水介质中ATRP法接枝改性真丝的制备及其结构性能研究
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摘要
摘要:原子转移自由基聚合(ATRP)是一种新的且有效的聚合方式,此聚合方法是一种分子量可控、分散性低的新型聚合方法。
本文在水介质中采用原子转移自由基聚合法接枝改性真丝并进行了如下研究:
1.将2-溴异丁酰溴与真丝反应制备大分子引发剂,以甲基丙烯酸二甲氨乙酯(DMAEMA)为单体,CuBr/五甲基二乙烯三胺(PMDETA)为催化体系,水为介质,采用原子转移自由基聚合法制备接枝改性真丝。研究了原子转移自由基接枝共聚过程中单体浓度、催化剂和配体用量、反应温度、时间以及pH值等对接枝反应的影响。并对普通化学接枝和原子转移自由基聚合接枝工艺及所得真丝的优缺点进行了比较。得出原子转移自由基聚合法反应条件温和,分子量可控等优点。
2.研究了原子转移自由基聚合接枝改性前后真丝的各项性能,如强力、白度,回潮率,K/S等。通过傅立叶转换红外光谱,X-射线衍射和扫描电镜等对接枝真丝进行了结构分析。得出通过原子转移自由基聚合成功地将单体DMAEMA接枝到真丝上,对真丝的服用性能影响很小。
3.研究了原子转移自由基聚合接枝改性真丝的抗菌整理,季铵化后的真丝织物获得了耐久的抗菌效果。
Atom transfer radical polymerization (ATRP) is a new and efficient polymerization route, which could be used to prepare polymer with well controlled molecular weight and low polydispersity.
Studies on modified silk by ATRP grafting method in aqueous were done as follows:
1. Silk fibroin was reacted with 2-bromoisobutyryl bromide (BriB-Br) to obtain silk macroinitiator. The modified silk was prepared using dimethylaminoethyl methacrylate (DMAEMA) as monomer, CuBr/N, N, N', N", N" -pentamethyldiethylenetriamine (PMDETA) as catalyst system via atom transfer radical polymerization method in water aqueous. The effect of monomer concentration, dosage of catalyst and ligand, reacting temperature, time and pH value on the grafting was discussed. The advantage and disadvantages of grafted silk by traditional chemical grafting and ATRP grafting method were compared. The results showed that ATRP method has advantages of mild reaction condition and controlled molecular weight.
2. The mechanical properties, whiteness, moisture regain and K/S value of the untreated and grafted silk were measured. The structure of grafted silk was analyzed by FI-IR, XRD and SEM. The results indicated that DMAEMA monomer was triumphantly grafted onto silk by ATRP method, and it has little effect on silk wearability.
3. The anti-bacterial finish of ATRP grafted silk was studied, the quaternized silk has durable anti-bacterial effect.
本文在水介质中采用原子转移自由基聚合法接枝改性真丝并进行了如下研究:
1.将2-溴异丁酰溴与真丝反应制备大分子引发剂,以甲基丙烯酸二甲氨乙酯(DMAEMA)为单体,CuBr/五甲基二乙烯三胺(PMDETA)为催化体系,水为介质,采用原子转移自由基聚合法制备接枝改性真丝。研究了原子转移自由基接枝共聚过程中单体浓度、催化剂和配体用量、反应温度、时间以及pH值等对接枝反应的影响。并对普通化学接枝和原子转移自由基聚合接枝工艺及所得真丝的优缺点进行了比较。得出原子转移自由基聚合法反应条件温和,分子量可控等优点。
2.研究了原子转移自由基聚合接枝改性前后真丝的各项性能,如强力、白度,回潮率,K/S等。通过傅立叶转换红外光谱,X-射线衍射和扫描电镜等对接枝真丝进行了结构分析。得出通过原子转移自由基聚合成功地将单体DMAEMA接枝到真丝上,对真丝的服用性能影响很小。
3.研究了原子转移自由基聚合接枝改性真丝的抗菌整理,季铵化后的真丝织物获得了耐久的抗菌效果。
Atom transfer radical polymerization (ATRP) is a new and efficient polymerization route, which could be used to prepare polymer with well controlled molecular weight and low polydispersity.
