JP6043937B2 - Composition for inhibiting polymerization of vinyl aromatic monomer - Google Patents
Composition for inhibiting polymerization of vinyl aromatic monomer Download PDFInfo
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- JP6043937B2 JP6043937B2 JP2012180612A JP2012180612A JP6043937B2 JP 6043937 B2 JP6043937 B2 JP 6043937B2 JP 2012180612 A JP2012180612 A JP 2012180612A JP 2012180612 A JP2012180612 A JP 2012180612A JP 6043937 B2 JP6043937 B2 JP 6043937B2
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- 238000006116 polymerization reaction Methods 0.000 title claims description 36
- 239000000178 monomer Substances 0.000 title claims description 35
- 229920002554 vinyl polymer Polymers 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 title claims description 24
- 230000002401 inhibitory effect Effects 0.000 title claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 107
- -1 tetrahydro-2-furylmethyl group Chemical group 0.000 claims description 86
- 125000000217 alkyl group Chemical group 0.000 claims description 57
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- MMCCWBPRXIFTJE-UHFFFAOYSA-N n-ethyl-n-(oxolan-2-ylmethyl)hydroxylamine Chemical compound CCN(O)CC1CCCO1 MMCCWBPRXIFTJE-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BJOXIRAGBLTXIZ-UHFFFAOYSA-N n,n-bis(2-methoxyethyl)hydroxylamine Chemical compound COCCN(O)CCOC BJOXIRAGBLTXIZ-UHFFFAOYSA-N 0.000 description 4
- ITUWQZXQRZLLCR-UHFFFAOYSA-N n,n-dioctadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCCC ITUWQZXQRZLLCR-UHFFFAOYSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 4
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 231100000925 very toxic Toxicity 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005924 2-methylpentyloxy group Chemical group 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006607 3,3-dimethylbutyloxy group Chemical group 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000005925 3-methylpentyloxy group Chemical group 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
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、ビニル芳香族モノマーの重合を抑制するための組成物、その組成物を用いたビニル芳香族モノマーの精製方法および、その組成物を用いたビニル芳香族モノマーの重合を抑制する方法に関するものである。 The present invention relates to a composition for suppressing polymerization of vinyl aromatic monomers, a method for purifying vinyl aromatic monomers using the composition, and a method for suppressing polymerization of vinyl aromatic monomers using the composition. Is.
スチレンおよびα−メチルスチレンのようなビニル芳香族モノマーは、高温下に重合しやすい性質を有する。一方、このようなビニル芳香族モノマーを製造、精製等する際に、高温下に晒される場合がある。このような高温下において、ビニル芳香族モノマーが重合してポリマーが生成すると、ビニル芳香族モノマーの収率が低下するのみならず、製造、精製等工程において用いる装置に汚れとして付着するため、生産効率が著しく低下するという問題点がある。 Vinyl aromatic monomers such as styrene and α-methylstyrene have the property of being easily polymerized at high temperatures. On the other hand, when such a vinyl aromatic monomer is produced and purified, it may be exposed to high temperatures. When the vinyl aromatic monomer is polymerized at such a high temperature to produce a polymer, not only the yield of the vinyl aromatic monomer is reduced, but also the product is attached to the equipment used in the production, purification, and other processes as dirt. There is a problem that the efficiency is significantly reduced.
このような重合を防ぐため、従来から様々な化合物が重合抑制剤として用いられている。重合抑制剤としては、重合禁止剤と重合遅延剤の２種類に分類される。前記重合禁止剤は、重合を完全に停止することが可能であるが、特定の時間を経過すると、重合を停止する活性が失活してしまう。前記重合遅延剤は、重合禁止剤ほど完全ではないが、重合を抑制することができる。ただし、時間の経過と共に、重合を抑制する能力は徐々に低下していく。このような性質を鑑み、通常は、重合を防ぐために、重合禁止剤と重合遅延剤の２種類を併用している。 In order to prevent such polymerization, various compounds have been conventionally used as polymerization inhibitors. The polymerization inhibitors are classified into two types, polymerization inhibitors and polymerization retarders. Although the polymerization inhibitor can completely stop the polymerization, the activity to stop the polymerization is deactivated after a specific time. The polymerization retarder is not as complete as the polymerization inhibitor, but can inhibit polymerization. However, the ability to suppress polymerization gradually decreases with time. In view of such properties, usually two types of polymerization inhibitors and polymerization retarders are used in combination in order to prevent polymerization.
従来、ビニル芳香族モノマー用重合遅延剤として知られている化合物の中で、４，６−ジニトロ−２−ｓｅｃ−ブチルフェノール（ＤＮＢＰ）に代表されるニトロフェノール化合物は、非常に毒性が強いことが知られている。例えば、ＤＮＢＰは、毒物及び劇物取締法では、医薬用外毒物に指定されている。 Among the compounds conventionally known as polymerization retarders for vinyl aromatic monomers, nitrophenol compounds represented by 4,6-dinitro-2-sec-butylphenol (DNBP) are very toxic. Are known. For example, DNBP is designated as a pharmaceutical poison by the Poisonous and Deleterious Substances Control Law.
