JPH0417213B2 - - Google Patents
Info
- Publication number
- JPH0417213B2 JPH0417213B2 JP18893483A JP18893483A JPH0417213B2 JP H0417213 B2 JPH0417213 B2 JP H0417213B2 JP 18893483 A JP18893483 A JP 18893483A JP 18893483 A JP18893483 A JP 18893483A JP H0417213 B2 JPH0417213 B2 JP H0417213B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- average molecular
- group
- formula
- reaction
- 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.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 101
- 239000005011 phenolic resin Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 229920001568 phenolic resin Polymers 0.000 claims description 44
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 41
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 41
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 56
- 238000004458 analytical method Methods 0.000 description 48
- 239000000203 mixture Substances 0.000 description 42
- 238000005227 gel permeation chromatography Methods 0.000 description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 30
- 239000007795 chemical reaction product Substances 0.000 description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 28
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 229920003986 novolac Polymers 0.000 description 20
- 230000003247 decreasing effect Effects 0.000 description 19
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 14
- 239000011976 maleic acid Substances 0.000 description 14
- 238000007259 addition reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- -1 furoyl Chemical group 0.000 description 12
- 239000007858 starting material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000012756 surface treatment agent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N para-hydroxystyrene Natural products OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 6
- 230000008707 rearrangement Effects 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical class CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229930003836 cresol Chemical class 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-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
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 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
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- YGBVAGIVGBLKFE-UHFFFAOYSA-N 2-phenylbut-1-en-1-ol Chemical compound CCC(=CO)C1=CC=CC=C1 YGBVAGIVGBLKFE-UHFFFAOYSA-N 0.000 description 1
- MKHXOKALQIHXPI-UHFFFAOYSA-N 2-phenylprop-1-en-1-ol Chemical compound OC=C(C)C1=CC=CC=C1 MKHXOKALQIHXPI-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 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
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
本発明は、ヒドロキシスチレン系重合体とフエ
ノール樹脂とを反応させて得られるような新規は
付加重合体製法に関する。
さらに詳しくは、本発明は、一般式（）
〔式中、CMはビニル系単量体、ｌは０を含む
任意の数であり、R1はCl，BrまたはＩ、０≦p1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、
The present invention relates to a novel method for producing addition polymers, such as those obtained by reacting hydroxystyrene polymers and phenolic resins. More specifically, the present invention relates to the general formula () [In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦p 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-,
【式】または[expression] or
【式】０≦ｑ≦１
であり、R5は水素、メチル基またはエチル基で
あり、R6は水素、水酸基または炭酸基１〜20の
飽和炭化水素基であり、R7およびR8はそれぞれ
水素、炭素数１〜８の飽和炭化水素基またはフリ
ル基であり、０≦ｕ≦１，０≦v1≦８，１≦v2≦
50であり、R2，R3およびR9はそれぞれ
または
（ここにおいて、CM，ｌ，R1，R4，Ｙ，R5，
R6，R7，R8およびｕは上記と同じであり、０≦
ｔ≦１，０≦s1≦２，１≦s2≦50，m1は３以上の
任意の数、m2は１以上の任意の数である）であ
り、０≦p2≦１，０≦p3≦１，０≦ｗ≦１であ
り、n1は３以上の任意の数、n2は２以上の任意の
数、n3は１以上の任意の数である〕で表わされる
基本構造を有する、ヒドロキシスチレン系重合体
とフエノール樹脂の付加重合体をヒドロキシスチ
レン系重合体とフエノール樹脂を反応させて製造
する方法に関する。
本発明で「ヒドロキシスチレン系重合体」とい
う用語は、以下の説明、殊にR5の定義から明ら
かなように、ヒドロキシスチレンのみならずイソ
プロペニルフエノールおよびヒドロキシ−α−エ
チルスチレン重合体それらの共重合体およびそれ
らとビニル系単量体をも含む意味で用いられてい
る。
本発明に係る方法で得られるヒドロキシスチレ
ン系重合体とフエノール樹脂の付加重合体につい
てさらに説明すれば当該付加重合体は、幹部分が
ヒドロキシスチレン系重合体セグメントからなる
ブロツクとフエノール樹脂セグメントからなるブ
ロツクとからなり、該幹部分にヒドロキシスチレ
ン系重合体のブロツクおよび／またはフエノール
樹脂のブロツクがグラフトしてなる重合体であ
り、例えばヒドロキシスチレン系重合体のセグメ
ントをＡ、フエノール樹脂のセグメントをＢとし
て、それらの結合態様の一例を模型的に示せば下
記簡略式（）のとおりである。
（）
また、本発明に係る当該付加重合体の製法にお
けるヒドロキシスチレン系重合体とフエノール樹
脂との付加反応は、分解と再配列を含むものであ
つて、ビニル重合物と付加縮合樹脂の分解、再配
列によるブロツク的グラフト重合反応と言うこと
ができる。
従来、ノボラツク樹脂は300℃まで安定である
と言われている（A.Knop，W.Schei′Chemistry
and Application of Phenolic Resins′P86
（1979，Springre Verlag，Berlin，Heiderberg，
New York））。しかして、ノボラツク樹脂は酸
触媒の存在下で加熱すると開裂によりオキシベン
ジルカチオンが生成し、次にこれがすぐに再結合
し、再配列が起ることが知られている。（堀内、
工化、63巻、1651頁（1963））。また、ノボラツク
樹脂の再配列はアルカリ触媒の存在下でも起るこ
とも知られている（堀内、工化、66巻、145頁
（1963））。しかし、ビニル重合によるヒドロキシ
スチレン系重合体と、付加縮合によるフエノール
系樹脂とを反応させて付加重合体を得る試みは従
来報告されていない。
ところで、ヒドロキシスチレン系重合体は機能
性高分子とし種々の多くの用途を有するものであ
るが、本発明者らは、このヒドロキシスチレン系
重合体の分子量分布を広くしたり、分岐を多くし
たりすることによつて、その成形性、加工性、可
撓性、粘度指数向上性、溶解性、粘着性、他の樹
脂との相溶性等の物性を改善すべく種々検討した
結果、図らずも、ビニル重合系のヒドロキシスチ
レン系重合体と付加縮合系のフエノール樹脂とを
反応させることによつて、未だ提案されたことの
ない上記一般式（）で表わされる基本構造を有
するヒドロキシスチレン系重合体とフエノール樹
脂の付加重合体が得られることを見出した。この
ヒドロキシスチレン系重合体とフエノール樹脂の
付加重合体は、出発原料の重合体よりも分子量が
大きく、骨格構造も、幹部分がヒドロキシスチレ
ン系重合体のブロツクとフエノール樹脂のブロツ
クとのブロツク重合体であつたり、該幹部分にヒ
ドロキシスチレン系重合体のブロツクおよび／ま
たはフエノール樹脂のブロツクがグラフトしてい
る分岐構造を有していたりして、出発原料の重合
体とは大きく異なる新規な化合物である。そし
て、この付加重合体は、成形性、加工性に優れて
いるほか、分岐を多く有することに起因すると考
えられるが、可撓性、粘度指数向上性、無機材料
に対する密着性、塗膜性、他の有機材料との相溶
性、粘着性、さらには溶解性等において優れてお
り、これらの優れた特性により、例えば感光性樹
脂、酸化防止剤、キレート剤、金属表面処理剤、
高分子マトリツクス剤、高分子触媒、高分子金属
錯体、ガスバリヤー性フイルム、水処理膜、有機
液体処理膜等の種々の用途に有用である。また、
この付加重合体は容易に各種置換基を導入するこ
とができ、各種置換基を導入することにより付加
価値を高めることも可能である。
また、本発明者らは、このヒドロキシスチレン
系重合体とフエノール樹脂の付加重合体の金属表
面処理剤としての有用性の関し、次のような知見
を得ている。すなわち、本付加重合体は、そのま
までも金属表面処理剤として有用であるが、本付
加重合体はホルムアルデヒドにより容易にフエノ
ール核の未反応位置にメチロール基を導入するこ
とができ、このメチロール基を導入した本付加重
合体は金属表面処理剤として一層優れた性能を有
している。本付加重合体あるいはそのメチロール
化物は、金属表面処理の中でも、特に冷延鋼板、
高強度鋼板、炭素鋼、亜鉛、アルミニウム、亜鉛
メツキ鋼、スズメツキ鋼あるいは鉛メツキ鋼等に
対するリン酸塩（例えば、リン酸亜鉛、リン酸
鉄、リン酸マンガン、リン酸カルシウム等）ある
いはクロム酸処理の後処理剤として有用である。
本付加重合体あるいはそのメチロール化物を金属
表面処理剤として用いると、処理された金属表面
の防錆性、耐熱性、耐久性、加工性、潤滑性さら
には塗料の付着性等が向上される。
したがつて本発明の要旨は、一般式（）
（式中、CMはビニル系単量体、ｌは０を含む
任意の数であり、R1はCl，BrまたはＩ、０≦p1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、[Formula] 0≦q≦1, R 5 is hydrogen, a methyl group, or an ethyl group, R 6 is hydrogen, a hydroxyl group, or a saturated hydrocarbon group with 1 to 20 carbonate groups, and R 7 and R 8 are Each is hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, and 0≦u≦1, 0≦v 1 ≦8, 1≦v 2 ≦
50, and R 2 , R 3 and R 9 are each or (Here, CM, l, R 1 , R 4 , Y, R 5 ,
R 6 , R 7 , R 8 and u are the same as above, and 0≦
t≦1, 0≦s 1 ≦2, 1≦s 2 ≦50, m 1 is any number greater than or equal to 3, m 2 is any number greater than or equal to 1), and 0≦p 2 ≦1, 0≦p 3 ≦1, 0≦w≦1, n 1 is any number greater than or equal to 3, n 2 is any number greater than or equal to 2, and n 3 is any number greater than or equal to 1.] The present invention relates to a method for producing an addition polymer of a hydroxystyrene polymer and a phenolic resin having a basic structure by reacting a hydroxystyrene polymer and a phenolic resin. In the present invention, the term "hydroxystyrene polymer" refers not only to hydroxystyrene but also to isopropenylphenol and hydroxy-α-ethylstyrene polymers, as is clear from the following explanation, especially the definition of R5 . The term is used to include polymers and vinyl monomers. To further explain the addition polymer of a hydroxystyrene polymer and a phenolic resin obtained by the method according to the present invention, the addition polymer consists of a block in which the trunk portion is composed of a hydroxystyrene polymer segment and a block composed of a phenolic resin segment. It is a polymer in which a hydroxystyrene polymer block and/or a phenolic resin block is grafted to the trunk portion, for example, the hydroxystyrene polymer segment is A and the phenolic resin segment is B. , an example of their bonding mode is shown in the following simplified formula (). () Furthermore, the addition reaction between the hydroxystyrene polymer and the phenolic resin in the method for producing the addition polymer according to the present invention includes decomposition and rearrangement, and includes decomposition and rearrangement of the vinyl polymer and addition condensation resin. This can be said to be a block graft polymerization reaction due to rearrangement. Traditionally, novolac resins are said to be stable up to 300℃ (A. Knop, W. Schei'Chemistry).
and Application of Phenolic Resins′P86
(1979, Springer Verlag, Berlin, Heiderberg,
New York)). It is known that when novolac resins are heated in the presence of an acid catalyst, oxybenzyl cations are generated by cleavage, which are then immediately recombined to cause rearrangement. (Horiuchi,
Koka, vol. 63, p. 1651 (1963)). It is also known that the rearrangement of novolac resins occurs even in the presence of an alkali catalyst (Horiuchi, Koka, Vol. 66, p. 145 (1963)). However, no attempt has been made to obtain an addition polymer by reacting a hydroxystyrene polymer obtained by vinyl polymerization with a phenolic resin obtained by addition condensation. By the way, hydroxystyrene-based polymers are functional polymers that have many different uses. As a result of various studies aimed at improving its physical properties such as moldability, processability, flexibility, viscosity index improvement, solubility, adhesiveness, and compatibility with other resins, we unexpectedly found that By reacting a vinyl polymerized hydroxystyrene polymer with an addition condensation type phenol resin, a hydroxystyrene polymer having a basic structure represented by the above general formula (), which has not been proposed yet, is produced. It has been found that an addition polymer of phenolic resin and phenolic resin can be obtained. This addition polymer of hydroxystyrene polymer and phenolic resin has a larger molecular weight than the starting material polymer, and its skeletal structure is a block polymer with a hydroxystyrene polymer block and a phenolic resin block as the backbone. It is a novel compound that is significantly different from the starting material polymer because it has a branched structure in which a hydroxystyrene polymer block and/or a phenol resin block are grafted to the trunk portion. be. In addition to excellent moldability and processability, this addition polymer has excellent flexibility, improved viscosity index, adhesion to inorganic materials, coating properties, and is thought to be due to its large number of branches. It has excellent compatibility with other organic materials, adhesiveness, and even solubility, and these excellent properties make it suitable for use in photosensitive resins, antioxidants, chelating agents, metal surface treatment agents, etc.
