CN106397640B - 水溶性抗菌压克力高分子银盐 - Google Patents
水溶性抗菌压克力高分子银盐 Download PDFInfo
- Publication number
- CN106397640B CN106397640B CN201610236034.XA CN201610236034A CN106397640B CN 106397640 B CN106397640 B CN 106397640B CN 201610236034 A CN201610236034 A CN 201610236034A CN 106397640 B CN106397640 B CN 106397640B
- Authority
- CN
- China
- Prior art keywords
- water
- silver
- silver salt
- carboxylic acid
- soluble
- 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.)
- Active
Links
- 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 title claims abstract description 78
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 46
- 229920000058 polyacrylate Polymers 0.000 title abstract 8
- -1 sodium carboxylate Chemical class 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 229920002521 macromolecule Polymers 0.000 claims description 58
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 44
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 235000015424 sodium Nutrition 0.000 claims 6
- 239000007864 aqueous solution Substances 0.000 abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 abstract description 16
- 239000012535 impurity Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 159000000000 sodium salts Chemical class 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000000108 ultra-filtration Methods 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 229920002125 Sokalan® Polymers 0.000 description 20
- 239000004584 polyacrylic acid Substances 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000012266 salt solution Substances 0.000 description 9
- 150000003384 small molecules Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 235000008429 bread Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 206010052428 Wound Diseases 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 229960003600 silver sulfadiazine Drugs 0.000 description 3
