JP2010090297A - Phenol resin - Google Patents
Phenol resin Download PDFInfo
- Publication number
- JP2010090297A JP2010090297A JP2008262599A JP2008262599A JP2010090297A JP 2010090297 A JP2010090297 A JP 2010090297A JP 2008262599 A JP2008262599 A JP 2008262599A JP 2008262599 A JP2008262599 A JP 2008262599A JP 2010090297 A JP2010090297 A JP 2010090297A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- phenol
- compound
- resin
- saccharides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 79
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 133
- 150000001720 carbohydrates Chemical class 0.000 claims description 58
- 229930091371 Fructose Natural products 0.000 claims description 26
- 239000005715 Fructose Substances 0.000 claims description 26
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 26
- 150000002989 phenols Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 hydroxycumyl group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 11
- 239000004902 Softening Agent Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 54
- 229940126062 Compound A Drugs 0.000 description 43
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 43
- 239000007787 solid Substances 0.000 description 36
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 27
- 229920001568 phenolic resin Polymers 0.000 description 26
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 235000014633 carbohydrates Nutrition 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 229920002472 Starch Polymers 0.000 description 10
- 235000019698 starch Nutrition 0.000 description 10
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 9
- 239000008107 starch Substances 0.000 description 9
- 235000000346 sugar Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920001353 Dextrin Polymers 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- 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 4
- 235000019425 dextrin Nutrition 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical compound CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229920002670 Fructan Polymers 0.000 description 1
- 102000004366 Glucosidases Human genes 0.000 description 1
- 108010056771 Glucosidases Proteins 0.000 description 1
- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 description 1
- 102000004195 Isomerases Human genes 0.000 description 1
- 108090000769 Isomerases Proteins 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- FTSSQIKWUOOEGC-RULYVFMPSA-N fructooligosaccharide Chemical compound OC[C@H]1O[C@@](CO)(OC[C@@]2(OC[C@@]3(OC[C@@]4(OC[C@@]5(OC[C@@]6(OC[C@@]7(OC[C@@]8(OC[C@@]9(OC[C@@]%10(OC[C@@]%11(O[C@H]%12O[C@H](CO)[C@@H](O)[C@H](O)[C@H]%12O)O[C@H](CO)[C@@H](O)[C@@H]%11O)O[C@H](CO)[C@@H](O)[C@@H]%10O)O[C@H](CO)[C@@H](O)[C@@H]9O)O[C@H](CO)[C@@H](O)[C@@H]8O)O[C@H](CO)[C@@H](O)[C@@H]7O)O[C@H](CO)[C@@H](O)[C@@H]6O)O[C@H](CO)[C@@H](O)[C@@H]5O)O[C@H](CO)[C@@H](O)[C@@H]4O)O[C@H](CO)[C@@H](O)[C@@H]3O)O[C@H](CO)[C@@H](O)[C@@H]2O)[C@@H](O)[C@@H]1O FTSSQIKWUOOEGC-RULYVFMPSA-N 0.000 description 1
- 229940107187 fructooligosaccharide Drugs 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000004043 trisaccharides Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、鋳造用鋳型、成型材料、エポキシ硬化剤、各種バインダ等に用いられるフェノール樹脂に関する。 The present invention relates to a phenol resin used for casting molds, molding materials, epoxy curing agents, various binders and the like.
植物は、繰り返し同じ土地で生産でき、石油や鉱物よりも短時間で再生される資源である。そのため、植物由来の原料を使用したプラスチックは、いわゆるカーボンニュートラルの材料であり、石油等の鉱物資源から製造したプラスチックよりも二酸化炭素排出量を削減できる。
植物由来の原料を使用したプラスチックとしては、熱可塑性であるポリ乳酸が広く知られている。しかしながら、植物由来の熱可塑性プラスチックは耐熱性が低く利用分野が限られるという問題を有していた。
そこで、耐熱性の向上を目的として、植物由来材料を用いた熱硬化性のプラスチックの開発が進められている。例えば、特許文献１には、フェノール類と砂糖類及び澱粉類の混合物とを、酸性触媒の存在下で反応させて得たフェノール樹脂が開示されている。
As a plastic using plant-derived raw materials, thermoplastic polylactic acid is widely known. However, plant-derived thermoplastics have a problem that their heat resistance is low and their fields of use are limited.
Therefore, for the purpose of improving heat resistance, development of thermosetting plastics using plant-derived materials is underway. For example, Patent Document 1 discloses a phenol resin obtained by reacting a mixture of phenols with sugars and starches in the presence of an acidic catalyst.
ところが、特許文献１に記載のフェノール樹脂は高軟化点で成型時の流動性が低く、硬化物を得るための成型の際の成型加工性が不充分であった。
また、従来のフェノール樹脂では、硬化時におけるホルムアルデヒドおよびアミン等の有害な分解ガスの発生の問題から、フェノール樹脂の硬化物を得る際に使用するヘキサメチレンテトラミン等の硬化剤量が少なくて済むものが求められる。しかしながら、特許文献１に記載のフェノール樹脂では、硬化剤の使用量を少なくすることはできなかった。
本発明は、低軟化点で成型時の流動性が高くて成型加工性に優れ、しかも硬化物を得る際の硬化剤の使用量を低減できるフェノール樹脂を提供することを目的とする。
However, the phenol resin described in Patent Document 1 has a high softening point and low fluidity at the time of molding, and the molding processability at the time of molding to obtain a cured product is insufficient.
Also, with conventional phenol resins, the amount of curing agent such as hexamethylenetetramine used to obtain a cured product of phenol resin is small because of the generation of harmful decomposition gases such as formaldehyde and amine during curing. Is required. However, the phenol resin described in Patent Document 1 cannot reduce the amount of curing agent used.
