WO2022215553A1 - リグニン変性ノボラック型フェノール樹脂およびその製造方法、ならびに成形材料、樹脂組成物および砥石 - Google Patents
リグニン変性ノボラック型フェノール樹脂およびその製造方法、ならびに成形材料、樹脂組成物および砥石 Download PDFInfo
- Publication number
- WO2022215553A1 WO2022215553A1 PCT/JP2022/014561 JP2022014561W WO2022215553A1 WO 2022215553 A1 WO2022215553 A1 WO 2022215553A1 JP 2022014561 W JP2022014561 W JP 2022014561W WO 2022215553 A1 WO2022215553 A1 WO 2022215553A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- phenolic resin
- modified
- type phenolic
- weight
- Prior art date
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 87
- 239000011342 resin composition Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000012778 molding material Substances 0.000 title claims description 23
- 229920005610 lignin Polymers 0.000 claims description 156
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 88
- 229920001568 phenolic resin Polymers 0.000 claims description 69
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 46
- 150000002989 phenols Chemical class 0.000 claims description 35
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 26
- 150000001299 aldehydes Chemical class 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000003377 acid catalyst Substances 0.000 claims description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 13
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 64
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000945 filler Substances 0.000 description 20
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000010411 cooking Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000002028 Biomass Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- -1 curdle Natural products 0.000 description 11
- 235000006408 oxalic acid Nutrition 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 239000006061 abrasive grain Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical compound CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 4
- 240000000731 Fagus sylvatica Species 0.000 description 4
- 235000010099 Fagus sylvatica Nutrition 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000012812 general test Methods 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- YHEWWEXPVKCVFY-UHFFFAOYSA-N 2,6-Dimethoxy-4-propylphenol Chemical compound CCCC1=CC(OC)=C(O)C(OC)=C1 YHEWWEXPVKCVFY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 3
- 229940076442 9,10-anthraquinone Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 3
- 241000218645 Cedrus Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- DXRKLUVKXMAMOV-UHFFFAOYSA-N 3-heptadecylcatechol Chemical compound CCCCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DXRKLUVKXMAMOV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002029 lignocellulosic biomass Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Chemical group OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical group CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical group CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical group CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical group CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical group CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical group CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical group CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical group CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- RGVIYLQXUDJMCP-UHFFFAOYSA-N 2-tridecylphenol Chemical group CCCCCCCCCCCCCC1=CC=CC=C1O RGVIYLQXUDJMCP-UHFFFAOYSA-N 0.000 description 1
- UVNKQUXHHOZJLS-UHFFFAOYSA-N 2-undecylphenol Chemical group CCCCCCCCCCCC1=CC=CC=C1O UVNKQUXHHOZJLS-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Chemical group CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- FXTKWBZFNQHAAO-UHFFFAOYSA-N 3-iodophenol Chemical compound OC1=CC=CC(I)=C1 FXTKWBZFNQHAAO-UHFFFAOYSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical group CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- DHURZBNESRVDPJ-UHFFFAOYSA-N 4-heptadecylphenol Chemical compound CCCCCCCCCCCCCCCCCC1=CC=C(O)C=C1 DHURZBNESRVDPJ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- QPOBYCLFKIMNOM-ZIKNSQGESA-N C(\C=C\C1=CC=C(C=C1)O)(=O)O.OC1=CC=C(C=C1)CCC Chemical compound C(\C=C\C1=CC=C(C=C1)O)(=O)O.OC1=CC=C(C=C1)CCC QPOBYCLFKIMNOM-ZIKNSQGESA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical group OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Chemical group CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000301850 Cupressus sempervirens Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Chemical group CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 1
- 235000001785 ferulic acid Nutrition 0.000 description 1
- 229940114124 ferulic acid Drugs 0.000 description 1
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- the present invention relates to a lignin-modified novolac-type phenolic resin, a method for producing the same, a molding material and resin composition containing the lignin-modified novolak-type phenolic resin, and a grindstone made of a cured product of the resin composition.
- Patent Document 1 discloses a technique for producing a lignin phenol resin having a weight average molecular weight of 5000 or less by reacting lignin having a weight average molecular weight of 5000 or less, phenols, and aldehydes in the presence of an acid catalyst. is described.
- the lignin phenolic resin is used as a molding material for friction materials.
- Patent Document 1 has room for improvement in terms of mechanical strength and heat resistance strength.
- the inventors of the present invention have been made in view of the above problems, and found that good processability is expressed in lignin-modified novolac-type phenolic resin having a high molecular weight by highly compounding by utilizing the lignin structure. Further, the present inventors have found that a molding material having excellent mechanical properties and heat resistance can be obtained by using a lignin-modified novolac phenolic resin having a weight average molecular weight of 5500 or more, and completed the present invention.
- a lignin-modified novolac-type phenolic resin having a weight average molecular weight of 5500 or more is provided.
- a molding material containing the lignin-modified novolak-type phenolic resin and a curing agent.
- a resin composition containing the lignin-modified novolac-type phenolic resin and hexamethylenetetramine.
- a grindstone made of a cured product of the above resin composition.
- lignins, phenols, and aldehydes are mixed in the presence of an acid catalyst under conditions where the molar ratio (F/P) of the aldehydes to the phenols is 0.5 or more.
- a step of obtaining a lignin-modified novolac-type phenolic resin by reacting with A method for producing a lignin-modified novolak-type phenolic resin is provided, wherein the lignin-modified novolak-type phenolic resin has a weight average molecular weight of 5,500 or more.
- a lignin-modified novolak-type phenolic resin whose cured product has excellent mechanical properties and heat resistance strength, and a method for producing the same are provided.
- the lignin-modified novolac-type phenolic resin of the present embodiment has a weight average molecular weight of 5500 or more.
- the lignin-modified novolak-type phenolic resin of the present embodiment has a high weight average molecular weight, so that the cured product has improved mechanical strength compared to conventional lignin-modified novolak-type phenolic resins.
- the lignin-modified novolac-type phenol resin has a lignin modification rate of 25% or more and 60% or less.
- the lignin-modified novolak-type phenolic resin of the present invention has a lignin-modified rate within the above range, so that it has excellent resin strength and is excellent in curability and moldability.
- the lignin-modified novolak-type phenolic resin having a weight average molecular weight of 5500 or more is prepared by combining lignins, phenols, and aldehydes in the presence of an acid catalyst, and the molar ratio of aldehydes to phenols (F/ It can be prepared by reacting under the condition that P) is 0.5 or more, preferably 0.5 or more and 1.2 or less.
- the upper limit of the molar ratio (F/P) is preferably 1.1 or less, more preferably 1.0 or less.
- the lower limit of the molar ratio (F/P) is preferably 0.55 or more, more preferably 0.6 or more. Lignin modification having the above-mentioned desired weight average molecular weight and lignin modification rate that achieves both workability and strength by conducting a reaction under conditions where the molar ratio (F/P) of aldehydes to phenols is within the above range. Novolak-type phenolic resins can be produced.
- Phenols Phenols, phenol derivatives and combinations thereof may be mentioned as the phenols used in the production of the lignin-modified novolac-type phenolic resin of the present embodiment.
- phenol derivative phenol having an optional substituent introduced into the benzene ring can be used.
- Substituents include hydroxy group; lower alkyl group such as methyl group and ethyl group; halogen atom such as fluorine, chlorine, bromine and iodine; amino group; nitro group;
- phenols that can be used include phenol, catechol, resorcinol, hydroquinone, o-cresol, m-cresol, p-cresol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-chloro Phenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m-amino Phenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-
- alkylphenols having 2 to 18 carbon atoms can also be used.
- Alkylphenols may have a branched chain in the alkyl chain or may have an unsaturated bond. Further, the substitution position of the alkyl chain on the benzene ring may be ortho, meta or para substitution.
- alkylphenols examples include ethylphenol, propylphenol, isopropylphenol, butylphenol, secondary butylphenol, tertiary butylphenol, amylphenol, tertiary aminophenol, hexylphenol, heptylphenol, octylphenol, tertiaryoctylphenol, nonylphenol, Tertiary nonylphenol, decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, cardanol, curdle, urushiol, hexadecylphenol, methyl curdle, heptadecylphenol, laccol, thiol, octadecyl Phenol is mentioned.
- alkylphenols vegetable oils such as cashew nut shell liquid (cashew oil) and sumac extract can be used.
- phenols it is preferable to use one or more selected from the group consisting of phenol, cresol, xylenol, alkylphenol and bisphenol, and from the viewpoint of production cost, phenol, cresol, butylphenol and bisphenol A are preferably used. is preferred.
- the lignins used in the production of the lignin-modified novolac-type phenolic resin of the present embodiment contain at least one selected from lignin and lignin derivatives.
- Lignin along with cellulose and hemicellulose, is a major structural component of plants and is one of the most abundant aromatic compounds in nature. Since lignin exists in plants as lignocellulose, part of which is bound together, lignin often refers to substances obtained from plants through decomposition, etc.
- Examples include kraft lignin, lignin sulfonic acid, soda lignin, pulp lignin such as soda-anthraquinone lignin; organosolv lignin; lignophenol obtained by adding phenol to high-temperature, high-pressure water-treated lignin or explosive lignin during extraction with concentrated sulfuric acid; phenolized lignin, and the like.
- the origin of lignin is not particularly limited, and includes wood and herbaceous plants that contain lignin and form woody parts, such as cedar, pine, cypress, and spruce. and broadleaf trees such as, rice, wheat, corn, and bamboo (herbs).
- lignin derivative refers to a unit structure that constitutes lignin, or a compound that has a structure similar to the unit structure that constitutes lignin.
