CN107022896B - Polyurethane -3- amino -5- methylisoxazole fiber producing processes and its application in food in the enrichment detection of heavy metal - Google Patents
Polyurethane -3- amino -5- methylisoxazole fiber producing processes and its application in food in the enrichment detection of heavy metal Download PDFInfo
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- CN107022896B CN107022896B CN201710166743.XA CN201710166743A CN107022896B CN 107022896 B CN107022896 B CN 107022896B CN 201710166743 A CN201710166743 A CN 201710166743A CN 107022896 B CN107022896 B CN 107022896B
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- fiber
- polyurethane
- methylisoxazole
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- 239000000835 fiber Substances 0.000 title claims abstract description 120
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 40
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 235000013305 food Nutrition 0.000 title claims abstract description 25
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 24
- 230000008569 process Effects 0.000 title abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 65
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 229920006306 polyurethane fiber Polymers 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- FKPXGNGUVSHWQQ-UHFFFAOYSA-N 5-methyl-1,2-oxazol-3-amine Chemical compound CC1=CC(N)=NO1 FKPXGNGUVSHWQQ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- -1 hexichol Methane diisocyanate isomers Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 51
- 239000013522 chelant Substances 0.000 abstract description 28
- 238000004458 analytical method Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000002798 spectrophotometry method Methods 0.000 abstract description 6
- 239000011651 chromium Substances 0.000 description 55
- 150000002500 ions Chemical class 0.000 description 32
- 238000010521 absorption reaction Methods 0.000 description 19
- 229910021645 metal ion Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229910052804 chromium Inorganic materials 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000007853 buffer solution Substances 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
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- 241000222519 Agaricus bisporus Species 0.000 description 4
- 241000222532 Agrocybe Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HONMCSLFRKBQHG-UHFFFAOYSA-N 1,3-diamino-1,3-diphenylurea Chemical compound C=1C=CC=CC=1N(N)C(=O)N(N)C1=CC=CC=C1 HONMCSLFRKBQHG-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101001047513 Mus musculus Lethal(2) giant larvae protein homolog 1 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000989 food dye Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000002649 immunization Methods 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/28023—Fibres or filaments
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Abstract
A kind of application the present invention provides polyurethane -3- amino -5- methylisoxazole fiber producing processes and its in food in the enrichment detection of heavy metal.Polyurethane -3- amino -5- methylisoxazole the fiber is as new function chelate fibre, its performance is stable, adsorption capacity is big, selectivity is single-minded, can elute completely, the advantages of further combined with spectrophotometry, for harmful heavy metal analysis detection in food, have many advantages, such as that at low cost, easy to operate, accuracy is high, for popularizing the analysis detection of heavy metal in food, have important practical significance.
Description
Technical field
The invention belongs to technical field of chemistry, in particular to a kind of system of polyurethane -3- amino -5- methylisoxazole fiber
Preparation Method and its application.
Background technique
Human material's production activity aggravation, the food pollution event of generation emerge one after another, and wherein heavy metal is most dangerous
One of harmful pollutants.The heavy metal of contaminated food generally refers to poison human body maximum 5 heavy metal species: Cr, Hg,
Pb, Cd and As.Heavy metal can be accumulated in the soil and is enriched with in animal and plant body, passed into human body using food chain, given
Human life health care belt carrys out great risk, once heavy metal in human body content is exceeded to cause various disagreeable illness.Weight in food
Rnetal contamination problem has caused the great attention and further investigation of whole world researcher, to heavy metal-polluted in variety classes food
Dye is monitored and analyzed detection research, for evaluation food quality, protection human health and maintains economic society sustainable strong
Kang Fazhan has important practical significance
The oxidation state of heavy metal chromium is from divalent to sexavalence, generally trivalent form, and wherein Cr VI is because industrialization makes
Using causes it largely to exist as a kind of oxidation state.Chromium is usually trivalent in human body, if it exists excessive hexavalent chromium meeting
Bring a series of health risks.In the environment, Cr VI is usually with CrO4 2-Or HCrO4 -Form exist, and trivalent chromium is then with Cr
(OH)n (3-n)+Form exist, the toxicity of chromium causes by Cr VI.Food is one of main source of exposure of heavy metal chromium.
Domestic and foreign scholars, which have carried out the analysis method of trace heavy metal in food, extensively and profoundly to be inquired into.Common detection
Method has AAS, UV-SP, AFS, electrochemical process, XRF, ICP-MS, colorimetric method, enzyme-linked immunization etc..In addition, because food inspection
Reality need, single analysis mode can not meet requirement, and therefore multiple instruments combination detection technique is more and more taken seriously, nowadays
Have become popular research field.Such as HPCE) and SP) be combined, HPCE and ICP-MS combination, HPLC and ICP-MS combination, IEC with
AFS combination etc..
The essential characteristic of heavy metal analysis is mainly that number of samples to be detected is huge, detection threshold value is lower in food, so
A kind of testing cost bottom, high sensitivity, detection method easy to operate are established to the pollution journey of heavy metal in accurate evaluation food
Degree and guarantee human health have very great significance.
