含全氟烷基抗菌剂的合成及其应用
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摘要
随着人们生活水平的不断提高和科学技术的发展，人们对自身的卫生保健意识日益增强。在致病菌的传播过程中，纺织品是一个重要的媒介，所以具有抗菌性能的织物正日益受到消费者的青睐。至今，种类众多的抗菌剂已被用来赋予织物抗菌性能。其中，季铵盐类表面活性剂因广谱的抗菌性能已广泛地应用于织物的抗菌整理。
但有时织物仅仅具有抗菌性能并不能确保穿着者的安全。例如为了保护病人和医护人员不被感染性的血液或体液传染，许多医用纺织品不仅要求具有良好的抗菌性能，同时要求有优良的拒血拒液等功能。战士用的军服同样有上述的要求。迄今，含全氟烷基化合物在织物的拒水拒油防污整理方面的应用非常广泛，不仅能显著降低织物的临界表面能，而且能保持整理后织物的透气性。
为制备一种能同时赋予织物抗菌和拒水拒油性能的多功能织物整理剂，我们首先设计并合成了新型的含全氟烷基和二烯丙基的季铵盐(PFDA)。PFDA的合成路线如Schemel所示。随后测定了PFDA的抗菌活性，PFDA对大肠杆菌8099(革兰氏阴性菌)和金黄色葡萄球菌ATCC 6538(革兰氏阳性菌)的最低抑菌浓度(MIC)均为7.8μg／ml。二烯丙基的引入使得PFDA能方便地作为阳离子聚合物单体用于均聚或共聚。于是我们通过乳液聚合得到PFDA与其他单体的共聚物乳液，并将其用于棉织物的整理。整理后的织物对大肠杆菌8099和金黄色葡萄球菌ATCC 6538的抑菌率分别达到99.9％和92.4％，拒油达到四级，但拒水效果不佳。
为了提高整理效果的耐久性，我们设计并合成了另一新型含氟烷基季按
盐(p「sc)，并在P「sC分子中引入硅氧偶联基团。pFsc的合成路线如S。lleme
2所示。实验表明，经pFsc整理后的棉织物显示出耐久的抗菌活性和极低
的临界表面能。经检测，整理后织物对金黄色葡萄球菌ATCC 6538的抑菌
率达到97.3%，即使经过十次水洗后，抑菌率仍然大于95%。拒水拒油性能
均达到5级，十次水洗之后也能达到4级。通过接触角测量的方法，我们估
算出整理后的棉织物临界表面能为丫。=20士1 mN/m，远低于人体血液的42士2
mN/m。
CFs(CFZ)71+
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Jones oxldation agent
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Ho(cH:)3N(CH公2
‘峡一
PTSA
e:3(e:2丫~义。日
c:3(eoZ丫、义
。~仑品介丫\51(oM·)3
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PFSC
PFSC
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SUbstrate
As the ever-growing demand for healthy living, there is a keen interest in materials capable of killing harmful microorganisms. Textile materials are suitable media for growing microorganisms. In the last few decades, the prevention of microbial attack on textile and wearers of textile materials has become increasingly important to consumers and textile producers. So far, various antimicrobial agents have been applied to impart antimicrobial properties to textile. Among them, the quaternary ammonium salts are widely used in antimicrobial finishing of textile.
However, the antimicrobial materials would not essentially mean ensured safety of us. For example, to protect patients and the surgical team from infectious blood and other body fluids, some medical materials should possess not only antimicrobial properties but also blood repellency properties. The same is in the case of battle suits. To provide the treated surface with a low critical surface tension, fluorochemicals are most abundantly used for their ability to lower the critical surface tension of the treated surface well below that of most 'fluid other than a fluorocarbon.
