CN112778475A - Phenolic resin for water-based adhesive and preparation method thereof - Google Patents
Phenolic resin for water-based adhesive and preparation method thereof Download PDFInfo
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- CN112778475A CN112778475A CN202011220648.1A CN202011220648A CN112778475A CN 112778475 A CN112778475 A CN 112778475A CN 202011220648 A CN202011220648 A CN 202011220648A CN 112778475 A CN112778475 A CN 112778475A
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- Prior art keywords
- formaldehyde
- phenol
- weight
- phenolic resin
- parts
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- Granted
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 88
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 52
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000853 adhesive Substances 0.000 title claims abstract description 19
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 270
- 239000000203 mixture Substances 0.000 claims abstract description 52
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002516 radical scavenger Substances 0.000 claims abstract description 40
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- -1 guanidine compound Chemical class 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 description 20
- 239000002657 fibrous material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000000428 dust Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000011491 glass wool Substances 0.000 description 8
- 238000007906 compression Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- DDYDBBBQYLFRJE-UHFFFAOYSA-N (diaminomethylideneamino)urea Chemical compound NC(=N)NNC(N)=O DDYDBBBQYLFRJE-UHFFFAOYSA-N 0.000 description 1
- FIANJMJGPIINHX-UHFFFAOYSA-N (methoxy-methyl-trimethylsilyloxysilyl) trimethyl silicate Chemical compound C[Si](C)(C)O[Si](C)(OC)O[Si](OC)(OC)OC FIANJMJGPIINHX-UHFFFAOYSA-N 0.000 description 1
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N 1,2-dimethylguanidine Chemical compound CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- AJGAPBXTFUSKNJ-UHFFFAOYSA-N 2-cyclohexylguanidine Chemical compound NC(=N)NC1CCCCC1 AJGAPBXTFUSKNJ-UHFFFAOYSA-N 0.000 description 1
- KEWLVUBYGUZFKX-UHFFFAOYSA-N 2-ethylguanidine Chemical compound CCNC(N)=N KEWLVUBYGUZFKX-UHFFFAOYSA-N 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- WEKTTWVMHDUBNR-UHFFFAOYSA-N [dimethoxy(trimethylsilyloxy)silyl] dimethyl trimethylsilyl silicate Chemical compound C[Si](O[Si](O[Si](O[Si](C)(C)C)(OC)OC)(OC)OC)(C)C WEKTTWVMHDUBNR-UHFFFAOYSA-N 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- DUMWHCLFZJQIGA-UHFFFAOYSA-N [methoxy(dimethyl)silyl] trimethyl silicate Chemical compound CO[Si](C)(C)O[Si](OC)(OC)OC DUMWHCLFZJQIGA-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- GDCXBZMWKSBSJG-UHFFFAOYSA-N azane;4-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1 GDCXBZMWKSBSJG-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- IAORIIYGIHOPHS-UHFFFAOYSA-N trimethyl trimethylsilyl silicate Chemical compound CO[Si](OC)(OC)O[Si](C)(C)C IAORIIYGIHOPHS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The invention relates to a phenolic resin, a composition thereof and a preparation method thereof. In particular to a phenolic resin for an aqueous adhesive and a preparation method thereof. The phenolic resin composition of the invention is prepared by mixing the following components in percentage by weight of 1: 1 to 1: 2 comprises phenol and formaldehyde, and comprises 0.1 to 20 parts by weight of the first formaldehyde scavenger and 15 to 40 parts by weight of the second formaldehyde scavenger, based on 100 parts by weight of the phenol.
Description
Technical Field
The invention relates to a phenolic resin and a preparation method thereof. In particular to a phenolic resin for a water-based adhesive and a preparation method thereof.
Background
Generally, resoles made by the condensation of phenol and an aldehyde in the presence of a basic catalyst have many commercially important uses. Since such a resol resin has a property of being cured by heat, it is mainly used as an adhesive which is cured under pressure by applying heat after being applied to a substrate.
In particular, phenolic resins prepared using formaldehyde as the aldehyde are an important class of resoles as described above, which are mainly used for adhesives used for artificial boards, plywood wood products, fiber products, laminate products, and the like. As an example, an adhesive resin used for a laminate product should exhibit good characteristics such as good substrate penetration that other resins do not need to exhibit, and can produce a laminate having good dimensional stability, little panel warpage, little moisture absorption, and high heat resistance blistering (blister) properties.
