaction time is 0.5-1.5h, optionally 0.8-1h.
得到苯酚甲醛树脂后,本申请实施例将所述苯酚甲醛树脂进行脱水和脱苯酚处理,得到苯酚酚醛树脂。在一些实施例中,采用高温高压的方式进行脱水和脱苯酚;所述脱水时的压力可选地为10~20KPa,进一步可选地为12~15KPa;脱水时的温度可选地为100~140℃,进一步可选地为110~130℃。所述脱苯酚时的压力可选地为0.1~10KPa,进一步可选地为1~5Mpa;脱苯酚时的温度可选地为150~200℃,进一步可选地为170~180℃。After obtaining the phenol-formaldehyde resin, in the embodiment of the present application, the phenol-formaldehyde resin is dehydrated and dephenolized to obtain a phenol-formaldehyde resin. In some embodiments, 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.
在本申请实施例中,将杂多酸盐和有机酸作为催化剂复合使用,在活性较高,而且定位效果明显的杂原子作用下,通过酚醛的缩聚反应,制备出不同含量邻位邻甲酚醛树脂。同时采用有机酸和杂多酸盐复合作为催化剂,催化能力较弱,反应缓和,可避免反应初期剧烈放热使树脂交联。而后在反应中期选用杂多酸作为催化剂,氢离解能力大,催化能力较强,可有效进一步提高缩聚反应速率,提高邻甲酚的转化率以及产率。缩短反应周期,降低生产成本。同时,采用本方法制备的苯酚酚醛树脂邻对位含量可控,软化点可控、色度低的产品。In the embodiments of this application, 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. At the same time, 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. Then, 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. At the same time, the phenolic phenolic resin prepared by this method has controllable ortho-para content, controllable softening point and low chroma.
本申请实施例通过杂多酸盐的类型和加入量来控制苯酚酚醛树脂邻对位的含量,合成邻位可控的苯酚酚醛树脂的反应机理为:通过选择杂多酸盐和有机酸混合催化体系,杂多酸盐提供弱酸性反应环境,突出苯酚环上邻位与对位处羟基“OH”的亲电子取代程度差异,并在合成过程中选择具有邻位引导功能的杂原子(如P、Si、Fe、Co等)和多原子(如Mo、W、V、Nb、Ta等),使甲醛能够优先与苯酚的邻位进行加成反应,形成一种不稳定的螯合物,它通过脱去一个羟基和杂原子、多原子继续与苯酚发生缩聚反应,形成邻位连接且活性较大的二酚基甲烷,同时控制杂原子、多原子的类型和含量,与甲醛继续反应继而形成不同邻位含量的苯酚酚醛树脂。In the embodiments of this application, 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. System, 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. By removing a hydroxyl group and heteroatoms and polyatoms, the polycondensation reaction with phenol continues to form ortho-linked and highly active diphenolmethane. At the same time, 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.
本申请实施例还提供了一种上述任意一项所述的方法制备得到的苯酚酚醛树脂,所述苯酚酚醛树脂的邻位含量为25~95%,残留酚≤1000ppm;加德纳色度≤1。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.
为了进一步说明本申请,下面结合具体实施例对本申请提供的技术方案进行详细地描述,但不能将它们理解为对本申请保护范围的限定。In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below in conjunction with specific examples, but they should not be understood as limiting the protection scope of the present application.
实施例1Example 1
S1、在氮气氛围下,按照摩尔比为0.5:1:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 0.5:1:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至75℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.3%的乙酸和苯酚摩尔质量5%的1-丁基-3-甲基咪唑磷钨杂多酸盐催化剂,加入完毕后搅拌反应2小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.2%磷钨酸后,于95℃条件下反应1小时;S3. Under a nitrogen atmosphere, add 0.2% phenol molar mass of phosphotungstic acid to the reaction solution in step 2), and react at 95°C for 1 hour;
S4、将步骤3)所得的溶液在110℃,压力20KPa下进行脱水后,升温至180℃,压力1KPa下进行脱苯酚,得到苯酚酚醛树脂。S4. 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.