In the light of the facts above mentioned, we first designed and synthesized a novel quaternary ammonium salt (PFDA), which contains both perfluoroalkyl and diallyl groups. PFDA was designed to be a multifunctional textile finishing agent capable of providing fabrics with barriers against microorganisms, water, oil, soil and blood. The synthesis of PFDA was outlined in Scheme 1. Consequently, the antimicrobial activities of compound PFDA were tested against Escherichia coli 8099 as a Gram-negative strain and Staphylococcus aureus ATCC 6538 as a Gram-positive strain. Both the minimum inhibitory concentration(MIC) values were 7.8 μ g/ml. Moreover, diallyl groups were innovatively introduced into the target molecular, which made itself a good monomer for polymerization. By emulsion copolymerization, we applied PFDA as one of monomers to give the copolymeric emulsion, which was used to treat the cotton fabrics by the pad-dry-cure method. The treated fabrics showed good antibacterial properties. The killing bacterial fates against E. coli 8099 and S. aureus ATCC 6538 were 99.9% and 92.4%, respectively. At the same time, the treated fabrics also showed good oil repellency but little waterproof property.
To obtain more accessible application and durable effect, another novel quaternary ammonium salt (PFSC) was designed and synthesized. The 3-(trimethoxysilyl)propyl group introduced into the molecule can bind to many material surfaces. That improved the durability of the treated materials as well as its scope of applications. The synthesis of PFSC was outlined in Scheme 2. PFSC was applied as a surface modification agent to provide the treated cotton fabrics with the durable antimicrobial activity and low critical surface energy simultaneously. The treated fabrics showed a 97.3 % killing bacterial rate against S. aureus ATCC 6538. Even after 10 laundering cycles, the antimicrobial activities of treated specimens still remained at a high level, reaching at 95.6%. The treated specimen also showed the super-low critical surface energy γc=20± l mN/m, which is markedly lower than 42+2 mN/m of man-made blood.
但有时织物仅仅具有抗菌性能并不能确保穿着者的安全。例如为了保护病人和医护人员不被感染性的血液或体液传染，许多医用纺织品不仅要求具有良好的抗菌性能，同时要求有优良的拒血拒液等功能。战士用的军服同样有上述的要求。迄今，含全氟烷基化合物在织物的拒水拒油防污整理方面的应用非常广泛，不仅能显著降低织物的临界表面能，而且能保持整理后织物的透气性。
为制备一种能同时赋予织物抗菌和拒水拒油性能的多功能织物整理剂，我们首先设计并合成了新型的含全氟烷基和二烯丙基的季铵盐(PFDA)。PFDA的合成路线如Schemel所示。随后测定了PFDA的抗菌活性，PFDA对大肠杆菌8099(革兰氏阴性菌)和金黄色葡萄球菌ATCC 6538(革兰氏阳性菌)的最低抑菌浓度(MIC)均为7.8μg／ml。二烯丙基的引入使得PFDA能方便地作为阳离子聚合物单体用于均聚或共聚。于是我们通过乳液聚合得到PFDA与其他单体的共聚物乳液，并将其用于棉织物的整理。整理后的织物对大肠杆菌8099和金黄色葡萄球菌ATCC 6538的抑菌率分别达到99.9％和92.4％，拒油达到四级，但拒水效果不佳。
为了提高整理效果的耐久性，我们设计并合成了另一新型含氟烷基季按
盐(p「sc)，并在P「sC分子中引入硅氧偶联基团。pFsc的合成路线如S。lleme
2所示。实验表明，经pFsc整理后的棉织物显示出耐久的抗菌活性和极低
的临界表面能。经检测，整理后织物对金黄色葡萄球菌ATCC 6538的抑菌
率达到97.3%，即使经过十次水洗后，抑菌率仍然大于95%。拒水拒油性能
均达到5级，十次水洗之后也能达到4级。通过接触角测量的方法，我们估
算出整理后的棉织物临界表面能为丫。=20士1 mN/m，远低于人体血液的42士2
mN/m。
CFs(CFZ)71+
SChemeZ
尹\/OH一二{竺逻竺~eo3(e:2丫卜办。日暨些二竺生e:3(e:2片人，洲八O。
l}
Jones oxldation agent
一(一)扮。~、/
Ho(cH:)3N(CH公2
‘峡一
PTSA
e:3(e:2丫~义。日
c:3(eoZ丫、义
。~仑品介丫\51(oM·)3
f
PFSC
PFSC
O
l
O一51
l
O
/\与/产\
2尹
!.
