CN116355162A - Modified bisphenol A type butanol etherified phenolic resin and preparation method and application thereof - Google Patents
Modified bisphenol A type butanol etherified phenolic resin and preparation method and application thereof Download PDFInfo
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- CN116355162A CN116355162A CN202111617623.XA CN202111617623A CN116355162A CN 116355162 A CN116355162 A CN 116355162A CN 202111617623 A CN202111617623 A CN 202111617623A CN 116355162 A CN116355162 A CN 116355162A
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- bisphenol
- butanol
- phenolic resin
- modified bisphenol
- catalyst
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 46
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 46
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 20
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 20
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 20
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006266 etherification reaction Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 235000013305 food Nutrition 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 235000020510 functional beverage Nutrition 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000003973 paint Substances 0.000 description 7
- 230000033444 hydroxylation Effects 0.000 description 6
- 238000005805 hydroxylation reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 amine salt Chemical class 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- 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
-
- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of modified bisphenol A type butanol etherified phenolic resin, which comprises the following steps: step one, feeding bisphenol A, cardanol and formaldehyde together, stirring and heating, and uniformly mixing; step two, adding an alkaline composite catalyst, and controlling the temperature to carry out methylolation reaction; step three, adding acid to neutralize alkalinity, stirring, standing, layering and dehydrating, washing, heating, standing, layering and dehydrating; step four, adding butanol into the rest product of the step three, heating and stirring, adding a catalyst and a solvent, and etherifying, refluxing and water diversion; and fifthly, cooling, decompressing and distilling, and regulating the solid content to obtain the modified bisphenol A type butanol etherified phenolic resin. The invention also discloses the modified bisphenol A butanol etherified phenolic resin prepared by the preparation method and application thereof, and a coating comprising the modified bisphenol A butanol etherified phenolic resin.
Description
Technical Field
The invention belongs to the technical field of phenolic resin preparation methods, and relates to a preparation method of modified bisphenol A type butanol etherified phenolic resin.
Background
The inner walls of canned beverages and food cans are provided with coatings to protect foods from being in direct contact with the cans, so that the cans are prevented from being corroded by the foods, the epoxy phenolic resin-based coating is a main product for three-piece can inner wall coatings in the domestic market due to good chemical corrosion resistance and processability, bisphenol A butanol etherified phenolic resin is widely applied in industry due to good compatibility and epoxy resin curing, and as the types of canned beverages and foods in the domestic are more and more, the requirements on safety and environmental protection of the can inner wall coatings are more and more strict, and the requirements on bisphenol A and formaldehyde monomer residues in the coatings are more and more strict, so that the existing synthesis process is optimized.
The bisphenol A type butanol etherified phenolic resin is commonly used at present, the formula and the process of the resin are disclosed in a patent CN102276776A, and the synthesis process is divided into two steps: firstly, respectively carrying out methylolation reaction on bisphenol A and formaldehyde under different temperature conditions under the condition of an alkali catalyst, then neutralizing, adding a proper amount of ammonia water to react with formaldehyde for absorption, standing for layering, separating upper layers of water and the like; and the second step is to add a very excessive amount of butanol to carry out etherification reaction under an acidic condition, then carry out reduced pressure distillation to obtain resin with proper solid content, and carry out layering residual water and etherification reaction water in the system by utilizing butanol and water azeotropy. The process has the following disadvantages: 1. the use of large amounts of formaldehyde, increasing the aldehyde to phenol ratio to reduce free bisphenol a, therefore there is still a risk of leaving small amounts of free bisphenol a; 2. the method adopts a mode of reacting excessive formaldehyde with ammonia water to form amine salt substances, standing and layering to separate upper water, so that a large amount of wastewater containing amine salt is generated, and negative effects are generated on products and the environment; 3. the hydroxymethylation time of the patent is 8-9 hours from the embodiment, the hydroxylation efficiency is low, and the product and the economic cost of the product are affected; 4. the etherification time of the patent takes 15 to 24 hours from the embodiment point of view of using phosphoric acid and the like for catalytic etherification, and the problems of low production efficiency and high cost are also existed; 5. in the process of azeotropic dehydration by utilizing butanol and water, the water solubility of n-butanol is good (the solubility of butanol in water is 80g/L (20 ℃), and the solubility of water in butanol is 250g/L (20 ℃), so that the problems that butanol is difficult to recycle and the raw material utilization rate of the butanol entering wastewater is low are generated.