However, known phenolic resins prepared using formaldehyde have a concentration of formaldehyde that releases formaldehyde to the surrounding environment when the treated substrate is processed, stored, and cured. In this case, it is known that formaldehyde is emitted to cause odor and cause diseases when inhaled by workers and brought into contact with eyes, mouth, and other parts of the body, and therefore, it is undesirable to emit formaldehyde into the surrounding environment during work, storage, and distribution using a resin.
Therefore, in order to reduce the amount of formaldehyde released from a phenol resin, a method of reducing the amount of formaldehyde released when processing, curing a phenol resin by adjusting the pH of the phenol resin to 5.5 or less using an acid catalyst has been proposed based on the characteristic that a phenol resin prepared from phenol and formaldehyde generally has alkalinity, but this method still has a limitation in controlling the amount of formaldehyde released, and when a phenol resin solution is acidified, it is reported that there is a problem that storage property is deteriorated due to the reduction in stability of a binder composition using the same.
Further, when a phenol resin is produced using phenol and formaldehyde, a method of minimizing the amount of formaldehyde released by a formaldehyde scavenger has been proposed, but since formaldehyde released by a condensation reaction reacts with the formaldehyde scavenger in a curing process of the resin, it has been found that this method has little effect on the adsorption of formaldehyde released from a final product.
Disclosure of Invention
Solves the technical problem
The present invention aims to provide a phenol resin which can be used as an aqueous binder for binding fibers, and an aqueous binder composition containing the phenol resin.
Specifically, an object of the present invention is to provide a phenol resin having excellent mechanical characteristics while reducing formaldehyde emission and a method for producing the same.
Solving means
In order to achieve the above object, the present invention provides a phenol resin composition comprising a phenol resin composition represented by the formula 1: 1 to 1: 2 comprises phenol and formaldehyde, and comprises 0.1 to 20 parts by weight of the first formaldehyde scavenger and 15 to 40 parts by weight of the second formaldehyde scavenger, based on 100 parts by weight of the phenol.
Also, the present invention provides a method for preparing a phenol resin, the method comprising: in the presence of a catalyst, by reacting a mixture of 1: 1 to 1: 2 to form a phenolic resin intermediate by an addition reaction of phenol and formaldehyde; and a step of mixing 0.1 to 20 parts by weight of a first formaldehyde scavenger and 15 to 40 parts by weight of a second formaldehyde scavenger based on 100 parts by weight of the phenol, and reacting the phenolic resin intermediate to form a phenolic resin.
Also, the present invention provides a phenol resin prepared according to the method and an aqueous adhesive composition comprising the same. Effects of the invention
By using the preparation method of the phenolic resin, the phenolic resin with extremely low formaldehyde emission can be prepared.
And, when using the phenolic resin containing the sameWhen bonding fibrous materials (particularly, inorganic fibrous materials), for example, even when bonding 40kg/m3To 200kg/m3Can also realize excellent mechanical physical properties.
Detailed Description
Hereinafter, the present invention will be described in detail.
The invention provides a phenolic resin composition.
The phenolic resin composition is prepared by mixing 1: 1 to 1: 2 comprises phenol and formaldehyde, and comprises 0.1 to 20 parts by weight of the first formaldehyde scavenger and 15 to 40 parts by weight of the second formaldehyde scavenger, based on 100 parts by weight of the phenol.
The phenolic resin composition may further comprise a catalyst for the addition reaction of the phenol and formaldehyde.
For example, the catalyst can be contained in a content of 1 to 15 parts by weight, for example, 2 to 12 parts by weight, based on 100 parts by weight of phenol, but is not limited thereto.
In the phenolic resin composition, the reaction of phenol with formaldehyde, the structures of the first formaldehyde scavenger, the second formaldehyde scavenger, the catalyst, and the like can be referred to the following description of the production method of the phenolic resin.
The invention provides a preparation method of phenolic resin.
