WO2021175617A1 - Particules polymères désoxygénantes - Google Patents
Particules polymères désoxygénantes Download PDFInfo
- Publication number
- WO2021175617A1 WO2021175617A1 PCT/EP2021/054145 EP2021054145W WO2021175617A1 WO 2021175617 A1 WO2021175617 A1 WO 2021175617A1 EP 2021054145 W EP2021054145 W EP 2021054145W WO 2021175617 A1 WO2021175617 A1 WO 2021175617A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- thermoplastic resin
- oxygen scavenging
- oxygen
- particles according
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 179
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 149
- 239000001301 oxygen Substances 0.000 title claims abstract description 149
- 230000002000 scavenging effect Effects 0.000 title claims abstract description 79
- 229920000642 polymer Polymers 0.000 title claims description 29
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 31
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 13
- -1 polyethylenes Polymers 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 150000001925 cycloalkenes Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920002959 polymer blend Polymers 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 6
- 239000004913 cyclooctene Substances 0.000 claims description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 6
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- 238000003921 particle size analysis Methods 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004708 Very-low-density polyethylene Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000554 ionomer Polymers 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 3
- 229920001866 very low density polyethylene Polymers 0.000 claims description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 2
- MZJCFRKLOXHQIL-CCAGOZQPSA-N (1Z,3Z)-cyclodeca-1,3-diene Chemical compound C1CCC\C=C/C=C\CC1 MZJCFRKLOXHQIL-CCAGOZQPSA-N 0.000 claims description 2
- XOTMHDVYZZBKEJ-NQJXNNKBSA-N (1e,5e,9e)-1,5,9-trimethylcyclododeca-1,5,9-triene Chemical compound C\C1=C/CC\C(C)=C\CC\C(C)=C\CC1 XOTMHDVYZZBKEJ-NQJXNNKBSA-N 0.000 claims description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 claims description 2
- RYOGZVTWMZNTGL-UHFFFAOYSA-N 1,5-dimethylcycloocta-1,5-diene Chemical compound CC1=CCCC(C)=CCC1 RYOGZVTWMZNTGL-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 2
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 claims description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 claims description 2
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 claims description 2
- ZOLLIQAKMYWTBR-UHFFFAOYSA-N cyclododeca-1,5,9-triene Chemical compound C1CC=CCCC=CCCC=C1 ZOLLIQAKMYWTBR-UHFFFAOYSA-N 0.000 claims description 2
- BESIOWGPXPAVOS-UPHRSURJSA-N cyclononene Chemical compound C1CCC\C=C/CCC1 BESIOWGPXPAVOS-UPHRSURJSA-N 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 33
- 230000004888 barrier function Effects 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 150000004291 polyenes Chemical class 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 229920003245 polyoctenamer Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 229920000508 Vectran Polymers 0.000 description 1
- 239000004979 Vectran Substances 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009646 cryomilling Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009644 cyrogenic grinding Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009645 freezer milling Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3322—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclooctene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
Definitions
- the present invention relates to oxygen scavenging particles, their preparation and use for packaging applications. Background of the invention
- a variety of useful products such as food products, beverages, pharmaceuticals, medical products, cosmetics, metal products, electronic products may be prone to a rapid quality deterioration and degradation in the presence of oxygen due to the oxidation.
- the so-called “passive” and “active” oxygen barrier protecting layers are used.
- the former is usually made of the suitable oxygen barrier materials with a low oxygen permeation rate, whereas the latter comprises oxygen scavenging materials capable of oxygen absorption. Due to the limited oxygen protection by the plastic passive oxygen barrier materials, the use of such materials alone cannot provide enough protection of the sensitive goods against oxygen over a long period of time.
- the initial oxygen concentration present inside the packaging can be quite high and cannot be reduced anymore, if only a passive barrier layer is used. Both problems can be solved by using the active oxygen scavengers.
- active oxygen absorbers may be distributed in the packaging material layer, e.g. in the form of a protective film or may be present in the form of particles, stickers, sachets etc. inside the packaging.
- Oxygen scavenging materials directly incorporated into the structure of the packaging can be formed through incorporation of inorganic powders and/or salts as part of the packaging, as described e.g. in US 5,153,038, US 5,116,660, US 5,143,769 or US 5,089,323.
- Another type of oxygen scavenging compositions distributed in the whole packaging material comprising transition metal catalysts and ethylenically unsaturated hydrocarbon polymers is disclosed in US 5,399,289.
- Incorporation of oxygen scavenging materials directly into the packaging material allows using the whole surface area of the packaging film for oxygen absorption.
- the rate of oxygen absorption by such scavengers distributed in thin films is usually limited by the reactivity of the oxygen scavenger itself, or if a passive oxygen barrier film is used, by diffusion through such an oxygen barrier film.
- Packaging materials including oxygen scavengers have mostly multilayer structures, which are prepared by rather sophisticated manufacturing processes.
- the used oxygen scavenger must be compatible with the materials of such multilayers.
- the use of oxygen scavengers in other forms, e.g. a sachet filled with oxygen scavenging particles, may be beneficial.
- particulate oxygen absorbing materials include iron-based compositions.
- Such oxygen absorbing compositions comprising metallic iron usually have good oxygen absorbing performance.
- the materials for packaging applications undergo a microwave irradiation treatment or metal detection for contamination inspection.
