整体型环氧树脂大孔聚合物的制备与表征
|
摘要
用三亚乙基四胺(TETA)作为固化剂,通过双酚A环氧树脂在聚乙二醇(PEG)介质中的聚合反应诱导相分离制备具有三维骨架结构的整体型环氧树脂大孔聚合物。固定PEG1000与PEG2000的质量比为6∶1,分别研究了环氧树脂与PEG的比例关系和TETA的用量对整体型大孔聚合物孔结构的影响,用FT-IR、SEM、BET和MIP对整体型大孔聚合物进行表征并将其用于重金属离子的吸附。结果表明,改变环氧树脂与PEG的比例关系或者TETA的用量都可以调控大孔聚合物的孔结构,其孔径为0.1~1μm。孔径最小的整体型大孔聚合物比表面积最大,约84.4m~2/g,但孔径较大的整体型大孔聚合物对重金属离子(Cu~(2+))的吸附性能更好,吸附量高达113.1mg/g。
With TETA as curing agent,3Dskeletal epoxy-based macroporous polymer monoliths were prepared by the polymerization-reaction-induced phase separation of bisphenol A epoxy resins in PEG medium.While the weight ratio of PEG1000 to PEG2000was fixed at 6/1,the influences of the weight ratio of epoxy to PEG and the amount of TETA on the pore structure of the macroporous polymer monoliths were studied respectively.Macroporous polymer monoliths were characterized by FT-IR,SEM,BET and MIP,and were used to adsorb heavy metal ions.Results show that the pore structure of macroporous polymer can be adjusted by changing the weight ratio of epoxy and PEG or the amount of TETA,and the pore sizes are adjusted in a range of 0.1-1μm.The monolithic macroporous polymer is minimum with minimum pore size reaches the maximum when the pore size possesses the maximum specific surface area,which is about 84.4m~2/g.On the other side,the macroporous polymer with larger pore size exhibit higher adsorption performance for Cu(Ⅱ)ions,which can reach up to 113.1mg/g.
With TETA as curing agent,3Dskeletal epoxy-based macroporous polymer monoliths were prepared by the polymerization-reaction-induced phase separation of bisphenol A epoxy resins in PEG medium.While the weight ratio of PEG1000 to PEG2000was fixed at 6/1,the influences of the weight ratio of epoxy to PEG and the amount of TETA on the pore structure of the macroporous polymer monoliths were studied respectively.Macroporous polymer monoliths were characterized by FT-IR,SEM,BET and MIP,and were used to adsorb heavy metal ions.Results show that the pore structure of macroporous polymer can be adjusted by changing the weight ratio of epoxy and PEG or the amount of TETA,and the pore sizes are adjusted in a range of 0.1-1μm.The monolithic macroporous polymer is minimum with minimum pore size reaches the maximum when the pore size possesses the maximum specific surface area,which is about 84.4m~2/g.On the other side,the macroporous polymer with larger pore size exhibit higher adsorption performance for Cu(Ⅱ)ions,which can reach up to 113.1mg/g.
引文
1 El Kadib A,Chimenton R,Sachse A,et al.Functionalized inorganic monolithic microreactors for high productivity in fine chemicals catalytic synthesis[J].Angew Chem Int Ed,2009,48(27):4969.
2 Fan R,Guo F M,Liu W H,et al.Research progresses of monolithic stationary phases used in HPLC prepared by in-situ polymerization and crosslinking[J].Mater Rev,2014,28(S1):279(in Chinese).范瑞,郭丰梅,刘文华,等.原位键合交联高效液相色谱整体柱的研究进展[J].材料导报,2014,28(专辑23):279.
3 Peroni D,Vanhoutte D,Vilaplana F,et al.Hydrophobic polymer monoliths as novel phase separators:Application in continuous liquid-liquid extraction systems[J].Anal Chim Acta,2012,720:63.
4 Nischang I,Brüggemann O.On the separation of small molecules by means of nano-liquid chromatography with methacrylate-based macroporous polymer monoliths[J].J Chromatogr A,2010,1217(33):5389
5 Sachse A,Galarneau A,Fajula F,et al.Functional silica monoliths with hierarchical uniform porosity as continuous flow catalytic reactors[J].Microp Mesop Mater,2011,140(1):58.
6 He P,Greenway G,Haswell S J.Development of a monolith based immobilized lipase micro-reactor for biocatalytic reactions in a biphasic mobile system[J].Process Biochem,2010,45(4):593.
7 Ponomareva E A,Volokitina M V,Vinokhodov D O,et al.Biocatalytic reactors based on ribonuclease A immobilized on macroporous monolithic supports[J].Anal Bioanal Chem,2013,405(7):2195.