In patent CN 108276539A, a synthesis process optimized for patent CN102276776a is disclosed, in which bisphenol F is used instead of bisphenol a in the first place, and the synthesis process is divided into three steps: firstly, respectively carrying out methylolation reaction on bisphenol F and formaldehyde under different temperature conditions under the presence of a base catalyst; secondly, butanol is added for etherification reaction under the acidic condition; thirdly, adding water for washing, and separating upper water after layering; butanol and water are removed by reduced pressure distillation. The process has the following disadvantages: 1. the solution to the problem of free bisphenol a is bisphenol F substitution, bisphenol F being a structural analogue of bisphenol a, which studies have shown also endocrine disrupting activity and other toxicities, which is a compromise alternative. 2. The synthetic route is dehydrated in vacuum after hydroxylation, and a large amount of fresh water is added to wash formaldehyde and neutralize to generate salt after the late etherification, especially butanol has good water solubility, so that the water contains a large amount of butanol after the water washing after the etherification, and the problems of raw material waste, large total sewage amount and high COD are caused. 3. The methylolation of the synthetic route is shortest and takes 3 hours, the etherification is shortest and takes 8 hours, and the problems of low production efficiency, high cost and corrosion of a reaction kettle exist.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide a preparation method of modified bisphenol A type butanol etherified phenolic resin. According to the method, the cardanol modified bisphenol A phenolic resin and the combined composite catalytic system are used for solving the harm of free bisphenol A/F, improving the hydroxylation efficiency and improving the comprehensive application performance of the product; the process adopts butanol and solvents such as toluene and the like to carry out azeotropic reflux to remove water, and water produced in the etherification process can be removed by utilizing the process, so that the etherification reaction is accelerated, the waste water amount is small, and the raw material utilization rate is high; the ion exchange resin is used for etherification catalysis, and the characteristics of ion exchange resin particles, a porous structure, stable release of hydrogen ions and the like are utilized, so that the catalysis efficiency is greatly improved, and the corrosion of a reaction kettle is reduced.
The invention provides a preparation method of modified bisphenol A type butanol etherified phenolic resin, which comprises the following steps:
step one, feeding bisphenol A, cardanol and formaldehyde together, stirring and heating, and uniformly mixing;
step two, adding an alkaline composite catalyst, and controlling the temperature to carry out methylolation reaction;
step three, adding acid to neutralize alkalinity, stirring, standing, layering and dehydrating, washing, heating, standing, layering and dehydrating; the salt formed after neutralization and unreacted formaldehyde can be removed by water washing;
step four, adding butanol into the rest product of the step three, heating and stirring, adding a catalyst and a solvent, and etherifying, refluxing and water diversion;
and fifthly, cooling, decompressing and distilling, and regulating the solid content to obtain the modified bisphenol A type butanol etherified phenolic resin.
In the first step, the molar ratio of the total amount of bisphenol A and cardanol to formaldehyde is 1: (1.5-2.5);
the mol ratio of bisphenol A to cardanol is (2.5-6.0): 1, a step of; preferably, (3.5-4.5): 1, a step of;
the mixing temperature is 40-60 ℃; preferably 45-55 deg.c.