Studies on modified silk by ATRP grafting method in aqueous were done as follows:
1. Silk fibroin was reacted with 2-bromoisobutyryl bromide (BriB-Br) to obtain silk macroinitiator. The modified silk was prepared using dimethylaminoethyl methacrylate (DMAEMA) as monomer, CuBr/N, N, N', N", N" -pentamethyldiethylenetriamine (PMDETA) as catalyst system via atom transfer radical polymerization method in water aqueous. The effect of monomer concentration, dosage of catalyst and ligand, reacting temperature, time and pH value on the grafting was discussed. The advantage and disadvantages of grafted silk by traditional chemical grafting and ATRP grafting method were compared. The results showed that ATRP method has advantages of mild reaction condition and controlled molecular weight.
2. The mechanical properties, whiteness, moisture regain and K/S value of the untreated and grafted silk were measured. The structure of grafted silk was analyzed by FI-IR, XRD and SEM. The results indicated that DMAEMA monomer was triumphantly grafted onto silk by ATRP method, and it has little effect on silk wearability.
3. The anti-bacterial finish of ATRP grafted silk was studied, the quaternized silk has durable anti-bacterial effect.
引文
[1] Akai H. The structure and ultrastructure of the silk gland[J]. Experientia, 1983,39:443-449.
[2]刘永成,邵正中,孙正宇.蚕丝蛋白的结构和功能[J].高分子通报, 1998, (3):17-23.
[3]加古武,片山明.真丝的结构[J].日本蚕丝学杂志, 1999, 68(3):15-20.
[4]钱国坻,梅士英等.国产家蚕丝素的化学组成研究[J].纺织学报, 1981, 2:2-9.
[5]魏凯.阻燃真丝纤维的研究[D].苏州大学,硕士论文, 2007.
[6]杜琮艮.真丝织物抗皱整理进展[J].丝绸, 1999, 2, 37-42.
[7] Amal,S.,Sahu,G.,Lenka,S.,Nayak,P.L.,J.Appl.. Characterization of methyl methacrylate grafted wool and silk fibres[J]. Polym.Sci.1987, 33, 1853.
[8] Tsukad,M, Takahasi,T, Kanda,C, Aoki,A, J.Seric. Journal of Sericulture Science of Jpnan.Sci.Jpn. 1985, 54, 423-425.
[9]黄才荣,陈国强.真丝的化学接枝改性技术[J].四川丝绸,2002, (3):21-25.
[10] Wang J S, Matyjaszewski K. Controlled/“living”radical polymerization Halogen atom transfer radical polymerization promoted by a Cu ( I)/ Cu ( II) redox process[J]. Macromolecules, 1995, 28 (23):7901-7910.
[11] Buckley R P,Szwarc M.Methyl affinities of ethylene tetrafluoroethylene and tetrachloroethylene[J].J Am Chem Soc,1956,78 (21):5696-5697.
[12] Webster O W,Hertler W R,Sogah D Y,et al.Group-transfer polymerization-1-A new concept for addition polymerization with organosilicon initiators. J Am Chem Soc,1983,105 (17):5706-5708.
[13] Aida T, Inoue S. Living polymerization of epoxide catalyzed by the porphyrin-chlorod -iethylaluminum systemstructure of the living end[J]. Macromolecules, 1981, l4 (5):1166-1169.
[14] Miyamoto M,Sawamoto M,Higashimura T.Living polymerization of isobutyl vinyl ether with hydrogen iodide/iodine initiating system [J].Macromolecules, 1984, 17(3): 265-268.
[15] Faust R,Kennedy J P. Living carbocationic polymerization IV Living polymerization of isobutylene[J].Journal of Polymer Science Part A: Polymer Chemistry, 1987, 25(7):1847-1869.