8 Ma J T,Jiang D D,Qi R F,et al.Application of monolithic column in microfluidic chip[J].J Instrumental Anal,2015,34(3):289(in Chinese).马玖彤,江丹丹,祁瑞芳,等.整体柱富集技术在微流控芯片系统中的应用[J].分析测试学报,2015,34(3):289.
9 Zhang J,Chen G,Tian M,et al.A novel organic-inorganic hybrid monolithic column prepared in-situ in a microchip and its application for the determination of 2-amino-4-chlorophenol in chlorzoxazone tablets[J].Talanta,2013,115:801.
10 Walsh Z,Paull B,Macka M.Inorganic monoliths in separation science:A review[J].Anal Chim Acta,2012,750:28.
11 Jandera P.Advances in the development of organic polymer monolithic columns and their applications in food analysis-A review[J].J Chromatogr A,2013,1313(20):37.
12 Sun X,He X,Chen L,et al.In-column“click”preparation of hydrophobic organic monolithic stationary phases for protein separation[J].Anal Bioanal Chem,2011,399(10):3407.
13 He L,Feng H J,Li J J,et al.Development and application of modification of organic polymer monolithic columns[J].J Instrumental Anal,2011,30(7):825(in Chinese).何丽,冯海建,李静杰,等.有机聚合物整体柱的改性与应用进展[J].分析测试学报,2011,30(7):825.
14 Hoegger D,Freitag R.Acrylamide-based monoliths as robust stationary phases for capillary electrochromatography[J].J Chromatogr A,2001,914:211.
15 Liu M Q,Liu H Y,Liu Y K,et al.Preparation and characterization of temperature-responsive poly(N-isopropylacrylamide-co-N,N′-methylenebisacrylamide)monolith for HPLC[J].J Chromatogr A,2011,1218(2):286.
16 Sinitsyna E S,Walter J G,Vlakh E G,et al.Macroporous methacrylate-based monoliths as platforms for DNA microarrays[J].Talanta,2012,93(2):139.
17 Hasegawa G,Kanamori K,Nakanishi K,et al.Fabrication of highly crosslinked methacrylate-based polymer monoliths with well-defined macropores via living radical polymerization[J].Polymer,2011,52(21):4644.
18 Zalusky A S,Olayo-Valles R,Taylor C J,et al.Mesoporous polystyrene monoliths[J].J Am Chem Soc,2001,123(7):1519.
19 Lee J,Yandek G R,Kyu T.Reaction induced phase separation in mixtures of multifunctional polybutadiene and epoxy[J].Polymer,2005,46(26):12511.
20 Zhang R F,Zhang L L.Preparation of 3-dimentional skeletal polymer via control of reaction-induced phase separation in epoxy/poly(ethylene glycol)blends[J].Polym Bull,2008,61(6):671.
21 Chen Y,Li D X.Analysis of error for pore structure of porous materials measured by MIP[J].Bull Chinese Ceram Soc,2006,25(4):198 (in Chinese).陈悦,李东旭.压汞法测定材料孔结构的误差分析[J].硅酸盐通报,2006,25(4):198.
22 Zhou H,Xie D X,Song C X,et al.Application of mercury intrusion method in manufacturing the alumina membrane[J].Exp Technol Manage,2010,27(9):31(in Chinese).周花,谢东星,宋春晓,等.压汞法在氧化铝陶瓷膜制备中的应用[J].实验技术与管理,2010,27(9):31.
23 Xie Z H,Zhang Y,Wang H L,et al.Influence of organic solvent/ionic liquid mixture system on solubility of cellulose[J].J Funct Mater,2014(22):22060(in Chinese).谢志海,张瑜,王海力,等.铜离子印迹聚合物的制备及吸附性能研究[J].功能材料,2014(22):22060.
24 Du Z Y,Yang H F,Qu H H,et al.Preparation of dithizone-anchored PHEMA microspheres and its adsorption properties for Cu2+[J].Chemistry,2009,72(9):803(in Chinese).杜志英,杨慧芬,瞿欢欢,等.双硫腙改性的聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)微球的制备及其对铜离子的吸附研究[J].化学通报,2009,72(9):803.
2 Fan R,Guo F M,Liu W H,et al.Research progresses of monolithic stationary phases used in HPLC prepared by in-situ polymerization and crosslinking[J].Mater Rev,2014,28(S1):279(in Chinese).范瑞,郭丰梅,刘文华,等.原位键合交联高效液相色谱整体柱的研究进展[J].材料导报,2014,28(专辑23):279.
3 Peroni D,Vanhoutte D,Vilaplana F,et al.Hydrophobic polymer monoliths as novel phase separators:Application in continuous liquid-liquid extraction systems[J].Anal Chim Acta,2012,720:63.
4 Nischang I,Brüggemann O.On the separation of small molecules by means of nano-liquid chromatography with methacrylate-based macroporous polymer monoliths[J].J Chromatogr A,2010,1217(33):5389
5 Sachse A,Galarneau A,Fajula F,et al.Functional silica monoliths with hierarchical uniform porosity as continuous flow catalytic reactors[J].Microp Mesop Mater,2011,140(1):58.
