JP4484726B2 - Polymerization inhibitor composition for vinyl acetate and polymerization inhibition method - Google Patents
Polymerization inhibitor composition for vinyl acetate and polymerization inhibition method Download PDFInfo
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- JP4484726B2 JP4484726B2 JP2005045386A JP2005045386A JP4484726B2 JP 4484726 B2 JP4484726 B2 JP 4484726B2 JP 2005045386 A JP2005045386 A JP 2005045386A JP 2005045386 A JP2005045386 A JP 2005045386A JP 4484726 B2 JP4484726 B2 JP 4484726B2
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- vinyl acetate
- acid
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- oxyl
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 96
- 238000006116 polymerization reaction Methods 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 73
- 239000003112 inhibitor Substances 0.000 title claims description 29
- 239000000203 mixture Substances 0.000 title claims description 25
- 230000005764 inhibitory process Effects 0.000 title claims description 12
- -1 quinone compound Chemical class 0.000 claims description 32
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000746 purification Methods 0.000 claims description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000002401 inhibitory effect Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 239000000174 gluconic acid Substances 0.000 claims description 8
- 235000012208 gluconic acid Nutrition 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 7
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 7
- 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 claims description 7
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 239000001630 malic acid Substances 0.000 claims description 7
- 235000011090 malic acid Nutrition 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- WSGDRFHJFJRSFY-UHFFFAOYSA-N 4-oxo-TEMPO Chemical group CC1(C)CC(=O)CC(C)(C)N1[O] WSGDRFHJFJRSFY-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 230000001629 suppression Effects 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical class [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- 150000007524 organic acids Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- LVRFTAZAXQPQHI-UHFFFAOYSA-N 2-hydroxy-4-methylvaleric acid Chemical compound CC(C)CC(O)C(O)=O LVRFTAZAXQPQHI-UHFFFAOYSA-N 0.000 description 4
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000010350 erythorbic acid Nutrition 0.000 description 3
- 229940026239 isoascorbic acid Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- MBIQENSCDNJOIY-UHFFFAOYSA-N 2-hydroxy-2-methylbutyric acid Chemical compound CCC(C)(O)C(O)=O MBIQENSCDNJOIY-UHFFFAOYSA-N 0.000 description 2
- FWVNWTNCNWRCOU-UHFFFAOYSA-N 2-hydroxy-3,3-dimethylbutanoic acid Chemical compound CC(C)(C)C(O)C(O)=O FWVNWTNCNWRCOU-UHFFFAOYSA-N 0.000 description 2
- NGEWQZIDQIYUNV-UHFFFAOYSA-N 2-hydroxy-3-methylbutyric acid Chemical compound CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 2
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- CKJMHSMEPSUICM-UHFFFAOYSA-N di-tert-butyl nitroxide Chemical class CC(C)(C)N([O])C(C)(C)C CKJMHSMEPSUICM-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 1
- GGMZLRIFEWTTGK-UHFFFAOYSA-N 2,2,5,5-tetramethyl-1-oxidopyrrolidin-1-ium Chemical compound CC1(C)CCC(C)(C)[NH+]1[O-] GGMZLRIFEWTTGK-UHFFFAOYSA-N 0.000 description 1
- HLBBQXTYDWELLT-UHFFFAOYSA-N 2-hydroxy-2-(2-hydroxy-4-methoxyphenyl)acetic acid Chemical compound COC1=CC=C(C(O)C(O)=O)C(O)=C1 HLBBQXTYDWELLT-UHFFFAOYSA-N 0.000 description 1
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- MSRXJQADDALUCI-UHFFFAOYSA-N 2-tert-butylnaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(C(C)(C)C)=CC(=O)C2=C1 MSRXJQADDALUCI-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- MJEDTBDGYVATPI-UHFFFAOYSA-N 4-hydroxy-TEMPO benzoate Chemical group C1C(C)(C)N([O])C(C)(C)CC1OC(=O)C1=CC=CC=C1 MJEDTBDGYVATPI-UHFFFAOYSA-N 0.000 description 1
- SFXHWRCRQNGVLJ-UHFFFAOYSA-N 4-methoxy-TEMPO Chemical group COC1CC(C)(C)N([O])C(C)(C)C1 SFXHWRCRQNGVLJ-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程における酢酸ビニルの重合抑制剤組成物および重合抑制方法に関するものである。 The present invention relates to a polymerization inhibitor composition for vinyl acetate and a polymerization inhibition method in the production process, purification process, storage or transport process of vinyl acetate.
酢酸ビニルは、極めて重合しやすく、製造工程、精製工程、反応工程において、熱、光、その他の要因により、しばしば重合トラブルを起こすことが知られている。このような重合は酢酸ビニルの製造工程、精製工程での汚れ（ファウリング）の原因となっている。このような汚れが、酢酸ビニルの製造工程、精製工程の製造タンク、蒸留塔（精留塔塔）、液送配管に付着すると、酢酸ビニルの製造・精製が制御できなくなり、操業に支障を来す場合がある。さらに製品品質の低下の原因ともなる。また、酢酸ビニルの汚れ、およびその重合反応物の除去は、人力による作業で行なわざるを得ないために、作業効率が悪く、その結果、長期間の運転停止を引き起こし、経済的損失が大きい。そこで、種々の酢酸ビニルの汚れ抑制剤、汚れ抑制方法や重合抑制剤、重合抑制方法が提案・実施されてきた。 It is known that vinyl acetate is very easily polymerized, and often causes polymerization troubles due to heat, light, and other factors in the production process, purification process, and reaction process. Such polymerization is a cause of fouling in the production process and the purification process of vinyl acetate. If such dirt adheres to the vinyl acetate production process, the purification process production tank, the distillation tower (rectification tower), or the liquid feed piping, the production and purification of vinyl acetate cannot be controlled, which hinders operations. There is a case. In addition, it may cause a reduction in product quality. Further, the removal of the vinyl acetate stains and the polymerization reaction product must be carried out by manual work, so that the work efficiency is poor. As a result, the operation is stopped for a long time, resulting in a large economic loss. Accordingly, various vinyl acetate stain inhibitors, stain inhibition methods, polymerization inhibitors, and polymerization inhibition methods have been proposed and implemented.