The cardanol is a modifier of bisphenol A type butanol etherified phenolic resin, can be alkylated with bisphenol A through the modification of the cardanol, reduces free phenol, ensures that a paint film has flexibility by using a long chain of the cardanol, and improves the adhesive force of the paint film;
in the second step, the alkaline composite catalyst consists of a main catalyst and an auxiliary catalyst;
the main catalyst mainly enables the methylolation reaction and condensation of bisphenol A and formaldehyde, the auxiliary catalyst can enable the hydroxylation of bisphenol A to be more thorough, and the product resin can not detect free bisphenol A;
the main catalyst is selected from one or more of sodium hydroxide and potassium hydroxide; preferably sodium hydroxide;
the auxiliary catalyst is selected from one or more of calcium hydroxide, calcium oxide, barium hydroxide and aluminum hydroxide; preferably, it is calcium hydroxide;
the mass ratio of the main catalyst to the auxiliary catalyst is (1.0-3.0): 1, a step of; preferably, (1.5-2.0): 1, a step of;
the mass ratio of the composite alkaline catalyst to bisphenol A is (0.01-0.05): 1, a step of; preferably, (0.02-0.04): 1, a step of;
the temperature of the methylolation reaction is 55-75 ℃, and the time of the methylolation reaction is 0.5-2 hours; preferably, the reaction temperature is 60-70 ℃ and the reaction time is 1 hour.
In the third step, the acid is one or more selected from citric acid, phosphoric acid and oxalic acid; preferably, citric acid;
the stirring time is 10-15 minutes; preferably 10 minutes;
the heating temperature is 40-60 ℃; preferably 50-55 deg.c.
In the fourth step, the mass of the added butanol is 1.0-3.0 times of that of bisphenol A; preferably 1.5 times; the butanol is used for dissolving resin obtained by etherification reaction;
the stirring temperature is 60-80 ℃; preferably 65-75deg.C;
the catalyst is selected from one or more of weak acid ion exchange resin and strong acid ion exchange resin; preferably, it is a strong acid type ion exchange resin;
the solvent is selected from one or more of toluene, xylene and isopropylbenzene; preferably toluene;
the etherification reaction temperature is 80-110 ℃, and the etherification reaction time is 2-4 hours; preferably, the reaction temperature is 80-100 ℃ and the reaction time is 4 hours.
In the fifth step, the temperature after cooling is 60-80 ℃; preferably, it is 70-75deg.C;
the distillation pressure is-60 Kpa to-85 Kpa; preferably from-70 Kpa to-75 Kpa;
the distillation time is 30-90 minutes; preferably 60 minutes;
the solid content is required to be adjusted to 55-65% by mass; preferably 60%.
The invention also provides the modified bisphenol A butanol etherified phenolic resin prepared by the method, and the molecular formula of the modified bisphenol A butanol etherified phenolic resin is shown as the formula (1):
wherein m=3-6, n=3-12; preferably, m=3-5, n=6-10.
The invention also provides a coating comprising the modified bisphenol A butanol etherified phenolic resin, which comprises the following components:
100 parts of the modified bisphenol A butanol etherified phenolic resin, 100-250 parts of epoxy resin with the solid content of 40 percent and 0.5-1.5 parts of organosilicon surface leveling agent; preferably, 100 parts of modified bisphenol A butanol etherified phenolic resin, 150-250 parts of epoxy resin with the solid content of 40% and 0.5-1.0 part of organosilicon surface leveling agent.
In a specific embodiment, the preparation method of the modified bisphenol A butanol etherified phenolic resin comprises the following steps:
(1) adding bisphenol A, cardanol and formaldehyde, wherein the total amount of the bisphenol A and the cardanol and the formaldehyde are mixed according to a mole ratio of 1: (1.5-2.5) feeding, stirring, heating to 40-60 ℃ and uniformly mixing;
(2) adding an alkaline composite catalyst, and controlling the temperature to be 55-75 ℃ to carry out methylolation reaction for 0.5-2 h;
(3) adding excessive acid to neutralize the alkaline catalyst, stirring for a period of time, standing for layering, and separating upper water;
(4) adding water into the step (3) for washing, heating to 40-60 ℃, standing for layering, and separating upper water;
(5) adding butanol into the lower material in the step (4), heating to 60-80 ℃ and stirring until the material is completely dissolved; adding ion exchange resin as catalyst of etherification reaction, and adding proper amount of solvent for azeotropic dehydration;
(6) etherification is carried out at the temperature of 80-110 ℃ and residual water and etherification generated water in the step (4) are removed by a reflux water diversion method, wherein the reaction time is 2-4 h;
(7) cooling to 60-80 ℃, decompressing and distilling to remove the solvent until the solid content is 55-65%, thus obtaining the modified bisphenol A butanol etherified phenolic resin.