It is useful for various uses such as polymeric matrix agents, polymeric catalysts, polymeric metal complexes, gas barrier films, water treatment membranes, and organic liquid treatment membranes. Also,
Various substituents can be easily introduced into this addition polymer, and added value can also be increased by introducing various substituents. Furthermore, the present inventors have obtained the following findings regarding the usefulness of this addition polymer of a hydroxystyrene polymer and a phenolic resin as a metal surface treatment agent. In other words, this addition polymer is useful as a metal surface treatment agent as it is, but this addition polymer can easily introduce methylol groups into unreacted positions of the phenol nucleus with formaldehyde, and this methylol group can be easily introduced into unreacted positions of the phenol nucleus. This addition polymer has even better performance as a metal surface treatment agent. This addition polymer or its methylolated product is useful for metal surface treatment, especially for cold-rolled steel sheets,
After treatment with phosphate (e.g. zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, etc.) or chromic acid on high-strength steel sheets, carbon steel, zinc, aluminum, galvanized steel, tin-plated steel, or lead-plated steel, etc. Useful as a processing agent.
When this addition polymer or its methylolated product is used as a metal surface treatment agent, the rust prevention, heat resistance, durability, workability, lubricity, and adhesion of paint to the treated metal surface are improved. Therefore, the gist of the present invention is the general formula () (In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦p 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-,
【式】または[expression] or
【式】０≦ｑ≦１で
あり、R5は水素、メチル基またはエチル基であ
り、ｎは３以上の任意の数である）で表わされる
基本構造を有するヒドロキシスチレン系重合体
と、一般式（）
（式中、R6は水素、水酸基または炭素数１〜
20の飽和炭化水素基でありR7およびR8はそれぞ
れ水素、炭素数１〜８の飽和炭化水素基またはフ
リル基であり、v2は１以上50までの任意の数、０
≦ｕ≦１であり、ｎは１以上の任意の数である）
で表わされる基本構造を有するフエノール樹脂と
を、溶媒の存在下または不存在下に、酸性触媒ま
たは塩基性触媒を用いて反応させることを特徴と
する、一般式（）
〔式中、CMはビニル系単量体、ｌは０を含む
任意の数であり、R1はCl，BrまたはＩ、０≦p1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、[Formula] 0≦q≦1, R 5 is hydrogen, a methyl group, or an ethyl group, and n is an arbitrary number of 3 or more. formula() (In the formula, R 6 is hydrogen, hydroxyl group, or has 1 to 1 carbon atoms.
20 saturated hydrocarbon groups, R 7 and R 8 are each hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, v 2 is any number from 1 to 50, 0
≦u≦1, and n is any number greater than or equal to 1)
General formula () characterized by reacting a phenolic resin having the basic structure represented by using an acidic catalyst or a basic catalyst in the presence or absence of a solvent. [In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦p 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-,
【式】または[expression] or
【式】０≦ｑ≦１
であり、R5は水素、メチル基またはエチル基で
あり、R6は水素、水酸基または炭素数１〜20の
飽和炭化水素基であり、R7およびR8はそれぞれ
水素、炭素数１〜８の飽和炭化水素基またフリル
基であり、０≦ｕ≦１、０≦v1≦８ １≦v2≦50
であり、R2，R3およびR9はそれぞれ
または
（ここにおいて、CM，ｌ，R1，R4，Ｙ，R5，
R6，R7，R8およびｕは上記と同じであり、０≦
ｔ≦１，０≦s1≦２，１≦s2≦50，m1は３以上の
任意の数、m2は１以上の任意の数である）であ
り、０≦p2≦１，０≦p3≦１，０≦ｗ≦１であ
り、n1は３以上の任意の数、n2は２以上の任意の
数、n3は１以上の任意の数である〕で表わされる
基本構造を有する、ヒドロキシスチレン系重合体
とフエノール樹脂との付加重合体の製法に存す
る。
上記各一般式において、ｎ，n1，n2，n3，m1、
m2，ｕ，v1，v2，ｌ，p1，p2、p3，ｑ，ｗ，s1，
s2およびｔはそれぞれ整数とは規定せず、ある一
定の範囲の任意の数と規定してある。重合体分子
当りで考えるならばｎおよびn3は当然整数であ
り、構成単位のブロツクごとに考えるならばn1，
n2，m1、m2，v1，v2，s2およびｌは整数であり、
そして単量体単位について考えるならばp1，p2、
p3，ｑ，ｗ，ｕ，s1およびｔも整数である。しか
しながら、重合体はその本質において混合物であ
り、そして重合体の性質はその混合物の性質とし
て把える方が、その個々の構成単位を問題にする
よりも正しい。したがつて、本発明において上記
各一般式は平均組成として表示してある。
本発明に係る方法で上記一般式（）で表わさ
れる付加重合体を製造するための出発物質として
用いるヒドロキシスチレン系重合体としては、一
般式（）
（式中、CMはビニル系単量体、ｌは０を含む
任意の数であり、R1はCl，BrまたはＩ、０≦p1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、[Formula] 0≦q≦1, R 5 is hydrogen, methyl group or ethyl group, R 6 is hydrogen, hydroxyl group or saturated hydrocarbon group having 1 to 20 carbon atoms, R 7 and R 8 are Each is hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, and 0≦u≦1, 0≦v 1 ≦8 1≦v 2 ≦50
and R 2 , R 3 and R 9 are respectively or (Here, CM, l, R 1 , R 4 , Y, R 5 ,
R 6 , R 7 , R 8 and u are the same as above, and 0≦
t≦1, 0≦s 1 ≦2, 1≦s 2 ≦50, m 1 is any number greater than or equal to 3, m 2 is any number greater than or equal to 1), and 0≦p 2 ≦1, 0≦p 3 ≦1, 0≦w≦1, n 1 is any number greater than or equal to 3, n 2 is any number greater than or equal to 2, and n 3 is any number greater than or equal to 1.] It consists in a method for producing an addition polymer of a hydroxystyrene polymer and a phenol resin, which has a basic structure. In each of the above general formulas, n, n 1 , n 2 , n 3 , m 1 ,
m 2 , u, v 1 , v 2 , l, p 1 , p 2 , p 3 , q, w, s 1 ,
s 2 and t are not defined as integers, but are defined as arbitrary numbers within a certain range. Naturally, n and n 3 are integers when considered per polymer molecule, and n 1 , when considered per block of constituent units.
n 2 , m 1 , m 2 , v 1 , v 2 , s 2 and l are integers,
And if we think about monomer units, p 1 , p 2 ,
p 3 , q, w, u, s 1 and t are also integers. However, a polymer is essentially a mixture, and it is more accurate to view the properties of a polymer as a property of the mixture than to consider its individual constituent units. Therefore, in the present invention, each of the above general formulas is expressed as an average composition. The hydroxystyrene polymer used as a starting material for producing the addition polymer represented by the above general formula () in the method according to the present invention includes the general formula () (In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦p 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-,
【式】または[expression] or
【式】０≦ｑ≦１で
あり、R5は水素、メチル基またはエチル基であ
り、ｎは３以上の任意の数である）で表わされれ
る基本構造を有するヒドロキシスチレン系重合体
が適当である。このヒドロキシスチレン系重合体
は、ヒドロキシスチレンあるいはイソプロベニル
フエノール（ヒドロキシ−α−メチルスチレン）
などの単独重合体または共重合体、あるいは上記
一般式（）に示すような置換基を有するヒドロ
キシスチレンあるいはイソプロベニルフエノール
などの単独重合体または共重合体、さらにはこれ
らのヒドロキシスチレン系単量体と他のビニル系
単量体との共重合体であり得る。重合単位のヒド
ロキシスチレンあるいはイソプロベニルフエノー
ルなどは、オルソ体、メタ体、バラ体あるいはこ
れらの各異性体の混合されたものであつてもよい
が、バラ体あるいはメタ体が好ましい、また、ヒ
ドロキシスチレン系重合体あるいはイソプロベニ
ルフエノール重合体などの中では、ヒドロキシス
チレン系重合体が、出発原料として高分子量のも
のが得られ易かつたり、目的物付加重合体を得る
ための分解、再配列を制御し易いので好ましい。
さらにまた、共重合体である場合の他のビニル系
単量体の例としては、スチレン、α−メチルスチ
レン、アクリロニトリル、塩化ビニル、アクリル
酸エステル、メタクリル酸エステル、無水マレイ
ン酸、あるいは各種有機酸のビニルエステルなど
があげられる。そして、共重合体における他のビ
ニル系単量体は、ヒドロキシスチレン系単量体に
対して重量比で0.05〜20の範囲が適当である。ま
た、上記一般式（）において、フエノール性水
酸基における置換基が[Formula] 0≦q≦1, R 5 is hydrogen, a methyl group, or an ethyl group, and n is an arbitrary number of 3 or more. Appropriate. This hydroxystyrene polymer is hydroxystyrene or isoprobenylphenol (hydroxy-α-methylstyrene).
or homopolymers or copolymers such as hydroxystyrene or isoprobenylphenol having a substituent as shown in the above general formula (), as well as these hydroxystyrene monomers. It may be a copolymer of vinyl monomer and other vinyl monomer. Hydroxystyrene or isoprobenylphenol as a polymerization unit may be an ortho form, a meta form, a bulk form, or a mixture of these isomers, but a bulk form or a meta form is preferable. Among styrene-based polymers and isoprobenylphenol polymers, hydroxystyrene-based polymers are easy to obtain as starting materials with high molecular weight, and are decomposed and rearranged to obtain target addition polymers. This is preferable because it is easy to control.
