CN106518904A - 一种可固载型吡啶季铵盐卤胺前置体及其合成方法和应用 - Google Patents
一种可固载型吡啶季铵盐卤胺前置体及其合成方法和应用 Download PDFInfo
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- -1 pyridine quaternary ammonium salt Chemical class 0.000 title claims abstract description 48
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000002243 precursor Substances 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
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- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 239000012267 brine Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229940088710 antibiotic agent Drugs 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000003115 biocidal effect Effects 0.000 claims description 12
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
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- 239000000243 solution Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
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- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
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- 230000000844 anti-bacterial effect Effects 0.000 abstract description 45
- 238000002360 preparation method Methods 0.000 abstract description 6
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- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 abstract description 3
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 abstract 1
- 241000192125 Firmicutes Species 0.000 abstract 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 14
- 229920000742 Cotton Polymers 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
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- 230000002070 germicidal effect Effects 0.000 description 4
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- 206010059866 Drug resistance Diseases 0.000 description 2
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- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
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- JMFBXUMHVSZUKY-UHFFFAOYSA-N 3-bromopropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCBr JMFBXUMHVSZUKY-UHFFFAOYSA-N 0.000 description 1
- MPOYBFYHRQBZPM-UHFFFAOYSA-N 3h-pyridin-4-one Chemical class O=C1CC=NC=C1 MPOYBFYHRQBZPM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N Oc1ccncc1 Chemical compound Oc1ccncc1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- GRFNBEZIAWKNCO-UHFFFAOYSA-N Oc1cnccc1 Chemical compound Oc1cnccc1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
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- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种可固载型吡啶季铵盐卤胺前置体Ⅰ及其合成方法和应用。合成方法为以5,5‑二甲基海因、二溴丙烷、羟基吡啶为原料,制备化合物Ⅲ,然后与γ‑氯(溴、碘)丙基三乙氧基硅烷在乙腈中回流反应7~48h制得抗菌剂化合物前置体Ⅰ。抗菌剂在抗菌材料中的应用:配制1~5wt%卤胺前置体溶液,对材料表面固载修饰,经过氯化制得抗菌材料。本发明合成方法易于操作,吡啶季铵盐单元的引入,使得抗菌剂水溶性增强,制备抗菌材料过程中有机溶剂的使用减少。抗菌实验表明所制备的抗菌材料对革兰氏阴性菌(E.coli ATCC25922)、革兰氏阳性菌(S.aureus ATCC25923)具有较好的杀菌活性。
Description
技术领域
本发明属于可固载型卤胺抗菌剂前置体的合成及其应用领域,具体涉及一类可固载型吡啶季铵盐卤胺前置体的合成及该类抗菌剂前置体在制备抗菌棉纺织品及其他抗菌材料中的应用。
背景技术
目前,有机抗菌剂的类型主要有季铵盐类、季膦盐、双胍类和卤胺类等,其中研究较多使用较广的为季铵盐类抗菌剂和卤胺类抗菌剂。然而季铵盐类抗菌剂大量长期的使用产生了环境二次污染问题并造成了细菌微生物的耐药性。卤胺类抗菌剂是一类含有一个或多个N-X键(X一般为Cl,Br)官能团的有机化合物,但N-Br键稳定性相对较差,容易向水中释放卤素而造成环境污染,故卤胺再次特指为键一般含有N-Cl键的化合物。卤胺类抗菌剂通过具备氧化性的氯原子进行杀菌,杀菌效率提高,抗菌谱广、并有容易再生的优点。但是卤胺水溶性往往较差,在水溶液中分散性不好,对卤胺分子的触杀进程颇为不利。有研究报导,将季铵盐结构单元引入到卤胺抗菌剂分子中提高了其亲水性,同时提高了卤胺抗菌剂杀菌效率(Adv.Heathcare Mater.2012,1,609)。中国专利CN 104926787公开了一种吡啶季铵盐型卤胺抗菌剂的制备方法,此方法在卤胺抗菌剂中引入了吡啶季铵盐,使卤胺抗菌剂的水溶性增强,并且其抗菌性能优于已报导的季铵盐型卤胺抗菌剂,属于有机小分子抗菌剂。
然而,一般有机小分子抗菌剂都存在二次污染以及难以回收利用的问题,所以非溶出型抗菌材料的研发备受关注。另一方面,有研究表明部分致病菌可以在材料表面存活数月,是导致细菌感染及交叉感染的主要途径之一。此外棉织物材料具有良好的吸水性透气性一直颇为人们衷爱,但同时面材料也为各类细菌等微生物提供了良好的生存和繁殖的环境,严重威胁了人类的健康。因此研究容易制备、抗菌广谱、可循环利用的抗菌棉织物及其他抗菌材料具有重大的意义。
2012年,Li等通过“点击”化学反应将季铵盐型卤胺前置体固载到棉织物表面,制备了可重复利用的抗菌棉织物(Adv.Heathcare Mater.2012,1,609)。但是,此方法需要预先在棉织物表面引入炔基,并且“click”反应需要以铜离子(Cu2+/抗坏血酸钠)做催化剂,而Cu2+对水生生物体具有一定的毒性。鉴于此,研制可用于棉织物等材料表面固载的吡啶季铵盐卤胺前置体的课题迫在眉睫。本专利申请旨在保护可固载型吡啶季铵盐卤胺前置体的合成方法及相应抗菌整理工艺。
发明内容
本发明的目的是提供一种可固载型吡啶季铵盐卤胺前置体的合成方法并应用于抗菌材料的制备。将吡啶季铵盐及卤胺前体结构同时固载到棉织物、硅胶等材料表面。吡啶季铵盐的引入使得抗菌剂前置体水溶性增强,避免了棉织物抗菌整理过程中有机试剂的大量使用。同时,细胞相容性较好,吡啶结构的引入使得卤胺杀菌效率提高,并且三乙氧基硅烷基团的引入可以固载于棉织物和硅胶等材料表面。抗菌剂前置体结构式为(Ⅰ)。
式(Ⅰ)中,R代表Cl,Br或I;n=2-12。
其中,以对羟基吡啶、间羟基吡啶或者邻羟基吡啶为链接单元将海因环卤胺前置体与硅氧烷组合成一分子,同时产生吡啶季铵盐单元。
羟基吡啶结构如式(Ⅳ)、(Ⅴ)、(Ⅵ):
本发明的可固载型吡啶季铵盐卤胺前置体的合成及相应抗菌材料制备方法为,以5,5-二甲基海因、二溴丙烷以及羟基吡啶为原料,制备化合物(Ⅲ)。然后与γ-氯(溴、碘)代丙基三乙氧基硅烷在乙腈中回流反应7~48h,制得抗菌剂化合物前置体(Ⅰ)。将抗菌剂化合物前置体(Ⅰ)配制抗菌剂前置体溶液,固载于材料表面,最后经过氯化制得抗菌材料。