Chelate fibre refers to that a kind of react by Cross-linked accesses all kinds of active group systems on fibrous polymer ontology
Standby polygamy bit-type high polymer can obtain multicomponent chelate object using different function base and the chelation of different metal ions, right
Metal ion adsorption capacity with higher and selective enrichment ability, in separation, enrichment and recycling metal ion and ocean
The fields such as the utilization of resources, sewage treatment, hydrometallurgy, analysis detection are widely used.In recent years, domestic various separation and concentration materials
Research it is gradually active, the kind of the adsorbed ionic species of this kind of material and material itself is also constantly opened up extensively, with regard to material
Main for material shape to be divided into two major classes, one kind is spherical resin；Another kind of linear fiber.Chelate fibre is developed recently
The fibre-like adsorption function high molecular material to get up.It is compared with resin, the specific surface area of chelate fibre is bigger, about sets
100 times of rouge, even if its specific surface area will also be higher by 5~6 times compared with macroreticular resin, very thin face shaping makes it
Area is big when contacting with fluid, and resistance is small, is easier to spread.Therefore, chelate fibre kinetic characteristics are excellent, and adsorption efficiency is high, inhale
Attached capacity is big, and elution is easier, and is suitable for for adsorbing trace heavy metal ion.In addition, chelate fibre possess it is higher it is flexible,
Mechanical tenacity can be used with various patterns, such as: adsorption column meets intensity, density, the size requirement of various applications,
It is acknowledged as one of the main attack research direction of adsorbent material.Currently, the type of chelate fibre is also very rich.Utilize polyurethane system
Standby being widely used property of functional material is especially enriched with various heavy metal ion for adsorbing, and disadvantage is exactly selectivity
Aspect is not often up to standard.
Summary of the invention
The present invention is directed to disadvantage mentioned above, provides a kind of polyurethane -3- amino -5- methylisoxazole fiber, is obtained with reaching
New function chelate fibre, performance is stable, adsorption capacity is big, selectivity is single-minded, can elute completely, purpose.
To achieve the above object, the present invention takes following technical proposals to realize:
The present invention provides a kind of polyurethane -3- amino -5- methylisoxazole fiber producing processes, comprising the following steps: step
Rapid a, the preparation of the polyurethane fiber containing carbamate groups: triethylamine is catalyst, utilizes excessive diphenyl-methane two
Diphenylisocyanate isomer carries out graft reaction on polyurethane fiber surface, and the free carbamate groups of Surface Realize are made
Polyurethane fiber；
The preparation of the polyurethane fiber of step b citric acid grafting: polyurethane fiber and lemon containing carbamate groups
The reaction of lemon acid, obtains the polyurethane fiber of citric acid grafting；
Polyurethane -3- amino -5- methylisoxazole fiber: step c is added in the polyurethane fiber of citric acid grafting and matches
Body 3- amino -5- methylisoxazole, reaction obtain polyurethane -3- amino -5- methylisoxazole fiber.
Further, in step a, after polyurethane fiber is cleaned with toluene, it is that solvent is warming up to 50 DEG C that toluene, which is added, is added
Diphenylmethane diisocyanate isomers, catalyst of triethylamine, stirred under nitrogen atmosphere react 2h, and filtering taking-up is cleaned with toluene
Repeatedly, it is prepared into the polyurethane fiber for closing and there are carbamate groups.
Further, in step b, the polyurethane fiber containing carbamate groups is added toluene and is warming up to 50 DEG C, is added
Citric acid, initiator potassium persulfate, stirred under nitrogen atmosphere react 6h, and fiber is cleaned repeatedly with anhydrous ether after experiment,
And be dried in vacuo under the conditions of 50 DEG C, it is prepared into citric acid grafted polyurethane fiber.
Preferably, in step c, reaction dissolvent is Isosorbide-5-Nitrae-dioxane.
Further, in step c, reaction dissolvent Isosorbide-5-Nitrae-dioxane is added in citric acid grafted polyurethane fiber, to fiber
In a solvent sufficiently swelling after be added ligand 3- amino -5- methylisoxazole, lead to nitrogen protection gas with the revolving speed of 150rpm at the uniform velocity
1-2h is stirred, the air in three-necked bottle is eliminated, reaction dissolvent is risen into reaction temperature and keeps constant temperature, it is anti-to continue at the uniform velocity stirring
It answers, is cooled to room temperature after reaction, successively with four kinds of reaction dissolvent, dehydrated alcohol, acetone, ether organic solvent circulation washings
Product 3-4 times is dried in 50 DEG C of vacuum ovens.
Further, reaction temperature is 55 DEG C in step c.
Further, the molar ratio of ligand and carboxyl on citric acid grafted polyurethane fiber is 5.
Further, the reaction time is 8h in step c.
The present invention also provides a kind of polyurethane -3- amino -5- methylisoxazole fiber, the polyurethane -3- amino -5-
Methylisoxazole fiber is obtained using above-mentioned preparation method.
The enrichment inspection of the present invention also provides a kind of in polyurethane -3- amino -5- methylisoxazole fiber food heavy metal
Application in survey.
Further, the heavy metal is hexavalent chromium.
