摘要
天然棉纤维,因具有手感柔软、可再生性、生物可降解性和吸湿性能优异等优点,被广泛应用于纺织领域,但在活性染料染色过程中,往往需要加入30～150g/l的无机盐来提高上染率和固色率,容易对环境造成污染;同时在服用过程中极易附着微生物,并为其繁殖和传播创造条件,从而造成纤维强力的损伤、产生污点和褪色、产生令人不愉快的气味,甚至造成疾病的传播,影响人体的健康。因此本文的研究目的就是制备一种水溶性超支化聚合物HBP-NH2及其季铵盐HBP-HTC,并将其应用于棉纤维的功能化改性,以提高棉纤维的染色性能和赋予其抗菌性能。
以丙烯酸甲酯和二亚乙基三胺为原料,通过缩聚反应制备了HBP-NH2;然后以2,3-环氧丙基三甲基氯化铵(GTMAC)为改性剂,继续与HBP-NH2反应,制备了HBP-HTC。分别采用FTIR、1HNMR和GPC对产物结构和分子量分布进行了分析,并讨论了HBP-NH2和HBP-HTC的溶解性能、紫外吸收性能及热性能等。
采用HBP-NH2水溶液直接改性棉织物以提高其染色性能,应用于部分活性染料的无盐染色,HBP-NH2直接法改性棉织物(HCF)取得了和未改性棉织物传统有盐染色相当的得色量、色牢度、匀染性能和透染性能。为了进一步提高棉织物的染色性能,先用NaIO4将棉织物轻微选择性氧化,然后与HBP-NH2反应,制得HBP-NH2接枝法改性棉织物(HGCF);FTIR分析表明,氧化棉纤维中的醛基和HBP-NH2发生了反应,并以共价键结合;在优选的工艺条件下,HCF和HGCF表面HBP-NH2的吸附量约为1.52 mg/g和3.68 mg/g;应用于活性染料无盐染色,HGCF的K/S值、耐摩擦色牢度、耐洗色牢度和匀染性能均令人满意。同时研究了水溶液中HCF和HGCF纤维表面的ζ电位、活性染料染色热力学、染色动力学以及HCF和HGCF染色色光的变化等。
以E. coli和S. aureus为例研究了HBP-HTC水溶液的抑菌性能,HBP-HTC的最小抑菌浓度约为20 ppm;采用HBP-HTC水溶液浸渍法处理棉织物以赋予其抗菌性能,测试结果表明,HBP-HTC整理棉织物对S. aureus和E. coli的抑菌率分别为99.92%和99.66%;洗涤20次后,仍保留99.00%的抑菌率,体现了一定的耐久性。
以HBP-NH2和AgNO3为原料一步法制备了纳米银胶体溶液;分别采用FTIR、DLS、TEM、UV-vis和XRD表征纳米银的形成;纳米银的平均粒径约为5～30 nm。以S. aureus和E. coli为例研究纳米银胶体溶液的抗菌性能,纳米银最小抑菌浓度为3μg/ml。采用20 mg/l纳米银胶体溶液对棉织物进行抗菌整理,抗菌棉织物对S. aureus和E. coli的抑菌率分别为99.01%和99.26%,洗涤20次后,仍保留98.77%的抑菌率,体现了优异的耐洗性能;同时采用SEM和XPS分析了纤维表面纳米银的形态和化学状态。
研究结果表明,超支化聚合物可应用于棉纤维的功能化改性,这不仅拓宽了超支化聚合物的应用领域,同时也为其它纺织纤维的功能化改性提供了一种新的思路。
Cotton, a most important natural textile, is widely used in clothing fields for its excellent properties such as regeneration, bio-degradation, softness, affinity to skin, and hygroscopic property. However, when dyeing cotton fabric with reactive dyes, large quantities of salt (30-150 g/l) are needed to overcome the static repulsion between cotton fibers and reactive dyes in order to promote dyeability and simultaneously result in heavy environmental pollution. In addition, cotton fabric is susceptible to micro-organisms, such as bacteria and fungi. When multiplying in cotton fabric, micro-organisms not only cause physicochemical degradation such as discoloration, mechanical strength loss, and foul odor generation, but also may adversely affect human health. The purpose of the present work is to synthesize a water-soluble amino-terminated hyperbranched polymer (HBP-NH2) and 2-Hydroxypropyltrimethylammonium chloride hyperbranched polymer (HBP-HTC). Then apply the HBP-NH2 and HBP-HTC to fuctional modification of cotton fabric to improve its dyeability and provide it with antimicrobial properties.