An object of the present invention is to provide a phenol resin that has a low softening point, has high fluidity during molding, is excellent in molding processability, and can reduce the amount of a curing agent used in obtaining a cured product.
本発明は、以下の構成を有する。
［１］下記式（１）で表わされる化合物を含有することを特徴とするフェノール樹脂。
（式（１）におけるＲ１，Ｒ２は、各々独立して、アルキル基、アルコキシ基、ハロゲン基、フェニル基、クミル基、ヒドロキシクミル基のいずれかである。）
The present invention has the following configuration.
[1] A phenol resin containing a compound represented by the following formula (1).
(R 1 and R 2 in the formula (1) are each independently an alkyl group, an alkoxy group, a halogen group, a phenyl group, a cumyl group, or a hydroxycumyl group.)
［２］ 糖質類とフェノール類との反応によって得られた［１］に記載のフェノール樹脂。
［３］ フルクトースを５質量％以上含有する糖質類とフェノール類との反応によって得られた［１］に記載のフェノール樹脂。
[2] The phenol resin according to [1] obtained by a reaction between a saccharide and a phenol.
[3] The phenol resin according to [1] obtained by a reaction between a carbohydrate containing 5% by mass or more of fructose and a phenol.
本発明のフェノール樹脂は、低軟化点で成型時の流動性が高くて成型加工性に優れ、しかも硬化物を得る際の硬化剤の使用量を低減できる。 The phenol resin of the present invention has a low softening point, high fluidity during molding, excellent molding processability, and can reduce the amount of a curing agent used in obtaining a cured product.
本発明のフェノール樹脂は、上記式（１）で表わされる化合物（以下、化合物Ａという。）を含有する。
式（１）におけるＲ１，Ｒ２は、各々独立して、水素原子、アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基等）、アルコキシ基（例えば、メトキシ基等）、ハロゲン基（例えば、ブロモ基等）、フェニル基、クミル基、ヒドロキシクミル基のいずれかである。これらの中でも、水素原子、アルキル基、ヒドロキシクミル基が好ましい。
Ｒがアルキル基、アルコキシ基、ハロゲン基、フェニル基、クミル基のいずれかである場合、Ｒの位置は、ヒドロキシ基に対してオルト位、メタ位、パラ位のいずれであってもよい。
The phenol resin of the present invention contains a compound represented by the above formula (1) (hereinafter referred to as compound A).
R 1 and R 2 in formula (1) are each independently a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), an alkoxy group (eg, methoxy group, etc.), halogen Group (for example, bromo group, etc.), phenyl group, cumyl group, or hydroxycumyl group. Among these, a hydrogen atom, an alkyl group, and a hydroxycumyl group are preferable.
When R is any one of an alkyl group, an alkoxy group, a halogen group, a phenyl group, and a cumyl group, the position of R may be any of an ortho position, a meta position, and a para position with respect to the hydroxy group.
化合物Ａを含む本発明のフェノール樹脂は、酸性触媒存在下、糖質類と、フェノール類および必要に応じてホルムアルデヒドとの反応によって製造される。
化合物Ａは、フェノール類とヒドロキシメチルフルフラールとの反応物であるが、ヒドロキシメチルフルフラールは糖質類に含まれていない。ヒドロキシメチルフルフラールは、フェノール類と糖質類との反応時に酸性触媒が存在することによって、糖質類から生成する。
The phenol resin of the present invention containing Compound A is produced by the reaction of carbohydrates with phenols and optionally formaldehyde in the presence of an acidic catalyst.
Compound A is a reaction product of phenols and hydroxymethylfurfural, but hydroxymethylfurfural is not contained in carbohydrates. Hydroxymethylfurfural is produced from carbohydrates due to the presence of an acidic catalyst during the reaction between phenols and carbohydrates.
化合物Ａが糖質類とフェノール類との反応物からなる場合には、化合物Ａの含有量は、フェノール樹脂全体を１００質量％とした際の１．０〜２５質量％であることが好ましく、１．５〜１７質量％であることがより好ましく、２．０〜１５質量％であることが特に好ましい。化合物Ａの含有量が１質量％以上であれば、流動性を充分に向上させることができ、２５質量％以下であれば、実用的な機械的物性を有する。
化合物Ａの含有量を前記範囲にするためには、例えば、フェノール類と糖質類との反応の際に、糖質類を１とした際にフェノール類を２〜２０倍にする方法、糖質類としてフルクトース、フルクトース含有糖類を選択する方法などを適用すればよい。
フェノール樹脂における化合物Ａ以外の成分としては、化合物Ａにさらにフェノール類および／または糖質類が反応した化合物が挙げられる。例えば、化合物Ａに１分子のフェノールが反応したもの、化合物Ａに１分子のヒドロキシメチルフルフラールが反応したもの、化合物Ａに１分子のフェノールと１分子のヒドロキシメチルフルフラールが反応したもの、化合物Ａに２分子以上のフェノールが反応したもの、化合物Ａに２分子以上のヒドロキシメチルフルフラールが反応したもの、化合物Ａに２分子以上のフェノールと２分子以上のヒドロキシメチルフルフラールが反応したものなどが挙げられる。
反応の際に、ホルムアルデヒドを共存させる場合には、一部のフェノールはホルムアルデヒドを介して化合物Ａに反応する。また、フェノール同士がアルデヒドを介して結合したものも生成する。
なお、フェノール樹脂における化合物Ａ以外の成分として、硬化剤は含まれない。
When compound A consists of a reaction product of carbohydrates and phenols, the content of compound A is preferably 1.0 to 25% by mass when the total phenol resin is 100% by mass, More preferably, it is 1.5-17 mass%, and it is especially preferable that it is 2.0-15 mass%. If the content of Compound A is 1% by mass or more, the fluidity can be sufficiently improved, and if it is 25% by mass or less, it has practical mechanical properties.
