CN117016542A - 一种高载银/锌量磷酸锆抗菌剂的制备方法 - Google Patents
一种高载银/锌量磷酸锆抗菌剂的制备方法 Download PDFInfo
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- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 75
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 68
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 41
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 108091007643 Phosphate carriers Proteins 0.000 claims description 9
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000009830 intercalation Methods 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- QMGSCCRUAVAONE-UHFFFAOYSA-N zinc zirconium Chemical compound [Zn].[Zn].[Zn].[Zr] QMGSCCRUAVAONE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 description 27
- -1 medical treatment Substances 0.000 description 13
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 239000000138 intercalating agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000016462 Phosphate Transport Proteins Human genes 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical compound [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种高载银/锌量磷酸锆抗菌剂的制备方法,通过磷酸锆载体的制备、插层磷酸锆的制备、离子交换、煅烧处理,得到高载银/锌量磷酸锆抗菌剂。本发明工艺简单、反应时间短、负载量可控、原料利用率高,有效解决了现有技术负载量低、反应时间长、负载量不可控、工艺成本高等缺点,从而能够更好地满足使用需求。
Description
技术领域
本发明涉及抗菌材料技术领域,尤其涉及一种高载银/锌量磷酸锆抗菌剂的制备方法。
背景技术
抗菌材料主要分为三大类:天然抗菌剂、有机抗菌剂和无机抗菌剂。天然抗菌剂是从动植物中提炼精制而成,具有抗菌效果好、对环境及人体危害较少的优点,但其耐热性较差,一般在150~180℃开始炭化分解,应用范围较窄。有机抗菌剂主要包含酰基苯胺类、咪唑类、噻唑类、异噻唑酮衍生物、双呱类、酚类等,具有较强的杀菌能力,但存在安全性较差、会产生微生物耐药性、化学稳定性较差、导致抗菌制品寿命短等缺点,其耐热性较差,在高温高压下容易分解失效,其分解产物甚至有毒。无机抗菌剂具有抑菌持久性、广谱性、较好的耐热性、较高的安全性、不产生耐药性等优点,因此无机抗菌剂在建材、医疗和纺织品等领域得到了广泛的应用。金属型抗菌剂是无机抗菌剂的重要组成部分,在众多抗菌金属离子中银离子的抗菌能力远超其他金属离子,因此银系无机抗菌剂的应用越来越广泛。目前国内外研究和应用最多的银系抗菌材料包括两大类:纳米银抗菌材料和载银型抗菌材料。
载银型抗菌材料主要是通过离子交换和物理吸附等作用,将银离子附着在无机材料的表面或介孔中使其具有抗菌效果,常见的载体有沸石、蒙脱石、可溶性玻璃、层状磷酸锆、羟基磷灰石、磷酸盐等。
磷酸锆又名磷酸氢锆,是一种层状化合物,不溶于水和有机溶剂,能耐较强的酸和一定的碱,具有较大的比表面积和表面电荷,是一种较强的固体酸,具备良好的离子交换特性,因此磷酸锆常用作无机抗菌剂的载体。常规的磷酸锆与金属阳离子交换的方法是将其置于金属离子水溶液中,通过控制反应时间和金属离子浓度等方式,将金属离子负载到磷酸锆中。目前这种方法需要过量的无机金属盐,或者经过长时间的离子交换反应,才能将银离子负载到磷酸锆中。但是这种方法银离子的载入量不可控,且溶液中会残留大量的银离子。由于银属于贵金属,其成本较高,溶液中的银离子需要回收,导致工艺难度增大,生产成本大大增加。总而言之,现有的制备磷酸锆载银抗菌剂的方法,存在着交换时间长、离子交换不完全、载银量不可控、载银量较低、工艺成本高等缺点,因此不能很好地满足需求。
