CN101426858A - 树脂配合用氧气吸收剂及其制备方法 - Google Patents
树脂配合用氧气吸收剂及其制备方法 Download PDFInfo
- Publication number
- CN101426858A CN101426858A CNA2007800138490A CN200780013849A CN101426858A CN 101426858 A CN101426858 A CN 101426858A CN A2007800138490 A CNA2007800138490 A CN A2007800138490A CN 200780013849 A CN200780013849 A CN 200780013849A CN 101426858 A CN101426858 A CN 101426858A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- oxygen absorber
- resin
- absorber
- iron powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 129
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 129
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 88
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 238000013329 compounding Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 14
- 150000005309 metal halides Chemical class 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 13
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910020679 Co—K Inorganic materials 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 33
- 239000002245 particle Substances 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 239000011362 coarse particle Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 238000010521 absorption reaction Methods 0.000 description 25
- -1 hydrated barta Chemical compound 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 238000007669 thermal treatment Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 150000002926 oxygen Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003595 mist Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920000554 ionomer Polymers 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004840 adhesive resin Substances 0.000 description 4
- 229920006223 adhesive resin Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229940045511 barium chloride Drugs 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- COLRBPHEBSHUAG-UHFFFAOYSA-L disodium bromide chloride Chemical compound [Na+].[Na+].[Cl-].[Br-] COLRBPHEBSHUAG-UHFFFAOYSA-L 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940094035 potassium bromide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
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- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
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Abstract
本发明涉及一种树脂配合用氧气吸收剂,其为含有铁粉、金属卤化物和碱性物质的混合粉末,其中,前述混合粉末通过粉末X射线衍射法测定的(110)面的峰的半宽度为0.20°/2θ(Co-Kα)以下,比表面积为0.5m2/g以上,且平均粒径为1~40μm。由此本发明的氧气吸收剂具有如下的特征:可以有效抑制氢气的产生,具有优异的安全性,并且具有优异的氧气吸收性能,且由于可抑制氧气吸收剂制备工序中粗大颗粒的产生而具有高生产率。另外,具有由含有本发明的树脂配合用氧气吸收剂的氧气吸收性树脂组合物制成的层的氧气吸收性容器有如下性能:内容物的保存性优异,并且表面凹凸少且外观特性优异,没有由于氢气产生而导致容器膨胀或破裂的危险。
Description
技术领域
本发明涉及树脂配合用氧气吸收剂及其制备方法,更具体地说,本发明涉及有效抑制伴随氧气吸收反应的氢气的产生,并且具有优异的氧气吸收性、安全性和外观特性的树脂配合用氧气吸收剂及其制备方法。
背景技术
以往使用金属罐、玻璃瓶、各种塑料容器等作为包装容器,但从重量轻、抗冲击性、尤其成本的观点来看,塑料容器被用到各种用途中。
然而,在金属罐和玻璃瓶中,通过容器壁的氧气透过为零,与此相对,在塑料容器的情况下,通过器壁的氧气透过的量为不能忽视的程度,这样,在内容物的保存性方面成为问题。
为了提高包装容器的内容物的保存性,使用如下的容器:将防止来自外部的氧气透过的气体阻隔性树脂与尽量捕集容器内残留氧气的氧气吸收性材料组合的容器。
在通常用作氧气吸收性材料的铁系氧气吸收剂的氧气吸收反应中,水分的存在是必需的,所述铁与水分反应而产生氢气,所产生的氢气有可能使包装体产生凹凸或者导致包装体膨胀或破裂。
作为抑制氧气吸收剂产生氢气的方法,已经有人提出了各种现有技术。例如,日本特开2000-248111号公报中提出了在氧气吸收剂中添加水难溶性的碱性物质的方法,另外,日本特开2000-279147号公报中提出了对氧气吸收剂实施热处理的方法等。
发明内容
然而,用上述专利文献1和2中所记载的氧气吸收剂,难以充分抑制氢气的产生,如果为了充分抑制氢气产生量而进行过度的处理,就会有氧气吸收性能降低的问题。此外,专利文献2中所记载的方法具有氧气吸收剂在热处理时烧结且生成大量的粗大颗粒的问题。尤其,在应用于薄膜、薄壁容器的情况下,该粗大颗粒成为外观不良的原因,因此需要通过分级操作来除去,当粗大颗粒量大的情况下,成品率降低且生产率恶化。
因此,本发明的目的是提供树脂配合用氧气吸收剂,该树脂配合用氧气吸收剂能够有效抑制氢气的产生,且具有优异的氧气吸收性能和外观特性,并且具有高的生产率。
本发明的另一个目的是提供制备所述树脂配合用氧气吸收剂的方法和氧气吸收性容器,其中,所述氧气吸收性容器由含有所述树脂配合用氧气吸收剂的氧气吸收性树脂组合物制成,并且内容物保存性和外观特性优异。
根据本发明,提供了一种树脂配合用氧气吸收剂,其特征在于,其为含有铁粉、金属卤化物和碱性物质的混合粉末,其中,前述混合粉末通过粉末X射线衍射法测定的(110)面的峰的半宽度为0.20°/2θ(Co-Kα)以下,比表面积为0.5m2/g以上,且平均粒径为1~40μm。
