【作者】 余义开；

【导师】 张跃军；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2013， 博士

【摘要】 固色剂作为提高织物染料色牢度的化学助剂,其所起的作用取决于织物的种类、染料的种类及固色剂自身的特性等。本文基于已有的文献,介绍了从织物纤维,到棉织物染料,再到棉织物活性染料树脂型固色剂的发展历程和研究进展,指出了存在的若干问题,进而给出了本文研究工作的内容和意义。针对聚二甲基二烯丙基氯化铵(PDMDAAC)固色剂对棉纤维活性染料固色后摩擦牢度尤其是湿摩擦牢度较差的弱点,本文以设计改性单体为出发点,对其结构进行改性,同时通过控制制备工艺来调节改性聚合物相对分子质量大小及分布,开展了PDMDAAC改性固色剂的控制合成、性能改进及固色机理研究。具体的研究内容包括以下几个方面。第一PDMDAAC固色剂的相对分子质量控制、性能及固色机理为了获得提高PDMDAAC固色性能的新途径,依托本课题组的前期工作基础和聚合反应原理,设计通过调节合成工艺条件和加料方式来调控PDMDAAC相对分子质量大小及分布；对系列化相对分子质量PDMDAAC样品进行了结构表征和固色性能测定；对其色淀固色机理进行了验证。结果表明,采用一次性加入单体连续滴加引发剂的方式,通过调节初始单体质量分数及引发剂用量可以获得特征粘度为0.18-0.81dL/g、分散系数为1.22-1.92的PDMDAAC系列化固色剂；固色性能研究发现特征粘度值在1.00-2.00dL/g的样品性能优良且稳定,对两种代表性染料染色的棉织物其干摩、白布沾色及原样褪色等固色牢度为4级、4-5级,湿摩擦牢度为3-4级,优于国产市售的PDMDAAC固色剂0.5级,并接近于市售进口的阳离子型固色剂Fix。红外光谱证实,PDMDAAC与染料间季铵盐与染料中磺酸根的络合反应形成了沉淀物,而固色剂在棉织物的吸附则为分子间范德华作用力。由此可见,通过工艺控制使PDMDAAC在特定的相对分子质量大小范围是提高其固色性能的有效途径之一,但因色淀为离子键易水溶和与棉织物的作用为范氏分子间力的弱作用影响,PDMDAAC的湿摩擦牢度仍然有待提高。第二PDMDAAC共聚改性用阳离子单体的设计与合成为了PDMDAAC结构改进的需要,选择并设计合成了4种可用于对PDMDAAC进行共聚改性的功能性阳离子单体,交联性阳离子改性单体即三烯丙基甲基氯化铵(TAMAC)和3-氯-2-羟丙基三烯丙基氯化铵(CHTAAC),反应性阳离子改性单体N,N-二烯丙基-3-羟杂氮环丁烷氯化铵(DHAC)和3-氯-2-羟丙基甲基二烯丙基氯化铵(CHMDAAC);以红外分析及核磁共振分析等手段对其结构进行了表征,研究了其与基准单体二甲基二烯丙基氯化铵(DMDAAC)间的共聚反应活性等问题。结果表明,所得的各改性单体均具有预期结构,能与基准单体DMDAAC发生有效的共聚反应,由此为PDMDAAC固色剂进行共聚改性打下基础。第三微交联型PDMDAAC改性固色剂的控制合成、性能及固色机理为了提高PDMDAAC固色剂的固色性能,设计用交联性单体TAMAC和CHTAAC,分别与基准单体DMDAAC共聚,调节单体摩尔比例和聚合反应条件,以获得系列化微交联型PDMDAAC改性固色剂,对其结构进行表征并研究其固色性能和机理。结果表明,共聚改性获得了一系列结构及相对分子质量大小受控的TAMAC微交联改性PDMDAAC固色剂及CHTAAC微交联改性PDMDAAC固色剂,其固色性能研究表明,受控相对分子质量以特征粘度计为1.00-2.00dL/g左右的PDMDAAC引入摩尔含量为5%左右的交联性结构单元TAMAC时,改性固色剂的固色性能优良,尤其是湿摩擦牢度可进一步提高0.5级；优于市售国产的常用PDMDAAC固色剂1级及市售进口的常用同类阳离子型固色剂Fix0.5级,但优化性能的稳定范围较小。红外光谱(IR)及扫描电镜(SEM)等手段研究其固色机理的结果证实,所得微交联改性固色剂固色时其结构中的季铵盐阳离子结构均与阴离子染料间可形成难溶于水的色淀结构,提高了染料在棉织物上的色牢度,但其与棉织物间的整体作用依然较弱。由此说明,在相对分子质量得以受控的基础上,对PDMDAAC结构进行适当的微交联改性,其固色性能得以进一步提高。第四反应性PDMDAAC改性固色剂的控制合成、性能及固色机理为了提高PDMDAAC固色剂的固色性能,设计用反应性单体DHAC和CHMDAAC,分别与基准单体DMDAAC共聚,调节单体摩尔比例和聚合反应条件,以获得系列化反应性PDMDAAC改性固色剂,对其结构进行表征并研究其固色性能和机理。结果表明,共聚改性获得了一系列结构及相对分子质量大小受控的DHAC改性PDMDAAC固色剂及CHMDAAC改性PDMDAAC固色剂。其固色性能研究表明,受控相对分子质量以特征粘度计为1.00-2.00dL/g左右的PDMDAAC结构中分别进一步引入摩尔含量为1%左右的反应性结构单元DHAC及1%-5%左右的反应性结构单元CHMDAAC时,改性固色剂的固色性能尤其是湿摩擦牢度明显提高0.5级；优于市售国产的常用PDMDAAC固色剂1级及市售进口的常用同类阳离子型固色剂Fix0.5级。利用红外光谱(IR)及扫描电镜(SEM)等手段研究其固色机理的结果证实：不仅固色剂中的季铵盐阳离子结构与阴离子染料间可形成难溶于水的色淀结构,以此降低了染料的亲水性和增加染料在棉织物上的色牢度,而且,分子中的反应性DHAC或CHMDAAC结构单元在固色时经过180℃温度焙烘处理3min左右的条件,均可以与棉织物羟基形成有效的共价键合,来进一步提高固色剂固色性能。由此说明,在相对分子质量得以受控的基础上,在PDMDAAC基体结构中引入适量的反应性单元,其固色性能得以进一步提高。更多还原

【Abstract】 Dye-fixatives are usually used to improve the color fastness of anionic dyes on fabric, and their roles are determined by the species of fabrics and dyes, and the characteristics of dyes. The research progresses from fabric fibers, dyes for cotton fabric to resin dye-fixatives for anionic dyes on cotton fabric, were reviewed according to the literatures. The existing problems in the researches were pointed out. Based on these, the researches contents and their significations in this dissertation were illuminated. Considering the shortcomings of Poly (dimethyldiallylammonium chloride)(PDMDAAC) used as dye-fixatives for reactive dyes on cotton fabrics, the structural modifications of PDMDAAC with controlling the products’ molecular weights were done in this dissertation, and the studies on the controlled synthesis, properties, and dye-fixing mechanism of PDMDAAC-modified dye-fixatives were carried out, which were listed as follows.1. Molecular-weight-controlled synthesis, dye-fixing properties and dye-fixing mechanisms of PDMDAACIn order to to access one new way to improve dye-fixing properties, the molecular weights of PDMDAACs and their distrubtions were controlled by adjusting different synthesis conditions during polymerization, and meanwhile the structures, dye-fixing performances, and dye-fixing mechanisms of obtained PDMDAACs were also studied. The results showed, the molecular weight polydispersities and intrinsic viscosities of obtained PDMDAAC were1.22～1.92and0.18-0.81dL/g, respectively. Those PDMDAAC dye-fixatives with the controlled molecular weights represented with intrinsic viscosities of1.00-2.00dL/g and narrow molecular weight distributions could exhibit better dye-fixing properties:the dry rubbing fastness reached respectively4grades, the wet rubbing fastness reached respectively3-4grade, the color fastness to soaping and the white fabric staining both reached4-5grades, respectively. The dye-fixing fastnesses were better than those of commercial general PDMDAAC fixatives and near to that of commercial imported cationic Fixative FIX. In addition, the dye-fixing mechanisms of PDMDAAC dye-fixatives for reactive dyes on cotton fabrics showed, the molecular weights and their distributions of PDMDAAC would both play a important role in the development of the dye-fixing performances, and the basic cationic groups of PDMDAAC could form electrostatic forces with anionic dyes in the form of color lakes, but mainly form the weak Van der Waals forces with cotton fabric. Thus, it could be concluded that the dye-fixing properties of PDMDAAC dye-fixatives could be developed by controlled their molecular weights.2. Design and synthesis of cationic monomers for PDMDAAC modificationFor the further modifications of PDMDAAC, several groups of cationic functional monomers:triallylmethylammonium chloride (TAMAC),3-chloro-2-hydroxypropyltriallyl-ammonium chloride (CHTAAC), N-dially-3-hydroxy-azetidinium chloride (DHAC), and3-chloro-2-hydroxypropylmethyldiallylammonium chloride (CHMDAAC) were designed and synthesized. Their structures and copolymerization abilities with DMDAAC were also studied. The results showed, all the obtained monomers exhibited expected strucutues and could be well copolymerized with DMDAAC, which were suitable for application in PDMDAAC modifications.3. Controlled-synthesis, dye-fixing properties and dye-fixing mechanisms of slightly crosslinked PDMDAACIn order to improve the dye-fixing properties of PDMDAAC-based dye-fixatives, two series of slightly crosslinked PDMDAAC-modified dye-fixatives