Furthermore, examples of other vinyl monomers in the case of copolymers include styrene, α-methylstyrene, acrylonitrile, vinyl chloride, acrylic esters, methacrylic esters, maleic anhydride, and various organic acids. Examples include vinyl esters. The weight ratio of other vinyl monomers in the copolymer to the hydroxystyrene monomer is suitably in the range of 0.05 to 20. In addition, in the above general formula (), the substituent on the phenolic hydroxyl group is
【式】である場合の例
をあげれば、アセチル、プロピオニル、ブチリ
ル、バレリル、パルミトイル、ステアロイル、オ
レオイル、フロイル、ベンゾイル、トルオイル、
ナフトイル等があげられ、また該置換基が
Examples of formulas include acetyl, propionyl, butyryl, valeryl, palmitoyl, stearoyl, oleoyl, furoyl, benzoyl, toluoyl,
naphthoyl etc., and the substituent is
【式】の場合の例をあげれば、メチルスルホ
ニル、エチルスルホニル、ベンゼンスルホニル、
ナフタレンスルホニル等があげられる。さらにま
た、本発明方法で用いるヒドロキシスチレン系重
合体は、任意の方法で製造されたものであり得
て、その来歴は問わない。例えば、パラヒドロキ
シスチレン単独重合体であるポリパラヒドロキシ
スチレンは、パラヒドロキシスチレンをカチオン
重合、ラジカル重合、有機酸により水溶液重合あ
るいは熱重合することによつて容易に調整され
る。有機酸による重合では重量平均分子量千から
数十万の重合体が得られ、カチオン重合では数万
から数十万の重合体が得られ、熱重合では数千か
ら数万の重合体が得られ、またパラアセトキシス
チレンのラジカル重合の後加水分解することによ
り数十万から200万程度のオポリパラヒドロキシ
スチレンが得られる。
また、本発明方法で出発物質として用いつフエ
ノール樹脂としては、一般式（）
（式中、R6は水素、水酸基または炭素数１〜
20の飽和炭化水素基であり、R7およびR8はそれ
ぞれ水素、炭素数１〜８の飽和炭化水素基または
フリル基であり、v2は１以上50までの任意の数、
０≦ｕ≦１であり、ｎは１以上の任意の数であ
る）で表わされる基本構造を有するフエノール樹
脂が適当である。このフエノール樹脂としては、
フエノール、クレゾール、（オルソ体、メタ体、
バラ体あるいはこれらの混合物）、エチルフエノ
ール（オルソ体、メタ体、バラ体あるいはこれら
の混合物）、パラターシヤリブチルフエノール、
パラターシヤリミルフエノール、パラフエニルフ
エノール、レゾルシノール、ビスフエノールメタ
ン、ビスフエノールエタン、ビスフエノールＡ，
キシレノール（３，５−，３，４−，２，５−，
２，３−あるいはこれらの混合物）等のフエノー
ル系化合物と、ホルムアルデヒド、パラホルムア
ルデヒド、トリオキサン、メチラール、アセトア
ルデヒド、パラアルデヒド、アセタール、アセト
ン、フルフラール、プロピオンアルデヒド、ｎ−
ブシルアルデヒド、イソブチルアルデヒド、グリ
オキザール、等のアルデヒド化合物またはケトン
化合物との酸性触媒による一般的はノボラツク系
樹脂または塩基性触媒によるレゾール系樹脂等が
あげられ、また他の樹脂で変性（例えば、ロジ
ン、エステルガム、乾性油、合成ゴム、リグニン
等）したフエノール系樹脂があげられる（プラス
チク材料講座、フエノール樹脂、1970年日刊工
業新聞社）。
無論、必要に応じ上記のような各種フエノール
樹脂を混合して用いても差支えない。また、用い
るフエノール樹脂の分子量は特に制限する要はな
いが、一般に重量平均分子量300〜５万程度のも
のが適当である。
本発明のフエノール樹脂とヒドロキシスチレン
系重合体との付加反応は、必要に応じ有機溶媒の
存在下でもまた不存在下でも行ない得る。当該付
加反応に用いる有機溶媒としては、テトラヒドフ
ラン、ジオキサン等の環状エーテル、アセトニト
リル、ジメチルホルムアミド、ジメチルスルホキ
シド、ヘキサメチルホスホロトリアミド等の非プ
ロトン性極性有機溶媒が好ましく用いられる。
本発明のフエノール樹脂とヒドロキシスチレン
系重合体との付加反応に用いる触媒としては、酸
性触媒を用いる場合は、ギ酸、酢酸、プロピオン
酸、ｎ−酪酸、イソー酪酸、ｎ−吉草酸、イソー
吉草酸、メチルエチル酢酸、トリメチル酢酸、カ
プロン酸、ヘプトン酸、カプリル酸、ペラルゴン
酸、カプリン酸等の脂肪族飽和モノカルボン酸
類、シユウ酸、マロン酸、コハク酸、クルタル
酸、アジピン酸、ピメリン酸等の脂肪族ポリカル
ボン酸類、アクリル酸、ビニル酢酸、メタクリル
酸等の脂肪族不飽和モノカルボン酸類、マレイン
酸、フマル酸等の脂肪族不飽和ジカルボン酸類、
安息香酸、トルイル酸、フタル酸、サリチル酸等
の芳香族カルボン酸類等の有機カルボン酸、ある
いはｐ−トルエンスルホン酸等の有機スルホン酸
等が用いられる。
また、触媒として、塩基性触媒を用いる場合
は、水酸化ナトリウム、水酸化カリウム、水酸化
マグネシウム、水酸化カルシウム、水酸化ベリウ
ム等のアルカリ金属水酸化物あるいはアルカリ土
類水酸化物または、Ｎ，Ｎ−ジメチルアニリン、
ピリジン、ピコリン、イミダゾール、２−メチル
イミダゾール、トリフエニルアミン等の有機アミ
ン化合物が用いられる。
本発明方法におけるフエノール樹脂とヒドロキ
シスチレン系重合体との付加反応は、反応温度０
℃〜350℃、好ましくは80℃〜290℃の範囲内で、
反応時間は３分〜40時間、好ましくは20分〜８時
間で行なわれるのが適当である。フエノール樹脂
の仕込み比はヒドロキシスチレン系重合体100重
量部当り、１〜1000重量部、好ましくは３〜500
重量部の範囲内が適当である。本発明方法では、
フエノール樹脂とヒドロキシスチレン系重合体の
仕込み比に応じて、この仕込み比とほぼ同様の比
率でフエノール樹脂成分とヒドロキシスチレン系
重合体成分を有する重合体が得られる。溶媒を使
用する場合には、溶媒中の出発物質のフエノール
樹脂とヒドロキシスチレン系重合体の両者の濃度
は重量パーセントで80％以下、好ましくは50％以
下とするのが適当である。触媒の使用量は出発物
質のフエノール樹脂とヒドロキシスチレン系重合
体との合計100重量部当り、0.1〜100重量部、好
ましくは0.5〜10重量部の範囲内であるのが適当
である。
本発明方法における付加反応は、出発物質のフ
エノール樹脂とヒドロキシスチレン系重合体を熔
融状態あるいは溶媒に溶解させて、液相で反応を
行なうのが望ましく、出発物質を固体のままで反
応を行なうと、目的物のヒドロキシスチレン系重
合体とフエノール樹脂の付加重合体が架橋により
ゲル化物となることがある。
本発明方法における付加反応は真空下、減圧
下、常圧下、加圧下のいずれにしても行ない得る
が、真空下、減圧下または常圧下で行なうのが望
ましい。また、水素、一酸化炭素あるいはアミン
等の還元性雰囲気下で反応を行なうのが望まし
い。空気あるいは酸素等の酸化性雰囲気下では、
フエノール樹脂とヒドロキシスチレン系重合体と
は、フエノール核を有するために、酸化的重合が
起きて、樹脂や重合体の着色あるいは酸化架橋に
よるゲル化物が生じることがある。本発明方法に
おける付加反応は、触媒として、有機カルボン酸
類を用いるのが望ましい。有機スルホン酸類の場
合には、酸性度が強すぎるための分解再配列や付
加反応が早すぎて制御が困難になることや三次元
網状化によるゲル化物が生じることがある。した
がつて、触媒として有機スルホン酸を用いるとき
は、低温でしかもその添加量が少ない方が好まし
い。
この付加反応を溶媒の不存在下で行なつた場合
には、反応終了後、必要に応じて、低分子フエノ
ール化合物を例えばフイルムエバポレーター等に
より除去精製した後、付加反応生成物をそのまま
各種用途に供することができる。また、溶媒の存
在下で反応を行なつた場合には、反応終了後、付
加反応生成物を非溶剤、例えば、水、石油エーテ
ル、ヘキサンベンゼン等を用いて再沈澱させる等
の手段によつて目的物の付加重合体を単離しても
よいし、また反応終了後、溶媒及び低分子フエノ
ール化合物を必要に応じて、エバピレーター等に
より除去した後、付加反応生成物をそのまま各種
用途に供することもできる。
本発明方法で得られた付加重合体の平均分子量
は、出発物質として用いたフエノール樹脂とヒド
ロキシスチレン系重合体の各平均分子量によつて
定まるところのこれら出発原料の混合物の平均分
子量によつて変化するが、常にこの出発原料の混
合物の平均分子量より大きくなる。本発明に係る
この付加重合体の平均分子量は、一般に重量平均
分子量で500以上、可溶性のものの場合は一般に
1000〜100万程度、好ましくは2000〜20万程度が
その用途面からみて適当であり、また架橋物の場
合は一般にガラス転移温度が90〜220℃程度のも
のが適当である。
以下に実施例を示して本発明を更に説明する
が、これはあくまでも単なる例示にすぎない。ま
た、以下の実施例において、“％”は特記しない
限り、“重量％”を意味する、。尚、得られた生成
物の量は、用いた触媒のうち生成物中に混入した
触媒の量をも含めて示してある。
実施例 １
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン（丸善石油（株）製、商品名レジンＭ）10.0ｇ
と重量平均分子量1440、数平均分子量885、オリ
ゴマー含有量11.57％のフエノールノボラツク樹
脂（日本化薬（株）製、商品名PN2）10.0ｇとを
室温で粉砕混合した。この混合物は、ゲルパーミ
エーシヨンクロマトグラフイー（GPC）により
テトラヒドロフラン（THF）を溶媒として分子
量を測定したところ、重量平均分子量3410、数平
均分子量1380、オリゴマー含有量7.15％であつ
た。この混合物10ｇを攪拌機、温度計、還流冷却
器付の50mlの三ツ口フラスコに入れ、オイルバス
上で240℃で均一に攪拌溶解させた後、さらに触
媒としてマレイン酸0.4ｇを240℃添加し、240℃
で２時間攪拌反応させた。その結果10.3ｇの反応
生成物を得た。この反応生成物はメタノール、テ
トラヒドロフラン（THF）等に易溶であつた。
またTHFを溶媒とするGPCにより分子量を測定
したところ、重量平均分子量5340、数平均分子量
1550、オリゴマー含有量5.16％であつた。すなわ
ち、分子量が増大（重量平均分子量の場合、反応
前に較べて反応後は1.57倍に増大）しており、一
方オリゴマーは減少（0.72倍）していた。また熱
分析の結果、図１に示すように単なる室温での混
合物のガラス転移温度（Tg）124℃が、反応後は
128℃に増大していた。またIR，13C−NMR分析
の結果から、下記式の構造のポリパラヒドロキシ
スチレンとフエノール樹脂の付加重合体であるこ
とを確認した。
図２は240℃２時間攪拌反応後の生成物のIRス
ペクトルである。
次に、反応生成物をTHFに溶融させ、分取
GPCにより分画したクロマトグラフを図３に示
した。分画１は24カウントから34カウント、分画
２は34カウントから41カウントである。分画１は
再度GPC測定したところ、数平均分子量9300、
重量平均分子量13000であつた。図４にこの分画
１のGPCクロマトグラフを示した。
分画１の13C−NMRスペクトルを図５に示し
た。尚分画１はベンゼン（少量のクロロホルムを
含む）溶媒にて再沈殿精製を行なつた。
13C−NMR結果；30％重アセトン中27℃（０点
はTMSのカーボン）において、
Examples of [Formula] include methylsulfonyl, ethylsulfonyl, benzenesulfonyl,
Examples include naphthalenesulfonyl. Furthermore, the hydroxystyrene polymer used in the method of the present invention may be produced by any method, and its origin does not matter. For example, polyparahydroxystyrene, which is a parahydroxystyrene homopolymer, is easily prepared by subjecting parahydroxystyrene to cationic polymerization, radical polymerization, aqueous solution polymerization with an organic acid, or thermal polymerization. Polymerization using an organic acid yields a polymer with a weight average molecular weight of 1,000 to several hundreds of thousands, cationic polymerization yields a polymer with a weight average molecular weight of tens to hundreds of thousands, and thermal polymerization yields a polymer with a weight average molecular weight of 1000 to 100,000. Also, by hydrolyzing the radical polymerization of para-acetoxystyrene, several hundred thousand to about two million opoly-parahydroxystyrene can be obtained. Furthermore, the phenolic resin used as a starting material in the method of the present invention has the general formula () (In the formula, R 6 is hydrogen, hydroxyl group, or has 1 to 1 carbon atoms.