例えば、ハイドロキノン、ベンゾキノン、ｔ−ブチルカテコールを使用する方法（例えば特許文献１参照）、酢酸ビニルの蒸留工程の蒸留段階を通してｐ−アルキルフェノールを溶解状態で維持させて蒸留を行なう方法（例えば特許文献１、特許文献２参照）、ニトロキシルラジカル類を用いる方法（例えば特許文献３、特許文献４参照）等が開示されている。しかし、依然として、満足しうるような汚れの発生を抑制する酢酸ビニルの重合の抑制方法を得るには至っていない。そのため、より優れた酢酸ビニルの重合抑制剤および重合抑制方法が強く望まれている。 For example, a method using hydroquinone, benzoquinone and t-butylcatechol (see, for example, Patent Document 1), a method in which p-alkylphenol is maintained in a dissolved state throughout the distillation step of vinyl acetate (for example, Patent Document 1). And Patent Document 2), methods using nitroxyl radicals (see, for example, Patent Document 3 and Patent Document 4), and the like are disclosed. However, a method for suppressing the polymerization of vinyl acetate that suppresses the occurrence of satisfactory stains has not yet been obtained. Therefore, a better vinyl acetate polymerization inhibitor and polymerization suppression method are strongly desired.
本発明は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程における酢酸ビニルの重合を抑制し、さらに重合によって生じる汚れの発生を効果的に抑制する酢酸ビニルの重合抑制剤組成物および重合抑制方法を提供することにある。 The present invention relates to a vinyl acetate polymerization inhibitor composition and a polymerization inhibitor that inhibits the polymerization of vinyl acetate in the production process, purification process, storage or transport process of vinyl acetate, and further effectively suppresses the occurrence of soiling caused by the polymerization. To provide a method.
本発明者らは、酢酸ビニルの重合特性を詳細に検討した結果、特定の有機酸と、特定のキノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を組み合わせて同時に使用することにより、酢酸ビニルの重合を極めて効率良く抑制することを見出し、本発明を成すに至った
即ち、請求項１に係る発明は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程において、（Ａ）一般式（１）（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ヒドロキシル基あるいはカルボキシル基を有してもよい炭素数１から８のアルキル基を示す。）で表されるα−ヒドロキシカルボン酸、アスコルビン酸および／又はその水溶性塩から選ばれた１種以上と、（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を有効成分として含むことを特徴とする酢酸ビニルの重合抑制剤組成物である。
As a result of examining the polymerization characteristics of vinyl acetate in detail, the present inventors use a combination of a specific organic acid and one or more selected from a specific quinone compound, a phenol compound, and a nitroxyl radical compound at the same time. Thus, the present inventors have found that the polymerization of vinyl acetate can be suppressed very efficiently, and have led to the present invention. That is, the invention according to claim 1 is a process for producing, purifying, storing or transporting vinyl acetate (A ) -Hydroxy represented by the general formula (1) (wherein X and Y each independently represents a hydrogen atom, a hydroxyl group or a C1-C8 alkyl group which may have a carboxyl group). One or more selected from carboxylic acid, ascorbic acid and / or water-soluble salt thereof, and (B) a quinone compound, a phenol compound, a nitroxyl radical compound A polymerization inhibitor composition of vinyl acetate which comprises one or more selected et as an active ingredient.
請求項２に係る発明は、請求項１記載の酢酸ビニルの重合抑制剤組成物であり、（Ａ）が、グリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸および／又はそれらの水溶性塩から選ばれた１種以上であることを特徴としている。 The invention according to claim 2 is the vinyl acetate polymerization inhibitor composition according to claim 1, wherein (A) is glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, gluconic acid, heptonic acid and / or It is characterized by being at least one selected from those water-soluble salts.
請求項３に係る発明は、請求項１又は２記載の酢酸ビニルの重合抑制剤組成物であり、（Ｂ）が、１，４−ベンゾキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、１，４−ナフトキノン、４−ｔｅｒｔ−ブチルカテコール、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシルから選ばれた１種以上であることを特徴としている。 The invention according to claim 3 is the vinyl acetate polymerization inhibitor composition according to claim 1 or 2, wherein (B) is 1,4-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 1,4-naphthoquinone, 4 1 selected from -tert-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl It is characterized by more than seeds.
請求項４に係る発明は、請求項１乃至３のいずれか記載の酢酸ビニルの重合抑制剤組成物であり、（Ａ）と（Ｂ）を重量比で０．５：９９.５〜７０：３０の比率で含むことを特徴としている。 The invention according to claim 4 is the vinyl acetate polymerization inhibitor composition according to any one of claims 1 to 3, wherein (A) and (B) are in a weight ratio of 0.5: 99.5 to 70: It is characterized by being included at a ratio of 30.