实施例2Example 2
S1、在氮气氛围下,按照摩尔比为1.2:1.8:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于40℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 1.2:1.8:1, and stir at 40°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解完全后,分5批加入苯酚摩尔质量0.3%的草酸和苯酚摩尔质量8%的1-丁基-3-甲基咪唑磷钨杂多酸盐催化剂,加入完毕后搅拌反应3小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.1%磷钼酸后,于85℃条件下反应1.5小时;S3. Under a nitrogen atmosphere, add phenol molar mass 0.1% phosphomolybdic acid to the reaction solution in step 2), and react at 85°C for 1.5 hours;
S4、将步骤3)所得的溶液在120℃,压力15KPa下进行脱水后,升温至190℃,压力10KPa下进行脱苯酚,得到苯酚酚醛树脂。S4. 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.
实施例3Example 3
S1、在氮气氛围下,按照摩尔比为0.65:2:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于40℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle according to a molar ratio of 0.65:2:1, and stir at 40°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至80℃,搅拌溶解完全后,分5批加入苯酚摩尔质量0.7%的乙二酸和苯酚摩尔质量10%的1-(3-磺酸基)丙基吡啶磷钨杂多酸盐催化剂,加入完毕后搅拌反应1小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.3%磷钨酸后,于100℃条件下反应0.5小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.3% phosphotungstic acid to the reaction solution in step 2), and react at 100°C for 0.5 hours;
S4、将步骤3)所得的溶液在120℃,压力20KPa下进行脱水后,升温至200℃,压力5KPa下进行脱苯酚,得到苯酚酚醛树脂。S4. 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.
实施例4Example 4
S1、在氮气氛围下,按照摩尔比为0.6:0.90:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于40℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 0.6:0.90:1, and stir at 40°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.6%的草酸和苯酚摩尔质量12%的溴化1-丁基-3-甲基咪唑硅钼杂多酸盐催化剂,加入完毕后搅拌反应2小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.3%硅钨酸后,于90℃条件下反应1小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.3% silicotungstic acid to the reaction solution in step 2), and react at 90°C for 1 hour;
S4、将步骤3)所得的溶液在110℃,压力10KPa下进行脱水后,升温至200℃,压力10KPa下进行脱苯酚,得到苯酚酚醛树脂。S4. 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.
实施例5Example 5
S1、在氮气氛围下,按照摩尔比为0.5:1:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 0.5:1:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至75℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.3%的乙酸和苯酚摩尔质量8%的1-丁基-3-甲基咪唑磷钨杂多酸盐催化剂,加入完毕后搅拌反应2小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.2% 磷钨酸后,于95℃条件下反应1小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.2% phosphotungstic acid to the reaction solution in step 2), and react at 95°C for 1 hour;
S4、将步骤3)所得的溶液在110℃,压力20KPa下进行脱水后,升温至180℃,压力1KPa下进行脱苯酚,得到苯酚酚醛树脂。S4. 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.
实施例6Example 6
S1、在氮气氛围下,按照摩尔比为0.5:1:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 0.5:1:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至75℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.3%的乙酸和苯酚摩尔质量12%的1-丁基-3-甲基咪唑磷钨杂多酸盐催化剂,加入完毕后搅拌反应2小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.2%磷钨酸后,于95℃条件下反应1小时;S3. Under a nitrogen atmosphere, add 0.2% phenol molar mass of phosphotungstic acid to the reaction solution in step 2), and react at 95°C for 1 hour;
S4、将步骤3)所得的溶液在110℃,压力20KPa下进行减压脱水后,升温至180℃,压力1KPa下进行减压脱苯酚,得到苯酚酚醛树脂。S4. 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.
对比例1Comparative example 1
S1、在氮气氛围下,按照摩尔比为0.55:0.80:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于40℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle according to a molar ratio of 0.55:0.80:1, and stir at 40°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.6%的草酸,加入完毕后搅拌反应3小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.5%磷钨酸后,于90℃条件下反应2小时;S3. Under a nitrogen atmosphere, add 0.5% phenol molar mass of phosphotungstic acid to the reaction solution in step 2), and react at 90°C for 2 hours;
S4、将步骤3)所得的溶液在110℃,压力20KPa下进行减压脱水后,升温至200℃,压力1KPa下进行减压脱苯酚,得到苯酚酚醛树脂。S4. 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.
对比例2Comparative example 2
S1、在氮气氛围下,按照摩尔比为0.60:0.90:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle according to a molar ratio of 0.60:0.90:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解 完全后,分4批加入苯酚摩尔质量0.4%的乙酸,加入完毕后搅拌反应5小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.8%草酸后,于85℃条件下反应4小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.8% oxalic acid to the reaction solution in step 2), and react at 85°C for 4 hours;
S4、将步骤3)所得的溶液在105℃,压力20KPa下进行减压脱水后,升温至190℃,压力1KPa下进行减压脱苯酚,得到苯酚酚醛树脂。S4. 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.