- the use of iron particles in such application is restricted. Therefore, there is a need for providing particulate oxygen scavengers, which are active in the absence of moisture and are preferably not based on metal iron.
- Particulate oxygen scavengers based on oxidizable polymers and transition metal compounds incorporated in some matrix systems are known.
- JP 2004123970 A discloses pellets with a typical size of more than 2.5 mm, comprising a polyamide resin, an oxidizable organic compound, e.g. one comprising carbon-carbon double bonds, and a transition metal catalyst, which can be used for producing multilayer containers with an oxygen-absorbing gas barrier layer.
- EP2017308A1 discloses an oxygen-absorbing resin composition
- This oxygen-absorbing composition is made by melt-kneading the components and cutting the obtained mixture into pellets. The resulting pellets are then melted and converted to thin films using the compression molding machine. These films are used as oxygen absorbents in multilayered structures and containers.
- Particulate oxygen scavengers based on oxidizable polymers which can be used directly, i.e. without incorporation into the packaging material, and showing a high oxygen absorption rate and capacity, are not disclosed in the prior art.
- the object of the present invention is that of providing a particulate system based on an oxidizable polymer applicable as an efficient oxygen scavenger, which is active in the absence of moisture.
- the overall oxygen absorption capacity of such particles should be at least 100 ml_ O2 / (g active material).
- the oxygen absorption rate of the oxygen scavenger should be easily adjustable according to the requirements of a particular application and can for instance be at least 10 ml_ C>2/(g active materialx24 h). Such oxygen scavenging particles should not stick together or agglomerate and be easily pourable.
- Another object of the present invention is that of providing an appropriate process for manufacturing the above-described particulate oxygen scavenger.
- the invention provides oxygen scavenging particles comprising an oxidizable thermoplastic resin (A) and a transition metal compound, wherein the number average particle size dso of the particles is 20 pm -2000 pm, as determined by laser diffraction particle size analysis; the span of the particle size distribution (dgo-dioj/dso is more than 1.2, as determined by laser diffraction particle size analysis; the bulk density of the particles is at most 80% of the material density of the same particles.
- thermoplastic resin (A) is active oxygen absorbents with a high total oxygen absorption capacity. Their activity is independent of the water content. The oxygen absorption rate of such particles can be easily adjusted to the specific needs of the chosen application.
- the oxidizable thermoplastic resin (A) is preferably selected from the group consisting of polymers containing carbon-carbon double bonds, polyesters, polyamides or mixtures thereof.
- Suitable polyesters are for example polyglycolide or polyglycolic acid (PGA), polylactide acid (PLA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), Vectran.
- PGA polyglycolide or polyglycolic acid
- PLA polylactide acid
- PCL polycaprolactone
- PHA polyhydroxyalkanoate
- PB polyhydroxybutyrate
- PBS polyethylene adipate
- PBS polybutylene succinate
- PBT poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
- PET polyethylene terephthalate
- PA 6 Nylon polyamide 6
- PA 66 polyamide 66
- polyamide 6T produced by a co-polymerization of hexamethylenediamine and terephthalic acid, co-polymer of paraphenylenedi
- thermoplastic resin (A) used in the inventive oxygen scavenging particles preferably contains carbon-carbon double bonds, such as are present in alkenes, dienes or polyenes.
- carbon-carbon double bond in the context of the present invention does not include conjugated double bonds contained in an aromatic or heteroaromatic ring.
- the thermoplastic resin (A) preferably has carbon-carbon double bonds substantially in the main chain.
- the term “main chain” is referred to the polymer backbone, which is the longest single sequence of atoms present in the polymer.
- the term “substantially in the main chain” means in the context of the present invention that at least 90%, more preferably at least 95%, more preferably at least 98% of all polymer double bonds are present in the polymer main chain.
- Such polymer side chains of the thermoplastic resin (A) preferably contain substantially no double bonds.
- the thermoplastic resin (A) containing carbon-carbon double bonds substantially in the main chain usually shows a less intensive odour during and after its use as oxygen absorber.
- the amount of carbon-carbon double bonds contained in the thermoplastic resin (A) is preferably at least 0.001 mol/g resin, more preferably at least 0.005 mol/g resin, more preferably at least 0.01 mol/g resin.
- thermoplastic resin (A) can also be produced by ring-opening metathesis of a cyclic alkene (cycloalkene), having one, two or more double bonds, e.g. a cyclodiene, a cyclotriene etc.
- cycloalkene cyclic alkene having one, two or more double bonds
- Cycloalkene is preferably selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene, cycloocta-1, 5-diene, 1,5-dimethylcycloocta-1, 5-diene, cyclodecadiene, norbornadiene, cyclododeca-1,5,9-triene, trimethylcyclododeca-1 ,5,9-triene, norbornene (bicyclo[2.2.1]hept-2-ene), 5-(3'-cyclohexenyl)-2-norbornene, 5-ethyl-2-norbornene, 5- vinyl-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene and mixtures thereof.
- Cyclooctene is an outstanding cycloalkene because of its availability and ease of handling. It is preferable when the cycloalkene used for synthesis of the thermoplastic resin (A) comprises cyclooctene and particularly preferable when it consists of this monomer. Polyoctenamer produced by ring-opening metathesis of cyclooctene is e.g. manufactured under the name VISPARENT ® 8021 by Evonik Industries AG. It is also possible to use two or more cycloalkenes to form the thermoplastic resin (A).