In short, the invention has the benefit that
Polyurethane -3- amino -5- methylisoxazole fiber of the invention chooses 3- amino -5- methylisoxazole as ligand
Condensation reaction occurs with homemade citric acid grafted polyurethane fiber (PUCA), is prepared for a kind of completely new chelate fibre: poly- ammonia
Ester -3- amino -5- methylisoxazole fiber (AMIF).
The present invention uses triethylamine for catalyst, utilizes excessive diphenylmethane diisocyanate isomers (4,4-MDI)
Graft reaction is carried out in polyurethane (PU) fiber surface, so that the free carbamate groups of Surface Realize (PU-NCO), then
Using the high response of hydroxyl in carbamate groups and citric acid (CA), carboxyl-reactive group (PU-CA) is introduced on surface.
The IR Characterization of PU-NCO fiber shows, except original PU fiber characteristic absorption peak (C-H, C=O, Ph) outside, PU-NCO fiber exists
There are isocyanate groups characteristic absorption peaks outstanding at 2360cm- and 2330cm-, and in PU-CA fiber infrared spectrum
This characteristic absorption peak does not occur again.Therefore, it selects citric acid as intermediate herein, prepares containing-COOH function base
Polyurethane-modified fiber (PU-CA) and using it as parent, with to Cr (VI) ion have good sequestering power organic heterocyclic
Condensation reaction occurs for ligand 3- amino -5- methylisoxazole, obtains the new function chelate fibre of high comprehensive performance.
The present invention further obtains the optimum synthesis condition of AMIF fiber are as follows: reaction dissolvent is Isosorbide-5-Nitrae-dioxane, instead
It is 7.98h between seasonable, reaction temperature is 54.68 DEG C, and molar ratio 5.02, obtaining prediction maximum conversion is 71.68%.
Further, AMIF fiber has good selective adsorption capacity and adsorption capacity to Cr (VI) and is easy to wash
It is de-.Static Adsorption result of study shows that AMIF is 201mg/g respectively to Cr (VI) ion saturated extent of adsorption；Study on dynamic adsorption
The result shows that AMIF meets Thomas model to the Dynamic Adsorption process of Cr (VI) ion, dynamic saturated extent of adsorption is respectively
228.2mg/g.In desorption experiment, 4% thiourea solution is 100% to the desorption efficiency of Cr (VI) ion on AMIF.SEM,
TGA respectively characterizes the structure of AMIF absorption front and back.The results show that AMIF fiber is matched by nitrogen-atoms and Cr (VI) ion
Position is declined in conjunction with rear thermal stability；Rear thermal stability has been in conjunction with Cr (VI) ion coordination by nitrogen-atoms for AMIF fiber
It improves.AMIF fiber is suitable for carrying out adsorption-desorption operation to heavy metal ion respectively at 225 DEG C or less.
Further, the present invention provides one kind to have the advantages that good separating effect, strong antijamming capability, testing cost are low etc.
Chelate fibre separation and preconcentration-visible spectrophotometry detection content of heavy metal in foods method.The present invention is with heavy metal
The easily exceeded edible mushroom dried product of content (agrocybe, agaricus bisporus), tealeaves (Mount Huang Mao Feng, Iron Guanyin) are used as research object, benefit
It is enriched with Cr therein (VI) ion at optimum conditions with AMIF fiber, and same by UV-VIS spectrophotometry and ICP
Shi Jinhang detection.Two methods testing result is almost the same, and Cr (VI) is without departing from national limit standard in sample.Precision,
Recovery of standard addition all shows that this method is able to satisfy analysis detection requirement.It can be seen that the method improves UV-vis spectroscopy light
The detection of degree method limits, it is made to be expected to be widely applied in food heavy metal analysis.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the polyurethane fiber crossed without any working process under 5000 times.
Fig. 2 is scanning electron microscope (SEM) photograph of the PUCA under 5000 times.
Fig. 3 is scanning electron microscope (SEM) photograph of the AMIF made from embodiment 1 under 5000 times.
Fig. 4 is the scanning electron microscope (SEM) photograph under 5000 times after the absorption of AMIF made from embodiment 1 Cr.Fig. 5 is embodiment 1
The infrared spectrogram of PUCA and AMIF obtained.
Fig. 6 is influence of the reaction temperature to polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.
Fig. 7 is the influence reacted molar ratio and compare polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.
Fig. 8 is influence of the reaction time to polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.
Fig. 9 be under different pH value polyurethane -3- amino -5- methylisoxazole fiber to the adsorption effect of different heavy metals.
Figure 10 is the kinetic curve of AMIF absorption Cr (VI).
Figure 11 is the dynamic desorption curve of AMIF.
Specific embodiment
The present invention will be described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
Step 1:
It accurately weighs the original PU fiber of 2.0g and cleans 30min with toluene, be placed in the three-necked bottle that capacity is 500mL and be added
200mL toluene is warming up to 50 DEG C, and 2.69mL diphenylmethane diisocyanate isomers (4,4-MDI), 1.64mL catalysis is being added
Agent triethylamine (TEA), stirred under nitrogen atmosphere react 2h, and filtering taking-up is cleaned for several times with toluene, are prepared into PU-NCO fiber.