对比例3Comparative example 3
S1、在氮气氛围下,按照摩尔比为0.45:0.76:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle at a molar ratio of 0.45:0.76:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至75℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.3%的乙酸和苯酚摩尔质量5%的1-丁基-3-甲基咪唑磷钨杂多酸盐催化剂,加入完毕后搅拌反应2小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.2%草酸后,于95℃条件下反应1小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.2% oxalic acid to the reaction solution in step 2), and react at 95°C for 1 hour;
S4、将步骤3)所得的溶液在110℃,压力20KPa下进行减压脱水后,升温至180℃,压力10KPa下进行减压脱苯酚,得到不同邻位含量的酚醛树脂。S4. After dehydrating the solution obtained in step 3) under reduced pressure at 110°C and a pressure of 20KPa, the temperature was raised to 180°C and the phenol was removed under reduced pressure at a pressure of 10KPa to obtain phenolic resins with different ortho-position contents.
对比例4Comparative example 4
S1、在氮气氛围下,按照摩尔比为0.60:0.90:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle according to a molar ratio of 0.60:0.90:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.2%的乙酸,加入完毕后搅拌反应5小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.8%草酸后,于85℃条件下反应4小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.8% oxalic acid to the reaction solution in step 2), and react at 85°C for 4 hours;
S4、将步骤3)所得的溶液在105℃,压力20KPa下进行减压脱水后,升温至190℃,压力1KPa下进行减压脱苯酚,得到苯酚酚醛树脂。S4. 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.
对比例5Comparative example 5
S1、在氮气氛围下,按照摩尔比为0.60:0.90:1的比例将苯酚、多聚甲醛和纯水投至反应釜中,于50℃下搅拌60min,得到透明溶液;S1. Under a nitrogen atmosphere, add phenol, paraformaldehyde and pure water into the reaction kettle according to a molar ratio of 0.60:0.90:1, and stir at 50°C for 60 minutes to obtain a transparent solution;
S2、在氮气氛围下,将所述步骤1)的溶液加热升温至70℃,搅拌溶解完全后,分4批加入苯酚摩尔质量0.8%的乙酸,加入完毕后搅拌反应5小时;S2. 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;
S3、在氮气氛围下,向所述步骤2)的反应液中加入苯酚摩尔质量0.8%草酸后,于85℃条件下反应4小时;S3. Under nitrogen atmosphere, add phenol molar mass 0.8% oxalic acid to the reaction solution in step 2), and react at 85°C for 4 hours;
S4、将步骤3)所得的溶液在105℃,压力20KPa下进行减压脱水后,升温至190℃,压力1KPa下进行减压脱苯酚,得到苯酚酚醛树脂。S4. 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.
对实施例1~6和对比例1~5制备的苯酚酚醛树脂根据相应的检测标准和方法对软化点、邻对位含量、残留酚和色度进行测试,具体检测结果如表1所示。The phenol novolac resins prepared in Examples 1 to 6 and Comparative Examples 1 to 5 were tested according to corresponding testing standards and methods for softening point, ortho-para position content, residual phenol and chromaticity. The specific test results are shown in Table 1.
表1 苯酚酚醛树脂的检测结果Table 1 Test results of phenol novolac resin
由表1可以看出,实施例1~6所制备得到的苯酚酚醛树脂的邻位比例为25-95%、残留酚≤1000ppm、色度≤1,软化点符合设计要求。It can be seen from Table 1 that 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.
对实施例1、5~6及对比例2、4~5重复进行操作3次,具体检测结果如 表2所示。Repeat the operation 3 times for Examples 1, 5-6 and Comparative Examples 2, 4-5, and the specific test results are shown in Table 2.
