SG192979A1 - Synergistic polymerization inhibitor composition and method - Google Patents
Synergistic polymerization inhibitor composition and method Download PDFInfo
- Publication number
- SG192979A1 SG192979A1 SG2013064969A SG2013064969A SG192979A1 SG 192979 A1 SG192979 A1 SG 192979A1 SG 2013064969 A SG2013064969 A SG 2013064969A SG 2013064969 A SG2013064969 A SG 2013064969A SG 192979 A1 SG192979 A1 SG 192979A1
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- Singapore
- Prior art keywords
- polymerization
- polymerization inhibitor
- vinyl monomer
- captive
- composition
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 110
- 239000003112 inhibitor Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims description 17
- 230000002195 synergetic effect Effects 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 97
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 54
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 15
- 229950000688 phenothiazine Drugs 0.000 claims description 15
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 14
- 150000002696 manganese Chemical class 0.000 claims description 13
- HZZYXQYXUHBZJB-UHFFFAOYSA-N 10-benzylphenothiazine Chemical group C12=CC=CC=C2SC2=CC=CC=C2N1CC1=CC=CC=C1 HZZYXQYXUHBZJB-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- MWMNLODKRHNFPJ-UHFFFAOYSA-N 10-(1-phenylethyl)phenothiazine Chemical compound C12=CC=CC=C2SC2=CC=CC=C2N1C(C)C1=CC=CC=C1 MWMNLODKRHNFPJ-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 15
- -1 vinyl alcohols Chemical class 0.000 description 15
- 238000007792 addition Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 7
- 239000003607 modifier Substances 0.000 description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- 125000006519 CCH3 Chemical group 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- DJTZIDSZSYWGKR-UHFFFAOYSA-N acetic acid tetrahydrate Chemical compound O.O.O.O.CC(O)=O DJTZIDSZSYWGKR-UHFFFAOYSA-N 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 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
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 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
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000012453 solvate Substances 0.000 description 1
- 239000011877 solvent mixture 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Please be informed that the "follow up required item" does not work properly. For TOC and SL indication there is a follow-up required item although there is no warning in Bibadmin. See following example : A vinyl monomer polymerization inhibitor composition comprising a liquid mixture comprising a vinyl monomer and a polymerization inhibiting effective amount of a captive polymerization inhibitor, wherein the composition lacks a fugitive polymerization inhibitor of polymerization of the vinyl monomer and the captive polymerization inhibitor independently is characterizable as being an inhibitor of polymerization of the vinyl monomer and polymerization of the vinyl monomer is inhibited by the captive polymerization inhibitor, and wherein the captive polymerization inhibitor is a compound of formula (I): or a first acid addition salt thereof, wherein R1 is hydrogen or (C1-C3)alkyl.
Description
Synergistic Polymerization Inhibitor Composition and Method
This application claims priority from provisional application serial number 61/450,734, filed
March 9, 2011, which is incorporated herein by reference in its entirety.
The present invention relates to a vinyl monomer polymerization inhibitor composition and method of inhibiting polymerization of a vinyl monomer therein.
Vinyl monomers include vinyl alcohols and esters and acrylic monomers. Vinyl monomers are widely used in chemical industry. For example, acrylic monomers are used to prepare polyacrylate-type polymers (e.g., poly(acrylic acids) and poly(methacrylic acids)), which are useful as, among other things, additives (e.g., for use in rubbers, coatings and adhesives) and ingredients in fibers and other articles. A major problem with the vinyl monomers is premature polymerization. In the absence of sufficient amounts of polymerization inhibitors, vinyl monomers undesirably polymerize during manufacture, purification, handling, and storage operations. A unique solution to this problem is mentioned in WO 2010/096512 A1, which relates to a monomer polymerization inhibitor composition comprising a captive polymerization inhibitor and a fugitive polymerization inhibitor. The fugitive polymerization inhibitor is characterizable as being capable of evaporating with a distillable monomer from a first location (e.g., distillation pot) and condensing with the distillable monomer at a second location (e.g., in a distillation tower).