具体过程包括如下步骤:
合成抗菌剂前置体(Ⅰ)的步骤为:
a.将羟基吡啶置于有机溶剂中,加入碱性物质,85℃搅拌30~60min,再向体系中加入溴丙基海因溴化合物(Ⅱ),82~110℃反应1~12h,反应结束后,除去有机溶剂,再加入水和乙酸乙酯,洗涤后萃取2~3次,收集乙酸乙酯相,浓缩并柱层析提纯得到化合物,结构如式(Ⅲ)
b.将化合物(Ⅲ)置于乙腈中,再将硅氧烷加入体系中,回流反应7~48h,经过柱色谱分离提纯得到化合物,结构如式(Ⅰ)。
c.将待处理材料浸没在有机溶剂中30~60min,除去材料表面的油性物质及其他杂质,之后将材料浸没在抗菌剂前置体Ⅰ质量浓度为1~5wt%的溶液中,其中乙醇与水的体积比为1:1~1:5。随后取出材料,置于90~120℃下固化30~60min。用蒸馏水洗涤多次,并浸泡在饱和氯化钠溶液中10~60min,再次洗涤。
d.将涂覆后的材料浸渍于含有活性卤素的溶液中10~40min,最后用去离子水洗涤多次。最后在45~65℃下干燥,并储存于黑暗条件下。
进一步地,在上述技术方案中,步骤a所述的羟基吡啶为2-羟基吡啶、3-羟基吡啶、4- 羟基吡啶中的一种。
进一步地,在上述技术方案中,步骤a所述的有机溶剂为丙酮、乙腈、甲醇、N,N-二甲基甲酰胺一种或多种。
进一步地,在上述技术方案中,步骤a所述的碱性物质为无水碳酸钾、氢氧化钠、氢氧化钾、乙醇钠一种或多种。
进一步地,在上述技术方案中,步骤b所述的硅氧烷为γ-氯丙基三乙氧基硅烷、γ-溴丙基三乙氧基硅烷、γ-碘丙基三乙氧基硅烷的一种。
进一步地,在上述技术方案中,步骤c所述的有机溶剂为丙酮、乙醇一种或混合物。
进一步地,在上述技术方案中,步骤d中活性卤素溶液为稀释10~100倍的家用漂白水,pH值为7.0~11.0。
合成反应式如下:
本发明的有益效果在于,以羟基吡啶为连接单元,将硅氧烷及海因环卤胺前置体以共价键的形式键合到棉织物、二氧化硅等材料表面,具有良好的抗菌效果。吡啶季铵盐单元的引入一方面加快了卤胺结构的杀菌效率,有望解决目前季铵盐类抗菌剂造成的细菌等微生物的耐药性问题,另一方面使得卤胺前置体水溶性增强,避免了制备抗菌材料过程中有机溶剂的大量使用,同时固载修饰后的抗菌材料并且经稀漂白水浸泡洗涤可实现抗菌性能的再生。
附图说明
图1是实施例3制备的抗菌棉织物的红外谱图。
具体实施方式
下面通过实施例进一步说明本发明的特点,但本专利的保护范围不受实施例限制。
实施例1
称取3-羟基吡啶(1.52g,16mmol)置于100mL乙腈中,搅拌溶解。称取无水碳酸钾(6.63g,48mmol)加入体系中加热回流4h。在将由5,5-二甲基海因,溴丙基海因(4.98g,20mmol)加入体系中,回流反应4h后,过滤除去无水碳酸钾后,减压蒸馏除去乙腈。以甲醇/二氯甲烷为洗脱剂,收集含有产物的有机相,减压除溶剂后,得到化合物2。
1H NMR(500 MHz,Chloroform-d)δ8.30(dd,J=2.7,1.0 Hz,1H),8.21(dd,J=4.2,1.8 Hz,1H),7.26–7.13(m,2H),4.06(t,J=6.0 Hz,2H),3.73(t,J=6.8 Hz,2H),2.23-2.09(m,2H),1.43(s,6H).13C NMR(126 MHz,Chloroform-d)δ177.13,156.00,154.93,142.31,138.10,123.83,121.19,66.09,58.71,36.05,27.88,25.12.HRMS calcd.forC13H17N3O3[M+H]+264.1270,found:264.1343.
将化合物2(0.5 g,1.90 mmol)置于乙腈中,再将γ-碘丙基三乙氧基硅烷硅烷化合物3(0.90g)加入到反应体系中,回流反应过夜。然后经过柱色谱分离提纯,以甲醇/二氯甲烷为洗脱剂,收集含有产物的有机相,减压除溶剂后,即得到化合物4。
1H NMR(500 MHz,Chloroform-d)δ9.10(dd,J=2.6,1.4 Hz,1H),8.65(m,1.2 Hz,1H),8.08–8.04(m,1H),8.00(dd,J=8.8,5.8 Hz,1H),6.51(s,1H),4.96(t,J=7.1 Hz,2H),4.42(t,J=5.5Hz,2H),3.84(q,J=7.0 Hz,6H),3.71(t,J=6.3 Hz,2H),2.24-2.07(m,4H),1.47(s,6H),1.23(t,J=7.0 Hz,9H);13C NMR(126 MHz,Chloroform-d)δ177.53,158.23,155.91,136.60,132.38,131.91,128.25,69.42,63.77,58.88,58.79,35.13,27.57,25.93,25.24(d,J=2.4 Hz),18.35,6.62.
HRMS calcd.for C22H38N3O6Si[M-I]+468.2530,found:468.2528.