請求項５に係る発明は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程において、酢酸ビニルを含む工程液に（Ａ）一般式（１）（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ヒドロキシル基あるいはカルボキシル基を有してもよい炭素数１から８のアルキル基を示す。）で表されるα−ヒドロキシカルボン酸、アスコルビン酸および／又はその水溶性塩から選ばれた１種以上と、（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を同時に用いることを特徴とする酢酸ビニルの重合抑制方法である。
According to the fifth aspect of the present invention, in the vinyl acetate production process, purification process, storage or transport process, the process liquid containing vinyl acetate contains (A) general formula (1) (wherein X and Y are each independently hydrogen An alkyl group having 1 to 8 carbon atoms which may have an atom, a hydroxyl group or a carboxyl group.) Selected from α-hydroxycarboxylic acid, ascorbic acid and / or a water-soluble salt thereof A method for inhibiting the polymerization of vinyl acetate, comprising simultaneously using one or more selected from the above and (B) a quinone compound, a phenol compound, and a nitroxyl radical compound.
請求項６に係る発明は、請求項５記載の酢酸ビニルの重合抑制方法であり、（Ａ）が、グリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸および／又はそれらの水溶性塩から選ばれた１種以上であることを特徴としている。 The invention according to claim 6 is the method for inhibiting polymerization of vinyl acetate according to claim 5, wherein (A) is glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, gluconic acid, heptonic acid and / or their It is characterized by being at least one selected from water-soluble salts.
請求項７に係る発明は、請求項５又は６記載の酢酸ビニルの重合抑制方法であり、（Ｂ）が、１，４−ベンゾキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、１，４−ナフトキノン、４−ｔｅｒｔ−ブチルカテコール、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシルから選ばれた１種以上であることを特徴としている。 The invention according to claim 7 is the method for inhibiting polymerization of vinyl acetate according to claim 5 or 6, wherein (B) is 1,4-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 1,4-naphthoquinone, 4-tert. One or more selected from -butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl It is characterized by being.
請求項８に係る発明は、請求項５乃至７のいずれか記載の酢酸ビニルの重合抑制方法であり、工程液中の酢酸ビニルに対して（Ａ）と（Ｂ）を重量比で０．５：９９．５〜７０：３０の比率で添加することを特徴としている。 The invention according to claim 8 is the method for inhibiting polymerization of vinyl acetate according to any one of claims 5 to 7, wherein (A) and (B) are added in a weight ratio of 0.5 to the vinyl acetate in the process liquid. : 99.5 to 70:30.
本発明の酢酸ビニルの重合抑制剤および酢酸ビニルの重合抑制方法により、酢酸ビニルの製造工程、精製工程、貯蔵工程および輸送工程における酢酸ビニルの重合を効果的に抑制し、さらに酢酸ビニルの重合により生じる酢酸ビニルを含む工程液に接する箇所の汚れの付着を防止する。その結果、酢酸ビニル製造時の操業の安定化、酢酸ビニルの品質の向上に大きく寄与することができる。 The vinyl acetate polymerization inhibitor and the vinyl acetate polymerization suppression method of the present invention effectively inhibits vinyl acetate polymerization in the vinyl acetate production process, purification process, storage process and transport process, and further by vinyl acetate polymerization. Prevents the adhesion of stains at locations in contact with the process liquid containing vinyl acetate. As a result, it can greatly contribute to the stabilization of operations during the production of vinyl acetate and the improvement of the quality of vinyl acetate.
本発明は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程において、当該工程の装置類およびそれらの付帯装置類に酢酸ビニルの重合物による汚れが付着・蓄積して、製造あるいは精製工程の操業や酢酸ビニルの製品品質に支障を来たすことを防止する酢酸ビニルの重合抑制剤組成物あり、（Ａ）特定の有機酸および／又はその水溶性塩と、（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を有効成分として含むことを特徴とする酢酸ビニルの重合抑制剤組成物である。さらに、当該工程において、酢酸ビニルを含む工程液に対して、（Ａ）特定の有機酸および／又はその水溶性塩（以下「（Ａ）成分」とする）と、（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上（以下、「（Ｂ）成分」とする）を同時に用いることを特徴とする酢酸ビニルの重合抑制方法である。 In the production process, purification process, storage or transport process of vinyl acetate, the contamination of vinyl acetate polymer adheres to and accumulates in the equipment of the process and their auxiliary equipment, and the production or purification process. There is a polymerization inhibitor composition of vinyl acetate that prevents the operation and the product quality of vinyl acetate from being hindered, (A) a specific organic acid and / or water-soluble salt thereof, and (B) a quinone compound, a phenol compound, A vinyl acetate polymerization inhibitor composition comprising, as an active ingredient, one or more selected from nitroxyl radical compounds. Furthermore, in the said process, with respect to the process liquid containing vinyl acetate, (A) specific organic acid and / or its water-soluble salt (henceforth "(A) component"), (B) quinone compound, phenol A method of inhibiting the polymerization of vinyl acetate, comprising simultaneously using one or more selected from a compound and a nitroxyl radical compound (hereinafter referred to as “component (B)”).