20 saturated hydrocarbon groups, R 7 and R 8 are each hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, v 2 is any number from 1 to 50,
A phenolic resin having a basic structure represented by 0≦u≦1, where n is an arbitrary number of 1 or more is suitable. As this phenolic resin,
Phenol, cresol, (ortho form, meta form,
ethylphenol (ortho form, meta form, bulk form or mixture thereof), paratertiary butylphenol,
Paratertiarymilphenol, paraphenylphenol, resorcinol, bisphenolmethane, bisphenol ethane, bisphenol A,
Xylenol (3,5-,3,4-,2,5-,
2,3- or mixtures thereof) and formaldehyde, paraformaldehyde, trioxane, methylal, acetaldehyde, paraldehyde, acetal, acetone, furfural, propionaldehyde, n-
Generally, novolac resins are produced by acidic catalysts with aldehyde compounds such as butyraldehyde, isobutyraldehyde, glyoxal, or ketone compounds, or resol resins are modified by basic catalysts, and modified with other resins (for example, rosin , ester gum, drying oil, synthetic rubber, lignin, etc.) (Plastic Materials Course, Phenol Resin, Nikkan Kogyo Shimbun, 1970). Of course, the various phenolic resins mentioned above may be mixed and used as required. The molecular weight of the phenol resin used is not particularly limited, but a weight average molecular weight of about 300 to 50,000 is generally suitable. The addition reaction between the phenolic resin and the hydroxystyrene polymer of the present invention can be carried out in the presence or absence of an organic solvent, as required. As the organic solvent used in the addition reaction, cyclic ethers such as tetrahydrofuran and dioxane, aprotic polar organic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphorotriamide are preferably used. When an acidic catalyst is used as the catalyst for the addition reaction between the phenolic resin and the hydroxystyrene polymer of the present invention, examples of the catalyst include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, and isovaleric acid. , aliphatic saturated monocarboxylic acids such as methylethyl acetic acid, trimethylacetic acid, caproic acid, heptonic acid, caprylic acid, pelargonic acid, capric acid, oxalic acid, malonic acid, succinic acid, curtaric acid, adipic acid, pimelic acid, etc. aliphatic polycarboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid, vinyl acetic acid, and methacrylic acid; aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid;
Organic carboxylic acids such as aromatic carboxylic acids such as benzoic acid, toluic acid, phthalic acid, and salicylic acid, or organic sulfonic acids such as p-toluenesulfonic acid are used. In addition, when using a basic catalyst as a catalyst, an alkali metal hydroxide or alkaline earth hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, beryum hydroxide, or N, N-dimethylaniline,
Organic amine compounds such as pyridine, picoline, imidazole, 2-methylimidazole, and triphenylamine are used. The addition reaction between the phenolic resin and the hydroxystyrene polymer in the method of the present invention is carried out at a reaction temperature of 0.
within the range of ℃~350℃, preferably 80℃~290℃,
The reaction time is suitably 3 minutes to 40 hours, preferably 20 minutes to 8 hours. The charging ratio of the phenolic resin is 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, per 100 parts by weight of the hydroxystyrene polymer.
A range of parts by weight is appropriate. In the method of the present invention,
Depending on the charging ratio of the phenolic resin and the hydroxystyrene polymer, a polymer having the phenolic resin component and the hydroxystyrene polymer component can be obtained in substantially the same ratio as this charging ratio. When a solvent is used, it is appropriate that the concentrations of both the starting materials, phenolic resin and hydroxystyrene polymer, in the solvent are 80% or less, preferably 50% or less, in terms of weight percent. The amount of the catalyst used is suitably within the range of 0.1 to 100 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the phenolic resin and hydroxystyrene polymer as starting materials. In the addition reaction in the method of the present invention, it is preferable to conduct the reaction in a liquid phase by dissolving the starting materials, the phenolic resin and the hydroxystyrene polymer, in a molten state or in a solvent. In some cases, the desired addition polymer of a hydroxystyrene polymer and a phenolic resin becomes a gel due to crosslinking. The addition reaction in the method of the present invention can be carried out under vacuum, reduced pressure, normal pressure, or increased pressure, but it is preferably carried out under vacuum, reduced pressure, or normal pressure. Further, it is desirable to carry out the reaction in a reducing atmosphere such as hydrogen, carbon monoxide or amine. In an oxidizing atmosphere such as air or oxygen,
Since phenolic resins and hydroxystyrene polymers have phenol nuclei, oxidative polymerization may occur, resulting in coloring of the resin or polymer or formation of gelled products due to oxidative crosslinking. In the addition reaction in the method of the present invention, it is desirable to use organic carboxylic acids as a catalyst. In the case of organic sulfonic acids, the acidity is too strong, so decomposition, rearrangement and addition reactions occur too quickly, making control difficult, and gelation may occur due to three-dimensional reticulation. Therefore, when using an organic sulfonic acid as a catalyst, it is preferable to use it at a low temperature and in a small amount. When this addition reaction is carried out in the absence of a solvent, after the completion of the reaction, if necessary, the low molecular weight phenol compound is removed and purified using, for example, a film evaporator, and then the addition reaction product is directly used for various purposes. can be provided. In addition, when the reaction is carried out in the presence of a solvent, after the reaction is completed, the addition reaction product can be reprecipitated using a non-solvent such as water, petroleum ether, hexanebenzene, etc. The target addition polymer may be isolated, or after the reaction is complete, the solvent and low-molecular-weight phenol compound may be removed using an evaporator or the like as necessary, and the addition reaction product may be used as is for various purposes. can. The average molecular weight of the addition polymer obtained by the method of the present invention varies depending on the average molecular weight of the mixture of these starting materials, which is determined by the respective average molecular weights of the phenolic resin and hydroxystyrene polymer used as starting materials. However, it is always greater than the average molecular weight of this mixture of starting materials. The average molecular weight of the addition polymer according to the present invention is generally 500 or more in terms of weight average molecular weight, and in the case of a soluble one, generally
A value of about 10,000 to 1,000,000, preferably about 2,000 to 200,000 is appropriate from the viewpoint of its use, and in the case of crosslinked products, it is generally appropriate to have a glass transition temperature of about 90 to 220°C. The present invention will be further explained below with reference to Examples, but these are merely illustrative. In addition, in the following examples, "%" means "% by weight" unless otherwise specified. Note that the amount of the product obtained includes the amount of the catalyst mixed into the product among the catalysts used. Example 1 10.0 g of polyparahydroxystyrene (manufactured by Maruzen Sekiyu Co., Ltd., trade name Resin M) with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66%.
and 10.0 g of a phenol novolac resin (manufactured by Nippon Kayaku Co., Ltd., trade name PN2) having a weight average molecular weight of 1440, a number average molecular weight of 885, and an oligomer content of 11.57% were pulverized and mixed at room temperature. The molecular weight of this mixture was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and found to have a weight average molecular weight of 3410, a number average molecular weight of 1380, and an oligomer content of 7.15%. 10 g of this mixture was placed in a 50 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, stirred and dissolved uniformly at 240°C on an oil bath, and then 0.4 g of maleic acid was added as a catalyst at 240°C. ℃
The mixture was stirred and reacted for 2 hours. As a result, 10.3g of reaction product was obtained. This reaction product was easily soluble in methanol, tetrahydrofuran (THF), etc.
In addition, when the molecular weight was measured by GPC using THF as a solvent, the weight average molecular weight was 5340, and the number average molecular weight was 5340.
1550, with an oligomer content of 5.16%. That is, the molecular weight increased (in the case of weight average molecular weight, it increased 1.57 times after the reaction compared to before the reaction), while the oligomer decreased (0.72 times). Additionally, as a result of thermal analysis, as shown in Figure 1, the glass transition temperature (Tg) of the mixture at room temperature was 124℃, but after the reaction, the glass transition temperature (Tg) of the mixture was 124℃.
The temperature had increased to 128℃. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that it was an addition polymer of polyparahydroxystyrene and phenol resin having the structure shown below. Figure 2 shows the IR spectrum of the product after the stirring reaction at 240°C for 2 hours. Next, the reaction product was dissolved in THF and fractionated.
A chromatograph obtained by fractionation by GPC is shown in FIG. Fraction 1 is 24 counts to 34 counts, and fraction 2 is 34 counts to 41 counts. Fraction 1 was measured again by GPC, and the number average molecular weight was 9300.
The weight average molecular weight was 13,000. FIG. 4 shows a GPC chromatograph of this fraction 1. The 13C-NMR spectrum of fraction 1 is shown in FIG. Fraction 1 was purified by reprecipitation using a benzene (containing a small amount of chloroform) solvent. 13C-NMR results: At 27℃ in 30% heavy acetone (0 point is TMS carbon),
【式】また は[Formula] Also teeth
【式】【formula】
【式】【formula】
【式】
帰属炭 ケミカルシフト
Ce 40.0
Cf 45.8
Cg 115.7
Cl 120.5
Ch 129.3
130.5
Cm ｛131.2
132.0
Cn 133.7
136.6
Ci ｛137.0
137.4
Cp 152.6
Cj 153.5
Ck 155.7
また、出発ポリパラヒドロキシスチレンの数平
均分子量2800より重合度は23である。フエノール
ボラツク樹脂の数平均分子量885より縮合度は８
である。分画１の数平均分子量は9300であるの
で、重合度と縮合度は77−88（約80）である。
13C−NMRスぺクトルにおいて、Cj153.5ppm
は[Formula] Attributed coal Chemical shift Ce 40.0 Cf 45.8 Cg 115.7 Cl 120.5 Ch 129.3 130.5 Cm {131.2 132.0 Cn 133.7 136.6 Ci {137.0 137.4 Cp 152.6 Cj 153.5 Ck 155.7 In addition, the number average molecular weight of the starting polyparahydroxystyrene is 2800, so the degree of polymerization is is 23. Since the number average molecular weight of phenol volak resin is 885, the degree of condensation is 8.
