新型天然纤维材料离子交换树脂合成与应用研究
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摘要
本文以棉花、木材和树皮为原料，合成一系列新型天然纤维材料类离子交换树
脂：多乙烯多胺基棉纤维（CFDETA，CFTETA，CFTEPA），长链季铵基棉纤维
（LCQACF），羧基木粉（CWP），氨基木粉（EDAW，HDAW，TETAW）以及改性树
皮（FMB，EMB，AMB）。讨论了上述五类离子交换树脂的合成工艺条件、化学性
能、对重金属离子和阳离子型染料的吸附特性，以及LCQACF的杀菌能力。这五
类离子交换树脂均为创新合成，未见文献报导。
通过元素分析，红外光谱、质谱以及核磁共振谱对相关产品进行了鉴定。
合成多乙烯多胺基棉纤维：CFDETA，CFTETA，CFTEPA，系统研究了它们
的最佳合成工艺条件、吸附铜离子的热力学与动力学特征，并详细探讨了其吸附机
理。研究表明：在棉纤维经碱化、环氧化、烯胺化成多乙烯多胺基棉纤维过程中，环
氧化是关键反应。棉纤维环氧值的大小受配比、反应时间、反应温度等因素的影响。
其最佳工艺条件为：环氧化温度20℃，环氧化反应时间10小时，环氧氯丙烷：棉纤
维=3：1（W/W）；烯胺化温度50℃，催化剂碳酸钠1克。铜离子与多乙烯多胺基
在棉纤维上形成四齿配体螫合物，为平面正方形结构。CFDTA、CFTETA、
CFTEPA吸附铜离子的热效应△H分别为－26．79KJ·mol－1，－41．55KJ·
mol－1，－47．07KJ·mol－1；铜离子的吸附行为遵循Langmuir吸附等温式，为单分
子层吸附。三种改性棉纤维具有吸附容量大、再生性能好的特点。
合成具有杀菌、吸附双功能长链季铵基棉纤维──LCQACF，其中间体环氧
基季铵盐（EDMDC）为创新化合物。讨论了EDMDC的反应条件及反应动力学，研
究结果表明：环氧基长链季铵盐接枝到棉纤维上之后，仍具有强效的杀菌力，可快
速杀灭金黄色葡萄球菌和大肠杆菌。同时，LCQACF还可吸附水溶液中的铜离子，
其离子交换容量可达 47mg·g-1（以 Cu2+计）。经过再生之后，LCQACF可反复吸
附，多次杀菌。
通过接枝共聚、环氧化、氨化等方法对木粉进行化学改性，合成新型弱酸性阳
离子交换树脂──CWP和新型弱碱性阴离子交换树脂──EDAW，HDAW，
TETAW。研究结果表明：在一定温度下，采用适宜的引发剂及单体的用量，可得到
高接枝率，低均聚率的接枝共聚物（PANW，PAAW）。二者在酸性条件下水解所得
CWP，酸值低，收率高；在碱性条件下水解所得CWP，酸值高，收率低。本试验所合
成的CWn对Cu‘”的吸附容量可达soing·g－‘，对碱性桃红的吸附容量可达
500mg·g－‘。同时还表明：EDAW、HDAW和TETAW在pH＝5～6范围内对
Cu汁吸附容量最大，分别为33ms·s叫S7ms·s一＊3ms·s＊。上述两类离子交
换树脂均具有良好的再生性能。
合成了三种树皮类离子交换树脂：EMB、FMB、AMB。研究表明：通过化学改
性，既保持了树皮中的有效成份，又改善了树皮的化学稳定性。EMB、FMB和
AMB对Cu汁的吸附容量分别为71mg·g＊J8mg·g＊和91mg·g1，对碱性桃
红的吸附容量分别为95mg·g叫E4mg·g叫和110mg·g叫。它们属于弱酸性阳
离子交换树脂，在 90 C以上温度下长时间受热，吸附容量有所降低。
New types of ion exchange resins from natural fiber materials such as:
polyethylenepolyamino cotton fibers (CFDETA, CFTETA, CFTEPA ),long chain
quaternary amino cotton fiber(LCQACF),carboxyl wood powder(CPW), amino
wood powders (EDAW, HDAW, TETAW ) and chemically modified barks
(FMB,EMB,AMB) were prepared. The five kinds of ion exchange resins' opti-
mum synthetic processes, chemical characteristics, adsorption properties and the
germicidal power of LCQACF were discussed. These ion exchange resins were
first synthesized. They have not been reported in literature.