- UEJSSZHHYBHCEL-UHFFFAOYSA-N silver(1+) sulfadiazinate Chemical compound [Ag+].C1=CC(N)=CC=C1S(=O)(=O)[N-]C1=NC=CC=N1 UEJSSZHHYBHCEL-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920000142 Sodium polycarboxylate Polymers 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- FSZIKKZELSJHJS-UHFFFAOYSA-L disodium;2-methylprop-2-enoate;prop-2-enoate Chemical compound [Na+].[Na+].[O-]C(=O)C=C.CC(=C)C([O-])=O FSZIKKZELSJHJS-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Chemical group 0.000 description 1
- LHKBLYRMQQGIOD-UAIGNFCESA-M sodium;(z)-but-2-enedioic acid;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O.OC(=O)\C=C/C(O)=O LHKBLYRMQQGIOD-UAIGNFCESA-M 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/02—Local antiseptics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- General Chemical & Material Sciences (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Toxicology (AREA)
Abstract
本发明涉及一种水溶性抗菌压克力高分子银盐,该水溶性抗菌压克力高分子银盐的分子链上含有羧酸钠基和羧酸银基,其制备是以含有羧酸钠(‑COONa)官能团的压克力高分子,利用该压克力高分子的羧酸钠基和银的盐类在水中进行金属离子交换,以得到含有羧酸银(‑COOAg)官能团的水溶性压克力高分子,然后再利用超过滤膜(Ultrafiltration membrane)将交换后产生的钠盐去除,以得到几乎不含杂质的水溶性抗菌压克力高分子银盐的水溶液,最后再将水溶性抗菌压克力高分子银盐从该水溶液中分离出来,利用该方法得到的水溶性抗菌压克力高分子的羧酸银基和羧酸钠基的摩尔比可以高达66/34。
Description
技术领域
本发明涉及一种水溶性抗菌压克力高分子银盐,该水溶性抗菌压克力高分子银盐的分子链上同时含有羧酸钠基以及羧酸银基两种官能团,其制备方法是利用金属离子交换的方式,将含有羧酸钠官能团的压克力高分子上的羧酸钠基,用银盐在水中进行金属离子交换成羧酸银基,然后利用超过滤的方法将其副产物钠盐以及其他小分子的杂质去除,以得到几乎不含杂质的水溶性抗菌压克力高分子银盐的水溶液,最后再将水溶性抗菌压克力高分子银盐从该水溶液中分离出来。
背景技术
细菌对人类的生活有着无比大的影响,它影响人类的健康,导致疾病与死亡,因此抗菌变成了必要性的工作,到目前为止大部分的抗菌剂都是以小分子的形态存在,它们用在抗菌药剂或当作食物保存剂,也可以作为对水或土壤消毒杀菌使用,小分子抗菌剂存在着无法解决的缺点,例如残留对环境的毒性、较短暂的抗菌效果、容易被吸收所造成对人体的危害等,解决这些问题的方式便是使用高分子抗菌剂。一般高分子抗菌剂是将具有抗菌效果的分子接在高分子主链上,这样可以降低抗菌分子的毒性、减低对环境的影响、增加其抗菌效率与选择性以及增长其抗菌效果的时间(请参阅Biomacromolecules,2007,vol.8,No.5,page 1359-1384)。
由于许多的抗菌应用是在有水或亲水的环境中进行,例如化妆品的防腐及保存、杀菌洗手液、抗菌清洁剂等,因此水溶性的抗菌高分子确实有其应用上的需求。
自古以来,银的杀菌效果即为人们所熟知与应用,早期人类用银制成餐具,发觉银餐具装盛的牛奶或食物,比较不容易腐坏,到近期银在杀菌应用上更是扩展到了纳米银与银离子的形态。
银离子的应用大部分是以银的无机盐形式使用,例如硝酸银、醋酸银和硫代硫酸银,除了上述的银盐外,银的盐类几乎都不溶于水或略溶于水。
除了银的无机盐类以外,银离子也可以和有机小分子复合或称为银的有机盐,最有名的是磺胺嘧啶银盐(silver sulfadiazine),广泛的被应用在烧烫伤的伤口处理以及杀菌,但是磺胺嘧啶银盐也不溶于水。
以上不论是银的无机盐或有机复合物,都属于小分子的抗菌剂,所以它们都具有小分子抗菌剂的缺点,再加上水溶性的需求,因此水溶性含银的高分子复合物或称为高分子银盐的开发与研究确实有其必要性。
银离子可以和高分子复合,高分子和银的复合物同样也有不易溶于水的问题,早在1934年,英国专利GB420533(A)就揭露了聚丙烯酸银的制备方法,虽然使用的原料聚丙烯酸钠溶于水,但是所得到的聚丙烯酸银是不溶于水的,该专利主要是将聚丙烯酸银作为一般塑料使用,并未考虑到其抗菌的效用。