- a lignin derivative has a phenol derivative as a unit structure. Since this unit structure has carbon-carbon bonds and carbon-oxygen-carbon bonds that are chemically and biologically stable, it is less susceptible to chemical deterioration and biological decomposition.
- the lignin derivatives include guaiacylpropane (ferulic acid) represented by formula (A) of formula (1) below, syringylpropane (sinapic acid) represented by formula (B) below, and formula (C) below. 4-hydroxyphenylpropane (coumaric acid) and the like.
- the composition of the lignin derivative varies depending on the biomass used as the raw material.
- Lignin derivatives containing guaiacylpropane structures are mainly extracted from conifers.
- Lignin derivatives containing guaiacylpropane and syringylpropane structures are mainly extracted from broad-leaved trees.
- Lignin derivatives containing guaiacylpropane, syringylpropane and 4-hydroxyphenylpropane structures are mainly extracted from herbs.
- the lignin derivative is preferably obtained by decomposing biomass. Since biomass is carbon dioxide captured and fixed in the atmosphere during the process of photosynthesis, biomass contributes to suppressing the increase of carbon dioxide in the atmosphere. can contribute to the suppression of degeneration.
- Biomass includes lignocellulosic biomass. Lignocellulosic biomass includes leaves, bark, branches and wood of plants containing lignin, processed products thereof, and the like. Plants containing lignin include the above-mentioned broadleaf trees, conifers, and herbaceous plants.
- Methods for decomposing biomass include chemical treatment, hydrolysis, steam explosion, supercritical water treatment, subcritical water treatment, mechanical treatment, sulfate cresol method, and pulp manufacturing method. mentioned. From the viewpoint of environmental load, a steam explosion method, a subcritical water treatment method, and a mechanical treatment method are preferable. From a cost point of view, the pulping method is preferred. Moreover, from the viewpoint of cost, it is preferable to use a by-product of biomass utilization.
- a lignin derivative can be prepared, for example, by decomposing biomass in the presence of various cooking liquids or solvents at 150 to 400° C. and 1 to 40 MPa for 8 hours or less. Further, lignin derivatives can be prepared by the methods disclosed in JP-A-2009-084320 and JP-A-2012-201828.
- lignin derivatives include those obtained by decomposing lignocellulose in which lignin, cellulose and hemicellulose are combined.
- Lignin derivatives may include lignin decomposition products, cellulose decomposition products, hemicellulose decomposition products, etc., which are mainly composed of compounds having a lignin skeleton.
- the lignin derivative may also contain biomass-derived or process-derived inorganic substances, but when used for the application of the present embodiment, the content of inorganic substances is 10% by mass or less with respect to the entire lignin derivative used. preferable.
- the lignin derivative preferably has many reaction sites on which the curing agent acts through electrophilic substitution reaction on the aromatic ring. At least one of the ortho-position and para-position of the ring is preferably unsubstituted, and lignin derived from coniferous trees and grasses containing many guaiacyl nucleus and 4-hydroxyphenyl nucleus structures as aromatic units of lignin is preferable.
- the lignin derivative those disclosed in JP-A-2009-084320 and JP-A-2012-201828 can be used.
- the lignin derivative may be a lignin derivative having a functional group (lignin secondary derivative) in addition to the basic structure described above.
- the functional groups possessed by the lignin secondary derivative are not particularly limited, for example, two or more of the same functional groups capable of reacting with each other or those capable of reacting with other functional groups are suitable. Specific examples thereof include epoxy groups, methylol groups, vinyl groups having carbon-carbon unsaturated bonds, ethynyl groups, maleimide groups, cyanate groups, isocyanate groups, and the like. Among these, lignin derivatives into which methylol groups are introduced (methylolated) are preferably used. Such a lignin secondary derivative undergoes self-crosslinking due to self-condensation reaction between methylol groups, and also crosslinks with alkoxymethyl groups and hydroxyl groups in the following cross-linking agent. As a result, a lignin-modified novolak-type phenolic resin having a homogeneous and rigid skeleton and excellent solvent resistance can be obtained.
- the lignin derivative used in this embodiment may have a carboxyl group.
- Lignin obtained by the pulp process or high-temperature high-pressure water treatment may have carboxyl groups.
- a lignin-modified novolak-type phenolic resin obtained from a lignin derivative having a carboxyl group has many cross-linking points for a curing agent described below, so that the cross-linking density of the obtained cross-linked product can be improved, resulting in solvent resistance. It is possible to obtain a crosslinked product excellent in
- the carboxyl group can be confirmed by the presence or absence of absorption of a peak at 172 to 174 ppm when subjected to 13 C-NMR analysis attributed to the carboxyl group. can.
- the lignins used in the production of the lignin-modified novolak-type phenol resin of the present embodiment have a weight average molecular weight of, for example, 2,000 or more and 100,000 or less.
- the lower limit of the weight average molecular weight is preferably 2,500 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
- the upper limit of the weight average molecular weight is preferably 90,000 or less, more preferably 80,000 or less, still more preferably 75,000 or less.
- the lignins used in the production of the lignin-modified novolac-type phenolic resin of the present embodiment have a number average molecular weight of, for example, 200 or more and 5,000 or less.
- the lower limit of the number average molecular weight is preferably 300 or higher, more preferably 350 or higher, and even more preferably 400 or higher.
- the upper limit of the number average molecular weight is preferably 4,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.
- Lignins having a number-average molecular weight within the above range are preferable because they are excellent in reactivity and therefore excellent in workability in the production process of the lignin-modified novolac-type phenolic resin.
- the obtained lignin-modified novolak phenolic resin can have excellent curability, and the cured product thereof can have high mechanical strength.
- the number average molecular weight is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography, and can be determined by the method in Examples.
- a lignin derivative is dissolved in a solvent to prepare a measurement sample.
- the solvent used at this time is not particularly limited as long as it can dissolve the lignin derivative, but from the viewpoint of the measurement accuracy of gel permeation chromatography, for example, tetrahydrofuran and N-methyl-2-pyrrolidone are preferable. .
- the molecular weight of the lignins of the present embodiment can contain insoluble matter due to biomass, process-derived inorganic substances, and plant-derived high molecular weight organic matter
- the molecular weight of the lignins is obtained by selecting an appropriate solvent and filtering the insoluble matter. be done.
- the insoluble content of the lignins used is preferably 30% by mass or less in an appropriate solvent.
- the molecular weight of the lignin-modified novolac-type phenolic resin can be similarly obtained by filtering the insoluble matter.
- the content of insoluble matter in the lignin-modified novolak-type phenol resin is preferably 15% by mass or less, more preferably 10% by mass or less.
- the amount of the content is in the above range, the lignin-modified novolac phenolic resin has good curability, and can be cured uniformly.
- the GPC system “HLC-8320GPC (manufactured by Tosoh)” is connected in series with “TSKgelGMHXL (manufactured by Tosoh)”, which is an organic general-purpose column packed with a styrenic polymer packing material, and “G2000HXL (manufactured by Tosoh)”. do.
- TSKgelGMHXL manufactured by Tosoh
- G2000HXL manufactured by Tosoh
- the molecular weight of the standard polystyrene used to create the calibration curve is not particularly limited, but for example, weight average molecular weights of 1,090,000, 427,000, 190,000, 96,400, Standard polystyrenes of 37,900, 18,100, 10,200, 5,970, 2,630, 1,050 and 500 (manufactured by Tosoh) can be used.
- the softening point of the lignins used in the production of the lignin-modified novolac-type phenolic resin of the present embodiment is preferably 90°C or higher, more preferably 110°C or higher, and even more preferably 130°C or higher.
- lignins with high softening points that cannot be measured can be used.
- the resulting modified novolac-type phenolic resin has a high molecular weight, low fluidity, and poor workability.
- the lignin-modified novolac-type phenolic resin of the present embodiment has unexpectedly good processability despite the high lignin-modified rate obtained from such lignins and the high molecular weight lignin-modified phenolic resin. .
- the volatile content of the lignins used in the present embodiment is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
- the main volatile matter is often water. For example, it is calculated by spreading 4 g in an aluminum cup and drying it at 80° C. for 20 hours.
- the softening point of lignins can be measured according to JISK2207 using a ring and ball type softening point tester (for example, ASP-MG2 type manufactured by Meltec Co., Ltd.).
- a ring and ball type softening point tester for example, ASP-MG2 type manufactured by Meltec Co., Ltd.
- the lignin contains a large amount of water, it is measured after being completely dried at 70°C or less.
- a good sample cannot be prepared due to the heat melting property of lignins with a hot plate of 150 to 200° C., it is determined that the softening point is too high to be measured.
- lignins obtained by decomposing biomass When using lignins obtained by decomposing biomass, a large amount of low-molecular-weight components may be mixed in, which may cause volatile matter, odor, and a decrease in softening point during heating. These components can be used as they are, or can be removed by heating or drying the lignins to adjust the softening point and odor.
- Aldehydes used in the production of the lignin-modified novolac-type phenolic resin of the present embodiment include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, and n-butyraldehyde.
- caproaldehyde caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, paraxylene dimethyl ether and the like.
- Preferred are formaldehyde, paraformaldehyde, trioxane, polyoxymethylene, acetaldehyde, paraxylene dimethyl ether and combinations thereof.
- Aldehydes may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable to use formaldehyde or acetaldehyde from the viewpoint of productivity and low cost.
- any acid catalyst can be used as long as it can be used as a reaction catalyst, and organic acids, inorganic acids, and combinations thereof can be used.
- Organic acids include acetic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, sulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and the like.
- Inorganic acids include hydrochloric acid, sulfuric acid, sulfate esters, phosphoric acid, phosphate esters, and the like.
- the molar ratio (F/P) of aldehydes to phenols is, for example, 0.5 or more, preferably 0.55 or more, more preferably is greater than or equal to 0.6.