The products were analyzed by EA, FT-IR, MS and NMR.
The synthetic conditions, the adsorption mechanism, the thermodynamic and
kinetic characteristics of adsorption to Cu2+ for the polyethylenepolyamino cotton
fibers were first systematically studied. The experiment results showed that the
epoxidation of cotton fiber was the most important in the process. The epoxide
value was determined by the reactants ratio, reaction time and temperature. Its
optimum synthetic conditions as follows: epoxidation temperature 20℃,epoxida-
tion time 10hrs,cotton: epichlorohydrin = 3: 1 (w/w) ; enamic reaction tempera-
ture 50℃,catalyst (Na2CO3) lg. Cu2+ and amino converted into inner-orbital
complexes when Cu2+ was adsorbed on polyethylenepolyamino cotton fibers.
They formed quaterdentate ligands. When Cu2+ was adsorbed by CFDETA,
CFTETA and CFTEPA, their respective adsorption enthalpies(△H) were -26.
79 KJ/mol, - 41. 55KJ/mol and -47. 07KJ/mol. Its adsorption process abided
by Langmuir isotherm and was monomolecure adsorption.
LCQACF was first prepared. It not only could be used as a kind of adsor-
bent, butalso could be used as a kind of bactericide. The experiment results
showed that LCQACF could POwerfully kill staphylicocus aureus and bacilluscol-
i. In the meantime, LCQAF could adsorb metal ions. Its adsorPtion capacity
to Cu2+ was about 47mg/g. LCQACF also had powerfu1 sterilization ability and
adsorptiOn capacity after being regenerated.
PANW and PAAW were synthesized through the graft coPOlyInrization of
acrylonitrile or acry1andde and wood powder. They were hydrolyzed into the car-
boxyl wood POwder by base or acid. The experiment results showed that high
copolyInechtion ratio resultants were prepared by suitable initiator and
monomer. In acid condition, the carboxy1 wood powder was high vield and low
acid value. In base condition, it wa8 low yield and high acid value. The adsorP--
..
tion caPacities of it to Cu2+ and to basic pink dye were 39. 0mg/g and 500mg/g re-
spectively.
Three kinds of amino wood powders (EDAW HDAW, TETAW) were made
by alkalization, ePOxidation and andnhation. The optimum reation conditions
were discussed. The ad8orption capacities of EDAW, HDAW and TETAW to
Cuz+ were 33mg/g, 27mg/g and 43mg/g respectively when PH= 5~6. The re-
sults also showed that the carboxyl wood powder and the andno wood powder
had gOOd ability to be regenerated.
This paper also discussed the reaction conditions of three kinds of chendcally
modified barks: FMB, EMB and AMB. The experiment results showed that the
chemical modifications not only retained the effective composition of bark, but
also improved its chemica1 stability. The adsorption capacities of FMB, EMB and
AMB to Cuz+ and to basic pink dye were 71mg/g, 78mg/g, 91mg/gI and 95mg/
g, 94mg/g, 1l0Ing/g respectively. They were weak acid anion exchange resins.
When they were heated Iong time, their adsorption capacities becam lower.