また、ビニル芳香族モノマーではなくジエン化合物の重合抑制剤として、ピペリジン−１−オキシル化合物と、Ｎ，Ｎ−ジ置換ヒドロキシルアミン化合物との組み合わせが知られている（特許文献１参照）。この組み合わせは、酸素存在下で、用いられることが特徴である。 Further, a combination of a piperidine-1-oxyl compound and an N, N-disubstituted hydroxylamine compound is known as a polymerization inhibitor for a diene compound rather than a vinyl aromatic monomer (see Patent Document 1). This combination is characterized by being used in the presence of oxygen.
前記のように、従来のニトロフェノール化合物は、非常に毒性が強い。そこで、本発明は、ビニル芳香族モノマーの重合を抑制するための、毒性が低い、安全な重合抑制剤の提供を目的とする。 As mentioned above, conventional nitrophenol compounds are very toxic. Therefore, an object of the present invention is to provide a safe polymerization inhibitor having low toxicity for suppressing the polymerization of vinyl aromatic monomers.
本発明は、一般式（Ｉ）で表されるヒドロキシルアミンを含むビニル芳香族モノマーの重合を抑制するための組成物である。
式中、Ｒ1は、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数６〜１２のアリール基、または炭素数７〜３０のアラルキル基であり、
Ｒ2は、炭素数１０〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数７〜３０のアラルキル基またはテトラヒドロ−２−フリルメチル基である。
In the formula, R 1 is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups, or an aralkyl group having 7 to 30 carbon atoms,
R 2 is an alkyl group having 10 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or an aralkyl having 7 to 30 carbon atoms. Group or a tetrahydro-2-furylmethyl group.
本発明は、安全性の高いビニル芳香族モノマーの重合抑制剤であり、かつ、効率よくビニル芳香族モノマーの重合を抑制することができるという利点がある。 The present invention has an advantage that it is a highly safe vinyl aromatic monomer polymerization inhibitor and can efficiently inhibit the polymerization of the vinyl aromatic monomer.
本発明者は、種々検討した結果、特定量の酸素存在下に、特定なヒドロキシルアミンがビニル芳香族モノマーの重合を抑制することができるという、新たな知見を見出した。この特定なヒドロキシルアミンは安全な化合物であり、かつ、効率よく重合を抑制することが可能であった。このような新たな知見に基づき、本発明者は、本発明を完成した。 As a result of various studies, the present inventor has found a new finding that a specific hydroxylamine can suppress polymerization of a vinyl aromatic monomer in the presence of a specific amount of oxygen. This specific hydroxylamine was a safe compound and could efficiently inhibit polymerization. Based on such new knowledge, the present inventor completed the present invention.
本発明は、一般式（Ｉ）で表されるヒドロキシルアミンを含むビニル芳香族モノマーの重合を抑制するための組成物である。
式中、Ｒ1は、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数６〜１２のアリール基、または炭素数７〜３０のアラルキル基であり、
Ｒ2は、炭素数１０〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数７〜３０のアラルキル基またはテトラヒドロ−２−フリルメチル基である。
In the formula, R 1 is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 12 aryl groups, or an aralkyl group having 7 to 30 carbon atoms,
R 2 is an alkyl group having 10 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or an aralkyl having 7 to 30 carbon atoms. Group or a tetrahydro-2-furylmethyl group.
本発明において、ビニル芳香族モノマーとは、芳香族化合物にビニル基が置換した化合物を意味し、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ジビニルベンゼン等が挙げられる。 In the present invention, the vinyl aromatic monomer means a compound in which a vinyl group is substituted on an aromatic compound, and examples thereof include styrene, α-methylstyrene, vinyl toluene, and divinylbenzene.
