JP6480442B2 - 塩化ビニリデン系ヘテロポリマーを生成するためのプロセス - Google Patents
塩化ビニリデン系ヘテロポリマーを生成するためのプロセス Download PDFInfo
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- JP6480442B2 JP6480442B2 JP2016528139A JP2016528139A JP6480442B2 JP 6480442 B2 JP6480442 B2 JP 6480442B2 JP 2016528139 A JP2016528139 A JP 2016528139A JP 2016528139 A JP2016528139 A JP 2016528139A JP 6480442 B2 JP6480442 B2 JP 6480442B2
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- vinylidene chloride
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 53
- 229920000140 heteropolymer Polymers 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 claims description 29
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 20
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 13
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- MXJGWNPVKBVVTM-UHFFFAOYSA-N 5-tert-butyl-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC=NC2=C1 MXJGWNPVKBVVTM-UHFFFAOYSA-N 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- -1 2-hydroxy-4-octoxyphenyl Chemical group 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012508 resin bead Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000013799 ultramarine blue Nutrition 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
-
- 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
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Description
147℃の融点、86,000Mwの分子量を有し、2%のエポキシ化大豆油を含有する塩化ビニリデン/アクリル酸メチルコポリマーを、従来の懸濁重合技法を使用して、300mLのクエン酸ボトル反応器中の懸濁重合によって生成した。得られたポリマーを単離し、乾燥させて収率91%の生成物を得た。PVDC生成物は、くすんだ白色または灰白色の外観を有していた。CIE白色度は、73.2であった。生成物は、366nmの紫外線光下で蛍光を発しなかった。
比較例1と同様の方法で、147℃の融点、86,000Mwの分子量を有し、2%のエポキシ化大豆油を含有する塩化ビニリデン/アクリル酸メチルコポリマーを、従来の懸濁重合技法を使用して、300mLのクエン酸塩ボトル反応器中の懸濁重合によって生成した。この実施例では例外的に、100ppmの2,2′−(2,5−チオフェニレンジイル)ビス(5−tert−ブチルベンゾキサゾール)を、重合の前に塩化ビニリデン/アクリル酸メチルモノマー混合物中に溶解した。得られたポリマーを単離し、乾燥させて収率91%の生成物を得た。PVDC生成物は、明るい白色の外観を有していた。CIE白色度は、106.3であった。生成物は、366nmの紫外線光下で蛍光を発した。
152℃の融点を有する一連の塩化ビニリデン/アクリル酸メチルコポリマーを、従来の懸濁重合技法を使用して、300mLのクエン酸ボトル反応器中の懸濁重合によって生成した。重合の前に、Solvent Violet 13(SV−13、CAS 81−48−1、ヒドロキシ−4−(p−トリルアミノ)アントラセン−9,10−ジオン)染料を、表1に示される濃度でエポキシ化亜麻仁油中に溶解した。次に1.2重量%のこれらの混合物を、塩化ビニリデン/アクリル酸メチルモノマー混合物に添加した。得られたポリマーを単離し、乾燥させて表1に記される収率及び分子量を得た。得られた実施例2及び3のバイオレット色は、樹脂ビーズ全体で均一であり、分離による色変化の兆候を示さなかった。
152℃の融点を有する一連の塩化ビニリデン/アクリル酸メチルコポリマーを、従来の懸濁重合技法を使用して、300mLのクエン酸塩ボトル反応器中の懸濁重合によって生成した。重合の前に、Solvent violet 33(SV−33、CAS 86090−40−6、アントラキノン染料)染料を、表2に示される濃度でエポキシ化大豆油中に溶解した。次に1.2重量%のこれらの混合物を、塩化ビニリデン/アクリル酸メチルモノマー混合物に添加した。得られたポリマーを単離し、乾燥させて表2に記される収率及び分子量を得た。得られた実施例4、5、及び6のバイオレット色は、樹脂ビーズ全体で均一であり、分離による色変化の兆候を示さなかった。