A problem addressed by the present invention includes providing a vinyl monomer polymerization inhibitor composition comprising a captive polymerization inhibitor that inhibits polymerization of a vinyl monomer unexpectedly better than phenothiazine inhibits such polymerization, and wherein the composition lacks a fugitive polymerization inhibitor of the vinyl monomer.
In a first embodiment the present invention provides a vinyl monomer polymerization inhibitor composition comprising a liquid mixture comprising a vinyl monomer and a polymerization inhibiting effective amount of a captive polymerization inhibitor, wherein the composition lacks a fugitive polymerization inhibitor of polymerization of the vinyl monomer and the captive polymerization inhibitor independently is characterizable as being a synergistically effective inhibitor of polymerization of the vinyl monomer and polymerization of the vinyl monomer is synergistically inhibited by the captive polymerization inhibitor, and wherein the captive polymerization inhibitor is a compound of formula (I): ve
C0"
S , or a first acid addition salt thereof, wherein Rlis hydrogen or (C1-Cy)alkyl.
In some aspects of the first embodiment the vinyl monomer is an acrylic monomer, preferably an acrylic acid-type monomer of formula (M):
RB 0
GA R'
R14 0” (M)
R' , wherein Rs hydrogen or (C1-Cjg)alkyl and each of R12 0 rH independently is hydrogen or (C-Cg)alkyl.
In a second embodiment, the present invention provides a method of synergistically inhibiting polymerization of a vinyl monomer, the method comprising contacting together a vinyl monomer with a polymerization inhibiting effective amount of a captive polymerization inhibitor so as to give the invention composition.
The invention composition is one that is capable of functioning in the method of the second embodiment. The invention composition is useful in manufacture, purification, handling, and storage of vinyl monomers (e.g., vinyl alcohols and esters and acrylic monomers) as an inhibitor of polymerization of the vinyl monomers in, for example, vessels such as distillation pots, storage vessels, and transportation vessels.
Additional embodiments are described in the remainder of the specification.
The embodiments of the present invention summarized previously and the Abstract are incorporated here by reference. As used herein, the term “vinyl monomer” means a molecule containing the structural fragment H,C=C(H)- and having a molecular weight of < 1,000 grams per mole (g/mol). The term “acrylic monomer” means a vinyl monomer with the structural fragment,
Shp
LL7CE08 _s , wherein represent portions of covalent bonds. The term “captive polymerization inhibitor” means a substance that does not evaporate from a distillation pot during distillation of the vinyl monomer (e.g., acrylic monomer) therefrom. The term “fugitive polymerization inhibitor” means a substance that is capable of evaporating and condensing in a polymerization inhibiting amount with the acrylic. The term “inhibit” means to delay onset of, reduce degree of, or, preferably, prevent that which is being inhibited. The phrase “synergistically effective inhibitor of polymerization” means a substance that prevents visual appearance of solid poly(vinyl monomer) (e.g., poly(acrylic monomer)) for an average time value of at least 70 hours, which is about two times the average time value obtainable with phenothiazine per se. The time is determined using the following procedure: seal a glass vial containing a liquid mixture of the vinyl monomer (e.g., acrylic monomer) and 100 ppm of the substance or 100 ppm of the substance and 20 ppm of an inhibitor modifier, based on total weight of the liquid mixture. Place the vial in a mineral oil bath thermostated at 113 °C. Record time to the visual appearance of the solid poly(vinyl monomer) (e.g., poly(acrylic monomer)) anywhere in the vial (i.e., in the liquid mixture or on wall of vial above the liquid mixture). Repeat 4 times. Average the five times to give the average time value. The term “inhibitor modifier” means a substance (e.g., a manganese salt) that generates or regenerates the compound from a derivative thereof. The term “lacks” and the like (e.g., lacking) means entirely absent. The term “polymerization inhibiting effective amount” means an absolute weight (e.g., in grams) or relative weight (e.g., expressed in parts per million (ppm) or weight percent (wt%)) of a substance that is sufficient to delay onset of, reduce degree of, or, preferably, prevent polymerization. The phrase “polymerization is synergistically inhibited” and the like means where a polymerizable monomer is exposed to polymerization conditions (a chemical process resulting in bonding between two or more molecules of the polymerizable monomer to produce an organic oligomer or polymer thereof) and the polymerizable monomer is in contact with the captive polymerization inhibitor, rate of the chemical process is significantly lowered compared to a rate of the chemical process in presence of the comparator inhibitor, phenothiazine.