表2 苯酚酚醛树脂的检测Table 2 Detection of phenol novolac resin
由表2可以看出,本申请实施例提供的方法,反应产物稳定,每批次苯酚酚醛树脂中邻对位含量几乎无差别。同时将实施例1、5~6进行对比可知,随着杂多酸盐用量的增加,苯酚酚醛树脂中邻位含量逐渐增加,呈现规律性变化,而对比例2、4~5中并不呈现规律性变化。可知本申请提供的技术方案,可以根据杂多酸盐的用量来控制苯酚酚醛树脂中邻对位的含量,进而可以按实际产品性能需求进行生产。具体控制邻对位的方法为:采用本申请提供的技术方案,在制备前先确定所采用的具体反应原料、杂多酸盐、杂多酸、原 料用量,具体反应条件、工艺,先进行小批次试验,确定得到的苯酚酚醛树脂中邻对位的含量,再根据该产品中邻对位含量对杂多酸盐的用量进行调整,再次试验,以便得到目标邻对位含量的苯酚酚醛树脂,之后即可进行工业化生产。It can be seen from Table 2 that the reaction product of the method provided in the embodiment of the present application is stable, and there is almost no difference in the ortho-para position content in each batch of phenol novolac resin. At the same time, comparing Examples 1 and 5-6, it can be seen that with the increase in the amount of heteropoly acid salt, the ortho-position content in the phenol novolac resin gradually increases, showing regular changes, but does not occur in Comparative Examples 2, 4-5 Regular changes. It can be seen that the technical solution provided by this application can control the ortho-para position in the phenol novolac resin according to the amount of heteropolyacid salt, and then the production can be carried out according to actual product performance 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.
其中:苯酚酚醛树脂的邻对位含量、残留酚、软化点和色度测试方法如下:Among them: The test methods for ortho-para content, residual phenol, softening point and colorimetry of phenol phenolic resin are as follows:
1.邻对位含量的检验1. Inspection of ortho-para position content
1.1试验装置1.1 Test device
安捷伦气相色谱Agilent GC
1.2试样1.2 Sample
称取0.1-1mg树脂,再加入乙腈约20g左右后,同时记录下加入乙腈的准确质量,盖好盖子,摇匀,待测。Weigh 0.1-1mg of resin, add about 20g of acetonitrile, record the exact mass of acetonitrile added, cover the lid, shake well, and wait for measurement.
1.3试验步骤和试验结果1.3 Test procedures and test results
1)设置液相条件:ODS C18色谱柱(4.6mmI.D.x 250mm x 5um)、流速为0.7mL/min、流动相为水和乙腈、检测器为UV(波长为275nm)、柱温为30℃、进样量为20ul;1) Set the liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D. , the injection volume is 20ul;
2)液相色谱基线稳定后,进样进行检测;2) After the liquid chromatography baseline is stable, inject samples for detection;
3)根据谱图中峰面积进行计算,测试的结果记录到检验报告中。3) Calculate based on the peak area in the spectrum, and record the test results in the inspection report.
2.苯酚含量的检验2. Inspection of phenol content
2.1试验装置2.1 Test device
安捷伦气相色谱Agilent GC
2.2试样2.2 Sample
称取0.1-1mg树脂,再加入乙腈约20g左右后,同时记录下加入乙腈的准确质量,盖好盖子,摇匀,待测。Weigh 0.1-1mg of resin, add about 20g of acetonitrile, record the exact mass of acetonitrile added, cover the lid, shake well, and wait for measurement.
2.3试验步骤和试验结果2.3 Test procedures and test results
1)设置液相条件:ODS C18色谱柱(4.6mmI.D.x 250mm x 5um)、流 速为0.7mL/min、流动相为水和乙腈、检测器为UV(波长为275nm)、柱温为30℃、进样量为20ul;1) Set the liquid phase conditions: ODS C18 chromatographic column (4.6mmI.D. , the injection volume is 20ul;
2)液相色谱基线稳定后,进样进行检测;2) After the liquid chromatography baseline is stable, inject samples for detection;
3)计算残留酚的峰面积,与内标曲线对比后,测试的结果记录到检验报告中。3) Calculate the peak area of residual phenol, compare it with the internal standard curve, and record the test results in the inspection report.
3.色度3. Chroma
3.1依据标准3.1 According to standards
依据GBT12007.1-1989环氧树脂颜色测定方法对环氧树脂进行测试。The epoxy resin was tested according to GBT12007.1-1989 epoxy resin color determination method.
