JP2000514451A - 重合防止剤 - Google Patents
重合防止剤Info
- Publication number
- JP2000514451A JP2000514451A JP10505750A JP50575098A JP2000514451A JP 2000514451 A JP2000514451 A JP 2000514451A JP 10505750 A JP10505750 A JP 10505750A JP 50575098 A JP50575098 A JP 50575098A JP 2000514451 A JP2000514451 A JP 2000514451A
- Authority
- JP
- Japan
- Prior art keywords
- oxyl
- tetramethylpiperidin
- component
- weight
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 38
- 239000003112 inhibitor Substances 0.000 title description 33
- 239000000203 mixture Substances 0.000 claims abstract description 75
- -1 radical compound Chemical class 0.000 claims abstract description 58
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 230000002028 premature Effects 0.000 claims abstract description 14
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 238000004821 distillation Methods 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- SXPLGYBFGPYAHS-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SXPLGYBFGPYAHS-UHFFFAOYSA-N 0.000 claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- RVWJIVLFXACVCQ-UHFFFAOYSA-N (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC1CC(C)(C)N(O)C(C)(C)C1 RVWJIVLFXACVCQ-UHFFFAOYSA-N 0.000 claims description 3
- JURKUHPHNMPLCP-UHFFFAOYSA-N (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) 4-tert-butylbenzoate Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)OC1CC(C)(C)N(O)C(C)(C)C1 JURKUHPHNMPLCP-UHFFFAOYSA-N 0.000 claims description 3
- CRGBPDJWOLULDY-UHFFFAOYSA-N (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) acetate Chemical compound CC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 CRGBPDJWOLULDY-UHFFFAOYSA-N 0.000 claims description 3
- IYKZUARSRNSVTC-UHFFFAOYSA-N (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 IYKZUARSRNSVTC-UHFFFAOYSA-N 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- JZUGBDQHUIWNOA-UHFFFAOYSA-N 1-hydroxy-4-[2-(1-hydroxy-2,2,6,6-tetramethyl-3-oxopiperidin-4-yl)ethyl]-2,2,6,6-tetramethylpiperidin-3-one Chemical compound O=C1C(C)(C)N(O)C(C)(C)CC1CCC1C(=O)C(C)(C)N(O)C(C)(C)C1 JZUGBDQHUIWNOA-UHFFFAOYSA-N 0.000 claims description 3
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 claims description 3
- XHAYUUAFYPMOHE-UHFFFAOYSA-N 2,6-ditert-butyl-4-(dimethylamino)phenol Chemical compound CN(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XHAYUUAFYPMOHE-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical group CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- WJZRRMYMGWLZDY-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,2-dicarboxylate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)C1=CC=CC=C1C(=O)OC1CC(C)(C)N(O)C(C)(C)C1 WJZRRMYMGWLZDY-UHFFFAOYSA-N 0.000 claims description 3
- MYKPPUUOBUFFML-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,4-dicarboxylate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)C1=CC=C(C(=O)OC2CC(C)(C)N(O)C(C)(C)C2)C=C1 MYKPPUUOBUFFML-UHFFFAOYSA-N 0.000 claims description 3
- SIXHNVLZVKYFOR-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) hexanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SIXHNVLZVKYFOR-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 229940116351 sebacate Drugs 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 3