The preparation method of the phenolic resin comprises the following steps: in the presence of a catalyst, by reacting a mixture of 1: 1 to 1: 2 to form a phenolic resin intermediate by an addition reaction of phenol and formaldehyde; and a step of mixing 0.1 to 20 parts by weight of a first formaldehyde scavenger and 15 to 40 parts by weight of a second formaldehyde scavenger based on 100 parts by weight of the phenol, and reacting the phenolic resin intermediate to form a phenolic resin.
The catalyst creates basic conditions for the addition reaction of phenol and formaldehyde, and a basic catalyst is preferably used, and the kind of the basic catalyst is not particularly limited, and for example, at least one or more of an alkaline earth metal hydroxide and an amine group-containing compound may be used. As the alkaline earth metal hydroxide, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, or a mixture thereof can be used, and as the amine group-containing compound, ammonia, triethylamine, or a mixture thereof can be used.
The amount of the catalyst used may be an amount sufficient to participate in the addition reaction of the phenol and formaldehyde, but is not particularly limited thereto, but if the amount of the catalyst used is too small, the reaction rate of the addition reaction decreases, possibly causing the release of formaldehyde in the reactants, and thus, for example, the catalyst can be preferably used in a content of 1 to 15 parts by weight, for example, 3 to 13 parts by weight, based on 100 parts by weight of phenol. The present invention includes the step of forming a phenolic resin intermediate by performing an addition reaction of phenol and formaldehyde in the presence of a catalyst as described above.
Specifically, in view of the content of formaldehyde remaining after the addition reaction and the amount of formaldehyde released from the prepared resin, the formaldehyde is preferably added in a molar ratio of 1: 2 (phenol: formaldehyde) or less. For example, the ratio of 1: 1 to 1: 2 (phenol: formaldehyde) using the phenol and formaldehyde, or can be reacted in a molar ratio of 1: 1.3 to 1: a molar ratio of 1.8 was used.
For the reaction sequence or temperature of the addition reaction, for example, the catalyst is added after dissolving phenol in the aqueous solution in which the formaldehyde is dissolved, and the reaction may be performed at a temperature of 40 to 95 ℃, for example, 40 to 80 ℃ in consideration of the stability of the solution, but is not limited thereto.
Through the addition reaction, formaldehyde is added to at least one of 2 ortho (-ortho) and 1 para (-para) positions based on a hydroxyl group (-OH) in phenol, so that a hydroxymethyl (-CH) group may be formed2OH) substituted form of the phenolic resin intermediate.
The product of the addition reaction may contain not only the phenolic resin intermediate but also unreacted phenol, formaldehyde, water, and the like, but preferably, the addition reaction is performed so that no phenol remains.
In this case, a step of mixing a formaldehyde scavenger in the product of the addition reaction to remove the unreacted formaldehyde is included.
Specifically, the formaldehyde scavenger may include 0.1 to 20 parts by weight of the first formaldehyde scavenger and 15 to 40 parts by weight of the second formaldehyde scavenger based on 100 parts by weight of the phenol, and these may be mixed for use.
In the case of producing a phenol resin from phenol and formaldehyde, the inventors of the present invention have confirmed that the amount of formaldehyde released from the finally produced phenol resin can be greatly reduced by adding a formaldehyde scavenger to remove the residual formaldehyde after the formation of the phenol resin intermediate. In addition, it was confirmed that, in the case of using a guanidine compound together with urea as the formaldehyde scavenger, the emission amount of formaldehyde is reduced and the emission amount of a reactant (for example, phenol) remaining in addition to formaldehyde and the emission amount thereof are greatly reduced, and it was confirmed that the phenol resin prepared in this case has excellent mechanical and physical properties.
When only urea is used as the formaldehyde scavenger, the adhesive composition comprising the thus prepared phenol resin may cause a problem that physical properties such as strength and water resistance of a thermoset product thereof are deteriorated. Therefore, the first formaldehyde scavenger preferably comprises a guanidine compound or a salt thereof, and the guanidine compound may comprise at least one selected from the group consisting of 2-cyanoguanidine, guanidinyl urea, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and cyanoguanidine. More specifically, the first formaldehyde scavenger may comprise cyanoguanidine.
The first formaldehyde scavenger may be used in an amount of 0.1 to 20 parts by weight, for example 3 to 10 parts by weight, based on 100 parts by weight of the phenol.
