JPH0572404B2 - - Google Patents
Info
- Publication number
- JPH0572404B2 JPH0572404B2 JP59267745A JP26774584A JPH0572404B2 JP H0572404 B2 JPH0572404 B2 JP H0572404B2 JP 59267745 A JP59267745 A JP 59267745A JP 26774584 A JP26774584 A JP 26774584A JP H0572404 B2 JPH0572404 B2 JP H0572404B2
- Authority
- JP
- Japan
- Prior art keywords
- para
- reaction
- cresol
- polymer
- benzene
- 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 - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000005804 alkylation reaction Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 18
- -1 phenol compound Chemical class 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- 150000001896 cresols Chemical class 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 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
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 4
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KSMBFKMHJGVFQO-UHFFFAOYSA-N 2-[2-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1C(C)(C)O KSMBFKMHJGVFQO-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 description 1
- KPZBEZVZFBDKCG-UHFFFAOYSA-N 2,4-dibutylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1 KPZBEZVZFBDKCG-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- PZPVXSMCRLNVRD-UHFFFAOYSA-N 2,6-dibutylphenol Chemical compound CCCCC1=CC=CC(CCCC)=C1O PZPVXSMCRLNVRD-UHFFFAOYSA-N 0.000 description 1
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 1
- SIRZAUFJHUZRTI-UHFFFAOYSA-N 3-methoxy-2-methylphenol Chemical compound COC1=CC=CC(O)=C1C SIRZAUFJHUZRTI-UHFFFAOYSA-N 0.000 description 1
- SOYWOKSOKVRZRZ-UHFFFAOYSA-N 3-methoxy-4-methylphenol Chemical compound COC1=CC(O)=CC=C1C SOYWOKSOKVRZRZ-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Description
（産業上の利用分野）
本発明は新規なフエノール重合体の製造法に関
する。
（従来技術）
従来、特殊フエノール樹脂の製造法としては、
フエノール類とジアルケニルベンゼン例えばパラ
あるいはメタ−ジイソプロペニルベンゼンとをブ
レンステツド酸あるいはルイス酸などのアルキル
化反応触媒を用いて60〜120℃で反応させ、重合
体を得る方法が知られている（米国特許第
3004953号明細書）。
また、同様の樹脂製造法として、フエノール水
酸基の両オルト位が水素であるフエノール化合物
とジオレフイン化合物とを金属アルミニウムを用
いてオルトアルキル化反応させ、重合体を得る方
法も知られている（米国特許第3996198号）。
他方、クレゾール２分子と、ビス（１−ヒドロ
キシ−１−メチルエチル）ベンゼン１分子とが脱
水縮合した結晶性のクレゾール誘導体も知られて
いる（特開昭58−121231号公報）。
一方、エポキシ樹脂用硬化剤としてのフエノー
ル重合体は従来からフエノール類のノボラツク樹
脂が用いられているが、これは低分子量であるた
め、硬化物のガラス転移温度が低く、より耐熱性
の高い高分子量のフエノール重合体が望まれてい
る。
また、酸化防止剤としては、２，６−ジターシ
ヤリーブチルパラクレゾールが広く用いられてい
るが、沸点が265℃のため、ポリプロピレン等の
熱可塑性樹脂との混練条件下（270〜350℃）では
揮散してしまう。このため、熱可塑性樹脂の酸化
防止剤には、ペンタエリスリチル−テトラキス
〔３−（３，５−ジターシヤリーブチル−４−ヒド
ロキシフエニル）プロピオネート〕などが用いら
れているが、近年熱可塑性樹脂の加工温度は上昇
してきており、特にエンジニアリングプラスチツ
クスでは、350℃にも達し、この酸化防止剤でも
揮散してしまう。このため、耐熱性のフエノール
系酸化防止剤が強く望まれている。
（発明が解決しようとする問題点）
上記米国特許第3004953号明細書には、特殊フ
エノール樹脂の分子量、構造および繰返し単位な
どは記載されていないが、本発明者らが、パラク
レゾールとパラジイソプロペニルベンゼンとを用
いて、米国特許第3004953号明細書に記載の発明
の追試を行ない、反応の様子を高速液体クロマト
グラフイーで分析したところ、パラジイプロペニ
ルベンゼンのパラクレゾールへのアルキル化反応
生成物以外に、パラジイソプロペニルベンゼンの
単独重合体が多量に生成すると同時に、未反応の
パラクレゾールが多量に残存することが見出され
た。すなわち、上記米国特許第3004953号明細書
に記載の発明によつて得られる重合体は、上記ア
ルキル化反応生成物と上記単独重合体の組成物と
なつており、得られた樹脂の単位重量当りのフエ
ノール水酸基量は配合から計算される値に比べて
少ない値になつている。このため、この特殊フエ
ノール樹脂をエポキシ樹脂硬化剤として使用した
場合、フエノール樹脂中に硬化反応に関与しない
パラジイソプロペニルベンゼンの単独重合体が混
存するので、得られた硬化物は橋かけ密度が減少
し、ガラス転移点の低い、耐熱性に劣るという問
題がある。また、この特殊フエノール樹脂を酸化
防止剤として使用した時は、フエノール水酸基が
熱可塑性樹脂に発生したラジカルを補足するわけ
であるから、単位重量当りのフエノール性水酸基
量が少ない樹脂は、熱可塑性樹脂に多量に添加し
なければ酸化防止剤としての硬化が発揮しないと
いう欠点を有している。
また、米国特許第3996198号明細書に記載の方
法は、金属アルミニウムとフエノール化合物を最
初に反応させてアルミニウムフエノラートを形成
させ、このフエノラートにジアルケニルベンゼン
を該フエノラートのアルミニウムで触媒作用させ
てオルトアルキル化反応させるものである。ゆえ
に、生成重合体中には、アルミニウムが含まれ、
これを除去してフエノール重合体とするために
は、塩酸等の酸で加水分解する必要があり、反応
工程が増えるという欠点がある。
他方、上記した特開昭58−121231号公報に記載
されるクレゾール誘導体は、いずれも分子内に２
個のフエノール水酸基しか有しておらず、通常の
２官能エポキシ樹脂と反応させた場合には線状の
硬化物となり、ガラス転移点が低く、使用にたえ
ず、３官能以上の特殊なエポキシ樹脂を用いた場
合にしか３次元硬化物を与えないという問題があ
る。また、酸化防止剤として使用する場合、これ
らクレゾール誘導体はいずれも融点が185℃以下
の分子量374の結晶性化合物であり、熱可塑性樹
脂との混練条件下（270〜350℃）では大半が揮散
してしまうという本質的問題を伴う。
本発明はこのような問題を解決すべくなされた
もので、エポキシ樹脂の硬化剤、熱可塑性樹脂の
酸化防止剤などに有用なフエノール重合体の製造
法を提供することを目的とする。
（問題点を解決するための手段）
本発明は、一般式〔〕
(Industrial Application Field) The present invention relates to a novel method for producing a phenol polymer. (Prior art) Conventionally, the manufacturing method for special phenolic resin is as follows:
A known method is to react phenols and dialkenylbenzenes such as para- or meta-diisopropenylbenzene at 60 to 120°C using an alkylation catalyst such as Brønsted acid or Lewis acid to obtain a polymer ( US Patent No.