It is. Since the number average molecular weight of fraction 1 is 9300, the degree of polymerization and degree of condensation are 77-88 (approximately 80). In the 13C-NMR spectrum, Cj153.5ppm
teeth
【式】【formula】
【式】【formula】
【式】でありCk155.7ppmは 主として[Formula] and Ck155.7ppm is mainly
【式】（【formula】(
【式】の場合
には末端となる）であるからCjの炭素濃度とCk
の炭素濃度との比Ck／Cj＝6.0と
In the case of [formula], it becomes the terminal), so the carbon concentration of Cj and Ck
The ratio of carbon concentration to Ck/Cj=6.0
【式】Cpが非常に小さいこと
を考えると、Ck＝66，Cj＝11，Cp＝３とすると
Ck＋Cj＋Cp＝80量体（分画１の重合度と縮合度
の合計）となる。
ここでポリパラヒドロキシスチレン部分を
（21−23量体）、フエノールノボラツク部分を○●
○●○○○○（８量体）とし、ｏ，p′一体を○，
ｏ，o′一体を●とすると、上記分画１は以下の様
に書くことが出来る。
（３置換フエノールは１／80のため検出が困難）等。
次に分画２の13C−NMRスペクトルを図６に
示した。
13C−NMR結果；30％重アセトン中27℃（０
点はTMSのカーボン）において、[Formula] Considering that Cp is very small, if Ck=66, Cj=11, Cp=3
Ck + Cj + Cp = 80-mer (total of polymerization degree and condensation degree of fraction 1). Here, the polyparahydroxystyrene part
(21−23 mer), the phenol novolak moiety is ○●
○●○○○○ (octamer), and o and p′ are ○,
If o, o' together is represented by ●, the above fraction 1 can be written as follows. (Tri-substituted phenols are difficult to detect because they are 1/80). Next, the 13C-NMR spectrum of fraction 2 is shown in FIG. 13C-NMR result; 27℃ (0
The point is TMS carbon),
【式】【formula】
【式】【formula】
【式】 帰属炭素 ケミカルシフト ｏ，o′−の−CH2− 31 ｏ，p′−の−CH2− 35.1 ｐ，p′−の−CH2Ce 40.8 Cf 45.8ブロード Cg 115.7 Cl 120.1 Cp 128.9 Ch 129.3シヨルダー Cm 130.4 131.7 Cn 133.5 Ci 137.9シヨルダー Cp 152.3 Cj 153.0 153.6 Ck 156.0 156.1 各炭素の濃度比は（印の炭素） 120.1ppmの[Formula] Attributed carbon Chemical shift o, o'- -CH 2 - 31 o, p'- -CH 2 - 35.1 p, p'- -CH 2 Ce 40.8 Cf 45.8 Broad Cg 115.7 Cl 120.1 Cp 128.9 Ch 129.3 shoulder Cm 130.4 131.7 Cn 133.5 Ci 137.9 shoulder Cp 152.3 Cj 153.0 153.6 Ck 156.0 156.1 The concentration ratio of each carbon is (carbon marked) 120.1 ppm
【式】（ｏ，o′−）が １個 153.6ppmの[Formula] (o, o'-) is 1 piece 153.6ppm
【式】（ｏ，p′−）が２ 個 153.0ppmの[Formula] (o, p'-) is 2 Individual 153.0ppm
【式】が２個 40.8ppmの2 [expressions] 40.8ppm
【式】 が４個より【formula】 is more than 4
【式】が２個 156.0と156.1ppmの2 [expressions] 156.0 and 156.1ppm
【式】【formula】
【式】が６個より末端[Formula] is more terminal than 6
【式】が
４個以上より分画２の構造はモデル的に以下の様
に書くことが出来る。
実施例 ２
反応時間を３時間30分にした以外は全て実施例
１と同様にして反応を行なつた。得られた反応生
成物（得られた量：10.2ｇ）はメタノール、
THF等に易溶でありGPC分析の結果、重量平均
分子量が6620、数平均分子量1660、オリゴマー含
有量5.06％であり、分子量が反応前と比較して増
大し、オリゴマーが減少していた。またIR，13C
−NMR分析の結果から、ポリパラヒドロキシス
チレンとフエノール樹脂の付加重合体が生成して
いることを確認した。
実施例 ３
反応温度を150℃にし、触媒としてのマレイン
酸の量を0.2ｇ（２重量％）にした以外は全て実
施例１と同様にして反応を行なつた。得られた反
応生成物（得られた量：10.1ｇ）はメタノール、
THF等に易溶であり、GPC分析の結果、重量平
均分子量が8520、数平均分子量1410、オリゴマー
含有量6.62％であり、分子量が反応前と比較して
増大し、オリゴマー量が減少していた。またIR，
13C−NMR分析の結果から、ポリパラヒドロキ
シスチレンとフエノール樹脂の付加重合体が生成
していることを確認した。
実施例 ４
触媒としてのマレイン酸の量を0.8ｇ（８重量
％）にした以外は全て実施例１と同様にして反応
を行なつた。得られた反応生成物（得られた量：
10.6ｇ）はメタノール、THF等に可溶であり、
GPC分析の結果、重量平均分子量が8900、数平
均分子量が1690、オリゴマー含有量5.01％であ
り、分子量が反応前と比較して増大し、オリゴマ
ー量が減少していた。またIR，13C−NMR分析
の結果から、ポリパラヒドロキシスチレンとフエ
ノール樹脂の付加重合体が生成していることを確
認した。
実施例 ５
触媒としてのマレイン酸の量を2.0ｇ（17重量
％）にした以外は全て実施例１と同様にして反応
を行なつた。得られた反応生成物（得られた量：
11.6ｇ）はメタノール、THF等に可溶であり、
GPC分析の結果、重量平均分子量が42690、数平
均分子量1930、オリゴマー含有量4.34％であり、
分子量が反応前と比較して増大し、オリゴマー量
が減少していた。またIR，13C−NMR分析の結
果から、ポリパラヒドロキシスチレンとフエノー
ル樹脂の付加重合体が生成していることを確認し
た。
実施例 ６
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン7.5ｇと重量平均分子量1440、数平均分子量
885、オリゴマー含有量11.57％のフエノールノボ
ラツク樹脂2.5ｇとを室温で粉砕混合した後、
GPC分析を行なつたところ、重量平均分子量
4450、数平均分子量1870、オリゴマー含有量3.37
％であつた。この混合物10ｇに触媒としてマレイ
ン酸0.4ｇを加え、実施例１と同様に240℃で２時
間攪拌反応させた。反応生成物（得られた量：
10.3ｇ）はメタノール、THFに易溶であり、
GPC分析の結果、重量平均分子量10060、数平均
分子量2320、オリゴマー含有量2.45％であり、分
子量が反応前と比較して増大し、オリゴマー量が
減少していた。またIR，13C−NMR分析の結果
から、ポリパラヒドロキシスチレンとフエノール
樹脂の付加重合体が生成していることを確認し
た。
実施例 ７
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン2.5ｇと重量平均分子量1440、数平均分子量
885、オリゴマー含有量11.57％のフエノールノボ
ラツク樹脂7.5ｇとを室温で粉砕混合した後、
GPC分析を行なつたところ、重量平均分子量
2330、数平均分子量1060、オリゴマー含有量9.16
％であつた。この混合物10ｇに触媒としてマレイ
ン酸0.4ｇを加え、実施例１と同様にして240℃で
２時間攪拌反応させた。反応生成物（得られた
量：10.2ｇ）はメタノール、THFに易溶であり、
GPC分析の結果、重量平均分子量3100、数平均
分子量1170、オリゴマー含有量7.83％であり、分
子量が反応前と比較して増大し、オリゴマー量が
減少していた。またIR，13C−NMR分析の結果
から、ポリパラヒドロキシスチレンとフエノール
樹脂の付加重合体が生成していることを確認し
た。
実施例 ８
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン8.3ｇと重量平均分子量1440、数平均分子量
885、オリゴマー含有量11.57％のフエノールノボ
ラツク樹脂1.7ｇとを室温で粉砕混合した後、
GPC分析を行なつたところ、重量平均分子量
4750、数平均分子量2180、オリゴマー含有量2.69
％であつた。この混合物10ｇに触媒としてマレイ
ン酸0.4ｇを加え、実施例１と同様に240℃で２時
間攪拌反応させた。反応生成物（得られた量：
10.3ｇ）はメタノール、THFに易溶であり、
GPC分析の結果、重量平均分子量11970、数平均
分子量2890、オリゴマー含有量1.81％であり、分
子量が反応前と比較して増大し、オリゴマー量が
減少していた。またIR，13C−NMR分析の結果
から、ポリパラヒドロキシスチレンとフエノール
樹脂の付加重合体が生成していることを確認し
た。
実施例 ９
反応温度を210℃にし、触媒としてマレイン酸
の代りにシユウ酸を0.2ｇにした以外は全て実施
例１と同様にして反応を行なつた。得られた反応
生成物（得られた量：10.0ｇ）は、着色が非常に
少ない白薄黄色ポリマーであつた。この生成ポリ
マーはメタノール。THF等に易溶であり、GPC
分析の結果、重要平均分子量が3630、数平均分子
量が1390、オリゴマー含有量6.01％であり、分子
量が反応前と比較して、少し増加し、オリゴマー
量が減少していた。またIR，13C−NMR分析の
結果から、ポリパラヒドロキシスチレンとフエノ
ール樹脂の付加重合体が生成していることを確認
した。またこの生成ポリマー中にはシユウ酸は含
有されていないことも、IR，13C−NMR分析の
結果から確認した。
実施例 10
反応温度を150℃にし、反応時間を30分にし、
触媒としてマレイン酸の代りにｐ−トルエンスル
ホン酸を0.1ｇにした以外は全て実施例１と同様
にして反応を行なつた。得られた反応生成物（得
られた量：10.1ｇ）はTHF等に可溶であり、
GPC分析の結果、重量平均分子量が5230、数平
均分子量が1455、オリゴマー含有量6.62％であ
り、分子量が反応前と比較して増大し、オリゴマ
ー量が減少していた。また、IR，13C−NMR分
析の結果から、ポリパラヒドロキシスチレンとフ
エノール樹脂の付加重合体が生成していることを
確認した。
実施例 11
触媒としてのマレイン酸の代りにｐ−トルエン
スルホン酸を0.1ｇにした以外は全て実施例１と
同様にして、240℃で２時間反応を行なつた。得
られた反応生成物（得られた量：10.1ｇ）は一部
ゲル化していたため、THF可溶部と不溶部に分
離したところ、THF不溶部は3.5ｇであり、
THF可溶部は6.4ｇであつた。このTHF可溶部
をGPC分析した結果、重量平均分子量が20410、
数平均分子量が1180、オリゴマー含有量が8.77％
であり、重量平均分子量が反応前と比較して、著
しく増大していた。またオリゴマー含有量は反応
前の7.15％が反応後THF可溶部は8.77％と実施例
１−10とは逆に増大していた。またIR，13C−
NMR分析の結果から、ポリパラヒドロキシスチ
レンとフエノール樹脂の付加重合体が生成してい
ることを確認した。
実施例 12
重量平均分子量9300、数平均分子量4540、オリ
ゴマー含有量1.03％のポリパラヒドロキシスチレ
ン５ｇと重量平均分子量1440、数平均分子量885、
オリゴマー含有量11.57％のフエノールノボラツ
ク樹脂５ｇとを室温で粉砕混合した。この混合物
は、GPC分析の結果から、重量平均分子量5410、
数平均分子量2030、オリゴマー含有量6.35％であ
つた。この混合物10ｇに触媒としてシユウ酸0.5