美国专利5,709,870揭露了一种含银的羰基甲基纤维素钠,利用银离子和钠离子交换,只是其银含量非常的低,低于1%。
而已知可以溶于水的含银压克力高分子可以在2001年发表的文章(Pharmaceutical chemistry Journal,2001,vol.35,No 5,Page 252-253)发现,该文章叙述一种含银的聚丙烯酸高分子,分子式是(CH2CHCOOH)n-(CH2CHCOOAg)m,其中n=9000~40000以及m=100~3000,银含量在1~10%,该含银的聚丙烯酸高分子可以溶于水,而且具有抗菌效果,文中并未叙述其制造方法。其制备方法在RU2220982中叙述,根据RU2220982中所叙述,其制备方法仅是将硝酸银水溶液加入聚丙烯酸水溶液中混合,搅拌30到60分钟,然后在50℃干燥,得到灰色透明产物。这种做法很明显的并未将含银的聚丙烯酸高分子分离纯化。
所以到目前为止世上并未有不含杂质的水溶性抗菌压克力高分子银盐被设计及合成出来。
发明内容
本发明涉及一种水溶性抗菌压克力高分子银盐,为了得到含银量高而且可以水溶的压克力高分子银盐,本发明设计了一种水溶性抗菌压克力高分子银盐,其高分子链上同时含有羧酸钠与羧酸银两种特性不同的官能团,利用羧酸钠的高度水溶性以弥补羧酸银所带来的水不溶性,本发明所设计的水溶性抗菌压克力高分子银盐的制备可以利用含有羧酸钠(-COONa)官能团的压克力高分子,将该压克力高分子的羧酸钠基和银的盐类在水中进行金属离子交换,以得到含有羧酸银(-COOAg)官能团的水溶性压克力高分子,然后再利用超过滤(Ultrafiltration)将金属离子交换后产生的钠盐去除,以得到几乎不含其他杂质的水溶性抗菌压克力高分子银盐的水溶液,然后再将该水溶性抗菌压克力高分子银盐从水溶液中分离出来。
利用羧酸钠基和银盐进行金属离子交换以得到羧酸银基,早已为人所知并加以利用,例如EP0710877B1和EP1069468B1提到了利用羧酸钠基和银盐交换得到一些有机羧酸银,问题是这些有机羧酸银对水的溶解度都不佳。
本发明的水溶性抗菌压克力高分子银盐,其制备方法是利用金属离子交换,将含有羧酸钠官能团的压克力高分子和银盐在水中进行金属离子交换,将压克力高分子中部分的羧酸钠基交换成羧酸银基,使得高分子链中同时带有羧酸钠基与羧酸银基两种官能团,虽然羧酸银基会导致不溶的结果,但是利用高分子链中同时具有羧酸钠基而使得这个高分子链可以溶于水,这样就可以得到可水溶性的压克力高分子银盐。应注意的是交换的比例必须控制一定比例以下,否则所得到的压克力高分子银盐中羧酸钠基的含量太低,会导致该压克力高分子银盐不溶于水。
但是金属离子交换完后的水溶液中除了水溶性抗菌压克力高分子银盐外,还存在着交换得到的钠盐副产物以及其他由原料中带来的小分子的杂质,如果不除去,对水溶性抗菌压克力高分子银盐会有不良的影响。传统去除高分子杂质的沉淀法并无法去除钠盐,因为如果用沉淀法去除水溶性抗菌压克力高分子银盐的杂质,沉淀所需的非溶剂必须是可以和水相溶,但又不溶水溶性抗菌压克力高分子银盐的溶剂,一般优选丙酮或甲基乙基酮,可是丙酮或甲基乙基酮对钠盐的溶解性非常差,因此金属离子交换得到的钠盐副产物可能会随着水溶性抗菌压克力高分子银盐沉淀出来,而无法达到去除杂质的目的。
本发明的水溶性抗菌压克力高分子银盐,其制备方法是利用超过滤(Ultrafiltration)对分子大小具有选择性的特性,将离子交换后所得到的钠盐以及其他小分子杂质通过超过滤去除,得到几乎不含杂质的抗菌压克力高分子银盐的水溶液,方法简单便利,在成本上相对有利。
经过超过滤处理后的水溶性压克力高分子银盐水溶液,其内所含的杂质已经非常的少,之后将水分去除便可以得到抗菌压克力高分子银盐。将水分去除可以用一般的蒸馏、减压蒸馏、喷雾干燥或沉淀干燥等方法。
本发明中所谓的含羧酸钠官能团的压克力高分子可以是聚丙烯酸钠、聚甲基丙烯酸钠、丙烯酸-马来酸共聚物的钠盐、甲基丙烯酸-马来酸的钠盐、丙烯酸钠-甲基丙烯酸钠共聚物、丙烯酸钠与其他压克力单体的共聚物或甲基丙烯酸钠与其他压克力单体的共聚物,这些含羧酸钠基的高分子由于分子链中含有大量的羧酸钠基,所以可溶于水。
本发明中制备水溶性压克力高分子银盐所使用的银盐主要是硝酸银或醋酸银,使用这两种银盐的原因是他们对水的溶解度比其他银盐高,但不代表其他银盐不能使用于本发明,只要是对水的溶解度大于0.0001的银盐都可以使用,当使用的银盐溶解度低时,金属离子交换时含羧酸钠基的压克力高分子水溶液的浓度必须配合银盐的溶解度而降低。