Preferably, the second formaldehyde scavenger comprises urea, for example, the urea can remove unreacted formaldehyde remaining during the addition reaction of phenol and formaldehyde together with the first formaldehyde scavenger, and significantly reduce the amount of formaldehyde released and improve the mechanical strength of the product. And with lower raw material costs, the cost competitiveness of the final phenolic resin binder can be enhanced when urea is used.
The second formaldehyde scavenger may be used in an amount of 15 to 40 parts by weight, for example 15 to 35 parts by weight, 20 to 35 parts by weight, based on 100 parts by weight of the phenol.
Comprising the step of mixing the first formaldehyde scavenger and the second formaldehyde scavenger in an addition reaction product containing the phenolic resin intermediate, and then subjecting the phenolic resin intermediate to a condensation reaction to form a phenolic resin.
The condensation reaction of the phenolic resin intermediate is preferably carried out at a temperature lower than the curing temperature of the phenolic resin to be produced, and for example, may be preferably carried out at 40 ℃ to 95 ℃, specifically at 40 ℃ to 80 ℃. If the reaction temperature is outside the above temperature range and is too low, there is a problem that the reaction rate is too slow, and if the reaction temperature is too high, the condensation reaction rate is too fast, and the molecular weight of the phenol resin becomes too large, so that the compatibility with the solvent may be reduced or gelation may occur. Therefore, the method for preparing a phenol resin of the present invention easily removes unreacted residues such as unreacted reactants of phenol, formaldehyde, etc., and shortens the preparation time of the phenol resin since a step of additionally removing or recovering a catalyst, a solvent, etc. is not performed, thereby also exhibiting an energy saving effect.
The completion of the condensation reaction is not limited thereto, and for example, the unreacted formaldehyde content in the final phenol resin can be confirmed by measurement. Specifically, when the content of unreacted formaldehyde in the final phenol resin is, for example, less than 1%, preferably less than 0.5%, the end of the reaction can be confirmed.
When the phenolic resin of the present invention is prepared, a pH adjuster for adjusting pH may be further included, for example, the pH adjuster may be boric acid or the like.
The invention provides a phenolic resin prepared according to the preparation method.
The phenolic resin may be prepared by polycondensation of a phenolic resin intermediate prepared by reacting phenol and formaldehyde in a ratio of 1: 1 to 1: 2 (phenol: formaldehyde) in a molar ratio of 2, and an addition reaction. Specifically, the ratio of 1: 1.3 to 1: 1.8 in a molar ratio. When the formaldehyde is mixed at a molar ratio larger than the molar ratio, there may occur a problem that the emission amount of formaldehyde released from the phenol resin increases.
The phenolic resin exhibits excellent heat resistance, flame retardancy, electrical insulation, mechanical strength, and the like. Although not limited thereto, for example, the phenolic resin may exhibit a viscosity of 10cps to 200cps, specifically 10cps to 100cps, when the viscosity is measured by a Brookfield Viscometer at 25 ℃.
The present invention provides an aqueous adhesive composition comprising a phenolic resin prepared in the manner described above.
The phenol resin may be included as a main resin of the aqueous binder composition, and for its content, for example, a solid component of the phenol resin may be included in a content of 5 to 40 weight percent, specifically 5 to 20 weight percent or 5 to 15 weight percent, based on the total weight of the aqueous binder composition, but is not limited thereto.
The aqueous binder composition further includes a silicon-containing compound as a binder, so that an effect of increasing the adhesion to the fibrous material can be exhibited.
As the silicon-containing compound, a silane-based compound, a siloxane compound, or a mixture thereof can be used.
Examples of the silane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3-ureidopropyltriethoxysilane, trimethoxysilylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and the like, Vinyltriacetoxysilane, vinyltrimethoxysilane, or a mixture thereof, and more preferably, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or a mixture thereof can be used, but not limited thereto.
The siloxane compound is a generic name of an organosilicon compound in the form of a circular or chain oligomer or polymer containing siloxane bonds. Examples of the siloxane compound include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, tetramethyltetramethoxytrisiloxane, hexamethyltetramethoxytetrasiloxane, and a mixture thereof, but are not limited thereto.