In order to make the content of Compound A within the above range, for example, in the reaction of phenols and carbohydrates, the method of increasing the phenols 2 to 20 times when the carbohydrates are set to 1, sugar What is necessary is just to apply the method etc. which select fructose and fructose containing saccharides as quality.
Examples of components other than Compound A in the phenol resin include compounds obtained by further reacting Compound A with phenols and / or carbohydrates. For example, compound A is reacted with one molecule of phenol, compound A is reacted with one molecule of hydroxymethylfurfural, compound A is reacted with one molecule of phenol and one molecule of hydroxymethylfurfural, compound A Examples include those in which two or more molecules of phenol have reacted, compound A in which two or more molecules of hydroxymethylfurfural have reacted, compound A in which two or more molecules of phenol and two or more molecules of hydroxymethylfurfural have reacted.
When formaldehyde is allowed to coexist in the reaction, a part of phenol reacts with compound A via formaldehyde. Moreover, what couple | bonded phenols through the aldehyde also produces | generates.
In addition, a hardening | curing agent is not contained as components other than the compound A in a phenol resin.
また、フェノール樹脂には、例えば、顔料、離型剤、酸化防止剤、シランカップリング剤、紫外線吸収剤などの添加剤が含まれてもよい。 Moreover, additives, such as a pigment, a mold release agent, antioxidant, a silane coupling agent, a ultraviolet absorber, may be contained in a phenol resin, for example.
フェノール樹脂を得るために用いるフェノール類としては、例えば、フェノール、クレゾール、キシレノール、プロピルフェノール、ブチルフェノール、ブチルクレゾール、フェニルフェノール、クミルフェノール、メトキシフェノール、ブロモフェノール、ビスフェノールＡなどが挙げられる。
これらの中でも、反応性が高く、しかも入手容易な点で、フェノール、クレゾール、キシレノール、ビスフェノールＡが好ましい。
Examples of the phenols used for obtaining the phenol resin include phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, bisphenol A, and the like.
Among these, phenol, cresol, xylenol, and bisphenol A are preferable because they are highly reactive and easily available.
糖質類としては、単糖類、２糖類、３糖類、少糖類、多糖類が挙げられる。具体的には、グルコース、フルクトース、マンノース、ガラクトース、アラビノース、キシロース、マルトース、イソマルソース、ラクトース、スクロース、トレハロース、ラフィノース、異性化糖、デキストリン、オリゴ糖、フラクタン、フラクオリゴ糖、澱粉、粗澱粉、アミロース、アミロペクチン、廃棄糖蜜（澱粉かす）などが挙げられる。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
これらの中でも、ヒドロキシメチルフルフラールを生成しやすく、化合物Ａが得られやすいことから、フルクトース、フルクトースを含有する糖類が好ましい。フルクトース含有糖類としては、具体的には、異性化糖、ショ糖が挙げられる。
また、糖質類は、ヒドロキシメチルフルフラールを生成しやすく、化合物Ａが得られやすいことから、澱粉液化処理液であることも好ましい。澱粉を液化処理する方法としては、例えば、水溶液化した澱粉を酸または酵素によって糖化する方法などが挙げられる。糖化に使用できる酸としては、例えば、硫酸、パラトルエンスルホン酸、キシレンスルホン酸、フェノールスルホン酸などが挙げられ、酵素としては、例えば、アミラーゼ、グルコシダーゼ、イソメラーゼなどが挙げられる。
Examples of carbohydrates include monosaccharides, disaccharides, trisaccharides, oligosaccharides, and polysaccharides. Specifically, glucose, fructose, mannose, galactose, arabinose, xylose, maltose, isomaltose, lactose, sucrose, trehalose, raffinose, isomerized sugar, dextrin, oligosaccharide, fructan, fructooligosaccharide, starch, crude starch, amylose, Examples include amylopectin, waste molasses (starch residue), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these, since it is easy to produce | generate hydroxymethylfurfural and compound A is easy to be obtained, fructose and the saccharide containing fructose are preferable. Specific examples of the fructose-containing saccharide include isomerized sugar and sucrose.
Moreover, since saccharides are easy to produce | generate hydroxymethylfurfural and compound A is easy to be obtained, it is also preferable that it is a starch liquefaction process liquid. Examples of the method for liquefying starch include a method of saccharifying starch in an aqueous solution with an acid or an enzyme. Examples of the acid that can be used for saccharification include sulfuric acid, paratoluenesulfonic acid, xylenesulfonic acid, and phenolsulfonic acid. Examples of the enzyme include amylase, glucosidase, and isomerase.
糖質類は、フルクトースを、糖質類の固形分全体を１００質量％とした際に５質量％以上含有することが好ましく、３０質量％以上含有することがより好ましく、５５質量％以上含有することが特に好ましい。さらには、糖質類の１００質量％がフルクトースであることが最も好ましい。糖質類がフルクトースを５質量％以上含有すれば、化合物Ａを充分量形成できるため、フェノール樹脂の流動性をより高くでき、成型加工性をより向上させることができる。 The carbohydrates preferably contain 5% by mass or more, more preferably 30% by mass or more, more preferably 55% by mass or more of fructose when the total solid content of the carbohydrates is 100% by mass. It is particularly preferred. Further, it is most preferable that 100% by mass of the carbohydrates is fructose. If the saccharides contain 5% by mass or more of fructose, a sufficient amount of Compound A can be formed, so that the fluidity of the phenol resin can be increased and the molding processability can be further improved.
フェノール樹脂を得る際の糖質類とフェノール類との質量比率は、糖質類を１とした際にフェノール類が２〜２０倍であることが好ましく、３〜６倍であることがより好ましい。フェノール類が糖質類の２倍以上であれば、反応率を高くして収率を高くできる上に分子量を高くでき、２０倍以下であれば、得られるフェノール樹脂について充分な天然由来率を確保できる。
また、糖質類を１とした際にフェノール類が２〜２０倍であれば、フェノール樹脂中の化合物Ａを、フェノール樹脂全体を１００質量％とした際の１〜２５質量％にすることが容易になる。
The mass ratio of saccharides to phenols in obtaining the phenol resin is preferably 2 to 20 times, more preferably 3 to 6 times the phenols when the saccharides is 1. . If phenols are 2 times or more of carbohydrates, the reaction rate can be increased to increase the yield, and the molecular weight can be increased. If it is 20 times or less, sufficient natural origin rate is obtained for the resulting phenol resin. It can be secured.
Moreover, if phenols are 2 to 20 times when carbohydrates are set to 1, the compound A in the phenol resin may be 1 to 25% by mass when the entire phenol resin is 100% by mass. It becomes easy.
糖質類とフェノール類とを反応させる際には、酸性触媒が用いられる。酸性触媒としては、例えば、鉱酸類（例えば、塩酸、硫酸等）、有機酸類（例えば、パラトルエンスルホン酸、シュウ酸等）などが使用される。
酸性触媒の使用量は、糖質類の固形分とフェノール類との合計を１００質量％とした際に０．１〜５０質量％であることが好ましく、０．２〜１０質量％であることがより好ましい。酸性触媒の使用量が０．１質量％以上であれば、充分な量の化合物Ａを生成でき、５０質量％以下であれば、酸分解やゲル化を抑制できる。
An acidic catalyst is used when reacting carbohydrates and phenols. As the acidic catalyst, for example, mineral acids (for example, hydrochloric acid, sulfuric acid, etc.), organic acids (for example, paratoluenesulfonic acid, oxalic acid, etc.) are used.
The amount of the acidic catalyst used is preferably 0.1 to 50% by mass, and preferably 0.2 to 10% by mass, when the total of the solid content of saccharides and phenols is 100% by mass. Is more preferable. If the usage-amount of an acidic catalyst is 0.1 mass% or more, sufficient quantity of the compound A can be produced | generated, and if it is 50 mass% or less, acid decomposition and gelatinization can be suppressed.
反応温度は２０〜２００℃であることが好ましく、１２０〜１６０℃であることがより好ましい。反応温度が２０℃以上であれば、充分に反応させることができ、２００℃以下であれば、分解を抑制できる。
反応時間は０．５〜２０時間であることが好ましく、１〜３時間であることがより好ましい。反応時間が０．５時間以上であれば、高い収率でフェノール樹脂を得ることができ、２０時間以下であれば、生産性の低下を抑制できる。
The reaction temperature is preferably 20 to 200 ° C, more preferably 120 to 160 ° C. If reaction temperature is 20 degreeC or more, it can be made to react sufficiently, and if it is 200 degrees C or less, decomposition | disassembly can be suppressed.
The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 3 hours. If the reaction time is 0.5 hours or longer, a phenol resin can be obtained in a high yield, and if it is 20 hours or shorter, a decrease in productivity can be suppressed.
上記化合物Ａを含有するフェノール樹脂は、低軟化点で流動性が高く、成型加工性に優れている。また、天然成分の糖質類を用いているから、二酸化炭素排出量を削減できる。
また、化合物Ａはアルデヒド基を有するため、本発明のフェノール樹脂は、硬化剤が共存しなくても、酸性触媒の存在下で硬化して、硬化物を形成できる。したがって、本発明のフェノール樹脂を硬化する際に、ホルムアルデヒド発生の原因になる硬化剤（例えば、ヘキサメチレンテトラミン、ベンジルアミン、ベンゾオキサジン、アゾメチン等）の使用量を減らすことができる。
The phenol resin containing the compound A has a low softening point, high fluidity, and excellent molding processability. In addition, carbon dioxide emissions can be reduced due to the use of natural carbohydrates.
Moreover, since the compound A has an aldehyde group, the phenol resin of the present invention can be cured in the presence of an acidic catalyst to form a cured product even in the absence of a curing agent. Therefore, when the phenol resin of the present invention is cured, the amount of a curing agent (for example, hexamethylenetetramine, benzylamine, benzoxazine, azomethine, etc.) that causes formaldehyde generation can be reduced.
本発明のフェノール樹脂は、例えば、鋳造用鋳型、成型材料、エポキシ硬化剤、布紙強化用バインダ、塗料、砥石用樹脂等に用いることができる。 The phenolic resin of the present invention can be used, for example, for casting molds, molding materials, epoxy curing agents, binders for reinforcing cloth, paints, grinding stone resins, and the like.
以下の実施例および比較例では、得られたフェノール樹脂について、化合物Ａの含有量、軟化点、流動性、天然由来率を以下の方法で調べた。
［化合物Ａの含有量］
得られたフェノール樹脂をテトラヒドロフランに溶解した溶液を測定試料とし、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）を下記条件により測定し、数平均分子量２０２のピーク面積率を化合物Ａの含有量とした。
・ＧＰＣ測定条件
ＧＰＣ測定装置：東ソー社製 ＨＬＣ８１２０ＧＰＣ
カラム：ＴＳＫｇｅｌ Ｇ３０００Ｈ＋Ｇ２０００Ｈ＋Ｇ２０００Ｈ
ピークの物質の同定：日本電子社製 質量分析計ＳＸ−１０２Ａ、及び日本電子社製 核磁気共鳴装置 ＬＡ−４００
［軟化点］
ＪＩＳ Ｋ ２２０７に準じて軟化点を測定した。
［流動性］
ＪＩＳ Ｋ ６９１０に準じて流動性を測定した。この流動性は、単位時間当たりの流動長さ［ｍｍ］を示しており、値が大きい程、流動性に優れる。
［天然由来率］
天然由来率 ＝１００−｛１００×［（フェノール仕込み質量）−（留去した未反応フェノール質量）］／（樹脂収量）｝
なお、この天然由来率が高い程、二酸化炭素排出量が少なくなる。
In the following Examples and Comparative Examples, the content, the softening point, the fluidity, and the natural origin rate of Compound A were examined for the obtained phenolic resin by the following methods.
[Content of Compound A]
A solution obtained by dissolving the obtained phenol resin in tetrahydrofuran was used as a measurement sample, gel permeation chromatography (GPC) was measured under the following conditions, and the peak area ratio of the number average molecular weight 202 was defined as the content of Compound A.
GPC measurement conditions GPC measurement device: HLC8120GPC manufactured by Tosoh Corporation
Column: TSKgel G3000H + G2000H + G2000H
Identification of peak substance: mass spectrometer SX-102A manufactured by JEOL Ltd. and nuclear magnetic resonance apparatus LA-400 manufactured by JEOL Ltd.
[Softening point]
The softening point was measured according to JIS K 2207.
[Liquidity]
The fluidity was measured according to JIS K 6910. This fluidity indicates the flow length [mm] per unit time, and the greater the value, the better the fluidity.
[Natural origin rate]
Natural origin rate = 100− {100 × [(phenol charge mass) − (distilled unreacted phenol mass)] / (resin yield)}
In addition, the higher the natural origin rate, the smaller the carbon dioxide emission.
（実施例１）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、グルコース３７６ｇ、パラトルエンスルホン酸７．５ｇを仕込んだ。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．６ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール３３３ｇを留去し、１０６０ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表１に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、フェノール樹脂１００質量％に対してパラトルエンスルホン酸１質量％を添加して、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
Example 1
1128 g of phenol, 376 g of glucose, and 7.5 g of paratoluenesulfonic acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.5% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. .
Next, the mixture was heated to 150 ° C. while removing water generated during the temperature increase, and stirred for 1 hour while maintaining 150 ° C., and then neutralized by adding 1.6 g of sodium hydroxide dissolved in a small amount of water. did. Thereafter, 333 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 1060 g of resin.
Table 1 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% of para-toluenesulfonic acid was added with respect to 100 mass% of phenol resin, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例２）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、フルクトース２２６ｇ、パラトルエンスルホン酸６．８ｇを仕込んだ。なお、フェノールと糖質類との質量比率は５：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．５ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール６８６ｇを留去し、３９１ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表１に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂を、１８０℃で３０分間加熱したところ、硬化してテトラヒドロフランに完全に不溶となった。
(Example 2)
1128 g of phenol, 226 g of fructose, and 6.8 g of paratoluenesulfonic acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. In addition, the mass ratio of phenol and saccharides was 5: 1, and the addition amount of p-toluenesulfonic acid was 0.5% by mass with respect to the total amount of solids of saccharides and phenol of 100% by mass. .
Next, the mixture was heated to 150 ° C. while removing the water generated during the temperature increase, stirred for 1 hour while maintaining 150 ° C., and then neutralized by adding 1.5 g of sodium hydroxide dissolved in a small amount of water. did. Then, 686 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 391 g of resin.
Table 1 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when the obtained phenol resin was heated at 180 ° C. for 30 minutes, it was cured and became completely insoluble in tetrahydrofuran.
（実施例３）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、群栄化学工業製異性化糖ＨＦ５５（フルクトース含有率５５質量％、固形分濃度７５質量％）３７６ｇ（固形分２８２ｇ）、シュウ酸７０．５ｇを仕込んだ。なお、フェノールと糖質類との質量比率は４：１、シュウ酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール６００ｇを留去し、８１２ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表１に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂を、１８０℃で３０分間加熱したところ、硬化して、テトラヒドロフランに完全に不溶となった。
(Example 3)
In a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser, 1128 g of phenol, isomerized sugar HF55 (fructose content 55 mass%, solid content concentration 75 mass%) 370 g (solid content) manufactured by Gunei Chemical Industry Co., Ltd. 282 g) and 70.5 g of oxalic acid were charged. The mass ratio of phenol to saccharides was 4: 1, and the amount of oxalic acid added was 0.5% by mass with respect to 100% by mass of the total content of saccharides solids and phenol.
Subsequently, it heated to 150 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 150 degreeC. Thereafter, 600 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 812 g of resin.
Table 1 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when the obtained phenol resin was heated at 180 ° C. for 30 minutes, it was cured and became completely insoluble in tetrahydrofuran.
（実施例４）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、群栄化学工業製異性化糖ＨＦ９５（フルクトース含有率９５質量％、固形分濃度７５質量％）５０１ｇ（固形分３７６ｇ）、パラトルエンスルホン酸７．５ｇを仕込んだ。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．７ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール６８６ｇを留去し、７１３ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表１に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂を、１８０℃で３０分間加熱したところ、硬化して、テトラヒドロフランに完全に不溶となった。
Example 4
In a three-necked flask with an internal volume of 2 L equipped with a thermometer, a stirrer, and a cooling tube, 1128 g of phenol, isomerized sugar HF95 (fructose content 95 mass%, solid content concentration 75 mass%) 501 g (solid content) 376 g) and 7.5 g of paratoluenesulfonic acid were charged. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.5% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. .
Next, the mixture was heated to 150 ° C. while removing water generated during the temperature increase, and stirred for 1 hour while maintaining 150 ° C., and then neutralized by adding 1.7 g of sodium hydroxide dissolved in a small amount of water. did. Thereafter, 686 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 713 g of resin.
Table 1 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when the obtained phenol resin was heated at 180 ° C. for 30 minutes, it was cured and became completely insoluble in tetrahydrofuran.
（実施例５）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、群栄化学工業製デキストリン ＧＬＤ（フルクトース含有率０質量％、固形分濃度７０質量％）５３７ｇ（固形分３７６ｇ）、パラトルエンスルホン酸４．５ｇを仕込んだ。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．０ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール４０９ｇを留去し、９８５ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表１に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
(Example 5)
In a 3 L three-neck flask equipped with a thermometer, a stirrer, and a condenser tube, phenol 1128 g, dextrin GLD (fructose content 0 mass%, solid content concentration 70 mass%) 537 g (solid content 376 g) manufactured by Gunei Chemical Industry Co., Ltd. Then, 4.5 g of paratoluenesulfonic acid was charged. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.5% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. .
Next, the mixture was heated to 150 ° C. while removing water generated during the temperature increase, and stirred for 1 hour while maintaining 150 ° C., and then neutralized by adding 1.0 g of sodium hydroxide dissolved in a small amount of water. did. Thereafter, 409 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 985 g of resin.
Table 1 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例６）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、タピオカ澱粉（フルクトース含有率０質量％、固形分濃度８８質量％）４２７ｇ（固形分３７６ｇ）、硫酸１．５ｇを仕込んだ。なお、フェノールと糖質類との質量比率は３：１、硫酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．１質量％であった。
次いで、昇温途中で生成する水を除きながら１５０℃まで加熱し、１５０℃を保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム０．３ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール３３７ｇを留去し、１０５５ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表２に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
(Example 6)
In a 3 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube, phenol 1128 g, tapioca starch (fructose content 0 mass%, solid content concentration 88 mass%) 427 g (solid content 376 g), sulfuric acid 1.5 g Was charged. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of sulfuric acid was 0.1% by mass with respect to the total amount of solids of saccharides and phenol of 100% by mass.
Next, the mixture was heated to 150 ° C. while removing water generated during the temperature increase, stirred for 1 hour while maintaining 150 ° C., and then neutralized by adding 0.3 g of sodium hydroxide dissolved in a small amount of water. did. Thereafter, 337 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 1055 g of resin.
Table 2 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例７）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、水道水１１２８ｇ、タピオカ澱粉（フルクトース含有率０質量％、固形分濃度８８質量％）４２７ｇ（固形分３７６ｇ）、パラトルエンスルホン酸７．５を仕込み、１００℃にて１時間攪拌した。８０℃以下に冷却した後、フェノール１１２８ｇを添加し、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．６ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール５０５ｇを留去し、８９０ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表２に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
(Example 7)
To a 2 L three-necked flask equipped with a thermometer, stirrer, and condenser, tap water 1128 g, tapioca starch (fructose content 0 mass%, solid content concentration 88 mass%) 427 g (solid content 376 g), paratoluene sulfone The acid 7.5 was charged and it stirred at 100 degreeC for 1 hour. After cooling to 80 ° C. or lower, 1128 g of phenol was added, and the mixture was heated to 150 ° C. while removing water generated during the temperature increase. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.5% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. .
After stirring for 1 hour while maintaining at 150 ° C., 1.6 g of sodium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 505 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 890 g of resin.
Table 2 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例８）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、砂糖を精製する際に発生する廃棄糖蜜（フルクトース含有率５０質量％、固形分濃度８０質量％）４７０ｇ（固形分３７６ｇ）、３５質量％塩酸８．６ｇを仕込み、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は３：１、塩酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．２質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム３．３ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール３３５ｇを留去し、１０５７ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表２に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
(Example 8)
In a 2 L three-neck flask equipped with a thermometer, stirrer, and condenser, 1128 g of phenol, 470 g of molasses (fructose content 50 mass%, solid content concentration 80 mass%) generated when refining sugar 376 g) and 8.6 g of 35% by mass hydrochloric acid were charged, and the mixture was heated to 150 ° C. while removing water produced during the temperature elevation. The mass ratio of phenol to saccharides was 3: 1, and the amount of hydrochloric acid added was 0.2% by mass with respect to 100% by mass of the total amount of saccharides solids and phenol.
The mixture was stirred for 1 hour while being kept at 150 ° C., and then neutralized by adding 3.3 g of sodium hydroxide dissolved in a small amount of water. Thereafter, 335 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 1057 g of resin.
Table 2 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例９）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、群栄化学工業製デキストリン ＧＬＤ（フルクトース含有率０質量％、固形分濃度７０質量％）５０３ｇ（固形分３５２ｇ）、群栄化学工業製異性化糖ＨＦ９５（フルクトース含有率９５質量％、固形分濃度７５質量％）３２ｇ（固形分２４ｇ）、パラトルエンスルホン酸４．５ｇを仕込み、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．３質量％であった。また、糖質類中のフルクトース含有量は６質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．０ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール４６８ｇを留去し、９３０ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表２に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
Example 9
In a three-necked flask with an internal volume of 2 L equipped with a thermometer, a stirrer, and a cooling tube, phenol 1128 g, Gunei Chemical Dextrin GLD (fructose content 0 mass%, solid content concentration 70 mass%) 503 g (solid content 352 g) , Isomerized sugar HF95 (fructose content 95 mass%, solid content concentration 75 mass%) 32 g (solid content 24 g), paratoluenesulfonic acid 4.5 g, manufactured by Gunei Chemical Industry Co., Ltd. While removing, it was heated to 150 ° C. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.3% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. . The fructose content in the carbohydrates was 6% by mass.