- the cycloalkenes may be substituted with alkyl groups, aryl groups, alkoxy groups, carbonyl groups, alkoxycarbonyl groups and/or halogen atoms.
- Suitable catalysts for ring-opening metathesis of cycloalkenes are for example tungsten complexes (US3597406, US4095033, DE2619197), molybdenum complexes (EP0218138; Polymer 1995, 36, 2787-2796) and ruthenium complexes (J. Am. Chem.
- Ruthenium carbenes in particular are very widely applicable and tolerate all common chemical groups (EP0626402, US8324334, US2016/159942). Very particularly suitable are ruthenium- carbene complexes which, as one of their characteristic features, bear an N-heterocyclic carbene ligand.
- the thermoplastic resin (A) preferably has a weight-average molecular weight (Mw) of 5000 g/mol to 500 000 g/mol, preferably of 10 000 g/mol to 250 000 g/mol and more preferably of 20 000 to 200 000 g/mol.
- Mw weight-average molecular weight
- the molecular weight can be determined by means of Gel Permeation Chromatography (GPC) against a styrene standard. The measurement is based on DIN 55672-1.
- GPC Gel Permeation Chromatography
- the thermoplastic resin (A) can comprise a certain amount of oligomers, i.e. polymer molecules with a relatively low molecular weight, e.g. of less than 1000 g/mol. The presence of these oligomers may cause the oxygen scavenging particles to have an undesired odour. Therefore, the thermoplastic resin (A) preferably comprises less than 6%, more preferably less than 4%, more preferably less than 2%, more preferably less than 1 % by weight of the oligomers having a molecular weight of 1000 or less.
- the amount of oligomers having a molecular weight of 1000 or less can be reduced using the appropriate extraction techniques, for instance those described in WO 2018146236 A1 or WO 2017009411 A1 , or by other methods such as membrane techniques including diafiltration, as described e.g. in WO 2017060363 A1.
- the desired molecular weight may for example be established using at least one chain transfer agent in the ring-opening metathesis reaction, which allows chain growth to be terminated.
- Suitable chain transfer agents are known from the literature and include for example acyclic alkenes having one or more nonconjugated double bonds which may be terminal or internal and which preferably do not bear any substituents.
- Such compounds are, for example, pent-1-ene, hex-1 -ene, hept-1-ene, oct-1 -ene or pent-2-ene.
- Alkyl vinyl ethers do not fall within this definition as they are not usable as chain-transfer agents. The reason for this is that alkyl vinyl ethers deactivate the catalyst.
- employable as chain-transfer agents are cyclic compounds comprising a double bond in their side chain, for example vinylcyclohexene.
- the cis/trans ratio of the thermoplastic resin (A) can be adjusted by methods familiar to those skilled in the art. The ratio depends for example on used catalysts, solvents, stirring intensity, temperature or reaction time. It is preferable when the trans content of the thermoplastic resin (A) is at least 55%, preferably at least 70% and particularly preferably 75% to 85%.
- the cis/trans ratio can be determined by 1 H-NMR in deuterochloroform.
- thermoplastic resin (B) The thermoplastic resin (B)
- the oxygen scavenging particles according to the invention can further comprise a thermoplastic resin (B) other than the thermoplastic resin (A), the thermoplastic resin (B) preferably having an oxygen transmission rate (OTR) of higher than 80 ml_ C>2/(m 2 xdayxatm), more preferably higher than 150 ml_ C>2/(m 2 xdayxatm), more preferably higher than 300 ml_ C>2/(m 2 xdayxatm, more preferably higher than 500 ml_ C>2/(m 2 xdayxatm), more preferably higher than 1000 ml_ C>2/(m 2 xdayxatm), more preferably higher than 3000 ml_ C>2/(m 2 xdayxatm), more preferably higher than 5000 ml_ C>2/(m 2 xdayxatm).
- Oxygen transmission rate (OTR) is the amount of oxygen gas that passes through a substance film over a given period under standardized conditions (20 °C, 65% relative humidity).
- thermoplastic resin (B) with a relatively high OTR value can play the role of a suitable matrix polymer, which dilutes the active oxygen absorber thermoplastic resin (A) and facilitates the diffusion of oxygen through oxygen scavenging particles.
- a suitable matrix polymer which dilutes the active oxygen absorber thermoplastic resin (A) and facilitates the diffusion of oxygen through oxygen scavenging particles.
- the thermoplastic resin (B) can be selected from the group consisting of polyethylenes such as low-density polyethylene (LDPE), very-low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene (HDPE) and linear low-density polyethylene, polypropylene, polyesters, ethylene copolymers such as ethylene/vinyl acetate copolymers (EVA and VAE), ethylene/alkyl (meth)acrylate copolymers (EMA), ethylene/(meth)acrylic acid copolymers, ethylene/butyl acrylate (EBA) copolymers, ethylene/acrylic acid (EAA), polylactide, polyglycolide, ionomers, and mixtures thereof.
- polyethylenes such as low-density polyethylene (LDPE), very-low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene (HDPE) and linear low-density polyethylene, polyprop
- the oxygen scavenging particles according to the invention preferably comprise polymer blend comprising at least 5%, more preferably at least 10%, more preferably at least 20%, more preferably at least 25% by weight of the thermoplastic resin (A) and not more than 95 %, more preferably not more than 90 %, more preferably not more than 80 %, more preferably not more than 75 % by weight of the thermoplastic resin (B).