3004953 specification). In addition, as a similar resin production method, a method is known in which a phenol compound in which both ortho positions of the phenol hydroxyl group are hydrogen and a diolefin compound are ortho-alkylated using metal aluminum to obtain a polymer (U.S. Pat. No. 3996198). On the other hand, a crystalline cresol derivative in which two molecules of cresol and one molecule of bis(1-hydroxy-1-methylethyl)benzene are dehydrated and condensed is also known (Japanese Unexamined Patent Publication No. 121231/1982). On the other hand, phenolic novolak resins have traditionally been used as curing agents for epoxy resins, but because these have low molecular weights, the glass transition temperature of the cured product is low, and high heat resistance polymers are used. Molecular weight phenolic polymers are desired. In addition, 2,6-ditertiarybutyl para-cresol is widely used as an antioxidant, but since its boiling point is 265°C, it is mixed under conditions of kneading with thermoplastic resins such as polypropylene (270 to 350°C). Then it will evaporate. For this reason, pentaerythrityl-tetrakis [3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate] and the like are used as antioxidants for thermoplastic resins; Processing temperatures for resins have been rising, especially for engineering plastics, reaching 350 degrees Celsius, causing even this antioxidant to volatilize. For this reason, heat-resistant phenolic antioxidants are strongly desired. (Problems to be Solved by the Invention) Although the above specification of US Pat. No. 3,004,953 does not describe the molecular weight, structure, repeating unit, etc. of the special phenol resin, the present inventors have discovered that para-cresol and para-diiso A follow-up test of the invention described in US Pat. No. 3,004,953 was conducted using propenylbenzene, and the reaction was analyzed by high performance liquid chromatography. It was found that, in addition to p-cresol, a large amount of a homopolymer of p-diisopropenylbenzene was produced, and at the same time, a large amount of unreacted p-cresol remained. That is, the polymer obtained by the invention described in US Pat. No. 3,004,953 is a composition of the alkylation reaction product and the homopolymer, and the amount per unit weight of the resulting resin is The amount of phenol hydroxyl groups in is smaller than the value calculated from the formulation. Therefore, when this special phenolic resin is used as an epoxy resin curing agent, a homopolymer of paradiisopropenylbenzene that does not participate in the curing reaction coexists in the phenolic resin, so the resulting cured product has a reduced crosslinking density. However, there are problems in that it has a low glass transition point and poor heat resistance. In addition, when this special phenolic resin is used as an antioxidant, the phenolic hydroxyl groups capture the radicals generated in the thermoplastic resin, so resins with a small amount of phenolic hydroxyl groups per unit weight are suitable for thermoplastic resins. It has the disadvantage that it does not exhibit its curing effect as an antioxidant unless it is added in large amounts. Additionally, the method described in U.S. Pat. No. 3,996,198 involves first reacting metal aluminum and a phenolic compound to form an aluminum phenolate, and then catalyzing dialkenylbenzene on the phenolate with the aluminum of the phenolate. This is an alkylation reaction. Therefore, the produced polymer contains aluminum,
In order to remove this and obtain a phenol polymer, it is necessary to hydrolyze it with an acid such as hydrochloric acid, which has the drawback of increasing the number of reaction steps. On the other hand, all of the cresol derivatives described in JP-A-58-121231 mentioned above have 2 in the molecule.