The invention also provides application of the modified bisphenol A butanol etherified phenolic resin in food can inner wall coating and functional beverage coating.
The beneficial effects of the invention include: 1) The cardanol modified bisphenol A phenolic resin is combined with a composite catalyst, so that free bisphenol A and cardanol are alkylated, the resin is subjected to mild polycondensation and more sufficient hydroxylation by the composite catalyst, the synthetic resin is free of free bisphenol A, the hydroxylation time only needs 0.5-2 hours, and the toughness of a cardanol long alkyl chain is utilized to synergistically improve the comprehensive performance of the product, so that the product is more environment-friendly and has economic benefits, and the comprehensive application performance of the product is improved; 2) The alkaline composite catalyst is adopted, so that the formaldehyde reaction efficiency is improved, and the total formaldehyde consumption is reduced, thereby reducing the aldehyde-containing wastewater production. 3) Before butanol etherifying resin, adding toluene and other solvents which are suitable for azeotropic reflux water removal and have poor water solubility, recycling the solvents in a reflux water diversion mode for dehydration, and directly using the solvents for subsequent product production without treatment after reduced pressure distillation of the solvents, so that the problems that water-containing butanol cannot be directly recycled and a large amount of butanol-containing wastewater is solved, water generated by etherification is instantaneously removed, and etherification reaction can be promoted;
4) The strong acid cation exchange resin is added as the etherification catalyst, so that the etherification efficiency is greatly improved, the etherification time is shortened to 2-4 hours at least 8 hours compared with the etherification time in the prior patent implementation, and the synthesis process with higher production efficiency and economic benefit is provided. The modified bisphenol A butanol etherified phenolic resin is used in the coating of the inner wall of a food can, so that the coating has good adhesive property and chemical corrosion resistance, and is harmless to human health.
Drawings
FIG. 1 is a GPC chart of a resin sample obtained in example 1 of the present invention.
FIG. 2 is a GPC chart of a resin sample obtained in example 2 of the present invention.
FIG. 3 is a GPC chart of a resin sample obtained in example 3 of the present invention.
FIG. 4 is a GPC chart of a resin sample obtained in comparative example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
Example 1
300g of bisphenol A,50g of cardanol and 210g of formaldehyde with 38% content are added into a 2000mL four-neck flask, stirring and heating to 50 ℃, adding 1.75g of sodium hydroxide and 1.75g of calcium hydroxide, heating to 60 ℃, sampling after keeping the temperature for 1.0h, detecting the content of free bisphenol A by using a high performance liquid chromatography, adding 4.1g of oxalic acid after the content of bisphenol A is not detected, stirring for 10min, standing and layering, removing upper water, adding 130g of process water and washing for 10min, standing and layering, removing upper water, adding 450g of n-butanol and dissolving a lower product, adding 150g of toluene, 17.5g of styrene sulfonic acid type ion exchange resin, heating to 85 ℃ and keeping the temperature constant for 4h, separating the free water by using a reflux water separating device, cooling to 75 ℃, removing the solvent by vacuum distillation under-70 Kpa until the solid content is 65%, and obtaining the GPC chart of the modified bisphenol A type butanol phenolic resin sample, wherein 90% of hydroxymethyl is subjected to etherification by NMR test.
Example 2
275g of bisphenol A,75g of cardanol and 240g of formaldehyde with 38% content are added into a 2000mL four-neck flask, stirring and heating to 50 ℃, adding 2.5g of sodium hydroxide and 1.0g of calcium hydroxide, heating to 60 ℃, keeping the temperature for 1.5h, sampling, detecting the content of free bisphenol A by using a high performance liquid chromatography, detecting the content of bisphenol A, adding 4.1g of oxalic acid, stirring for 10min, standing and layering, removing upper water, adding 130g of process water and washing for 10min, standing and layering, removing upper water, adding 450g of n-butanol and dissolving lower product, adding 150g of toluene, 17.5g of styrene sulfonic acid type ion exchange resin, heating to 95 ℃ and keeping the temperature for 3h, separating the free water by using a reflux water separating device, cooling to 75 ℃, removing solvent by vacuum distillation under reduced pressure of-70 KPa until the solid content is 65%, and obtaining the modified bisphenol A type etherified phenolic resin sample, wherein GPC chart of the etherified phenolic resin is shown in figure 2, and the etherified hydroxymethyl with 91% by NMR test.