- the transition metal compound used in the oxygen scavenging particles according to the invention comprises a transition metal, which can be selected from the group consisting of iron, cobalt, nickel and manganese. Cobalt is particularly preferable.
- the term “transition metal compound” means in the context of the present invention any substance, comprising the transition metal chemically bound with at least one other chemical element. Thus, transition metal itself such as iron, cobalt, nickel or manganese is not a “transition metal compound” in the context of the invention, whereas e.g. a transition metal salt is.
- the suitable transition metal compound is preferably soluble in the molten thermoplastic resin (A) and/or in the polymer blend of the thermoplastic resins (A) and (B).
- soluble means in the context of the present invention that at least 0.001 %, more preferably at least 0.01%, more preferably at least 0.1% by weight (related to the polymer weight) of a transition metal compound can be dissolved in in the molten thermoplastic resin (A) and/or in the polymer blend of the thermoplastic resins (A) and (B).
- transition metal salts of carboxylic acids especially the carboxylic acids comprising 3-30 carbon atoms, such as e.g.
- linear, branched or cyclic pentanoic acid C5), hexanoic acid (C6), heptanoic acid (C7), octanoic acid (C8), nonanoic acid (C9), decanoic acid (D10), undecanoic acid (C11), dodecanoic acid (C12), tridecanoic acid (C13), tetradecanoic acid (C14), pentadecanoic acid (C15), hexadecanoic acid (C16), heprtadecanoic acid (C17), octadecanoic acid (C18), nonadecanoic acid (C19), icosanoic acid (C20), and the mixtures thereof.
- Particularly preferable as the transition metal compound is cobalt stearate.
- the transition metal compound is preferably well dispersed in the thermoplastic resin (A) and/or in the polymer blend of the thermoplastic resins (A) and (B) and shows an average particle size of not more than 1000 p , more preferably less than 500 pm, more preferably less than 300 pm, more preferably less than 200 pm, more preferably less than 100 pm
- the average particle size of such transition metal compound particles in the polymer matrix can be determined using transmission electron microscopy (TEM).
- TEM transmission electron microscopy
- the transition metal compound is preferably dispersed in the polymer blend comprising at least 10 % by weight of the thermoplastic resin (A) and not more than 90 % by weight of the thermoplastic resin (B).
- the oxygen scavenging particles of the invention have the number average particle size d5o of 20 pm -2000 pm, preferably 20 pm -1800 pm, more preferably 20 pm -1500 pm,
- a number average particle size dso of the particles can be determined according to ISO 13320:2009 by laser diffraction particle size analysis. The resulting measured particle size distribution is used to define the median dso, which reflects the particle size not exceeded by 50% of all particles, as the number average particle size.
- the dio and dso values can be determined according to ISO 13320:2009 by laser diffraction particle size analysis. The resulting measured particle size distribution is used to define the values dio and dgo, which reflects the particle size not exceeded by 10% or 90% of all particles, respectively.
- the span of the particle size distribution of the oxygen scavenging particles of the invention (dgo-dioj/dso is more than 1.2, preferably more than 1.3, more preferably more than 1.4, more preferably more than 1.5, more preferably more than 1.6, more preferably more than 1.7, more preferably more than 1.8, more preferably more than 1.9.
- the oxygen absorption rate of the oxygen scavenging particles of the invention can be adjusted according to the requirements of a particular application by choosing the appropriate particle size and/or particle size distribution.
- the oxygen absorption rate of the particles measured according to ASTM F 2714-08 can be at least 10 ml_ O2 / (g thermoplastic resin (A) c 24 h), more preferably at least 20 ml_ O2 / (g thermoplastic resin (A) c 24 h), more preferably at least 30 ml_ O2 / (g thermoplastic resin (A) c 24 h), more preferably at least 40 ml_ O2 / (g thermoplastic resin (A) c 24 h), more preferably at least 50 ml_ O2 / (g thermoplastic resin (A) c 24 h).
- Oxygen absorption can be determined according to ASTM F2714-08 “Standard test method for oxygen headspace analysis of packages using fluorescent decay”, e.g. at 23 °C, a 50% relative humidity and using a 250 ml_ headspace filled with air (initial oxygen concentration 21 vol%).
- the oxygen scavenging particles according to the invention usually possess a high total oxygen absorption capacity, i.e. the total amount of oxygen, which can be absorbed by the particles.
- the total oxygen absorption capacity of the oxygen scavenging particles of the invention is preferably at least 100 ml_ O2 / (g thermoplastic resin (A)), more preferably at least 150 ml_ O2 / (g thermoplastic resin (A)), more preferably at least 200 ml_ O2 / (g thermoplastic resin (A)), more preferably at least 250 ml_ O2 / (g thermoplastic resin (A)).
- the bulk density of the oxygen scavenging particles of the present invention is at most 80%, preferably at most 75%, more preferably at most 70%, more preferably at most 65%, more preferably at most 60% of the material density of the same particles.
- Bulk density also called apparent density, poured density or volumetric density, is defined as the mass of the particles of the material divided by the total volume they occupy.
- the total volume includes particle volume, inter-particle void volume, and internal pore volume. A substantial, measurable volume of many particles is usually used for determining the bulk density of particles.
- the material density is defined as the mass of the material divided by the total volume occupied by this material and does not include inter-particle void volume.