ｇを加え、その他は実施例１と同様にして240℃
で２時間反応させた。反応生成物（得られた量：
10.0ｇ）はメタノール、THFに易溶であり、
GPC分析の結果、重量平均分子量5930、数平均
分子量2080、オリゴマー含有量4.96％であり、分
子量が反応前と比較して増大し、オリゴマー量が
減少していた。またIR，13C−NMR分析の結果
から、ポリパラヒドロキシスチレンとフエノール
樹脂の付加重合体が生成していることを確認し
た。
実施例 13
重量平均分子量3010、数平均分子量1600、オリ
ゴマー含有量1.24％のポリパラヒドロキシスチレ
ン５ｇと重量平均分子量1440、数平均分子量885、
オリゴマー含有量11.57％のフエノールノボラツ
ク樹脂５ｇとを室温で粉砕混合した。この混合物
はGPC分析の結果から、重量平均分子量2230、
数平均分子量995、オリゴマー含有量6.40％であ
つた。この混合物10ｇに触媒としてフタル酸0.8
ｇを加え、その他は実施例１と同様にして240℃
で２時間反応させた。反応生成物（得られた量：
10.7ｇ）はメタノール、THFに易溶であり、
GPC分析の結果、重量平均分子量3250、数平均
分子量1310、オリゴマー含有量5.96％であり、分
子量が反応前と比較して増大し、オリゴマー量が
減少していた。またIR，13C−NMR分析の結果
から、ポリパラヒドロキシスチレンとフエノール
樹脂の付加重合体が生成していることを確認し
た。
実施例 14
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン5.0ｇと重量平均分子量960、数平均分子量730、
オリゴマー含有量13.71％のオルソクレゾールノ
ボラツク樹脂（日本化薬（株）製、商品名OCN）
5.0ｇとを室温で粉砕混合した。この混合物は、
GPC分析の結果から、重量平均分子量3160、数
平均分子量1320、オリゴマー含有量8.18％であつ
た。この混合物10ｇに触媒としてカプリル酸1.0
ｇを加えて、220℃で５時間攪拌反応させた。反
応生成物（得られた量：10.9ｇ）はメタノール、
THFに易溶であり、GPC分析の結果、重量平均
分子量6830、数平均分子量1780、オリゴマー含有
量4.88％であり、分子量が反応前と比較して増大
し、オリゴマー量が減少していた。またIR，13C
−NMR分析の結果から、ポリパラヒドロキシス
チレンとフエノール樹脂（クレゾールノボラツク
樹脂）の付加重合体が生成していることを確認し
た。
実施例 15
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン5.0ｇと重量平均分子量2420、数平均分子量
1140、オリゴマー含有量7.3％のフエノールアセ
トアルデヒド樹脂（ビスフエノールエタンを0.3
重量％水酸化ナトリウムにて215〜220℃にて、20
〜30mmHgの減圧下で１時間分解させ縮合させ
た樹脂；下式で示される構造を有する）5.0ｇと
を室温で粉砕混合
した。この混合物はGPC分析の結果から、重量
平均分子量3890、数平均分子量1580、オリゴマー
含有量5.0％であつた。この混合物に触媒として、
水酸化カリウム0.2ｇを加えて、220℃で20〜
30mmHgの減圧下で１時間攪拌させた。反応生
成物（得られた量：10.0ｇ）はメタノール、
THFに可溶であり、GPC分析の結果から、重量
平均分子量13430、数平均分子量2580、オリゴマ
ー含有量3.2％であり、分子量が反応前と比較し
て増大し、オリゴマー量が減少していた。また
IR，13C−NMR分析の結果から、ポリパラヒド
ロキシスチレンとフエノール樹脂（フエノールア
セトアルデヒド樹脂）の付加重合体が生成してい
ることを確認した。
実施例 16
重量平均分子量7300、数平均分子量3650、オリ
ゴマー含有量1.83％のポリメタヒドロキシスチレ
ン5.0ｇと重量平均分子量960、数平均分子量730、
オリゴマー含有量13.71％のオルソクレゾールノ
ボラツク樹脂5.0ｇとを室温で粉砕混合した。こ
の混合物は、GPC分析の結果から、重量平均分
子量4150、数平均分子量1690、オリゴマー含有量
7.71％であつた。この混合物10ｇに触媒としてフ
マル酸0.5ｇを加えて210℃で３時間攪拌反応させ
た。反応生成物（得られた量：10.5ｇ）はメタノ
ール、THFに易溶であり、GPC分析の結果から、
重量平均分子量7910、数平均分子量1960、オリゴ
マー含有量5.16％であり、分子量が反応前と比較
して増大し、オリゴマー量が減少していた。ま
た、IR，13C−NMR分析の結果から、クレゾー
ルノボラツク樹脂を付加したポリメタヒドロキシ
スチレンとフエノール樹脂（クレゾールノボラツ
ク樹脂）の付加重合体が生成していることを確認
した。
実施例 17
重量平均分子量8300、数平均分子量3950、オリ
ゴマー含有量0.79％のブロム化ポリパラヒドロキ
シスチレン（フエノール核１個当り1.52個のブロ
ムが導入されている）10ｇと重量平均分子量
1440、数平均分子量885、オリゴマー含有量11.57
％のフエノールノボラツク樹脂５ｇとを室温で粉
砕混合した。この混合物はGPC分析の結果から、
重量平均分子量6130、数平均分子量2480、オリゴ
マー含有量4.38％であり、またブロム含有量は
32.3％であつた。この混合物10ｇに触媒として、
コハク酸0.5ｇを加え、その他は実施例１と同様
にして240℃で２時間反応させた。反応生成物
（得られた量：10.3ｇ）はメタノール、THFに可
溶であり、GPC分析の結果、重量平均分子量
9170、数平均分子量2820、オリゴマー含有量3.17
％であり、分子量が反応前と比較して増大し、オ
リゴマー量が減少していた。尚、この得られた反
応生成物の原素分析をしたところ、そのブロム含
有量は32.3％で反応前と同じであつた（パラヒド
ロキシスチレン核１個当り1.52個のブロムが導入
されていた）。また、IR，13C−NMR分析の結果
から、ブロム化ポリパラヒドロキシスチレンとフ
エノール樹脂の付加重合体が生成していることを
確認した。
実施例 18
パラヒドロキシスチレンとスチレンとのラジカ
ル共重合体（パラヒドロキシスチレン含有量67モ
ル％）であつて、重量平均分子量が8950、数平均
分子量3310、オリゴマー含有量1.21％である共重
合体を用い、この共重合体9.0ｇと重量平均分子
量1440、数平均分子量885、オリゴマー含有量
11.57％のフエノールノボラツク樹脂5.0ｇとを室
温で粉砕混合した。この混合物は、GPC分析の
結果から、重量平均分子量6120、数平均分子量
2200、オリゴマー含有量4.87％であつた。この混
合物10.0ｇに触媒として、マレイン酸0.4ｇを加
えて、230℃で４時間攪拌反応させた。反応生成
物（得られた量：10.3ｇ）はメタノール、THF
に易溶であり、GPC分析の結果、重量平均分子
量10770、数平均分子量2500、オリゴマー含有量
4.10％であり、分子量が反応前と比較して増大
し、オリゴマー量が減少していた。また、IR，
13C−NMR分析の結果から、パラヒドロキシス
チレンとスチレンとの共重合体とフエノール樹脂
の付加重合体が生成していることを確認した。
実施例 19
重量平均分子量5350、数平均分子量2800、オリ
ゴマー含有量2.66％のポリパラヒドロキシスチレ
ン9.9ｇと重量平均分子量1440、数平均分子量
885、オリゴマー含有量11.57％のフエノールノボ
ラツク樹脂0.1ｇとを室温で粉砕混合した後、
GPC分析を行なつたところ、重量平均分子量
5300、数平均分子量2775、オリゴマー含有量2.75
％であつた。この混合物10.0ｇに触媒としてマレ
イン酸0.4ｇを加え、実施例１と同様にして、240
℃で２時間攪拌反応させた。反応生成物は10.3ｇ
であり、メタノール、THFに易溶であり、GPC
分析の結果、重量平均分子量15400、数平均分子
量4030、オリゴマー含有量1.04％であり、分子量
が反応前と比較して増大し、オリゴマー量が減少
していた。また、IR，13C−NMR分析の結果か
ら、ポリパラヒドロキシスチレンとフエノール樹
脂の付加重合体が生成していることを確認した。
実施例 20
触媒としてマレイン酸0.4ｇの代りに、イミダ
ゾール0.4ｇ用いた以外は全て実施例１と同様に
して反応を行つた。得られた反応生成物（得られ
た量：10.35ｇ）はメタノール、THFに易溶であ
り、GPC分析の結果、重量平均分子量4440、数
平均分子量1450、オリゴマー含有量6.85％であ
り、分子量が反応前と比較して増大し、オリゴマ
ー量が減少していた。また、IR，13C−NMR分
析の結果から、ポリパラヒドロキシスチレンとフ
エノール樹脂の付加重合体が生成していることを
確認した。
参考例 １
実施例１で得られたポリパラヒドロキシスチレ
ンとフエノール樹脂の付加重合体を用いて以下の
ようにして金属表面処理剤としての評価を行なつ
たところ非常に優れた金属表面処理剤であること
が確認された。
冷延鋼板を強アルカリ洗浄液で前処理を行なつ
た後、熱水リンス、65℃でのリン酸亜鉛水溶液に
よるパーカライジング処理を施した後、上記ポリ
パラヒドロキシスチレンとフエノール樹脂の付加
重合体の５％アルカリ水溶液（ポリマー濃度約10
重量％）で60℃で後処理を行なつた後、完全にリ
ンスを行ない、150℃で10分間乾燥を行なつた後、
熱硬化性のアクリル塗装を行なつた。得られたプ
レートについて、ASTM−B117−61法の塩水噴
霧試験を672時間行なつてもプレートは腐食が認
められない良好な性能を示した。Since [Formula] is 4 or more, the structure of fraction 2 can be written as a model as follows. Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 3 hours and 30 minutes. The obtained reaction product (obtained amount: 10.2 g) was methanol,
It is easily soluble in THF, etc., and as a result of GPC analysis, the weight average molecular weight was 6620, the number average molecular weight was 1660, and the oligomer content was 5.06%, indicating that the molecular weight had increased and the oligomer content had decreased compared to before the reaction. Also IR, 13C
- From the results of NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 3 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 150° C. and the amount of maleic acid as a catalyst was 0.2 g (2% by weight). The obtained reaction product (obtained amount: 10.1 g) was methanol,
It is easily soluble in THF, etc., and as a result of GPC analysis, the weight average molecular weight is 8520, the number average molecular weight is 1410, and the oligomer content is 6.62%, and the molecular weight has increased and the oligomer amount has decreased compared to before the reaction. . Also, IR,
From the results of 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin was produced. Example 4 The reaction was carried out in the same manner as in Example 1 except that the amount of maleic acid as a catalyst was changed to 0.8 g (8% by weight). Reaction product obtained (obtained amount:
10.6g) is soluble in methanol, THF, etc.