发明内容
本发明的目的在于克服现有技术的不足,提供一种工艺简单、反应时间短、负载量可控的高载银/锌量磷酸锆抗菌剂的制备方法,以解决现有技术负载量低、反应时间长、负载量不可控、工艺成本高等缺点,从而更好地满足使用需求。
本发明的目的通过以下技术方案予以实现:
本发明提供的一种高载银/锌量磷酸锆抗菌剂的制备方法,包括以下步骤:
(1)磷酸锆载体的制备
按照摩尔比磷酸∶氧氯化锆=10~40∶1,在浓度为3~12mol/L的磷酸溶液中加入氧氯化锆搅拌混合后,转至油浴锅中并安装回流装置,在80~150℃温度下反应12~48h,将反应产物抽滤洗涤至中性,干燥后得到磷酸锆载体;
(2)插层磷酸锆的制备
按照摩尔比磷酸锆∶插层剂=2~5∶1,在浓度为1~3mol/L的插层剂水溶液中加入所述磷酸锆载体,经搅拌反应、抽滤、干燥得到插层磷酸锆;所述插层剂为苯胺、正丁胺、正庚胺、正葵胺、十八烷醇、二十烷醇、三十烷醇、2-甲基吡啶、2-乙基吡啶中的一种或其组合;
(3)离子交换
按照摩尔比金属离子∶Zr4+=1~6∶7,将所述插层磷酸锆分散到浓度为1~3mol/L的金属离子溶液中搅拌反应5~12h进行离子交换,所述金属离子溶液为银盐溶液、锌盐溶液、或银盐溶液和锌盐溶液的混合液;所得产物经抽滤、洗涤至中性、干燥,得到载银/锌磷酸锆前驱体;
(4)磷酸锆抗菌剂的制备
将所述载银/锌磷酸锆前驱体在900~1200℃温度下进行煅烧处理,保温1~3h,研磨粉碎后即得到高载银/锌量磷酸锆抗菌剂。
进一步地,本发明所述步骤(3)的银盐溶液和锌盐溶液的混合液,按照摩尔比银∶锌=1∶1~5。所述银盐为醋酸银或硝酸银,所述锌盐为硝酸锌、醋酸锌、硫酸锌或氯化锌。
本发明具有以下有益效果:
(1)本发明利用磷酸锆是一种固体酸,对布朗斯特碱有很强的亲和力,因此将烷基胺、烷醇、吡啶等客体插入层间区域,同时仍保持其层状结构完整,实现了在室温条件下、较短的时间内完成金属离子交换与负载,通过调节金属离子与锆的摩尔比可以准确的制备出单独载银量为1~20%、单独载锌量为1~20%、银锌共负载银和锌的含量为1~28%(其中银的含量为1~14%、锌的含量为1~14%)的抗菌剂。
(2)本发明对步骤(3)经离子交换负载后进行抽滤处理所得的抽滤液进行金属离子检测,金属离子的利用率达到了100%,无需回收金属离子,提高了原料的利用率,降低了生产成本。
(3)本发明制备高载银/锌量的磷酸锆抗菌剂过程离子交换时间短,金属离子可以完全交换,原料利用率高,生产工艺简单。
下面将结合实施例对本发明作进一步的详细描述。
具体实施方式
实施例一:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,其步骤如下:
(1)磷酸锆载体的制备
在40mL浓度为3mol/L的磷酸溶液中加入4g氧氯化锆搅拌混合后,转至油浴锅中并安装回流装置,在120℃温度下反应24h,将反应产物抽滤洗涤至中性,在80℃干燥12h后,得到磷酸锆载体;
(2)插层磷酸锆的制备
在浓度为1mol/L的十八烷醇水溶液中加入上述磷酸锆载体,搅拌反应5h后,经抽滤、洗涤、干燥得到插层磷酸锆;
(3)离子交换
按照摩尔比Ag+∶Zr4+=1∶7,将上述插层磷酸锆分散到醋酸银溶液(浓度为1mol/L)中搅拌反应5h进行离子交换,所得产物经抽滤、洗涤至中性、干燥,得到载银磷酸锆前驱体;
(4)磷酸锆抗菌剂的制备
将上述载银磷酸锆前驱体放入马弗炉中,在1000℃温度下进行煅烧处理,保温1h,研磨粉碎后即得到高载银量磷酸锆抗菌剂。
实施例二:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例一不同之处在于:步骤(2)中插层剂为正葵胺,步骤(3)中按照摩尔比Ag+∶Zr4+=2∶7。
实施例三:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例一不同之处在于:步骤(2)中插层剂为2-甲基吡啶,步骤(3)中按照摩尔比Ag+∶Zr4+=3∶7。
实施例四:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例一不同之处在于:步骤(3)中按照摩尔比Ag+∶Zr4+=4∶7。
实施例五:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,其步骤如下:
(1)磷酸锆载体的制备
在40mL浓度为3mol/L的磷酸溶液中加入4g氧氯化锆搅拌混合后,转至油浴锅中并安装回流装置,在120℃温度下反应24h,将反应产物抽滤洗涤至中性,在80℃干燥12h后,得到磷酸锆载体;
(2)插层磷酸锆的制备
在浓度为1mol/L的十八烷醇水溶液中加入上述磷酸锆载体,搅拌反应5h后,经抽滤、洗涤、干燥得到插层磷酸锆;
(3)离子交换
按照摩尔比(Ag++Zn2+)∶Zr4+=2∶7,将上述插层磷酸锆分散到醋酸银溶液(浓度为1mol/L)和醋酸锌溶液(浓度为1mol/L)的混合液(按照摩尔比Ag+∶Zn2+=1∶1)中,搅拌反应5h进行离子交换,所得产物经抽滤、洗涤至中性、干燥,得到载银/锌磷酸锆前驱体;
(4)磷酸锆抗菌剂的制备
将上述载银/锌磷酸锆前驱体放入马弗炉中,在1000℃温度下进行煅烧处理,保温1h,研磨粉碎后即得到高载银锌量磷酸锆抗菌剂。
实施例六:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例五不同之处在于:步骤(2)中插层剂为正葵胺,步骤(3)中按照摩尔比(Ag++Zn2+)∶Zr4+=4∶7。
实施例七:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例五不同之处在于:步骤(2)中插层剂为2-甲基吡啶,步骤(3)中按照摩尔比(Ag++Zn2+)∶Zr4+=6∶7。
实施例八:
本实施例一种高载银/锌量磷酸锆抗菌剂的制备方法,与实施例一不同之处在于:步骤(3)中将插层磷酸锆分散到醋酸锌溶液(浓度为1mol/L)中,按照摩尔比Zn+∶Zr4+=4∶7。
分别以上述实施例一、实施例五未进行步骤(2)插层磷酸锆(其他步骤相同)为对比例一、对比例二。本发明实施例和对比例制得的磷酸锆抗菌剂的载银/锌量的测试结果如表1所示。
表1本发明实施例和对比例制得的磷酸锆抗菌剂的载银/锌量的测试结果
表1结果表明,本发明实施例一、二、三、四单独负载银离子时,随着银离子浓度的提高,载银量也随之增加,载银量可以达到19.85%;实施例五、六、七银锌共同负载时,随着银离子和锌离子浓度的提高,载银量和载锌量也随着增加,载银量可以达到13.44%、载锌量可以达到13.71%。实施例八单独负载锌离子,载锌量可以达到19.89%。
对比例一、二所用的载体为未经插层处理的磷酸锆载体,银离子和锌离子在短时间内难以与层间的氢离子发生离子交换,载银、锌量(均小于1%)远远低于本发明实施例。
对本发明实施例步骤(3)经离子交换负载后进行抽滤处理所得的抽滤液进行银离子和锌离子检测。取5mL的抽滤液加入一定量的NaCl,未发现AgCl白色沉淀,说明Ag+全部负载到磷酸锆中;取5mL的抽滤液加入过量的NaOH,呈现强碱性,再滴入一滴硫化钠,未发现白色沉淀,说明抽滤液中无锌离子残留。本发明银离子和锌离子的利用率达到了100%而无需回收,提高了原料的利用率,降低了生产成本。
Claims (3)
1.一种高载银/锌量磷酸锆抗菌剂的制备方法,其特征在于包括以下步骤:
(1)磷酸锆载体的制备
按照摩尔比磷酸∶氧氯化锆=10~40∶1,在浓度为3~12mol/L的磷酸溶液中加入氧氯化锆搅拌混合后,转至油浴锅中并安装回流装置,在80~150℃温度下反应12~48h,将反应产物抽滤洗涤至中性,干燥后得到磷酸锆载体;
(2)插层磷酸锆的制备
按照摩尔比磷酸锆∶插层剂=2~5∶1,在浓度为1~3mol/L的插层剂溶液中加入所述磷酸锆载体,经搅拌反应、抽滤、干燥得到插层磷酸锆;所述插层剂为苯胺、正丁胺、正庚胺、正葵胺、十八烷醇、二十烷醇、三十烷醇、2-甲基吡啶、2-乙基吡啶中的一种或其组合;
(3)离子交换
按照摩尔比金属离子∶Zr4+=1~6∶7,将所述插层磷酸锆分散到浓度为1~3mol/L的金属离子溶液中搅拌反应5~12h进行离子交换,所述金属离子溶液为银盐溶液、锌盐溶液、或银盐溶液和锌盐溶液的混合液;所得产物经抽滤、洗涤至中性、干燥,得到载银/锌磷酸锆前驱体;
(4)磷酸锆抗菌剂的制备
将所述载银/锌磷酸锆前驱体在900~1200℃温度下进行煅烧处理,保温1~3h,研磨粉碎后即得到高载银/锌量磷酸锆抗菌剂。
2.根据权利要求1所述的高载银/锌量磷酸锆抗菌剂的制备方法,其特征在于:所述步骤(3)的银盐溶液和锌盐溶液的混合液,按照摩尔比银∶锌=1∶1~5。
3.根据权利要求1或2所述的高载银/锌量磷酸锆抗菌剂的制备方法,其特征在于:所述银盐为醋酸银或硝酸银,所述锌盐为硝酸锌、醋酸锌、硫酸锌或氯化锌。
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