[16] Fayt R, Forte R, Jacobs C, et al. New initiator system for the living anionic polymerization of tert-alkyl acrylates [J].Macromolecules, 1987, 20(6):1442-l444.
[17] Reetz Manfred T. New Methods for the Anionic Polymerization of Activated Olefins[J].Angewandte Chemie International Edition in English, 1988, 27 (7):994-998.
[18] Georges M K, Veregin R P N, Gordon P M K, et al. Narrow molecular weight resins by a free-radical polymerization process[J].Macromolecules, 1993, 26(11):2987-2988.
[19] Wang J S, Matyjaszewski K. Controled”living”radical polymerization atom transfer radical polymerization in the presence of transition metal complexes[J]. J Am Chem Soc, 1995, l17:5614.
[20]何天白,胡汉杰.海外高分子科学的新进展[M].北京:化学工业出版社, 2001.
[21]郭建华,韩哲文,吴平平.原子转移自由基聚合的研究进展[J].高分子通报,1998, (3):32-36.
[22]隋智慧,张西怀等.新型两性树脂复鞣剂的应用研究[J].皮革化工, 2001,19(1):23.
[23] LESKO,et al. Method of Treating Leather with Improved Retaining agents[P]. U. S. Patent 5, 1998, 820-633.
[1]陈国强.甲基丙烯酸羟丙酯接枝交联真丝绸结构与性能的研究[J].浙江丝绸工学院学报, 1998, 15(4):277-281.
[2]王平.真丝织物接枝共聚的研究[J].浙江丝绸工学院学报,1987, (1):36-42.
[3]钟安华,郭维婵.用4594对真丝绸接枝改性[J].广西纺织科技, 1999, (1):11-14.
[4]陈美云,吕晶.甲基丙烯酸丁酯在真丝织物上接枝的探讨[J].丝绸, 1997, (4):14.
[5]曹雪琴,杨慎举.真丝纤维的丙烯酰胺接枝改性研究[J].丝绸, 2004, (2):16-19.
[1]何天白,胡汉杰.海外高分子科学的新进展[M].北京:化学工业出版社,1997,5-18.
[2] Wang J S, Matyjaszewski K. Controlled/”living”radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu(I) / Cu(1I)redox process[J].Macromolecules, 1995,28:7901-7910.
[3] Georges M K, Vereqin R P N,Kaxmaier P M.Narrow molecular weight resins by a free-radical polymerization process[J].Macromolecules,1993,26:2987-2988.
[4] Wang J S,Matyjaszewski K.Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes [J].J. Am. Chem. Soc., 1995,117:5614-5615.
[5] Kato M, Kamigaito M, Sawamoto M, et al.Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine)ruthenium(II) /methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization [J].Macromolecules,1995,28:1721-1723.
[6] Li M, Matyjaszewski K. Further Progress in Atom Transfer Radical Polymerizations Conducted in a Waterborne System [J]. J. Polym. Sci. Part A. Polym. Chem., 2003, 41: 3606-3614.
[7]赵洪池,杨鹏,梁淑君.活性自由基乳液聚合的研究进展[J].信息记录材料, 2005, 6(3): 41-46.
[8]汤建萍,曾宪标.原子转移自由基聚合反应及其进展[J].宜春学院学报, 2003, 25(2): 40-43.
[9] Carlmark, Anna, Malmstrom, Eva E. ATRP grafting from cellulose fibers to create block-copolymer grafts[J]. Biomacromolecules, 2003, 4(6): 1740-1745.
[10] Petr Vlcek, Miroslav Janata, Petra Látalová,Jaroslav Krí?, et al. Controlled grafting of cellulose diacetate[J]. Polymer, 2006, 47(8): 2587-2595.
[11] Wang Jing-yuan, Zhang Kai, Li Hong-tu, et al. Surface-initiated atom transfer radical polymerization on spherical silicon gel in water -borne system at ambient temperature[J].Materials Chemistry and Physics, 2006, 96(2): 477-482.