Conflict Resolution: what is written in the present specification controls any conflict with what is written in a patent, patent application, or patent application publication, or a portion thereof that is incorporated by reference. The structure controls any conflict with a compound name. Any non-international system of units value controls any conflict with an International System (SI) of
Units value. A drawing controls any conflict with the written description thereof.
Numerical ranges: any lower limit of a range of numbers, or any preferred lower limit of the range, may be combined with any upper limit of the range, or any preferred upper limit of the range, to define a preferred aspect or embodiment of the range. Unless otherwise indicated, each range of numbers includes all numbers, both rational and irrational numbers, subsumed in that range (e.g., “from 1 to 5” includes, for example, 1, 1.5, 2, 2.75, 3, 3.81, 4, and 5).
The term “(C-Cqg)alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 18 carbon atoms that is unsubstituted. Examples of (C1-C;g)alkyl are (Cy-Cqglalkyl (e.g., a (Cyg)alkyl such as CH3(CHj)17-) and (C{-Cg)alkyl, which includes (C1-Cz)alkyl, including methyl, ethyl, 1-propyl, and 2-propyl; and (C4-Cg)alkyl, including 1-butyl (also known as normal- 5S butyl or n-butyl), 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, and 1- octyl. The term “(C1-Cy)alkyl-O-" means the (C1-Cy)alkyl bonded to an oxygen atom radical.
The captive polymerization inhibitor is especially useful for inhibiting polymerization of the vinyl monomer (e.g., acrylic monomer) in a distillation vessel (pot), storage vessel, or conduit (e.g., piping and tubing).
A polymerization inhibiting effective amount of the captive polymerization inhibitor (i.e., compound of formula (I)) can be varied depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, and presence or absence of other captive polymerization inhibitors. An invention process may be initiated with a larger polymerization inhibiting effective amount than is believed required.
Thereafter the polymerization inhibiting effective amount can be allowed to decrease (e.g., as polymerization inhibitor is reacted) until a desirable steady-state amount of polymerization inhibitor is obtained under the conditions (e.g., as evidenced by achieving a desired time interval between vessel cleanings). A person of ordinary skill in the art would be able to determine appropriate polymerization inhibiting effective amounts under particular circumstances without undue experimentation. A preferred first polymerization inhibiting effective amount of the compound of formula (I) is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
The captive polymerization inhibitors do not include derivatives of the vinyl monomer (e.g., acrylic monomer).
In some embodiments the captive polymerization inhibitor is the compound of formula (I) wherein R1 is hydrogen. In some embodiments Rlis (C1-Cy)alkyl. In some embodiments Rlis ethyl, 1-propyl, or 2-propyl, and more preferably, Rlis methyl. In some embodiments the compound of formula (I) is N-benzyl-phenothiazine, in other embodiments N-(1- phenylethyl)phenothiazine, and in still other embodiments the first acid addition salt thereof.
Synthesis of the compound of formula (I) is not critical to the invention and all successful syntheses are contemplated. In some embodiments the compound of formula (I) is synthesized by alkylating a corresponding intermediate amino compound of formula (IA) as shown below in
Scheme 1.
Scheme 1. «
H R} Non- N nucleophilic + LG base
X X aprotic solvent (1A) (IB) 0) wherein R! is as described for formula (I) and LLG is a leaving group. In Scheme 1, an amino compound of formula (IA) and a compound of formula (IB) having a leaving group are contacted in the presence of a non-nucleophilic strong base and aprotic solvent at a nucleophilic displacement temperature, preferably from about 0 °C to about 100 °C, to give the compound of formula (I).