本発明において対象となる工程は、酢酸ビニル化合物の製造工程、酢酸ビニル製造後の酢酸ビニルの精製工程、製造および精製した酢酸ビニルを貯蔵・保管する貯蔵工程、および製造、精製および貯蔵・保管した酢酸ビニルを移送・輸送する輸送工程であり、さらに各工程で酢酸ビニルを含む工程液と接する周辺設備・機器を含む循環系や回収系も包含する。具体的には、製造工程における酢酸ビニルの合成反応塔および反応後の反応物排出ラインや回収循環ライン、精製工程における精製塔への酢酸ビニルのフィード配管や予熱ラインおよび冷却ラインさらに循環ライン、貯蔵工程における保管タンクや貯蔵タンク、輸送工程における移送タンクおよび輸送タンクさらにその移送ラインなどがある。 The target processes in the present invention include a production process of a vinyl acetate compound, a purification process of vinyl acetate after the production of vinyl acetate, a storage process for storing and storing the produced and purified vinyl acetate, and a production, purification, storage and storage. It is a transport process for transporting and transporting vinyl acetate, and further includes a circulation system and a recovery system including peripheral equipment and devices that come into contact with a process liquid containing vinyl acetate in each process. Specifically, vinyl acetate synthesis reaction tower in the production process, reaction product discharge line and recovery circulation line after the reaction, vinyl acetate feed piping, preheating line and cooling line to the purification tower in the purification process, circulation line, storage There are storage tanks and storage tanks in the process, transfer tanks and transport tanks in the transport process, and their transfer lines.
本発明において対象となる酢酸ビニルは、特に限定されるものではなく、通常の酢酸ビニルの製造方法により得られる酢酸ビニルである。具体的には、触媒の存在下、反応塔にエチレンガス、酢酸、酸素ガス（分子状酸素）を導入して反応させて粗酢酸ビニルを得、蒸留によって精製して得られる酢酸ビニルである。代表的な製造方法としては、Pd系触媒を用いるエチレンのＩＣＩ法（液相）、Ｂａｙｅｒ法（気相）、Ｎａｔｉｏｎａｌ Ｄｉｓｔｉｌｌｅｒｓ（原Ｍｉｌｌｅｎｎｉｕｍ）法があり、いずれの方法で製造された酢酸ビニルにも適用することができる。 The vinyl acetate used in the present invention is not particularly limited, and is vinyl acetate obtained by a normal method for producing vinyl acetate. Specifically, it is vinyl acetate obtained by introducing ethylene gas, acetic acid, and oxygen gas (molecular oxygen) into a reaction tower in the presence of a catalyst to cause reaction to obtain crude vinyl acetate and purifying it by distillation. Typical production methods include the ICI method (liquid phase), the Bayer method (gas phase), and the National Distillers (original Millennium) method of ethylene using a Pd-based catalyst. Can be applied.
本発明の酢酸ビニルの重合抑制剤組成物（以下「本発明の重合抑制剤組成物」とする。）は、酢酸ビニルの製造工程、精製工程、貯蔵およびその輸送工程において用いられる（Ａ）有機酸および／又はその水溶性塩と、（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を有効成分として含むことを特徴とする酢酸ビニルの重合抑制剤組成物である。 The vinyl acetate polymerization inhibitor composition of the present invention (hereinafter referred to as “the polymerization inhibitor composition of the present invention”) is used in the production process, purification process, storage and transport process of vinyl acetate (A) Organic A polymerization inhibitor composition of vinyl acetate comprising an acid and / or a water-soluble salt thereof and (B) one or more selected from a quinone compound, a phenol compound, and a nitroxyl radical compound as active ingredients. .
本発明の（Ａ）成分で用いる有機酸としては、α−ヒドロキシカルボン酸、アスコルビン酸がある。α−ヒドロキシカルボン酸は一般式（１）で表され、式中、Ｘ、Ｙは水素原子、ヒドロキシル基あるいはカルボキシル基を有してもよい炭素数１から８のアルキル基である。具体的には、２−ヒドロキシ−4−メチルペンタン酸、２−ヒドロキシブタン酸、２−ヒドロキシヘキサン酸、２−ヒドロキシ−３，３−ジメチルブタン酸、２−ヒドロキシ−２−メチルプロパン酸、２−ヒドロキシ−３−メチルブタン酸、マンデル酸、２−ヒドロキシ−４−メトキシマンデル酸、４−ヒドロキシ−３−メトキシマンデル酸、２−ヒドロキシ−２−メチルブタン酸、グリセリン酸、グリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸等であり、好ましくはグリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、グルコン酸、ヘプトン酸、より好ましくはクエン酸、グルコン酸である。これらのα−ヒドロキシカルボン酸の多くはヒドロキシル基が置換している炭素がキラル中心であるために光学活性であり、本発明においては何れか一方の異性体のみを使用しても、両者の等量混合物であるラセミ体を使用してもよい。通常は、経済的な見地から安価な異性体が選ばれる。 Examples of the organic acid used in the component (A) of the present invention include α-hydroxycarboxylic acid and ascorbic acid. The α-hydroxycarboxylic acid is represented by the general formula (1), wherein X and Y are alkyl groups having 1 to 8 carbon atoms which may have a hydrogen atom, a hydroxyl group or a carboxyl group. Specifically, 2-hydroxy-4-methylpentanoic acid, 2-hydroxybutanoic acid, 2-hydroxyhexanoic acid, 2-hydroxy-3,3-dimethylbutanoic acid, 2-hydroxy-2-methylpropanoic acid, 2 -Hydroxy-3-methylbutanoic acid, mandelic acid, 2-hydroxy-4-methoxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-hydroxy-2-methylbutanoic acid, glyceric acid, glycolic acid, lactic acid, tartaric acid, Citric acid, malic acid, gluconic acid, heptonic acid and the like, preferably glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, gluconic acid and heptonic acid, more preferably citric acid and gluconic acid. Many of these α-hydroxycarboxylic acids are optically active because the carbon substituted with a hydroxyl group is a chiral center. In the present invention, even if only one of the isomers is used, Racemic mixtures that are quantitative mixtures may be used. Usually, cheap isomers are selected from an economic point of view.