[12] Sang Beom Lee , Richard R. Permanent Nonleaching Antibacterial Surfaces.1.Synthesis by Atom Transfer Radical Polymerization[J]. Biomacromolecules, 2004, 5: 877-882.
[13] Ashford E J, Naldi V,Dell R O,et al.Novel routes to controlled structure water-soluble polymers: Atom transfer radical polymerization of sodium methacrylate in aqueous media[J].American Chemical Society, Polymer Priprints, Division of Polymer Chemistry, 1999, 40:405-406.
[14] Nanda A K, Matyjaszewski K. Effect of [bpy]/[Cu(I)] ratio, solvent, counterion, and alkyl bromides on the activation rate constants in atom transfer radical polymerization[J]. Macromolecules, 2003, 36: 599-604.
[15] Nanda A K, Matyjaszewski K. Effect of [PMDETA]/[Cu(I)] ratio, monomer, solvent, counterion, ligand, and alkyl bromide on the activation rate constants in atom transfer radical polymerization[J]. Macromolecules, 2003, 36: 1487-1493.
[16]陈瑾.原子转移自由基聚合新催化体系的研究[D].苏州大学,2004,17-18.
[1]赵国玺.表面活性剂作用原理[M].北京:中国轻工业出版社, 2003, 26-28.
[2]王俊起,王友斌,薛金荣等.纺织品抗菌功能测试方法研究[J].中国卫生工程学,2003, (3): 129-132.
[3] Testing for antibacterial activity and efficacy on textile products[S]. Japanese lndustry Standard,Reference,number:JISL1902:2002(E)
[4]郑华英,王斌,孙敏等.抗菌织物检验方法的研究[J].中国卫生检验杂志, 2004, (2): 168-170.
[5]中华人民共和国纺织行业标准织物抗菌性能试验方法[S]. FZ/T0l021-1992.
[6]中华人民共和国国家标准《一次性使用卫生用品卫生标准》[S]. GB15979-2002.
[7]王俊起,王友斌.抗菌织物测试方法的研究(续)一纺织标准与质量[J]. 2003, (l): 26-28.
[1]陈国强.一缩二乙二醇二甲基丙烯酸酯接枝真丝的结构[J].高分子学报,2002,3:379-384.
[2] Freddi G,Shiozaki H,Allara G,Gto Y,Yasui H,Tsukada M.J SD C,1996 ,112(3) :88～94.
[3] Tsukada M,Freddi G,Ishiguro Y,Shiozaki H.J Appl Polym Sci ,1993 ,50:1519～1527.
[4]Ishikawa H,Tsukada M,Doizume T,Hirabayashi K.Sen2ⅠGakkaishi ,1972 ,28:91～93.
[2]刘永成,邵正中,孙正宇.蚕丝蛋白的结构和功能[J].高分子通报, 1998, (3):17-23.
[3]加古武,片山明.真丝的结构[J].日本蚕丝学杂志, 1999, 68(3):15-20.
[4]钱国坻,梅士英等.国产家蚕丝素的化学组成研究[J].纺织学报, 1981, 2:2-9.
[5]魏凯.阻燃真丝纤维的研究[D].苏州大学,硕士论文, 2007.
[6]杜琮艮.真丝织物抗皱整理进展[J].丝绸, 1999, 2, 37-42.
[7] Amal,S.,Sahu,G.,Lenka,S.,Nayak,P.L.,J.Appl.. Characterization of methyl methacrylate grafted wool and silk fibres[J]. Polym.Sci.1987, 33, 1853.
[8] Tsukad,M, Takahasi,T, Kanda,C, Aoki,A, J.Seric. Journal of Sericulture Science of Jpnan.Sci.Jpn. 1985, 54, 423-425.
[9]黄才荣,陈国强.真丝的化学接枝改性技术[J].四川丝绸,2002, (3):21-25.