Examples of aprotic solvents are tetrahydrofuran, 1,2-dimethoxyethane, and dioxane. Examples of the non-nucleophilic base are sodium hydride, potassium hydride, potassium hexamethyldisilazide (KHMDS), and lithium diisopropylamide (LDA). Examples of leaving groups are iodo, bromo, chloro, an activated hydroxyl, trifluoromethanesulfonate, trifluoroacetate, and tosylate. In some embodiments, such activated hydroxyls are prepared from a compound of formula (IB) wherein LG is HO- and a coupling agent such as, for example, triphenylphosphine with either diisopropylazodicarboxylate (DIAD), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC, EDCI, or EDAC), N,N'-carbonyldiimidazole (CDI), or N,N'- dicyclohexylcarbodiimide (DCC), and optionally with 1-hydroxybenzotriazole (HOBt); and (benzotriazol-1-yloxy)tripyrrolidino- phosphonium hexafluorophosphate.
Other syntheses of the compound of formula (I) are contemplated. For example when Rlis hydrogen, the compound of formula (I) can be synthesized by coupling the compound of formula (IA) with an acid halide of formula halo-C(=0)-phenyl or acid anhydride of formula phenyl-C(=0)- O-C(=0)-phenyl to give a penultimate carboxamide of formula (IC):
JQ
CLO
X
(IC) . The carboxamide of formula (IC) can then be reduced (e.g., lithium aluminum hydride in tetrahydrofuran) to give the compound of formula (I) wherein Rlis H.
The invention further contemplates employing acid addition salts of the compound of formula (I). The term “acid addition salt” means an ionic substance comprising an organic cation and an organic, or preferably inorganic anion. The organic cation comprises a protonated form of phenothiazine or the compound of formula (I). The anion comprises a residual of an organic or, preferably, inorganic compound having at least one proton characterized by a pKa value of less than 7 (i.e., a residual of a Brgnsted acid). Preferred acid addition salts comprise from 0.9 to 1.1 mole equivalents of a monoprotic Brgnsted acid, from 0.45 to 0.55 mole equivalents of a diprotic
Brgnsted acid, or from 0.3 to 0.37 mole equivalents of a triprotic Brgnsted acid, all per mole of phenothiazine or the compound of formula (I). Preferred Brgnsted acids include hydrochloric, nitric, phosphoric, sulfuric, hydrobromic, hydroiodic, phosphorus, formic, and acetic acids.
In some embodiments the invention composition further comprises at least one additional captive polymerization inhibitor of the vinyl monomer (e.g., acrylic monomer). In some embodiments the additional captive polymerization inhibitor is a manganese salt that is Mn(HCO," )2, Mn((C1-Cg)alkylCO5),, or potassium permanganate. In some embodiments the manganese salt is employed in a method of the second embodiment as the inhibitor modifier in combination with the captive polymerization inhibitor. In some embodiments the manganese salt is Mn(HCO5"),. In some embodiments the manganese salt is Mn((C{-Cg)alkylCO,"),, and more preferably manganese(II) acetate, including manganese(Il) acetate (Mn(O,CCH3)5) and manganese(Il) acetate tetrahydrate (Mn(O,CCH3), + 4H50). In some embodiments the manganese salt is potassium permanganate. In some embodiments the additional captive polymerization inhibitor is hydroquinone. In some embodiments the additional captive polymerization inhibitor is phenothiazine or a second mixture of molecular oxygen and phenothiazine, or a second acid addition salt thereof. The term “phenothiazine” and “‘phenothiazine per se” each mean the compound of the following formula:
H
CL
S :
The additional captive polymerization inhibitor, when used, is employed in its own independent polymerization inhibiting effective amount. A polymerization inhibiting effective amount of the manganese salt, hydroquinone, or phenothiazine can vary depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, presence or absence of other captive polymerization inhibitors, and amount of inhibitor modifier, if any, that is present. The person of ordinary skill in the art would be able to determine appropriate polymerization inhibiting effective amounts under particular circumstances without undue experimentation. A preferred polymerization inhibiting effective amount of the manganese salt, hydroquinone, or phenothiazine independently is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
In some embodiments the invention composition further comprises a first mixture of an N- oxyl compound and the manganese salt that is Mn(HCO,")7, Mn((C{-Cg)alkylCO5"),, or potassium permanganate. The term “N-oxyl compound” means a chemical substance having a
SX
N-O structural fragment, 4 , wherein the - represents a radical (electron) and each —3 represents a portion of a covalent bond to a quaternary carbon atom. Preferably, the N-oxyl compound is 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl; 2,2,6,6-tetramethylpiperidine- 1-oxyl; tris(2,2,6,6-tetramethylpiperidine-1-oxyl-4-yl)-phosphite; and, more preferably, 4-hydroxy-2,2,6,6- tetramethylpiperidine-1-oxyl. The terms “4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl” and “4- hydroxy-TEMPO” are synonymous and each mean a compound of the following formula:
HO~ N—-O , wherein the * represents a radical (electron).