また、本発明の（Ａ）成分で用いるアスコルビン酸は、特に限定されるものではなく、天然系および合成系のアスコルビン酸が使用できる。さらにアスコルビン酸の光学異性体であるエリソルビン酸、イソアスコルビン酸等も用いることができる。 The ascorbic acid used in the component (A) of the present invention is not particularly limited, and natural and synthetic ascorbic acid can be used. Furthermore, erythorbic acid, isoascorbic acid and the like, which are optical isomers of ascorbic acid, can also be used.
本発明の有機酸の水溶性塩は、完全中和あるいは部分中和のナトリウム塩、カリウム塩およびこれらの複合塩である。本発明において、これらの有機酸および／又はその水溶性塩の１種あるいは２種以上を組み合わせて用いても良い。 The water-soluble salt of the organic acid of the present invention is a completely neutralized or partially neutralized sodium salt, potassium salt or a complex salt thereof. In the present invention, one or more of these organic acids and / or water-soluble salts thereof may be used in combination.
本発明の（Ｂ）成分で用いるキノン化合物は、ベンゾキノン、ナフトキノンおよびこれらの誘導体である。具体的には、１，４−ベンゾキノン、２−メチル−１，４−ベンゾキノン、２−ｔｅｒｔ−ブチル−１，４−ベンゾキノン、１，４−ナフトキノン、１，２−ナフトキノン、２−メチル−１，４−ナフトキノン、２−ｔｅｒｔ−ブチル−１，４−ナフトキノン、２−ヒドロキシ−１，４−ナフトキノンである。 The quinone compounds used in the component (B) of the present invention are benzoquinone, naphthoquinone and derivatives thereof. Specifically, 1,4-benzoquinone, 2-methyl-1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, 2-methyl-1 , 4-naphthoquinone, 2-tert-butyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone.
本発明の（Ｂ）成分で用いるフェノール化合物は、ハイドロキノンおよびその誘導体、カテコールおよびその誘導体、ピロガロールなどある。具体的には、ハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、４−ｔｅｒｔ−ブチルカテコール、ピロガロールである。 Examples of the phenol compound used in the component (B) of the present invention include hydroquinone and derivatives thereof, catechol and derivatives thereof, and pyrogallol. Specifically, hydroquinone, hydroquinone monomethyl ether, catechol, 4-tert-butylcatechol, and pyrogallol.
本発明の（Ｂ）成分で用いるニトロキシルラジカル化合物は、室温で安定に存在しうるフリーラジカルを有する化合物であり、ジ−ｔｅｒｔ−ブチルニトロキサイド、２，２，６，６−テトラメチルピペリジン−１−オキシルおよびその誘導体、２,２,５,５−テトラメチルピロリジン−１−オキサイドおよびその誘導体である。具体的には、ジ−ｔｅｒｔ−ブチルニトロキサイド、２,２,６,６−テトラメチルピペリジン−１−オキシル、４−ヒドロキシ−２,２,６,６−テトラメチルピペリジン−１−オキシル、４−オキソ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−メトキシ−２,２,６,６−テトラメチルピペリジン−１−オキシル、４−アセトキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルがある。中でも好ましくは、１，４−ベンゾキノン、ハイドロキノン、４−ｔｅｒｔ−ブチルカテコール、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルである。これらの１種あるいは２種以上を組み合わせて用いても良い。 The nitroxyl radical compound used in the component (B) of the present invention is a compound having a free radical that can exist stably at room temperature, and is di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine. -1-oxyl and its derivatives 2,2,5,5-tetramethylpyrrolidine-1-oxide and its derivatives. Specifically, di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6 There are 6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Among these, 1,4-benzoquinone, hydroquinone, 4-tert-butylcatechol, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable. You may use 1 type or in combination of 2 or more types of these.
本発明の酢酸ビニル重合抑制剤組成物は、（Ａ）成分と（Ｂ）成分を含む重合抑制剤組成物であり、（Ａ）成分単独あるいは（Ｂ）成分単独では予想し得なかった優れた酢酸ビニルの重合抑制効果を発揮するものである。特に（Ａ）成分が（Ｂ）成分に対して、少量を同時に用いても優れた効果を発揮する。（Ａ）成分と（Ｂ）成分の配合比率は酢酸ビニルの重合抑制の要求程度によって適宜選択されるものであり、通常、重量比として０．５：９９．５〜７０：３０、好ましくは１：９９〜６０：４０、より好ましくは５：９５〜５０：５０である。この配合比率の範囲は、重合抑制効果をもとにして見出されたものであり、この範囲を超えると本発明の効果が得られない場合がある。 The vinyl acetate polymerization inhibitor composition of the present invention is a polymerization inhibitor composition comprising the component (A) and the component (B), and was excellent in that the component (A) alone or the component (B) could not be expected. It exhibits the effect of inhibiting the polymerization of vinyl acetate. In particular, the (A) component exhibits an excellent effect even when a small amount is simultaneously used with respect to the (B) component. The blending ratio of the component (A) and the component (B) is appropriately selected according to the degree of requirement for inhibiting the polymerization of vinyl acetate, and is usually 0.5: 99.5 to 70:30, preferably 1 as a weight ratio. : 99-60: 40, more preferably 5: 95-50: 50. The range of this blending ratio is found based on the polymerization inhibitory effect, and if it exceeds this range, the effects of the present invention may not be obtained.