As a result of GPC analysis, the weight average molecular weight was 8900, the number average molecular weight was 1690, and the oligomer content was 5.01%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 5 The reaction was carried out in the same manner as in Example 1 except that the amount of maleic acid as a catalyst was changed to 2.0 g (17% by weight). Reaction product obtained (obtained amount:
11.6g) is soluble in methanol, THF, etc.
As a result of GPC analysis, the weight average molecular weight was 42690, the number average molecular weight was 1930, and the oligomer content was 4.34%.
The molecular weight increased compared to before the reaction, and the amount of oligomers decreased. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 6 7.5 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 1440 and a number average molecular weight
885, and 2.5 g of phenolic novolak resin with an oligomer content of 11.57% were ground and mixed at room temperature.
GPC analysis revealed that the weight average molecular weight
4450, number average molecular weight 1870, oligomer content 3.37
It was %. 0.4 g of maleic acid was added as a catalyst to 10 g of this mixture, and the mixture was reacted with stirring at 240° C. for 2 hours in the same manner as in Example 1. Reaction product (amount obtained:
10.3g) is easily soluble in methanol and THF,
As a result of GPC analysis, the weight average molecular weight was 10,060, the number average molecular weight was 2,320, and the oligomer content was 2.45%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 7 2.5 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 1440 and a number average molecular weight
885, and 7.5 g of phenolic novolak resin with an oligomer content of 11.57% were pulverized and mixed at room temperature.
GPC analysis revealed that the weight average molecular weight
2330, number average molecular weight 1060, oligomer content 9.16
It was %. 0.4 g of maleic acid was added as a catalyst to 10 g of this mixture, and the mixture was reacted with stirring at 240° C. for 2 hours in the same manner as in Example 1. The reaction product (obtained amount: 10.2 g) is easily soluble in methanol and THF,
As a result of GPC analysis, the weight average molecular weight was 3100, the number average molecular weight was 1170, and the oligomer content was 7.83%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 8 8.3 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 1440 and a number average molecular weight
885 and 1.7 g of phenol novolak resin with an oligomer content of 11.57% were pulverized and mixed at room temperature.
GPC analysis revealed that the weight average molecular weight
4750, number average molecular weight 2180, oligomer content 2.69
It was %. 0.4 g of maleic acid was added as a catalyst to 10 g of this mixture, and the mixture was reacted with stirring at 240° C. for 2 hours in the same manner as in Example 1. Reaction product (amount obtained:
10.3g) is easily soluble in methanol and THF,
As a result of GPC analysis, the weight average molecular weight was 11,970, the number average molecular weight was 2,890, and the oligomer content was 1.81%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 9 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 210° C. and 0.2 g of oxalic acid was used instead of maleic acid as a catalyst. The reaction product obtained (obtained amount: 10.0 g) was a white, pale yellow polymer with very little coloration. The polymer produced is methanol. Easily soluble in THF etc., GPC
The analysis results showed that the critical average molecular weight was 3630, the number average molecular weight was 1390, and the oligomer content was 6.01%, indicating that the molecular weight had increased slightly and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. It was also confirmed from the results of IR and 13C-NMR analysis that this produced polymer did not contain oxalic acid. Example 10 The reaction temperature was 150°C, the reaction time was 30 minutes,
The reaction was carried out in the same manner as in Example 1 except that 0.1 g of p-toluenesulfonic acid was used instead of maleic acid as a catalyst. The obtained reaction product (obtained amount: 10.1 g) is soluble in THF etc.
As a result of GPC analysis, the weight average molecular weight was 5230, the number average molecular weight was 1455, and the oligomer content was 6.62%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin was produced. Example 11 The reaction was carried out at 240° C. for 2 hours in the same manner as in Example 1 except that 0.1 g of p-toluenesulfonic acid was used instead of maleic acid as a catalyst. The obtained reaction product (obtained amount: 10.1 g) was partially gelled, so when it was separated into a THF-soluble part and an insoluble part, the THF-insoluble part was 3.5 g.
The THF soluble portion was 6.4 g. As a result of GPC analysis of this THF soluble part, the weight average molecular weight was 20410,
Number average molecular weight is 1180, oligomer content is 8.77%
The weight average molecular weight was significantly increased compared to before the reaction. Further, the oligomer content was 7.15% before the reaction, and the THF soluble portion after the reaction was 8.77%, which was an increase contrary to Example 1-10. Also, IR, 13C−
From the results of NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 12 5 g of polyparahydroxystyrene with a weight average molecular weight of 9300, a number average molecular weight of 4540, and an oligomer content of 1.03% and a weight average molecular weight of 1440, a number average molecular weight of 885,
5 g of phenolic novolac resin having an oligomer content of 11.57% was ground and mixed at room temperature. From the results of GPC analysis, this mixture has a weight average molecular weight of 5410,
The number average molecular weight was 2030, and the oligomer content was 6.35%. 0.5 oxalic acid as a catalyst to 10 g of this mixture
g, and otherwise the same procedure as in Example 1 at 240°C.
The mixture was allowed to react for 2 hours. Reaction product (amount obtained:
10.0g) is easily soluble in methanol and THF,
As a result of GPC analysis, the weight average molecular weight was 5930, the number average molecular weight was 2080, and the oligomer content was 4.96%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 13 5 g of polyparahydroxystyrene with a weight average molecular weight of 3010, a number average molecular weight of 1600, and an oligomer content of 1.24% and a weight average molecular weight of 1440, a number average molecular weight of 885,
5 g of phenolic novolac resin having an oligomer content of 11.57% was ground and mixed at room temperature. From the results of GPC analysis, this mixture has a weight average molecular weight of 2230,
The number average molecular weight was 995 and the oligomer content was 6.40%. 0.8 phthalic acid as a catalyst to 10 g of this mixture
g, and the other conditions were the same as in Example 1 at 240°C.
The mixture was allowed to react for 2 hours. Reaction product (amount obtained:
10.7g) is easily soluble in methanol and THF,
As a result of GPC analysis, the weight average molecular weight was 3250, the number average molecular weight was 1310, and the oligomer content was 5.96%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenolic resin was produced. Example 14 5.0 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 960, a number average molecular weight of 730,
Orthocresol novolak resin with oligomer content of 13.71% (manufactured by Nippon Kayaku Co., Ltd., trade name OCN)
5.0g were ground and mixed at room temperature. This mixture is
The results of GPC analysis showed that the weight average molecular weight was 3160, the number average molecular weight was 1320, and the oligomer content was 8.18%. Caprylic acid 1.0 as a catalyst to 10g of this mixture
g was added thereto, and the mixture was stirred and reacted at 220°C for 5 hours. The reaction product (obtained amount: 10.9 g) was methanol,
It is easily soluble in THF, and as a result of GPC analysis, the weight average molecular weight was 6830, the number average molecular weight was 1780, and the oligomer content was 4.88%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Also IR, 13C
- From the results of NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin (cresol novolak resin) was produced. Example 15 5.0 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 2420 and a number average molecular weight
1140, phenolic acetaldehyde resin with oligomer content 7.3% (bisphenolethane 0.3
wt% sodium hydroxide at 215-220℃, 20
5.0g of resin decomposed and condensed under reduced pressure of ~30mmHg for 1 hour; did. From the results of GPC analysis, this mixture had a weight average molecular weight of 3890, a number average molecular weight of 1580, and an oligomer content of 5.0%. In this mixture, as a catalyst,
Add 0.2g of potassium hydroxide and heat at 220℃ for 20~
The mixture was stirred for 1 hour under reduced pressure of 30 mmHg. The reaction product (obtained amount: 10.0g) was methanol,
It is soluble in THF, and the results of GPC analysis show that it has a weight average molecular weight of 13,430, a number average molecular weight of 2,580, and an oligomer content of 3.2%, indicating that the molecular weight has increased and the amount of oligomers has decreased compared to before the reaction. Also
From the results of IR and 13C-NMR analyses, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin (phenolacetaldehyde resin) was produced. Example 16 5.0 g of polymethahydroxystyrene with a weight average molecular weight of 7300, a number average molecular weight of 3650, and an oligomer content of 1.83% and a weight average molecular weight of 960, a number average molecular weight of 730,
5.0 g of orthocresol novolac resin having an oligomer content of 13.71% was ground and mixed at room temperature. From the results of GPC analysis, this mixture has a weight average molecular weight of 4150, a number average molecular weight of 1690, and an oligomer content.
It was 7.71%. 0.5 g of fumaric acid was added as a catalyst to 10 g of this mixture, and the mixture was stirred and reacted at 210° C. for 3 hours. The reaction product (obtained amount: 10.5 g) is easily soluble in methanol and THF, and from the results of GPC analysis,
The weight average molecular weight was 7910, the number average molecular weight was 1960, and the oligomer content was 5.16%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analyses, it was confirmed that an addition polymer of polymethahydroxystyrene added with cresol novolac resin and phenol resin (cresol novolac resin) was produced. Example 17 10 g of brominated polyparahydroxystyrene (1.52 bromines are introduced per phenol nucleus) with a weight average molecular weight of 8300, a number average molecular weight of 3950, and an oligomer content of 0.79% and a weight average molecular weight of
1440, number average molecular weight 885, oligomer content 11.57
% of phenol novolak resin were ground and mixed at room temperature. From the results of GPC analysis, this mixture is
The weight average molecular weight is 6130, the number average molecular weight is 2480, the oligomer content is 4.38%, and the bromine content is
It was 32.3%. 10g of this mixture as a catalyst,
0.5 g of succinic acid was added, and otherwise the reaction was carried out in the same manner as in Example 1 at 240°C for 2 hours. The reaction product (obtained amount: 10.3 g) was soluble in methanol and THF, and as a result of GPC analysis, the weight average molecular weight was
9170, number average molecular weight 2820, oligomer content 3.17
%, the molecular weight increased and the oligomer amount decreased compared to before the reaction. Furthermore, elemental analysis of the obtained reaction product revealed that its bromine content was 32.3%, the same as before the reaction (1.52 bromine atoms were introduced per parahydroxystyrene nucleus). . Furthermore, from the results of IR and 13C-NMR analyses, it was confirmed that an addition polymer of brominated polyparahydroxystyrene and phenol resin was produced. Example 18 A radical copolymer of parahydroxystyrene and styrene (parahydroxystyrene content: 67 mol%) with a weight average molecular weight of 8950, a number average molecular weight of 3310, and an oligomer content of 1.21% was prepared. 9.0 g of this copolymer, weight average molecular weight 1440, number average molecular weight 885, oligomer content
5.0 g of 11.57% phenolic novolac resin was ground and mixed at room temperature. From the results of GPC analysis, this mixture has a weight average molecular weight of 6120 and a number average molecular weight of 6120.
2200, and the oligomer content was 4.87%. 0.4 g of maleic acid was added as a catalyst to 10.0 g of this mixture, and the mixture was stirred and reacted at 230° C. for 4 hours. The reaction product (obtained amount: 10.3g) was methanol, THF
As a result of GPC analysis, the weight average molecular weight is 10,770, the number average molecular weight is 2,500, and the oligomer content is
The molecular weight was 4.10%, indicating that the molecular weight had increased and the amount of oligomers had decreased compared to before the reaction. Also, IR,
From the results of 13C-NMR analysis, it was confirmed that a copolymer of parahydroxystyrene and styrene and an addition polymer of phenol resin were produced. Example 19 9.9 g of polyparahydroxystyrene with a weight average molecular weight of 5350, a number average molecular weight of 2800, and an oligomer content of 2.66% and a weight average molecular weight of 1440 and a number average molecular weight
885, and 0.1 g of phenolic novolak resin with an oligomer content of 11.57% were pulverized and mixed at room temperature.