3.2测试仪器3.2 Test instruments
1)纳氏比色管25ml1) Nessler colorimetric tube 25ml
2)分析天平2) Analytical balance
3)容量瓶25ml、100ml3) Volumetric flask 25ml, 100ml
4)移液管4) Pipette
3.3试验步骤3.3 Test steps
1)按照标准配制1-16号加德纳色标溶液;1) Prepare Gardner color standard solution No. 1-16 according to the standard;
2)将4份质量的环氧树脂溶于6份质量的丙酮中;2) Dissolve 4 parts by mass of epoxy resin in 6 parts by mass of acetone;
3)将配置好的溶液导入比色管中,与配置好的加德纳色标进行比对,颜色接近即为色度。3) Introduce the prepared solution into the colorimetric tube and compare it with the prepared Gardner color scale. The color is close to the chromaticity.
4)根据测试结果完成测试报告。4) Complete the test report based on the test results.
4.软化点的测试4. Test of softening point
4.1依据标准4.1 According to standards
依据GB/T 12007.6-1989环氧树脂软化点测定方法对环氧树脂进行测试。The epoxy resin was tested according to the GB/T 12007.6-1989 epoxy resin softening point determination method.
4.2测试仪器4.2 Test instruments
1)沥青软化点测试仪1)Asphalt softening point tester
4.3试验步骤4.3 Test steps
1)将树脂熔融后导入样品环中,使树脂液面高于环,冷却后用加热刀刮 平;1) Melt the resin and introduce it into the sample ring so that the resin liquid level is higher than the ring. After cooling, use a heating knife to scrape it flat;
2)将样品环放入沥青软化点仪中,加热介质为甘油,设置升温速率为5℃/min,直至树脂软化后钢球落到下底板的温度为软化点。2) Place the sample ring into the asphalt softening point meter, use glycerol as the heating medium, and set the heating rate to 5°C/min until the temperature at which the steel ball falls to the lower bottom plate after the resin softens is the softening point.
3)根据测试结果完成测试报告。3) Complete the test report based on the test results.
以上所述仅是本申请的部分实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本申请原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本申请的保护范围。The above are only some of the embodiments of the present application. It should be pointed out that those of ordinary skill in the technical field can also make several improvements and modifications without departing from the principles of the present application. These improvements and modifications can also be made. should be regarded as the scope of protection of this application.
Claims (10)
- 一种苯酚酚醛树脂的制备方法,其特征在于,包括如下步骤:A method for preparing phenol novolac resin, which is characterized in that it includes the following steps:1)将苯酚、甲醛和水混合,得到透明溶液;1) Mix phenol, formaldehyde and water to obtain a transparent solution;2)将所述透明溶液与有机酸和杂多酸盐混合,进行搅拌反应,得到第一反应液;2) Mix the transparent solution with an organic acid and a heteropolyacid salt, and perform a stirring reaction to obtain a first reaction solution;3)将第一反应液和杂多酸混合,进行反应,得到苯酚甲醛树脂;3) Mix the first reaction solution and the heteropoly acid to react to obtain a phenol formaldehyde resin;4)将所述苯酚甲醛树脂进行脱水和脱苯酚处理,得到苯酚酚醛树脂;4) The phenol-formaldehyde resin is dehydrated and dephenolized to obtain a phenol-formaldehyde resin;所述步骤1)~3)均在氮气氛围下进行。The steps 1) to 3) are all performed under nitrogen atmosphere.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤1)中混合时的温度为40~60℃;所述甲醛与苯酚的摩尔比为1:(0.3~0.7);所述水和苯酚的摩尔比为1:(0.5~1.2)。The preparation method according to claim 1, characterized in that 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 water The molar ratio to phenol is 1:(0.5~1.2).