Step 2: taking above-mentioned fiber 1.0g, is placed in addition 100mL toluene in the three-necked bottle that capacity is 250mL and is warming up to
It 50 DEG C, is added 200mg citric acid (CA), appropriate initiator potassium peroxydisulfate, stirred under nitrogen atmosphere reacts 6h, after experiment
Fiber is cleaned for several times with anhydrous ether, and is dried in vacuo under the conditions of 50 DEG C, and citric acid grafted polyurethane fiber (PU- is prepared into
CA)。
Step 3:
Accurately weighing 30mgPU-CA fiber to be placed on capacity with electronic balance is then to add in the three-necked bottle of 100mL
80ml1,4- dioxane.After fiber in a solvent sufficiently be swollen after a certain amount of AMI ligand is added, lead to nitrogen protection gas with
The revolving speed of 150rpm at the uniform velocity stirs 1-2h, it is allowed to eliminate the air in three-necked bottle, rapidly rises to reaction dissolvent certain
Temperature simultaneously keeps constant temperature, and continuation is at the uniform velocity stirred to react a period of time.Be cooled to room temperature after reaction, successively with reaction dissolvent,
Four kinds of dehydrated alcohol, acetone, ether organic solvents recycle washed product 3-4 times, obtain AMIF and dry in 50 DEG C of vacuum ovens
It does spare.
Fig. 1 is the scanning electron microscope (SEM) photograph of the polyurethane fiber crossed without any working process under 5000 times.Fig. 1 can be with
It sees, the surface smoother of original PU fiber, almost without spot, gravure and crackle etc..
Fig. 2 is scanning electron microscope (SEM) photograph of the PUCA under 5000 times.As seen from Figure 2 citric acid grafting after fiber surface compared with
Slightly coarse before grafting, gravure also has intensification.Fig. 3 is scanning electron microscope (SEM) photograph of the AMIF made from embodiment 1 under 5000 times.Such as Fig. 3
Shown, its surface of AMIF fiber surface is relatively smooth, almost without gravure, after chemical modification, and polyurethane fiber structure
On strand crosslinking combine and become loose, along with the destruction in partially crystallizable region, the surface of fiber is caused to start to become thick
It is rough.Fig. 4 is the scanning electron microscope (SEM) photograph under 5000 times after the absorption of AMIF made from embodiment 1 Cr.Comparison diagram 3 and Fig. 4, AMIF
Surface before absorption is relatively smooth, and many equally distributed acicular substances occurs after adsorbing heavy metal.By front
Analysis is it is found that acicular substance is probably Cr (VI) ion of the corresponding absorption of fiber.
Fig. 5 is the infrared spectrogram of AMIF made from embodiment 1.As shown in figure 5, due in heterocyclic ligand AMI
1560cm-1Locate primary amine-NH2Bending vibration absorption peak does not occur in AMIF；1507cm in AMIF-1And 1428cm-1Vibration
Absorption peak illustrates the presence of five-ring heterocycles.It is possible thereby to prove that AMI is successfully grafted on PU-CA fiber.
The synthetic route of AMIF is as follows:
According to the content of N in sample, the function base conversion ratio and functional group content of chelate fibre can pass through following formula
Son calculates:
In above formula, x is the function base conversion ratio of chelate fibre, and F0 is that parent citric acid is grafted in spandex fibre (PU-CA)
Functional group content (- COOHmmol/g), ne are the number of nitrogen-atoms in ligand molecular, N0
For the conjunction nitrogen quantity (%) of PU-CA fiber, Ne is the conjunction nitrogen quantity (%) of fiber after synthesis, is fiber after synthetic reaction
Gain in weight (g/mol).
Embodiment 2
The reaction dissolvent of step 3 in embodiment 1 is changed to different solvents, as a result as shown in the table.
Elemental analysis result of 1 AMIF of table under three kinds of reaction dissolvents
As shown in table 1, the optimum response solvent of AMI and fiber chelating is Isosorbide-5-Nitrae-dioxane.
Embodiment 3
Under optimum response solvent condition, the reaction temperature that step 3 is different in embodiment 1 is replaced, remaining is completely the same as implementation
The step of example 1, is identical, converts to inquire into reaction temperature to synthesis of polyurethane -3- amino -5- methylisoxazole fiber function base
The influence of rate.Fig. 6 is influence of the reaction temperature to polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.As shown in fig. 6,
When reaction temperature is in lower range (25 DEG C -55 DEG C), the function base conversion ratio of chelate fibre increases with temperature and is increased,
It may be because the higher reaction system that represents of temperature can be more from the extraneous energy that obtain, the organic heterocyclic ligand for obtaining energy becomes
It is more active, accelerate active site on fiber to spread and concentrate, carry out reaction fiercer, function base conversion ratio is not
It is disconnected to improve.But after temperature continues to increase and is more than certain value, excessively active heterocyclic ligand may before reaching active site
Denaturation is decomposed in the reaction system, is also just not suitable for continuing condensation reaction, instead conversion ratio is declined.To sum up,
The optimal reactive temperature for determining AMIF chelate fibre is 55 DEG C.