The mixture was stirred for 1 hour while being kept at 150 ° C., and then neutralized by adding 1.0 g of sodium hydroxide dissolved in a small amount of water. Thereafter, 468 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 930 g of resin.
Table 2 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（実施例１０）
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、群栄化学工業製デキストリン ＧＬＤ（フルクトース含有率０質量％、固形分濃度７０質量％）２６９ｇ（固形分１８８ｇ）、群栄化学工業製異性化糖ＨＦ９５（フルクトース含有率９５質量％、固形分濃度７５質量％）２５０ｇ（固形分１８８ｇ）、パラトルエンスルホン酸４．５ｇを仕込み、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．３質量％であった。また、糖質類中のフルクトース含有量は３５．６質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１．０ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール５２８ｇを留去し、８６９ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表２に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、部分的に硬化して、テトラヒドロフランに一部不溶となった。
(Example 10)
In a three-necked flask with an internal volume of 2 L equipped with a thermometer, a stirrer, and a condenser, 1128 g of phenol, 269 g of dextrin GLD (fructose content 0 mass%, solid content concentration 70 mass%) manufactured by Gunei Chemical Industry (solid content 188 g) , Isomerized sugar HF95 (fructose content 95% by mass, solid content concentration 75% by mass) 250 g (solid content 188 g), paratoluenesulfonic acid 4.5 g, prepared by Gunei Chemical Industry Co., Ltd. While removing, it was heated to 150 ° C. In addition, the mass ratio of phenol and saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 0.3% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. . The fructose content in the carbohydrates was 35.6% by mass.
The mixture was stirred for 1 hour while being kept at 150 ° C., and then neutralized by adding 1.0 g of sodium hydroxide dissolved in a small amount of water. Thereafter, 528 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 869 g of resin.
Table 2 shows the content, softening point, fluidity, and naturally derived ratio of Compound A in the obtained phenolic resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minutes, it hardened | cured partially and became insoluble in tetrahydrofuran partially.
（比較例１）
温度計、攪拌装置、冷却管を備えた内容量３Ｌの三口フラスコに、フェノール１１２８ｇ、グルコース１１２８ｇ、硫酸１１．３ｇを仕込み、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は１：１、硫酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．５質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム９．２ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール２２６ｇを留去し、１１７２ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表３に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、全く硬化せず、テトラヒドロフランに完全溶解した。
(Comparative Example 1)
A 3 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 1128 g of phenol, 1128 g of glucose and 11.3 g of sulfuric acid, and heated to 150 ° C. while removing water produced during the temperature increase. The mass ratio of phenol to saccharides was 1: 1, and the amount of sulfuric acid added was 0.5% by mass with respect to the total amount of saccharides solids and phenol 100% by mass.
The mixture was stirred for 1 hour while maintaining at 150 ° C., and then neutralized by adding 9.2 g of sodium hydroxide dissolved in a small amount of water. Thereafter, 226 g of unreacted phenol was distilled off under reduced pressure of 200 ° C. and 11 kPa to obtain 1172 g of resin.
Table 3 shows the content, softening point, fluidity, and naturally occurring ratio of Compound A in the obtained phenol resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minute (s), it did not harden | cure at all but melt | dissolved completely in tetrahydrofuran.
（比較例２）
温度計、攪拌装置、冷却管を備えた内容量３Ｌの三口フラスコに、フェノール１１２８ｇ、グルコース１１２８ｇ、パラトルエンスルホン酸６７．８ｇを仕込み、昇温途中で生成する水を除きながら１５０℃まで加熱した。なお、フェノールと糖質類との質量比率は１：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して３．０質量％であった。
１５０℃に保ったまま、１時間攪拌した後、少量の水に溶解させた水酸化ナトリウム１４．５ｇを添加して中和した。その後、２００℃、１１ｋＰａの減圧下で未反応のフェノール１１９ｇを留去し、１２９４ｇの樹脂を得た。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表３に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、全く硬化せず、テトラヒドロフランに完全溶解した。
(Comparative Example 2)
A 3 L three-neck flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 1128 g of phenol, 1128 g of glucose, and 67.8 g of paratoluenesulfonic acid, and heated to 150 ° C. while removing water generated during the temperature increase. . In addition, the mass ratio of phenol and saccharides was 1: 1, and the addition amount of p-toluenesulfonic acid was 3.0% by mass with respect to 100% by mass of the total amount of saccharides solids and phenol. .
The mixture was stirred for 1 hour while maintaining at 150 ° C., and then neutralized by adding 14.5 g of sodium hydroxide dissolved in a small amount of water. Thereafter, 119 g of unreacted phenol was distilled off under reduced pressure at 200 ° C. and 11 kPa to obtain 1294 g of resin.
Table 3 shows the content, softening point, fluidity, and naturally occurring ratio of Compound A in the obtained phenol resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minute (s), it did not harden | cure at all but melt | dissolved completely in tetrahydrofuran.
