CN1327765C - 用于环丙烯的湿气活化的输送体系 - Google Patents
用于环丙烯的湿气活化的输送体系 Download PDFInfo
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- CN1327765C CN1327765C CNB2005100685103A CN200510068510A CN1327765C CN 1327765 C CN1327765 C CN 1327765C CN B2005100685103 A CNB2005100685103 A CN B2005100685103A CN 200510068510 A CN200510068510 A CN 200510068510A CN 1327765 C CN1327765 C CN 1327765C
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- CN
- China
- Prior art keywords
- composition
- cyclopropylene
- cyclodextrin
- encapsulation agent
- hygroscopicity
- 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.)
- Expired - Fee Related
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- 150000001943 cyclopropenes Chemical class 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000005538 encapsulation Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 4
- 239000005977 Ethylene Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 34
- 125000004980 cyclopropylene group Chemical group 0.000 claims description 31
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 22
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical group OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 22
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 22
- 229920000858 Cyclodextrin Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 201000004792 malaria Diseases 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical class O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 cyclopropene compound Chemical class 0.000 abstract description 9
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 abstract 3
- 239000008393 encapsulating agent Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 40
- SHDPRTQPPWIEJG-UHFFFAOYSA-N 1-methylcyclopropene Chemical compound CC1=CC1 SHDPRTQPPWIEJG-UHFFFAOYSA-N 0.000 description 39
- 239000005969 1-Methyl-cyclopropene Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 239000004775 Tyvek Substances 0.000 description 3
- 229920000690 Tyvek Polymers 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 229960002920 sorbitol Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 241000360590 Erythrites Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 208000037824 growth disorder Diseases 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229960001855 mannitol Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133317—Intermediate frames, e.g. between backlight housing and front frame
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
本发明涉及新的用于环丙烯的输送体系，其中含有环丙烯和分子包封剂络合物的组合物还进一步含有利用潮湿的空气使环丙烯从分子包封剂中释放的其它组分。本发明也提供使环丙烯从这种组合物中释放的方法和向植物中输送环丙烯来抑制植物中的乙烯响应的方法。
Description
本发明涉及新的用于环丙烯的输送体系，其中含有环丙烯和分子包封剂络合物的组合物还进一步含有利用潮湿的空气使环丙烯从分子包封剂中释放的其它组分。这种环丙烯和其衍生物(比如，甲基环丙烯)能够抑制植物中乙烯的响应。环丙烯/分子包封剂络合物为储存和运输典型地为反应性气体并且高度不稳定的环丙烯提供了一种方便的方法。为了延长植物的储藏期限，这种络合物也为向植物中输送这些化合物提供了方便的方法。
众所周知乙烯通过与植物中的某些受体结合能够引起植物或植物局部(包括，例如，花卉、叶子、水果)和蔬菜的过早死亡。乙烯也促使叶子变黄和生长萎缩，以及促使早熟的水果、花卉和叶子脱落。因为乙烯所引发的这些问题，非常活跃和大量的研究目前关注于调查防止或减少乙烯对植物的有害影响的方法。美国专利No.5,518,988公开了使用环丙烯和其衍生物，包括1-甲基环丙烯，作为有效试剂来阻碍乙烯的影响。然而，这些化合物的一个主要问题在于它们典型地是不稳定的气体，当压缩时存在爆炸的危险。为了使环丙烯的反应性稳定并从而提供储存、运输、和向植物中施用或输送这些活泼化合物的方便而且安全的方法，解决上述问题的一种方法是将环丙烯结合到分子包封剂络合物中。对于最活泼的环丙烯、1-甲基环丙烯而言，优选的分子包封剂是环糊精，其中最优选α-环糊精。通过简单地向分子包封剂络合物中加水来实现将这些活泼化合物施用或输送到植物中。根据美国专利No.6,017,849公开的方法制备所述络合物，该专利提供的材料为粉末形式。
当将粉末加入水中时，上述提及的1-甲基环丙烯/α-环糊精络合物非常快速地释放出1-甲基环丙烯。然而，为了实现所述释放，需要大量的水，水量至少为1-甲基环丙烯/α-环糊精络合物重量的10倍，优选20倍。用气体(比如，空气或氮气)鼓泡也对释放有益。有利的是，在不使用额外的水而且没有气体鼓泡的条件下获得环丙烯从络合物中的完全释放。这将允许使用者直接在装运的容器中，而不是在巨大的处理容器、箱或房间中用环丙烯气体对花卉、水果或蔬菜进行直接处理。美国专利No.6,426,319公开了利用α-环糊精络合物的用于环丙烯的输送体系，其要求很少的水。该输送体系通过使络合物与下述吸水性材料混合来实施：比如一种或多种有机材料，比如超吸收性聚合物，比如聚丙烯酸钠(交联的)、多糖、丙烯酰胺/丙烯酸酯共聚物和羧甲基纤维素；一种或多种无机的易潮解化合物，比如氯化钙、氯化镁、氯化锂、氯化锌、硝酸镁和硝酸铝；和其结合物和混合物。
本发明人已经出乎意料地发现某些有限数量的材料在引起环丙烯从α-环糊精络合物中释放方面特别有效，其仅仅利用少量从潮湿的空气中提取的水。所以，本发明涉及一种组合物，其包含：
a)分子包封剂，其中包封一种或多种下式的环丙烯：
其中，R是氢或取代或未取代的烷基、链烯基、炔基、环烷基、环烷基烷基、苯基、或萘基；其中取代基，当存在时，独立地是卤素、烷氧基、或取代或未取代的苯氧基；
b)一种或多种吸湿性或易潮解材料，其选自一种或多种聚醚、一种或多种多元醇、或其混合物；
c)非必要的，一种或多种基材；和
d)非必要的，一种或多种助剂。
如在本文中所使用的，如果没有另外指明，所有的百分比是重量百分比，所有的份数是重量份，而且它们包括端值和可以结合。所有的比值是重量比，而且所有的比值范围包括端值和可以结合。所有的摩尔范围包括端值和可以结合。
如在本文中所使用的，术语“烷基”表示直链和支链的(C1-C20)基团，其包括，例如，甲基、乙基、正丙基、异丙基、1-乙基丙基、正丁基、叔丁基、异丁基、2，2-二甲基丙基、戊基、辛基和癸基。术语“链烯基”和“炔基”表示(C3-C20)链烯基和(C3-C20)炔基，比如，2-丙烯基、2-丁烯基、3-丁烯基、2-甲基-2-丙烯基和2-丙炔基。术语“环烷基烷基”表示被(C3-C7)环烷基取代的(C1-C15)烷基，比如，环丙基甲基、环丙基乙基、环丁基甲基和环戊基乙基。术语“卤代烷基”表示其中一个或多个氢原子被卤原子置换的烷基。术语“卤素”表示氟、氯、溴和碘。
在本发明的一个实施方案中，R是(C1-C10)烷基。在一个优选实施方案中，R是(C1-C8)烷基。在一个更优选的实施方案中，R是(C1-C4)烷基。最优选，R是甲基。
为了本发明的目的，术语“络合物”表示其中包封环丙烯的分子包封剂。有用的包封剂包括取代或未取代的环糊精、冠醚和沸石。在本发明的一个优选实施方案中，包封剂是α-环糊精、β-环糊精或γ-环糊精。在本发明的另一个优选实施方案中，特别是当环丙烯为1-甲基环丙烯时，包封剂为α-环糊精。该优选的包封剂将依赖于R基团的大小而改变。然而，本领域的技术人员可以理解，任何环糊精或环糊精的混合物、环糊精聚合物、改性的环糊精、或其混合物都可以用于本发明。可以从Wacker Biochem Inc.(Adrian，MI)或CerestarUSA(Hammond，IN)以及其它出售者购得环糊精。
本发明适用的环糊精是利用美国专利No.5,518,988和6,017,849公开的方法制备的已知材料。再利用美国专利No.6,017,849公开的通常方法，通过使环丙烯与分子包封剂的溶液或淤浆接触，然后分离出络合物的方法制备本发明的环丙烯-分子包封剂络合物。在1-甲基环丙烯的情况下，气体经α-环糊精的水溶液鼓泡，络合物首先从α-环糊精的水溶液中沉淀，然后经过滤分离。
各种各样的聚醚、多元醇或其混合物可以用于本发明的组合物中。它们包括，例如，多元醇比如，甘油、赤藓醇、木糖醇、甘露糖醇、麦芽糖醇和山梨糖醇；聚醚比如，聚乙二醇和聚丙二醇；和其混合物。经常需要在该组合物中包括一种或多种助剂，比如，增量剂、粘合剂、增塑剂、润滑剂、表面活性剂、润湿剂、铺展剂、分散剂、粘着剂、粘合剂、消泡剂、增稠剂和乳化剂。可以在JohnW.McCutcheon，Inc.的出版物“Detergents and Emulsifiers，Annual”(Allured Publishing Company，Ridgewood，New Jersey，U.S.A)中找到本领域中经常使用的这些助剂。
在本发明的一个实施方案中，络合物与一种或多种聚醚、一种或多种多元醇、或其混合物混合，非必要地还与助剂混合(例如，粘合剂比如乙基纤维素)，然后将混合物在基材上涂布一层，所述基材比如纸或塑料薄膜。所述基材可以是任何所述络合物能够在其上涂布而且不与所述络合物发生反应的材料。所述涂布方法可以借助压力实施，或者通过加热或使用溶剂来促进。可以使用本领域技术人员已知的任何涂布方法将粉末状的络合物涂布在基材上，只要该方法不会显著地降解粉末状的络合物、引起环丙烯的过早释放、或者阻止环丙烯的释放。然后，涂布的基材可以就这样使用，或者可以放置在保护性的封套或夹层结构中，保护性的封套或夹层结构可以由各种水蒸汽可渗透的材料制得，所述水蒸汽可渗透的材料比如滤纸或多孔塑料，例如TyvekTM牌的保护性材料。当将这种夹层结构放置在潮湿的环境中时，比如典型的用于储存花卉、水果和蔬菜的环境，1-甲基环丙烯气体被释放。尽管本发明的输送体系可以提供1-甲基环丙烯的缓慢释放，但是一些实施方案可以利用薄涂层而且可以提供相对快速的1-甲基环丙烯的释放。这一相同的方法可以等同地适用于其它环丙烯/分子包封剂络合物。
术语“潮湿的环境”或“潮湿的空气”表示其中的相对湿度高于50％，优选高于70％，和最优选高于80％的环境。在本发明的一个实施方案中，在50％的相对湿度下，在存在和不存在吸湿性或易潮解材料的两种条件下，环丙烯从分子包封剂中释放的速率是相似的；但是在80％的相对湿度下，环丙烯从分子包封剂中释放的速率在存在吸湿性或易潮解材料的条件下比不存在吸湿性或易潮解材料条件下的释放速率更快。术语“相似”表示在20％的范围之内；术语“更快”表示速度快20％以上。
上述结合物可以放置在各种组成的封套或夹层结构中，或者可以包括在多层薄膜体系中。在一个实施方案中，夹层结构由顶层和底层构成，其中至少一层是水蒸汽可渗透的。直到正好要使用之前，所述夹层结构可以一直储存在水蒸气不可渗透的容器中。可选择地，直到正好要使用之前，所述涂布的基材自身可以一直放置在水蒸气不可渗透的容器中。这种容器包括，例如，小瓶、密封的薄金属袋、密封的塑料或聚合物袋、聚合物微球、多层膜、和整体(monolithic)聚合物结构。
本发明的组合物可以包含0.01-99wt％的络合物、1-99.99wt％的吸湿性或易潮解材料、0-99wt％的基材、和0-99wt％的一种或多种助剂。在一个实施方案中，本发明的组合物包含：
1-甲基环丙烯/α-环糊精络合物 0.01-95％
吸湿性或易潮解材料 5-95％
基材 0-94.99％
助剂 0-50％。
在另一个实施方案中，本发明的组合物包含：
1-甲基环丙烯/α-环糊精络合物 0.1-25％
吸湿性或易潮解材料 5-75％
基材 20-93％
助剂 0-50％。
在仍然另一个实施方案中，本发明的组合物包含：
1-甲基环丙烯/α-环糊精络合物 0.5-5％
吸湿性或易潮解材料 5-25％
基材 30-90％
助剂 0-20％。
由于分子量的差异、被包封剂吸收的环丙烯和吸湿性或易潮解材料的吸水能力，对于不同的环丙烯、不同的包封剂和吸湿性或易潮解材料而言，这些比例可以改变。本领域技术人员可以容易地确定这些不同结合物的最佳比例。
本发明的另一个实施方案是一种向植物输送环丙烯化合物来抑制植物中的乙烯响应的方法，该方法包括使本发明的组合物在植物存在下与水接触的步骤。
通过以下实施例举例说明本发明的一些实施方案。
在下述实施例中，根据美国专利No.6,017,849的方法制备1-甲基环丙烯/α-环糊精络合物。
实施例1：1-甲基环丙烯在潮湿的环境中释放
将一种由下述组分组成的混合物涂布在纸上：
1-甲基环丙烯/α-环糊精络合物 0.31g
山梨糖醇 0.33g
柠檬酸乙酰基三丁酯 0.47g
乙基纤维素 1.40g和
丙酮 7.50g。
蒸发丙酮并测定(通过称量)所制得的涂层为26g/平方米(m2)。将涂布的纸张在密封的玻璃容器中暴露于100％的相对湿度中，4小时内有高于9 0％的预期的1-甲基环丙烯释放。
实施例2：1-甲基环丙烯在潮湿的环境中释放
将一种由下述组分组成的混合物涂布在纸上：
1-甲基环丙烯/α-环糊精络合物 0.29g
聚乙二醇 0.97g
乙基纤维素 0.97g和
丙酮 7.70g。
蒸发丙酮并测定(通过称量)所制得的涂层为22g/平方米(m2)。将涂布的纸张在密封的玻璃容器中暴露于100％的相对湿度中，4小时内有高于90％的预期的1-甲基环丙烯释放。
实施例3：1-甲基环丙烯在潮湿的环境中释放
将由2.5g 1-甲基环丙烯/α-环糊精络合物和97.5g聚乙二醇组成的混合物涂布在纸上。
测定(通过称量)所制得的涂层为25g/平方米(m2)。将涂布的纸张夹在涂有粘合剂的聚丙烯和TyvekTM保护性材料之间。将该夹层结构在密封的玻璃容器中暴露于91％的相对湿度中，2小时内有高于90％的预期的1-甲基环丙烯释放。
实施例4：1-甲基环丙烯通过湿度的释放
将由2.5g 1-甲基环丙烯/α-环糊精络合物和97.5g聚乙二醇组成的混合物涂布在纸上。
测定(通过称量)所制得的涂层为25g/平方米(m2)。将涂布的纸张放置于纸封套中。将该封套在密封的玻璃容器中暴露于100％的相对湿度中，2小时内有高于90％的预期的1-甲基环丙烯释放。
实施例5：1-甲基环丙烯通过湿度的释放
将由2.5g 1-甲基环丙烯/α-环糊精络合物和97.5g聚乙二醇组成的混合物涂布在纸上。
测定(通过称量)所制得的涂层为25g/平方米(m2)。将涂布的纸张夹在滤纸片之间。将该夹层结构在密封的玻璃容器中暴露于100％的相对湿度中，2小时内有高于90％的预期的1-甲基环丙烯释放。
实施例6：1-甲基环丙烯通过湿度的释放
将由2.5g 1-甲基环丙烯/α-环糊精络合物和97.5g聚乙二醇组成的混合物涂布在纸上。
测定(通过称量)所制得的涂层为25g/平方米(m2)。将涂布的纸张夹在TyvekTM保护性材料的片之间。将该夹层结构在密封的玻璃容器中暴露于100％的相对湿度中，2小时内有高于90％的预期的1-甲基环丙烯释放。
实施例A(对比例)：1-甲基环丙烯通过湿度的释放
利用1800磅的压制压力，将由2.5g 1-甲基环丙烯/α-环糊精络合物、5g氯化钙和92.5g乳糖组成的混合物制片成为直径0.50英寸、大约0.275g的平面圆片。将该小片在密封的玻璃容器中暴露于90％的相对湿度中，在6-7小时内，最大只有42-45％的预期的1-甲基环丙烯释放。
实施例B(对比例)：1-甲基环丙烯通过湿度的释放
利用1800磅的压制压力，将由2.5g 1-甲基环丙烯/α-环糊精络合物、5g氯化钙和92.5g乳糖组成的混合物制片成为直径0.50英寸、大约0.275g的平面圆片。将该小片在密封的玻璃容器中暴露于100％的相对湿度中，在6-7小时内，最大只有52-58％的预期的1-甲基环丙烯释放。
Claims (10)
1.一种组合物，其包含：
a)分子包封剂，选自取代或未取代的环糊精、冠醚和沸石，其中包封一种或多种下式的环丙烯：
其中，R是氢或取代或未取代的烷基、链烯基、炔基、环烷基、环烷基烷基、苯基、或萘基；其中取代基，当存在时，独立地是卤素、烷氧基、或取代或未取代的苯氧基；和
b)一种或多种吸湿性或易潮解材料，其选自一种或多种聚醚、一种或多种多元醇、或其混合物。
2.权利要求1的组合物，其中R为(C1-C8)烷基。
3.权利要求1的组合物，其中R为甲基。
4.权利要求1的组合物，其中分子包封剂是环糊精或环糊精的混合物。
5.权利要求1的组合物，其中分子包封剂是α-环糊精。
6.权利要求1的组合物，其进一步包括：
a)一种或多种基材；或
b)一种或多种助剂；或
c)一种或多种基材和一种或多种助剂。
7.权利要求1的组合物，其中：
a)在50％的相对湿度下，在存在和不存在吸湿性或易潮解材料的两种条件下，环丙烯从分子包封剂中释放的速率相差20wt％以内；和
b)在80％的相对湿度下，环丙烯从分子包封剂中释放的速率在存在吸湿性或易潮解材料的条件下比不存在吸湿性或易潮解材料条件下的释放速率高20wt％。
8.一种制造的制品，其含有封闭在水不可渗透容器中的权利要求1的组合物。
9.一种从权利要求1的组合物中释放环丙烯的方法，其包含使该组合物与潮湿的空气接触的步骤。
10.一种向植物中输送环丙烯化合物来抑制植物中的乙烯响应的方法，其包含使权利要求1的组合物在该植物存在下与潮湿的空气接触的步骤。
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| US56838304P | 2004-05-05 | 2004-05-05 | |
| US60/568,383 | 2004-05-05 |
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| EP (1) | EP1593306B1 (zh) |
| JP (1) | JP4270465B2 (zh) |
| KR (1) | KR100653359B1 (zh) |
| CN (1) | CN1327765C (zh) |
| AU (1) | AU2005201845B2 (zh) |
| BR (1) | BRPI0501606B1 (zh) |
| CA (1) | CA2504840C (zh) |
| CY (1) | CY1114076T1 (zh) |
| DK (1) | DK1593306T3 (zh) |
| ES (1) | ES2409341T3 (zh) |
| IL (1) | IL168237A (zh) |
| MX (1) | MXPA05004847A (zh) |
| MY (1) | MY144495A (zh) |
| NZ (1) | NZ539684A (zh) |
| PL (1) | PL1593306T3 (zh) |
| PT (1) | PT1593306E (zh) |
| SI (1) | SI1593306T1 (zh) |
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| CN104650390A (zh) * | 2011-03-27 | 2015-05-27 | 塞尔瑞星技术有限公司 | 环糊精组合物、物品以及方法 |
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| CN102119718B (zh) * | 2010-12-10 | 2013-06-19 | 山东营养源食品科技有限公司 | 一种环丙烯类保鲜剂及其制备方法 |
| US10182567B2 (en) | 2011-03-27 | 2019-01-22 | Cellresin Technologies, Llc | Cyclodextrin compositions, articles, and methods |
| JP5562992B2 (ja) * | 2011-04-05 | 2014-07-30 | ローム アンド ハース カンパニー | 制御放出組成物 |
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| CN104936447B (zh) * | 2012-11-30 | 2018-03-06 | 塞尔瑞星技术有限公司 | 控制释放组合物及使用方法 |
| US8822382B2 (en) | 2013-05-05 | 2014-09-02 | Nazir Mir | Hydrocolloid systems for reducing loss of volatile active compounds from their liquid formulations for pre- and post harvest use on agricultural crops |
| US8802140B2 (en) * | 2013-05-05 | 2014-08-12 | Nazir Mir | Situ mixing and application of hydrocolloid systems for pre- and post harvest use on agricultural crops |
| TW201503831A (zh) * | 2013-07-11 | 2015-02-01 | Agrofresh Inc | 用於揮發性化合物之濕度活化的調配物 |
| TW201534217A (zh) * | 2013-07-11 | 2015-09-16 | Agrofresh Inc | 顆粒配方之方法及組成物 |
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| US9421793B2 (en) | 2014-06-26 | 2016-08-23 | Cellresin Technologies, Llc | Electrostatic printing of cyclodextrin compositions |
| CN105437676B (zh) * | 2014-08-14 | 2020-03-24 | 上海利统生化制品有限公司 | 用于阻碍植物乙烯反应的层合物及其制备方法 |