It has only one phenolic hydroxyl group, and when reacted with a normal bifunctional epoxy resin, it becomes a linear cured product, has a low glass transition point, and is suitable for constant use. There is a problem in that a three-dimensional cured product can only be obtained when using this method. In addition, when used as antioxidants, these cresol derivatives are all crystalline compounds with a melting point of 185°C or less and a molecular weight of 374, and most of them volatilize under the conditions of kneading with thermoplastic resin (270 to 350°C). This is accompanied by the essential problem of The present invention was made to solve these problems, and an object of the present invention is to provide a method for producing a phenol polymer useful as a curing agent for epoxy resins, an antioxidant for thermoplastic resins, and the like. (Means for solving the problem) The present invention is based on the general formula []
【化】
（ただし、式中R1は炭素数１〜５のアルキル基
またはアルコキシ基であり、R2およびR3は水素
又は炭素数１〜５のアルキル基若しくはアルコキ
シ基であり、R2とR3は同一でも相違していても
よい）で表わされるフエノール化合物１モルに対
して一般式〔〕[Chemical formula] (However, in the formula, R 1 is an alkyl group or an alkoxy group having 1 to 5 carbon atoms, R 2 and R 3 are hydrogen or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and R 2 and R 3 may be the same or different) per mole of the phenol compound represented by the general formula []
【化】
（ただし、式中R4、R5、R6、R7、R8およびR9は
水素または炭素数１〜５のアルキル基であり、こ
れらは同一でも相違していてもよい）で表わされ
るビス（ヒドロキシアルキル）ベンゼン化合物を
0.67〜1.33モルの範囲でアルキル化反応触媒下に
反応させることを特徴とする一般式〔〕[Chemical formula] (However, in the formula, R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these may be the same or different.) A bis(hydroxyalkyl)benzene compound represented by
General formula characterized by reacting under an alkylation reaction catalyst in the range of 0.67 to 1.33 mol []
【化】
（ただし、式中R1、R2、R3、R4、R5、R6、R7、
R8及びR9は上記と同一である）
で表わされる繰り返し単位を平均2.5〜75個有す
るフエノール重合体の製造法に関する。
本発明に用いられる一般式〔〕で表わされる
フエノール化合物としては、具体的には、オルト
−またはパラ−クレゾール、オルト−またはパラ
−メトキシフエノール、オルト−またはパラ−エ
チルフエノール、オルト−またはパラ−プロピル
フエノール、オルト−またはパラ−ブチルフエノ
ール、オルト−またはパラ−アミルフエノール、
オルト−またはパラ−シクロペンチルフエノー
ル、２，３−ジメチルフエノール、３，４−ジメ
チルフエノール、２，５−ジメチルフエノール、
３−メトキシ−２−メチルフエノール、３−メト
キシ−４−メチルフエノール、２，３，５−トリ
メチルフエノール、３，４，５−トリメチルフエ
ノール等が挙げられ、これらは単独でまたは混合
物として使用される。このように、フエノール性
水酸基に対してオルト位およびパラ位の３個所の
うち２個所が水素原子であるフエノール化合物が
用いられる。これは、ビス（ヒドロキシアルキ
ル）ベンゼンがアルキル化反応してゲル化せずに
高分子量の線状フエノール重合体を生成せしめる
に２個所のアルキル化反応部位を必要とするため
である。
また、分子量調節剤としての効果を有するフエ
ノール性水酸基に対してオルト位およびパラ位の
３個のうち１個所だけが水素原子であるフエノー
ル化合物、具体的には２，４−ジメチルフエノー
ル、２，６−ジメチルフエノール、２，４−ジブ
チルフエノール、２，６−ジブチルフエノールな
ども併用できるが、これらのフエノール化合物
は、その使用量が式〔〕のフエノール化合物に
対して０〜５モル％とされる。
さらに、フエノール性水酸基に対してオルト位
およびパラ位の３個が全て水素原子であるフエノ
ール化合物、具体的にはフエノール、メタクレゾ
ール、３，５−ジメチルフエノール、３−メトキ
シフエノールなどが挙げられるが、これらはその
使用量が一般式〔〕で表わされるフエノール化
合物に対して０〜５モル％であれば添加使用する
ことができる。
また、一般式〔〕で表わされるビス（１−ヒ
ドロキシ−１−アルキルエチル）ベンゼン化合物
としてはメタ−ビス（１−ヒドロキシ−１−メチ
ルエチル）ベンゼン、パラ−ビス（１−ヒドロキ
シ−１−メチルエチル）ベンゼン、メタ−ビス
（１−ヒドロキシエチル）ベンゼン、パラ−ビス
（１−ヒドロキシエチル）ベンゼン、メタ−ビス
（１−ヒドロキシ−１−エチルエチル）ベンゼン、
パラ−ビス（１−ヒドロキシ−１−エチルエチ
ル）ベンゼンなどが挙げられ、これらは単独で、
または混合物として用いることができる。
反応を進行せしめるに用いられる触媒は、アル
キル化反応触媒である。この触媒としては陽イオ
ン交換樹脂、あるいはゼオライト、シリカ−アル
ミナなどの固体酸を用いることができるが、反応
を不均一系反応で行なうより均一系反応とした方
が操作上容易なので、ブレンステツド酸である硫
酸、塩酸、リン酸などの鉱酸、パラトルエンスル
ホン酸などの有機酸、ルイス酸である三弗化ホウ
素、三弗化ホウ素の錯体触媒などが好ましい。こ
れらアルキル化反応触媒の使用量は、上記フエノ
ール化合物と上記ビス（ヒドロキシアルキル）ベ
ンゼンの合計量に対して0.2〜10重量％が好まし
い。0.2重量％未満の場合は反応時間が長くなる