[10] Wang J S, Matyjaszewski K. Controlled/“living”radical polymerization Halogen atom transfer radical polymerization promoted by a Cu ( I)/ Cu ( II) redox process[J]. Macromolecules, 1995, 28 (23):7901-7910.
[11] Buckley R P,Szwarc M.Methyl affinities of ethylene tetrafluoroethylene and tetrachloroethylene[J].J Am Chem Soc,1956,78 (21):5696-5697.
[12] Webster O W,Hertler W R,Sogah D Y,et al.Group-transfer polymerization-1-A new concept for addition polymerization with organosilicon initiators. J Am Chem Soc,1983,105 (17):5706-5708.
[13] Aida T, Inoue S. Living polymerization of epoxide catalyzed by the porphyrin-chlorod -iethylaluminum systemstructure of the living end[J]. Macromolecules, 1981, l4 (5):1166-1169.
[14] Miyamoto M,Sawamoto M,Higashimura T.Living polymerization of isobutyl vinyl ether with hydrogen iodide/iodine initiating system [J].Macromolecules, 1984, 17(3): 265-268.
[15] Faust R,Kennedy J P. Living carbocationic polymerization IV Living polymerization of isobutylene[J].Journal of Polymer Science Part A: Polymer Chemistry, 1987, 25(7):1847-1869.
[16] Fayt R, Forte R, Jacobs C, et al. New initiator system for the living anionic polymerization of tert-alkyl acrylates [J].Macromolecules, 1987, 20(6):1442-l444.
[17] Reetz Manfred T. New Methods for the Anionic Polymerization of Activated Olefins[J].Angewandte Chemie International Edition in English, 1988, 27 (7):994-998.
[18] Georges M K, Veregin R P N, Gordon P M K, et al. Narrow molecular weight resins by a free-radical polymerization process[J].Macromolecules, 1993, 26(11):2987-2988.
[19] Wang J S, Matyjaszewski K. Controled”living”radical polymerization atom transfer radical polymerization in the presence of transition metal complexes[J]. J Am Chem Soc, 1995, l17:5614.
[20]何天白,胡汉杰.海外高分子科学的新进展[M].北京:化学工业出版社, 2001.
[21]郭建华,韩哲文,吴平平.原子转移自由基聚合的研究进展[J].高分子通报,1998, (3):32-36.
[22]隋智慧,张西怀等.新型两性树脂复鞣剂的应用研究[J].皮革化工, 2001,19(1):23.
[23] LESKO,et al. Method of Treating Leather with Improved Retaining agents[P]. U. S. Patent 5, 1998, 820-633.
[1]陈国强.甲基丙烯酸羟丙酯接枝交联真丝绸结构与性能的研究[J].浙江丝绸工学院学报, 1998, 15(4):277-281.
[2]王平.真丝织物接枝共聚的研究[J].浙江丝绸工学院学报,1987, (1):36-42.
[3]钟安华,郭维婵.用4594对真丝绸接枝改性[J].广西纺织科技, 1999, (1):11-14.
[4]陈美云,吕晶.甲基丙烯酸丁酯在真丝织物上接枝的探讨[J].丝绸, 1997, (4):14.
[5]曹雪琴,杨慎举.真丝纤维的丙烯酰胺接枝改性研究[J].丝绸, 2004, (2):16-19.
[1]何天白,胡汉杰.海外高分子科学的新进展[M].北京:化学工业出版社,1997,5-18.
[2] Wang J S, Matyjaszewski K. Controlled/”living”radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu(I) / Cu(1I)redox process[J].Macromolecules, 1995,28:7901-7910.
[3] Georges M K, Vereqin R P N,Kaxmaier P M.Narrow molecular weight resins by a free-radical polymerization process[J].Macromolecules,1993,26:2987-2988.
[4] Wang J S,Matyjaszewski K.Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes [J].J. Am. Chem. Soc., 1995,117:5614-5615.
[5] Kato M, Kamigaito M, Sawamoto M, et al.Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine)ruthenium(II) /methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization [J].Macromolecules,1995,28:1721-1723.