前記式（Ｉ）における炭素数１〜１８のアルキル基としては、炭素数１〜１８の直鎖または分岐鎖状のアルキル基を意味し、炭素数１〜１２の直鎖または分岐鎖状のアルキル基が好ましく、炭素数１〜８の直鎖または分岐鎖状のアルキル基がより好ましい。または、前記式（Ｉ）における炭素数１〜１８のアルキル基は、炭素数１０〜１８の直鎖または分岐鎖状のアルキル基が好ましく、炭素数１２〜１８の直鎖または分岐鎖状のアルキル基がより好ましい。前記炭素数１〜８の直鎖または分岐鎖状のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｉ−ペンチル基、ｓｅｃ−ペンチル基、ｔ−ペンチル基、２−メチルブチル基、ｎ−ヘキシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、４−メチルペンチル基、１−エチルブチル基、２−エチルブチル基、３−エチルブチル基、１，１−ジメチルブチル基、２，２−ジメチルブチル基、３，３−ジメチルブチル基、１−エチル−１−メチルプロピル基、ｎ−ヘプチル基、１−メチルヘキシル基、２−メチルヘキシル基、３−メチルヘキシル基、４−メチルヘキシル基、５−メチルヘキシル基、１−エチルペンチル基、２−エチルペンチル基、３−エチルペンチル基、４−エチルペンチル基、１，１−ジメチルペンチル基、２，２−ジメチルペンチル基、３，３−ジメチルペンチル基、４，４−ジメチルペンチル基、１−プロピルブチル基、ｎ−オクチル基、１−メチルヘプチル基、２−メチルヘプチル基、３−メチルヘプチル基、４−メチルヘプチル基、５−メチルヘプチル基、６−メチルヘプチル基、１−エチルヘキシル基、２−エチルヘキシル基、３−エチルヘキシル基、４−エチルヘキシル基、５−エチルヘキシル基、１，１−ジメチルヘキシル基、２，２−ジメチルヘキシル基、３，３−ジメチルヘキシル基、４，４−ジメチルヘキシル基、５，５−ジメチルヘキシル基、１−プロピルペンチル基、および２−プロピルペンチル基等が挙げられる。前記炭素数１０〜１８の直鎖または分岐鎖状のアルキル基としては、例えば、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基およびオクタデシル基等が挙げられる。 The alkyl group having 1 to 18 carbon atoms in the formula (I) means a linear or branched alkyl group having 1 to 18 carbon atoms, and a linear or branched alkyl group having 1 to 12 carbon atoms. Group is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable. Alternatively, the alkyl group having 1 to 18 carbon atoms in the formula (I) is preferably a linear or branched alkyl group having 10 to 18 carbon atoms, and a linear or branched alkyl group having 12 to 18 carbon atoms. Groups are more preferred. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl. Group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3 -Methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 4, 4-dimethylpentyl group, 1-propylbutyl group, n-octyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methyl Heptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl Group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, and 2-propylpe Chill group, and the like. Examples of the linear or branched alkyl group having 10 to 18 carbon atoms include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl groups. It is done.
前記式（Ｉ）における炭素数１０〜１８のアルキル基としては、炭素数１０〜１８の直鎖または分岐鎖状のアルキル基を意味し、炭素数１２〜１８の直鎖または分岐鎖状のアルキル基が好ましく、炭素数１４〜１８の直鎖または分岐鎖状のアルキル基がより好ましい。前記炭素数１０〜１８の直鎖または分岐鎖状のアルキル基としては、例えば、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基およびオクタデシル基等が挙げられる。 The alkyl group having 10 to 18 carbon atoms in the formula (I) means a linear or branched alkyl group having 10 to 18 carbon atoms, and a linear or branched alkyl group having 12 to 18 carbon atoms. Group is preferable, and a linear or branched alkyl group having 14 to 18 carbon atoms is more preferable. Examples of the linear or branched alkyl group having 10 to 18 carbon atoms include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl groups. It is done.
前記式（Ｉ）における炭素数１〜１８のアルコキシ基としては、炭素数１〜１８のアルキル基とオキシ基の組み合わせを意味し、例えば、炭素数１〜１８の直鎖または分岐鎖状のアルキル基とオキシ基の組み合わせ、好ましくは炭素数１〜１２の直鎖または分岐鎖状のアルキル基とオキシ基の組み合わせ（炭素数１〜１２のアルコキシ基）、より好ましくは炭素数１〜８の直鎖または分岐鎖状のアルキル基とオキシ基の組み合わせ（炭素数１〜８のアルコキシ基）である。炭素数１〜１８のアルキル基については、前記のとおりである。前記炭素数１〜８のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロピルオキシ基、ｉ−プロピルオキシ基、ｎ−ブチルオキシ基、ｉ−ブチルオキシ基、ｓｅｃ−ブチルオキシ基、ｔ−ブチルオキシ基、ｎ−ペンチルオキシ基、ｉ−ペンチルオキシ基、ｓｅｃ−ペンチルオキシ基、ｔ−ペンチルオキシ基、２−メチルブトキシ基、ｎ−ヘキシルオキシ基、ｉ−ヘキシルオキシ基、ｔ−ヘキシルオキシ基、ｓｅｃ−ヘキシルオキシ基、２−メチルペンチルオキシ基、３−メチルペンチルオキシ基、１−エチルブチルオキシ基、２−エチルブチルオキシ基、１，１−ジメチルブチルオキシ基、２，２−ジメチルブチルオキシ基、３，３−ジメチルブチルオキシ基、および１−エチル−１−メチルプロピルオキシ基などが挙げられる。さらに好適にはメトキシ基、エトキシ基、ｎ−プロピルオキシ基、ｉ−プロピルオキシ基、ｎ−ブチルオキシ基、ｉ−ブチルオキシ基、ｓｅｃ−ブチルオキシ基、およびｔ−ブチルオキシ基などが挙げられる。 In the formula (I), the alkoxy group having 1 to 18 carbon atoms means a combination of an alkyl group having 1 to 18 carbon atoms and an oxy group, for example, a linear or branched alkyl having 1 to 18 carbon atoms. A combination of a group and an oxy group, preferably a linear or branched alkyl group having 1 to 12 carbon atoms and an oxy group (an alkoxy group having 1 to 12 carbon atoms), more preferably a straight chain having 1 to 8 carbon atoms. It is a combination of a chain or branched alkyl group and an oxy group (an alkoxy group having 1 to 8 carbon atoms). The alkyl group having 1 to 18 carbon atoms is as described above. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butyloxy group, an i-butyloxy group, a sec-butyloxy group, and a t-butyloxy group. , N-pentyloxy group, i-pentyloxy group, sec-pentyloxy group, t-pentyloxy group, 2-methylbutoxy group, n-hexyloxy group, i-hexyloxy group, t-hexyloxy group, sec -Hexyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 1-ethylbutyloxy group, 2-ethylbutyloxy group, 1,1-dimethylbutyloxy group, 2,2-dimethylbutyloxy group , 3,3-dimethylbutyloxy group, and 1-ethyl-1-methylpropyloxy group . More preferable examples include a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butyloxy group, an i-butyloxy group, a sec-butyloxy group, and a t-butyloxy group.