本发明的树脂配合用氧气吸收剂优选具有下列特征:
1、铁粉表面被氧化铁覆盖,铁粉中的金属铁含量为60~85重量%;
2、铁粉中的金属铁量由于在氧气存在下的热处理而降低;
3、碱性物质为氢氧化钙或者氧化钙;
4、相对于100重量份铁粉,碱性物质以0.5~2重量份的量配合。
根据本发明,还提供了含有上述树脂配合用氧气吸收剂的氧气吸收性树脂组合物。
根据本发明,进一步提供了含有上述氧气吸收性树脂组合物的氧气吸收性容器。
根据本发明,进一步还提供了树脂配合用氧气吸收剂的制备方法,其特征在于,将铁粉、金属卤化物和碱性物质混合和粉碎,然后在氧气存在下进行热处理。
本发明的树脂配合用氧气吸收剂具有如下特征:可以有效抑制氢气的产生,具有优异的安全性,且具有优异的氧气吸收性能,而且由于可抑制氧气吸收剂制备工序中的粗大颗粒的产生,所以具有高的生产率。
另外,具有由含有本发明的树脂配合用氧气吸收剂的氧气吸收性树脂组合物制成的层的氧气吸收性容器有如下性能:内容物的保存性优异,且表面凹凸少、外观特性优异,没有由于氢气的产生而导致容器膨胀或破裂的危险。
如前述,作为抑制氢气产生的方法中所采用的氧气吸收剂,以往已知由含有铁粉、金属卤化物和碱性物质的混合粉末制成,然而,在本发明中发现,在这种组成的氧气吸收剂中,尤其混合粉末通过粉末X射线衍射法测定的(110)面的峰的半宽度为0.20°/2θ(Co-Kα)以下,比表面积为0.5m2/g以上,且平均粒径为1~40μm,由此抑制氢气产生的效果和氧气吸收性能两者可明显优于以往的氧气吸收剂。
本发明的通过粉末X射线衍射法测定的(110)面的峰表示铁粉晶体的峰,该(110)面的峰的半宽度大时,意味着铁粉的晶格畸变大。在本发明的氧气吸收剂中,由于所述(110)面的峰的半宽度小,为0.20°/2θ(Co-Kα)以下,由此认为,铁粉的晶格畸变小。
本发明发现了该铁粉的晶格畸变影响了氧气吸收反应中的氢气的产生。也就是说,如从后述的实施例的结果所看到的,除了(110)面的峰的半宽度大于0.20°/2θ(Co-Kα)以外,与实施例1同样的氧气吸收剂(比较例5)产生大量氢气,不能满足抑制氢气产生的效果,因此可以认识到,(110)面的峰的半宽度为0.20°/2θ(Co-Kα)以下对于抑制氢气产生的效果是临界性的。
另外,在本发明的树脂配合用氧气吸收剂中,比表面积(BET比表面积)为0.5m2/g以上,尤其1.0m2/g以上,在氧气吸收能力方面是重要的。氧气吸收剂的比表面积与氧气吸收性能密切相关。由于比表面积不足0.5m2/g的氧气吸收剂不能获得充分的氧气吸收速度,所以在应用于容器的情况下,内容物保存性能变差。进一步,平均粒径(中值粒径)在1~40μm,尤其在5~30μm范围内,从良好保持所使用的薄膜、容器的外观特性的观点来看是重要的。在平均粒径为40μm以上的情况下,尤其为薄膜、薄壁容器时,在容器表面产生凹凸,有损害外观或者产生密封不良的情况,另外有不能获得充分的氧气吸收性能的情况。另外,在平均粒径为1μm以下的情况下,由于作业中的粉末形成或氧化导致自发放热,进而粉尘爆炸的危险性增高,所以可操作性极度降低。
如后述,本发明的树脂配合用氧气吸收剂由于将铁粉、金属卤化物和碱性物质的混合粉末在氧气存在下进行热处理,因此铁粉表面被氧化铁覆盖,铁粉中的金属铁量降低。尤其,在本发明中,铁粉中的金属铁含量适宜为60~85重量%。像这样铁粉表面被氧化铁覆盖,由此认为产生氢气的反应被钝化,氢气的产生量得到抑制。虽然担心铁粉表面氧化会导致氧气吸收性能降低,但通过控制氧化程度,使得铁粉中的金属铁含量为60~85质量%,可以抑制氧气吸收性能的降低,维持高的氧气吸收性能。
附图说明
图1是示出了本发明的氧气吸收性容器的一个实例的截面结构的图。
具体实施方式
(原材料)
作为可以在本发明的氧气吸收剂中使用的铁粉,可以使用还原铁粉、雾化铁粉、电解铁粉、羰基铁粉等公知的铁粉,其中,可以优选使用多孔质且具有较大比表面积的还原铁粉,尤其为旋转式还原铁粉(rotary reduced iron powder)。因旋转式还原铁粉具有高纯度、大的比表面积,所以具有优异的氧气吸收性能。