Example 3
250g of bisphenol A,100g of cardanol and 280g of formaldehyde with 38% content are added into a 2000mL four-neck flask, stirring and heating to 50 ℃, adding 3.0g of sodium hydroxide and 0.5g of calcium hydroxide, heating to 60 ℃, keeping the temperature for 2.0h, sampling, detecting the content of free bisphenol A by using a high performance liquid chromatography, detecting the content of bisphenol A, adding 4.1g of oxalic acid, stirring for 10min, standing for layering, removing upper water, adding 130g of process water for washing for 10min, standing for layering, removing upper water, adding 450g of n-butanol for dissolving a lower product, adding 150g of toluene, 17.5g of styrene sulfonic acid type ion exchange resin, heating to 105 ℃ for keeping the temperature constant for 2h, separating the free water by using a reflux water separating device, cooling to 75 ℃, removing the solvent by vacuum distillation under-70 Kpa until the solid content is 65%, and obtaining the modified bisphenol A type etherified phenolic resin sample, wherein GPC chart is shown in figure 3, and the etherified hydroxymethyl is 93% by NMR test.
Comparative example 1
350g of bisphenol A and 460.5g of formaldehyde with 38% content are added into a 2000mL four-neck flask, the flask is heated to 80 ℃, cooled to below 40 ℃ after complete dissolution, 25% of sodium hydroxide is added, the temperature is raised to 40 ℃ and kept constant for 3 hours, then the temperature is raised to 65 ℃ and kept constant for 6 hours, 50% of sulfuric acid 15g is added, sodium hydroxide is neutralized, stirring is carried out for 15 minutes, 20% of ammonia water 100g is added to remove unreacted formaldehyde, the flask is stirred and kept stand for layering, 1400g of n-butanol is separated, 85% of phosphoric acid is added under stirring, the pH is adjusted to 6, the temperature is raised to 100 ℃ and kept constant for 16 hours, the solvent is removed by pressure distillation until the solid content is 65%, the GPC chart of the prepared resin sample is shown in figure 4, and 86% of hydroxymethyl is etherified by butanol in NMR test.
Table 1 shows the results of the synthetic resin test of examples 1 to 3 of the present invention and comparative example 1:
TABLE 1 test results of synthetic resins of examples 1-3 and comparative example 1
| Category(s) | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Solid content, percent | 64.8 | 65.3 | 65.0 | 65.1 |
| Viscosity at-25deg.C, cps | 196 | 232 | 219 | 216 |
| Free formaldehyde, percent | 0.04 | 0.05 | 0.07 | 0.20 |
| Free bisphenol A%, percent | 0 | 0 | 0 | 0.17 |
| Number average molecular weight | 1044 | 1079 | 1428 | 1049 |
| Weight average molecular weight | 2066 | 2248 | 2677 | 2563 |
Comparative example 2
Adding 350g of bisphenol F and 621.6g of formaldehyde with 38% content into a 2000mL four-neck flask, heating to 80 ℃, cooling to below 40 ℃ after complete dissolution, adding 28.0g of 25% sodium hydroxide, heating to 60 ℃, keeping the temperature for 4 hours, starting sampling, detecting the free formaldehyde content, cooling to 7.0-9.0%, vacuum dehydrating below 50 ℃, dehydrating to 55-60 ℃ under 40-60 Torr vacuum, adding 490g of butanol, stirring uniformly, adjusting the pH to 4.5-5.5 with 25% sulfuric acid, heating, keeping the material in an azeotropic reflux state under normal pressure, carrying out butanol etherification reaction, keeping reflux reaction for 10 hours, adding 500g of water for washing, adjusting the temperature to 55-60 ℃, standing for layering, removing the water phase of the lower layer, carrying out vacuum distillation on the resin solution of the upper layer, heating to 60-65 ℃ under 40 Torr vacuum, stopping vacuum, adjusting the solid content of the resin with butanol to 65%, and preparing the resin sample and using the high-efficiency liquid phase to test the free bisphenol F:1.08%, free bisphenol A:0, NMR test showed 80% of the hydroxymethyl groups etherified with butanol.