- the material density of e.g. a polymer moulding can be determined by dividing the mass of the moulding by its volume, which can be calculated from the known dimension of the moulding.
- the material density of e.g. the polymer particles can be determined in a similar way.
- the volume of the particles of the known mass in this case can be substituted by the volume of water or other liquid, which is displaced by the particles submerged into the liquid.
- the material density of the moulding can be measured, which is prepared by melting and solidifying the particles.
- the bulk density of the oxygen scavenging particles of the invention is preferably less than 0.70 g/cm 3 , more preferably less than 0.65 g/cm 3 , more preferably less than 0.60 g/cm 3 , more preferably less than 0.55 g/cm 3 , more preferably less than 0.50 g/cm 3 .
- the oxygen scavenging particles of the invention can further comprise particles with a BET surface area of at least 5 m 2 /g, more preferably at least 10 m 2 /g, more preferably at least 20 m 2 /g, more preferably at least 30 m 2 /g, more preferably at least 50 m 2 /g, which may further facilitate the oxygen absorption and diffusion in the oxygen scavenging particles.
- Such particles are preferably porous.
- the non-limiting examples of such particles are activated carbons, fumed silicas, zeolites. These particles can function as spacers between the oxygen scavenging particles of the invention and increase the overall oxygen absorption and flowability of the oxygen scavenging particles.
- Such particles may also additionally be odour-scavengers.
- the oxygen scavenging particles of the invention can further comprise an odour scavenging agent.
- odour scavenging agents includes physical adsorbents like activated carbons, zeolites, and chemical absorbents like amine compounds, hydrazine derivatives, urea derivatives, guanidine derivatives, both unsupported and supported on the suitable carriers.
- the oxygen scavenging particles according to the invention can comprise further oxidizable components, other than the oxidizable thermoplastic resin (A), for example such as iron powder.
- the oxygen scavenging particles according to the invention can further comprise one or more antioxidants or stabilizers in order to retard the degradation of the components during the further processing including compounding, moulding etc.
- Suitable stabilizers may be selected from the group of the sterically hindered phenols, for example 2,5-di- tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4,4’-thiobis(6-tert-butylphenol), 2,2’- methylenebis(4-methyl-6-tertbutylphenol), octadecyl 3-(3’,5’-di-tert-butyl-4’- hydroxyphenyl)propionate, 4,4’-thiobis-(6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2- hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,6-di(tert-
- the quantity thereof can be one that prevents the oxidation of the components of the particles during production and processing; however, the quantity thereof should advantageously be below that which adversely affects the oxygen scavenging activity of the particles.
- the quantity required can depend on the components present in the particles, on the specific antioxidant used, and on the nature of thermal processing used.
- the antioxidants are typically used in the amount from 0.01% to 1% by weight, related to the mass of the particles.
- additives that can be present in the inventive particles are fillers, pigments, colorants, processing aids, plasticizers, antifogging agents and antiblocking agents, without any restriction thereto.
- the invention further provides a process for producing oxygen scavenging particles according to the invention, comprising the following steps: a) melt extrusion of at least one component comprising a thermoplastic resin (A), a transition metal compound and optionally a thermoplastic resin (B) and breaking up the obtained extrudates into particles; b) optional crushing of the particles obtained in step a).
- step a) of the process at least one component comprising the thermoplastic resin (A), the transition metal compound and optionally the thermoplastic resin (B) is melt extruded and the obtained extrudates, which are typically cooled down by means of water, air or other cooling means, are broken up into particles (pellets), e.g. by cutting the extrudates.
- Step a) of the process can comprise one, two or more sequential melt extrusion steps.
- the masterbatch compound containing the transition metal and the thermoplastic resin (B) can contain 0.1% to 20%, preferably 0.5% to 15% by weight of the transition metal compound and can be further diluted by a further co-extrusion with the thermoplastic resin (B).
- Melt extrusion is the processing of polymeric materials above their melting in order to effect molecular level mixing of the components and to achieve the required shape.
- Step a) may be conducted by means of a mono-extrusion or a co-extrusion. Any suitable type of extruder can be employed in step b) of the process, e.g. a twin-screw extruder.
- the temperature during conducting of step a) of the process preferably does not exceed 240 °C, preferably is maintained in the range of from about 120°C to about 240°C, or in the range of from about 150°C to about 230°C, preferably in the range of from about 180°C to about 220°C. If the temperature exceeds this range, in particular the upper limit, there is a risk of discoloration and/or degradation of the material of the particles, as well as the presence of undesired burnt aromas.
- the lower limit is generally determined by the temperature at which the material can be suitably processed, in the form of a melt.
- the pressure during conducting of step a) of the process is preferably maintained in the range of from about 5 bar to about 80 bar, or in the range of from about 10 bar to about 50 bar, preferably in the range of from about 15 bar to about 40 bar.
- the preferred average residence time during the extrusion step a) of the process may vary in a broad range, e.g. be from 0.01 minutes to 30 minutes, more preferably from 0.05 minutes to 20 minutes, more preferably from 0.1 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes.
- Particle size of the particles obtained in step a) of the process depend on the type of the die used in the extruder. If a smaller particle size is required, the particles obtained in step a) of the process can further be crushed in optional step b) of the process using any suitable means, e.g. grinding or milling. Cryogenic grinding is a particularly preferable type of crushing applied in step b) of the process.