作为本发明的氧气吸收剂中使用的金属卤化物,可以列举碱金属、碱土金属或其它铜、锌、铁等的卤化物,具体地说,可列举氯化钠,溴化钠,碘化钠,氯化钾,溴化钾,碘化钾,氯化钙,氯化镁和氯化钡等。但在本发明中,尤其优选使用氯化钠。
相对于100重量份作为氧气吸收剂的主组分的铁粉,金属卤化物优选以0.1~10重量份,尤其优选以1~5重量份的量配合。如果金属卤化物的量少于上述范围,则难以获得预期的氧气吸收性能;另一方面,如果金属卤化物的量超过上述范围,则由于氧气吸收剂中铁粉的配合比率降低而可能导致性能降低,并且金属卤化物有可能从由配合氧气吸收剂的树脂组合物制成的包装体中渗出,可能给外观、内容物等带来恶性影响。
作为本发明中使用的碱性物质,例如,可以列举氢氧化镁、氢氧化钙、氢氧化锶、氢氧化钡、碳酸镁、碳酸钙、碳酸锶、碳酸钡等。但在本发明中,尤其优选使用氢氧化钙或者氢氧化钙的脱水物即氧化钙。
相对于100重量份铁粉,碱性物质优选以0.5~2重量份,尤其优选以1~2重量份的量配合。如果碱性物质的量低于上述范围,则抑制氢气产生的效果低于碱性物质的量在上述范围内的情况,另一方面,如果碱性物质的量超过上述范围,氧气吸收性能低于碱性物质的量在上述范围内的情况。
(制备方法)
本发明的树脂配合用氧气吸收剂大致按下述方式制备。
根据需要,将使用的旋转式还原铁粉粗粉碎为40~100μm的平均粒径,然后,在该铁粉中添加规定量的金属卤化物和碱性物质并混合,同时将该混合物微粉碎为1~40μm的平均粒径。此时,机械的混合和粉碎导致在铁粉中产生晶格畸变,但在本发明中通过后述热处理缓和了晶格畸变。
混合和粉碎可采用振动式磨机、球磨机、管式磨机或高速混合器等目前公知的装置。另外,可以采用粉碎和混合不同时进行,将含有金属卤化物和碱性物质的溶液喷雾于制成适当粒度的铁粉的表面上并覆盖该铁粉的方法。
接着,将该微粉碎物分级,以除去粒径大于90μm的粗大颗粒,然后,进行热处理。分级操作可以通过筛分、气动分级等方式来进行。热处理可缓和由于上述混合和粉碎所产生的晶格畸变,并且在铁粉表面上形成氧化铁,但由于铁粉中的金属含量适宜为60~85重量%,所以优选是将在氧气(空气)的存在下的热处理与在惰性气体氛围下、优选氮气氛围下的热处理结合进行。
具体地说,优选的是,在氧气的存在下进行热处理,并且在前述工序之前和/或之后在氮气氛围下进行热处理。在氧气氛围下的优选的热处理温度为400~600℃,更优选为500~550℃,优选的热处理时间为2~12小时,更优选为4~10小时。在氮气氛围下的优选热处理温度为400~600℃,更优选为500~550℃,优选的热处理时间为0~6小时,更优选为0~2小时。
由此可以充分缓和由混合和粉碎所造成的铁粉的晶格畸变,并且可以在铁粉表面形成氧化铁,并使铁粉中的金属含量在上述范围内,从而不会损害铁粉所具有的氧气吸收性能,还可以抑制氢气的产生。
在该热处理时,存在于微粉碎物中的碱性物质抑制了由于微粉碎物的烧结所造成的粗大颗粒化。粒径大于90μm的粗大颗粒通过热处理后的分级可以除去,但从后述实施例的结果可以看出,与在微粉碎物中不含碱性物质的比较例2和3相比,在微粉碎物中包含氢氧化钙的实施例1和2的分级所除去的粗大颗粒量更少。也就是说,通过在碱性物质的存在下进行热处理,可以改善成品率的降低,提高生产率。
(氧气吸收性树脂组合物)
本发明的氧气吸收性树脂组合物可以通过将上述树脂配合用氧气吸收剂与树脂配合并混合来获得。混合可以是熔融共混、干混的任一个,在配合少量的氧气吸收剂的情况下,优选制备含有高浓度氧气吸收剂的母料,然后将该母料混合到树脂中。
对可与本发明的氧气吸收剂配合的树脂没有限制,可以配合以往包装材料所用的热塑性树脂。具体地说,本发明的氧气吸收剂可以与下列树脂配合:烯烃系树脂,例如低、中或高密度聚乙烯,聚丙烯,乙烯-丙烯共聚物,聚1-丁烯,乙烯-1-丁烯共聚物,丙烯-1-丁烯共聚物,乙烯-丙烯-1-丁烯共聚物,聚甲基-1-戊烯,乙烯-醋酸乙烯共聚物,乙烯-(甲基)丙烯酸共聚物,离子交联烯烃共聚物(离聚物),乙烯-乙烯醇共聚物或它们的共混物等;苯乙烯系树脂,例如聚苯乙烯,苯乙烯-丁二烯共聚物,苯乙烯-异戊二烯共聚物、ABS树脂等;聚酯,例如聚对苯二甲酸乙二醇酯,聚萘二甲酸乙二醇酯,聚对苯二甲酸四亚甲基二醇酯,二醇改性的聚对苯二甲酸乙二醇酯,聚乳酸,聚丁二酸丁二醇酯等;聚酰胺,例如尼龙6,尼龙66等;聚碳酸酯等。
相对于每100重量份这些树脂,本发明的氧气吸收剂的配合量优选为1~100重量份,尤其优选为5~70重量份的范围。如果氧气吸收剂的配合量少于上述范围,则不能获得预期的氧气吸收性能;另一方面,如果超过上述范围,则成型性、作为包装体的特性有可能降低。
(氧气吸收性容器)
本发明的氧气吸收性容器优选具有多层结构,该多层结构含有由配合了上述氧气吸收剂的氧气吸收性树脂组合物制成的层,尤其优选是由氧气吸收性树脂组合物制成的层作为中间层的多层容器。
图1是示出本发明的氧气吸收性容器的一个实例的截面结构的图,从外层侧依次包括含有二氧化钛的聚丙烯外层1、粘合剂树脂层2a、气体阻隔性树脂层3、粘合剂树脂层2b、氧气吸收性树脂层4、含有二氧化钛的聚丙烯内层5。在该具体实例中,在外层1和内层5中含有二氧化钛,由于氧气吸收性树脂层4中的铁粉,着色被掩盖,并且通过在外层侧形成气体阻隔层,可以有效地防止氧气从外部透过,并与氧气吸收性树脂层相互依赖,内容物的保存性优异。
对构成内层和外层的树脂没有限制,可以列举以下树脂:烯烃系树脂,例如低、中或高密度聚乙烯,聚丙烯,乙烯-丙烯共聚物,聚1-丁烯,乙烯-1-丁烯共聚物,丙烯-1-丁烯共聚物,乙烯-丙烯-1-丁烯共聚物,聚甲基-1-戊烯,乙烯-醋酸乙烯共聚物,乙烯-(甲基)丙烯酸共聚物,离子交联烯烃共聚物(离聚物)或者它们的共混物等;苯乙烯系树脂,例如聚苯乙烯,苯乙烯-丁二烯共聚物,苯乙烯-异戊二烯共聚物、ABS树脂等;聚酯,例如聚对苯二甲酸乙二醇酯,聚萘二甲酸乙二醇酯,聚对苯二甲酸四亚甲基二醇酯,二醇改性的聚对苯二甲酸乙二醇酯,聚乳酸、聚丁二酸丁二醇酯等;聚酰胺,例如尼龙6,尼龙66等;聚碳酸酯等。
另外,在层压时,可以使用粘合剂树脂,对该粘合剂树脂没有限制,可以使用乙烯-丙烯酸共聚物,离子交联烯烃共聚物,马来酸酐接枝的聚乙烯,马来酸酐接枝的聚丙烯,丙烯酸接枝的聚烯烃,乙烯-醋酸乙烯共聚物,共聚聚酯,共聚聚酰胺等,它们可以单独使用1种,或者将2种以上组合使用。
作为构成气体阻隔层的树脂,可以使用乙烯-乙烯醇共聚物、尼龙MXD6、聚乙醇酸等气体阻隔性树脂。尤其在薄膜容器的情况下,可以进一步优选使用铝箔和金属箔如钢箔,薄的无机薄膜沉积膜,通过将聚乙烯醇、聚丙烯酸系等气体阻隔性材料涂布于基材薄膜上所形成的气体阻隔性涂膜。
在该多层容器中,由本发明的氧气吸收性树脂组合物制成的层通常优选为5~300μm,尤其优选为10~100μm的范围,另一方面,内层和外层通常优选为5~1000μm,尤其优选为10~500μm的范围。
除了具有由本发明的氧气吸收性树脂组合物制成的层以外,本发明的氧气吸收性容器可以通过本身公知的方法来制造。
在同时挤出多层时,用对应于各树脂层的挤出机熔融混炼后,通过T形模具、圆形模具等多层多重模具挤出成规定的形状。另外,用对应于各树脂层的注塑机熔融混炼后,共注塑或者依次注塑到注塑模型内,制造多层容器或者容器用的预成型体。另外,可以采用干燥层压、夹层层压、挤压涂布等层压方法。
成形物可以采用薄膜、片材、用于形成瓶子或管子的型坯或管材、用于形成瓶子或管子的预成型体等形式。通过将挤出物用一对分型模夹断以及将流体吹入到其内部,可以容易地由型坯、管材或预成型体形成瓶子。此外,将管材或者预成型体冷却,然后,加热到拉伸温度,以便在轴向上拉伸,同时在圆周方向上通过流体压力吹制拉伸,获得吹制拉伸瓶。此外,通过真空成型、压缩空气成型、挤胀成型、柱塞辅助(plug-assiste)成型等方式,可以由薄膜或片材获得杯状、盘状等包装容器。
此外,在多层薄膜的情况下,通过将其重叠或折叠为袋状,将周围热封,可以形成袋状容器。
实施例
以下通过实施例和比较例来具体地说明本发明,其中实施例和比较例中的氧气吸收性能和氢气产生量的评价方法如以下所述。
<实施例1~2、比较例1~6的氧气吸收性能和氢气产生量的评价方法>