前記式（Ｉ）における炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基としては、前記炭素数１〜１８のアルキル基に、前記炭素数１〜１８のアルコキシ基が置換したものを意味する。前記炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基としては、炭素数１〜１２のアルコキシ基で置換された炭素数１〜１２のアルキル基が好ましく、炭素数１〜８のアルコキシ基で置換された炭素数１〜８のアルキル基がより好ましい。前記炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基としては、例えば、メトキシメチル基、２−メトキシエチル基、エトキシメチル基、２−エトキシエチル基、ｎ−プロピルオキシメチル基等が挙げられる。 As the C1-C18 alkyl group substituted with the C1-C18 alkoxy group in Formula (I), the C1-C18 alkyl group includes the C1-C18 alkoxy group. Means a replacement. The alkyl group having 1 to 18 carbon atoms substituted with the alkoxy group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms. A C1-C8 alkyl group substituted with a -8 alkoxy group is more preferred. Examples of the alkyl group having 1 to 18 carbon atoms substituted by the alkoxy group having 1 to 18 carbon atoms include a methoxymethyl group, a 2-methoxyethyl group, an ethoxymethyl group, a 2-ethoxyethyl group, and n-propyloxy. A methyl group etc. are mentioned.
前記式（Ｉ）における炭素数６〜１２のアリール基としては、例えばフェニル基、ナフチル基等を含み、単にナフチル基といった場合は１−ナフチル基、２−ナフチル基を含む。また、そのベンゼン環上およびナフタレン環上に前記のハロゲン原子、低級アルキル基、シアノ基、ニトロ基、トリフルオロメチル基などの置換基を有していてもよい。 The aryl group having 6 to 12 carbon atoms in the formula (I) includes, for example, a phenyl group, a naphthyl group, and the like, and in the case of a simple naphthyl group, includes a 1-naphthyl group and a 2-naphthyl group. Further, the halogen atom, lower alkyl group, cyano group, nitro group, trifluoromethyl group and the like may be present on the benzene ring and naphthalene ring.
前記式（Ｉ）における炭素数７〜３０のアラルキル基としては、前記の炭素数１〜１８のアルキル基に前記の炭素数６〜１２のアリール基が結合したものを意味する。前記炭素数７〜３０のアラルキル基は、炭素数１〜１２の直鎖または分岐鎖状のアルキル基に前記炭素数６〜１２のアリール基が結合した炭素数７〜２４のアラルキル基が好ましく、炭素数１〜８の直鎖または分岐鎖状のアルキル基に前記炭素数６〜１２のアリール基が結合した炭素数７〜２０のアラルキル基がより好ましい。前記炭素数７〜３０のアラルキル基としては、例えば、ベンジル基、１−フェニルエチル基、２−フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルヘキシル基、ナフチルメチル基、ナフチルエチル基、ナフチルプロピル基、ナフチルブチル基、ナフチルペンチル基、ナフチルヘキシル基等が挙げられる。 The aralkyl group having 7 to 30 carbon atoms in the formula (I) means a group in which the aryl group having 6 to 12 carbon atoms is bonded to the alkyl group having 1 to 18 carbon atoms. The aralkyl group having 7 to 30 carbon atoms is preferably an aralkyl group having 7 to 24 carbon atoms in which the aryl group having 6 to 12 carbon atoms is bonded to a linear or branched alkyl group having 1 to 12 carbon atoms, More preferred is an aralkyl group having 7 to 20 carbon atoms in which the aryl group having 6 to 12 carbon atoms is bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, naphthylmethyl group, and naphthyl. Examples include an ethyl group, a naphthylpropyl group, a naphthylbutyl group, a naphthylpentyl group, and a naphthylhexyl group.