- Cryogenic grinding also known as freezer milling, freezer grinding, and cryomilling, is the act of cooling or chilling a material and then reducing it into a small particle size.
- the oxygen scavenging particles according to the invention can be used as oxygen scavenger, particularly for preserving food products, beverages, pharmaceuticals, medical products, cosmetics, metal products, and electronic products from oxidation.
- the oxygen scavenging particles of the invention can generally be used as oxygen scavenger in the temperature range from -20°C to 100°C, preferably from 0°C to 50°C, more preferably from 4°C to 30°C.
- the oxygen absorption rate increases with increasing temperature. Therefore, the quantity of the employed oxygen scavenger may be increased in order to efficiently use it at lower temperatures.
- the invention further provides a container comprising the oxygen scavenging particles according to the invention.
- container means in the context of the present invention any object for holding goods, such as bags, boxes, bottles, cans and other packaging types.
- the oxygen scavenging particles can be placed inside of such containers and can be used instead of or additionally to other means for preservation of the corresponding goods against the oxidation, such as oxygen barrier layers or coatings.
- Polymers usually used as passive oxygen barrier layer include polyethylenes, for example low-density polyethylene, very low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene and linear low-density polyethylene, polyesters, for example polyethylene terephthalate (PET) or polyethylene naphthenate (PEN); polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); polycaprolactone polymers and ethylene copolymers, for example ethylene/vinyl acetate copolymers (EVA and VAE), ethylene/alkyl (meth)acrylate copolymers (EMA), ethylene/vinyl alcohol copolymers (EVOH), poly(vinyl alcohol) (PVOH), ethylene/(meth)acrylic acid copolymers, ethylene/butyl acrylate (EBA) copolymers, ethylene/vinyl alcohol, ethylene/acrylic acid (EAA), polylactide, ionomers
- poly(ethylene/vinyl alcohol) EVOH
- poly(vinyl alcohol) PVOH
- polyethylene terephthalate PET
- polyamides for example polycaprolactam (nylon-6), metaxylyleneadipamide (MXD6), hexamethyleneadipamide (nylon-6,6) and various amide copolymers.
- the invention further comprises a sachet comprising the oxygen scavenger particles of the invention.
- the term “sachet” means in the context of the present invention any bag, packet, pouch or package holding its content, i.e. the oxygen scavenging particles together.
- the inventive sachet can be a constituent of the container according to the invention.
- the inventive sachet can be covered by an odour-protecting layer, which prevents the migration of unpleasantly smelling components of the oxygen scavenger particles outside the sachet but is permeable for oxygen.
- odour-protecting layers are described e.g. in WO1998012250A1. Examples
- Oxygen absorption was determined according to ASTM F2714-08 “Standard test method for oxygen headspace analysis of packages using fluorescent decay” at 23 °C, 50% relative humidity and using a 250 ml_ headspace filled with air (initial oxygen concentration 21 vol%). The results are summarized in Table 1. Table 1 Oxygen absorption experiments
- the results of the oxygen absorption experiments summarized in Table 1 show that the relatively big oxygen scavenging particles from the comparative example 1 achieve only a low oxygen absorption rate and are therefore not suitable for oxygen absorption applications.
- the cryogenically grinded particles prepared in example 1, on the contrary, show a very high rate of oxygen absorption.
- the rate of oxygen absorption depends on the quantity of the oxygen scavenging material applied in relation to the amount of oxygen available.
- the last line of Table 1 shows that sufficient quantity of oxygen scavenging particles can lead to the complete and fast absorption of all oxygen available in the container.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
L'invention concerne des particules désoxygénantes comprenant une résine thermoplastique oxydable (A) et un composé de métal de transition, la taille de particule moyenne en nombre d50 des particules étant de 20 µm à 2000 µm, l'étendue de la distribution granulométrique (d90-d10)/d50 étant supérieur à 1,2, la densité apparente des particules représentant au plus 80 % de la densité de matière desdites particules. L'invention concerne également la préparation de telles particules et leur utilisation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20160926 | 2020-03-04 | ||
EP20160926.0 | 2020-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021175617A1 true WO2021175617A1 (fr) | 2021-09-10 |
Family
ID=69770619