傾向があり、10重量％を越える場合は、反応終了
後の触媒除去が煩雑になりやすくなる。
本発明においては、上記フエノール化合物と、
上記ビス（ヒドロキシアルキル）ベンゼン化合物
とのモル比をフエノール化合物1.0モルに対して
ビス（ヒドロキシアルキル）ベンゼンを0.67〜
1.33モルとして反応させることが好ましい。この
理由は、生成するフエノール重合体の分子量に関
係し、フエノール化合物1.0モルに対して、ビス
（ヒドロキシアルキル）ベンゼンが、0.67モル未
満あるいは1.33モルを越えるモル数であれば、フ
エノール重合体の分子量が低下し、高分子量のフ
エノール重合体を得るのが困難になる。
反応温度は好ましくは60〜130℃とされる。こ
の理由は、反応温度が60℃未満の場合、反応の進
行が遅く、また反応温度が130℃を越える場合、
生成するフエノール重合体が着色し易いからであ
る。本発明では、反応の進行とともに、水が生成
するので、好ましくは用いた溶媒と水との共沸点
温度で行なわれる。
ここで用いる溶媒としては、ｎ−ヘキサン、シ
クロヘキサンなどのパラフイン系溶媒、アセト
ン、メチルエチルケトンなどのケトン系溶媒、メ
タノール、エタノールなどのアルコール系溶媒、
ベンゼン、トルエン、キシレン、クロロベンゼン
などの芳香族溶媒を挙げることができるが、水と
共沸組成を形成し、生成する重合体を溶解させ、
しかもそれ自身は反応に関与しない溶媒であるこ
とが好ましく、具体的にはベンゼン、トルエン、
キシレン、クロロベンゼなどの芳香族溶媒が好ま
しい。
反応終了後は、水および水酸化ナトリウム、水
酸化カリウム、炭酸ナトリウム、炭酸水素ナトリ
ウム等の１〜２％希アルカリ水溶液で反応液を水
洗あるいは中和水洗して触媒を除去する方法、炭
酸ナトリウム、炭酸水素ナトリウム、酸化マグネ
シウム等のアルカリ粉末を加え、撹拌ののち、中
和塩を過して触媒を除去する方法、あるいはト
リエチルアミン、トリエタノールアミン、モルホ
リン等のアミンを加え触媒を中和する方法等の処
理が行なわれる。触媒の中和水洗除去、中和後の
過による除去あるいは中和を終えた反応液は、
そのまま加熱減圧下に反応溶媒を除去し、フエノ
ール重合体を単離することができる。しかし、分
析の結果、微量の残存モノマーおよびオリゴマー
が存在する場合は、メタノール、エタノールなど
のアルコール性溶媒、あるいはヘキサン、シクロ
ヘキサンなどのパラフイン系溶媒と言つたフエノ
ール重合体の貧溶媒で再沈させるのが好ましい。
このようにして得られるフエノール重合体は、
無色あるいは淡黄色の非結晶状樹脂状物であり、
一般式〔〕で表わされる繰返し単位を、数平均
分子量に基づいて、平均2.5〜75個有するもので
ある。数平均分子量は、使用する原料によりその
範囲が異なるが、494〜68000の範囲にある。例え
ば、クレゾールとビス（１−ヒドロキシ−１−メ
チルエチル）ベンゼンを原料とするときは、数平
均分子量は550〜20000である。
このようにして得られるフエノール重合体は、
貯蔵中のブロツキングを防止するためには、軟化
点が70℃以上であるものが好ましく、他の樹脂又
はゴムとの相溶性の点からは、一般式〔〕で表
わされる繰返し単位が平均2.5〜30個のものが特
に好ましい。また、重合体の末端の構造は、ビス
（ヒドロキシアルキル）ベンゼン１モルに対する
フエノール化合物のモル数によつて異なり、フエ
ノール化合物のモル比が1.0を越えるときは、平
均して末端がフエノール基となつている。同様
に、モル比が１以下の場合は、平均してビス（ヒ
ドロキシアルキル）ベンゼンに２個存在するヒド
ロキシアルキル基のうちの１個が未反応の状態で
存在することになる。
本発明の製造法によつて得られるフエノール重
合体はアルキル化剤の単独重合体を含有せず、一
般式〔〕で表わされる繰返し単位を有する重合
体である。この理由は、ジイソプロペニルベンゼ
ンの二重結合は反応性が高く、60℃以上でアルキ
ル化反応以外に、二重結合同士による重合を引き
起こしてしまうが、これに対し、本発明で用いる
ビス（ヒドロキシアルキル）ベンゼンは二重結合
の無い２官能のアルコールであり、本発明の反応
条件下では単独重合も起こさないためと考えられ
る。
また、本発明の製造法によるフエノール重合体
と上記した特開昭58−121231号公報に記載のクレ
ゾール誘導体との相違は、クレゾール誘導体が２
官能のフエノールモノマーで結晶性化合物である
のに対して、本発明の製造法によるフエノール重
合体は一般式〔〕で表わされる繰返し単位を有
する重合体であつて、非結晶性の樹脂状物であ
る。また、これらを合成する反応条件も大きく異
なり、クレゾール誘導体の場合、ビス（１−ヒド
ロキシ−１−メチルエチル）ベンゼン１モルに対
して、クレゾールを2.0〜10モル、好ましくは2.0
〜６モルとクレゾールが大過剰の反応条件下で行
なうことが必要となつている。
（発明の効果）
本発明により、エポキシ樹脂の硬化剤、熱可塑
性樹脂の酸化防止剤などに有用な新規なフエノー
ル重合体を得ることができる。
（実施例）
次に本発明の実施例を示す。
実施例 １
油水分離器を取付けた1000mlガラス製三つ口フ
ラスコに、パラクレゾール108ｇ（1.00モル）、メ
タ−ビス（１−ヒドロキシ−１−メチルエチル）
ベンゼン184ｇ（0.95モル）、トルエン150ｇおよ
びパラトルエンスルホン酸7.5ｇを仕込み撹拌し
ながら昇温した。フラスコ内の温度が95℃になつ
た時点で水がトルエンと一緒に留出し始めた。フ
ラスコ内の温度を105℃のまま８時間反応を行な
つた。この時留出した水の量は34mlであり、メタ
−ビス（１−ヒドロキシ−１−メチルエチル）ベ
ンゼンはほぼ完全に反応したことがわかる。
反応終了後、フラスコ内の反応液を１の分液
ロートへ移し、これにトルエン150ｇを加えたの
ち、イオン交換水で５回洗浄を繰返してパラトル
エンスルホン酸を除去した。トルエン溶液をエバ
ポレーターにかけ、溶媒トルエンを200ｇ除去し
たのち、500mlのメタノールに溶液を撹拌しなが
ら注ぎ、白色沈殿を得た。沈殿を減圧乾燥したと
ころ、240ｇの白色粉末を得た。この重合体をゲ
ルパーミエーシヨンクロマトグラフイーで分析し
たところ、標準ポリスチレン換算で数平均分子量
が1650、これに基づく繰返し単位数は平均6.2で
ある。また重量平均分子量が2750、これに基づく
繰返し単位数は平均10.3であつた。また、環球式
軟化点測定器で軟化点を測定したところ、軟化点
は135℃であつた。さらに、この重合体の耐熱性
を見るために熱天秤分析を行なつた。空気雰囲気
下で毎分10℃の昇温速度で加熱を続けたところ、
320℃から減量が始まつたが、350℃における減量
の割合は３重量％であり、エンジニアリングプラ
スチツクス用の酸化防止剤として十分使用できる
耐熱性を有していることがわかつた。
また、重クロロホルムを溶媒としてNMRスペ
クトルを分析したところ、2.3ppmにパラクレゾ
ールに基づくメチル基のシグナルが存在すること
から重合体中にパラクレゾールが組込まれている
ことがわかつた。また、メタ−ビス（１−ヒドロ
キシ−１−メチルエチル）エンゼンに基づく４個
のメチル基のシグナルは0.9〜1.7ppmに存在し、
このプロトン積分強度は上述のパラクレゾールに
基づくメチル基のプロトン積分強度の3.42倍存在
した。このことから、得られた重合体の平均的構
造は次のように示される。[Chemical formula] (However, in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 ,