Conclusion: as shown by the test results of the resin synthesized in the example, the free bisphenol A is 0 in the test of the modified bisphenol A type butanol etherified phenolic resin synthesized by the process of the invention, and the free bisphenol A in the comparative example 1: 0.17 percent, thus the invention better improves the residue of free bisphenol A in the modified bisphenol A butanol etherified phenolic resin. Free bisphenol F in comparative example 2: 1.08%, free bisphenol A:0, although there is no bisphenol A residue in comparative example 2, more bisphenol F is remained, and researches show that bisphenol F, which is a structural analogue of bisphenol A, also has endocrine disrupting activity and other toxicity, so the process thoroughly solves the harm of free bisphenol A/F residue; as can be seen from the comparison examples, the modified bisphenol A butanol etherified phenolic resin synthesized by the process of the present invention has a methylolation time of at most 2 hours and an etherification time of at most 4 hours, while the prior art has a methylolation time of at least 4 hours and an etherification time of at least 8 hours, so that the efficiency of producing the modified bisphenol A butanol etherified phenolic resin by the process of the present invention is significantly improved.
Example 4
Preparing a food can coating:
100 parts of modified bisphenol A butanol etherified phenolic resin prepared in the embodiment 1 of the invention, 250 parts of epoxy resin with the solid content of 40% and 0.7 part of organosilicon surface leveling agent are used for preparing a coating 1; 100 parts of modified bisphenol A butanol etherified phenolic resin prepared in the embodiment 2 of the invention, 250 parts of epoxy resin with the solid content of 40% and 0.7 part of organosilicon surface leveling agent are used for preparing a coating 2; 100 parts of modified bisphenol A butanol etherified phenolic resin prepared in the embodiment 3 of the invention, 250 parts of epoxy resin with the solid content of 40% and 0.7 part of organosilicon surface leveling agent are used for preparing a coating 3; coating 4 was prepared using 100 parts of the resin of comparative example 1 with 250 parts of an epoxy resin having a solids content of 40% and 0.7 part of a silicone surface leveling agent. These coatings were applied to tinplate metal plates according to GB1727 and baked at 200℃for 15 minutes to make coatings for testing.
Tin coating test:
paint film adhesion was determined using GB/T1720.
Acid resistance: detecting 3% glacial acetic acid solution; sulfur resistance; 1% Na 2 S (pH adjusted with lactic acid=5.5-6.0) solution detection; salt tolerance: 2% NaCl solution was measured, and the above solutions were all cooked in an autoclave at 129℃for 30min, the above results were expressed as excellent medium difference, excellent: the coating is intact; the difference is: the coating was obviously broken.
Table 2 shows paint film adhesion test tables for paints 1 to 4 containing phenolic resins of examples 1 to 3 of the present invention and comparative example 1, respectively:
TABLE 2 paint film adhesion test Table for paints 1 to 4 containing phenolic resins of examples 1 to 3, comparative example 1, respectively, of the present invention
| Coating 1 | Coating 2 | Coating 3 | Coating 4 | |
| 3% glacial acetic acid | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Good grade (good) |
| 1％Na2S | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| 2％NaCl | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Adhesion/grade | 1 | 1 | 1 | 2 |
From the comparative coating test results and the comparative adhesion test results, the food can coatings prepared by the modified resins of examples 1-3 of the present invention all have an adhesion of 1 grade, which is superior to comparative example 1; the food can coating prepared by the modified resin in the embodiment 1-3 has excellent acid resistance, sulfur resistance and salt resistance, and the sulfur resistance and the salt resistance are equivalent to those of the comparative embodiment, and the acid resistance is better; therefore, the toughness of the product is increased through the cardanol modified resin, the synergistic gain effect is achieved, and the better comprehensive performance is achieved.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (9)
1. The preparation method of the modified bisphenol A type butanol etherified phenolic resin is characterized by comprising the following steps:
step one, feeding bisphenol A, cardanol and formaldehyde together, stirring and heating, and uniformly mixing;
secondly, adding an alkaline composite catalyst, and controlling the temperature to carry out methylolation reaction;
step three, stirring, standing, layering and dewatering after acid neutralization, and then washing, heating, standing, layering and dewatering;
step four, adding butanol into the rest product of the step three, heating and stirring, adding a catalyst and a solvent, and etherifying, refluxing and water diversion;
and fifthly, cooling, decompressing and distilling, and adjusting the solid content to obtain the modified bisphenol A type butanol etherified phenolic resin.