可固载型吡啶季铵盐卤胺前置体合成如下:
实施例2
将棉织物浸没在丙酮中60 min,除去棉织物表面的油性物质及其他杂质,将退浆后的棉织物浸没在含有抗菌剂前置体化合物4溶液中并放置15 min(质量浓度4 wt%,1:1乙醇/水混合溶剂),之后在105℃下固化60 min。然后将棉织物用蒸馏水洗涤多次,并浸泡在饱和氯化钠溶液中30 min,随后蒸馏水洗涤多次,并浸渍于稀释100倍的漂白水中40min,再用去离子水多次洗涤,保证织物游离态的卤素离子彻底除去。最后在45℃下干燥,并储存于黑暗条件下。
抗菌棉织物的制备及应用过程如下:
表征:
红外图的分析:如附图1,与未处理的棉织物相比,固载抗菌剂前置体化合物4的红外谱图,在1698.89cm-1、1763.71cm-1出现是C=O的伸缩振动吸收峰;在1579.83cm-1出现N-H的变形振动。并且经过漂白水氯化后,C=O峰由于N-Cl键的诱导作用,波数移动至1706.37cm-1
棉织物的抗菌测试:
对空白棉织物、接枝抗菌剂前置体化合物4并氯化的抗菌棉织物分别进行了大肠杆菌(E.coli ATCC25922)、金黄色葡萄球菌(S.aureus ATCC 25923)的抗菌性能测试。具体方法为:将0.25mL浓度约为107~108的细菌悬浮液滴加到三块直径为2.54cm的圆形棉织物上,使其均匀分布,然后将相同大小棉织物置于最上方,用重物压紧使得菌液与纤维充分接触。分别5和10min后,以一定量硫代硫酸钠溶液猝灭材料上可能残存的活性氯,然后逐级稀释并置于营养琼脂平板培养16~24h,最后以平板计数法确定活菌的数量,抗菌测试结果如表1所示。
表1是发明实施例2制备的表面修饰有吡啶季铵盐卤胺分子的棉织物材料对大肠杆菌(E.coli ATCC25922)及金黄色葡萄球菌(S.aureus ATCC 25923)的抗菌活性测试结果。
表1.抗菌棉织物抗菌测试结果
a)大肠杆菌菌浓度为7.50×106CFU/mL(Colony-Forming Units);b金黄色葡萄球菌菌浓度为8.30×107CFU/mL 。
Claims (8)
1.一种可固载型吡啶季铵盐卤胺前置体,其特征在于,化合物结构式为(Ⅰ):
式(Ⅰ)中,R选自Cl,Br或I;n为2-12的整数。
2.如权利要求1所述的可固载型吡啶季铵盐卤胺前置体的合成方法,其特征在于,合成该前置体(Ⅰ)的步骤为:
(1)将羟基吡啶置于有机溶剂中,加入碱性物质,85℃搅拌30~60min。再向体系中加入溴烷基海因化合物(Ⅱ),于82~110℃反应1~12h,反应结束后,真空条件下除去有机溶剂,再加入水和乙酸乙酯,萃取后浓缩有机相,经柱层析可得化合物,结构如式(Ⅲ):
式(Ⅱ)、(Ⅲ)中,n=2-12;
(2)将化合物(Ⅲ)置于乙腈中,再将γ-卤丙基三乙氧基硅烷加入反应体系中,加热回流7~48h,经过柱色谱分离提纯得到化合物,结构如式(Ⅰ)。
3.根据权利要求2所述可固载型吡啶季铵盐卤胺前置体的合成方法,其特征在于,所述步骤(1)中羟基吡啶选自对羟基吡啶、间羟基吡啶或者邻羟基吡啶。
4.根据权利要求2所述可固载型吡啶季铵盐卤胺前置体的合成方法,其特征在于,步骤(1)所述的有机溶剂为丙酮、乙腈、甲醇、N,N-二甲基甲酰胺中的一种或多种。
5.根据权利要求2所述可固载型吡啶季铵盐卤胺前置体的合成方法,其特征在于,步骤(1)所述的碱性物质为无水碳酸钾、氢氧化钠、氢氧化钾、乙醇钠中的一种或多种。
6.根据权利要求2所述可固载型吡啶季铵盐卤胺前置体的合成方法,其特征在于,步骤(2)所述的γ-卤丙基三乙氧基硅烷硅氧烷为γ-氯丙基三乙氧基硅烷、γ-溴丙基三乙氧基硅烷、γ-碘丙基三乙氧基硅烷中的一种。
7.如权利要求1所述的可固载型吡啶季铵盐卤胺前置体在制备抗菌材料的应用,其特征在于,将可固载型吡啶季铵盐卤胺前置体用乙醇与水配制成质量浓度为1~5wt%的(Ⅰ)的溶液,其中乙醇与水的体积比为1:1~1:5;将待处理的材料浸渍于所述溶液中,浸渍15~60min后固液分离,在90~120℃下固化30~60min;随后用水洗涤2-3次,将固载后的材料浸泡在饱和氯化钠溶液中10~60min,再次洗涤;最后将处理后的抗菌材料浸渍于含有活性卤素的溶液中10~60min,固液分离,将材料水洗多次并烘干,即制备成抗菌材料;
所述待处理材料为棉织物、硅胶中的一种。
8.根据权利要求7所述可固载型吡啶季铵盐卤胺前置体在抗菌材料中的应用,其特征在于,含有活性卤素溶液为稀释10~100倍的漂白水,pH值为7.0~11.0。
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