As the silicon-containing compound, 3-aminopropyltriethoxysilane (A-1100) may be contained and used most preferably.
The silicon-containing compound can be included in an amount of 0.001 to 10 weight percent, for example, 0.01 to 5 weight percent, 0.01 to 2 weight percent, or 0.01 to 0.5 weight percent, based on the weight of the phenolic resin solids content in the aqueous binder composition. When contained in an amount within the range, the adhesive strength with the fibrous material can be greatly improved.
Also, the aqueous adhesive composition may further include a curing accelerator as an additive.
The curing accelerator may include, for example, at least one selected from the group consisting of ammonium sulfate (ammonium sulfate), ammonium tetraoxysulfate (VI) (Cas No.7783-20-2), ammonium p-toluenesulfonate, an acrylic resin including citrate (Citric acid salt) and carboxylic acid, but is not limited thereto.
The curing accelerator can be included in an amount of 0.01 to 20 weight percent, for example, 1 to 20 weight percent, 1 to 17 weight percent, or 3 to 15 weight percent, based on the weight of the phenolic resin solids content in the aqueous binder composition. When contained in the content within the range, an effect of increasing the bonding speed of the aqueous adhesive composition with the fibrous material to thereby shorten the working time can be exhibited, and the problem of impurity mixing can be improved.
In addition, the aqueous adhesive composition may optionally contain one or more additives as needed within a range that can achieve the object of the present invention, in addition to the above-described components. Examples of such additives include a water repellent agent for improving water resistance of the fibrous material, a rust inhibitor for preventing corrosion of equipment, a dust preventive oil for reducing a dust generation rate of the product, a buffer agent for adjusting pH, and the like, but are not limited thereto, and additives generally used in the art may be included. The amount of the additive used is not particularly limited, and for example, can be used in the range of 0.1 to 10 weight percent based on the total weight of the aqueous binder resin, but is not limited thereto.
Also, the aqueous binder composition may use water such as industrial water, groundwater, process water, purified water, etc. as a diluent (or solvent) for uniformly applying the components to the fibrous material, and the content of the diluent may be the remaining amount of the aqueous binder composition excluding the above components. Also, the content of the solid component in the composition can be adjusted by adjusting the content of the diluent, as necessary. For example, the diluent may be included such that the total amount of solid components in the composition amounts to 5 to 40 weight percent, specifically 5 to 30 weight percent, preferably 5 to 20 weight percent, more preferably 5 to 15 weight percent.
Also, the present invention provides a method for binding fibrous materials by using the aqueous adhesive composition.
In this case, the fibrous material to be bonded includes inorganic fibers (for example, rock wool, glass wool, ceramic fibers, etc.) and organic fibers such as fibers obtained from natural or synthetic resins, but is not limited thereto. In the present invention, as the "fibrous material", glass fiber, rock wool, or the like can be preferably used.
The method for bonding fibrous materials of the present invention may comprise a step of heat curing after spraying the aqueous binder composition of the present invention to the fibrous materials.
Preferably, the aqueous binder composition is sprayed onto the fibrous material in the form of an uncured aqueous solution or dispersion.
The heat treatment for the thermal curing is carried out at a temperature of 140 ℃ or more, for example, 140 ℃ to 300 ℃, preferably 150 ℃ to 250 ℃. If the heat treatment temperature is lower than the range, the problem of non-curing may occur, and if the heat treatment temperature exceeds the range, excessive curing may occur, thereby causing dust and binder to decompose.
The aqueous binder content comprised in the fibrous material bonded according to the bonding method of fibrous material of the present invention may be from 1.5 to 15 weight percent, more preferably from 1.5 to 10 weight percent, relative to the total weight of the bonded fibrous material.
The fibrous material may have a formaldehyde emission of 0.008mg/m3Hr or less or 0.006mg/m3Hr or less. When the aqueous binder of the present invention is used to bind fibers, the binding result may exhibit excellent physical properties in terms of formaldehyde emission, tensile strength, dust rate, recovery rate, excellent moldability, color change upon outdoor storage, incombustibility, and the like.
The present invention will be described more specifically with reference to examples.