在层压了钢箔的内容积约85mL的不透气性塑料杯容器内部,以二者不接触的方式投入约0.03g的氧气吸收剂和1.0mL的蒸馏水,使用不透气性的铝箔层压薄膜制的热封盖材料,在空气中进行热密封。将其在22℃下保存,使用气相色谱装置(岛津制作所制造,GC-3BT)分析1小时后的容器内的气体组成。由所得结果计算每单位重量氧气吸收剂的氧气吸收量。
氢气产生量的评价如下:氧气吸收剂向容器内的投入量为0.3g,由在22℃下保存15天后的容器内气体组成分析结果计算每单位重量氧气吸收剂的氢气产生量。
<实施例3、比较例7的氧气吸收性能和氢气产生量的评价方法>
在层压了钢箔的内容积约85mL的不透气性塑料杯容器内部,以二者不接触的方式投入约16cm2的氧气吸收片材和约1.0mL的蒸馏水,使用不透气性的铝箔层压薄膜制的热封盖材料,在空气中进行热密封。将其在22℃下保存,使用气相色谱装置分析30天后的容器内的气体组成。由所得结果计算每单位面积氧气吸收片材的氧气吸收量。
氢气产生量的评价如下:在氮气氛围下将杯子进行热密封,使容器内的初始氧气浓度为1%以下。由在22℃下保存30天后的容器内气体组成分析结果计算每单位面积的氧气吸收片材的氢气产生量。
(实施例1)
将100重量份的旋转式还原铁粉(金属铁量90%,平均粒径45μm)、2重量份食盐和1重量份氢氧化钙一起混合,使用振动式球磨机粉碎处理10小时,然后通过使用180目筛进行分级,以除去90μm以上的粗大颗粒,获得混合微粉碎物。将50kg这样获得的微粉碎物填充到内容积230L的间歇式旋转炉内,在6rpm的转速、10L/分钟的氮气流量、550℃的条件下热处理8小时(升温2小时,冷却8小时)。另外,在热处理时,代替氮气,以10L/分钟的流量引入空气达6小时,以促进表面氧化。使用180目筛将所获得的热处理氧气吸收剂分级,以除去90μm以上的粗大颗粒,获得氧气吸收剂。该氧气吸收剂的比表面积为1.8m2/g,平均粒径(中值粒径)为23μm,X射线衍射测得的铁的(110)面峰的半宽度为0.12°/2θ,金属铁含量为80%。表1示出了所得的氧气吸收剂的、通过制备工序中的两次分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
表1中的氧气吸收量和氢气产生量的“比较”栏是表示以后述比较例1的氧气吸收剂为基准的百分率的数值。氧气吸收量的比较值为80%以上、或者氢气产生量的比较值为1%以下评为优质品。粗大颗粒量为20%以下评价为优质品。
(实施例2)
以与实施例1相同的方式获得氧气吸收剂,只是氢氧化钙的添加量为2重量份,在间歇式旋转炉内填充的混合微粉碎物的量为25kg。该氧气吸收剂的比表面积为1.0m2/g,平均粒径为23μm,X射线衍射测得的铁的(110)面峰的半宽度为0.13°/2θ,金属铁含量为67%。表1示出了所得的氧气吸收剂的、通过制备工序中的两次分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例1)
以与实施例1相同的方式获得氧气吸收剂,只是不添加氢氧化钙,而且不进行热处理和热处理之后的分级。该氧气吸收剂的比表面积为2.4m2/g,平均粒径为23μm,X射线衍射测得的铁的(110)面峰的半宽度为0.29°/2θ,金属铁含量为88%。表1示出了所得的氧气吸收剂的、通过分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例2)
以与实施例2相同的方式获得氧气吸收剂,只是不添加氢氧化钙。该氧气吸收剂的比表面积为1.8m2/g,平均粒径为24μm,X射线衍射测得的铁的(110)面峰的半宽度为0.12°/2θ,金属铁含量为67%。表1示出了所得的氧气吸收剂的、通过制备工序中的两次分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例3)
以与实施例1相同的方式获得氧气吸收剂,只是不添加氢氧化钙,而且热处理时间从8小时延长至10小时。另外,热处理过程中的空气吹送条件与实施例1相同。该氧气吸收剂的比表面积为1.3m2/g,平均粒径为26μm,X射线衍射测得的铁的(110)面峰的半宽度为0.11°/2θ,金属铁含量为78%。表1示出了所得的氧气吸收剂的、通过制备工序中的两次分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例4)