本発明の酢酸ビニル重合抑制剤組成物の製造は、特に限定されるものではなく、（Ａ）成分と（Ｂ）成分を混合して本発明の重合抑制剤組成物を調製する方法と、（Ａ）成分と（Ｂ）成分を溶剤に溶解して本発明の重合抑制剤組成物を調製する方法があり、いずれを用いてもよい。（Ａ）成分と（Ｂ）成分を溶剤に溶解して調製する場合、用いる溶剤は対象とする工程や用いた有機酸およびその水溶性塩を考慮して適時選択すればよく、通常、水、エチレングリコール、エタノール等が挙げられ、好ましくは水である。溶剤は、１種あるいは２種以上が用いられる。（Ａ）成分と（Ｂ）成分を溶剤に溶解して重合抑制剤を調製する場合、（Ａ）成分と（Ｂ）成分の濃度は、取扱性を考慮して通常、（Ａ）成分、（Ｂ）成分をそれぞれ１〜５０重量％濃度である。また、（Ａ）成分と（Ｂ）成分の合計濃度として、１〜５０重量％濃度である。また、本発明の効果を妨げない範囲で、本発明の酢酸ビニルの重合抑制剤に従来より使用されている他の重合抑制剤を配合することができる。 Production of the vinyl acetate polymerization inhibitor composition of the present invention is not particularly limited, and the method of preparing the polymerization inhibitor composition of the present invention by mixing the component (A) and the component (B); There is a method of preparing the polymerization inhibitor composition of the present invention by dissolving the component A) and the component (B) in a solvent, and any of them may be used. When the component (A) and the component (B) are prepared by dissolving in a solvent, the solvent to be used may be appropriately selected in consideration of the target process and the organic acid used and its water-soluble salt. Examples thereof include ethylene glycol and ethanol, and water is preferred. One kind or two or more kinds of solvents are used. When preparing a polymerization inhibitor by dissolving the component (A) and the component (B) in a solvent, the concentrations of the component (A) and the component (B) are usually (A) component, ( B) Each component has a concentration of 1 to 50% by weight. The total concentration of the component (A) and the component (B) is 1 to 50% by weight. Moreover, the other polymerization inhibitor conventionally used can be mix | blended with the polymerization inhibitor of the vinyl acetate of this invention in the range which does not prevent the effect of this invention.
本発明の酢酸ビニルの重合抑制方法（以下、「本発明の重合抑制方法」とする。）は、酢酸ビニルの製造工程、精製工程、貯蔵あるいは輸送工程において、当該工程の装置類およびそれらの付帯装置類に酢酸ビニルの重合物による汚れが付着・蓄積して、製造あるいは精製工程の操業や酢酸ビニルの製品品質に支障を来たすことを防止する酢酸ビニルの重合抑制方法であり、（Ａ）成分の有機酸および／又はその水溶性塩と、（Ｂ）成分のキノン化合物、フェノール化合物、ニトロキシルラジカル化合物から選ばれた１種以上を同時に用いることを特徴とする酢酸ビニルの重合抑制方法である。 The method for inhibiting polymerization of vinyl acetate of the present invention (hereinafter referred to as “the method of inhibiting polymerization of the present invention”) is a process for producing vinyl acetate in the production process, purification process, storage or transport process, and their associated equipment. This is a method for inhibiting the polymerization of vinyl acetate, which prevents contamination due to vinyl acetate polymer from adhering to and accumulating on the equipment, thereby affecting the operation of the production or purification process and the product quality of vinyl acetate. A method for inhibiting the polymerization of vinyl acetate, comprising simultaneously using at least one selected from the group consisting of an organic acid and / or a water-soluble salt thereof and a quinone compound, a phenol compound, and a nitroxyl radical compound as component (B). .
本発明の重合抑制方法は、酢酸ビニルを含む工程液に（Ａ）成分と（Ｂ）成分を同時に用いる重合抑制方法であり、（Ａ）成分単独あるいは（Ｂ）成分単独では予想し得なかった優れた酢酸ビニルの重合抑制効果を発揮するものである。特に（Ａ）成分が（Ｂ）成分に対して、少量を同時に用いても優れた効果を発揮する。 The polymerization suppression method of the present invention is a polymerization suppression method in which the component (A) and the component (B) are simultaneously used in a process liquid containing vinyl acetate, and cannot be expected with the component (A) alone or the component (B) alone. It exhibits an excellent vinyl acetate polymerization inhibitory effect. In particular, the (A) component exhibits an excellent effect even when a small amount is simultaneously used with respect to the (B) component.