前記式（Ｉ）において、Ｒ1が、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、または炭素数７〜３０のアラルキル基であり、Ｒ2が、炭素数１０〜１８のアルキル基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数７〜３０のアラルキル基またはテトラヒドロ−２−フリルメチル基であるのが好ましい。このような式（Ｉ）のヒドロキシルアミンを含む組成物は、ビニル芳香族モノマーの重合を効率よく抑制することが可能だからである。前記式（Ｉ）において、炭素数１〜１８のアルキル基、炭素数１〜１２のアルコキシ基で置換された炭素数１〜１２のアルキル基、または炭素数７〜２４のアラルキル基であり、Ｒ2が、炭素数１２〜１８のアルキル基、炭素数１〜１２のアルコキシ基で置換された炭素数１〜１２のアルキル基、炭素数７〜２４のアラルキル基またはテトラヒドロ−２−フリルメチル基であるのがより好ましく、炭素数１〜１８のアルキル基、炭素数１〜８のアルコキシ基で置換された炭素数１〜８のアルキル基、または炭素数７〜２０のアラルキル基であり、Ｒ2が、炭素数１４〜１８のアルキル基、炭素数１〜８のアルコキシ基で置換された炭素数１〜８のアルキル基、炭素数７〜２０のアラルキル基またはテトラヒドロ−２−フリルメチル基であるのがさらに好ましい。また、Ｒ1が炭素数１〜１８のアルキル基であり、Ｒ2がテトラヒドロ−２−フリルメチル基である化合物、Ｒ1およびＲ2がそれぞれ独立して、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基である化合物、Ｒ1およびＲ2がそれぞれ独立して、炭素数７〜３０のアラルキル基である化合物、ならびに、Ｒ1が炭素数１０〜１８のアルキル基であり、Ｒ2が炭素数１０〜１８のアルキル基である化合物が、さらに好ましい。 In the formula (I), R 1 is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. R 2 is an alkyl group having 10 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or tetrahydro-2- A furylmethyl group is preferred. This is because such a composition containing hydroxylamine of the formula (I) can efficiently inhibit the polymerization of the vinyl aromatic monomer. In the formula (I), an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 24 carbon atoms, R 2 is an alkyl group having 12 to 18 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 7 to 24 carbon atoms, or a tetrahydro-2-furylmethyl group. More preferably, it is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 2 Is an alkyl group having 14 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a tetrahydro-2-furylmethyl group. No Further preferred. In addition, R 1 is an alkyl group having 1 to 18 carbon atoms, R 2 is a tetrahydro-2-furylmethyl group, and R 1 and R 2 are each independently an alkoxy group having 1 to 18 carbon atoms. A substituted compound having 1 to 18 carbon atoms, R 1 and R 2 are each independently an aralkyl group having 7 to 30 carbon atoms, and R 1 is an alkyl having 10 to 18 carbon atoms Further preferred are compounds in which R 2 is an alkyl group having 10 to 18 carbon atoms.
前記式（Ｉ）の化合物としては、Ｎ−エチル−Ｎ−テトラヒドロフルフリルヒドロキシルアミン（ＥＴＨＦ）、ビス（２−メトキシエチル）ヒドロキシルアミン、ジベンジルヒドロキシルアミンおよびビス（オクタデシル）ヒドロキシルアミンが、さらに好ましい。 As the compound of the formula (I), N-ethyl-N-tetrahydrofurfurylhydroxylamine (ETHF), bis (2-methoxyethyl) hydroxylamine, dibenzylhydroxylamine and bis (octadecyl) hydroxylamine are more preferable. .
本発明の組成物において、一種類の式（Ｉ）で表される化合物、または二種類以上の式（Ｉ）で表される化合物を含んでもよい。 The composition of the present invention may contain one type of compound represented by formula (I) or two or more types of compounds represented by formula (I).
また、本発明は、ビニル芳香族モノマーを含有する混合物を加熱下に蒸留してビニル芳香族モノマーを単離する工程を含むビニル芳香族モノマーの精製方法である。この製造方法は、単離工程において、本発明の組成物を加えた前記混合物を酸素存在下に加熱下に蒸留することを特徴とする。 Moreover, this invention is a purification method of a vinyl aromatic monomer including the process of distilling the mixture containing a vinyl aromatic monomer under a heating, and isolating a vinyl aromatic monomer. This production method is characterized in that, in the isolation step, the mixture to which the composition of the present invention has been added is distilled under heating in the presence of oxygen.
前記精製方法において、ビニル芳香族モノマーを含有する混合物を蒸留する地点の上流で、連続的または断続的に、本発明の組成物を添加することができる。または、本発明の組成物が加熱条件下で著しく安定な場合、前記精製方法において、ビニル芳香族モノマーを含有する混合物を蒸留する地点より前の異なる導入地点において、連続的または断続的に、本発明の組成物を添加してもよい。 In the purification method, the composition of the present invention can be added continuously or intermittently upstream of the point where the mixture containing the vinyl aromatic monomer is distilled. Alternatively, if the composition of the present invention is remarkably stable under heating conditions, the purification process may be carried out continuously or intermittently at different points of introduction prior to the point of distillation of the mixture containing the vinyl aromatic monomer. Inventive compositions may be added.
本発明のビニル芳香族モノマーの精製方法において、前記蒸留工程における酸素濃度は、例えば、１０，０００ｐｐｍ以下であり、好ましくは５，０００ｐｐｍ以下であり、より好ましくは２，０００ｐｐｍ以下である。また、前記蒸留工程における酸素濃度は、例えば、０．１ｐｐｍ以上であり、好ましくは１ｐｐｍ以上であり、より好ましくは１０ｐｐｍ以上である。 In the method for purifying a vinyl aromatic monomer of the present invention, the oxygen concentration in the distillation step is, for example, 10,000 ppm or less, preferably 5,000 ppm or less, more preferably 2,000 ppm or less. Moreover, the oxygen concentration in the said distillation process is 0.1 ppm or more, for example, Preferably it is 1 ppm or more, More preferably, it is 10 ppm or more.
