蚕丝蛋白涂复涤纶织物的研究
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摘要
本研究利用丝素、丝胶和壳聚糖等生物资源高分子溶液涂复涤纶织物，把涤纶织物的高强度、高弹性与蚕丝蛋白等天然高分子的人体亲和性、舒适性进行有机结合，通过涂复整合成蚕丝蛋白涂复涤纶织物的新功能面料，对合成纤维的天然化研究具有重要意义。
丝素蛋白的制备及丝素溶液特性的研究发现，中性盐制备的丝素分子量呈连续分布，不同方法制取的丝素蛋白分子量大小变化不大，大部分集中在20.1kD以上。不同条件下的H_2SO_4制备的丝素分子量为4kD的肽段最多。丝素溶液是不稳定的，在室温条件下存放时，容易降解为分子量更小的多肽或者氨基酸。
随着H_2SO_4浓度的升高，水解时间的延长及水解温度的提高，水解丝素的含氮量、粗蛋白含量、氨基态氮含量、水解度都随之升高。硫酸水解丝素过程中一些氨基酸被破坏，随着水解温度的升高，酪氨酸含量逐渐减少，甘氨酸含量少于丙氨酸。水解温度、硫酸浓度及水解时间对水解度、丝素粉的回收率和总氨基酸含量的影响极显著，对平均肽链长度影响不显著。水解温度和硫酸浓度在丝素的制备中是重要因素。
120℃高温条件下制备的丝胶溶液的分子量主要集中在97～40kD之间，100℃温度条件下制备的丝胶溶液的分子量主要集中在50kD以上。
化学刻蚀减量处理方法条件直接关系到涤纶织物的涂复整理效果。本研究中选择确定化学减量率为8％左右的处理条件。即NaOH、乙二胺浓度、1227的浓度分别为：0.8％(w／w)、20％(v／v)、0.4％(v／v)、70℃水浴、处理1h。通过化学刻蚀减量处理，在涤纶纤维上引入-NH_2、-COOH和-OH等活性基团，并在纤维表面形成裂缝和凹槽，使丝素等生物资源高分子与涤纶产生化学交联和物理吸附作用，为涤纶织物面料的涂复整理创造条件。
丝素、丝素／壳聚糖、丝胶、丝胶／丝素4种溶液涂复整理涤纶织物，并用EH(多胺多醇低分子缩合物)作为交联剂：(1)平均涂复增重率在8％以上。(2)用丝素、丝素／壳聚糖混合液涂复整理涤纶织物的热水溶失保持率达到80％以上；而丝胶涂复整理涤纶织物的热水保持率平均为70％左右；丝胶／丝素混合液涂复整理涤纶织物的热水溶失保持率在75％左右。(3)涂复整理涤纶织物的回潮率提高了2.2～3.8倍。(4)涂复整理涤纶织物的断裂强度和断裂伸长比化学刻蚀减量处理的涤纶织物有所提高，断裂强度与原织物(CK)相比有所降低，但相差不大。(5)织物的硬挺度有明显提高。(6)织物的厚度提高了5.88％～17.65％。(7)织物透气性都有不同程度的降低。(8)涤纶织物经过涂复液整理后，其静电压峰值和静电压衰减时间都得到了明显的改善。(9)根据扫描电镜观察，织物形态有显著差异。(10)涂复整理涤纶织物的红外光谱图中，非常明显的出现了涂复液的特征吸收光谱。
根据涂复整理涤纶织物的理化性能、形态特征和分子结构的变化，揭示了蚕丝蛋白涂复整理涤纶织物的机理：一是物理的机械吸附作用，使涂复液固定在涤纶织物上；二是涂复液与涤纶织物纤维之间存在较强的分子间作用力，蚕丝蛋白的结晶度高，分子结构由无定形向β-折叠结构转化。为进一步利用蚕丝蛋白等生物资源高分子涂复整理涤纶织物，研制新服用功能织物材料，提供了科学依据。
PET fabric was coated using bioresources macromolecule solution, silk fibroin, sericin and chitosan, and so forth in present study. Through coating moisture absorption, wearing property of PET fabric were improved. By combining merit of PET fabric and nature macromolecule, the newly prepared fabric have the characterization of nature and man-made fibers. This is very important significance to silk-like-finishing of man-made fiber.
The preparation of silk fibroin solution and its characteristic were studied in this paper, the result found SF could be dissolved in salt solution, its MW were detected by SDS-PAGE. The results revealed that MW of SF presented with continuous distributing, which concentrated above 20.1kD, no significant difference was found in different salt solutions. SF was also dissolved in H2SO4 solution in different conditions. The SF was separated on gel. The content of the polypeptides with 4.0kD MW were most by using SDS-PAGE. The SF solutions were instable and easily decomposed to low polypeptides and single amino acids.
With increase of sulfuric acid concentration, temperature or prolonging of hydrolysis time, total nitrogen, crude protein and amino nitrogen of samples all increased. Some amino acids, like Trp and Ser, were easily destroyed during the hydrolysis. Tyr content was gradually decreased with the increase of hydrolyzing temperature. Gly content was less than Ala during the hydrolysis.