N尸\甲八
+、
O
。义V入(。:2)7。:3
SUbstrate
As the ever-growing demand for healthy living, there is a keen interest in materials capable of killing harmful microorganisms. Textile materials are suitable media for growing microorganisms. In the last few decades, the prevention of microbial attack on textile and wearers of textile materials has become increasingly important to consumers and textile producers. So far, various antimicrobial agents have been applied to impart antimicrobial properties to textile. Among them, the quaternary ammonium salts are widely used in antimicrobial finishing of textile.
However, the antimicrobial materials would not essentially mean ensured safety of us. For example, to protect patients and the surgical team from infectious blood and other body fluids, some medical materials should possess not only antimicrobial properties but also blood repellency properties. The same is in the case of battle suits. To provide the treated surface with a low critical surface tension, fluorochemicals are most abundantly used for their ability to lower the critical surface tension of the treated surface well below that of most 'fluid other than a fluorocarbon.
In the light of the facts above mentioned, we first designed and synthesized a novel quaternary ammonium salt (PFDA), which contains both perfluoroalkyl and diallyl groups. PFDA was designed to be a multifunctional textile finishing agent capable of providing fabrics with barriers against microorganisms, water, oil, soil and blood. The synthesis of PFDA was outlined in Scheme 1. Consequently, the antimicrobial activities of compound PFDA were tested against Escherichia coli 8099 as a Gram-negative strain and Staphylococcus aureus ATCC 6538 as a Gram-positive strain. Both the minimum inhibitory concentration(MIC) values were 7.8 μ g/ml. Moreover, diallyl groups were innovatively introduced into the target molecular, which made itself a good monomer for polymerization. By emulsion copolymerization, we applied PFDA as one of monomers to give the copolymeric emulsion, which was used to treat the cotton fabrics by the pad-dry-cure method. The treated fabrics showed good antibacterial properties. The killing bacterial fates against E. coli 8099 and S. aureus ATCC 6538 were 99.9% and 92.4%, respectively. At the same time, the treated fabrics also showed good oil repellency but little waterproof property.
To obtain more accessible application and durable effect, another novel quaternary ammonium salt (PFSC) was designed and synthesized. The 3-(trimethoxysilyl)propyl group introduced into the molecule can bind to many material surfaces. That improved the durability of the treated materials as well as its scope of applications. The synthesis of PFSC was outlined in Scheme 2. PFSC was applied as a surface modification agent to provide the treated cotton fabrics with the durable antimicrobial activity and low critical surface energy simultaneously. The treated fabrics showed a 97.3 % killing bacterial rate against S. aureus ATCC 6538. Even after 10 laundering cycles, the antimicrobial activities of treated specimens still remained at a high level, reaching at 95.6%. The treated specimen also showed the super-low critical surface energy γc=20± l mN/m, which is markedly lower than 42+2 mN/m of man-made blood.
引文
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2．何中琴译，王雪良校，印染译丛，1999，13，86-93．