Embodiment 4
Under the conditions of optimum response solvent, reaction temperature, the reaction molar ratio ratio that step 3 is different in embodiment 1 is replaced,
Remaining completely with embodiment 1 the step of it is identical, thus inquire into reaction molar ratio compare synthesis of polyurethane -3- amino -5- methyl it is different
The influence of oxazole fiber function base conversion ratio.
Fig. 7 is the influence reacted molar ratio and compare polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.Research is matched
Body and influence of the parent molar ratio to chelate fibre function base conversion ratio have very important practical significance.It is not only me
Determine the important parameter of best synthetic technological condition, also play beneficial effect economizing on resources, drop low cost aspect.From reality
It tests from the point of view of result, in the experimentation of different ligand-modified graft fibres, the influence of molar ratio is not quite similar.Just open
When the beginning, the conversion ratio of the function base of AMIF increases as molar ratio increases, and peak is reached at 5: 1, continues increase mole
Than, and the function base conversion ratio of AMIF has larger reduction, the final optimum response molar ratio for determining AMIF is 5.
Embodiment 5
Under conditions of above-mentioned optimum response solvent, optimal reaction temperature, optimum response molar ratio, the reaction time pair is investigated
The influence result of function base conversion ratio.
Fig. 8 is influence of the reaction time to polyurethane -3- amino -5- methylisoxazole fiber conversion ratio.
Reaction time, the variation of graft fibres function base conversion ratio was obvious, with the increasing in reaction time between 4h-8h
Add and increases；But wherein the function base conversion ratio of AMIF fiber is almost unchanged, this illustrate the reaction time be also influence react into
An important factor for journey.Shorten the reaction time, reaction is not thorough, and a large amount of unreacted ligand, unreacted active site are left.
Extend the reaction time, the abundant activation and ligand for being conducive to fiber-reactive site are sufficiently diffused on site, are conducive to reaction and are filled
Divide and carry out, but be more than certain time, reaction basically reaches balance, and conversion ratio would not also further increase, it may be possible to because instead
After balance should being reached, chelate fibre occurs ligand dissociation and falls off or generate other by-products to make the reduction of function base conversion ratio.
Therefore, the extension time is conducive to fiber and organic heterocyclic ligand thoroughly reacts, but is more than certain time, and the function base of fiber converts
Rate is presented downward trend or no longer changes.Therefore, the optimum reacting time of AMIF is 8h respectively.
Embodiment 6
Staticadsorption experiment
The dry fiber for accurately weighing 10mg is placed in the iodine flask of 100mL, and the HAc-NaAc buffer solution of 25mL is added to soak
Profit for 24 hours after, certain density metal ion solution 5mL is added, chelate fibre is not added as blank control, at a certain temperature in
The constant temperature oscillation of 100rpm revolving speed is to after balancing, the accurate content for measuring residual ion in solution.Mixed metal solion can
Each metal ion content is measured with ICP method, single Cr (VI) solion can use ultraviolet spectrophotometry (50% phosphoric acid
For the Diphenyl carbohydrazide of 0.25mL and 0.2% as color developing agent, selecting 540nm is measurement wavelength) measurement concentration.It counts as the following formula
Calculate adsorbance Q.
In formula Co, Ce respectively be absorption before, metal ion solution concentration (mg/mL) after adsorption equilibrium；Q is chelate fibre
Static saturated adsorption capacity (mg/g)；V represents the volume (mL) of metal ion solution；M is the weight (g) of chelate fibre.
A certain amount of potassium bichromate is weighed, the standard solution for the Cr (VI) that concentration is 1mg/L is made into, then uses deionized water
It is diluted to different concentration, using deionized water as reference solution, surveys above-mentioned each solution in the case where wavelength is 540nm
Absorbance value.After carrying out blank correction, the relationship between different absorbance values and the concentration of Cr (VI) is obtained.When Cr (VI) contains
When amount is within the scope of 0~0.2mgL-1, absorbance value and hexavalent chromium concentration are in good linear relationship, equation of linear regression
Are as follows: y=1.064x+0.002, x is the concentration of chromium in colorimetric cylinder, unit mgL-1, related coefficient 0.9992, Cr in formula
(VI) standard curve.
It accurately weighs the dry AMIF of 15.0mg to be placed in iodine flask, is separately added into the buffer solution of 25mL difference pH, impregnates
After for 24 hours, the certain density mixed metal solion of 5mL is moved into, in shaken at room temperature (100r/min) to adsorption equilibrium.It surveys
The concentration for determining remaining each metal ion species in solution calculates the static saturated adsorption to each metal ion species of chelate fibre
Amount is ordinate mapping, the relationship of research pH and fibers adsorption performance with adsorbance by abscissa of pH value.Fig. 9 is different pH
It is worth lower polyurethane -3- amino -5- methylisoxazole fiber to the adsorption effect of different heavy metals.As shown in figure 9, pH is to adsorbance
Influence it is very big, AMIF fiber shows to have Selective adsorption to Cr (VI) and adsorption capacity is higher, and to other five kinds of weights
The adsorbance of metal ion is lower, illustrates that AMIF fiber is strong to the selective adsorption capacity of Cr (VI) ion, can reach point
From effect.