添加する本発明の組成物のヒドロキシルアミンの量は、重合が抑制されるべきビニル芳香族モノマーの重量に応じて、適宜、選択すればよい。具体的には、前記ヒドロキシルアミンの量は、ビニル芳香族モノマーの重量に基づき、例えば１０ｐｐｍ〜３０００ｐｐｍ、好ましくは１００ｐｐｍ〜２０００ｐｐｍ、より好ましくは２００ｐｐｍ〜１５００ｐｐｍである。 What is necessary is just to select suitably the quantity of the hydroxylamine of the composition of this invention added according to the weight of the vinyl aromatic monomer by which superposition | polymerization should be suppressed. Specifically, the amount of hydroxylamine is, for example, 10 ppm to 3000 ppm, preferably 100 ppm to 2000 ppm, more preferably 200 ppm to 1500 ppm, based on the weight of the vinyl aromatic monomer.
また、本発明は、酸素存在下に、本発明の重合抑制用組成物を用いて、ビニル芳香族モノマーの重合を抑制する方法である。この際の酸素濃度は、例えば、１０，０００ｐｐｍ以下であり、好ましくは５，０００ｐｐｍ以下であり、より好ましくは２，０００ｐｐｍ以下である。また、前記酸素濃度は、例えば、０．１ｐｐｍ以上であり、好ましくは１ｐｐｍ以上であり、より好ましくは１０ｐｐｍ以上である。本発明における酸素は、酸素と不活性ガスとの混合ガスであってもよい。不活性ガスとしては、窒素、ヘリウム、アルゴン等が挙げられる。 Moreover, this invention is a method of suppressing superposition | polymerization of a vinyl aromatic monomer using the composition for superposition | polymerization suppression of this invention in oxygen presence. The oxygen concentration at this time is, for example, 10,000 ppm or less, preferably 5,000 ppm or less, and more preferably 2,000 ppm or less. Moreover, the said oxygen concentration is 0.1 ppm or more, for example, Preferably it is 1 ppm or more, More preferably, it is 10 ppm or more. The oxygen in the present invention may be a mixed gas of oxygen and an inert gas. Examples of the inert gas include nitrogen, helium, and argon.
前記抑制する方法において、用いる本発明の組成物のヒドロキシルアミンの量は、重合が抑制されるビニル芳香族モノマーの重量に応じて、適宜、選択すればよい。具体的には、前記ヒドロキシルアミンの量は、ビニル芳香族モノマーの重量に基づき、例えば１０ｐｐｍ〜３０００ｐｐｍ、好ましくは１００ｐｐｍ〜２０００ｐｐｍ、より好ましくは２００ｐｐｍ〜１５００ｐｐｍである。 In the suppression method, the amount of hydroxylamine in the composition of the present invention to be used may be appropriately selected according to the weight of the vinyl aromatic monomer whose polymerization is suppressed. Specifically, the amount of hydroxylamine is, for example, 10 ppm to 3000 ppm, preferably 100 ppm to 2000 ppm, more preferably 200 ppm to 1500 ppm, based on the weight of the vinyl aromatic monomer.
［スチレン］
市販のスチレンは、活性アルミナ（たとえばSigma-Aldrich社製Inhibitor remover）充填カラムを通過させて、安定剤（tert-ブチルカテコール）を除去した後、以下の実験で用いた。
[styrene]
Commercially available styrene was used in the following experiment after passing through a column packed with activated alumina (for example, Sigma-Aldrich Inhibitor remover) to remove the stabilizer (tert-butylcatechol).
［試験装置および重合防止効果評価試験方法］
温度コントローラーつき熱電対、コンデンサーおよびガス吹き込み用ガラスチューブを備えた１００ｍＬ三つ首フラスコに、スチレン（１００ｇ）およびヒドロキシルアミン化合物（１２０ｍｇ、スチレンの重量に対して１，２００ｐｐｍ）を加えてスチレン溶液を得た。
[Test equipment and polymerization prevention effect evaluation test method]
To a 100 mL three-necked flask equipped with a thermocouple with a temperature controller, a condenser, and a glass tube for gas blowing, styrene (100 g) and a hydroxylamine compound (120 mg, 1,200 ppm based on the weight of styrene) were added to prepare a styrene solution. Obtained.
次に、濃度調整された酸素と窒素の混合ガスを１００ｍＬ／分の速度で前記スチレン溶液中に３０分間注入（スパージング）することにより、所定酸素濃度雰囲気を確立した。このスパージングは以下のサンプリングが終了するまで継続した。 Next, a mixed gas of oxygen and nitrogen whose concentration was adjusted was injected (sparging) into the styrene solution at a rate of 100 mL / min for 30 minutes to establish a predetermined oxygen concentration atmosphere. This sparging continued until the following sampling was completed.
あらかじめ４０℃に調整したオイルバスに前記スチレン溶液を含む三つ首フラスコを浸漬させ、前記スチレン溶液の温度が４０分間で１２０℃に到達するように加熱した。 The three-necked flask containing the styrene solution was immersed in an oil bath adjusted to 40 ° C. in advance, and heated so that the temperature of the styrene solution reached 120 ° C. in 40 minutes.
前記スチレン溶液の温度が１２０℃へ到達した後、ただちに、コンデンサー上部からテフロンチューブを挿入し、余分の酸素が混入しないように、約０．５ｍＬのスチレン溶液を三つ首フラスコ中の前記スチレン溶液から採取した。以後、１２０℃において３０分経過毎に約０．５ｍＬのスチレン溶液を１８０分間にわたって採取した。 Immediately after the temperature of the styrene solution reaches 120 ° C., a Teflon tube is inserted from the top of the condenser, and about 0.5 mL of the styrene solution is added to the styrene solution in the three-necked flask so that excess oxygen is not mixed. From. Thereafter, about 0.5 mL of a styrene solution was collected for 180 minutes every 30 minutes at 120 ° C.
経過時間ごとに採取したスチレン溶液はトルエンで適当に希釈した。その希釈液へメタノールを添加することにより生じた濁度を測定した。一方、予め標準ポリスチレンにより作成した濃度と濁度との検量線を用いて、採取したスチレン溶液におけるポリマー濃度を求めた。得られた結果を表１および図１〜４に示す。図１には、ヒドロキシルアミン化合物として、Ｎ−エチル−Ｎ−テトラヒドロフルフリルヒドロキシルアミンを用いた実施例と比較例の結果、図２には、ヒドロキシルアミン化合物として、ビス（２−メトキシエチル）ヒドロキシルアミンを用いた実施例と比較例の結果、図３には、ヒドロキシルアミン化合物として、ジベンジルヒドロキシルアミンを用いた実施例と比較例の結果、図４には、ヒドロキシルアミン化合物としてビス（オクタデシル）ヒドロキシルアミンを用いた実施例と比較例の結果を示す。
The styrene solution collected at each elapsed time was appropriately diluted with toluene. Turbidity generated by adding methanol to the diluted solution was measured. On the other hand, the polymer concentration in the collected styrene solution was determined using a calibration curve of the concentration and turbidity previously prepared with standard polystyrene. The obtained results are shown in Table 1 and FIGS. FIG. 1 shows the results of Examples and Comparative Examples using N-ethyl-N-tetrahydrofurfurylhydroxylamine as the hydroxylamine compound, and FIG. 2 shows bis (2-methoxyethyl) hydroxyl as the hydroxylamine compound. As a result of Examples and Comparative Examples using amine, FIG. 3 shows results of Examples and Comparative Examples using dibenzylhydroxylamine as a hydroxylamine compound, and FIG. 4 shows bis (octadecyl) as a hydroxylamine compound. The result of the Example using a hydroxylamine and a comparative example is shown.
表１および図１に示すように、ヒドロキシルアミン化合物として、Ｎ−エチル−Ｎ−テトラヒドロフルフリルヒドロキシルアミンを用いた場合（実施例１〜５）には、ヒドロキシルアミン化合物を有さない（比較例１）場合と比べて、副生する重合体の生成を遅延させることが確認できた。また、ヒドロキシルアミン化合物として、Ｎ−エチル−Ｎ−テトラヒドロフルフリルヒドロキシルアミンを用いても、酸素不在下（比較例２）の場合と比べて、酸素存在下（実施例１〜５）の場合には、副生する重合体の生成を遅延させることが確認できた。 As shown in Table 1 and FIG. 1, when N-ethyl-N-tetrahydrofurfurylhydroxylamine was used as the hydroxylamine compound (Examples 1 to 5), no hydroxylamine compound was present (Comparative Example). 1) It was confirmed that the production of the by-product polymer was delayed as compared with the case. Further, even when N-ethyl-N-tetrahydrofurfurylhydroxylamine is used as the hydroxylamine compound, in the presence of oxygen (Examples 1 to 5) as compared with the absence of oxygen (Comparative Example 2). Was confirmed to delay the production of the by-product polymer.
表１および図２に示すように、ヒドロキシルアミン化合物として、ビス（２−メトキシエチル）ヒドロキシルアミンを用いた場合（実施例６）には、ヒドロキシルアミン化合物を有さない（比較例１）場合と比べて、副生する重合体の生成を遅延させることが確認できた。また、ヒドロキシルアミン化合物として、ビス（２−メトキシエチル）ヒドロキシルアミンを用いても、酸素不在下（比較例４）の場合と比べて、酸素存在下（実施例６）の場合には、副生する重合体の生成を遅延させることが確認できた。 As shown in Table 1 and FIG. 2, when bis (2-methoxyethyl) hydroxylamine is used as the hydroxylamine compound (Example 6), there is no hydroxylamine compound (Comparative Example 1). In comparison, it was confirmed that the production of the by-product polymer was delayed. Further, even when bis (2-methoxyethyl) hydroxylamine is used as the hydroxylamine compound, by-product is produced in the presence of oxygen (Example 6) as compared to the case of absence of oxygen (Comparative Example 4). It was confirmed that the production of the polymer was delayed.
表１および図３に示すように、ヒドロキシルアミン化合物として、ジベンジルヒドロキシルアミンを用いた場合（実施例７）には、ヒドロキシルアミン化合物を有さない（比較例１）場合と比べて、副生する重合体の生成を遅延させることが確認できた。また、ヒドロキシルアミン化合物として、ジベンジルヒドロキシルアミンを用いても、酸素不在下（比較例５）の場合と比べて、酸素存在下（実施例７）の場合には、副生する重合体の生成を遅延させることが確認できた。 As shown in Table 1 and FIG. 3, when dibenzylhydroxylamine was used as the hydroxylamine compound (Example 7), as a by-product, compared with the case without the hydroxylamine compound (Comparative Example 1). It was confirmed that the production of the polymer was delayed. In addition, even when dibenzylhydroxylamine is used as the hydroxylamine compound, a by-product polymer is formed in the presence of oxygen (Example 7) as compared to the absence of oxygen (Comparative Example 5). Was confirmed to delay.
表１および図４に示すように、ヒドロキシルアミン化合物として、ビス（オクタデシル）ヒドロキシルアミンを用いた場合（実施例８）には、ヒドロキシルアミン化合物を有さない（比較例１）場合と比べて、副生する重合体の生成を遅延させることが確認できた。また、ヒドロキシルアミン化合物として、ビス（オクタデシル）ヒドロキシルアミンを用いても、酸素不在下（比較例６）の場合と比べて、酸素存在下（実施例８）の場合には、副生する重合体の生成を遅延させることが確認できた。 As shown in Table 1 and FIG. 4, when bis (octadecyl) hydroxylamine was used as the hydroxylamine compound (Example 8), compared with the case without the hydroxylamine compound (Comparative Example 1), It was confirmed that the production of the by-product polymer was delayed. In addition, even when bis (octadecyl) hydroxylamine is used as the hydroxylamine compound, a by-product polymer is formed in the presence of oxygen (Example 8) as compared to the absence of oxygen (Comparative Example 6). It was confirmed that the generation of was delayed.
本発明は、ビニル芳香族モノマーの製造方法における精製工程において、重合抑制目的でも適用できる。 The present invention can also be applied for the purpose of inhibiting polymerization in the purification step in the method for producing a vinyl aromatic monomer.
Claims (3)
前記単離工程において、一般式（Ｉ）で表されるヒドロキシルアミンを含むビニル芳香族モノマーの重合を抑制するための組成物を加えた前記混合物を酸素存在下に加熱下に蒸留し、
前記蒸留工程における酸素濃度が、１００ｐｐｍ以上１０，０００ｐｐｍ以下であるビニル芳香族モノマーの精製方法。
式（Ｉ）中、Ｒ1は、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、または炭素数７〜３０のアラルキル基であり、
Ｒ2は、炭素数１０〜１８のアルキル基、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基、炭素数７〜３０のアラルキル基またはテトラヒドロ−２−フリルメチル基である。 A method for purifying a vinyl aromatic monomer comprising a step of distilling a mixture containing a vinyl aromatic monomer under heating to isolate the vinyl aromatic monomer,
In the isolation step, the mixture added with the composition for inhibiting the polymerization of the vinyl aromatic monomer containing hydroxylamine represented by the general formula (I) is distilled under heating in the presence of oxygen,
A method for purifying a vinyl aromatic monomer, wherein an oxygen concentration in the distillation step is 100 ppm or more and 10,000 ppm or less .
In formula (I) , R 1 is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Yes,
R 2 is an alkyl group having 10 to 18 carbon atoms , an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a tetrahydro-2-furylmethyl group. It is.
Ｒ R 11 は炭素数１〜１８のアルキル基であり、ＲIs an alkyl group having 1 to 18 carbon atoms and R 22 はテトラヒドロ−２−フリルメチル基であるか、Is a tetrahydro-2-furylmethyl group,
Ｒ R 11 およびＲAnd R 22 がそれぞれ独立して、炭素数１〜１８のアルコキシ基で置換された炭素数１〜１８のアルキル基であるか、Are each independently an alkyl group having 1 to 18 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms,
Ｒ R 11 およびＲAnd R 22 がそれぞれ独立して、炭素数７〜３０のアラルキル基であるか、または、Are each independently an aralkyl group having 7 to 30 carbon atoms, or
Ｒ R 11 は炭素数１０〜１８のアルキル基であり、ＲIs an alkyl group having 10 to 18 carbon atoms and R 22 は炭素数１０〜１８のアルキル基である請求項１に記載の精製方法。The purification method according to claim 1, wherein is an alkyl group having 10 to 18 carbon atoms.
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| US4409408A (en) * | 1982-09-24 | 1983-10-11 | Atlantic Richfield Company | Inhibiting polymerization of vinyl aromatic monomers |
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| US5648574A (en) * | 1992-10-21 | 1997-07-15 | Betzdearborn Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
| US5446220A (en) * | 1994-08-24 | 1995-08-29 | Betz Laboratories, Inc. | Methods for inhibiting vinyl aromatic monomer polymerization |
| US5489720A (en) * | 1994-06-30 | 1996-02-06 | Betz Laboratories, Inc. | Methods for inhibiting vinyl aromatic monomer polymerization |
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