脂：多乙烯多胺基棉纤维（CFDETA，CFTETA，CFTEPA），长链季铵基棉纤维
（LCQACF），羧基木粉（CWP），氨基木粉（EDAW，HDAW，TETAW）以及改性树
皮（FMB，EMB，AMB）。讨论了上述五类离子交换树脂的合成工艺条件、化学性
能、对重金属离子和阳离子型染料的吸附特性，以及LCQACF的杀菌能力。这五
类离子交换树脂均为创新合成，未见文献报导。
通过元素分析，红外光谱、质谱以及核磁共振谱对相关产品进行了鉴定。
合成多乙烯多胺基棉纤维：CFDETA，CFTETA，CFTEPA，系统研究了它们
的最佳合成工艺条件、吸附铜离子的热力学与动力学特征，并详细探讨了其吸附机
理。研究表明：在棉纤维经碱化、环氧化、烯胺化成多乙烯多胺基棉纤维过程中，环
氧化是关键反应。棉纤维环氧值的大小受配比、反应时间、反应温度等因素的影响。
其最佳工艺条件为：环氧化温度20℃，环氧化反应时间10小时，环氧氯丙烷：棉纤
维=3：1（W/W）；烯胺化温度50℃，催化剂碳酸钠1克。铜离子与多乙烯多胺基
在棉纤维上形成四齿配体螫合物，为平面正方形结构。CFDTA、CFTETA、
CFTEPA吸附铜离子的热效应△H分别为－26．79KJ·mol－1，－41．55KJ·
mol－1，－47．07KJ·mol－1；铜离子的吸附行为遵循Langmuir吸附等温式，为单分
子层吸附。三种改性棉纤维具有吸附容量大、再生性能好的特点。
合成具有杀菌、吸附双功能长链季铵基棉纤维──LCQACF，其中间体环氧
基季铵盐（EDMDC）为创新化合物。讨论了EDMDC的反应条件及反应动力学，研
究结果表明：环氧基长链季铵盐接枝到棉纤维上之后，仍具有强效的杀菌力，可快
速杀灭金黄色葡萄球菌和大肠杆菌。同时，LCQACF还可吸附水溶液中的铜离子，
其离子交换容量可达 47mg·g-1（以 Cu2+计）。经过再生之后，LCQACF可反复吸
附，多次杀菌。
通过接枝共聚、环氧化、氨化等方法对木粉进行化学改性，合成新型弱酸性阳
离子交换树脂──CWP和新型弱碱性阴离子交换树脂──EDAW，HDAW，
TETAW。研究结果表明：在一定温度下，采用适宜的引发剂及单体的用量，可得到
高接枝率，低均聚率的接枝共聚物（PANW，PAAW）。二者在酸性条件下水解所得
CWP，酸值低，收率高；在碱性条件下水解所得CWP，酸值高，收率低。本试验所合
成的CWn对Cu‘”的吸附容量可达soing·g－‘，对碱性桃红的吸附容量可达
500mg·g－‘。同时还表明：EDAW、HDAW和TETAW在pH＝5～6范围内对
Cu汁吸附容量最大，分别为33ms·s叫S7ms·s一＊3ms·s＊。上述两类离子交
换树脂均具有良好的再生性能。
合成了三种树皮类离子交换树脂：EMB、FMB、AMB。研究表明：通过化学改
性，既保持了树皮中的有效成份，又改善了树皮的化学稳定性。EMB、FMB和
AMB对Cu汁的吸附容量分别为71mg·g＊J8mg·g＊和91mg·g1，对碱性桃
红的吸附容量分别为95mg·g叫E4mg·g叫和110mg·g叫。它们属于弱酸性阳
离子交换树脂，在 90 C以上温度下长时间受热，吸附容量有所降低。
New types of ion exchange resins from natural fiber materials such as:
polyethylenepolyamino cotton fibers (CFDETA, CFTETA, CFTEPA ),long chain
quaternary amino cotton fiber(LCQACF),carboxyl wood powder(CPW), amino
wood powders (EDAW, HDAW, TETAW ) and chemically modified barks
(FMB,EMB,AMB) were prepared. The five kinds of ion exchange resins' opti-
mum synthetic processes, chemical characteristics, adsorption properties and the
germicidal power of LCQACF were discussed. These ion exchange resins were
first synthesized. They have not been reported in literature.