- the upper limit of the molar ratio (F/P) of aldehydes to phenols is, for example, 1.2 or less, preferably 1.1 or less, and more preferably 1.0 or less.
- a lignin-modified novolac type having a weight average molecular weight of 5500 or more and improved workability and strength.
- a phenolic resin can be obtained.
- the step of reacting lignins, phenols, and aldehydes in the presence of an acid catalyst includes heating lignins and phenols at 70°C to 120°C.
- the following step of mixing under heating to disperse lignins to obtain a mixture (step 1), a step of mixing an acid catalyst simultaneously with step 1 or after step 1 (step 2), and after step 2, A step of mixing aldehydes (step 3) may be included.
- the step of reacting lignins, phenols and aldehydes in the presence of an acid catalyst is carried out at a temperature of, for example, 60°C to 120°C, preferably 80°C to 100°C. , with a reaction time of 10 minutes to 100 minutes. This allows the reaction to proceed efficiently and sufficiently.
- the starting materials are uniformly mixed, and the resulting lignin-modified novolak-type phenolic resin can be cured uniformly due to intermolecular entanglement and intermolecular action, and thus has excellent dimensional accuracy. Molding can be achieved.
- the reaction time is not particularly limited, and may be appropriately determined according to the type of starting materials, the molar ratio of the mixture, the amount and type of catalyst used, and the reaction conditions.
- the reaction mixture after the reaction may be post-treated.
- post-treatment for example, distillation under heating (eg, 150° C. or higher), distillation under normal pressure, distillation under reduced pressure, or a combination thereof can be used.
- steps 1, 2 and 3 are preferably carried out without a solvent, but an organic solvent or water may be used as the solvent.
- Hydrous lignin may be used instead of adding water.
- organic solvents include alcohols, ketones, esters, ethers, and hydrocarbons. Alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, octanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin and the like.
- Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and the like.
- Esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.
- Ethers include propyl ether, dioxane, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl carbitol, ethyl carbitol.
- Hydrocarbons include toluene, xylene, pentane, hexane, cyclohexane, heptane, octane, decane, solvent naphtha, industrial gasoline, petroleum ether, petroleum benzine, ligroin and the like. These may be used alone or in combination of two or more.
- the method of the present embodiment can shorten the process time and increase the yield of the resin compared to the conventional case of increasing the molecular weight at the reaction ratio of phenols, lignins and aldehydes. be able to.
- the properties of the obtained lignin-modified novolac-type phenolic resin can be adjusted within a desired range.
- the lignin-modified novolac-type phenolic resin of this embodiment obtained by the above method has a weight average molecular weight of 5500 or more.
- the weight average molecular weight of the lignin-lignin-modified novolak-type phenolic resin of the present embodiment is, for example, 5,500 or more and 50,000 or less, preferably 6000 or more and 45,000 or less, more preferably 7,000 or more and 40, 000 or less.
- the lignin-modified novolac-type phenolic resin having a weight average molecular weight within the above range has excellent curing properties, and the cured product thereof has high mechanical strength.
- the lignin-modified novolac-type phenol resin of the present embodiment has a lignin modification rate of 25% or more and 60% or less, preferably 30% or more and 55% or less, more preferably 35% or more and 55% or less. .
- the lignin-modified novolac-type phenol resin of the present invention has a lignin-modified rate within the above range, so that it has excellent resin strength and heat resistance, and is excellent in curability and moldability.
- the lignin-modified novolac-type phenolic resin of the present embodiment can be provided in the form of fine powder, granules, pellets, and varnish, for example.
- the form of the lignin-modified novolak-type phenolic resin can be appropriately selected depending on the application.
- the lignin-modified novolak-type phenolic resin of the present embodiment obtained as described above is suitably used as a molding material for transfer molding and injection molding, for example. More specifically, the lignin-modified novolac-type phenolic resin of the present embodiment described above is molded by blending a curing agent (crosslinking agent) and, if necessary, other components, and kneading at a predetermined temperature. Provided as material.
- a molding material containing the lignin-modified novolak-type phenolic resin of the present embodiment can be injection-molded, and its molded article is excellent in mechanical properties such as strength and elastic modulus.
- an amine-based curing agent can be used as the curing agent used for the molding material of this embodiment.
- amine-based curing agent for example, hexamethylenetetramine, hexamethoxymethylolmelamine, and the like can be used as the amine-based curing agent.
- amine-based curing agent for example, hexamethylenetetramine is preferably used.
- the content of the curing agent is, for example, 7 to 30 parts by weight, preferably 10 to 25 parts by weight, with respect to 100 parts by weight of the lignin-modified novolac-type phenolic resin.
- a molding material having good curability can be obtained by setting the amount within the above numerical range.
- the molding material of this embodiment may further contain a filler. That is, the molding material can contain a lignin-modified novolak-type phenolic resin, a curing agent and a filler.
- fillers for example, fiber base materials, organic fillers, inorganic fillers, etc. can be used.
- a fibrous base material is a filler having a fibrous form.
- the organic fillers and inorganic fillers may be either particulate fillers or platelet fillers, respectively.
- a plate-like filler is a filler having a plate-like shape.
- a particulate filler is a filler having a shape other than fibrous or plate-like, including irregular shapes. These may be used alone or in combination of two or more.
- a granular inorganic filler for example, a granular inorganic filler can be used, such as glass beads, glass powder, calcium carbonate, talc, silica, aluminum hydroxide, clay and mica.
- fibrous fillers examples include glass fiber, carbon fiber, asbestos fiber, metal fiber, wollastonite, attapulgite, sepiolite, rock wool, aluminum borate whisker, potassium titanate fiber, calcium carbonate whisker, titanium oxide whisker, fibrous inorganic fillers such as ceramic fibers; fibrous organic fillers such as aramid fibers, polyimide fibers, and poly(paraphenylenebenzobisoxazole fibers); May be used in combination.
- Plate-like fillers and granular fillers include, for example, talc, kaolin clay, calcium carbonate, zinc oxide, calcium silicate hydrate, mica, glass flakes, glass powder, magnesium carbonate, silica, titanium oxide, and alumina.
- aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, fibrous Pulverized fillers and the like can be mentioned.
- the content of the filler in the molding material is, for example, 25 parts by mass to 500 parts by mass, preferably 50 parts by mass to 400 parts by mass, more preferably 100 parts by mass of the lignin-modified novolac-type phenolic resin. is 100 parts by mass to 300 parts by mass.
- a molding material containing the lignin-modified novolak-type phenolic resin can have excellent mechanical strength by setting it to the above lower limit or more. By making it equal to or less than the above upper limit, production stability of the crosslinked body (molded body) can be enhanced.
- the resin material for manufacturing the molded body of the present embodiment can contain other components other than the components described above within a range that does not impair the purpose of the present invention.
- other components include additives such as elastomers, curing accelerators, resin components, release agents, pigments, flame retardants, adhesion improvers, and coupling agents.
- elastomer examples include, but are not limited to, acrylonitrile-butadiene rubber, isoprene, styrene-butadiene rubber, ethylene-propylene rubber, and the like. Among these, acrylonitrile-butadiene rubber is preferred. Toughness can be imparted particularly by using an elastomer.
- the curing accelerator is not particularly limited, and ordinary curing accelerators can be used.
- oxides or hydroxides of alkaline earth metals such as magnesium oxide, calcium hydroxide, barium hydroxide, salicylic acid and aromatic carboxylic acids such as benzoic acid.
- the curing accelerator is used in an amount of, for example, 0.5 to 20 parts by mass with respect to 100 parts by mass of the lignin-modified novolac-type phenolic resin.
- the resin component examples include urea resins, resins having a triazine ring such as melamine resins, bismaleimide resins, polyurethane resins, silicone resins, resins having a benzoxazine ring, cyanate ester resins, polyvinyl butyral resins, and polyvinyl acetate. resin. Moreover, these multiple types can also be used in combination if necessary.
- release agent examples include stearic acid, calcium stearate, zinc stearate, and polyethylene.
- Examples of the pigment include carbon black.
- the resin material of the present embodiment is obtained by melting and kneading a lignin-modified novolak-type phenol resin, a curing agent, and a filler, if used, with a kneader, a roll, etc. in advance, and then uniformly mixing with the above other components, or , All raw material components to be blended are melt-kneaded by a kneading device such as a roll, a co-kneader, a twin-screw extruder, or a combination of rolls and other mixing devices, and then granulated or pulverized.
- the molding material is provided in the form of powder, granules, tablets, sheets, or the like.
- the method of molding the molding material is not particularly limited, but transfer molding, compression molding, injection molding and the like can be used, for example.
- Molded articles of the present embodiment include, for example, automobiles, aircraft, railroad vehicles, ships, general-purpose machines, household appliances, cooking utensils and molded articles used for peripheral parts thereof, or their housings, structural and mechanical parts. , molded products used for electric and electronic parts.
- the lignin-modified novolac-type phenol resin of the present embodiment is suitably used as a resin composition for resinoid grindstones. More specifically, the lignin-modified novolac-type phenolic resin of the present embodiment described above is provided as a powdery resin composition for a resinoid grindstone by blending hexamethylenetetramine.
- the resin composition of the present embodiment contains the lignin-modified novolac-type phenol resin of the present embodiment and hexamethylenetetramine, so that it has excellent curability, and the cured product of the resin composition is used as a grindstone. It has an appropriate degree of mechanical strength and elastic modulus.
- the resin composition of the present embodiment is provided, for example, in the form of granules.
- the resin composition is provided in the form of powder particles, it is preferable to pulverize the resin composition so that the average particle diameter is 10 ⁇ m or more and 60 ⁇ m or less from the viewpoint of handling. From the viewpoint of grindstone strength, 15 ⁇ m or more and 45 ⁇ m is more preferable.
- the amount of hexamethylenetetramine is preferably 2% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 17% by mass, relative to the lignin-modified novolac-type phenol resin. % or less, more preferably 8 mass % or more and 15 mass % or less. If the amount of hexamethylenetetramine is less than the above lower limit, curing of the lignin-modified novolac-type phenolic resin may be insufficient. Cracks and blisters may occur in the resulting cured product.
- the resin composition of the present embodiment described above is used to produce a resinoid grindstone.
- the resinoid grindstone of the present embodiment is obtained by adding abrasive grains to the resin composition described above, but other fillers, additives, and the like can be optionally used.
- Abrasive grains that can be used include, for example, alumina oxide, silicon carbide, diamond, etc., and these play a role in developing the grinding performance of the whetstone.
- Examples of fillers that can be used include inorganic fillers such as cryolite, iron sulfide, iron oxide, barium sulfate, and quicklime, and organic fillers such as thermosetting resin powder, rice husks, and wood flour.
- additives that can be used include silane coupling agents, furfuryl alcohol, furfural, creosote oil, other organic solvents, or liquid resol-type phenolic resins, which improve adhesion with abrasive grains. Therefore, it can be used after wetting the surface of the abrasive grains.
- a method for producing a resinoid grindstone from the resin composition of the present embodiment for example, first, liquid resol-type phenolic resin is mixed with abrasive grains and well kneaded to obtain abrasive grains with wet surfaces, and then the abrasive grains of the present embodiment are obtained.
- a powdery resin composition containing lignin-modified novolac-type phenolic resin and hexamethylenetetramine, and if necessary, the above fillers and additives are added to prepare resin-coated grains;
- the resulting resin-coated grains are molded into a desired shape with a mold heated to room temperature or 40 to 80° C., and the molded product is heated and sintered for 10 to 50 hours. .
- the conditions for heating and firing are not particularly limited, but, for example, the temperature may be raised from room temperature to 200° C. over 10 to 24 hours, held at the peak temperature for 3 to 10 hours, and then gradually cooled.
- the grindstone of this embodiment obtained by the above method has excellent bending strength and water resistance, and therefore has excellent grinding performance.
- a lignin derivative used for synthesizing a lignin-modified novolak-type phenolic resin was prepared by the following procedure. To 1500 parts by weight of cedar wood flour with a moisture content of 50%, 5000 parts by weight of pure water as a cooking liquid, 180 parts by weight of sodium hydroxide, 120 parts by weight of sodium carbonate and 7.5 parts by weight of 9,10-anthraquinone as a cooking aid. , charged into a stainless steel autoclave facility with a capacity of 10 L, and digested at 170°C for 3 hours while stirring.
- the cooking liquor was cooled to room temperature, the pulp component was removed with a screen, and the black liquor containing lignin was separated. Dilute sulfuric acid was added to the separated black liquor to adjust the pH to 8, and the resulting precipitate was centrifuged. After washing twice with 500 parts by mass of water, the precipitate was suspended in 5 times the amount of water and readjusted to pH 2 with dilute sulfuric acid. The precipitated lignin is centrifuged again, washed with water, filtered under suction, spread on a vat, air-dried, and dried in a vacuum oven at 70°C or less. 150 parts by weight (in terms of solid content) were obtained from parts by mass.
- the solid content of lignin was calculated from the residual rate after putting a 4 g sample in an aluminum cup and drying it by heating at 135° C. for 1 hour. (Preparation of lignin-modified phenolic resin) Subsequently, a lignin-modified novolak-type phenolic resin was synthesized by the following procedure. Add 100 parts by weight of phenol to a four-necked flask equipped with a stirrer, a cooling tube and a thermometer, gradually add 40 parts by weight of the lignin derivative solid content, mix and disperse at 60 ° C. or higher, and add 1 part of oxalic acid.
- Preparation Example A2 (Preparation of lignin derivative) Preparation Example A1 except that, when adjusting the pH to 2 and centrifuging, adding water again and centrifuging increased the number of water washings and drying at 80°C or less in a vacuum oven.
- a lignin derivative was prepared by the same method.
- Preparation of lignin-modified phenolic resin Same as Preparation Example A1 except that 40 parts by weight of lignin derivative solid content and 1.4 parts by weight of oxalic acid were added to 100 parts by weight of phenol and mixed at 70°C or higher for 30 minutes. As a result, 127.9 parts by weight of lignin-modified phenolic resin A2 was obtained.
- Preparation Example A3 (Preparation of lignin derivative) As a cooking liquor, 5000 parts by weight of pure water, 150 parts by weight of sodium hydroxide, 80 parts by weight of sodium sulfide, 70 parts by weight of sodium carbonate, and 7.5 parts by weight of 9,10-anthraquinone as a cooking aid. The same as Preparation Example A1 except that it was used, and when adjusting to pH 2 and centrifuging, adding water again and centrifuging to increase the number of water washings and drying at 80 ° C. or less in a reduced pressure oven. A lignin derivative was prepared by the method.
- Preparation Example A4 (Preparation of lignin derivative) Beech wood flour having a moisture content of 50% is digested at 195°C for 1 hour using 3000 parts by weight of ethanol and 2250 parts by weight of water as a cooking liquor, and ethanol is fractionally distilled from the cooking liquor. A lignin derivative was obtained in the same manner as in Preparation Example A1 except that the obtained aqueous solution was centrifuged and freeze-dried to obtain a lignin derivative having a solid content of 90% or more.
- Preparation Example A5 (Preparation of lignin derivative) A lignin derivative was obtained in the same manner as in Preparation Example A1. (Preparation of lignin-modified phenolic resin) 100 parts by weight of phenol, 41.7 parts by weight of lignin derivative solid content and 1.4 parts by weight of oxalic acid were added, and 57.8 parts by weight of 37% formaldehyde aqueous solution was added to obtain the desired phenol. 140.6 parts by weight of lignin-modified phenolic resin A5 was obtained in the same manner as in Preparation Example A1, except that 2.1 parts by weight of cashew shell oil was added, mixed and taken out after reaching the concentration.
- Preparation Example A7 (Preparation of Lignin Derivative) A lignin derivative was obtained in the same manner as in Preparation Example A3, except that beech wood flour having a water content of 50% was used. Further, the lignin derivative was dispersed in acetone, filtered, and the acetone was removed from the filtrate at 70° C. or lower, followed by drying to obtain a low molecular weight lignin derivative.
- Preparation of lignin-modified phenol resin Preparation Example A1 was used except that 100 parts by weight of phenol, 33.3 parts by weight of lignin derivative solid content, 1.3 parts by weight of oxalic acid, and 58.6 parts by weight of 37% aqueous formaldehyde solution were used. Similarly, 121.6 parts by weight of lignin-modified phenolic resin A7 was obtained.
- the weight-average molecular weight, number-average molecular weight, and softening temperature of the obtained lignin derivative were measured by the GPC method or the ring and ball softening point tester, respectively. The results are shown in Table 1 as "Characteristics of Lignin”. Also, the weight average molecular weight, number average molecular weight and lignin modification rate of the obtained lignin-modified novolac phenolic resin were measured. These measurement results are shown in Table 1 as "Characteristics of lignin-modified phenolic resin".
- the lignin-modified novolac phenol resin component of the present embodiment may contain a component with a particularly high molecular weight
- the value excluding the high molecular weight component exceeding the standard polystyrene number average molecular weight of 42,7000 is also referred to in the table ( ). written inside.
- glass fiber glass milled fiber, manufactured by Nitto Boseki Co., Ltd., standard fiber diameter 10 ⁇ 1.5 ⁇ m, average fiber length 90 ⁇ m
- additives Stearic acid (manufactured by NOF Corporation) and 8 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation, #5)
- a resin composition was obtained.
- Phenolic resin A1 lignin-modified novolak-type phenolic resin A1 of Preparation Example A1
- Phenolic resin A2 lignin-modified novolac-type phenolic resin A2 of Preparation Example A2
- Phenolic resin A3 lignin-modified novolak-type phenolic resin A3 of Preparation Example A3
- Phenolic resin A4 lignin-modified novolac-type phenolic resin A4 of Preparation Example A4
- Phenolic resin A6 lignin-modified novolac-type phenolic resin A6 of Preparation Example A6
- Phenolic resin A7 lignin-modified novolac-type phenolic resin A7 of Preparation Example A7 - Phenolic resin A8: unmodified novolak-
- Preparation Example B1 (Preparation of lignin derivative) As a cooking liquor, 5000 parts by weight of pure water, 150 parts by weight of sodium hydroxide, 80 parts by weight of sodium sulfide, 70 parts by weight of sodium carbonate, and 7.5 parts by weight of 9,10-anthraquinone as a cooking aid. A lignin derivative was obtained in the same manner as in Preparation Example A1, except that it was used.
- Preparation of lignin-modified phenolic resin Preparation Example A1 was prepared except that 100 parts by weight of phenol, 37.4 parts by weight of lignin derivative solid content, 1.5 parts by weight of oxalic acid, and 51.2 parts by weight of 37% aqueous formaldehyde solution were used. 125.0 parts by weight of lignin-modified phenolic resin B1 was obtained in the same manner as above.
- Preparation Example B2 (Preparation of lignin derivative) Beech wood flour having a moisture content of 50% is digested at 195°C for 1 hour using 3000 parts by weight of ethanol and 2250 parts by weight of water as a cooking liquor, and ethanol is fractionally distilled from the cooking liquor. A lignin derivative was obtained in the same manner as in Preparation Example A1 except that the obtained aqueous solution was centrifuged and freeze-dried to obtain a lignin derivative having a solid content of 90% or more.
- Preparation Example B3 (Preparation of lignin derivative) Beech wood flour having a moisture content of 50% is digested at 195°C for 1 hour using 3000 parts by weight of ethanol and 2250 parts by weight of water as a cooking liquor, and ethanol is fractionally distilled from the cooking liquor. A lignin derivative was obtained in the same manner as in Preparation Example A1 except that the obtained aqueous solution was centrifuged and freeze-dried to obtain a lignin derivative having a solid content of 90% or more.
- the weight-average molecular weight, number-average molecular weight, and softening temperature of the obtained lignin derivative were measured by the GPC method or the ring and ball softening point tester, respectively. The results are shown in Table 1 as "Characteristics of Lignin”. Also, the weight average molecular weight, number average molecular weight and lignin modification rate of the obtained lignin-modified novolac phenolic resin were measured. These measurement results are shown in Table 1 as "Characteristics of lignin-modified phenolic resin".
- the lignin-modified novolak phenol resin component of the present embodiment may contain a component with a particularly high molecular weight
- the value excluding the high molecular weight component exceeding the standard polystyrene number average molecular weight of 427,000 is also referred to in the table ( ). written inside.
- Phenolic resin B1 lignin-modified novolac-type phenolic resin B1 of Preparation Example B1
- Phenolic resin B2 lignin-modified novolak-type phenolic resin B2 of Preparation Example B2
- Phenolic resin B3 lignin-modified novolak-type phenolic resin B3 of Preparation Example 3
- Phenolic resin B4 lignin-modified novolak-type phenolic resin
- ⁇ Preparation of grindstone test piece> 1200 parts of alumina abrasive grains, Saclandum A#60 (manufactured by Nihon Carlit Co., Ltd.) and 24 parts of wetter liquid phenolic resin PR-55331 (manufactured by Sumitomo Bakelite Co., Ltd.) were used. After kneading for 4 minutes using a Shinagawa kneader, 144 parts of each phenolic resin or unmodified phenolic resin prepared in the above preparation example was added and further kneaded for 2 minutes to produce coated grains. The state of the coated grains was checked immediately after kneading and after storage for 12 hours at 25° C.
- the coated grain was put into a mold and press-molded so that the molded product had a size of 100 mm ⁇ 25 mm ⁇ 15 mm and a bulk specific gravity of 2.0, and the molded product was placed on a stainless iron plate. Place this in a hot air circulation dryer with a programmable function, and dry from room temperature to 80°C for 5 hours, from 80°C to 100°C for 5 hours, from 100°C to 120°C for 10 hours, from 120°C to 130°C for 4 hours. 130° C. to 170° C. for 7 hours, held at 180° C. for 10 hours, and then cooled to room temperature over 5 hours for curing to produce a grindstone test piece.
- a hot air circulation dryer with a programmable function
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
Description
前記リグニン変性ノボラック型フェノール樹脂の重量平均分子量が5500以上である、リグニン変性ノボラック型フェノール樹脂の製造方法が提供される。
本実施形態のリグニン変性ノボラック型フェノール樹脂は、その重量平均分子量が5500以上である。本実施形態のリグニン変性ノボラック型フェノール樹脂は、高い重量平均分子量を有することにより、その硬化物が、従来のリグニン変性ノボラック型フェノール樹脂に比べて向上した機械的強度を有する。
本実施形態の5500以上の重量平均分子量を有するリグニン変性ノボラック型フェノール樹脂は、リグニン類と、フェノール類と、アルデヒド類とを、酸触媒の存在下、フェノール類に対するアルデヒド類のモル比(F/P)が0.5以上、好ましくは0.5以上1.2以下である条件で反応させることにより、作製することができる。モル比(F/P)の上限値は1.1以下が好ましく、1.0以下がより好ましい。モル比(F/P)の下限値は0.55以上が好ましく、0.6以上がより好ましい。フェノール類に対するアルデヒド類のモル比(F/P)が上記範囲である条件下で、反応を行うことにより、加工性と強度を両立した上述の所望の重量平均分子量およびリグニン変性率を有するリグニン変性ノボラック型フェノール樹脂が生成し得る。
本実施形態のリグニン変性ノボラック型フェノール樹脂の製造に用いられるフェノール類としては、フェノール、フェノール誘導体及びこれらの組み合わせが挙げられる。フェノール誘導体としては、ベンゼン環に任意の置換基が導入されたフェノールを使用できる。置換基としては、ヒドロキシ基;メチル基、エチル基等の低級アルキル基;フッ素、塩素、臭素、ヨウ素等のハロゲン原子;アミノ基;ニトロ基;カルボキシ基等が挙げられる。用いることができるフェノール類の具体例としては、フェノール、カテコール、レソルシノール、ヒドロキノン、o-クレゾール、m-クレゾール、p-クレゾール、o-フルオロフェノール、m-フルオロフェノール、p-フルオロフェノール、o-クロロフェノール、m-クロロフェノール、p-クロロフェノール、o-ブロモフェノール、m-ブロモフェノール、p-ブロモフェノール、o-ヨードフェノール、m-ヨードフェノール、p-ヨードフェノール、o-アミノフェノール、m-アミノフェノール、p-アミノフェノール、o-ニトロフェノール、m-ニトロフェノール、p-ニトロフェノール、2,4-ジニトロフェノール、2,4,6-トリニトロフェノール、サリチル酸、p-ヒドロキシ安息香酸及びこれらの組み合わせ等が挙げられる。フェノール類は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本実施形態のリグニン変性ノボラック型フェノール樹脂の製造に用いられるリグニン類は、リグニンおよびリグニン誘導体から選択される少なくとも1つを含む。
リグニンは、セルロース及びヘミセルロースとともに、植物体の構造を形成する主要成分であり、また、自然界に最も豊富に存在する芳香属化合物の1つである。リグニンは植物中では一部が結合してリグノセルロースとして存在しているため、リグニンとは植物から分解等を経て得られるものを指すことが多く、例としては、クラフトリグニン、リグニンスルホン酸、ソーダリグニン、ソーダ-アントラキノンリグニン等のパルプリグニン;オルガノソルブリグニン;高温高圧水処理リグニンまたは爆砕リグニンに、濃硫酸にて抽出等時にフェノールが付加するリグノフェノール;フェノール化リグニン等が挙げられる。リグニンの由来は特に限定されず、リグニンを含み木質部が形成される木材や草本類等が挙げられ、スギ、マツ、ヒノキ、及び、トウヒ等の針葉樹、ブナ、白樺、ナラ、ケヤキ、及び、ユーカリ等の広葉樹、イネ、ムギ、トウモロコシ及びタケ等のイネ科植物(草本類)が挙げられる。
ゲル浸透クロマトグラフィーによって分子量を測定する方法において、まず、リグニン誘導体を溶媒に溶解させ、測定サンプルを調製する。このときに用いられる溶媒は、リグニン誘導体を溶解できるものであれば特に限定されるものではないが、ゲル浸透クロマトグラフィーの測定精度の観点から、例えば、テトラヒドロフラン、N-メチル-2-ピロリドンが好ましい。本実施形態のリグニン類は、バイオマス、プロセス由来の無機物、植物由来の高分子量有機物による不溶分を含みうるため、リグニン類の分子量は、適正な溶媒を選択するとともに、不溶分はろ過して求められる。また得られるリグニン変性ノボラック型フェノール樹脂のリグニン変性率を高めるためには、使用するリグニン類の不溶分は適正な溶媒下で30質量%以下が好ましい。またリグニン変性ノボラック型フェノール樹脂の分子量は、同様に不溶分をろ過して求められる。リグニン変性ノボラック型フェノール樹脂中の不溶分含有は、15質量%以下が好ましく、10質量%以下がより好ましい。上記含有量の量が上記程度であれば、リグニン変性ノボラック型フェノール樹脂は良好な硬化性を有し、特に、均一に硬化し得る。
本実施形態のリグニン変性ノボラック型フェノール樹脂の製造に用いられるアルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、ポリオキシメチレン、クロラール、ヘキサメチレンテトラミン、フルフラール、グリオキザール、n-ブチルアルデヒド、カプロアルデヒド、アリルアルデヒド、ベンズアルデヒド、クロトンアルデヒド、アクロレイン、テトラオキシメチレン、フェニルアセトアルデヒド、o-トルアルデヒド、サリチルアルデヒド、パラキシレンジメチルエーテル等が挙げられる。好ましくは、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、ポリオキシメチレン、アセトアルデヒド、パラキシレンジメチルエーテル及びこれらの組み合わせ等が挙げられる。アルデヒド類は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。これらの中でも、生産性および安価な観点から、ホルムアルデヒドまたはアセトアルデヒドを用いることが好ましい。
本実施形態のリグニン変性ノボラック型フェノール樹脂の製造に用いられる酸触媒としては、反応の触媒として使用できるものであればよく、有機酸、無機酸及びこれらの組み合わせを使用することができる。有機酸としては、酢酸、ギ酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、安息香酸、サリチル酸、スルホン酸、フェノールスルホン酸、パラトルエンスルホン酸等が挙げられる。無機酸としては、塩酸、硫酸、硫酸エステル、リン酸、リン酸エステル等が挙げられる。
これに対して、本実施形態の方法は、従来のフェノール類とリグニン類とアルデヒド類の反応比率で分子量を高める場合と比較して、プロセス時間が短くすることができ、樹脂の収率を高めることができる。また、フェノール類に対するアルデヒド類のモル比(F/P)を上記範囲とするとともに、用いるリグニン類の分子量、分子量分布、添加量を調整することにより、得られるリグニン変性ノボラック型フェノール樹脂の特性や樹脂材料の物性を所望の範囲に調整することができる。
上述のようにして得られた本実施形態のリグニン変性ノボラック型フェノール樹脂は、例えば、トランスファー成形、射出成形用の成形材料として好適に用いられる。より具体的には、上述の本実施形態のリグニン変性ノボラック型フェノール樹脂は、硬化剤(架橋剤)、および必要に応じて、その他の成分を配合し、所定の温度で混練することにより、成形材料として提供される。本実施形態のリグニン変性ノボラック型フェノール樹脂を含む成形材料は、射出成形が可能であり、その成形品は、強度および弾性率などの機械的物性において優れる。
本実施形態のリグニン変性ノボラック型フェノール樹脂は、レジノイド砥石用の樹脂組成物として好適に用いられる。より具体的には、上述の本実施形態のリグニン変性ノボラック型フェノール樹脂は、ヘキサメチレンテトラミンを配合することにより、レジノイド砥石用の粉末状樹脂組成物として提供される。本実施形態の樹脂組成物は、本実施形態のリグニン変性ノボラック型フェノール樹脂とヘキサメチレンテトラミンとを含むことにより、硬化性に優れるとともに、当該樹脂組成物の硬化物は、砥石として使用するのに適切な程度の機械的強度および弾性率を有する。本実施形態の樹脂組成物は、例えば、粉粒体の形態で提供される。樹脂組成物が粉粒状の形態で提供される場合、取り扱い性の観点から、平均粒径が10μm以上60μm以下となるよう粉砕することが好ましい。砥石強度の観点からは、15μm以上45μmがより好ましい。
上述の本実施形態の樹脂組成物は、レジノイド砥石を作製するために用いられる。本実施形態のレジノイド砥石は、上述の樹脂組成物に砥粒を加えて得られるものであるが、この他充填材、添加剤などを任意に使用することができる。砥粒としては、例えば、酸化アルミナ、炭化珪素、ダイヤモンド等を使用することができ、これらは砥石の研削を発現させる役割がある。充填材としては、例えば、氷晶石、硫化鉄、酸化鉄、硫酸バリウム、生石灰等の無機フィラー、熱硬化性樹脂粉末、籾殻、木粉などの有機フィラー等を使用することができ、これらは砥石の研削性能を向上させる役割がある。添加剤としては、例えば、シランカップリング剤、フルフリルアルコール、フルフラール、クレオソート油、その他の有機溶剤、又は液状レゾール型フェノール樹脂等を使用することができ、砥粒との接着性を向上させるために砥粒表面に濡らしてから使用できる。
<リグニン変性ノボラック型フェノール樹脂の調製>
(リグニン誘導体の調製)まず、リグニン変性ノボラック型フェノール樹脂の合成に用いるリグニン誘導体を以下の手順により調製した。
含水率50%のスギ木粉1500重量部に、蒸解液として純水5000重量部、水酸化ナトリウム180重量部、炭酸ナトリウム120質量部および蒸解助剤として9,10-アントラキノン7.5重量部を、容量10Lのステンレススチール製オートクレーブ設備に仕込み、撹拌下、170℃で3時間蒸解反応を行った。反応後の蒸解液を室温まで冷却し、パルプ成分をスクリーンで除去した後、リグニンを含む黒液を分離した。分離した黒液に希硫酸を加えてpH8に調整して、生じた沈澱を遠心分離した。500質量部の水で2回洗浄した後、沈澱を5倍量の水に懸濁し、希硫酸でpH2に再調整した。沈澱したリグニンを再度遠心分離し、水で洗浄した後、吸引濾過し、バットに広げて風乾して、70℃以下で減圧オーブン乾燥を行い、固形分70%以上の褐色粉末状のアルカリリグニン140質量部から150重量部(固形分換算)を得た。リグニンの固形分率はアルミカップに4gサンプルを入れ、135℃1時間で加熱乾燥させた後の残存率から算出した。
(リグニン変性フェノール樹脂の調製)続いてリグニン変性ノボラック型フェノール樹脂を以下の手順により合成した。
撹拌機、冷却管及び温度計を備えた四口フラスコにフェノール100重量部を加え、リグニン誘導体固形分40重量部を徐々に添加して60℃以上で混合して分散させて、シュウ酸を1.4重量部加え、37%ホルムアルデヒド水溶液58.6重量部を60分かけて徐添して100℃で反応させて、添加後に100℃にて60分反応させて、常圧及び減圧脱水で150℃以上に昇温して所望のフェノール濃度になったところで取り出し、128.1重量部のリグニン変性ノボラック型フェノール樹脂A1を得た。
(リグニン誘導体の調製)pH2に調整して遠心分離する際に、再度水を加えて遠心分離することで水洗回数を増やして、減圧オーブンにて80℃以下で乾燥したこと以外は、調製例A1と同じ方法により、リグニン誘導体を調製した。
(リグニン変性フェノール樹脂の調製)フェノール100重量部に、リグニン誘導体固形分40重量部とシュウ酸1.4重量部を加えて、70℃以上で30分混合したこと以外は、調製例A1と同様にして、127.9重量部のリグニン変性フェノール樹脂A2を得た。
(リグニン誘導体の調製)蒸解液として、純水5000重量部、水酸化ナトリウム150重量部、硫化ナトリウム80重量部、炭酸ナトリウム70質量部および蒸解助剤として9,10-アントラキノン7.5重量部を用いたこと、pH2に調整して遠心分離する際に、再度水を加えて遠心分離することで水洗回数を増やして、減圧オーブンにて80℃以下で乾燥したこと以外は、調製例A1と同じ方法により、リグニン誘導体を調製した。
(リグニン変性フェノール樹脂の調製)フェノール100重量部に、リグニン誘導体固形分37.4重量部とシュウ酸1.5重量部を加えて70℃以上で30分混合して、37%ホルムアルデヒド水溶液51.2重量部を用いたこと以外は、調製例A1と同様にして、124.2重量部のリグニン変性フェノール樹脂A3を得た。
(リグニン誘導体の調製)含水率50%のブナ木粉に、蒸解液としてエタノール3000重量部、水2250重量部を用いて、195℃1時間で蒸解して、蒸解液からエタノールを分留して得られた水溶液を遠心分離して、凍結乾燥して固形分90%以上のリグニン誘導体を得たこと以外は調製例A1と同様にして、リグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分60重量部、シュウ酸1.6重量部を加えて、37%ホルムアルデヒド水溶液51.6重量部を用いたこと以外は、調製例A1と同様にして、138.1重量部のリグニン変性フェノール樹脂A4を得た。
(リグニン誘導体の調製)調製例A1と同様にして、リグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分41.7重量部、シュウ酸1.4重量部を加えて、37%ホルムアルデヒド水溶液57.8重量部を用いて、所望のフェノール濃度に達した後にカシュー殻オイルを2.1重量部添加して混合して取り出したこと以外は、調製例A1と同様にして、140.6重量部のリグニン変性フェノール樹脂A5を得た。
(リグニン誘導体の調製)含水率50%のスギ木粉200重量部に、蒸解液として純水567重量部を、容量10Lのステンレススチール製オートクレーブ設備に仕込み、撹拌下、300℃1時間処理を行った。反応後の蒸解液を室温まで冷却し、濾別して、リグニンを含む固形分を得た。得られた分固形分をアセトン250部に12時間浸漬した。これをろ過して、ろ液からアセトンを70℃以下で留去して乾燥することでリグニン誘導体15.2重量部を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分43.5重量部、シュウ酸1.4重量部、37%ホルムアルデヒド水溶液73.3重量部を用いたこと以外は、調製例A1と同様にして、143.7重量部のリグニン変性フェノール樹脂A6を得た。
(リグニン誘導体の調製)含水率50%のブナ木粉を用いたこと以外は、調製例A3と同様にしてリグニン誘導体を得た。さらにリグニン誘導体をアセトンに分散させて、ろ過し、ろ液から70℃以下でアセトンを粒去して乾燥させることで低分子化したリグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分33.3重量部、シュウ酸1.3重量部、37%ホルムアルデヒド水溶液58.6重量部を用いたこと以外は調製例A1と同様にして、121.6重量部のリグニン変性フェノール樹脂A7を得た。
また得られたリグニン変性ノボラック型フェノール樹脂の重量平均分子量、数平均分子量およびリグニン変性率を測定した。これらの測定結果を表1に、「リグニン変性フェノール樹脂の特性」として示す。なお、本実施形態のリグニン変性ノボラックフェノール樹脂成分は、特に高分子量の成分を含むことがあったため、標準ポリスチレン数平均分子量42,7000を超える高分子量成分を除外した値も参考に表中( )内に記した。
各実施例および各比較例において、表1に示すリグニン変性フェノール樹脂100質量部にヘキサメチレンテトラミン(硬化剤)15質量部を常温で添加し、粉砕混合してフェノール変性リグニン樹脂組成物を調製した。
得られたフェノール変性リグニン樹脂組成物に対し、ガラス繊維(充填材、ガラスミルドファイバー、日東紡績(株)製、基準繊維径10±1.5μm、平均繊維長90μm)160重量部、添加剤(ステアリン酸(日本油脂社製)、カーボンブラック(三菱化学社製、#5))8重量部を配合し、約90℃の加熱ロールで約5分間混練し、冷却後粉砕して、フェノール変性リグニン樹脂組成物(成形材料)を得た。
(フェノール樹脂)
・フェノール樹脂A1:調製例A1のリグニン変性ノボラック型フェノール樹脂A1
・フェノール樹脂A2:調製例A2のリグニン変性ノボラック型フェノール樹脂A2
・フェノール樹脂A3:調製例A3のリグニン変性ノボラック型フェノール樹脂A3
・フェノール樹脂A4:調製例A4のリグニン変性ノボラック型フェノール樹脂A4
・フェノール樹脂A5:調製例A5のリグニン変性ノボラック型フェノール樹脂A5
・フェノール樹脂A6:調製例A6のリグニン変性ノボラック型フェノール樹脂A6
・フェノール樹脂A7:調製例A7のリグニン変性ノボラック型フェノール樹脂A7
・フェノール樹脂A8:未変性ノボラック型フェノール樹脂A8(Mw=9640、Mn=940)
得られた成形材料を、175℃、20MPa、3minの条件で、トランスファー成形し、さらに180℃、8hで加熱処理し、成形品(硬化物)を得た。得られた成形品を以下の項目について評価した。結果を表1に示す。