金属离子交换在水溶液中进行,先将含羧酸钠官能团的压克力高分子溶于水中,再将银盐的水溶液缓慢加入,持续搅拌即可,在加入银盐的水溶液时,由于加入点瞬间的银量很高,所以会有白色不溶于水的压克力高分子银盐产生,但是只要持续搅拌,这些不溶于水的压克力高分子银盐也会和水溶液中其他含羧酸钠基的压克力高分子进行金属离子交换,而渐渐形成水溶性压克力高分子银盐。银盐可加入的最大量就是当这些白色不溶于水的压克力高分子银盐不会随着搅拌时间的增加而溶解时的银盐加入量,将该银盐的最大加入量换算成摩尔当量时,会发现其低于所使用含羧酸钠官能团的压克力高分子中羧酸钠基的摩尔当量数,也就是本发明的压克力高分子银盐具有水溶特性的必要条件是其结构中仍然必须保留有足够量的羧酸钠基,羧酸钠基如果不足,压克力高分子银盐则无法溶于水。
超过滤主要是以薄膜过滤的形式进行,使用的超过滤薄膜可以筛选的分子量从1000至1000000,取决于薄膜上的孔隙度大小,至于在实际进行分离时,超过滤薄膜的选用则取决于所使用含羧酸钠官能团的压克力高分子的分子量,选用的超过滤薄膜其可筛选分子量必须低于所使用含羧酸钠基的压克力高分子的分子量至少一个量级以下,例如所使用含羧酸钠官能团的压克力高分子的分子量是10万,则选用的超过滤薄膜其可筛选分子量最好是至少1万以下。而使用的薄膜可以是平面膜或中空纤维膜,适用的薄膜模组可以是板框式模组、螺旋卷式模组或中空纤维式模组。
在操作时,将由金属离子交换后所得到的水溶性抗菌压克力高分子银盐水溶液直接或经稀释后放入一个储槽中,以帮浦从储槽中抽出,加压经超过滤薄膜模组的入口打入模组中,由超过滤薄膜模组出口出来的浓缩滤液则回到储槽中,通过薄膜的通过液则另行收集处理,如此操作,将经金属离子交换后所得到的水溶性抗菌压克力高分子银盐水溶液不断循环地通过超过滤薄膜模组,其中经离子交换所得到的钠盐会通过薄膜到通过液中,水溶性抗菌压克力高分子银盐则会留在浓缩滤液中,如此即可达到去除杂质和浓缩的效果。浓缩后得到的水溶性抗菌压克力高分子银盐水溶液,可以再稀释,以同样的操作,再去除杂质和浓缩,该操作可以进行多次,以去除钠盐及其他小分子的杂质以得到几乎不含杂质的水溶性抗菌压克力高分子银盐的水溶液。
最后再利用传统的方法将水溶性抗菌压克力高分子银盐从其水溶液中分离出来,这些方法包含一般的蒸馏、减压蒸馏、喷雾干燥或沉淀干燥等方法。
交换比例的实验:
将500ml的纯水倒在1升的玻璃烧杯中,将0.5克的聚羧酸钠(分子量>8,000,000)加入烧杯中,将水温控制在40℃,以磁石搅拌使其溶解,之后将10g的10%硝酸银水溶液分十次加入烧杯中,每次加入的间隔为半小时,搅拌持续不断,水温控制在40℃,每次加入半小时后观察溶液状态,得到如下表1的结果。
表1
由表1可以得知当-COOAg/(-COOAg+-COONa)的摩尔比大于0.77以上时所得到的聚丙烯酸银盐便无法溶于水,而此时银与聚丙烯酸银盐的重量比是52%,-COOAg/(-COOAg+-COONa)的摩尔比最好小于0.66以得到可以水溶的聚丙烯酸银盐,或银与聚丙烯酸银盐的重量比在47%以下时,聚丙烯酸银盐是可以水溶的。
具体实施方式
聚丙烯酸银盐的制备:
取10g聚丙烯酸钠(分子量>8,000,000)加入2升40℃纯水中,以每分钟一万转的高速搅拌3分钟,得到非常粘稠的透明液体,之后将50%的硝酸银水溶液10g,分5次,在持续每分钟一万转的高速搅拌下,间隔30秒的加入,加完后,维持搅拌5分钟至溶液呈现澄清透明的状态,此时的溶液粘度大大下降,成为流动良好的透明水溶液。
将所得的溶液稀释至10升,利用直径3分米长度12分米的螺旋卷式超过滤膜模组(薄膜的筛选分子量是10万),将该稀释的溶液浓缩至1升,在浓缩过程初期,取通过液100ml,加入氯化钠,并未发现有白色氯化银的产生,可见所有加入的硝酸银都已和聚丙烯酸钠中的羧酸钠基进行金属离子交换,产生羧酸银基,而且经金属离子交换所得到的聚丙烯酸银盐仍然留在浓缩液中而未通过薄膜被滤出。
再将所得的1升浓缩液稀释至10升,重复以上的超过滤操作再浓缩至1升,然后再稀释,再浓缩至1升,如此便可以得到几乎不含杂质的聚丙烯酸银盐水溶液。
取该浓缩的聚丙烯酸银盐水溶液10ml,倒入持续搅拌的1升丙酮中,沉淀出聚丙烯酸银盐,过滤后干燥得到几乎不含杂质的聚丙烯酸银盐,该聚丙烯酸银盐可以再溶于水得到聚丙烯酸银盐水溶液。
抗菌试验:
配制含银量100ppm的聚丙烯酸银盐水溶液,取一个1厘米见方的土司面包,将100ppm的聚丙烯酸银盐水溶液喷洒在土司面包上使其完全湿润,再取另一个1厘米见方的土司面包,将纯水喷洒在土司面包上使其完全湿润,将这两片土司面包放在潮湿的环境中,在室温30℃的条件下观察,结果如表2。
表2
1天 | 2天 | 3天 | 4天 | 5天 | 6天 | 7天 | |
含浸聚丙烯酸银盐的土司 | 无发霉 | 无发霉 | 无发霉 | 无发霉 | 无发霉 | 无发霉 | 无发霉 |
含浸纯水的土司 | 无发霉 | 发霉 | 发霉 | 发霉 | 发霉 | 发霉 | 发霉 |
由表2中的结果可以看出聚丙烯酸银盐具有很好的抗菌效果。
Claims (4)
1.一种水溶性抗菌压克力高分子银盐,其高分子链中含有两种官能团,一种是羧酸钠基,另一种是羧酸银基,其羧酸银基和羧酸钠基的摩尔比低于66/34。