[6] Li M, Matyjaszewski K. Further Progress in Atom Transfer Radical Polymerizations Conducted in a Waterborne System [J]. J. Polym. Sci. Part A. Polym. Chem., 2003, 41: 3606-3614.
[7]赵洪池,杨鹏,梁淑君.活性自由基乳液聚合的研究进展[J].信息记录材料, 2005, 6(3): 41-46.
[8]汤建萍,曾宪标.原子转移自由基聚合反应及其进展[J].宜春学院学报, 2003, 25(2): 40-43.
[9] Carlmark, Anna, Malmstrom, Eva E. ATRP grafting from cellulose fibers to create block-copolymer grafts[J]. Biomacromolecules, 2003, 4(6): 1740-1745.
[10] Petr Vlcek, Miroslav Janata, Petra Látalová,Jaroslav Krí?, et al. Controlled grafting of cellulose diacetate[J]. Polymer, 2006, 47(8): 2587-2595.
[11] Wang Jing-yuan, Zhang Kai, Li Hong-tu, et al. Surface-initiated atom transfer radical polymerization on spherical silicon gel in water -borne system at ambient temperature[J].Materials Chemistry and Physics, 2006, 96(2): 477-482.
[12] Sang Beom Lee , Richard R. Permanent Nonleaching Antibacterial Surfaces.1.Synthesis by Atom Transfer Radical Polymerization[J]. Biomacromolecules, 2004, 5: 877-882.
[13] Ashford E J, Naldi V,Dell R O,et al.Novel routes to controlled structure water-soluble polymers: Atom transfer radical polymerization of sodium methacrylate in aqueous media[J].American Chemical Society, Polymer Priprints, Division of Polymer Chemistry, 1999, 40:405-406.
[14] Nanda A K, Matyjaszewski K. Effect of [bpy]/[Cu(I)] ratio, solvent, counterion, and alkyl bromides on the activation rate constants in atom transfer radical polymerization[J]. Macromolecules, 2003, 36: 599-604.
[15] Nanda A K, Matyjaszewski K. Effect of [PMDETA]/[Cu(I)] ratio, monomer, solvent, counterion, ligand, and alkyl bromide on the activation rate constants in atom transfer radical polymerization[J]. Macromolecules, 2003, 36: 1487-1493.
[16]陈瑾.原子转移自由基聚合新催化体系的研究[D].苏州大学,2004,17-18.
[1]赵国玺.表面活性剂作用原理[M].北京:中国轻工业出版社, 2003, 26-28.
[2]王俊起,王友斌,薛金荣等.纺织品抗菌功能测试方法研究[J].中国卫生工程学,2003, (3): 129-132.
[3] Testing for antibacterial activity and efficacy on textile products[S]. Japanese lndustry Standard,Reference,number:JISL1902:2002(E)
[4]郑华英,王斌,孙敏等.抗菌织物检验方法的研究[J].中国卫生检验杂志, 2004, (2): 168-170.
[5]中华人民共和国纺织行业标准织物抗菌性能试验方法[S]. FZ/T0l021-1992.
[6]中华人民共和国国家标准《一次性使用卫生用品卫生标准》[S]. GB15979-2002.
[7]王俊起,王友斌.抗菌织物测试方法的研究(续)一纺织标准与质量[J]. 2003, (l): 26-28.
[1]陈国强.一缩二乙二醇二甲基丙烯酸酯接枝真丝的结构[J].高分子学报,2002,3:379-384.
[2] Freddi G,Shiozaki H,Allara G,Gto Y,Yasui H,Tsukada M.J SD C,1996 ,112(3) :88～94.
[3] Tsukada M,Freddi G,Ishiguro Y,Shiozaki H.J Appl Polym Sci ,1993 ,50:1519～1527.
[4]Ishikawa H,Tsukada M,Doizume T,Hirabayashi K.Sen2ⅠGakkaishi ,1972 ,28:91～93.