The products were analyzed by EA, FT-IR, MS and NMR.
The synthetic conditions, the adsorption mechanism, the thermodynamic and
kinetic characteristics of adsorption to Cu2+ for the polyethylenepolyamino cotton
fibers were first systematically studied. The experiment results showed that the
epoxidation of cotton fiber was the most important in the process. The epoxide
value was determined by the reactants ratio, reaction time and temperature. Its
optimum synthetic conditions as follows: epoxidation temperature 20℃,epoxida-
tion time 10hrs,cotton: epichlorohydrin = 3: 1 (w/w) ; enamic reaction tempera-
ture 50℃,catalyst (Na2CO3) lg. Cu2+ and amino converted into inner-orbital
complexes when Cu2+ was adsorbed on polyethylenepolyamino cotton fibers.
They formed quaterdentate ligands. When Cu2+ was adsorbed by CFDETA,
CFTETA and CFTEPA, their respective adsorption enthalpies(△H) were -26.
79 KJ/mol, - 41. 55KJ/mol and -47. 07KJ/mol. Its adsorption process abided
by Langmuir isotherm and was monomolecure adsorption.
LCQACF was first prepared. It not only could be used as a kind of adsor-
bent, butalso could be used as a kind of bactericide. The experiment results
showed that LCQACF could POwerfully kill staphylicocus aureus and bacilluscol-
i. In the meantime, LCQAF could adsorb metal ions. Its adsorPtion capacity
to Cu2+ was about 47mg/g. LCQACF also had powerfu1 sterilization ability and
adsorptiOn capacity after being regenerated.
PANW and PAAW were synthesized through the graft coPOlyInrization of
acrylonitrile or acry1andde and wood powder. They were hydrolyzed into the car-
boxyl wood POwder by base or acid. The experiment results showed that high
copolyInechtion ratio resultants were prepared by suitable initiator and
monomer. In acid condition, the carboxy1 wood powder was high vield and low
acid value. In base condition, it wa8 low yield and high acid value. The adsorP--
..
tion caPacities of it to Cu2+ and to basic pink dye were 39. 0mg/g and 500mg/g re-
spectively.
Three kinds of amino wood powders (EDAW HDAW, TETAW) were made
by alkalization, ePOxidation and andnhation. The optimum reation conditions
were discussed. The ad8orption capacities of EDAW, HDAW and TETAW to
Cuz+ were 33mg/g, 27mg/g and 43mg/g respectively when PH= 5~6. The re-
sults also showed that the carboxyl wood powder and the andno wood powder
had gOOd ability to be regenerated.
This paper also discussed the reaction conditions of three kinds of chendcally
modified barks: FMB, EMB and AMB. The experiment results showed that the
chemical modifications not only retained the effective composition of bark, but
also improved its chemica1 stability. The adsorption capacities of FMB, EMB and
AMB to Cuz+ and to basic pink dye were 71mg/g, 78mg/g, 91mg/gI and 95mg/
g, 94mg/g, 1l0Ing/g respectively. They were weak acid anion exchange resins.
When they were heated Iong time, their adsorption capacities becam lower.