The hydrolyzing temperature, sulfuric acid concentration and hydrolyzing time had significantly distinct effect on DH, silk fibroin powder recovery (%) and total amino acid content, however not significantly distinct effect on average polypeptide chain length by Variance analysis. Hydrolyzing temperature and sulfuric acid concentration were more importantly impact factors in the experiment.
Molecular weight of sericin prepared at high temperature (120℃) were presented with continuous distributing between 97-40kD, however the MW of sericin prepared at 100℃mostly concentrated above 50kD.
The chemical treatment of PET fabric play vital role in coating effect. In this study the chemical treatment with about 8% reduction rate was selected, the concrete condition are as follows: Concentration of sodium hydroxide (NaOH), ethylene diamine, catalyst 1227 were 0.8% (w/w) 20% (v/v), 0.4% (v/v) respectively, water bath at 70℃for one hour. Through chemical eroded reduction treatment of terylene, active groups, such as hydroxyl, amino groups, carboxyl were introduced and generate small cranny or groove on the PET fabric surface, which can make the silk fibroin fix on PET fiber.
In the study, PET fabric were coated with SF, SF/CS, sericin, sericin/SF, and using EH as cross-linking agent. The results were as follows, (1) average weight- increasing rate were all more than 8%. (2) Average the residual percentage after hot-water washing of silk fibroin, SF/CS, sericin /silk fibroin coating PET fabric were about 75%, the residual percentage after hot-water washing of sericin was about 70%. (3) Moisture regain of PET fabric coated with four kinds of solution is improved, which is 2.2-3.8 times of non-coated PET fabric. (4) After coating, breaking strength and breaking elongation of PET fabric were improved.(5) Stiffness of different treatment were improved obviously. (6) Thickness of different treatment PET fabric were increased, which was higher 8.82 %-14.71% than non-coated fabric.(7) Breathe freely of different treatment PET fabric had been reduced in different degree.(8) Anti-static properties of different treatment PET fabric were improved. (9) From scan electron microscopy (SEM) images of PET fabric, there were distinctly different of surface characteristic between before and after coated. (10) Characteristic spectrogram of the coating solution appeared in infra-red spectrogram of PET fabric coated.
According to the physical-chemical properties, morphological character and molecular structure transformation, the mechanism were analyzed. The physical sorption made the coating fix on fabric; on the other hand, intermolecular force exist between the coating solution and PET fabric, the force can increase the crystal degree of protein, which make the structure convert from amorphism conformation intoβ-sheet conformation . This provided the science foundation for developing new functional fabric by using bioresources macromolecule, such as silk proteins.
丝素蛋白的制备及丝素溶液特性的研究发现，中性盐制备的丝素分子量呈连续分布，不同方法制取的丝素蛋白分子量大小变化不大，大部分集中在20.1kD以上。不同条件下的H_2SO_4制备的丝素分子量为4kD的肽段最多。丝素溶液是不稳定的，在室温条件下存放时，容易降解为分子量更小的多肽或者氨基酸。
随着H_2SO_4浓度的升高，水解时间的延长及水解温度的提高，水解丝素的含氮量、粗蛋白含量、氨基态氮含量、水解度都随之升高。硫酸水解丝素过程中一些氨基酸被破坏，随着水解温度的升高，酪氨酸含量逐渐减少，甘氨酸含量少于丙氨酸。水解温度、硫酸浓度及水解时间对水解度、丝素粉的回收率和总氨基酸含量的影响极显著，对平均肽链长度影响不显著。水解温度和硫酸浓度在丝素的制备中是重要因素。
120℃高温条件下制备的丝胶溶液的分子量主要集中在97～40kD之间，100℃温度条件下制备的丝胶溶液的分子量主要集中在50kD以上。
化学刻蚀减量处理方法条件直接关系到涤纶织物的涂复整理效果。本研究中选择确定化学减量率为8％左右的处理条件。即NaOH、乙二胺浓度、1227的浓度分别为：0.8％(w／w)、20％(v／v)、0.4％(v／v)、70℃水浴、处理1h。通过化学刻蚀减量处理，在涤纶纤维上引入-NH_2、-COOH和-OH等活性基团，并在纤维表面形成裂缝和凹槽，使丝素等生物资源高分子与涤纶产生化学交联和物理吸附作用，为涤纶织物面料的涂复整理创造条件。
丝素、丝素／壳聚糖、丝胶、丝胶／丝素4种溶液涂复整理涤纶织物，并用EH(多胺多醇低分子缩合物)作为交联剂：(1)平均涂复增重率在8％以上。(2)用丝素、丝素／壳聚糖混合液涂复整理涤纶织物的热水溶失保持率达到80％以上；而丝胶涂复整理涤纶织物的热水保持率平均为70％左右；丝胶／丝素混合液涂复整理涤纶织物的热水溶失保持率在75％左右。(3)涂复整理涤纶织物的回潮率提高了2.2～3.8倍。(4)涂复整理涤纶织物的断裂强度和断裂伸长比化学刻蚀减量处理的涤纶织物有所提高，断裂强度与原织物(CK)相比有所降低，但相差不大。(5)织物的硬挺度有明显提高。(6)织物的厚度提高了5.88％～17.65％。(7)织物透气性都有不同程度的降低。(8)涤纶织物经过涂复液整理后，其静电压峰值和静电压衰减时间都得到了明显的改善。(9)根据扫描电镜观察，织物形态有显著差异。(10)涂复整理涤纶织物的红外光谱图中，非常明显的出现了涂复液的特征吸收光谱。
根据涂复整理涤纶织物的理化性能、形态特征和分子结构的变化，揭示了蚕丝蛋白涂复整理涤纶织物的机理：一是物理的机械吸附作用，使涂复液固定在涤纶织物上；二是涂复液与涤纶织物纤维之间存在较强的分子间作用力，蚕丝蛋白的结晶度高，分子结构由无定形向β-折叠结构转化。为进一步利用蚕丝蛋白等生物资源高分子涂复整理涤纶织物，研制新服用功能织物材料，提供了科学依据。