The HBP-NH2 was synthesized from methyl acrylate and diethylene triamine by polycondensation. Then the HBP-HTC was synthesized from HBP-NH2 and 2, 3-Epoxypropyltrimethylammonium chloride (GTMAC) as a grafting agent in aqueous solution. Their molecular weights and possible structure were characterized by Gel permeation chromatography (GPC), Fourier transform infrared spectrophotometry (FTIR) and Nuclear magnetic resonance spectroscopic (1H-NMR) respectively. Dissolution characteristic, thermal performance and UV absorbing capability of the HBP-NH2 and HBP-HTC were also studied for their application in textile fields.
In order to improve the dyeability of the cotton fabric with reactive dyes, the cotton fabric was pretreated with HBP-NH2 aqueous solution directly. The dyed HBP-NH2 pretreated cotton fabric (HCF) exhibited similar K/S value even in the absence of electrolyte when dyed with some reactive dyes. The washing fastness, rubbing fastness and levelling properties of the dyed HCF in salt-free dyeing were also good in comparison to the dyed CF in conventional dyeing. To further improve the dyeability of the cotton fabric and achieve salt-free dyeing with reactive dyes, the oxidized cotton farbics were obtained firstly by selective oxidation of cotton fabric with sodium periodate aqueous solution. Subsequently, the HBP-NH2 grafted oxidized cotton fabric (HGCF) was prepared by the reaction between the oxidized cotton fabric and the HBP-NH2 as a grafting agent in aqueous solution. Fourier transform infrared spectrophotometry (FTIR) indicated that all the aldehyde group of the oxidized cotton fibers have reacted with amino groups of HBP-NH2. Under the selected conditions, the amount of the HBP-NH2 adsorbed or grafted onto the HCF and HGCF is about 1.52 mg/g and 3.68 mg/g respectively.The dyed HGCFs with reactive dyes in salt-free dyeing displayed markedly enhanced colour strength, and the washing fastness, rubbing fastness and leveling properties were satisfactory. In order to reveal the mechanism of salt-free dyeing on HCF and HGCF with reactive dyes, theζ-potential of HCF and HGCF in the liquid phase, dyeing thermodynamics, dyeing dynamics and hue changes of HCF and HGCF dyed with reactive dyes were examined.
The antimicrobial activity the HBP-HTC aqueous solution was studied against Gram-negative bacteria E. coli and Gram-positive bacteria S. aureus. The minimum inhibitory concentration of the HBP-HTC aqueous solution is about 20 ppm. The cotton fabric was treated with HBP-HTC aqueous solution by the impregnation method to provide it with antimicrobial properties. The antimicrobial activities of the HBP-HTC treated cotton fabrics were evaluated quantitatively. The results indicated that the HBP-HTC treated cotton fabric showed 99.92% of bacterial reduction to S. aureus and 99.66% of bacterial reduction to E. coli, respectively. The antimicrobial activities of the HBP-HTC treated cotton fabrics were maintained at over 99.00% reduction level even after being exposed to 20 consecutive home laundering conditions.
Nano-silver colloidal solutions were prepared in one step by mixing AgNO3 aqueous solution and HBP-NH2 aqueous solution. The formation of silver colloid nanoparticles was characterized by Fourier Transform Infrared Spectrophotometry (FTIR), Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM), UV/Visible Absorption Spectrophotometry and X-ray Diffraction (XRD). The produced silver colloidal nanoparticles have average sizes ranged from 5 to 30 nm. The antimicrobial activity of the nano-silver colloidal solutions was evaluated quantitatively against E. coli and S. aureus. The minimum inhibitory concentration of the nano-silver colloidal solution is about 3μg/ml. To provide cotton fabrics with antibacterial properties, cotton fabric samples were treated with 20 mg/l nano-silver colloidal solution by the impregnation method. The silver-treated cotton fabrics showed excellent and durable antimicrobial effect against both S. aureus and E. coli. Still over 98.77 % of bacterial reduction was maintained even after exposure to 20 consecutive home laundering conditions. In addition, the Ag-clusters on the cotton fabrics were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS).
All these studies indicated that hyperbranched polymer can be applied to functional modification of cotton. And these studies may widen the application fields of the hyperbranched polymer and provide a new idea for functional modification of other fibres or fabrics.
引文
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