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62SHUKLA S R,SAKHARDANE V D.Metal ion removal by dyed cellulose material[J].J.Appl.Polym.Sci.,1991,41:829~835．
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64 RANDALL J M, et al.Binding of heavy metal ions by formaldehyde polymerized peanut skins [J].J.Appl.Polym.Sci.,1978,22:379-387．
65 PA WAN K, DARA S S.Binding heavy metal ions with polymerized onion skin[J].J.Polym.Sci.,1981,19:397-402．
66 SUEMITSU R.UENISHI R.The use of dyestuff-treated rice hulls for removal of heavy metal from waste water [J].J.Appl.Polym.Sci.,1986,31:75-83．
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75MITSUHIRO M,et al.Binding of heavy metal ions by chemically modified woods[J].J.Appl.Polym.Sci.,1987,34;1013~1023．
76 宋湛谦,HAN J S,等.花旗松和槿麻纤维的硝酸化学改性[J].林产化学与工业,1999,19(1) :1~5．
77Ba, Huynh Van; Ishizu, Atsushi and Nakano,Junzo; Mokuzagakkashi, 1980 11:738-742．
78DENCE C W.; Halogenation and Nitration, LIGNINS Occurrence, Formation ,Structure and Reaction,Edited by K.V.Sarkanen and C.H.Ludwig, Wiley Interscience,1971．
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59 WANG U P,CHIN J.[J].Inst.Chem.Eng.,1972,3(1) : 15．
60 NAGATY A, MUSTAFA B ,MANSOUR O Y.Lignocellulose-polymer composite I[J].J.Appl.Polym.Sci.,1979,23(11) :3263．
61 ODOZI T O.Studis on binding metal ions with polymerized corn cob and a composite resin with sawdust and onion skin[J].Agricultural Wastes, 1985, 12:13-21．
62SHUKLA S R,SAKHARDANE V D.Metal ion removal by dyed cellulose material[J].J.Appl.Polym.Sci.,1991,41:829~835．
63 SHUKLA S R,SAKHARDANE V D.Column studies on metal ion removal by dyed cellulose material[J].J.Appl.Polym.Sci.,1992,44:910-930．
64 RANDALL J M, et al.Binding of heavy metal ions by formaldehyde polymerized peanut skins [J].J.Appl.Polym.Sci.,1978,22:379-387．
65 PA WAN K, DARA S S.Binding heavy metal ions with polymerized onion skin[J].J.Polym.Sci.,1981,19:397-402．
66 SUEMITSU R.UENISHI R.The use of dyestuff-treated rice hulls for removal of heavy metal from waste water [J].J.Appl.Polym.Sci.,1986,31:75-83．
67 MARSHALL W E.Agricultural byproducts as metal absorbents:sorption properties and resistance to mechanical abrasion [J].J.Chem.Technol.Biotechnol.,1996,66(2) : 192-198．
68 NAMASIVYAM C.Removal of dyes from aqueous solution by cellulosic waste orange peel[J].Bioresource Technol., 1996,57(1) :37-43．
69 木村优,山下博美,驹田顺子.[J].分析化学(日),1986． 35:400~403．
70ORHAN Y,BUYUKGUNOR H.The removal of using agricultural wastes [J].Water Sci.Technol.,1993,28(2) :247-255．
71RANDALL J M,BERMANN R L.Use of bark to remove heavy metal ions from waste solutions[J].Forest Products Journal, 1974,24(9) :80-84．
72RANDALL J M,HAUTALE E.Modified barks a s scavengers for heavy metals ions[J].Forest Products Journal, 1976,26(8) :46-50．
73RANDALL J M.Variations in effectiveness of barks as scavengers for heavymetals ions[J].Forest Products Journal, 1977,27(11) :51~56．
74NAG A.Utilization of charred sawdust as an absorbent of dyes toxic salts and oil from water process[J].Saf.Environ.Prot.,1995,73(B4) :299~304．
75MITSUHIRO M,et al.Binding of heavy metal ions by chemically modified woods[J].J.Appl.Polym.Sci.,1987,34;1013~1023．
76 宋湛谦,HAN J S,等.花旗松和槿麻纤维的硝酸化学改性[J].林产化学与工业,1999,19(1) :1~5．
77Ba, Huynh Van; Ishizu, Atsushi and Nakano,Junzo; Mokuzagakkashi, 1980 11:738-742．
78DENCE C W.; Halogenation and Nitration, LIGNINS Occurrence, Formation ,Structure and Reaction,Edited by K.V.Sarkanen and C.H.Ludwig, Wiley Interscience,1971．
79LIETH H.Human Ecology 1973,11(4) :303-332
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