R 8 and R 9 are the same as above) The present invention relates to a method for producing a phenol polymer having an average of 2.5 to 75 repeating units. Specifically, the phenol compound represented by the general formula [] used in the present invention includes ortho- or para-cresol, ortho- or para-methoxyphenol, ortho- or para-ethylphenol, ortho- or para- propylphenol, ortho- or para-butylphenol, ortho- or para-amylphenol,
ortho- or para-cyclopentylphenol, 2,3-dimethylphenol, 3,4-dimethylphenol, 2,5-dimethylphenol,
Examples include 3-methoxy-2-methylphenol, 3-methoxy-4-methylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, etc., which may be used alone or as a mixture. . In this way, a phenol compound is used in which two of the three positions, the ortho position and the para position relative to the phenolic hydroxyl group, are hydrogen atoms. This is because two alkylation reaction sites are required for bis(hydroxyalkyl)benzene to undergo an alkylation reaction and produce a high molecular weight linear phenol polymer without gelation. In addition, phenolic compounds having a hydrogen atom at only one of the three ortho and para positions relative to the phenolic hydroxyl group, which have the effect of acting as a molecular weight regulator, are specifically 2,4-dimethylphenol, 2, 6-dimethylphenol, 2,4-dibutylphenol, 2,6-dibutylphenol, etc. can also be used in combination, but the amount of these phenol compounds to be used is 0 to 5 mol% relative to the phenol compound of formula []. Ru. Further, phenolic compounds in which all three ortho and para positions with respect to the phenolic hydroxyl group are hydrogen atoms, specific examples include phenol, metacresol, 3,5-dimethylphenol, and 3-methoxyphenol. , these can be added and used if the amount used is 0 to 5 mol% relative to the phenol compound represented by the general formula []. In addition, as the bis(1-hydroxy-1-alkylethyl)benzene compound represented by the general formula [], meta-bis(1-hydroxy-1-methylethyl)benzene, para-bis(1-hydroxy-1-methyl ethyl)benzene, meta-bis(1-hydroxyethyl)benzene, para-bis(1-hydroxyethyl)benzene, meta-bis(1-hydroxy-1-ethylethyl)benzene,
Examples include para-bis(1-hydroxy-1-ethylethyl)benzene, which alone,
Or it can be used as a mixture. The catalyst used to drive the reaction is an alkylation reaction catalyst. As this catalyst, a cation exchange resin or a solid acid such as zeolite or silica-alumina can be used, but since it is easier to perform a homogeneous reaction than a heterogeneous reaction, Bronsted acid is used as the catalyst. Preferred are mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, organic acids such as para-toluenesulfonic acid, boron trifluoride which is a Lewis acid, and complex catalysts of boron trifluoride. The amount of these alkylation reaction catalysts used is preferably 0.2 to 10% by weight based on the total amount of the phenol compound and the bis(hydroxyalkyl)benzene. If it is less than 0.2% by weight, the reaction time tends to be longer, and if it exceeds 10% by weight, removal of the catalyst after the reaction is likely to be complicated. In the present invention, the above phenol compound and
The molar ratio of bis(hydroxyalkyl)benzene to the above bis(hydroxyalkyl)benzene compound is 0.67 to 1.0 mol of the phenol compound.