（比較例３）
温度計、攪拌装置、冷却管を備えた内容量３Ｌの三口フラスコに、フェノール１１２８ｇ、グルコース２８２ｇ、パラトルエンスルホン酸０．１４ｇを仕込んだ。なお、フェノールと糖質類との質量比率は４：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して０．０１質量％であった。粘稠で有機溶剤に不溶であり、樹脂化反応はしていないことがわかった。
そのため、化合物Ａの含有量、軟化点、流動性、天然由来率を求めなかった。
(Comparative Example 3)
1128 g of phenol, 282 g of glucose, and 0.14 g of paratoluenesulfonic acid were charged into a 3 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The mass ratio of phenol to saccharides was 4: 1, and the addition amount of paratoluenesulfonic acid was 0.01% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. . It was found to be viscous and insoluble in organic solvents and not undergoing a resinification reaction.
Therefore, the content, softening point, fluidity, and natural origin rate of Compound A were not determined.
（比較例４）
温度計、攪拌装置、冷却管を備えた内容量３Ｌの三口フラスコに、フェノール１０００ｇ、ショ糖（フルクトース含有率０質量％、フラクトース構造ユニット５０質量％）を３００ｇ、澱粉（フルクトース含有率０質量％）２３ｇ（固形分２０ｇ）、パラトルエンスルホン酸５０ｇを仕込み、徐々に昇温した。なお、フェノールと糖質類との質量比率は３：１、パラトルエンスルホン酸の添加量は、糖質類の固形分とフェノールの合計量１００質量％に対して３．８質量％であった。
次いで、１３０℃で３時間、生成する水を除きながら反応させた後に、内温を１８０℃まで昇温し、反応を終了した。その後、フラスコ内に、メチルイソブチルケトン２０００ｇを添加し、希釈した後に、パラトルエンスルホン酸を除去した。
次いで、常圧で１３０℃にて脱水反応を行い、１８０℃にて脱水反応を行って、樹脂８８０ｇを得た。その際に留去したフェノールは３３１ｇであった。
得られたフェノール樹脂中の化合物Ａの含有量、軟化点、流動性、天然由来率を表３に示す。
得られたフェノール樹脂はテトラヒドロフランに完全溶解した。また、得られたフェノール樹脂１００質量％に対して１質量％のパラトルエンスルホン酸を添加し、１８０℃で３０分間加熱したところ、全く硬化せず、テトラヒドロフランに完全溶解した。
(Comparative Example 4)
In a 3 L three-necked flask equipped with a thermometer, a stirrer, and a condenser, 1000 g of phenol, 300 g of sucrose (fructose content 0 mass%, fructose structure unit 50 mass%), starch (fructose content 0 mass%) ) 23 g (solid content 20 g) and p-toluenesulfonic acid 50 g were charged, and the temperature was gradually raised. The mass ratio of phenol to saccharides was 3: 1, and the addition amount of paratoluenesulfonic acid was 3.8% by mass with respect to the total amount of saccharides solids and phenol of 100% by mass. .
Subsequently, after making it react for 3 hours, removing the water to produce | generate at 130 degreeC, internal temperature was heated up to 180 degreeC and reaction was complete | finished. Thereafter, 2000 g of methyl isobutyl ketone was added to the flask and diluted, and then paratoluenesulfonic acid was removed.
Subsequently, a dehydration reaction was performed at 130 ° C. under normal pressure, and a dehydration reaction was performed at 180 ° C. to obtain 880 g of resin. The phenol distilled off at that time was 331 g.
Table 3 shows the content, softening point, fluidity, and naturally occurring ratio of Compound A in the obtained phenol resin.
The obtained phenolic resin was completely dissolved in tetrahydrofuran. Moreover, when 1 mass% para-toluenesulfonic acid was added with respect to 100 mass% of obtained phenol resins, and it heated at 180 degreeC for 30 minute (s), it did not harden | cure at all but melt | dissolved completely in tetrahydrofuran.
化合物Ａを含有する実施例１〜１０のフェノール樹脂は軟化点が低く、流動性に優れ、しかも天然由来率が高かった。また、実施例１〜１０のフェノール樹脂は、ヘキサメチレンテトラミンが共存しなくても、酸性触媒の存在下で完全硬化または部分硬化した。
これに対し、化合物Ａを含有していない比較例１，２，４のフェノール樹脂は軟化点が高く、流動性が低かった。さらに、酸性触媒の存在下では、完全硬化も部分硬化も確認されなかった。
なお、比較例３はフェノール樹脂が得られなかった。酸性触媒量が少なかったため、と思われる。
The phenol resins of Examples 1 to 10 containing Compound A had a low softening point, excellent fluidity, and a high natural origin rate. Further, the phenol resins of Examples 1 to 10 were completely cured or partially cured in the presence of an acidic catalyst even when hexamethylenetetramine did not coexist.
In contrast, the phenolic resins of Comparative Examples 1, 2, and 4 that did not contain Compound A had a high softening point and low fluidity. Furthermore, neither complete curing nor partial curing was confirmed in the presence of an acidic catalyst.
In Comparative Example 3, no phenol resin was obtained. This is probably because the amount of acidic catalyst was small.
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| JP2010126695A (en) * | 2008-11-28 | 2010-06-10 | Gun Ei Chem Ind Co Ltd | Phenolic resin for curing epoxy resin, and epoxy resin composition |
| JP2011132339A (en) * | 2009-12-24 | 2011-07-07 | Gun Ei Chem Ind Co Ltd | Thermosetting molding material and molded product |
| WO2011132579A1 (en) * | 2010-04-20 | 2011-10-27 | 群栄化学工業株式会社 | Biomass phenol resin production method and thermosetting material |
| JP2017082057A (en) * | 2015-10-26 | 2017-05-18 | まり子 吉岡 | Phenol liquefaction resin |
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