The invention further contemplates compositions further comprising a combination of any two or more of the aforementioned additional captive polymerization inhibitors.
A polymerization inhibiting effective amount of 4-hydroxy-TEMPO can vary depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, presence or absence of other captive polymerization inhibitors, and amount of the manganese salt present. The person of ordinary skill in the art would be able to determine appropriate polymerization inhibiting effective amounts under particular circumstances without undue experimentation. A preferred polymerization effective inhibiting amount of the N-oxyl compound such as 4-hydroxy-TEMPQ is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
The present invention further contemplates compositions further comprising the inhibitor modifier. Examples of the inhibitor modifier are molecular oxygen and the manganese salt (e.g., when no additional captive polymerization inhibitor is employed or when the invention composition further comprises the N-oxyl compound (e.g., the 4-hydroxy-2,2,6,6-tetramethylpiperidine- 1-oxyl).
As mentioned before, preferably the acrylic monomer is the acrylic acid-type monomers of formula (M). Preferred is the acrylic acid-type monomer of formula (M) wherein one of rH or! is (C1-Cg)alkyl and the remainder of RI ors hydrogen. In some embodiments, Rls (Cq-
Cqg)alkyl. In some embodiments, rR is (Cy-C1galkyl. In some embodiments, rR is (Cq-
Cg)alkyl. In some embodiments, Rs (C1-Cgalkyl and each of R120 R14is hydrogen. In some embodiments, rR1Z jg (C1-Cg)alkyl and each of rl 1 R13, and R14 is hydrogen. In some embodiments, R13 is (C1-Cgalkyl and each of Rr! 1 R12, and R14 is hydrogen. In some embodiments, R14 is (C1-Cgalkyl and each of RI oRI3 js hydrogen. In some embodiments, each of R11 to R14 is hydrogen, i.e., the acrylic acid-type monomer of formula (M) is acrylic acid itself.
Also preferred is the acrylic acid-type monomer of formula (M) wherein two of RI 0 R14 is (Cq-
Cgalkyl and the remainder of RI oRrM is hydrogen. More preferably, Ris one of the two of
Ro R14 that is (C1-Cglalkyl. Also preferred is the acrylic acid-type monomer of formula (M) wherein three of R11 0 R14 is (C1-Cg)alkyl and the remainder of Ro RM is hydrogen.
Preferably in the acrylic acid-type monomer of formula (M), each (C-Cg)alkyl is (C;-Cz)alkyl and, more preferably, methyl.
In some embodiments the fugitive polymerization inhibitor that is lacking in the invention composition is a nitroso compound of formula (II):
O
Il
Nn N m , wherein m is an integer of from 1 to 3 and each R* independently is hydrogen, (C;-Cy)alkyl, (C;-C3)alkyl-O-, fluoro, or chloro.