It is preferable to react at 1.33 mol. The reason for this is related to the molecular weight of the phenol polymer to be produced. decreases, making it difficult to obtain a high molecular weight phenol polymer. The reaction temperature is preferably 60 to 130°C. The reason for this is that when the reaction temperature is less than 60℃, the reaction progresses slowly, and when the reaction temperature exceeds 130℃,
This is because the produced phenol polymer is easily colored. In the present invention, since water is produced as the reaction progresses, the reaction is preferably carried out at the azeotropic temperature of the solvent used and water. Solvents used here include paraffinic solvents such as n-hexane and cyclohexane, ketone solvents such as acetone and methyl ethyl ketone, alcoholic solvents such as methanol and ethanol,
Aromatic solvents such as benzene, toluene, xylene, and chlorobenzene can be mentioned, but they form an azeotropic composition with water and dissolve the resulting polymer,
Moreover, it is preferable that the solvent itself does not participate in the reaction, and specifically, benzene, toluene,
Aromatic solvents such as xylene and chlorobenze are preferred. After the reaction is completed, the catalyst is removed by washing or neutralizing the reaction solution with water and a 1-2% dilute alkali aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc., sodium carbonate, A method in which an alkali powder such as sodium hydrogen carbonate or magnesium oxide is added and, after stirring, the catalyst is removed by passing through a neutralized salt, or a method in which an amine such as triethylamine, triethanolamine, or morpholine is added to neutralize the catalyst. processing is performed. Neutralize the catalyst by washing it with water, removing it by filtration after neutralization, or removing the reaction solution after neutralization.
The reaction solvent can be removed under heating and reduced pressure to isolate the phenol polymer. However, if the analysis results show that trace amounts of residual monomers and oligomers are present, re-precipitating with a poor solvent for phenolic polymers such as an alcoholic solvent such as methanol or ethanol, or a paraffinic solvent such as hexane or cyclohexane is necessary. is preferred. The phenol polymer obtained in this way is
It is a colorless or pale yellow amorphous resinous substance,
It has an average of 2.5 to 75 repeating units represented by the general formula [] based on the number average molecular weight. The number average molecular weight varies depending on the raw materials used, but is in the range of 494 to 68,000. For example, when cresol and bis(1-hydroxy-1-methylethyl)benzene are used as raw materials, the number average molecular weight is 550 to 20,000. The phenol polymer obtained in this way is
In order to prevent blocking during storage, it is preferable that the softening point is 70°C or higher, and from the point of view of compatibility with other resins or rubbers, the repeating unit represented by the general formula [] is preferably 2.5 to 70°C on average. Particularly preferred is 30 pieces. Furthermore, the terminal structure of the polymer varies depending on the number of moles of the phenol compound per mole of bis(hydroxyalkyl)benzene, and when the molar ratio of the phenol compound exceeds 1.0, the terminal becomes a phenol group on average. ing. Similarly, when the molar ratio is 1 or less, one of the two hydroxyalkyl groups present in bis(hydroxyalkyl)benzene will exist in an unreacted state on average. The phenol polymer obtained by the production method of the present invention does not contain a homopolymer of an alkylating agent and has a repeating unit represented by the general formula [ ]. The reason for this is that the double bonds in diisopropenylbenzene are highly reactive and cause polymerization between double bonds in addition to alkylation reactions at temperatures above 60°C. This is thought to be because benzene (hydroxyalkyl) is a bifunctional alcohol without double bonds and does not undergo homopolymerization under the reaction conditions of the present invention. Furthermore, the difference between the phenol polymer produced by the production method of the present invention and the cresol derivative described in JP-A-58-121231 mentioned above is that the cresol derivative is
While the functional phenol monomer is a crystalline compound, the phenol polymer produced by the production method of the present invention is a polymer having a repeating unit represented by the general formula [], and is an amorphous resinous material. be. In addition, the reaction conditions for synthesizing these are also very different; in the case of cresol derivatives, 2.0 to 10 mol of cresol, preferably 2.0 mol, per 1 mol of bis(1-hydroxy-1-methylethyl)benzene.
It is necessary to carry out the reaction under conditions in which the amount of cresol is in large excess of ~6 mol. (Effects of the Invention) According to the present invention, a novel phenol polymer useful as a curing agent for epoxy resins, an antioxidant for thermoplastic resins, etc. can be obtained. (Example) Next, an example of the present invention will be shown. Example 1 108 g (1.00 mol) of para-cresol and meta-bis(1-hydroxy-1-methylethyl) were placed in a 1000 ml three-necked glass flask equipped with an oil-water separator.
184 g (0.95 mol) of benzene, 150 g of toluene and 7.5 g of para-toluenesulfonic acid were charged and the temperature was raised while stirring. When the temperature inside the flask reached 95°C, water began to distill out together with toluene. The reaction was carried out for 8 hours while keeping the temperature inside the flask at 105°C. The amount of water distilled out at this time was 34 ml, indicating that meta-bis(1-hydroxy-1-methylethyl)benzene had reacted almost completely. After the reaction was completed, the reaction solution in the flask was transferred to the separating funnel No. 1, to which 150 g of toluene was added, and then washing was repeated 5 times with ion-exchanged water to remove para-toluenesulfonic acid. After applying the toluene solution to an evaporator to remove 200 g of the toluene solvent, the solution was poured into 500 ml of methanol with stirring to obtain a white precipitate. When the precipitate was dried under reduced pressure, 240 g of white powder was obtained. When this polymer was analyzed by gel permeation chromatography, the number average molecular weight was 1650 in terms of standard polystyrene, and the average number of repeating units based on this was 6.2. Furthermore, the weight average molecular weight was 2750, and the average number of repeating units based on this was 10.3. Further, the softening point was measured using a ring and ball softening point measuring device, and the softening point was 135°C. Furthermore, thermobalance analysis was conducted to examine the heat resistance of this polymer. When heating was continued at a rate of 10°C per minute in an air atmosphere,
Although the weight loss started at 320°C, the weight loss rate at 350°C was 3% by weight, indicating that it had sufficient heat resistance to be used as an antioxidant for engineering plastics. Furthermore, when the NMR spectrum was analyzed using deuterated chloroform as a solvent, it was found that para-cresol was incorporated into the polymer because a signal of a methyl group based on para-cresol was present at 2.3 ppm. In addition, signals of four methyl groups based on meta-bis(1-hydroxy-1-methylethyl)enzene exist at 0.9 to 1.7 ppm,
This proton integrated intensity was 3.42 times the proton integrated intensity of the methyl group based on para-cresol mentioned above. From this, the average structure of the obtained polymer is shown as follows.