Preparation of examples and comparative examples, preparation of aqueous adhesive composition
Phenolic resins were prepared using the compositions of tables 1 and 2 below. Specifically, after formaldehyde (purity 37%) was added to phenol (solid content 100%), a sodium hydroxide solution (33 wt%) was dropped at 40 ℃ for 2 hours. Then, stirring was carried out at 60 ℃ for 4 hours to obtain a mixture containing a phenolic resin intermediate. After cyanoguanidine (Cas No.461-58-5), urea and boric acid were put into the obtained mixture, the mixture was stirred at 35 ℃ for 2 hours to obtain a phenol resin.
TABLE 1
TABLE 2
The prepared phenol resin (solid content: 45%) was used to prepare aqueous adhesive compositions having the compositions shown in tables 3 and 4 below. Specifically, a phenol resin, distilled water, silane A-1100, ammonium sulfate ((NH)4)2SO4) And stirred with a stirrer for 30 minutes to prepare an aqueous adhesive composition.
TABLE 3
TABLE 4
Experimental example bonding of fibrous materials Using an aqueous adhesive
The binder compositions of the examples and comparative examples were sprayed onto glass fibers descending to a collection chamber in an amount of 16L/min while fiberizing molten glass at a rate of 2100kg per hour by passing the molten glass through a spinner, and then subjected to a drying process to obtain glass wool insulation materials. For the prepared glass wool insulation material, physical properties thereof were measured by the following methods, and the results are shown in table 5.
(1) Resin adhesion rate
In order to measure the binder content in the bonded fibrous materials, after preparing a glass wool sample of 100mm (width) × 100mm (length) × 50mm (thickness), the weight loss before and after the heat treatment at 500 ℃ for 1 hour was measured in an oven.
(2) Compression ratio
From each of the glass wool insulating materials prepared as described above, 3 test pieces (250mm × 250mm × 100mm, width × length × thickness) were taken as samples. The size of the test piece was collected by cutting in half in the direction perpendicular to the thickness direction in consideration of the uniform collection surface. The test piece was adhered to a jig for measuring compressibility and then positioned at the center of a general-purpose testing machine. The displacement of compression was then measured under a load of 40kgf, and the number average value was calculated by measuring 3 times. In this case, the compression ratio is calculated by the following equation 1.
Mathematical formula 1
Compression ratio (%) [ (initial thickness-compression displacement)/initial thickness ] × 100
(3) Water absorption rate
3 samples of glass wool insulation cut to a size of 254mm × 254mm × 100mm (product thickness) (length × width × thickness) were prepared, and the weight (W1) was accurately measured to 0.01 g. Then, Water at normal temperature was filled from the bottom of the Water bath (Water bath) to 10 steps (Step) (30 mm per Step) and after the sample was placed, a Screen (square mesh wire) was fixed to be spaced 7 steps from the bottom. (if the square net wire cannot be fixed due to the buoyancy of the sample, the square net wire is fixed by applying a weight of 2kg or more.)
The sieve was fixed so as not to float in the water and absorbed the water for 15 minutes. The sample was removed after 15 minutes and the beads were dropped by holding one corner with a fingertip and standing vertically for 150. + -.5 seconds. Then, the weight (W3) was accurately measured to 0.01g after placing the sample on a previously weighed silver foil dish (W2) and averaged. In this case, the water absorption is calculated by the following equation 2.
Mathematical formula 2
Water absorption (%) [ (W3-W2)/W1] × 100
(4) Formaldehyde emission
Glass wool insulation was placed in the cell according to the cell method specified in KS M ISO16000 and KS M1998, and the air on day 7 was trapped, and then the trapped air was analyzed by liquid chromatography (HPLC). The specific test method followed the method set by the air purification Association and the results were judged on day 7.
(5) Dust rate
4 samples of size 1.5cm wide and 10cm long were made by cutting glass wool insulation. After weighing before measurement, the sample was placed in a dust rate meter and rocked left and right at a speed of 1 m/min. The total measurement time for each sample was 10 minutes, and the weight of the sample was weighed after the automatic stop of the measuring instrument. In this case, the dust rate is calculated by the following equation 3.