Compounds of formulas (I) and (M), 4-hydroxy-TEMPO, manganese salts, acid addition salts, inhibitor modifier, etc. useful in the present invention, and the fugitive inhibitor that is lacking, include solvates, including hydrates, thereof.
In the method of the second embodiment the vinyl monomer (e.g., acrylic monomer) is exposed to polymerizing conditions and thus becomes susceptible to being polymerized (e.g., susceptible to forming an oligomer or homopolymer), and any polymerization of the distillable monomer in the invention method is inhibited by the captive polymerization inhibitor(s). Examples of polymerizing conditions are exposure to a polymerizing agent (e.g., oxygen gas, water, or a {ree radical or initiator) or condition (e.g., free radical generation conditions such as ultraviolet light or a high temperature zone).
A preferred method of the second embodiment employs any one of the preferred acrylic acid-type monomer polymerization inhibitor compositions described herein and any one of the preferred acrylic acid-type monomers of formula (M) described herein. Another preferred of the second embodiment employs a mixture of any two or more of the preferred acrylic acid-type monomers of formula (M) described herein such as, for example, a mixture of acrylic acid and either ethyl acrylate or n-butyl acrylate.
Preferably in the method of the second embodiment employing the vinyl monomer (e.g., acrylic monomer) and captive polymerization inhibitor, the step comprises evaporating at least some of the vinyl monomer (e.g., acrylic monomer) and under a reduced pressure that is less than 90 kPa and an elevated temperature of the liquid mixture (e.g., distillation pot temperature) that is greater than 50 °C, and more preferably greater than 90 °C.
In a pilot plant or manufacturing setting, a vessel (e.g., distillation pot or reactor) containing the invention composition is in fluid communication with a distillation column. A preferred distillation column is one that contains dual-flow plates or trays. An example of such a dual-flow tray column is described in U.S. Patent Number US 7,306,204 B2. Preferably, distillation columns comprise, and the liquid mixture is in sequential fluid communication with, bottom, middle and upper zones, wherein the middle zone optionally defines a feed inlet. In a method of the second embodiment, preferably during steady state operation temperature in the bottom zone is within about 5 °C of the elevated temperature of the liquid mixture and reduced pressure in the top zone is within about 30 kPa of reduced pressure in the bottom zone. For illustration, a manufacturing scale dual- flow 40-tray column during steady state operation is characterized by a temperature of about 111 °C and reduced pressure of about 35 kPa in its bottom zone, a temperature of about 46 °C and reduced pressure of about 21 kPa in its top zone, and a temperature of about 56 °C in its middle zone.
The present invention contemplates batch (single addition of vinyl monomer (e.g., acrylic monomer)) and continuous (continuous addition or multiple separate additions of vinyl monomer (e.g., acrylic monomer)) to the vessel containing the invention composition. In batch or continuous processes, especially continuous processes, preferably one or more additional polymerization inhibiting effective amounts of the captive polymerization inhibitor are added to the vinyl monomer (e.g., acrylic monomer) in the vessel. For example in a continuous process employing a distillation vessel (e.g., distillation pot) and column, such one or more additional polymerization inhibiting effective amounts can be added to the distillation vessel containing vinyl monomer (e.g., acrylic monomer) so as to replace portions of the captive polymerization inhibitor lost to reaction thereof in the distillation vessel. The additions of the captive polymerization inhibitor independently comprise continuous or multiple separate additions and can be made by conventional means such as, for example, an addition funnel or valved feed line.
Materials: Acrylic acid, phenothiazine, 4-hydroxy- TEMPO and a number of manganese salts are commercially available from various suppliers including Sigma-Aldrich Company, St.
Louis, Missouri, USA.
Preparation 1: synthesis of N-benzylphenothiazine (1)
N
0
S . Add a solution of 2 grams (g; 0.01 mole (mol)) of phenothiazine in 10 milliliters (mL) of dry tetrahydrofuran (THF) under nitrogen gas atmosphere to a suspension of 1.0 g of sodium hydride (NaH; 0.042 mol) in 20 mL of dry THF at room temperature (Previously obtain the NaH by washing an 80% suspension of NaH in mineral oil with n-hexane.) Stir the mixture for 4 hours or until hydrogen gas is released and the color of mixture changes to orange.