本発明の重合抑制方法における（Ａ）成分および（Ｂ）成分の添加比率は、酢酸ビニルの重合抑制の要求程度によって適宜選択されるものであり、通常、重量比として０．５：９９．５〜７０：３０、好ましくは１：９９〜６０：４０、より好ましくは５：９５〜５０：５０である。この範囲は、重合抑制効果をもとにして見出されたものであり、この添加比率の範囲を超えると本発明の効果が得られない場合がある。 The addition ratio of the component (A) and the component (B) in the polymerization inhibition method of the present invention is appropriately selected depending on the degree of vinyl acetate polymerization inhibition required, and is usually 0.5: 99.5 as a weight ratio. -70: 30, preferably 1: 99-60: 40, more preferably 5: 95-50: 50. This range is found based on the polymerization inhibitory effect, and if the addition ratio is exceeded, the effect of the present invention may not be obtained.
本発明の重合抑制方法における（Ａ）成分および（Ｂ）成分の添加量は、通常、対象とする酢酸ビニルの工程の運転状況、酢酸ビニルの重合抑制の要求度、経済的観点などを加味して決定されもので一律に決めることはできないが、通常、酢酸ビニルを含む工程液中の酢酸ビニルに対して、それぞれ０．０５〜１０００ｐｐｍ、好ましくは０．５〜１００ｐｐｍである。（Ａ）成分および（Ｂ）成分の添加量が０．０５ｐｐｍより少ないと効果が十分に発揮されない場合があり、（Ａ）成分および（Ｂ）成分の添加量が１０００ｐｐｍより多くすることはなんら妨げるものではないが、添加量に見合った効果の向上がみられず、経済的な見地から不利なことがある。 The addition amount of the component (A) and the component (B) in the polymerization inhibiting method of the present invention usually takes into account the operating conditions of the target vinyl acetate process, the degree of vinyl acetate polymerization inhibition, and the economic viewpoint. However, it is generally 0.05 to 1000 ppm, preferably 0.5 to 100 ppm based on vinyl acetate in the process liquid containing vinyl acetate. When the addition amount of the component (A) and the component (B) is less than 0.05 ppm, the effect may not be sufficiently exerted, and it is impeded that the addition amount of the component (A) and the component (B) exceeds 1000 ppm. Although it is not a thing, the improvement of the effect commensurate with the amount of addition is not observed, which may be disadvantageous from an economic standpoint.
本発明の重合抑制方法における（Ａ）成分および（Ｂ）成分の添加箇所は、酢酸ビニルの製造工程や精製工程の運転状況、酢酸ビニルの重合の程度および汚れの程度等を考慮して適宜選択されるが、通常、障害が発生している箇所および酢酸ビニルの重合が生じる箇所の手前、酢酸ビニルの重合により生じた重合物が付着し汚れとなる箇所の手前である。具体的には、酢酸ビニル製造工程の反応塔手前の原料フィード液および循環ライン液、精製工程における精製塔のフィード液、貯蔵時や輸送時には保管タンク、貯蔵タンク、移送タンク等の貯蔵設備に添加される。 In the polymerization inhibiting method of the present invention, the addition position of the component (A) and the component (B) is appropriately selected in consideration of the operating conditions of the vinyl acetate production process and the purification process, the degree of polymerization of vinyl acetate, the degree of contamination, and the like. However, it is usually before the location where the failure occurs and the location where vinyl acetate polymerization occurs, and before the location where the polymer produced by the polymerization of vinyl acetate is attached and becomes soiled. Specifically, it is added to raw material feed liquid and circulation line liquid before the reaction tower in the vinyl acetate production process, purification tower feed liquid in the purification process, and storage equipment such as storage tanks, storage tanks, and transfer tanks during storage and transportation. Is done.
本発明の重合抑制方法における（Ａ）成分および（Ｂ）成分の添加方法は、特に限定されるものではなく、通常の薬液注入ポンプを用いて添加され、ある特定箇所に一括添加するか、あるいはいくつかの箇所に分けて添加するなどの方法があり、適宜選択される。 The addition method of the component (A) and the component (B) in the polymerization inhibition method of the present invention is not particularly limited, and is added using a normal chemical solution injection pump, or is added all at once to a specific location, or There are methods such as adding in several portions, and the method is appropriately selected.