6 He P,Greenway G,Haswell S J.Development of a monolith based immobilized lipase micro-reactor for biocatalytic reactions in a biphasic mobile system[J].Process Biochem,2010,45(4):593.
7 Ponomareva E A,Volokitina M V,Vinokhodov D O,et al.Biocatalytic reactors based on ribonuclease A immobilized on macroporous monolithic supports[J].Anal Bioanal Chem,2013,405(7):2195.
8 Ma J T,Jiang D D,Qi R F,et al.Application of monolithic column in microfluidic chip[J].J Instrumental Anal,2015,34(3):289(in Chinese).马玖彤,江丹丹,祁瑞芳,等.整体柱富集技术在微流控芯片系统中的应用[J].分析测试学报,2015,34(3):289.
9 Zhang J,Chen G,Tian M,et al.A novel organic-inorganic hybrid monolithic column prepared in-situ in a microchip and its application for the determination of 2-amino-4-chlorophenol in chlorzoxazone tablets[J].Talanta,2013,115:801.
10 Walsh Z,Paull B,Macka M.Inorganic monoliths in separation science:A review[J].Anal Chim Acta,2012,750:28.
11 Jandera P.Advances in the development of organic polymer monolithic columns and their applications in food analysis-A review[J].J Chromatogr A,2013,1313(20):37.
12 Sun X,He X,Chen L,et al.In-column“click”preparation of hydrophobic organic monolithic stationary phases for protein separation[J].Anal Bioanal Chem,2011,399(10):3407.
13 He L,Feng H J,Li J J,et al.Development and application of modification of organic polymer monolithic columns[J].J Instrumental Anal,2011,30(7):825(in Chinese).何丽,冯海建,李静杰,等.有机聚合物整体柱的改性与应用进展[J].分析测试学报,2011,30(7):825.
14 Hoegger D,Freitag R.Acrylamide-based monoliths as robust stationary phases for capillary electrochromatography[J].J Chromatogr A,2001,914:211.
15 Liu M Q,Liu H Y,Liu Y K,et al.Preparation and characterization of temperature-responsive poly(N-isopropylacrylamide-co-N,N′-methylenebisacrylamide)monolith for HPLC[J].J Chromatogr A,2011,1218(2):286.
16 Sinitsyna E S,Walter J G,Vlakh E G,et al.Macroporous methacrylate-based monoliths as platforms for DNA microarrays[J].Talanta,2012,93(2):139.
17 Hasegawa G,Kanamori K,Nakanishi K,et al.Fabrication of highly crosslinked methacrylate-based polymer monoliths with well-defined macropores via living radical polymerization[J].Polymer,2011,52(21):4644.
18 Zalusky A S,Olayo-Valles R,Taylor C J,et al.Mesoporous polystyrene monoliths[J].J Am Chem Soc,2001,123(7):1519.
19 Lee J,Yandek G R,Kyu T.Reaction induced phase separation in mixtures of multifunctional polybutadiene and epoxy[J].Polymer,2005,46(26):12511.
20 Zhang R F,Zhang L L.Preparation of 3-dimentional skeletal polymer via control of reaction-induced phase separation in epoxy/poly(ethylene glycol)blends[J].Polym Bull,2008,61(6):671.
21 Chen Y,Li D X.Analysis of error for pore structure of porous materials measured by MIP[J].Bull Chinese Ceram Soc,2006,25(4):198 (in Chinese).陈悦,李东旭.压汞法测定材料孔结构的误差分析[J].硅酸盐通报,2006,25(4):198.
22 Zhou H,Xie D X,Song C X,et al.Application of mercury intrusion method in manufacturing the alumina membrane[J].Exp Technol Manage,2010,27(9):31(in Chinese).周花,谢东星,宋春晓,等.压汞法在氧化铝陶瓷膜制备中的应用[J].实验技术与管理,2010,27(9):31.
23 Xie Z H,Zhang Y,Wang H L,et al.Influence of organic solvent/ionic liquid mixture system on solubility of cellulose[J].J Funct Mater,2014(22):22060(in Chinese).谢志海,张瑜,王海力,等.铜离子印迹聚合物的制备及吸附性能研究[J].功能材料,2014(22):22060.
24 Du Z Y,Yang H F,Qu H H,et al.Preparation of dithizone-anchored PHEMA microspheres and its adsorption properties for Cu2+[J].Chemistry,2009,72(9):803(in Chinese).杜志英,杨慧芬,瞿欢欢,等.双硫腙改性的聚(二甲基丙烯酸乙二醇酯-甲基丙烯酸羟乙酯)微球的制备及其对铜离子的吸附研究[J].化学通报,2009,72(9):803.