以与实施例1相同的方式获得氧气吸收剂,只是氢氧化钙的添加量为0.5重量份,不进行热处理和热处理之后的分级。该氧气吸收剂的比表面积为2.1m2/g,平均粒径为25μm,X射线衍射测得的铁的(110)面峰的半宽度为0.29°/2θ,金属铁含量为87%。表1示出了所得的氧气吸收剂的、通过分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例5)
以与比较例4相同的方式获得氧气吸收剂,只是氢氧化钙的添加量为1重量份。该氧气吸收剂的比表面积为2.0m2/g,平均粒径为20μm,X射线衍射测得的铁的(110)面峰的半宽度为0.30°/2θ,金属铁含量为87%。表1示出了所得的氧气吸收剂的、通过分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(比较例6)
以与比较例4相同的方式获得氧气吸收剂,只是氢氧化钙的添加量为2重量份。该氧气吸收剂的比表面积为1.9m2/g,平均粒径为20μm,X射线衍射测得的铁的(110)面峰的半宽度为0.30°/2θ,金属铁含量为86%。表1示出了所得的氧气吸收剂的、通过分级所除去的粗大颗粒量以及氧气吸收量和氢气产生量的测定结果。
(实施例3)
通过双轴挤出机(东芝机械制造,TEM-35B)将30重量份的实施例1获得的氧气吸收剂和70重量份的熔体指数(MI)为0.6(g/10min、230℃)的聚丙烯(PP)熔融混炼,制备配合氧气吸收剂的粒料。将该配合氧气吸收剂的粒料(PO)作为第一中间层,将乙烯-乙烯醇共聚物(EVOH;乙烯含量32mol%,皂化度99.6mol%)作为第二中间层,将PP与8重量%的钛白颜料配合而获得的白色PP作为内层和外层,以及用MI为1.0(g/10min、230℃)的马来酸酐改性的PP(ADH)作为粘合剂层,用由单轴挤出机、给料区、T形模具、冷却辊和片材拉伸装置构成的成型装置制备该4种6层片材(总厚度0.5mm,厚度构成比PP/ADH/EVOH/ADH/PO/PP=30/1/5/1/10/10)。表2示出了所得氧气吸收性片材的氧气吸收量和氢气产生量的测定结果。
(比较例7)
以与实施例3相同的方式获得氧气吸收性片材,只是使用比较例1中获得的氧气吸收剂代替实施例1中获得的氧气吸收剂。表2示出了所得氧气吸收性片材的氧气吸收量和氢气产生量的测定结果。
表2
Claims (7)
1.一种树脂配合用氧气吸收剂,其特征在于,其为含有铁粉、金属卤化物和碱性物质的混合粉末,其中,前述混合粉末通过粉末X射线衍射法测定的(110)面的峰的半宽度为0.20°/2θ(Co-Kα)以下,比表面积为0.5m2/g以上,且平均粒径为1~40μm。
2.根据权利要求1所述的树脂配合用氧气吸收剂,其中前述铁粉表面被氧化铁覆盖,铁粉中的金属铁含量为60~85重量%。
3.根据权利要求1所述的树脂配合用氧气吸收剂,其中前述碱性物质为氢氧化钙或者氧化钙。
4.根据权利要求1所述的树脂配合用氧气吸收剂,其中相对于100重量份铁粉,前述碱性物质以0.5~2重量份的量配合。
5.一种氧气吸收性树脂组合物,其含有权利要求1所述的树脂配合用氧气吸收剂。
6.一种氧气吸收性容器,其含有权利要求5所述的氧气吸收性树脂组合物。
7.一种树脂配合用氧气吸收剂的制备方法,其特征在于,将铁粉、金属卤化物和碱性物质混合和粉碎,然后在氧气存在下进行热处理。
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CN102947374A (zh) * | 2010-05-12 | 2013-02-27 | 多种吸附技术公司 | 包含除氧剂的可生物降解聚合物制品 |
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CN111630112B (zh) * | 2018-01-29 | 2022-07-22 | 东洋制罐株式会社 | 吸氧性树脂组合物及容器 |
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