本発明を実施例により更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（有機酸）
Ａ：２−ヒドロキシ−４−メチルペンタン酸（試薬、東京化成工業株式会社製）
Ｂ：２−ヒドロキシブタン酸（試薬、東京化成工業株式会社製）
Ｃ：２−ヒドロキシヘキサン酸（試薬、東京化成工業株式会社製）
Ｄ：２−ヒドロキシ−３，３−ジメチルブタン酸（試薬、東京化成工業株式会社製）
Ｅ：２−ヒドロキシ−２−メチルプロパン酸（試薬、東京化成工業株式会社製）
Ｆ：アスコルビン酸（試薬、東京化成工業株式会社製）
Ｇ：エリソルビン酸（試薬、東京化成工業株式会社製）
Ｈ：グリセリン酸（試薬、東京化成工業株式会社製）
Ｉ：グリコール酸（試薬、東京化成工業株式会社製）
Ｊ：乳酸（試薬、東京化成工業株式会社製）
Ｋ：酒石酸（試薬、東京化成工業株式会社製）
Ｌ：クエン酸（試薬、東京化成工業株式会社製）
Ｍ：リンゴ酸（試薬、東京化成工業株式会社製）
Ｎ：グルコン酸（試薬、東京化成工業株式会社製）
Ｏ：ヘプトン酸（試薬、東京化成工業株式会社製）
Ｐ：グリコール酸ナトリウム（試薬、東京化成工業株式会社製）
（キノン化合物）
ＢＱ：１，４−ベンゾキノン
ＮＱ：１，４−ナフトキノン
（フェノール化合物）
ＨＱ：ハイドロキノン
ＴＢＣ：４−ｔｅｒｔ−ブチルカテコール
（ニトロキシルラジカル化合物）
ＨＴＥＭＰＯ：４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル
ＯＴＥＭＰＯ ：４−オキソ２，２，６，６−テトラメチルピペリジン−１−オキシル
（その他）
Ｖ：２，６−ジ−ｔ−ブチル−４−メチルフェノール
Ｗ：Ｎ，Ｎ−ジエチルヒドロキシルアミン
(Organic acid)
A: 2-hydroxy-4-methylpentanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
B: 2-hydroxybutanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
C: 2-hydroxyhexanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
D: 2-hydroxy-3,3-dimethylbutanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
E: 2-hydroxy-2-methylpropanoic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
F: Ascorbic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
G: Erythorbic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
H: Glyceric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
I: Glycolic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
J: Lactic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
K: Tartaric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
L: Citric acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
M: Malic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
N: Gluconic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
O: Heptonic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
P: Sodium glycolate (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
(Quinone compound)
BQ: 1,4-benzoquinone NQ: 1,4-naphthoquinone (phenol compound)
HQ: Hydroquinone TBC: 4-tert-butylcatechol (nitroxyl radical compound)
HTEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl OTEMPO: 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (Other)
V: 2,6-di-t-butyl-4-methylphenol W: N, N-diethylhydroxylamine
〔重合抑制試験１〕
（試験液の調整）
８５ｇの酢酸ビニルと１０ｇの酢酸ならびに所定量の重合禁止剤組成物を、窒素ガス用バルブとサンプル抜き出しバルブを備えた、ステンレス製オートクレーブに入れた。窒素ガスを吹き込み、系内の酸素をのぞいた後、窒素ガスで、０．１ＭＰａに加圧して両方のバルブを閉じ、１１０℃のオイルバスに浸漬し、３時間加熱した。３時間加熱後、反応液約５ｇを採取し精秤した後、ヘキサン５０ｍｌに溶解させ、発生したポリマーを析出させた。ポリマーを１μｍガラス繊維瀘紙〔ミリポア社（Ｍｉｌｌｉｐｏｒｅ Ｃｏｒｐ．）製〕で瀘別し、生成したポリマーを分離した。分離したポリマーを５０℃で６時間乾燥した後、秤量し、反応液中の生成ポリマー量（重量ｐｐｍ）を算出した。結果を表１、表２に示した。
[Polymerization inhibition test 1]
(Adjustment of test solution)
85 g of vinyl acetate, 10 g of acetic acid and a predetermined amount of the polymerization inhibitor composition were placed in a stainless steel autoclave equipped with a nitrogen gas valve and a sample extraction valve. Nitrogen gas was blown in and the oxygen in the system was removed, and then pressurized to 0.1 MPa with nitrogen gas, both valves were closed, immersed in an oil bath at 110 ° C., and heated for 3 hours. After heating for 3 hours, about 5 g of the reaction solution was collected and precisely weighed, and then dissolved in 50 ml of hexane to precipitate the generated polymer. The polymer was separated by 1 μm glass fiber paper (Millipore Corp.), and the produced polymer was separated. The separated polymer was dried at 50 ° C. for 6 hours and then weighed to calculate the amount of polymer produced (weight ppm) in the reaction solution. The results are shown in Tables 1 and 2.
本発明の酢酸ビニル重合抑制方法は、（Ａ）α−ヒドロキシカルボン酸、有機酸および／又はその水溶性塩の単独使用、あるいは（Ｂ）キノン化合物、フェノール化合物、ニトロキシルラジカル化合物の１種以上の使用と比較しても同一添加量では、圧倒的に少ないポリマー生成量であり、優れた重合防止効果を発揮していることが分かる。 The vinyl acetate polymerization inhibition method of the present invention comprises (A) an α-hydroxycarboxylic acid, an organic acid and / or a water-soluble salt thereof alone, or (B) one or more of a quinone compound, a phenol compound and a nitroxyl radical compound. It can be seen that even when compared with the use of No. 1, the amount of the polymer added is overwhelmingly small, and an excellent polymerization preventing effect is exhibited.
Claims (8)
The vinyl acetate according to any one of claims 5 to 7, wherein (A) and (B) are added at a weight ratio of 0.5: 99.5 to 70:30 with respect to vinyl acetate in the process liquid. Polymerization suppression method.
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| JPH101505A (en) * | 1996-02-21 | 1998-01-06 | Nalco Exxon Energ Chem Lp | Method for inhibiting polymerization of vinyl acetate |
| JP2001247491A (en) * | 2000-03-02 | 2001-09-11 | Hakuto Co Ltd | Method for inhibiting polymerization of vinyl compound |
| JP2006069916A (en) * | 2004-08-31 | 2006-03-16 | Hakuto Co Ltd | Polymerization inhibitor for vinyl acetate and polymerization-inhibiting method |
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| JP2006232874A (en) | 2006-09-07 |
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