醋酸纤维的结构与性能研究
摘要
醋酸纤维是纤维素纤维经乙酰化以后,采用干法纺丝工艺纺制而成的一种化学纤维,具有与粘胶、涤纶纤维类似的特性；同时醋酸纤维也是一种生产过程无污染,废弃物可生物降解的生态环保型纤维。
实验采用傅立叶红外光谱仪、广角X-射线衍射仪,扫描电子显微镜,热重及差示扫描量热分析仪等对醋酸纤维的聚集态结构及形态结构进行了表征,并测试了热稳定性。同时,配制了一系列不同种类和用量的化学试剂溶液,对醋酸纤维的溶解性及失重率进行测试,并分别对酸碱处理后试样的粘度和酯化度进行了分析。结果表明：醋酸纤维中含有酯羰基及羟基等特征基团；具有晶态和非晶态共存的“两相”结构,结晶度为21.98%；其热稳定性较好,拉伸断裂强度为1.29cN/dtex。无机酸容易造成醋酸纤维的聚合度下降而使之溶解,碳酸钠则会使纤维发生去乙酰化作用而造成明显失重；而双氧水和保险粉对纤维的性能影响不大。
利用分散染料、阳离子染料、活性染料对醋酸纤维进行染色,测试了染色温度、pH值、染色时间及染料用量等因素对纤维上染百分率的影响,从而确定了染料的最佳染色工艺。结果表明：分散染料对醋酸纤维的上染百分率及耐水洗牢度均为最高,尤其以中温型和低温型染色效果最好；其最佳的染色工艺为：染色温度85℃,pH值5-6,染色时间80min；水洗牢度在4-5级。而阳离子染料及活性染料对醋酸纤维有一定程度的上染,其中阳离子染料的染色工艺和分散染料类似,活性染料的最佳工艺为：染色温度85℃,硫酸钠50g/L,染色时间80min。
采用分散红FB对醋酸纤维进行了染色热力学及动力学实验,并比较了在加入和未加入扩散剂NNO两种情况下纤维的染色热力学参数(亲和力-△μ0,染色热△H0,染色熵AS0)及染色动力学参数(扩散系数D,半染时间tl/2,比染色速率常数K')。结果发现分散染料对醋酸纤维的吸附机理符合能斯特(Nernst)型；加入扩散剂NNO以后,染料对纤维的亲和力下降,平衡染色吸附量减少；同时,加入扩散剂NNO之后,分散红FB在醋酸纤维中的扩散系数降低,平衡上染百分率有所下降,半染时间随之增加；比染色速率常数K'有所降低,这说明扩散剂NNO在一定程度上会影响到染色速率。
Cellulose acetate fiber is a kind of chemical fiber that formed by air spinning process from the ester derivative of cellulose, with some similar properties to viscose fiber and polyester filament. It also is considered ecologically friendly to the environment for its non-polluting production processes and biodegradable waste.
Aggregation structure and morphological structure were characterized by means of the modern material testing techniques and analytical methods such as FT-IR spectroscopy, SEM, X-ray diffraction, DSC-TG; meanwhile, the effect of different kinds of chemicals and its amount on the solubility and weight loss of cellulose acetate fiber were tested, and the viscosity of the samples treated with acid and the degree of esterification of the samples treated with alkaline were analysed. The results showed that:cellulose acetate fiber containing ester carbonyl and hydroxy group; the crystallinity of cellulose acetate is 21.98% with the coexistence of crystalline and amorphous "two-phase" structure, the thermal stability of cellulose acetate fiber is good and its breaking tenacity is 1.29 cN/dtex; inorganic acid could decrease the degree of polymerization of cellulos acetate easily,making it dissolved; and sodium carbonate would have a deacetylation effect on cellulose acetate with an appearant weight loss; however, the effect of hydrogen peroxide and hydrosulphite were less on the performance of cellulose acetate fiber.