JIS K 6911「熱硬化性プラスチック一般試験方法」に準拠して、25℃において、曲げ弾性率および曲げ強度を測定した。具体的には、精密万能試験機(島津製作所社製 オートグラフAG-Xplus)にて、2mm/分の速度で荷重をかけて三点曲げ試験を行った。
(曲げ強度(150℃)、曲げ弾性率(150℃))
150℃において、上記と同様にして、曲げ弾性率および曲げ強度を測定した。
(シャルピー衝撃強度)
JIS K 6911「熱硬化性プラスチック一般試験方法」に準拠してシャルピー衝撃強度を測定した。
(絶縁抵抗)
JIS K 6911「熱硬化性プラスチック一般試験方法」に準拠して絶縁抵抗を測定した。
<リグニン変性ノボラック型フェノール樹脂の調製>
各調製例に示す方法にて、リグニン変性ノボラック型フェノール樹脂を調整した。
(リグニン誘導体の調製)蒸解液として、純水5000重量部、水酸化ナトリウム150重量部、硫化ナトリウム80重量部、炭酸ナトリウム70質量部および蒸解助剤として9,10-アントラキノン7.5重量部を用いたこと以外は、調製例A1と同様にして、リグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分37.4重量部、シュウ酸1.5重量部、37%ホルムアルデヒド水溶液51.2重量部を用いたこと以外は、調製例A1と同様にして、125.0重量部のリグニン変性フェノール樹脂B1を得た。
(リグニン誘導体の調製)含水率50%のブナ木粉に、蒸解液としてエタノール3000重量部、水2250重量部を用いて、195℃1時間で蒸解して、蒸解液からエタノールを分留して得られた水溶液を遠心分離して、凍結乾燥して固形分90%以上のリグニン誘導体を得たこと以外は調製例A1と同様にして、リグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分38.5重量部、シュウ酸1.4重量部、37%ホルムアルデヒド水溶液55.2重量部を用いたこと以外は、調製例A1と同様にして、123.3重量部のリグニン変性フェノール樹脂B2を得た。
(リグニン誘導体の調製)含水率50%のブナ木粉に、蒸解液としてエタノール3000重量部、水2250重量部を用いて、195℃1時間で蒸解して、蒸解液からエタノールを分留して得られた水溶液を遠心分離して、凍結乾燥して固形分90%以上のリグニン誘導体を得たこと以外は調製例A1と同様にして、リグニン誘導体を得た。
(リグニン変性フェノール樹脂の調製)フェノール100重量部、リグニン誘導体固形分79.2重量部、シュウ酸1.8重量部、37%ホルムアルデヒド水溶液51.7重量部を用いたこと以外は、調製例A1と同様にして、156.7重量部のリグニン変性フェノール樹脂B3を得た。
また得られたリグニン変性ノボラック型フェノール樹脂の重量平均分子量、数平均分子量およびリグニン変性率を測定した。これらの測定結果を表1に、「リグニン変性フェノール樹脂の特性」として示す。
なお、本実施形態のリグニン変性ノボラックフェノール樹脂成分は、特に高分子量の成分を含むことがあったため、標準ポリスチレン数平均分子量427,000を超える高分子量成分を除外した値も参考に表中( )内に記した。
各実施例および各比較例において、表2に示すリグニン変性フェノール樹脂100質量部と、硬化剤としてのヘキサメチレンテトラミン10質量部を混合し、パルペライザ―にて微粉化して、粒径10~60μmの粉末状樹脂組成物を得た。
(フェノール樹脂)
・フェノール樹脂B1:調製例B1のリグニン変性ノボラック型フェノール樹脂B1
・フェノール樹脂B2:調製例B2のリグニン変性ノボラック型フェノール樹脂B2
・フェノール樹脂B3:調製例3のリグニン変性ノボラック型フェノール樹脂B3
・フェノール樹脂B4:調製例A6のリグニン変性ノボラック型フェノール樹脂A6
・フェノール樹脂B5:未変性ノボラック型フェノール樹脂B5(Mw=12640、Mn=1204)
得られた粉末状樹脂組成物のフローを、以下の方法により測定した。
(フロー(流れ))
フェノール樹脂、又は、リグニン変性フェノール樹脂100重量部と、ヘキサメチレンテトラミン10重量部を混合粉砕して得られた粉末状樹脂組成物を使って、JIS K 6910「フェノール樹脂試験方法」の流れA法に準拠してフロー(流れ)を測定した。
粉末状樹脂組成物のフローが長いほど、その硬化物は高い強度を有する。
各実施例、および各比較例において、アルミナ砥粒、サクランダムA#60 (日本カーリット(株)製)1200部とウェッター用液状フェノール樹脂PR-55331(住友ベークライト(株)製)24部とを、品川式混練機を用いて4分間混練を行い、上記調製例で調製した各フェノール樹脂または未変性フェノール樹脂144部を添加して、更に2分間混練を行ってコーテットグレインを製造した。コーテッドグレインは、混練直後と、25℃相対湿度60%の条件で12時間保存した後で状態を確認した。その後、成形物が100mm×25mm×15mmの大きさで、かさ比重2.0となるように、コーテッドグレインを金型に投入してプレス成形を行い、成形物をステンレス製の鉄板に載せた。これをプログラム機能の付いた熱風循環式の乾燥機に入れて、常温から80℃まで5時間、80℃から100℃まで5時間、100℃から120℃まで10時間、120℃から130℃まで4時間、130℃から170℃まで7時間、180℃で10時間保持、その後5時間かけて常温に冷却するプログラムを用いて硬化させ、砥石試験片を製造した。
得られた砥石試験片を、以下の項目について評価した。評価結果を表2に示す。
JIS K 6911「熱硬化性プラスチック一般試験方法」に準拠して、25℃において、曲げ弾性率および曲げ強度を測定した。具体的には、精密万能試験機(島津製作所社製 オートグラフAG-Xplus)にて、2mm/分の速度で荷重をかけて三点曲げ試験を行った。
(耐水強度)
耐水強度は試験片を80℃の水に2時間浸漬させて、取り出して常温曲げ強度と同様の条件で測定を行った。
(耐熱強度)
耐熱強度は試験片をセットして、恒温槽にて200℃下にして15分静置して、常温曲げ強度と同様の条件で測定を行った。結果を表2に示す。
Claims (13)
- 重量平均分子量が5500以上であるリグニン変性ノボラック型フェノール樹脂。
- 当該リグニン変性ノボラック型フェノール樹脂のリグニン変性率が、25%以上60%以下である、請求項1に記載のリグニン変性ノボラック型フェノール樹脂。
- 当該リグニン変性ノボラック型フェノール樹脂が、
リグニン類と、フェノール類と、アルデヒド類とを、酸触媒の存在下、前記フェノール類に対する前記アルデヒド類のモル比(F/P)が0.5以上である条件で反応させて得られる樹脂である、請求項1または2に記載のリグニン変性ノボラック型フェノール樹脂。 - 前記リグニン類の重量平均分子量が、2,000以上100,000以下である、請求項3に記載のリグニン変性ノボラック型フェノール樹脂。
- 請求項1乃至4のいずれか一項に記載のリグニン変性ノボラック型フェノール樹脂と、
硬化剤と、を含む、成形材料。 - 請求項1乃至4のいずれか一項に記載のリグニン変性ノボラック型フェノール樹脂と、
ヘキサメチレンテトラミンとを含む、樹脂組成物。 - 平均粒径が10μm以上60μm以下の粉末状である、請求項6に記載の樹脂組成物。
- 請求項7に記載の樹脂組成物の硬化物からなる砥石。
- リグニン類と、フェノール類と、アルデヒド類とを、酸触媒の存在下、前記フェノール類に対する前記アルデヒド類のモル比(F/P)が0.5以上である条件で反応させることにより、リグニン変性ノボラック型フェノール樹脂を得る工程を含み、
前記リグニン変性ノボラック型フェノール樹脂の重量平均分子量が5500以上である、
リグニン変性ノボラック型フェノール樹脂の製造方法。 - 前記リグニン変性ノボラック型フェノール樹脂のリグニン変性率が、25%以上50%以下である、請求項9に記載のリグニン変性ノボラック型フェノール樹脂の製造方法。
- 前記リグニンの重量平均分子量が、2,000以上100,000以下である、請求項9または10に記載のリグニン変性ノボラック型フェノール樹脂の製造方法。
- 前記リグニン類が、揮発分を60質量%以下の量で含む、請求項9乃至11のいずれか一項に記載のリグニン変性ノボラック型フェノール樹脂の製造方法。
- リグニン類と、フェノール類と、アルデヒド類とを、酸触媒の存在下、前記フェノール類に対する前記アルデヒド類のモル比(F/P)が0.5以上である条件で反応させる前記工程が、
前記リグニン類と前記フェノール類とを混合して混合物を得る工程と、
混合物を得る前記工程と同時、または混合物を得る前記工程の後に、前記酸触媒を混合する工程と、
酸触媒を混合する前記工程の後に、前記アルデヒド類を混合する工程と、
150℃以上で常圧、及び/又は、減圧蒸留する工程と、を含む、
請求項9乃至12のいずれか一項に記載のリグニン変性ノボラック型フェノール樹脂の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/551,005 US20240174786A1 (en) | 2021-04-06 | 2022-03-25 | Lignin-modified novolac-type phenol resin, method for producing same, molding material, resin composition, and grindstone |
JP2022559969A JP7279865B2 (ja) | 2021-04-06 | 2022-03-25 | リグニン変性ノボラック型フェノール樹脂の製造方法 |
CN202280026387.0A CN117120498A (zh) | 2021-04-06 | 2022-03-25 | 木质素改性酚醛清漆型酚醛树脂及其制造方法以及成型材料、树脂组合物和磨具 |
EP22784538.5A EP4321300A1 (en) | 2021-04-06 | 2022-03-25 | Lignin-modified novolac-type phenol resin, method for producing same, molding material, resin composition, and grindstone |
JP2023049656A JP2023076559A (ja) | 2021-04-06 | 2023-03-27 | リグニン変性ノボラック型フェノール樹脂およびその製造方法、ならびに成形材料、樹脂組成物および砥石 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-064596 | 2021-04-06 | ||
JP2021064596 | 2021-04-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022215553A1 true WO2022215553A1 (ja) | 2022-10-13 |
Family
ID=83545395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/014561 WO2022215553A1 (ja) | 2021-04-06 | 2022-03-25 | リグニン変性ノボラック型フェノール樹脂およびその製造方法、ならびに成形材料、樹脂組成物および砥石 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240174786A1 (ja) |
EP (1) | EP4321300A1 (ja) |
JP (2) | JP7279865B2 (ja) |
CN (1) | CN117120498A (ja) |