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| ES2820879R1 (es) | 2016-02-19 | 2021-06-21 | Hazel Tech Inc | Composiciones para la liberación controlada de ingredientes activos y métodos de preparación de las mismas |
| IL304085A (en) | 2018-04-27 | 2023-08-01 | Fresh Inset S A | Preparations and items containing complexes of 1-methylcyclopropane and alpha-cyclodextrin |
| CN109744308B (zh) * | 2019-02-01 | 2023-01-31 | 西安永泰生物科技有限公司 | 一种包封或吸附气体的涂膜方法及其气体的应用 |
| US11730166B2 (en) | 2020-02-03 | 2023-08-22 | Fresh Inset S.A. | Stable 1-methylcyclopropene compositions and uses thereof |
| US20210331990A1 (en) | 2020-04-27 | 2021-10-28 | Cellresin Technologies, Llc | Compositions and Methods for Differential Release of 1-Methylcyclopropene |
| WO2023288294A1 (en) | 2021-07-16 | 2023-01-19 | Novozymes A/S | Compositions and methods for improving the rainfastness of proteins on plant surfaces |
| WO2023225459A2 (en) | 2022-05-14 | 2023-11-23 | Novozymes A/S | Compositions and methods for preventing, treating, supressing and/or eliminating phytopathogenic infestations and infections |
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Also Published As
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| TW200536477A (en) | 2005-11-16 |
| MXPA05004847A (es) | 2005-11-10 |
| AU2005201845B2 (en) | 2011-01-06 |
| NZ539684A (en) | 2006-12-22 |
| TWI342188B (en) | 2011-05-21 |
| DK1593306T3 (da) | 2013-06-10 |
| IL168237A (en) | 2011-02-28 |
| PT1593306E (pt) | 2013-06-07 |
| EP1593306B1 (en) | 2013-03-13 |
| CA2504840C (en) | 2008-03-18 |
| US20050250649A1 (en) | 2005-11-10 |
| MY144495A (en) | 2011-09-30 |
| CN1692723A (zh) | 2005-11-09 |
| KR20060047597A (ko) | 2006-05-18 |
| SI1593306T1 (sl) | 2013-06-28 |
| EP1593306A2 (en) | 2005-11-09 |
| JP4270465B2 (ja) | 2009-06-03 |
| AU2005201845A1 (en) | 2005-11-24 |
| BRPI0501606B1 (pt) | 2014-06-03 |
| EP1593306A3 (en) | 2011-09-28 |
| ES2409341T3 (es) | 2013-06-26 |
| CA2504840A1 (en) | 2005-11-05 |
| KR100653359B1 (ko) | 2006-12-05 |
| JP2005320328A (ja) | 2005-11-17 |
| PL1593306T3 (pl) | 2013-08-30 |
| CY1114076T1 (el) | 2016-07-27 |
| BRPI0501606A (pt) | 2006-05-16 |
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