By dyeing cellulose acetate fiber with disperse dyes, cationic dyes and reactive dyes, the effects of the factors such as temperature, pH value, dyeing time and concentration on the dyeing uptake for cellulose acetate fiber were studyed, then the best dyeing conditions were determined. The results showed that:both the dye-uptake and fastness to washing of disperse dyes on cellulose acetate fiber were highest, especially for medium and low temperature types disperse dyes, and the best dyeing process is that:temperature 85℃, pH=5-6, dyeing time 80min; with the fastness to washing 4-5. For cationic dyes and reactive dyes, the dye-uptake were not high. The dyeing process of cationic dyes is similar to disperse dyes. For bi-functional reactive dyes, the best dyeing process is that:temperature 85℃, sodium sulphate 50g/L, dyeing time 80min.
Disperse Red FB was employed to research dyeing thermodynamic and kinetic of cellulose acetate fiber;furtherly it compared the thermodynamic parameters(affinity-Δμ0, dyeing enthalpyΔH0, dyeing entropyΔS0) and the kinetics parameters(diffusion coefficient D, half-dyeing time t1/2, dyeing rate constant K') of cellulose acetate fiber dyed with and without dispersing agent NNO. The results showed that it's dyeing adsorption mechanism belonged to Nernst distribution type. It found that when dyeing with dispersing agent NNO, both the affinity and the diffusion coefficient of Disperse Red FB in cellulose acetate fiber reduced, leading to a lower dye-uptake and longer half-dyeing time; and the reduced dyeing rate constant indicated that dispersing agent NNO would affect the dyeing rate to a certian extent.
实验采用傅立叶红外光谱仪、广角X-射线衍射仪,扫描电子显微镜,热重及差示扫描量热分析仪等对醋酸纤维的聚集态结构及形态结构进行了表征,并测试了热稳定性。同时,配制了一系列不同种类和用量的化学试剂溶液,对醋酸纤维的溶解性及失重率进行测试,并分别对酸碱处理后试样的粘度和酯化度进行了分析。结果表明：醋酸纤维中含有酯羰基及羟基等特征基团；具有晶态和非晶态共存的“两相”结构,结晶度为21.98%；其热稳定性较好,拉伸断裂强度为1.29cN/dtex。无机酸容易造成醋酸纤维的聚合度下降而使之溶解,碳酸钠则会使纤维发生去乙酰化作用而造成明显失重；而双氧水和保险粉对纤维的性能影响不大。
利用分散染料、阳离子染料、活性染料对醋酸纤维进行染色,测试了染色温度、pH值、染色时间及染料用量等因素对纤维上染百分率的影响,从而确定了染料的最佳染色工艺。结果表明：分散染料对醋酸纤维的上染百分率及耐水洗牢度均为最高,尤其以中温型和低温型染色效果最好；其最佳的染色工艺为：染色温度85℃,pH值5-6,染色时间80min；水洗牢度在4-5级。而阳离子染料及活性染料对醋酸纤维有一定程度的上染,其中阳离子染料的染色工艺和分散染料类似,活性染料的最佳工艺为：染色温度85℃,硫酸钠50g/L,染色时间80min。
采用分散红FB对醋酸纤维进行了染色热力学及动力学实验,并比较了在加入和未加入扩散剂NNO两种情况下纤维的染色热力学参数(亲和力-△μ0,染色热△H0,染色熵AS0)及染色动力学参数(扩散系数D,半染时间tl/2,比染色速率常数K')。结果发现分散染料对醋酸纤维的吸附机理符合能斯特(Nernst)型；加入扩散剂NNO以后,染料对纤维的亲和力下降,平衡染色吸附量减少；同时,加入扩散剂NNO之后,分散红FB在醋酸纤维中的扩散系数降低,平衡上染百分率有所下降,半染时间随之增加；比染色速率常数K'有所降低,这说明扩散剂NNO在一定程度上会影响到染色速率。
Cellulose acetate fiber is a kind of chemical fiber that formed by air spinning process from the ester derivative of cellulose, with some similar properties to viscose fiber and polyester filament. It also is considered ecologically friendly to the environment for its non-polluting production processes and biodegradable waste.