【化】
メタ−ビス（１−ヒトロキシ−１−メチルエチル）ベンゼンのメチル基プロトン量／パラクレゾールのメチル基プロ
トン量＝４×3n／3n＋３＝3.42／１
ゆえに、ｎは5.9となり、この値はゲルパーミ
エーシヨンクロマトグラフイーから求めた値（数
平均分子量に基づく）ともよく一致する。
実施例 ２
実施例１におけるパラクレゾールのかわりにオ
ルトクレゾールを用いた他は、仕込配合および反
応条件を実施例１とまつたく同一の方法で行な
い、白色沈殿を230ｇ得た。この重合体をゲルパ
ーミエーシヨンクロマトグラフイーで分析したと
ころ、標準ポリスチレン換算で数平均分子量は
1850（これに基づく繰返し単位数は平均6.9）、重
量平均分子量は3100（これに基づく繰返し単位数
は平均11.6）であつた。また、環球式軟化点測定
器で軟化点を測定したところ、軟化点は130℃で
あつた。
実施例 ３
実施例１とまつたく同一のフラスコに、パラエ
チルフエノール122ｇ（1.00モル）、パラ−ビス
（１−ヒドロキシ−１−メチルエチル）ベンゼン
184ｇ（0.95モル）、トルエン150ｇ、パラトルエ
ンスルホン酸7.7ｇを仕込み、以下の反応条件を
実施例１とまつたく同一の方法で行ない、白色粉
末を235ｇ得た。この重合体をゲルパーミエーシ
ヨンクロマトグラフイーで分析したところ、標準
ポリスチレン換算で数平均分子量が1700（これに
基づく繰返し単位数は平均6.1）、重量平均分子量
が2750（これに基づく繰返し単位数は平均9.8）で
あつた。また環球式軟化点測定器で軟化点を測定
したところ、軟化点は156℃であつた。
比較例 １
500ml三つ口フラスコにパラクレゾール54ｇ
（0.50モル）、パラ−ジイソプロペニルベンゼン79
（0.50モル）、トルエン130ｇおよびパラトルエン
スルホン酸3.3ｇを加え撹拌しながら昇温し、105
℃で８時間反応を行なつた。
反応終了後は実施例１と同様の処理を行ない、
72ｇの白色粉末を得た。この重合体をゲルパーミ
エーシヨンクロマトグラフイーで分析したとこ
ろ、標準ポリスチレン換算で数平均分子量が2350
重量平均分子量が3850であつた。また軟化点は
185℃であつた。さらに重クロロホルムを溶媒と
してNMRスペクトルを分析したところ、
7.19ppmにパラクレゾールのメタ位のベンゼン環
プロトンの鋭いピークが存在するが、パラ−ジイ
ソプロペニルベンゼンに由来するベンゼン環プロ
トン量に比べ、３分の１であつた。また、
2.3ppmにパラクレゾールに基づくメチル基プロ
トンが認められるが、2.1〜2.5ppmにやや幅広い
４本のピークが存在している。これらのことか
ら、得られた重合体はパラクレゾールとパラ−ジ
イソプロペニルベンゼンとの１：１の共重合体だ
けではなく、パラ−ジイソプロペニルベンゼンが
単独に重合したもの、またはパラ−ジイソプロペ
ニルベンゼンのオリゴマーにパラクレゾールが反
応した重合体が混在していると考えられる。
このことは、次の実験例に示すとおり、パラ−
ジイソプロペニルベンゼンが単独重合しやすいこ
とからも明らかである。
実施例 ４
200ml三つ口フラスコにパラ−ジイソプロペニ
ルベンゼン40ｇ、トルエン67ｇおよびパラトルエ
ンスルホン酸1.0ｇとを仕込み、撹拌しながら昇
温したところ、反応開始後20分、フラスコの温度
が85℃になつた時点で内容物が固化してしまつ
た。テトラヒドロフラン溶媒に溶解する部分だけ
をゲルパーミエーシヨンクロマトグラフイーで分
析したところ、排除限界50000以上の高分子量体
を含んだ数平均分子量8000にピークを有する重合
体であつた。[Chemical formula] Amount of methyl group protons in meta-bis(1-hydroxy-1-methylethyl)benzene/Methyl group proton amount in para-cresol = 4×3n/3n+3=3.42/1 Therefore, n is 5.9, and this value is It also agrees well with the value determined from gel permeation chromatography (based on number average molecular weight). Example 2 Except for using orthocresol in place of para-cresol in Example 1, the charge formulation and reaction conditions were carried out in exactly the same manner as in Example 1, and 230 g of a white precipitate was obtained. When this polymer was analyzed by gel permeation chromatography, the number average molecular weight was found to be
The weight average molecular weight was 1850 (the average number of repeating units based on this was 6.9), and the weight average molecular weight was 3100 (the average number of repeating units based on this was 11.6). Further, when the softening point was measured using a ring and ball softening point measuring device, the softening point was 130°C. Example 3 Into the same flask as in Example 1, 122 g (1.00 mol) of paraethylphenol and para-bis(1-hydroxy-1-methylethyl)benzene were added.