Mathematical formula 3
Dust rate ═ [ (after-measurement weight/before-measurement weight) -1] × 100
TABLE 5
From table 5 above, it was confirmed that the following phenol: the molar ratio of formaldehyde is less than 1: comparative example 1 of the phenol resin prepared at a ratio of 1 showed a formaldehyde emission of 0.008 or less, but had poor physical properties of resin adhesion rate, compression rate, and dust rate. And, when using a phenol: the molar ratio of formaldehyde is more than 1: 2 or comparative examples 3 and 4 in which the first formaldehyde scavenger or the second formaldehyde scavenger was not produced at the time of producing the phenol resin, the formaldehyde emission amount was too large, and thus the phenol resin was not suitable.
Furthermore, in the case of comparative examples 5 to 7 using the phenol resin prepared in such a manner that the content of the first formaldehyde scavenger and/or the second formaldehyde scavenger exceeds the present invention, it was confirmed that the effect thereof was poor in terms of dust rate, compression rate (strength), and water absorption rate (water resistance).
Claims (6)
1. A phenol resin composition characterized by comprising, as a main component,
mixing the raw materials in a ratio of 1: 1 to 1: the molar ratio of 2 comprises phenol and formaldehyde,
the formaldehyde scavenger comprises 0.1 to 20 parts by weight of a first formaldehyde scavenger and 15 to 40 parts by weight of a second formaldehyde scavenger, based on 100 parts by weight of the phenol.
2. The phenolic resin composition of claim 1, wherein the first formaldehyde scavenger comprises a guanidine compound or a salt thereof.
3. The phenolic resin composition of claim 1, wherein the second formaldehyde scavenger comprises urea.
4. The phenolic resin composition of claim 1, further comprising a catalyst in an amount of 1 to 15 parts by weight based on 100 parts by weight of the phenol.
5. An aqueous adhesive composition characterized by comprising a phenol resin formed using the phenol resin composition according to any one of claims 1 to 4.
6. A preparation method of phenolic resin is characterized by comprising the following steps:
in the presence of a catalyst, by reacting a mixture of 1: 1 to 1: 2 to form a phenolic resin intermediate by an addition reaction of phenol and formaldehyde; and
a step of mixing 0.1 to 20 parts by weight of a first formaldehyde scavenger and 15 to 40 parts by weight of a second formaldehyde scavenger based on 100 parts by weight of the phenol, and reacting the phenolic resin intermediate to form a phenolic resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0491153A (en) * | 1990-08-07 | 1992-03-24 | Showa Highpolymer Co Ltd | Incombustible binder for inorganic fiber |
| JP2002282996A (en) * | 2001-03-23 | 2002-10-02 | Sumitomo Bakelite Co Ltd | Component of novolak-type phenol resin for shell mold |
| US20030096922A1 (en) * | 2001-11-21 | 2003-05-22 | Georgia-Pacific Resin, Inc. | Resin/binder system for preparation of low odor fiberglass products |
| CN1585788A (en) * | 2001-11-21 | 2005-02-23 | 佐治亚·太平洋树脂公司 | Low formaldehyde emission phenol-formaldehyde resin and method for manufacture thereof |
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| KR940009226A (en) * | 1992-10-22 | 1994-05-20 | 석강봉 | Phenolic Resin for Inorganic Fiber Binder |
| JPH07309921A (en) * | 1994-05-16 | 1995-11-28 | Hitachi Chem Co Ltd | Production of phenol resin |
| KR100715468B1 (en) | 2006-01-25 | 2007-05-09 | 한국화학연구원 | Method for removing residual formaldehyde containg resol-phenol resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0491153A (en) * | 1990-08-07 | 1992-03-24 | Showa Highpolymer Co Ltd | Incombustible binder for inorganic fiber |
| JP2002282996A (en) * | 2001-03-23 | 2002-10-02 | Sumitomo Bakelite Co Ltd | Component of novolak-type phenol resin for shell mold |
| US20030096922A1 (en) * | 2001-11-21 | 2003-05-22 | Georgia-Pacific Resin, Inc. | Resin/binder system for preparation of low odor fiberglass products |
| CN1585788A (en) * | 2001-11-21 | 2005-02-23 | 佐治亚·太平洋树脂公司 | Low formaldehyde emission phenol-formaldehyde resin and method for manufacture thereof |
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