Then slowly add 2 ml. (0.017 mol) of benzyl bromide to the orange mixture at room temperature, and stir the resulting mixture overnight. Heat the mixture to 60 °C for 1 hour. The orange color fades. Pour the reaction mixture into ice-water that has been acidified with concentrated hydrochloric acid to pH 1. Extract the resulting aqueous mixture with ethyl acetate, dry it over anhydrous magnesium sulfate, and remove the solvent under vacuum. Purify the resulting extraction residue by column chromatography over neutral alumina eluting with a solvent mixture of n- hexane:ethyl acetate (50:1). Evaporate the solvents and recrystallized the residue from ethanol to give 2 g (60% yield) of N-benzylphenothiazine as white crystals. "H NMR spectrum is consistent with pure N-benzylphenothiazine. '"H NMR (CDCl3) (ppm): 7.25 — 7.40 (m, SH); 7.11 (d, 2H, J = 7.5 Hz); 7.00 (t, 2H, J = 8.0 Hz); 6.88 (t, 2H, J = 7.5 Hz); 6.67 (d, 2H, J = 8.0 Hz); 5.12 (s, 21).
Preparation 2: synthesis of N-(1-phenylethyl)-phenothiazine (2)
N
(X10
S . In a procedure similar to that of Preparation 1 except use (1- bromoethyl)benzene instead of benzyl bromide, prepare N-(1-phenylethyl)-phenothiazine. Product is purified by column chromatography on neutral alumina using n-hexane:ethyl acetate (50 : 1) mixture of solvents as an eluent. Evaporation of solvent gave N-(1-phenylethyl)-phenothiazine as a white solid in 65 % yield. 'H NMR spectrum is consistent with N-(1-phenylethyl)-phenothiazine. 'H
NMR (CDCl;) (ppm): 7.30 — 7.45 (m, SH, Ar-CH-); 7.14 (d, 2H, J = 7.5 Hz, Ar-PTZ); 6.85 7.05 (m, 4H, Ar-PT7); 6.74 (d, 2H, J = 7.0 Hz, Ar-PTZ); 5.42 (q, 1H, Ar-CH-CH;); 1.98 (d, 3H, J=7.0
Hz, CH-CHs).
Some embodiments of the invention are described in more detail in the following Examples.
Examples 1 and 2: compositions of acrylic acid and compound (1) or (2).
In two separate vials, mix 5 milliliters (mL) acrylic acid and an amount of compound (1) or (2) (Preparations 1 or 2) that is sufficient to produce a mixture having 100 ppm of the captive polymerization inhibitor, the mixture being the composition of Example 1 or 2, respectively. The compositions of Examples 1 and 2 are particularly useful for inhibiting polymerization of acrylic acid. Repeat Examples 1 and 2 four more times to give 5 vials for Examples 1 and 2.
Examples 3 and 4: inhibition of polymerization of acrylic acid with compound (1) or (2).
For Example 3, seal vials and heat the compositions of Example 1 and for Example 4 seal vials and heat the compositions of Example 2, all at 113 degrees Celsius (°C) and record time of first appearance of change in density (gel formation) in compositions. In five separate vials heat a
IS comparative, non-invention composition comprising 5 mL acrylic acid and 100 ppm of phenothiazine per se (P17) and likewise record time to gel formation. There are a total of 5 runs for each of Examples 3 and 4 and the comparative example. Gel formation times for Example 3 ranged from 81 hours to 97 hours; for Example 4 from 94 to 99 hours; and for comparator P17 from 31 hours to 34 hours. Average results are reported below in Table 1.