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2021/054145 WO2021175617A1 (fr) | 2020-03-04 | 2021-02-19 | Particules polymères désoxygénantes |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2021175617A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220403160A1 (en) * | 2021-06-22 | 2022-12-22 | Huizhou Northern Forest Co., Ltd. | Flame retardant and fully biodegradable plastic, manufacturing method of the same, and application of the same |
Citations (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3597406A (en) | 1969-04-30 | 1971-08-03 | Goodyear Tire & Rubber | Polymers of hydrocarbon substituted 1,5-cyclooctadienes and methods for their polymerization |
DE2619197A1 (de) | 1976-04-30 | 1977-11-17 | Huels Chemische Werke Ag | Verfahren zur polymerisation von cis,cis-cyclooctadien-(1,5) |
US4095033A (en) | 1976-04-01 | 1978-06-13 | Chemische Werke Huels Aktiengesellschaft | Process for the polymerization of cycloolefins |
EP0218138A1 (fr) | 1985-09-25 | 1987-04-15 | Massachusetts Institute Of Technology | Catalyseurs, leur procédé de production et leur utilisation pour la métathèse des oléfines |
US5089323A (en) | 1988-11-24 | 1992-02-18 | Sumitomo Chemical Co., Ltd. | Oxygen absorbing sheet |
US5116660A (en) | 1988-09-08 | 1992-05-26 | Mitsubishi Gas Chemical Company, Inc. | Deoxidizer film |
US5143769A (en) | 1988-09-22 | 1992-09-01 | Mitsubishi Gas Chemical Company, Inc. | Deoxidizer sheet |
US5153038A (en) | 1988-04-30 | 1992-10-06 | Toyo Seikan Kaisha, Ltd. | Plastic multi-layer vessel |
EP0626402A2 (fr) | 1993-05-27 | 1994-11-30 | Amoco Corporation | Procédé de préparation de polymères linéaires monofonctionnels et difonctionnels téléchéliques et compositions ainsi obtenues |
US5399289A (en) | 1992-10-01 | 1995-03-21 | W. R. Grace & Co.-Conn. | Compositions, articles and methods for scavenging oxygen which have improved physical properties |
WO1998012250A1 (fr) | 1996-09-18 | 1998-03-26 | Cryovac, Inc. | Polymere a teneur en acide lactique pour article desoxygenant |
EP1033080A2 (fr) | 1999-03-03 | 2000-09-06 | Kuraray Co., Ltd. | Composition de résine absorbant l'oxygène |
JP2004123970A (ja) | 2002-10-04 | 2004-04-22 | Toyo Seikan Kaisha Ltd | 酸素吸収樹脂ペレット、その製法及びこのペレットを用いた多層容器の製法 |
EP1464482A1 (fr) | 2001-12-25 | 2004-10-06 | Toyo Seikan Kaisya, Ltd. | Appareil de levage electrique |
EP1538176A1 (fr) | 2003-12-03 | 2005-06-08 | Kuraray Co., Ltd. | Composition absorbante pour l'oxygène |
JP2008201431A (ja) * | 2007-02-19 | 2008-09-04 | Kuraray Co Ltd | 発酵食品包装用包装材および包装体 |
EP2017308A1 (fr) | 2006-04-28 | 2009-01-21 | Kuraray Co., Ltd. | Composition de resine absorbant l'oxygene |
JP2010180389A (ja) | 2009-02-09 | 2010-08-19 | Kuraray Co Ltd | 酸素吸収性多層ペレット |
JP2011178140A (ja) * | 2010-03-04 | 2011-09-15 | Kuraray Co Ltd | 多層容器 |
US8324334B2 (en) | 2008-08-21 | 2012-12-04 | Materia, Inc. | Telechelic olefin metathesis polymers from renewable feedstocks |
JP2014012779A (ja) * | 2012-07-05 | 2014-01-23 | Kuraray Co Ltd | 酸素吸収性樹脂組成物およびそれを用いた包装材 |
US20160159942A1 (en) | 2013-07-23 | 2016-06-09 | Bostik Sa | Hydrocarbon-based polymers bearing an alkoxysilane end group |
WO2017009411A1 (fr) | 2015-07-14 | 2017-01-19 | Evonik Degussa Gmbh | Procédé de préparation de poly-alcénamères pour des applications d'emballage |
WO2017060363A1 (fr) | 2015-10-07 | 2017-04-13 | Evonik Degussa Gmbh | Procédé de préparation de poly-alcénamères pour des applications d'emballage |
WO2018146236A1 (fr) | 2017-02-10 | 2018-08-16 | Evonik Degussa Gmbh | Procédé de préparation de polyalcénamères pour des applications d'emballage |
-
2021
- 2021-02-19 WO PCT/EP2021/054145 patent/WO2021175617A1/fr active Application Filing
Patent Citations (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3597406A (en) | 1969-04-30 | 1971-08-03 | Goodyear Tire & Rubber | Polymers of hydrocarbon substituted 1,5-cyclooctadienes and methods for their polymerization |
US4095033A (en) | 1976-04-01 | 1978-06-13 | Chemische Werke Huels Aktiengesellschaft | Process for the polymerization of cycloolefins |
DE2619197A1 (de) | 1976-04-30 | 1977-11-17 | Huels Chemische Werke Ag | Verfahren zur polymerisation von cis,cis-cyclooctadien-(1,5) |
EP0218138A1 (fr) | 1985-09-25 | 1987-04-15 | Massachusetts Institute Of Technology | Catalyseurs, leur procédé de production et leur utilisation pour la métathèse des oléfines |
US5153038A (en) | 1988-04-30 | 1992-10-06 | Toyo Seikan Kaisha, Ltd. | Plastic multi-layer vessel |
US5116660A (en) | 1988-09-08 | 1992-05-26 | Mitsubishi Gas Chemical Company, Inc. | Deoxidizer film |
US5143769A (en) | 1988-09-22 | 1992-09-01 | Mitsubishi Gas Chemical Company, Inc. | Deoxidizer sheet |
US5089323A (en) | 1988-11-24 | 1992-02-18 | Sumitomo Chemical Co., Ltd. | Oxygen absorbing sheet |