2.根据权利要求1所述的水溶性抗菌压克力高分子银盐,其羧酸银基和羧酸钠基的摩尔比介于66/34和11/89之间。
3.一种水溶性抗菌聚丙烯酸银盐,其高分子链中含有两种官能团,一种是羧酸钠基,另一种是羧酸银基,其羧酸银基和羧酸钠基的摩尔比低于66/34。
4.根据权利要求3所述的水溶性抗菌聚丙烯酸银盐,其羧酸银基和羧酸钠基的摩尔比介于66/34和11/89之间。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW104112626A TWI537331B (zh) | 2015-04-21 | 2015-04-21 | 水溶性抗菌壓克力高分子銀鹽 |
TW104112626 | 2015-04-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106397640A CN106397640A (zh) | 2017-02-15 |
CN106397640B true CN106397640B (zh) | 2019-01-18 |
Family
ID=55755504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610236034.XA Active CN106397640B (zh) | 2015-04-21 | 2016-04-15 | 水溶性抗菌压克力高分子银盐 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9918478B2 (zh) |
EP (1) | EP3085234B1 (zh) |
JP (1) | JP6892739B2 (zh) |
CN (1) | CN106397640B (zh) |
ES (1) | ES2681508T3 (zh) |
PL (1) | PL3085234T3 (zh) |
TR (1) | TR201811817T4 (zh) |
TW (1) | TWI537331B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023044700A1 (zh) * | 2021-09-24 | 2023-03-30 | 世福莱德生技股份有限公司 | 治疗口腔黏膜炎的方法与水性凝胶 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2045080A (en) * | 1932-06-02 | 1936-06-23 | Agfa Ansco Corp | Manufacture of molded articles |
EP1094362A1 (en) * | 1999-10-20 | 2001-04-25 | Fuji Photo Film Co., Ltd. | Method for producing silver salt of organic acid and photothermographic material utilizing the same |
CN1068761C (zh) * | 1994-10-18 | 2001-07-25 | 联合株式会社 | 抗菌剂 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB420533A (en) | 1932-06-02 | 1934-12-03 | Ig Farbenindustrie Ag | Manufacture of metal salts of polymeric carboxylic acids and the production of shaped articles therefrom |
US3507840A (en) * | 1967-04-27 | 1970-04-21 | Nalco Chemical Co | Method of removing water from water-soluble polymers |
GB1587307A (en) * | 1977-03-04 | 1981-04-01 | Nitto Electric Ind Co | Antibacterial and antifungal material |
JPH0339363A (ja) * | 1989-07-07 | 1991-02-20 | Du Pont Mitsui Polychem Co Ltd | 抗菌性包装体または内装体および菌繁殖防止法 |
US5491059A (en) | 1994-10-31 | 1996-02-13 | Minnesota Mining And Manufacturing Company | Silver carboxylate compounds as silver sources in photothermographic and thermographic elements |