152℃の融点、91,000Mwの分子量を有し、1.2%のMYVACET9−40(蒸留アセチル化モノグリセリド、Eastman Chemical Products,Inc.CAS# 68990−54−5から入手可能)を含有する、2000グラムの塩化ビニリデン/アクリル酸メチルコポリマーを、実験室規模のProdex高光度混合器に添加した。1.0グラムのSolvent Violet 33アントラキノン染料(Mitsubishi Chemical CorporationからDIARESIN BLUE Jとして入手可能)も混合器に添加した。次に混合物を、3分間1800rpmで混合し、定期的に手で止めて、静電気によって混合器壁に付着した任意の物質を混合した。得られた生成物は、色濃度500ppmの、PVDCコポリマービーズの外面上に実質的に均一に塗布されたSolvent Violet 33である。しかしながら、染料がビーズの表面上のみにあるため、より小さい粒子を持つ分画への樹脂の分離は、表面積の局所増加を引き起こし、SV−33指示薬の濃度を増加させて、指示薬濃度の変化をもたらす。
170℃の融点、87,000Mwの分子量を有し、1.5%のエポキシ化大豆油及び5.1%のアセチルトリブチルクエン酸塩を含有する、2666.5グラムの塩化ビニリデン/アクリル酸メチルコポリマーを、実験室規模のProdex高光度混合器に添加した。0.68グラムのウルトラマリンブルーも混合器に添加した。次に混合物を、1分間1800rpmで混合し、定期的に手で止めて、混合器壁に付着した任意の物質を混合した。追加の54.4グラムのエポキシ化大豆油を、混合しながら混合器に添加し、定期的に止めて混合器壁に付着した任意の物質を混合しながら1分間混合する。得られた混合物は、250ppmのウルトラマリンブルーを含有し、青色であった。しかしながら、混合物中に著しい色変化があり、分離時に著しく悪化した。
試験方法は、以下を含む。
「分子量」は、ダルトンの重量平均分子量(Mw)である。それは、ポリスチレン較正を使用するサイズ排除クロマトグラフィによって測定される。試料調製は、ポリ塩化ビニリデン樹脂試料を、50℃でテトラヒドロフラン(THF)中に溶解することを含む。次にポリマーを、連続する2つのカラムを備えたHewlett Packard 1 100クロマトグラフ上でPolymer Laboratoriesソフトウェアを使用して、ゲル透過クロマトグラフィー(GPC)によって分子量の決定のために分析する。これらのカラムは、Polymer Laboratoriesから商品名PLGel 5μMIXED−Cで市販されている、5μスチレン/ジビニルベンゼンコポリマービーズを含む。溶剤は、窒素パージしたHPLCグレードTHFである。流量は、1.0ミリリットル/分であり、注入サイズは50マイクロリットルである。分子量決定は、10の分子量分布の狭いポリスチレン標準(Polymer Labsから商品名Narrow PSセット(約3,000,000〜2000Mp)で市販されている)を、それらの溶出体積と併せて使用することによって推測される。
れてもよく、したがって、参照は前述の明細書に対してではなく、本発明の範囲を示す添
付の特許請求の範囲に対して行われるべきである。
上記の開示に基づく発明の例として、以下のものが挙げられる。
[1] 塩化ビニリデンヘテロポリマーを調製するプロセスであって、
塩化ビニリデンを、アクリル酸アルキル、非塩化ビニリデン系ビニルモノマー、及びそれらの組み合わせからなる群から選択される少なくとも1つのコモノマーと、指示薬の存在下で共重合させることを含み、前記指示薬が、塩化ビニリデン、前記少なくとも1つのコモノマー、または前記塩化ビニリデン及び前記少なくとも1つのコモノマーの混合物中に可溶性である、前記プロセス。
[2] 前記指示薬が、2,2′−(2,5−チオフェニレンジイル)ビス(5−tert−ブチルベンゾキサゾール)である、[1]に記載の前記プロセス。
[3] 前記コモノマーが、アクリル酸メチルまたは塩化ビニルである、[1]または[2]に記載の前記プロセス。
[4] 前記共重合が、懸濁重合プロセス中に起こる、[1]〜[3]のいずれか一項に記載の前記プロセス。
[5] 前記共重合が、乳化重合プロセス中に起こる、[1]〜[4]のいずれか一項に記載の前記プロセス。
[6] 可塑剤及びエポキシ化油からなる群から選択される少なくとも1つの添加剤を添加することを更に含む、[1]〜[5]のいずれか一項に記載の前記プロセス。
[7] 前記指示薬が、前記共重合ステップの前に、塩化ビニリデン、前記コモノマー、及び前記添加剤からなる群から選択される少なくとも1つの少なくとも一部分と均一に混合される、[6]に記載の前記プロセス。
[8] 前記共重合ステップの前に、懸濁化剤を前記塩化ビニリデン及び少なくとも1つのコモノマーに添加することを更に含む、[1]〜[7]のいずれか一項に記載の前記プロセス。
Claims (4)
- 塩化ビニリデンヘテロポリマーを調製するプロセスであって、
塩化ビニリデンを、アクリル酸アルキル、非塩化ビニリデン系ビニルモノマー、及びそれらの組み合わせからなる群から選択される少なくとも1つのコモノマーと、指示薬の存在下で共重合させることを含み、前記指示薬は、2,2′−(2,5−チオフェニレンジイル)ビス(5−tert−ブチルベンゾキサゾール)であり、塩化ビニリデン、前記少なくとも1つのコモノマー、または前記塩化ビニリデン及び前記少なくとも1つのコモノマーの混合物中に可溶性であり、前記指示薬が、前記共重合の前に、塩化ビニリデン、前記少なくとも1つのコモノマー、または前記塩化ビニリデン及び前記少なくとも1つのコモノマーの混合物中に溶解される、前記プロセス。 - 前記コモノマーが、アクリル酸メチルまたは塩化ビニルである、請求項1に記載の前記プロセス。
- 前記共重合が、懸濁重合プロセス中に起こる、請求項1に記載の前記プロセス。
- 前記共重合が、乳化重合プロセス中に起こる、請求項1に記載の前記プロセス。
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