3. G.E. Evan, J. Sci. Dye. Color, 1984, 100(10), 304.
4．唐增荣，抗菌整理剂JNS2000在纺织品上的应用研究，印染助剂，2002，19(4)，23-26．
5．曾毓华编著，氟碳表面活性剂，第1版，北京，化学工业出版社，2001．
6．久保元伸，含氟防水防油剂(Ⅰ)：关于防水防油性能的机理，印染，1995，21(12)，37-41．
7．张翠芳，Huang W．，非织造外科手术服织物的拒液抗菌整理的一浴法应用，国外纺织技术，1999(9)，22-26．
8．薛迪庚编著，织物的功能整理，第1版，北京，中国纺织出版社，1995．
9．朱顺根，含氟织物整理剂，有机氟工业，1997，4，21-43．
10．陈拥军，李本高，汪燮卿，有机抗菌剂研究的新进展，石油炼制与化工，1997，28(1)，56-61．
11．董晓旭，抗菌高分子材料抗菌性检验方法的研究，工程塑料应用，2000，(2)，27-28．
12．谷朝南，精细化学药品(日)，1996，25(19)，5-14．
13．伍敏扬，魏运方，日本塑料与纤维用抗菌防霉剂的现状及发展趋势，精细石油化工，1998，(6)，14-18．
14．迟莉娜，抗菌整理及抗菌非织造布的开发应用，北京纺织，1999，20(1)，20-25．
15．高宝玉，含氰基季铵盐杀菌剂的结构与性能，山东大学学报(自然科学版)，1992，27(4)，453-460．
16. Theodora J., Chem. Pharm. Bull., 1994, 42(2), 392.
17. Diz M., Manresa A., Pinazo A., Erra P., Infate M.R., Synthesis, Surface Active Properties and Antimicrobial Activity of New Bis Quaternary Ammonium Compounds, J. Chem. Soc. Perkin. Trans Ⅱ, 1994, 2(8), 1871-1876.
18. Pernak J., Michalak L., Krysinski J., Synthesis and antimicrobial action of 1-alkoxymethyl- and 1-alkylthiomethyl-4-dimethylamino- pyridinium chlorides, Pharmzie, 1994, 49(7), 532-534.
19. Kourai H., Manabe Y., Matsutani E., Hasegawa Y., Nakagawa K., Antimicrobial activities of alkylallyldimethylammonium iodides and alkylallyldiethylammonium iodides, Bokin Bobai, 1995, 23(5), 271-280.
20. Hsu A.C., USP5411933, Bromopropargyl quarternary ammonium compounds having antimicrobial activity, 1994, March 11.
21．河合博，道康宁5700抗微生物处理剂，印染，1996，22(3)，38-42．
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2．何中琴译，王雪良校，印染译丛，1999，13，86-93．
3. G.E. Evan, J. Sci. Dye. Color, 1984, 100(10), 304.
4．唐增荣，抗菌整理剂JNS2000在纺织品上的应用研究，印染助剂，2002，19(4)，23-26．
5．曾毓华编著，氟碳表面活性剂，第1版，北京，化学工业出版社，2001．
6．久保元伸，含氟防水防油剂(Ⅰ)：关于防水防油性能的机理，印染，1995，21(12)，37-41．
7．张翠芳，Huang W．，非织造外科手术服织物的拒液抗菌整理的一浴法应用，国外纺织技术，1999(9)，22-26．
8．薛迪庚编著，织物的功能整理，第1版，北京，中国纺织出版社，1995．
9．朱顺根，含氟织物整理剂，有机氟工业，1997，4，21-43．
10．陈拥军，李本高，汪燮卿，有机抗菌剂研究的新进展，石油炼制与化工，1997，28(1)，56-61．
11．董晓旭，抗菌高分子材料抗菌性检验方法的研究，工程塑料应用，2000，(2)，27-28．
12．谷朝南，精细化学药品(日)，1996，25(19)，5-14．
13．伍敏扬，魏运方，日本塑料与纤维用抗菌防霉剂的现状及发展趋势，精细石油化工，1998，(6)，14-18．
14．迟莉娜，抗菌整理及抗菌非织造布的开发应用，北京纺织，1999，20(1)，20-25．
15．高宝玉，含氰基季铵盐杀菌剂的结构与性能，山东大学学报(自然科学版)，1992，27(4)，453-460．
16. Theodora J., Chem. Pharm. Bull., 1994, 42(2), 392.
17. Diz M., Manresa A., Pinazo A., Erra P., Infate M.R., Synthesis, Surface Active Properties and Antimicrobial Activity of New Bis Quaternary Ammonium Compounds, J. Chem. Soc. Perkin. Trans Ⅱ, 1994, 2(8), 1871-1876.
18. Pernak J., Michalak L., Krysinski J., Synthesis and antimicrobial action of 1-alkoxymethyl- and 1-alkylthiomethyl-4-dimethylamino- pyridinium chlorides, Pharmzie, 1994, 49(7), 532-534.
19. Kourai H., Manabe Y., Matsutani E., Hasegawa Y., Nakagawa K., Antimicrobial activities of alkylallyldimethylammonium iodides and alkylallyldiethylammonium iodides, Bokin Bobai, 1995, 23(5), 271-280.
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21．河合博，道康宁5700抗微生物处理剂，印染，1996，22(3)，38-42．
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