As shown in figure 9, AMIF fiber changes the adsorbance of Cr (VI) ion with the variation of pH, in pH4.0~5.0
In range, AMIF fiber to the adsorbance of Cr (VI) ion reach highest range and also can easily with other five heavy metal species ions
Separation, as the raising AMIF fiber of pH is good to the Selective Separation effect of Cr (VI) ion, adsorbance becomes with the variation of pH
Gesture is first to be gradually increased to reduce afterwards, and in pH=5.0, adsorbance is up to 201mg/g.
Embodiment 7
The adsorption kinetic data
It accurately weighs 15.0mgAMIF to be placed in iodine flask, is added in the buffer solution of Optimal pH and sufficiently impregnates for 24 hours, then
Certain density Cr (VI) solion 5mL is added, is adsorbed respectively in the at a temperature of 100rpm oscillation of 288K, 298K and 308K,
It is provided at pre-determined intervals, metal ion in solution concentration is measured by sampling, until adsorption test has reached balance.
Figure 10 is the kinetic curve of AMIF absorption Cr (VI).As shown in Figure 10, in the time range of 0~10h, AMIF
Cr (VI) adsorbance is risen quickly, thus it is speculated that because initial stage metal ion initial concentration is larger, in addition having in fiber enough
Adsorption site, the surface that metal ion can comparatively fast be distributed to fiber are then adsorbed, that is, it is larger to show as the rate of adsorption；But with
The progress of absorption, the active site on chelate fibre gradually decreases, when heavy metal ions concentration in solution gradually decreases, absorption speed
Rate will receive the repulsive interaction on steric restriction and solution and chelate fibre between heavy metal ion and reduce.In addition, for same
For a kind of fiber, other parameters are identical only to increase temperature, and adsorbance gradually increases, this illustrates that absorption is endothermic process；?
Within the scope of test temperature, heating can accelerate absorption to carry out, and improve the rate of adsorption and increase saturated extent of adsorption.
Embodiment 8
Dynamic adsorption test
The dry AMIF of 100.0mg is accurately weighed, is first sufficiently impregnated for 24 hours using Optimal pH buffer solution, is then charged into φ 3mm
In × 30cm dynamic adsorption post, the bottom end and top of adsorption column are sealed with cotton later.It will be molten with the buffering of optimal adsorption pH value
Cr (VI) solution for the various concentration that liquid is made into carried out column, the efflux and meter of Fractional Collections certain volume at different flow rates
Concentration of metal ions is calculated, until efflux concentration of metal ions is equal with influent concentration of metal ions.With the volume V of efflux
For abscissa, Ci/C0 is that ordinate makees dynamic adsorption curve and adsorbance is calculated as follows:
C0, Ci are influent and outflow concentration (unit is mg/mL) respectively in formula, and V is effluent volume (mL), m
It is dry fibers quality (g).
It is learnt from experimental result, the initial concentration of solution flow velocity and heavy metal ion is bigger, and breakthrough curve slope is also got over
Greatly, the time for reaching adsorption equilibrium is also shorter.This is because with the increase of flow velocity, connecing between fiber and heavy metal ion
The touching time shortens, i.e., penetration volume reduces, and breakthrough curve shifts to an earlier date, is unfavorable for adsorbing；And heavy metal ion initial concentration increases, and passes
Matter motive force also increases with it, and enables chelate fibre faster adsorption saturation.It follows that the initial concentration of heavy metal ion
Bigger, flow velocity is slower, is more conducive to the progress of Dynamic Adsorption process.However increasing heavy metal ion initial concentration can make to chelate
The saturated extent of adsorption of fiber increases, but also results in the utilization rate decline of adsorption column simultaneously.Therefore, 0.1mg/mL and 0.1mL/
Min is ideal initial concentration and flow velocity.Compared with saturated extent of adsorption when Static Adsorption, Dynamic Adsorption is due to can be with
Guarantee that chelate fibre is contacted with the heavy metal ion of high concentration always, saturation when saturated extent of adsorption can be higher than Static Adsorption is inhaled
Attached amount.
Embodiment 9
The fiber buffer solution and deionized water of adsorption saturation are crossed column to wash for several times, until not inhaled in pillar
Attached heavy metal ion washes away completely, and strippant is flowed through to the fibre columns of adsorption saturation with the speed of 0.10mL/min, until
Elution completely, makees dynamic desorption curve to its volume V with outflow concentration Ce.
The present embodiment selects strippant to carry out dynamic resolution to the AMIF fiber after adsorption saturation for 4% thiourea solution upper prop
It inhales, desorption flow velocity controls as 0.1mL/min.Shown in the result is shown in Figure 11, the AMIF for being adsorbed with Cr (VI) can be washed completely
De-, 5% thiourea solution of 30mL can desorb completely Cr on AMIF (VI)；.Elution curve peak is narrow and sharp as seen from Figure 9
It is sharp, without trailing phenomenon, elute more thorough.From this, the Dynamic Adsorption effect of fiber is fine, it is suitable in practical applications
Recycling, reduces costs.