were synthesized by copolymerization of TAMAC or CHTAAC and dimethyldiallylammonium chloride (DMDAAC), respectively. The structures of obtained dye-fixatives could be controlled by varying molar ratios of TAMAC or CHTAAC to DMDAAC during polymerization, and their molecular weights were possibly controlled by adjusting different polymerization conditions (initial monomer concentrations and initiator amount). The results showed, the dye-fixing properties of PDMDAAC-modified dye-fixatives could be further developed by incorporation of1%molar contents of TAMAC units into the main chains of molecular-weight-controlled PDMDAAC dye-fixatives. The dye-fixing properties of obtained PDMDAAC-modified dye-fixatives were better than those of commercial general PDMDAAC fixatives and commercial imported cationic Fixative FIX. In addition, the dye-fixing mechanisms of slightly crosslinked PDMDAAC-modified dye-fixatives for reactive dyes on cotton fabrics showed that the basic cationic groups of dye-fixatives could form electrostatic forces with anionic dyes, but still mainly form the weak forces with cotton fabric. Thus, the dye-fixing properties could be usually further developed by incorporation of crosslinking units into the main chains of molecular-weight-controlled PDMDAAC dye-fixatives.4. Controlled-synthesis, dye-fixing properties and dye-fixing mechanisms of reactive PDMDAAC-modified dye-fixativesIn order to improve the dye-fixing properties of PDMDAAC-based dye-fixatives, two series of reactive PDMDAAC-modified dye-fixatives were synthesized by the copolymerization of DHAC or CHMDAAC and dimethyldiallylammonium chloride (DMDAAC), respectively. The structures of obtained dye-fixatives could be controlled by varying molar ratios of DHAC to DMDAAC during polymerization, and their molecular weights were possibly controlled by adjusting different polymerization conditions (initial monomer concentrations and initiator amount). The results showed, the dye-fixing properties of PDMDAAC-modified dye-fixatives could be further developed by incorporation of7%molar contents of DHAC units or1%-5%molar contents of CHMDAAC units into the main chains of molecular-weight-controlled PDMDAAC dye-fixatives. The dye-fixing properties of obtained PDMDAAC-modified dye-fixatives were better than those of commercial general PDMDAAC fixatives and commercial imported cationic Fixative FIX. In addition, the dye-fixing mechanisms of PDMDAAC-modified dye-fixatives for reactive dyes on cotton fabrics showed that the reactive units (DHAC and CHMDAAC) of the obtained PDMDAAC-modified dye-fixatives could bring about the expected linking reactions with the hydroxyl groups of cotton (cellulose) baked at180℃for3min, and that the basic cationic groups in the polymers could bring out the electrostatic forces with anionic dyes. Thus, the dye-fixing properties could be usually further developed by incorporation of recctive units into the main chains of molecular-weight-controlled PDMDAAC dye-fixatives.更多还原