184 g (0.95 mol), 150 g of toluene, and 7.7 g of para-toluenesulfonic acid were charged, and the following reaction conditions were carried out in exactly the same manner as in Example 1 to obtain 235 g of white powder. When this polymer was analyzed by gel permeation chromatography, the number average molecular weight was 1700 in terms of standard polystyrene (based on this, the average number of repeating units was 6.1), and the weight average molecular weight was 2750 (based on this, the number of repeating units was The average was 9.8). Further, the softening point was measured using a ring and ball softening point measuring device, and the softening point was 156°C. Comparative example 1 54g of para-cresol in a 500ml three-necked flask
(0.50 mol), para-diisopropenylbenzene 79
(0.50 mol), 130 g of toluene and 3.3 g of para-toluenesulfonic acid were added, and the temperature was raised while stirring.
The reaction was carried out at ℃ for 8 hours. After the reaction was completed, the same treatment as in Example 1 was carried out,
72g of white powder was obtained. When this polymer was analyzed by gel permeation chromatography, the number average molecular weight was 2350 in terms of standard polystyrene.
The weight average molecular weight was 3850. Also, the softening point is
It was 185℃. Furthermore, when we analyzed the NMR spectrum using deuterated chloroform as a solvent, we found that
There was a sharp peak of the benzene ring proton at the meta position of para-cresol at 7.19 ppm, but the amount was one-third of the amount of benzene ring protons derived from para-diisopropenylbenzene. Also,
A methyl group proton based on para-cresol is observed at 2.3 ppm, but four slightly broad peaks are present at 2.1 to 2.5 ppm. From these facts, the obtained polymer is not only a 1:1 copolymer of para-cresol and para-diisopropenylbenzene, but also a monopolymer of para-diisopropenylbenzene or a copolymer of para-diisopropenylbenzene. It is thought that a polymer obtained by reacting para-cresol with an isopropenylbenzene oligomer is mixed therein. As shown in the following experimental example, this shows that the parameter
This is clear from the fact that diisopropenylbenzene is easily homopolymerized. Example 4 40 g of para-diisopropenylbenzene, 67 g of toluene, and 1.0 g of para-toluenesulfonic acid were placed in a 200 ml three-necked flask, and the temperature was raised while stirring. 20 minutes after the start of the reaction, the temperature of the flask reached 85°C. By this time, the contents had solidified. When only the portion soluble in tetrahydrofuran solvent was analyzed by gel permeation chromatography, it was found to be a polymer having a peak at a number average molecular weight of 8,000 and containing a high molecular weight substance with an exclusion limit of 50,000 or more.
Claims (1)
またはアルコキシ基であり、R2およびR3は水素
又は炭素数１〜５のアルキル基若しくはアルコキ
シ基であり、R2とR3は同一でも相違していても
よい）で表わされるフエノール化合物１モルに対
して一般式〔〕 【化】 （ただし、式中R4、R5、R6、R7、R8およびR9は
水素または炭素数１〜５のアルキル基であり、こ
れらは同一でも相違していてもよい）で表わされ
るビス（ヒドロキシアルキル）ベンゼン化合物を
0.67〜1.33モルの範囲でアルキル化反応触媒下に
反応させることを特徴とする一般式〔〕 【化】 （ただし、式中R1、R2、R3、R4、R5、R6、R7、
R8及びR9は上記と同一である） で表わされる繰り返し単位を平均2.5〜75個有す
るフエノール重合体の製造法。[Claims] 1 General formula [] [Chemical formula] (In the formula, R 1 is an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and R 2 and R 3 are hydrogen or a group having 1 to 5 carbon atoms. is an alkyl group or an alkoxy group, and R 2 and R 3 may be the same or different ). , R 6 , R 7 , R 8 and R 9 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these may be the same or different.
General formula [] [Chemical formula] characterized in that the reaction is carried out in the presence of an alkylation reaction catalyst in the range of 0.67 to 1.33 mol (However, in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 ,
R 8 and R 9 are the same as above) A method for producing a phenol polymer having an average of 2.5 to 75 repeating units.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26774584A JPS61145223A (en) | 1984-12-19 | 1984-12-19 | Production of phenolic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26774584A JPS61145223A (en) | 1984-12-19 | 1984-12-19 | Production of phenolic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61145223A JPS61145223A (en) | 1986-07-02 |
| JPH0572404B2 true JPH0572404B2 (en) | 1993-10-12 |
Family
ID=17448981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26774584A Granted JPS61145223A (en) | 1984-12-19 | 1984-12-19 | Production of phenolic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61145223A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992166B2 (en) | 2002-06-14 | 2006-01-31 | Sumitomo Chemical Company, Limited | Phenolic resin and method of producing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2567161B2 (en) * | 1990-08-20 | 1996-12-25 | 三井東圧化学株式会社 | Phenolic resin and method for producing the same |
| JP5977598B2 (en) * | 2012-06-22 | 2016-08-24 | 旭化成株式会社 | Method for improving flowability of polyamide resin composition |
| JPWO2023176766A1 (en) * | 2022-03-14 | 2023-09-21 | ||
| JPWO2023176765A1 (en) * | 2022-03-14 | 2023-09-21 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121231A (en) * | 1982-01-14 | 1983-07-19 | Sumitomo Chem Co Ltd | Novel cresol derivative and its preparation |
-
1984
- 1984-12-19 JP JP26774584A patent/JPS61145223A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121231A (en) * | 1982-01-14 | 1983-07-19 | Sumitomo Chem Co Ltd | Novel cresol derivative and its preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992166B2 (en) | 2002-06-14 | 2006-01-31 | Sumitomo Chemical Company, Limited | Phenolic resin and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61145223A (en) | 1986-07-02 |
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