PET fabric was coated using bioresources macromolecule solution, silk fibroin, sericin and chitosan, and so forth in present study. Through coating moisture absorption, wearing property of PET fabric were improved. By combining merit of PET fabric and nature macromolecule, the newly prepared fabric have the characterization of nature and man-made fibers. This is very important significance to silk-like-finishing of man-made fiber.
The preparation of silk fibroin solution and its characteristic were studied in this paper, the result found SF could be dissolved in salt solution, its MW were detected by SDS-PAGE. The results revealed that MW of SF presented with continuous distributing, which concentrated above 20.1kD, no significant difference was found in different salt solutions. SF was also dissolved in H2SO4 solution in different conditions. The SF was separated on gel. The content of the polypeptides with 4.0kD MW were most by using SDS-PAGE. The SF solutions were instable and easily decomposed to low polypeptides and single amino acids.
With increase of sulfuric acid concentration, temperature or prolonging of hydrolysis time, total nitrogen, crude protein and amino nitrogen of samples all increased. Some amino acids, like Trp and Ser, were easily destroyed during the hydrolysis. Tyr content was gradually decreased with the increase of hydrolyzing temperature. Gly content was less than Ala during the hydrolysis.
The hydrolyzing temperature, sulfuric acid concentration and hydrolyzing time had significantly distinct effect on DH, silk fibroin powder recovery (%) and total amino acid content, however not significantly distinct effect on average polypeptide chain length by Variance analysis. Hydrolyzing temperature and sulfuric acid concentration were more importantly impact factors in the experiment.
Molecular weight of sericin prepared at high temperature (120℃) were presented with continuous distributing between 97-40kD, however the MW of sericin prepared at 100℃mostly concentrated above 50kD.
The chemical treatment of PET fabric play vital role in coating effect. In this study the chemical treatment with about 8% reduction rate was selected, the concrete condition are as follows: Concentration of sodium hydroxide (NaOH), ethylene diamine, catalyst 1227 were 0.8% (w/w) 20% (v/v), 0.4% (v/v) respectively, water bath at 70℃for one hour. Through chemical eroded reduction treatment of terylene, active groups, such as hydroxyl, amino groups, carboxyl were introduced and generate small cranny or groove on the PET fabric surface, which can make the silk fibroin fix on PET fiber.
In the study, PET fabric were coated with SF, SF/CS, sericin, sericin/SF, and using EH as cross-linking agent. The results were as follows, (1) average weight- increasing rate were all more than 8%. (2) Average the residual percentage after hot-water washing of silk fibroin, SF/CS, sericin /silk fibroin coating PET fabric were about 75%, the residual percentage after hot-water washing of sericin was about 70%. (3) Moisture regain of PET fabric coated with four kinds of solution is improved, which is 2.2-3.8 times of non-coated PET fabric. (4) After coating, breaking strength and breaking elongation of PET fabric were improved.(5) Stiffness of different treatment were improved obviously. (6) Thickness of different treatment PET fabric were increased, which was higher 8.82 %-14.71% than non-coated fabric.(7) Breathe freely of different treatment PET fabric had been reduced in different degree.(8) Anti-static properties of different treatment PET fabric were improved. (9) From scan electron microscopy (SEM) images of PET fabric, there were distinctly different of surface characteristic between before and after coated. (10) Characteristic spectrogram of the coating solution appeared in infra-red spectrogram of PET fabric coated.
According to the physical-chemical properties, morphological character and molecular structure transformation, the mechanism were analyzed. The physical sorption made the coating fix on fabric; on the other hand, intermolecular force exist between the coating solution and PET fabric, the force can increase the crystal degree of protein, which make the structure convert from amorphism conformation intoβ-sheet conformation . This provided the science foundation for developing new functional fabric by using bioresources macromolecule, such as silk proteins.
引文
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