Application example
Sample: agrocybe, agaricus bisporus, Mount Huang Mao Feng, Iron Guanyin stochastic buying Mr. Yu supermarket.
(1) preprocess method
(1) edible mushroom: sample is washed with deionized for several times, 50 DEG C be dried to it is horizontal heavy.Weigh sample 1.0000g in
Polytetrafluoroethylene (PTFE) is cleared up in inner canister, and the mixed acid of 10mL is added, and (nitric acid: V/V=4: perchloric acid is stood in draught cupboard after 1)
Then 30% hydrogen peroxide of 4ml is added in 4h, stand the program progress micro-wave digestion for screwing outer tank afterwards for 24 hours according to table 2.Resolution terminates
Cooling is stood afterwards, and then acid is caught up in 145 DEG C of heating on electric jacket, is stopped heating when solution is soon done, is used several times after cooling
Residual point of dissolution filter in tank body is transferred in the volumetric flask of 100mL by the buffer solution of HAC-NaAC, as mother liquor to be measured, simultaneously
Prepare blank control.
2 micro-wave digestion program of table
(2) tealeaves: the tealeaves of purchase after dried, crushed cross 24 meshes, accurately weigh the smashed tealeaves of 1.0000g in
Polytetrafluoroethylene (PTFE) is cleared up in inner canister, the subsequent same edible mushroom of digestion procedure, several times will be residual in beaker with HAC-NaAC buffer
Divide dissolution filter to be transferred in the volumetric flask of 100mL, as mother liquor to be measured, while preparing blank control.
(3) preenrichment of sample-spectrophotometry measurement
The measurement of Cr (VI) in food
The heavy metal ion in 200ml sample liquid digested respectively to 2.0g edible mushroom dried product and tealeaves is enriched with
Detection.Using the AMIF fiber of 100mg when pH is 5, Cr (VI) ion in sample liquid is carried out with the rate of adsorption of 1mL/min
Dynamic Adsorption.After absorption completely, eluted with 4% thiocarbamide with Cr (VI) ion of the rate of 1mL/min to absorption.Elution
Content of beary metal in liquid is detected with UV-VIS spectrophotometry and ICP respectively, is obtained by calculation in four kinds of samples
Cr (VI) content.It the results are shown in Table 3, while by chromium limit standard specified in GB2762-2012 national food safety standard
It is listed in table 4:
Measurement result of the 3 two kinds of analysis methods of table to sample
Chromium limit index in 4 food of table
By Result For Determination of Chromium Content it is found that in the 4 kinds of food samples randomly selected, agrocybe, agaricus bisporus, Mount Huang Mao Feng and
Chromium content is respectively 0.392mg/kg, 0.127mg/kg, 0.238mg/kg, 0.321mg/kg in Iron Guanyin；In margin of safety
In range.In addition, the chromium content in this 4 kinds of food is directly measured with ICP-AES, the result basic one of two kinds of detection methods measurement
It causes, illustrates that the content of chromium is feasible to separation and preconcentration-ultraviolet-visible spectrophotometry for measuring edible mushroom dried product, in tealeaves
, and testing cost can be substantially reduced.
(4) precision measures
It is enriched with using agrocybe, agaricus bisporus and Iron Guanyin as foodstuff samples according to above-mentioned experimental method, gained prepare liquid difference
Do 7 parallel determinations.It the results are shown in Table shown in 6, relative standard deviation RSD (%) is respectively 1.46,4.04,1.17, is below
5%, illustrate that this method reproducibility is good, precision is high.
6 precision measurement result of table
(5) recovery testu
A certain amount of chromium standard solution is added, is handled according to the method for test, measures the content of chromium, calculates the rate of recovery, knot
Fruit is shown in Table 7, it is known that recovery of standard addition meets testing requirements between 98.0%~101.0%.
7 recovery testu result of table
The result shows that 100mg AMIF fiber is under the conditions of pH=5, flow velocity are 1mL/min to 0.1mg/mL in 600 ml
Cr (VI) ion adsorption effect it is best.Using 4% thiocarbamide with the rate of 1mL/min to the Cr being adsorbed on AMIF fiber
(VI) ion is eluted, and the rate of recovery is up to 100%.Measurement result shows that the content of Cr (VI) ion is in state in 4 kinds of samples
Within the scope of family's limit standard.Preenrichment-is ultraviolet-and the result of visible spectrophotometry and ICP measurement is almost the same, illustrate we
Chelate fibre used in method is strong to the accumulation ability of heavy metal, improves the detection limit of spectrophotometry, therefore can establish a kind of chela
The method of condensating fiber separation and preconcentration-ultraviolet-visible spectrophotometry detection content of heavy metal in foods, have good separating effect,
The advantages such as strong interference immunity, testing cost be low.
Although the invention has been described by way of example and in terms of the preferred embodiments, but it is not for limiting the present invention, any this field
Technical staff without departing from the spirit and scope of the present invention, may be by the methods and technical content of the disclosure above to this hair
Bright technical solution makes possible variation and modification, therefore, anything that does not depart from the technical scheme of the invention, and according to the present invention
Technical spirit any simple modifications, equivalents, and modifications that above embodiments are made, belong to the technology of the present invention side
The protection scope of case.