WO (1) | WO2022215553A1 (ja) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0343442A (ja) * | 1989-07-12 | 1991-02-25 | Hitachi Chem Co Ltd | リグノセルロース−フェノールノボラック樹脂及びリグノセルロース−フェノールノボラック樹脂形成物の製造法 |
JP2004307805A (ja) * | 2003-03-25 | 2004-11-04 | Sumitomo Bakelite Co Ltd | レジノイド砥石用ノボラック型フェノール樹脂及び組成物 |
JP2009084320A (ja) | 2007-09-27 | 2009-04-23 | Sumitomo Bakelite Co Ltd | リグニン誘導体及びその二次誘導体 |
JP2012201828A (ja) | 2011-03-25 | 2012-10-22 | Sumitomo Bakelite Co Ltd | リグニン誘導体の製造方法、リグニン二次誘導体の製造方法、リグニン誘導体およびリグニン二次誘導体 |
CN103145938A (zh) * | 2013-03-26 | 2013-06-12 | 山东圣泉化工股份有限公司 | 木质素改性酚醛树脂、其合成方法及包括其的砂轮 |
JP2013199561A (ja) | 2012-03-23 | 2013-10-03 | Akebono Brake Ind Co Ltd | 摩擦材 |
US20190390106A1 (en) * | 2017-01-27 | 2019-12-26 | Lawter, Inc. | Biorenewable resin composition for well treatment |
JP2020050814A (ja) * | 2018-09-28 | 2020-04-02 | 住友ベークライト株式会社 | フェノール変性リグニン樹脂を含む樹脂材料、それを用いたフェノール変性リグニン樹脂組成物および構造体 |
JP2021064596A (ja) | 2019-10-11 | 2021-04-22 | 呉剛 | 電球の検査と修理に便利であるランプホルダー |
JP2021138806A (ja) * | 2020-03-03 | 2021-09-16 | 住友ベークライト株式会社 | リグニン変性ノボラック型フェノール樹脂の製造方法、および架橋体の製造方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105873970B (zh) * | 2014-03-28 | 2019-09-10 | 住友电木株式会社 | 酚改性木质素树脂和其制造方法、以及树脂组合物、橡胶组合物和固化物 |
-
2022
- 2022-03-25 JP JP2022559969A patent/JP7279865B2/ja active Active
- 2022-03-25 WO PCT/JP2022/014561 patent/WO2022215553A1/ja active Application Filing
- 2022-03-25 US US18/551,005 patent/US20240174786A1/en active Pending
- 2022-03-25 EP EP22784538.5A patent/EP4321300A1/en active Pending
- 2022-03-25 CN CN202280026387.0A patent/CN117120498A/zh active Pending
-
2023
- 2023-03-27 JP JP2023049656A patent/JP2023076559A/ja active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0343442A (ja) * | 1989-07-12 | 1991-02-25 | Hitachi Chem Co Ltd | リグノセルロース−フェノールノボラック樹脂及びリグノセルロース−フェノールノボラック樹脂形成物の製造法 |
JP2004307805A (ja) * | 2003-03-25 | 2004-11-04 | Sumitomo Bakelite Co Ltd | レジノイド砥石用ノボラック型フェノール樹脂及び組成物 |
JP2009084320A (ja) | 2007-09-27 | 2009-04-23 | Sumitomo Bakelite Co Ltd | リグニン誘導体及びその二次誘導体 |
JP2012201828A (ja) | 2011-03-25 | 2012-10-22 | Sumitomo Bakelite Co Ltd | リグニン誘導体の製造方法、リグニン二次誘導体の製造方法、リグニン誘導体およびリグニン二次誘導体 |
JP2013199561A (ja) | 2012-03-23 | 2013-10-03 | Akebono Brake Ind Co Ltd | 摩擦材 |
CN103145938A (zh) * | 2013-03-26 | 2013-06-12 | 山东圣泉化工股份有限公司 | 木质素改性酚醛树脂、其合成方法及包括其的砂轮 |
US20190390106A1 (en) * | 2017-01-27 | 2019-12-26 | Lawter, Inc. | Biorenewable resin composition for well treatment |
JP2020050814A (ja) * | 2018-09-28 | 2020-04-02 | 住友ベークライト株式会社 | フェノール変性リグニン樹脂を含む樹脂材料、それを用いたフェノール変性リグニン樹脂組成物および構造体 |
JP2021064596A (ja) | 2019-10-11 | 2021-04-22 | 呉剛 | 電球の検査と修理に便利であるランプホルダー |
JP2021138806A (ja) * | 2020-03-03 | 2021-09-16 | 住友ベークライト株式会社 | リグニン変性ノボラック型フェノール樹脂の製造方法、および架橋体の製造方法 |
Non-Patent Citations (1)
Title |
---|
REN YU, LIN XU, WANG WENLIN, SHI ZHENGJUN, ZHENG ZHIFENG, LIU CAN: "Preparation of high molecular weight thermoplastic bio-based phenolic resin and fiber based on lignin liquefaction", MATERIALS RESEARCH EXPRESS, vol. 8, no. 1, 1 January 2021 (2021-01-01), pages 015308, XP055974910, DOI: 10.1088/2053-1591/abda68 * |
Also Published As
Publication number | Publication date |
---|---|
CN117120498A (zh) | 2023-11-24 |
JP2023076559A (ja) | 2023-06-01 |
JP7279865B2 (ja) | 2023-05-23 |
JPWO2022215553A1 (ja) | 2022-10-13 |
EP4321300A1 (en) | 2024-02-14 |
US20240174786A1 (en) | 2024-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kalami et al. | Replacing 100% of phenol in phenolic adhesive formulations with lignin | |
JP6541007B2 (ja) | フェノール変性リグニン樹脂及びその製造方法、並びに、樹脂組成物、ゴム組成物、及び硬化物 | |
JP6733546B2 (ja) | ゴム組成物およびリグニン誘導体の製造方法 | |
JP2023024831A (ja) | 改質リグニンの製造方法及び改質リグニン、並びに改質リグニン含有樹脂組成材料 | |
WO2007124400A2 (en) | Methods for producing modified aromatic renewable materials and compositions thereof | |
KR102678221B1 (ko) | 노볼락 페놀 수지, 상기 페놀 수지의 합성 방법 및 이의 용도 | |
JP7215046B2 (ja) | フェノール変性リグニン樹脂を含有する樹脂材料の製造方法、それを用いた構造体の製造方法 | |
US5300593A (en) | Lignin modified binding agents | |
Qiao et al. | Preparation and characterization of a Phenol-formaldehyde resin Adhesive obtained From Bio-ethanol Production residue | |
JP2020050814A (ja) | フェノール変性リグニン樹脂を含む樹脂材料、それを用いたフェノール変性リグニン樹脂組成物および構造体 | |
Xu et al. | Lignin-based phenol–formaldehyde (LPF) resins/adhesives | |
JP7279865B2 (ja) | リグニン変性ノボラック型フェノール樹脂の製造方法 | |
JPWO2018190171A1 (ja) | 摩擦材 | |
JP7459564B2 (ja) | リグニン変性ノボラック型フェノール樹脂の製造方法、および架橋体の製造方法 | |
JP7197064B1 (ja) | 摩擦材用熱硬化性樹脂組成物および摩擦材 | |
JP7538102B2 (ja) | リグニン組成物及びその使用 | |
JP7396549B1 (ja) | 樹脂組成物およびレジンコーテッドサンド | |
Omar et al. | The Use of Environmentally Friendly Bio-Oil in the Production of Phenol Formaldehyde (PF) Resin. | |
JP4402499B2 (ja) | 熱硬化性バイオマス樹脂組成物およびその成形品 | |
Zhang et al. | Effect of starch and lignin on physico‐chemical properties of phenol–starch resin and its resin core sand | |
JP7539638B2 (ja) | 摺動材 | |
JP7539639B2 (ja) | 摺動材 | |
WO2022145280A1 (ja) | リグニン組成物及びその使用 | |
JP2020094078A (ja) | 摺動材 | |
JP2023024830A (ja) | 改質リグニン及び改質ポリフェノールの製造方法、並びに改質リグニンを用いた樹脂組成材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2022559969 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22784538 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18551005 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022784538 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022784538 Country of ref document: EP Effective date: 20231106 |