Aggregation structure and morphological structure were characterized by means of the modern material testing techniques and analytical methods such as FT-IR spectroscopy, SEM, X-ray diffraction, DSC-TG; meanwhile, the effect of different kinds of chemicals and its amount on the solubility and weight loss of cellulose acetate fiber were tested, and the viscosity of the samples treated with acid and the degree of esterification of the samples treated with alkaline were analysed. The results showed that:cellulose acetate fiber containing ester carbonyl and hydroxy group; the crystallinity of cellulose acetate is 21.98% with the coexistence of crystalline and amorphous "two-phase" structure, the thermal stability of cellulose acetate fiber is good and its breaking tenacity is 1.29 cN/dtex; inorganic acid could decrease the degree of polymerization of cellulos acetate easily,making it dissolved; and sodium carbonate would have a deacetylation effect on cellulose acetate with an appearant weight loss; however, the effect of hydrogen peroxide and hydrosulphite were less on the performance of cellulose acetate fiber.
By dyeing cellulose acetate fiber with disperse dyes, cationic dyes and reactive dyes, the effects of the factors such as temperature, pH value, dyeing time and concentration on the dyeing uptake for cellulose acetate fiber were studyed, then the best dyeing conditions were determined. The results showed that:both the dye-uptake and fastness to washing of disperse dyes on cellulose acetate fiber were highest, especially for medium and low temperature types disperse dyes, and the best dyeing process is that:temperature 85℃, pH=5-6, dyeing time 80min; with the fastness to washing 4-5. For cationic dyes and reactive dyes, the dye-uptake were not high. The dyeing process of cationic dyes is similar to disperse dyes. For bi-functional reactive dyes, the best dyeing process is that:temperature 85℃, sodium sulphate 50g/L, dyeing time 80min.
Disperse Red FB was employed to research dyeing thermodynamic and kinetic of cellulose acetate fiber;furtherly it compared the thermodynamic parameters(affinity-Δμ0, dyeing enthalpyΔH0, dyeing entropyΔS0) and the kinetics parameters(diffusion coefficient D, half-dyeing time t1/2, dyeing rate constant K') of cellulose acetate fiber dyed with and without dispersing agent NNO. The results showed that it's dyeing adsorption mechanism belonged to Nernst distribution type. It found that when dyeing with dispersing agent NNO, both the affinity and the diffusion coefficient of Disperse Red FB in cellulose acetate fiber reduced, leading to a lower dye-uptake and longer half-dyeing time; and the reduced dyeing rate constant indicated that dispersing agent NNO would affect the dyeing rate to a certian extent.
引文
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[2]Final Draft International Standard.Textile--Man-Made Fiber—Generic Names[S].ISO/FDIS 2076:1999(E)
[3]侯庆华,戴玲.纺织用醋酯长丝的产品性能及应用[J].合成纤维,2006,(2)：1-5.
[4]梅洁,陈家楠,欧义芳.醋酸纤维素的现状与发展趋势[J].纤维素科学与技术,1999,7(4)：56-62.
[5]赵美玲.国外二醋酯及其纤维的生产与应用[J].合成纤维,1983(1)：21-24.
[6]金立国.醋酯纤维工业的现状和产品开发应用[J].针织工业,2002,(4)：42-43.
[7]江夏.醋酸纤维发展前景分析[J].人造纤维,1998,(6)：11-14.
[8]王石磊,张建波,张林.醋酸纤维在纺织中的应用[J].染整技术,2009,31(9)：7-10.
[9]南通醋酸纤维有限公司.竹浆粕合成的醋酸纤维素在制备纺织用醋酸纤维长丝中的应用[P].中国,CN101225557A.2008年7月.
[10]王玉仙,李德娴.醋酯丝绸的制造与染整[M].第1版.北京：中国纺织出版社,1988：3-22.
[11]http://www.celanese.com/process_diagram_tow_acetate.pdf.
[12]Atanu Biswas. Process for obtaining cellulose acetate from agricultural by-products [J] Carbohydrate Polymers,2006,(64):134-137.
[13]马孝田.醋酸纤维的制造[J].广东化纤,1994,(2)：27-34.
[14]李盛林,张晓莹,醋纤长丝性能、应用及开发对策[J].人造纤维,1998,(5)：30-34
[15]R.C.Law.Chemical Friber Interional.,2005,54(6):374-375
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