2. The preparation method according to claim 1, wherein in the first step, the molar ratio of the total amount of bisphenol a and cardanol to formaldehyde is 1: (1.5-2.5); and/or, the molar ratio of bisphenol A to cardanol is (2.5-6.0): 1, a step of; and/or the temperature of the mixing is 40-60 ℃.
3. The preparation method according to claim 1, wherein in the second step, the basic composite catalyst consists of a main catalyst and an auxiliary catalyst; the main catalyst is selected from one or more of sodium hydroxide and potassium hydroxide; the auxiliary catalyst is selected from one or more of calcium hydroxide, calcium oxide, barium hydroxide and aluminum hydroxide; the mass ratio of the main catalyst to the auxiliary catalyst is (1.0-3.0): 1, a step of; the mass ratio of the composite alkaline catalyst to bisphenol A is (0.01-0.05): 1, a step of; the temperature of the methylolation reaction is 55-75 ℃, and the time of the methylolation reaction is 0.5-2 hours.
4. The preparation method according to claim 1, wherein in the third step, the acid is one or more selected from the group consisting of citric acid, phosphoric acid and oxalic acid; the stirring time is 10-15 minutes; the heating temperature is 40-60 ℃.
5. The preparation method according to claim 1, wherein in the fourth step, the mass of the butanol added is 1.0 to 3.0 times that of bisphenol a, and the butanol is used for dissolving and etherifying the resin obtained; the stirring temperature is 60-80 ℃; the catalyst is selected from one or more of weak acid ion exchange resin and strong acid ion exchange resin; the solvent is selected from one or more of toluene, xylene and isopropylbenzene; the etherification reaction temperature is 80-110 ℃, and the etherification reaction time is 2-4 hours.
6. The method according to claim 1, wherein in the fifth step, the temperature after the temperature reduction is 60to 80 ℃; the distillation pressure is-60 Kpa to-85 Kpa; the distillation time is 30-90min; the solid content is required to be adjusted to 55-65% by mass.
7. A modified bisphenol a butanol etherified phenolic resin prepared according to the method of any one of claims 1-6 wherein the modified bisphenol a butanol etherified phenolic resin has the formula (1):
wherein m=3-6, n=3-12.
8. The use of the modified bisphenol a butanol etherified phenolic resin of claim 7 in food can inner wall coatings, functional beverage coatings.
9. A coating comprising the modified bisphenol a butanol etherified phenolic resin of claim 7, wherein the coating comprises the following components:
the modified bisphenol A type butanol etherified phenolic resin of claim 7, wherein the modified bisphenol A type butanol etherified phenolic resin comprises 100 parts, 100-250 parts of epoxy resin with solid content of 40% and 0.5-1.5 parts of organosilicon surface leveling agent.
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| CN117820579A (en) * | 2024-03-05 | 2024-04-05 | 山东海科创新研究院有限公司 | Phosphor-containing phenolic resin curing agent for copper-clad plate and obtained copper-clad plate |
| CN117820579B (en) * | 2024-03-05 | 2024-05-24 | 山东海科创新研究院有限公司 | Phosphor-containing phenolic resin curing agent for copper-clad plate and obtained copper-clad plate |
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