Claims (10)
1. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber, which is characterized in that the preparation method include with
Lower step:
Step a, the preparation of the polyurethane fiber containing carbamate groups: triethylamine is catalyst, utilizes excessive hexichol
Methane diisocyanate isomers carries out graft reaction on polyurethane fiber surface, and the free carbamate of Surface Realize is made
The polyurethane fiber of group；
Step b, the preparation of the polyurethane fiber of citric acid grafting: polyurethane fiber and citric acid containing carbamate groups
Reaction obtains the polyurethane fiber of citric acid grafting；
Polyurethane -3- amino -5- methylisoxazole fiber: ligand 3- is added in step c in the polyurethane fiber of citric acid grafting
Amino -5- methylisoxazole, reaction obtain polyurethane -3- amino -5- methylisoxazole fiber.
2. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber as described in claim 1, which is characterized in that step
In rapid a, after polyurethane fiber is cleaned with toluene, it is that solvent is warming up to 50 DEG C that toluene, which is added, adds diphenylmethane diisocyanates
Ester isomer, catalyst of triethylamine, stirred under nitrogen atmosphere react 2h, filtering taking-up cleaned repeatedly with toluene, be prepared into containing
The polyurethane fiber of carbamate groups.
3. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber as described in claim 1, which is characterized in that step
In rapid b, the polyurethane fiber containing carbamate groups is added toluene and is warming up to 50 DEG C, and citric acid, initiator over cure is added
Sour potassium, stirred under nitrogen atmosphere react 6h, and fiber is cleaned repeatedly with anhydrous ether after experiment, and vacuum under the conditions of 50 DEG C
It is dry, it is prepared into citric acid grafted polyurethane fiber.
4. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber according to claim 1, which is characterized in that
In step c, reaction dissolvent is Isosorbide-5-Nitrae-dioxane.
5. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber according to claim 4, which is characterized in that
In step c, reaction dissolvent Isosorbide-5-Nitrae-dioxane is added in citric acid grafted polyurethane fiber, is sufficiently swollen in a solvent to fiber
Ligand 3- amino -5- methylisoxazole is added afterwards, logical nitrogen protection gas at the uniform velocity stirs 1-2h with the revolving speed of 150rpm, by three-necked bottle
In air eliminate, reaction dissolvent is risen into reaction temperature and keeps constant temperature, continuation be at the uniform velocity stirred to react, cool down after reaction
To room temperature, successively recycled washed product 3-4 times with four kinds of reaction dissolvent, dehydrated alcohol, acetone, ether organic solvents, in 50 DEG C
It is dried in vacuum oven.
6. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber according to claim 5, which is characterized in that
Reaction temperature is 55 DEG C in step c.
7. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber according to claim 5, which is characterized in that
The molar ratio of carboxyl is 5 on ligand and citric acid grafted polyurethane fiber.
8. the preparation method of polyurethane -3- amino -5- methylisoxazole fiber according to claim 5, which is characterized in that
The reaction time is 8h in step c.
9. a kind of richness of polyurethane -3- amino -5- methylisoxazole fiber heavy metal in food as described in claim 1
Application in collection detection.
10. application as claimed in claim 9, which is characterized in that the heavy metal is hexavalent chromium.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352713A (en) * | 1999-05-25 | 2002-06-05 | 中部吉利斯德股份有限公司 | Metal chelate-forming fiber, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
| CN103790010A (en) * | 2013-10-30 | 2014-05-14 | 青岛大学 | Preparation of chelate fiber with side chain containing triazole heterocyclic ring |
| CN105107474A (en) * | 2015-08-03 | 2015-12-02 | 佛山市博新生物科技有限公司 | Chelating adsorbent for blood purification and preparation method for chelating adsorbent |
| WO2016117718A1 (en) * | 2015-01-20 | 2016-07-28 | Chang Sung Co., Ltd. | Electromagnetic wave shielding and absorbing sheet and manufacturing method of the same |
| CN106480710A (en) * | 2016-09-23 | 2017-03-08 | 安徽工程大学 | A kind of preparation method of feature PU AOPAN composite nano-fiber membrane |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352713A (en) * | 1999-05-25 | 2002-06-05 | 中部吉利斯德股份有限公司 | Metal chelate-forming fiber, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
| CN103790010A (en) * | 2013-10-30 | 2014-05-14 | 青岛大学 | Preparation of chelate fiber with side chain containing triazole heterocyclic ring |
| WO2016117718A1 (en) * | 2015-01-20 | 2016-07-28 | Chang Sung Co., Ltd. | Electromagnetic wave shielding and absorbing sheet and manufacturing method of the same |
| CN105107474A (en) * | 2015-08-03 | 2015-12-02 | 佛山市博新生物科技有限公司 | Chelating adsorbent for blood purification and preparation method for chelating adsorbent |
| CN106480710A (en) * | 2016-09-23 | 2017-03-08 | 安徽工程大学 | A kind of preparation method of feature PU AOPAN composite nano-fiber membrane |
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