Table 1: time to gel formation
Number number Average time to gel formation (hours)
As shown by the above data, the invention composition synergistically inhibits polymerization of vinyl monomer (e.g., acrylic monomer) and is especially useful in manufacture, purification, handling, and storage of acrylic monomers, especially acrylic acid-type monomers, as an inhibitor of polymerization of the acrylic monomers in, e.g., vessels and piping.
Claims (8)
- CLAIMS WHAT IS CLAIMED IS:I. A vinyl monomer polymerization inhibitor composition comprising a liquid mixture comprising a vinyl monomer and a polymerization inhibiting effective amount of a captive polymerization inhibitor, wherein the composition lacks a fugitive polymerization inhibitor of polymerization of the vinyl monomer and the captive polymerization inhibitor independently is characterizable as being a synergistically effective inhibitor of polymerization of the vinyl monomer and polymerization of the vinyl monomer is synergistically inhibited by the captive polymerization inhibitor, and wherein the captive polymerization inhibitor is a compound of formula (I): ve N (X )® ’ S , or a first acid addition salt thereof, wherein RI is hydrogen or (C1-Cy)alkyl.
- 2. The composition as in claim 1, wherein the vinyl monomer is an acrylic acid-type monomer of formula (M): RB 0 R! 1 R14 YX 0” (M) R12 . 11. , wherein R** is hydrogen or (C{-Cg)alkyl and each of R12 o R14 independently is hydrogen or (C;-Cg)alkyl.
- 3. The composition as in claims 1 or 2, wherein Rlis hydrogen.
- 4, The composition as in claim 1 or 2, wherein Rlis (C1-Cylalkyl.
- 5. The composition as in claim 1 or 2, wherein the captive polymerization inhibitor is N- benzyl-phenothiazine, N-(1-phenylethyl)phenothiazine, or the first acid addition salt thereof.
- 6. The composition as in claim 5, wherein the captive polymerization inhibitor is N-benzyl- phenothiazine or N-(1-phenylethyl)phenothiazine.
- 7. The composition as in any one of the preceding claims, wherein the composition further comprises: (a) a manganese salt that is Mn(HCO5"),, Mn((C1-Cg)alkylCO5 7), or potassium permanganate; (b) a first mixture of an N-oxyl compound and a manganese salt that is Mn(HCO5"),, Mn((C-Cg)alkylCOy7),, or potassium permanganate; (c) hydroquinone; (d) a second mixture of molecular oxygen and phenothiazine, or a second acid addition salt thereof, or (€) a combination of any two or more captive polymerization inhibitors of the foregoing (a) to (d).
- 8. A method of synergistically inhibiting polymerization of a vinyl monomer, the method comprising contacting together a vinyl monomer with a polymerization inhibiting effective amount of a captive polymerization inhibitor so as to give the polymerization inhibitor composition as in any one of claims 1 to 7.
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| PCT/US2012/024936 WO2012121836A1 (en) | 2011-03-09 | 2012-02-14 | Synergistic polymerization inhibitor composition and method |
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| CN104864266B (en) * | 2015-05-07 | 2017-11-17 | 中国海洋石油总公司 | A kind of unimolecule hydrate inhibitor |
| KR102652108B1 (en) * | 2018-08-24 | 2024-03-29 | 비엘 테크놀러지스 인크. | Synergistic Combination to Inhibit Polymerization |
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| US7220879B2 (en) * | 2004-10-01 | 2007-05-22 | Rohm And Haas Company | Method for inhibiting polymerization of (meth)acrylic acid and its esters using an inhibitor and a process for making a compound useful as such an inhibitor |
| WO2007020932A1 (en) * | 2005-08-19 | 2007-02-22 | Dow Corning Toray Co., Ltd. | A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group |
| CN101351449A (en) * | 2005-12-27 | 2009-01-21 | 株式会社Adeka | Nitroxyl compound, and polymerization inhibitor and polymerization inhibitor composition using same |
| WO2009032427A2 (en) * | 2007-08-31 | 2009-03-12 | Dow Global Technologies Inc. | Method of inhibiting polymerization and fouling in acrylic acid and acrylate processes |
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