US5399289A (en) | 1992-10-01 | 1995-03-21 | W. R. Grace & Co.-Conn. | Compositions, articles and methods for scavenging oxygen which have improved physical properties |
EP0626402A2 (fr) | 1993-05-27 | 1994-11-30 | Amoco Corporation | Procédé de préparation de polymères linéaires monofonctionnels et difonctionnels téléchéliques et compositions ainsi obtenues |
WO1998012250A1 (fr) | 1996-09-18 | 1998-03-26 | Cryovac, Inc. | Polymere a teneur en acide lactique pour article desoxygenant |
EP1033080A2 (fr) | 1999-03-03 | 2000-09-06 | Kuraray Co., Ltd. | Composition de résine absorbant l'oxygène |
EP1464482A1 (fr) | 2001-12-25 | 2004-10-06 | Toyo Seikan Kaisya, Ltd. | Appareil de levage electrique |
JP2004123970A (ja) | 2002-10-04 | 2004-04-22 | Toyo Seikan Kaisha Ltd | 酸素吸収樹脂ペレット、その製法及びこのペレットを用いた多層容器の製法 |
EP1538176A1 (fr) | 2003-12-03 | 2005-06-08 | Kuraray Co., Ltd. | Composition absorbante pour l'oxygène |
EP2017308A1 (fr) | 2006-04-28 | 2009-01-21 | Kuraray Co., Ltd. | Composition de resine absorbant l'oxygene |
JP2008201431A (ja) * | 2007-02-19 | 2008-09-04 | Kuraray Co Ltd | 発酵食品包装用包装材および包装体 |
US8324334B2 (en) | 2008-08-21 | 2012-12-04 | Materia, Inc. | Telechelic olefin metathesis polymers from renewable feedstocks |
JP2010180389A (ja) | 2009-02-09 | 2010-08-19 | Kuraray Co Ltd | 酸素吸収性多層ペレット |
JP2011178140A (ja) * | 2010-03-04 | 2011-09-15 | Kuraray Co Ltd | 多層容器 |
JP2014012779A (ja) * | 2012-07-05 | 2014-01-23 | Kuraray Co Ltd | 酸素吸収性樹脂組成物およびそれを用いた包装材 |
US20160159942A1 (en) | 2013-07-23 | 2016-06-09 | Bostik Sa | Hydrocarbon-based polymers bearing an alkoxysilane end group |
WO2017009411A1 (fr) | 2015-07-14 | 2017-01-19 | Evonik Degussa Gmbh | Procédé de préparation de poly-alcénamères pour des applications d'emballage |
WO2017060363A1 (fr) | 2015-10-07 | 2017-04-13 | Evonik Degussa Gmbh | Procédé de préparation de poly-alcénamères pour des applications d'emballage |
WO2018146236A1 (fr) | 2017-02-10 | 2018-08-16 | Evonik Degussa Gmbh | Procédé de préparation de polyalcénamères pour des applications d'emballage |
Non-Patent Citations (6)
Title |
---|
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 15 September 2011 (2011-09-15), KATAOKA, NAOKI ET AL: "Multilayer containers having oxygen-absorbing layers and gas-barrier layers and laminates for them", XP002799925, retrieved from STN Database accession no. 2011:1159416 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 23 January 2014 (2014-01-23), SHIMIZU, HIROSHI ET AL: "Oxygen-absorbing resin compositions with no generation of odors by oxygen absorption and packaging materials therewith", XP002799924, retrieved from STN Database accession no. 2014:102127 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 4 September 2008 (2008-09-04), KUROSAKI, KAZUHIRO ET AL: "Packaging materials with selective gas permeability and fermented food packages using them", XP002799927, retrieved from STN Database accession no. 2008:1068147 * |
J. AM. CHEM. SOC., vol. 115, 1993, pages 9858 - 9859 |
MACROMOLECULES, vol. 26, 1993, pages 4739 - 4741 |
POLYMER, vol. 36, 1995, pages 2787 - 2796 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220403160A1 (en) * | 2021-06-22 | 2022-12-22 | Huizhou Northern Forest Co., Ltd. | Flame retardant and fully biodegradable plastic, manufacturing method of the same, and application of the same |
US11976192B2 (en) * | 2021-06-22 | 2024-05-07 | Huizhou Northern Forest Co., Ltd. | Flame retardant and fully biodegradable plastic, manufacturing method of the same, and application of the same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1871836B1 (fr) | Polymeres desoxygenants | |
US5700554A (en) | Packaging articles suitable for scavenging oxygen | |
US7186464B2 (en) | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers | |
EP0507207B1 (fr) | Compositions, articles et méthodes pour l'élimination d'oxygène | |
JP3218040B2 (ja) | 低温において使用するための改良されたフイルムの形態の酸素掃去組成物、該組成物を含む多層構造体並びに該組成物を使用する方法 | |
JP4852214B2 (ja) | 酸素遮断性重合体と酸素脱ガス重合体との親和性ブレンドシステム | |
AU2013256532B2 (en) | Oxygen scavenging compositions | |
US8182888B2 (en) | Oxygen scavenging polymers | |
AU2013256532A1 (en) | Oxygen scavenging compositions | |
US7052628B2 (en) | Transition metal carboxylates as catalysts for oxygen scavenging | |
US7022258B2 (en) | Oxygen scavenging compositions comprising polymers derived from benzenedimethanol monomers | |
WO2021175617A1 (fr) | Particules polymères désoxygénantes | |
US7247390B1 (en) | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers | |
US11345534B2 (en) | Oxygen scavenging compositions, articles containing same, and methods of their use | |
EP2188231A1 (fr) | Composition piégeant l'oxygène | |
EP1890875A2 (fr) | Film multicouche piégeant l'oxygène |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21705557 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21705557 Country of ref document: EP Kind code of ref document: A1 |