GPC analysis revealed that the weight average molecular weight
5300, number average molecular weight 2775, oligomer content 2.75
It was %. 0.4 g of maleic acid was added as a catalyst to 10.0 g of this mixture, and 240
The mixture was stirred and reacted at ℃ for 2 hours. The reaction product is 10.3g
It is easily soluble in methanol and THF, and GPC
The analysis results showed that the weight average molecular weight was 15,400, the number average molecular weight was 4,030, and the oligomer content was 1.04%, indicating that the molecular weight had increased and the oligomer amount had decreased compared to before the reaction. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin was produced. Example 20 A reaction was carried out in the same manner as in Example 1 except that 0.4 g of imidazole was used instead of 0.4 g of maleic acid as a catalyst. The obtained reaction product (obtained amount: 10.35 g) is easily soluble in methanol and THF, and as a result of GPC analysis, the weight average molecular weight is 4440, the number average molecular weight is 1450, and the oligomer content is 6.85%. The amount of oligomers increased compared to before the reaction, and the amount of oligomers decreased. Furthermore, from the results of IR and 13C-NMR analysis, it was confirmed that an addition polymer of polyparahydroxystyrene and phenol resin was produced. Reference Example 1 The addition polymer of polyparahydroxystyrene and phenol resin obtained in Example 1 was evaluated as a metal surface treatment agent as follows, and it was found to be an extremely excellent metal surface treatment agent. It was confirmed that there is. After pre-treating the cold-rolled steel sheet with a strong alkaline cleaning solution, rinsing with hot water, and performing a parkerizing treatment with an aqueous zinc phosphate solution at 65°C, the addition polymer of polyparahydroxystyrene and phenolic resin 5 % alkaline aqueous solution (polymer concentration approx. 10
After post-treatment at 60°C (wt%), rinse thoroughly and dry at 150°C for 10 minutes.
A thermosetting acrylic coating was applied. The obtained plate showed good performance with no corrosion observed even after 672 hours of salt spray test according to ASTM-B117-61 method.
図１は実施例１におけるポリパラヒドロキシス
チレンとフエノールノボラツク樹脂の混合物およ
びそれを反応させて得られた反応生成物の熱分析
結果のグラフである。図２は実施例１で得られた
反応生成物のIRスペクトルであり、図３は該反
応生成物の分取GPCのクロマトグラフであり、
図４は該分取GPCの分画１を再度GPC測定した
クロマトグラフである。図５は上記分画１の13C
−NMRスペクトルであり、図６は上記分取GPC
の分画２の13C−NMRスペクトルである。
FIG. 1 is a graph showing the results of thermal analysis of a mixture of polyparahydroxystyrene and phenol novolak resin in Example 1 and a reaction product obtained by reacting the same. FIG. 2 is an IR spectrum of the reaction product obtained in Example 1, and FIG. 3 is a preparative GPC chromatograph of the reaction product,
FIG. 4 is a chromatograph obtained by re-GPC measurement of fraction 1 of the preparative GPC. Figure 5 shows 13C of fraction 1 above.
-NMR spectrum, and Figure 6 shows the preparative GPC described above.
13C-NMR spectrum of fraction 2.
Claims (1)
任意の数であり、R1はCl，BrまたはＩ、０≦P1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、【式】または【式】０≦ｑ≦１ であり、R5は水素、メチル基またはエチル基で
あり、ｎは３以上の任意の数である）で表わされ
る基本構造を有するヒドロキシスチレン系重合体
と、一般式（） （式中、R6は水素、水酸基または炭素数１〜
20の飽和炭化水素基であり、R7およびR8はそれ
ぞれ水素、炭素数１〜８の飽和炭化水素基または
フリル基であり、v2は１以上50までの任意の数、
０≦ｕ≦１であり、ｎは１以上の任意の数であ
る）で表わされる基本構造を有するフエノール樹
脂とを、溶媒の存在下または不存在下に、酸性触
媒または塩基性触媒を用いて反応させることを特
徴とする、一般式（） 〔式中、CMはビニル系単量体、ｌは０を含む
任意の数であり、R1はCl，BrまたはＩ、０≦P1
≦２であり、R4は炭素数１〜20のアルキル基、
アルケニル基または一価の芳香族基、Ｙは−０
−、【式】または【式】０≦ｑ≦１ であり、R5は水素、メチル基またはエチル基で
あり、R6は水素、水酸基または炭素数１〜20の
飽和炭化水素基であり、R7およびR8はそれぞれ
水素、炭素数１〜８の飽和炭化水素基またはフリ
ル基であり、０≦ｕ≦１，０≦v1≦８，１≦v2≦
50であり、R2，R3およびR9はそれぞれ または （ここにおいて、CM，ｌ，R1，R4，Ｙ，R5，
R6，R7，R8およびｕは上記と同じであり、０≦
ｔ≦１，０≦s1≦２，１≦s2≦50，m1は３以上の
任意の数、m2は１以上の任意の数である）であ
り、０≦p2≦１，０≦p3≦１，０≦ｗ≦１であ
り、n1は３以上の任意の数、n2は２以上の任意の
数、n3は１以上の任意の数である〕で表わされる
基本構造を有する、ヒドロキシスチレン系重合体
とフエノール樹脂の付加重合体の製法。 ２ 有機溶媒の存在下に反応が行なわれる特許請
求の範囲第１項記載の製法。 ３ 有機溶媒が非プロトン性有機溶媒である特許
請求の範囲第２項記載の製法。 ４ 有機溶媒の不存在下に反応が行なわれる特許
請求の範囲第１項記載の製法。 ５ 触媒がカルボン酸である特許請求の範囲第１
項記載の製法。 ６ ０〜350℃の反応温度下に反応が行なわれる
特許請求の範囲第１項記載の製法。[Claims] 1 General formula () (In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦P 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-, [Formula] or [Formula] 0≦q≦1, R 5 is hydrogen, a methyl group, or an ethyl group, and n is an arbitrary number of 3 or more). System polymer and general formula () (In the formula, R 6 is hydrogen, hydroxyl group, or has 1 to 1 carbon atoms.
20 saturated hydrocarbon groups, R 7 and R 8 are each hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, v 2 is any number from 1 to 50,
0≦u≦1, and n is an arbitrary number of 1 or more) using an acidic catalyst or a basic catalyst in the presence or absence of a solvent. General formula (), characterized by reacting [In the formula, CM is a vinyl monomer, l is any number including 0, R 1 is Cl, Br or I, 0≦P 1
≦2, R 4 is an alkyl group having 1 to 20 carbon atoms,
alkenyl group or monovalent aromatic group, Y is -0
-, [Formula] or [Formula] 0≦q≦1, R 5 is hydrogen, a methyl group or an ethyl group, R 6 is hydrogen, a hydroxyl group or a saturated hydrocarbon group having 1 to 20 carbon atoms, R 7 and R 8 are each hydrogen, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a furyl group, and 0≦u≦1, 0≦v 1 ≦8, 1≦v 2 ≦
50, and R 2 , R 3 and R 9 are each or (Here, CM, l, R 1 , R 4 , Y, R 5 ,
R 6 , R 7 , R 8 and u are the same as above, and 0≦
t≦1, 0≦s 1 ≦2, 1≦s 2 ≦50, m 1 is any number greater than or equal to 3, m 2 is any number greater than or equal to 1), and 0≦p 2 ≦1, 0≦p 3 ≦1, 0≦w≦1, n 1 is any number greater than or equal to 3, n 2 is any number greater than or equal to 2, and n 3 is any number greater than or equal to 1.] A method for producing an addition polymer of a hydroxystyrene polymer and a phenolic resin, which has a basic structure. 2. The manufacturing method according to claim 1, wherein the reaction is carried out in the presence of an organic solvent. 3. The manufacturing method according to claim 2, wherein the organic solvent is an aprotic organic solvent. 4. The production method according to claim 1, wherein the reaction is carried out in the absence of an organic solvent. 5 Claim 1 in which the catalyst is a carboxylic acid
Manufacturing method described in section. 6. The manufacturing method according to claim 1, wherein the reaction is carried out at a reaction temperature of 0 to 350°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18893483A JPS6081228A (en) | 1983-10-08 | 1983-10-08 | Addition polymer of hydroxystyrene polymer and phenolic resin and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18893483A JPS6081228A (en) | 1983-10-08 | 1983-10-08 | Addition polymer of hydroxystyrene polymer and phenolic resin and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6081228A JPS6081228A (en) | 1985-05-09 |
| JPH0417213B2 true JPH0417213B2 (en) | 1992-03-25 |
Family
ID=16232450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18893483A Granted JPS6081228A (en) | 1983-10-08 | 1983-10-08 | Addition polymer of hydroxystyrene polymer and phenolic resin and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6081228A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2863927B2 (en) * | 1988-03-15 | 1999-03-03 | マツダ株式会社 | Engine intake system |
-
1983
- 1983-10-08 JP JP18893483A patent/JPS6081228A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6081228A (en) | 1985-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2658885A (en) | Polymeric compositions from a hydrocarbon substituted phenol, an aldehyde, and a chloroepoxyalkane | |
| US2875178A (en) | Copolymer polyhydric phenol resin | |
| JP2000509097A (en) | Redistribution of polyphenylene ether and polyphenylene ether with novel structure | |
| US4403066A (en) | Composites made from liquid phenol formaldehyde resins | |
| JPH05393B2 (en) | ||
| US2478154A (en) | Polymeric aldehyde diesters and production thereof | |
| US2211048A (en) | Rubberlike products and process of making them | |
| US3800004A (en) | Phenolic based unsaturated polyester resin | |
| JPH0417213B2 (en) | ||
| AU627826B2 (en) | Process of preparation of high-molecular-weight epoxy dimer acid ester resin | |
| US3110699A (en) | Reaction products of ethylenically unsaturated polymers and phenolic compounds | |
| US5677414A (en) | Acetal derivatives of resole compounds | |
| JPH0518844B2 (en) | ||
| US2843566A (en) | Alkenylphenol-aldehyde | |
| JPS6352042B2 (en) | ||
| US4395521A (en) | Process for curing thermoset resins using phenyl esters of carboxylic acids as latent catalysts | |
| US3268479A (en) | Nitroso and oxime containing polymers | |
| US4309516A (en) | Polymers containing 2,5-oxolanylene segments | |
| US3063959A (en) | Aldol condensation product-phenol aldehyde condensation product and method for making same | |
| US3125544A (en) | Chjcho | |
| US3767622A (en) | Poly hydroxyarylpolymethylenesulfonium zwitterionic monomers and surface coatings therefrom | |
| US3821282A (en) | Polymerisable anthranilic acid esters | |
| US3800005A (en) | Polymerizates of hydroxyetherified phenolic resin esterified with unsaturated polycarboxylic acid and laminates therefrom | |
| US4371669A (en) | Polymers having improved water resistance and monomers for same | |
| Zoss et al. | Preparation and properties of alkylphenol-acetylene resins |