- 根据权利要求1所述的制备方法,其特征在于,所述甲醛为多聚甲醛或甲醛水溶液。The preparation method according to claim 1, characterized in that the formaldehyde is paraformaldehyde or a formaldehyde aqueous solution.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤2)中有机酸分批加入,所述有机酸为草酸、甲酸、乙酸、丁酸、苯甲酸和乙二酸中的一种或多种;所述有机酸的加入量为苯酚摩尔量的0.1%~1.0%。The preparation method according to claim 1, characterized in that in step 2), organic acid is added in batches, and the organic acid is one of oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid and oxalic acid. or more; the added amount of the organic acid is 0.1% to 1.0% of the molar amount of phenol.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤2)中杂多酸盐分批加入,所述杂多酸盐为1-丁基-3-甲基咪唑磷钨杂多酸盐、溴化1-丁基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钨杂多酸盐、1-(3-磺酸基)丙基吡啶磷钨杂多酸盐、1-丁基-3-甲基咪唑硅钨杂多酸盐、溴化1-丁基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钨杂多酸盐、1-(3-磺酸基)丙基吡啶硅钨杂多酸盐、1-丁基-3-甲基咪唑磷钼杂多酸盐、溴化1-丁基-3-甲基咪唑磷钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑磷钼杂多酸盐、 1-(3-磺酸基)丙基吡啶磷钼杂多酸盐、1-丁基-3-甲基咪唑硅钼杂多酸盐、溴化1-丁基-3-甲基咪唑硅钼杂多酸盐、1-(3-磺酸基)丙基-3-甲基咪唑硅钼杂多酸盐、1-(3-磺酸基)丙基吡啶硅钼杂多酸盐中的一种或几种;所述杂多酸盐的加入量为苯酚摩尔量的5%~20%。The preparation method according to claim 1, characterized in that in step 2), the heteropoly acid salt is added in batches, and the heteropoly acid salt is 1-butyl-3-methylimidazolium phosphotungstic heteropoly acid. Salt, 1-butyl-3-methylimidazolium phosphotungstic heteropoly salt bromide, 1-(3-sulfonate)propyl-3-methylimidazolium phosphotungstic heteropoly salt, 1-(3- Sulfonate) propylpyridinium phosphotungstic heteropoly acid salt, 1-butyl-3-methylimidazole silicotungstic heteropoly acid salt, bromide 1-butyl-3-methylimidazole silicotungsten heteropoly acid salt, 1-(3-sulfonate)propyl-3-methylimidazole silicotungsten heteropoly acid salt, 1-(3-sulfonate)propylpyridine silicotungsten heteropoly acid salt, 1-butyl-3- Methyl imidazole phosphomolybdenum heteropoly salt, 1-butyl-3-methylimidazole phosphomolybdenum heteropoly salt, bromide, 1-(3-sulfonate)propyl-3-methylimidazole phosphomolybdenum heteropoly salt acid salt, 1-(3-sulfonate)propylpyridinium phosphomolybdenum heteropoly acid salt, 1-butyl-3-methylimidazole molybdenum heteropoly acid salt, 1-butyl-3-methyl bromide Imidazole silicomolybdenum heteropoly acid salt, 1-(3-sulfonate)propyl-3-methylimidazole silicomolybdate heteropoly acid salt, 1-(3-sulfonate)propylpyridine silicomolybdate heteropoly acid salt One or more of them; the addition amount of the heteropolyacid salt is 5% to 20% of the molar amount of phenol.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤2)中搅拌反应的温度为60~100℃,时间为1~3h。The preparation method according to claim 1, characterized in that the temperature of the stirring reaction in step 2) is 60-100°C, and the time is 1-3 hours.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤3)中杂多酸分批加入,所述杂多酸为磷钨酸、硅钨酸、磷钼酸和硅钼酸中的一种或多种;所述杂多酸的加入量为苯酚摩尔量的0.1%~1.0%。The preparation method according to claim 1, characterized in that in step 3), heteropoly acid is added in batches, and the heteropoly acid is phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid. One or more kinds; the addition amount of the heteropolyacid is 0.1% to 1.0% of the molar amount of phenol.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤3)中反应的温度为60~100℃,时间为0.5~1.5h。The preparation method according to claim 1, characterized in that the reaction temperature in step 3) is 60-100°C and the reaction time is 0.5-1.5h.
- 根据权利要求1所述的制备方法,其特征在于,所述步骤4)中采用高温高压的方式进行脱水和脱苯酚;所述脱水时的压力为10~20KPa,温度为100~140℃;所述脱苯酚时的压力为0.1~10KPa,温度为150~200℃。The preparation method according to claim 1, characterized in that in 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 during dephenolization is 0.1-10KPa, and the temperature is 150-200°C.
- 一种根据权利要求1~9任意一项所述的方法制备得到的苯酚酚醛树脂,其特征在于,所述苯酚酚醛树脂的邻位含量为25~95%,残留酚≤1000ppm;加德纳色度≤1。A phenol novolac resin prepared according to the method of any one of claims 1 to 9, characterized in that the ortho position content of the phenol novolac resin is 25 to 95%, and the residual phenol is ≤1000 ppm; Gardner color degree≤1.
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