JPH08151310A (ja) * | 1994-11-29 | 1996-06-11 | Nippon Shokubai Co Ltd | 抗菌性重合体およびこれを含有する抗菌剤 |
JPH11158220A (ja) * | 1997-11-26 | 1999-06-15 | Japan Exlan Co Ltd | 抗菌性ポリマーとその製造方法並びに該ポリマー を含有する成形体 |
ATE346325T1 (de) | 1999-07-15 | 2006-12-15 | Fuji Photo Film Co Ltd | Ein verfahren zur herstellung lichtunempfindlicher silberfettsäuresalzkörner und ein apparat dafür |
RU2220982C9 (ru) | 2001-01-05 | 2016-04-20 | Иркутский институт химии им. А.Е.Фаворского СО РАН, Государственное учреждение "Научный центр реконструктивной и восстановительной хирургии Восточно-Сибирского научного центра СО РАМН" | Аргакрил - новое антисептическое и гемостатическое средство |
JP2004091779A (ja) * | 2002-08-09 | 2004-03-25 | Du Pont Mitsui Polychem Co Ltd | 抗菌性皮膜形成性水性分散液及びその用途 |
WO2008127287A2 (en) * | 2006-10-11 | 2008-10-23 | Biolife, L.L.C. | Materials and methods for wound treatment |
KR20090088168A (ko) * | 2008-02-14 | 2009-08-19 | (주)지알엔지니어링 | 합성수지 펠렛 표면에 나노화된 은(銀) 잉크의 피복을통한 은(銀) 나노 합성수지 펠렛 제조 방법 |
CN101812240A (zh) | 2009-11-19 | 2010-08-25 | 安徽华晶新材料有限公司 | 纳米银-高吸水性树脂复合材料及其辐射法生产工艺 |
-
2015
- 2015-04-21 TW TW104112626A patent/TWI537331B/zh active
-
2016
- 2016-04-13 US US15/097,653 patent/US9918478B2/en active Active
- 2016-04-15 CN CN201610236034.XA patent/CN106397640B/zh active Active
- 2016-04-18 EP EP16165723.4A patent/EP3085234B1/en active Active
- 2016-04-18 PL PL16165723T patent/PL3085234T3/pl unknown
- 2016-04-18 TR TR2018/11817T patent/TR201811817T4/tr unknown
- 2016-04-18 ES ES16165723.4T patent/ES2681508T3/es active Active
- 2016-04-19 JP JP2016083662A patent/JP6892739B2/ja active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2045080A (en) * | 1932-06-02 | 1936-06-23 | Agfa Ansco Corp | Manufacture of molded articles |
CN1068761C (zh) * | 1994-10-18 | 2001-07-25 | 联合株式会社 | 抗菌剂 |
EP1094362A1 (en) * | 1999-10-20 | 2001-04-25 | Fuji Photo Film Co., Ltd. | Method for producing silver salt of organic acid and photothermographic material utilizing the same |
Non-Patent Citations (1)
Title |
---|