- DRFYZAIGLPMIOS-UHFFFAOYSA-N (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)C1=CC=CC=C1 DRFYZAIGLPMIOS-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- KRRWGJFRYFSLFQ-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) 2-butylpropanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)C(CCCC)C(=O)OC1CC(C)(C)N(O)C(C)(C)C1 KRRWGJFRYFSLFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229940123457 Free radical scavenger Drugs 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KMEUSKGEUADGET-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)N1O KMEUSKGEUADGET-UHFFFAOYSA-N 0.000 description 1
- JNQKFUFFVSIIOS-UHFFFAOYSA-N 2,6-ditert-butyl-4-(dimethylamino)-3-methylphenol Chemical compound CN(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1C JNQKFUFFVSIIOS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MCRZWYDXIGCFKO-UHFFFAOYSA-L 2-butylpropanedioate Chemical compound CCCCC(C([O-])=O)C([O-])=O MCRZWYDXIGCFKO-UHFFFAOYSA-L 0.000 description 1
- JPHYFFRXJKGOED-UHFFFAOYSA-N 3-dodecyl-1-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione Chemical compound O=C1C(CCCCCCCCCCCC)CC(=O)N1C1CC(C)(C)N(O)C(C)(C)C1 JPHYFFRXJKGOED-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
- PQSBRHXGVPVYFJ-UHFFFAOYSA-N 4-(dimethylamino)benzenethiol Chemical compound CN(C)C1=CC=C(S)C=C1 PQSBRHXGVPVYFJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- YTDBCKBOORUCQU-UHFFFAOYSA-N 4-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)N(C(C)CCC(C)C)C1=CC=C(N)C=C1 YTDBCKBOORUCQU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- ZXDIQRGIYADNBI-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) butanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 ZXDIQRGIYADNBI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.早期重合に対して安定化したモノマー組成物であって、 a)フリー・ラジカル・イニシエーションによる重合が可能なエチレン性不飽 和モノマーまたはモノマー混合物と、 b)前記成分(a)の早期重合を防止するために十分な有効量の混合物と を含み、前記成分(b)の混合物が、 i)少なくとも1つの芳香族アミン及び少なくとも1つの有機酸を10:1〜 1:10のモル比で含む混合材料であって、成分(i)及び成分(ii)の全重 量の1〜99重量%を占める混合材料と、 ii)少なくとも1つの安定ラジカル化合物であって、成分(i)及び成分( ii)の全重量の99〜1重量%を占める安定ラジカル化合物と を含むモノマー組成物。 2.前記成分(i)の重量が50〜99重量%であり、前記成分(ii)の重量 が50〜1重量%である請求項1に記載の組成物。 3.前記成分(i)の重量が67〜99重量%であり、前記成分(ii)の重量 が33〜1重量%である請求項2に記載の組成物。 4.前記芳香族アミンの有機酸に対するモル比が3:1〜1:3である請求項1 乃至3のいずれか一項に記載の組成物。 5.前記芳香族アミンが構造式(1)、即ち、 を有し、前記QはO、SまたはN−Zであり、 さらに少なくとも1つのRが構造式(2)、即ち、 を有するアルキル・アミンであり、前記Y及びZは同一であるか、または異なり 、かつC1−C8の分枝若しくは直鎖のアルキルまたは水素を有し、Xは共有結合 またはC1−C4のアルキレンであり、残りの各Rはベンジル、C1−C4の分枝若 しくは直鎖のアルキルまたは水素であって、かつ1つ以上の環を形成すべく2つ 以上のRが互いに結合可能という条件を満たす請求項1乃至4のいずれか一項に 記載の組成物。 6.前記Qが酸素である請求項5に記載の組成物。 7.前記Xがメチレンである請求項5または6に記載の組成物。 8.前記Y及びZがメチルである請求項5乃至7のいずれか一項に記載の組成物 。 9.前記アミンは、 N,N−ジメチル−1,4−フェニレンジアミン、 3,5−ジ第3級ブチル-4−オキシ,N,N−ジメチルベンジルアミン、 3,5−ジ第3級ブチル−4−オキシ−N,N−ジエチルベンジルアミン、 N,N−ジメチル-2,6−ジ第3級ブチル-4−アミノ・フェノール、 1,4−フェニレンジアミン、 N,N−ジメチル−4−アミノチオフェノール及び N,N’−ビス−(1,4ジメチルペンチル)−1,4−フェニレンジアミン から選択される請求項1乃至8のいずれか一項に記載の組成物。 10.前記有機酸はカルボン酸である請求項1乃至9のいずれか一項に記載の組 成物。 11.前記有機酸はC6−C22のカルボン酸である請求項10に記載の組成物。 12.前記有機酸はC6−C18のカルボン酸である請求項11に記載の組成物。 13.前記安定ラジカル化合物は構造式3、即ち、 を有する立体障害を受けたニトロキシルであり、前記Rは水素、アルキルまたは アリルであり、前記Tは環を形成するために必要な基であり、2つ以上のT基は 結合基Eによって結合可能である請求項1乃至12のいずれか一項に記載の組成 物。 14.前記ニトロキシル化合物は、 1−オキシル−2,2,6,6−テトラメチルピペリジン、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−オール、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−オン、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル・アセテ ート、 1,オキシル−2,2,6,6−テトラメチルピペリジン−4−イル 2−エ チルヘキサノエート、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル・ステア レート、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル・ベンゾ エート、 1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル 4−te rt−ブチルベンゾエート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) サクシネート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) セバケート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) セバ ケート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) アジペート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) n−ブチルマロネート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) フタレート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) イソフタレート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) テレフタレート、 ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) ヘキサヒドロテレフタレート、 N,N’ビス(1−オキシル−2,2,6,6−テトラメチルピペリジン−4 −イル)アジポアミン、 N−(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) カプロラクタム、 N−(1−オキシル−2,2,6,6−テトラメチルピペリジン−4−イル) −ドデシルサクシニミド 2,4,6−トリス−(N−ブチル−N−(1−オキシル−2,2,6,6− テトラメチルピペリジン−4−イル)−s−トリアジン及び 4,4’−エチレンビス(1−オキシル−2,2,6,6−テトラメチルピペ リジン−3−オン) 4−アセチルアミノ2,2,6,6−テトラメチルピペリジン−N−オキシル から選択される請求項13に記載の組成物。 15.前記ニトロキシルは1−オキシル−2,2,6,6−テトラメチルピペリ ジン−4−オールまたはビス(1−オキシル−2,2,6,6−テトラメチルピ ペリジン−4−イル)セバケートである請求項14に記載の組成物。 16.蒸留、精製または貯蔵中におけるビニル芳香族化合物またはビニル脂肪族 化合物の早期重合を防止する方法であって、 蒸留、精製または貯蔵中における早期重合を防止するのに十分な有効量の混合 物を前記ビニル芳香族化合物またはビニル脂肪族化合物へ混入する工程を有し、 前記混合物が、 i)少なくとも1つの芳香族アミン及び少なくとも1つの有機酸を10:1〜 1:10のモル比で含む混合材料であって、成分(i)及び成分(ii)の全重 量の1〜99重量%を占める混合材料と、 ii)少なくとも1つの安定ラジカル化合物であって、成分(i)及び成分( ii)の全重量の99〜1重量%を占める安定ラジカル化合物と を含む方法。 17.前記混合物は請求項1乃至15のいずれか一項に記載の組成物を提供すべ く選択される請求項16に記載の方法。 18.請求項16または17に記載の方法。
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GB9614854.9 | 1996-07-15 | ||
GBGB9614854.9A GB9614854D0 (en) | 1996-07-15 | 1996-07-15 | Free radical scavengers |
PCT/GB1997/001908 WO1998002400A1 (en) | 1996-07-15 | 1997-07-15 | Polymerisation inhibitor |
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JP2000514451A true JP2000514451A (ja) | 2000-10-31 |
JP4195509B2 JP4195509B2 (ja) | 2008-12-10 |
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JP50575098A Expired - Fee Related JP4195509B2 (ja) | 1996-07-15 | 1997-07-15 | 重合防止剤 |
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EP (1) | EP0912471B1 (ja) |
JP (1) | JP4195509B2 (ja) |
KR (1) | KR100450603B1 (ja) |
AU (1) | AU3551297A (ja) |
BR (1) | BR9710315A (ja) |
CA (1) | CA2261064A1 (ja) |
CZ (1) | CZ294776B6 (ja) |
DE (1) | DE69724432T2 (ja) |
GB (1) | GB9614854D0 (ja) |
PL (1) | PL185930B1 (ja) |
WO (1) | WO1998002400A1 (ja) |
Cited By (1)
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JP2004527632A (ja) * | 2001-05-22 | 2004-09-09 | ジーイー・ベッツ・インコーポレイテッド | ビニルモノマーの重合を抑制する方法及び組成物 |
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US5932735A (en) * | 1997-06-13 | 1999-08-03 | Ciba Specialty Chemicals Corporation | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers |
US5955643A (en) * | 1997-10-17 | 1999-09-21 | Nalco/Exxon Energy Chemicals, L.P. | Composition and method for inhibiting polymerization during the anaerobic of styrene |
US6040488A (en) * | 1998-06-02 | 2000-03-21 | Ppg Industries Ohio, Inc. | Stabilization of vinylidene chloride |
EP1095006B1 (en) * | 1998-07-14 | 2008-12-24 | Ciba Holding Inc. | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth) acrylate monomers |
US6337426B1 (en) * | 1998-11-23 | 2002-01-08 | Nalco/Exxon Energy Chemicals, L.P. | Antifoulant compositions and processes |
WO2000036052A1 (en) * | 1998-12-17 | 2000-06-22 | Nalco/Exxon Energy Chemicals, L.P. | Inhibiting polymerization of vinyl aromatic monomers using synergistic mixtures containing nitroxide stabilizers |
US6274683B1 (en) * | 1999-06-30 | 2001-08-14 | Uniroyal Chemical Company, Inc. | Test method for evaluating soluble polymer growth when recycling inhibitor streams |
IT1307306B1 (it) * | 1999-12-24 | 2001-10-30 | Chimec Spa | Procedimento per impedire la formazione di fouling polimerico neltrattamento di cariche idrocarburiche contenenti olefine. |
US6639026B2 (en) | 2001-05-22 | 2003-10-28 | Ge Betz, Inc. | Methods and compositions for inhibiting polymerization of vinyl monomers |
US7118689B2 (en) | 2003-08-27 | 2006-10-10 | Ppg Industries Ohio, Inc. | Stabilized polychloroethylenes |
EP2233505A1 (en) | 2009-03-23 | 2010-09-29 | Total Petrochemicals Research Feluy | Stabilised compositions comprising olefins |
EP3673000A1 (en) * | 2017-08-24 | 2020-07-01 | Dow Global Technologies, LLC | Synergistic inhibitor combination for increased shelf life of urethane acrylate compositions |
CN113825723A (zh) | 2019-04-02 | 2021-12-21 | 埃科莱布美国股份有限公司 | 具有减少的酸用量的纯二氧化氯生成系统 |
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JPH05320217A (ja) * | 1992-05-21 | 1993-12-03 | Kuraray Co Ltd | (メタ)アクリル酸の重合防止方法 |
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KR960004882B1 (ko) * | 1991-07-24 | 1996-04-16 | 1996년04월16일 | 비닐-함유 화합물의 중합반응 억제제 |
US5254760A (en) * | 1992-07-29 | 1993-10-19 | Ciba-Geigy Corporation | Inhibiting polymerization of vinyl aromatic monomers |
US5488192A (en) * | 1993-07-23 | 1996-01-30 | Kourbatov | Method for inhibiting the polymerization of styrene |
EP0697386B1 (de) * | 1994-08-19 | 1998-11-25 | Hüls Aktiengesellschaft | Inhibierung der Polymerisation von Styrol |
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- 1997-07-15 CA CA002261064A patent/CA2261064A1/en not_active Abandoned
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JPH05320217A (ja) * | 1992-05-21 | 1993-12-03 | Kuraray Co Ltd | (メタ)アクリル酸の重合防止方法 |
Cited By (1)
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JP2004527632A (ja) * | 2001-05-22 | 2004-09-09 | ジーイー・ベッツ・インコーポレイテッド | ビニルモノマーの重合を抑制する方法及び組成物 |
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EP0912471B1 (en) | 2003-08-27 |
BR9710315A (pt) | 2000-01-11 |
WO1998002400A1 (en) | 1998-01-22 |
CZ10099A3 (cs) | 1999-05-12 |
EP0912471A1 (en) | 1999-05-06 |
CZ294776B6 (cs) | 2005-03-16 |
CA2261064A1 (en) | 1998-01-22 |
DE69724432T2 (de) | 2004-06-09 |
PL185930B1 (pl) | 2003-09-30 |
PL331244A1 (en) | 1999-07-05 |
DE69724432D1 (en) | 2003-10-02 |
JP4195509B2 (ja) | 2008-12-10 |
AU3551297A (en) | 1998-02-09 |
KR20000023783A (ko) | 2000-04-25 |
GB9614854D0 (en) | 1996-09-04 |
KR100450603B1 (ko) | 2004-09-30 |
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