Antimicrobial and hemostatic effects of silver-containg poly(acrylic acid)derivatives;M.G.Voronkov,等;《Pharmaceutical Chemistry Journal》;20010531;第35卷(第5期);参见对比文件1第252页左栏第1-4段,右栏第1-2段 * |
Also Published As
Publication number | Publication date |
---|---|
US9918478B2 (en) | 2018-03-20 |
EP3085234B1 (en) | 2018-06-06 |
TWI537331B (zh) | 2016-06-11 |
PL3085234T3 (pl) | 2018-10-31 |
TW201638193A (zh) | 2016-11-01 |
EP3085234A1 (en) | 2016-10-26 |
CN106397640A (zh) | 2017-02-15 |
TR201811817T4 (tr) | 2018-09-21 |
US20160309721A1 (en) | 2016-10-27 |
JP2016204372A (ja) | 2016-12-08 |
ES2681508T3 (es) | 2018-09-13 |
JP6892739B2 (ja) | 2021-06-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102669179B (zh) | 一种抗菌抗病毒处理剂及其制备方法与它的用途 | |
CN106492638B (zh) | 一种纳米银有机框架超滤膜的制备方法及利用其净水的方法 | |
CN101781374B (zh) | 壳聚糖和/或其衍生物铜复合物的制备方法及应用 | |
CN106065039B (zh) | 一种水溶性抗菌压克力高分子银盐的制备方法 | |
CN103342761A (zh) | 一种膜分离制备依诺肝素钠工艺 | |
CN103936885B (zh) | O-富马酯-n-三甲基壳聚糖季铵盐及其制法与应用 | |
CN106397640B (zh) | 水溶性抗菌压克力高分子银盐 | |
CN106804624A (zh) | 一种纳米壳寡糖/银复合诱导抗菌材料的制备方法 | |
CN103624268A (zh) | 新型抗癌荧光含糖银纳米团簇的制备方法 | |
CN104788581B (zh) | 一种提高酵母β‑D‑葡聚糖水溶性的硫酸酯化方法 | |
Pandit et al. | Chitosan biobased materials in textile industry | |
CN107602726B (zh) | 低分子量c6-羧基甲壳素及其制备方法 | |
KR20060115793A (ko) | 키토산 미립자 및 그 제조 방법 | |
Lingait et al. | A review on versatile applications of biomaterial/polycationic chitosan: An insight into the structure-property relationship | |
CN105732842A (zh) | 一种高生物活性甲壳素及其制备方法 | |
JP4813054B2 (ja) | 中性のキトサンヒドロゲルおよびその製造方法 | |
CN106719667A (zh) | 一种壳聚糖增效抗菌液的制备方法 | |
US20160369065A1 (en) | Functional Nanoparticle Composite Comprising Chitosan | |
CN108451903B (zh) | 一种聚维酮碘溶液及其制备方法 | |
CN102382206A (zh) | 壳寡糖季铵盐及其制备方法 | |
CN105085940B (zh) | 壳聚糖的快速溶解方法 | |
US20230287150A1 (en) | Method of industrial extraction of alginates from brown seaweed of the family sargassaceae of the order fucales | |
Albushabaa et al. | A quick overview of chitosan, its sources and applications-A review | |
CN102634074B (zh) | 甲壳素浆及其生产方法 | |
CN104490616B (zh) | 天然有机酸根褐藻氨酸螯合物在纤维中的应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |