超支化聚合物的改性及其在纺织印染中的应用研究
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摘要
超支化聚合物是一类具有准球形结构的高度支化大分子,含有大量的端基官能团,分子内部存在空腔,表现出高溶解性、低粘度、高化学反应活性等特点。由于超支化聚合物独特的结构和性能特征,目前它已成为高分子领域研究的热点。经过二十多年的发展和探索,超支化聚合物的合成方法已经趋于全面和成熟。加强改性研究,实现超支化聚合物的功能多样化,成为研究的一个新方向。
超支化聚合物种类众多,其中超支化聚酯已实现商业化,是目前研究较为成熟的一类超支化聚合物,其分子末端为活性较强的羟基,容易进行功能化改性。季铵盐类表面活性剂在纺织印染中的优势明显,应用广泛。本论文旨在探索超支化聚酯的季铵化改性,研究季铵化改性产物的结构与性能,探讨超支化聚酯季铵盐在涤纶碱减量、印染废水处理及其固色方面的应用。具体研究内容和结果如下：
1.超支化聚酯季铵盐的合成、表征及其性能
以环氧丙基三烷基氯化铵为阳离子改性剂,对超支化聚酯Boltorn H20和H30进行改性,利用H20和H30端羟基的活性和环氧基反应得到H20和H30的季铵盐衍生物。
以环氧丙基三甲基氯化铵(GTA)和超支化聚酯H20的合成为例,研究了超支化聚酯与环氧丙基三烷基氯化铵的反应条件,探讨了溶剂、催化剂种类(NaOH、Ba(OH)2、三乙胺、吡啶等)、反应物摩尔比、温度、时间等因素对反应产率的影响,找到一种切实可行的反应条件。结果表明,当n(H20)/n(GTA)=1:16, n(NaOH)/n(H20-OH)=0.5,反应温度为50℃的条件下反应24h,反应产率最高为61.1%。采用FTIR、1HNMR、13CNMR、元素分析(EA)等手段对产物的结构与性能进行表征。研究发现,增加催化剂的用量,升高反应温度和延长反应时间,均可提高反应产率,但过量的催化剂,过高的温度和过长的反应时间却可能导致GTA水解或使副反应加剧,使得反应产率有所下降。
为了得到具有更广泛用途的季铵盐类表面活性剂,在上述研究的基础上,选用两步法合成了端基含不同长链烷基的超支化聚酯季铵盐QHPE (H20CxN和H30CxN。其中x=8,12,14,16和18,为季铵盐改性端基中除环氧丙基和二甲基后烷基链的长度)。首先以环氧氯丙烷和多种长链叔胺(C8,C12,C14,C16和C18)为原料,得到了一系列含不同长链烷基的缩水甘油三烷基氯化铵(EDAC);然后以DMF为溶剂,在NaOH催化条件下,将得到的EDAC作为阳离子醚化剂对超支化聚酯进行改性,调节反应物的投料比合成了一系列水溶性的端基含长链的QHPE。采用FTIR、1HNMR、13CNMR、EA、TG等手段对产物结构进行表征,并探讨了其溶解性、热性能及水溶液性能等。
研究发现,超支化聚酯季铵盐在极性溶剂(如H2O、甲醇、乙醇、DMF、DMSO等)中溶解性很好,但在一些非极性溶剂和弱极性溶剂(如丙酮、THF、乙醚等)中溶解性较差。相同改性程度下,随着碳链的增长,聚合物在多数溶剂(如丙酮、THF等)中的溶解度逐渐增加,但由于长烷基链本身的疏水性质,碳链长度超过16后,溶解性能下降。此外,改性程度的差异也会影响聚合物的溶解性,一般随着反应物摩尔比的增加,季铵含量增加,在极性溶剂中的溶解性能增强。
与原料超支化聚酯相比,改性后QHPE的热性能发生了很大的变化,由于季铵盐的引入,所有改性产物的热分解温度均有所下降,其中H30C1N和H30C12N的初始分解温度在230℃左右,H30C16N和H30C18N的初始分解温度在175℃左右,均能满足纺织加工的要求。
季铵盐端基含长烷基链的QHPE水溶液具有表面活性,随着改性端基烷基链的增长,临界胶束浓度(CMC)迅速下降,其变化规律与常规季铵盐类表面活性剂相同。
2.超支化聚酯季铵盐在涤纶碱减量中的应用
碱减量(或称“仿真丝”)处理是改善涤纶织物吸湿性、舒适性,获得柔软手感的重要方法。因此研究了四种自制的季铵盐端基含不同长度碳链的QHPE (H30C8N、H30C12N、H30C16N和H30C18N)对涤纶碱减量处理的促进作用,分析了超支化促进剂的结构对涤纶织物碱减量的影响,并对影响碱减量的各种因素进行了探讨。
研究表明,促进剂QHPE对碱减量处理的促进作用与其季铵盐端基的碳链长度有关,其中季铵盐端基含8个碳的QHPE的促进效果不明显,而碳链长度超过12以后,促进作用迅速增加。减量率随促进剂浓度的增加而增大,碱减量达到平衡时,三种促进剂的浓度顺序为H30C18N 比较了碳链长度相同的超支化聚酯季铵盐(H30C16N)与常规季铵盐表面活性剂(十六烷基三甲基溴化铵)对碱减量促进作用的差异。结果显示,在促进剂浓度相同时,H30C16N的减量率大于十六烷基三甲基溴化铵。这主要基于以下两个原因：一是促进剂H30C16N是聚阳离子化合物,含有多个季铵阳离子,相互间存在协同作用,对溶液中OH-的吸引力更大；二是H30C16N的季铵离子体积大,与所携带的OH-的结合力较弱,OH-更裸露,因而亲核性更强；两者均使OH-更容易进攻酯羰基使酯键水解。
此外,超支化聚酯季铵盐作为碱减量促进剂,对织物白度影响较小,强力损失率比常规季铵盐类阳离子表面活性剂略低,是一种新型高效的碱减量促进剂。
3.超支化聚酯季铵盐对染料的絮凝脱色作用研究
印染废水是目前我国主要有害、难处理的工业废水之一,其特点是排放量大、色度深、有机污染物含量高、水质变化频率大,其中尤以染料的污染最为严重。本文合成得到的QHPE是一种聚阳离子高分子,具有良好的稳定性,分子结构中含有多种官能团,预计在水溶液中有很好的絮凝和螯合等作用。因此,研究了4种不同结构的QHPE (H20C1N-8、H20C1N、H30C1N和H20C12N)对以酸性黑24和酸性蓝80为代表的阴离子染料和以分散红73和分散蓝60为代表的非离子染料的絮凝脱色,探讨了影响絮凝效果的主要因素,初步分析了絮凝脱色效果与染料结构的关系以及超支化絮凝剂的絮凝机理。并在此基础上,研究了超支化絮凝剂QHPE对二元混合染料的脱色作用。
研究了絮凝剂的结构与浓度浓度、pH值以及染料初始浓度对脱色率的影响。结果表明,这四种絮凝剂对阴离子染料和非离子染料都有一定的絮凝性能。脱色效果与絮凝剂的结构有关,相同核心的QHPE,季铵盐取代程度越高,絮凝效果越好,即H2OC1N-8 系统地研究了絮凝剂H20C1N和H20C12N对分散、酸性、直接和活性四类八种染料的絮凝脱色性能。结果表明：脱色效果与染料的分子结构密切相关,絮凝剂对分子结构较小且呈线性的染料有较好的絮凝效果。
通过研究絮凝剂浓度、染液pH值以及絮凝剂和染料的结构与脱色率的关系可知,超支化絮凝剂与染料之间的相互作用主要包括静电中和、氢键、架桥连接以及包覆作用。
在二元酸性(酸性黑24和酸性蓝80)和二元分散(分散红73和分散蓝60)混合染料的絮凝脱色体系中,通过测定混合体系各组分的脱色率,发现絮凝过程中存在协同效应,即二元混合染料的脱色率比单染料存在时更高。由于絮凝剂与染料之间的结合力不同,混合染料的脱色还存在不同步现象,酸性黑24优先于酸性蓝80絮凝,分散红73优先于分散蓝60絮凝。
4.超支化聚酯季铵盐对直接染料的固色性能研究
超支化聚酯季铵盐QHPE与阴离子染料之间存在较强烈的相互作用(如静电、包覆等),预计能与染料形成不溶性盐,降低染料的水溶性,从而提高染色织物的色牢度。本文初步探讨了超支化聚酯季铵盐(H30C1N和H30C16N)对直接染料的固色性能。结果表明,超支化固色剂对直接染料具有较好的固色效果,其中H30C16N的固色增深作用比H30C1N强,即改性端基的碳链越长,固色性能越好,这种差异主要表现在皂洗牢度上。两者均能使湿摩擦牢度提高1级,但H30C1N对染色织物的皂洗牢度影响不大,而H30C16N能使沾色和褪色牢度分别提高1级和0.5级。
总之,本研究对超支化聚酯进行季铵盐改性,改性产物结合了超支化聚合物和季铵盐类化合物的优点,在印染领域显示了巨大的应用前景,拓宽了超支化聚酯的应用领域,同时也为其他超支化聚合物的功能化改性和应用提供了一种新的研究思路。
Hyperbranched polymers are torispherical irregular macromolecules with highly branched architecture, a large number of terminal functional groups and inner cavities, showing low viscosity, high solubility and chemical reactivity. Due to their unique chemical and physical properties, interest in hyperbranched polymers is growing rapidly. A great progress has been made in the synthesis and characterization methods during the past two decades. Investigations on the modification of hyperbranched polymers to obtain various functional materials become a new research direction.
A number of hyperbranched polymers have been synthesized, among which hyperbranched polyester is commercially available. Hyperbranched polyester is one of the most widely used hyperbranched polymers because of the activity of the terminal hydroxyl groups. Quaternary ammonium surfactants are widely used in dyeing and finishing of textiles because of their excellent performance. In this dissertation, a series of quaternary ammonium functionalized hyperbranched polyesters (QHPEs) with different lengths of the alkyl chain were synthesized. In addition, the applications of QHPEs on the alkaline hydrolysis of polyethylene terephthalate (PET) fabrics, dye wastewater treatment and color fixing effectiveness on direct-dyed cotton fabrics were studied. The details and key conclusions are described as follows:
1. Synthesis, characterization and properties of QHPEs
A novel kind of macromolecule, QHPE was synthesized by the reaction of hyperbranched polyester (HPE) and 2,3-epoxypropyl alkyl dimethyl ammonium chloride. Aliphatic hyperbranched polyester Boltorn H20 or H30 was chosen in this study. After modification, the hydroxyl terminal group of hyperbranched polyester was converted into ammonium functional group.
The optimum reaction conditions of the synthesis of QHPE were determined by the reaction of H20 and (2,3-epoxypropyl)trimethyl ammonium chloride (GTA). The reaction conditions, such as the solvent, catalyst, the molar ratio of the reactants, and reaction time and temperature were investigated, and feasible conditions were indicated for the synthesis of QHPE. FTIR,1H NMR,13C NMR, and elemental analysis (EA) were used to characterize the products. The results showed that under the conditions of n(H20)/n(GTA)=1:16, n(NaOH)/n(H20-OH)=0.5, reaction temperature 50℃and reaction time 24 h, the product was obtained in yield of 61.11%.
In order to obtain a novel kind of quaternary ammonium surfactant, a series of amphiphilic QHPEs with different lengths of the alkyl chain was synthesized. The synthesis of QHPE was carried out in two steps. In the first step, long chain alkyl epoxypropyl dimethyl ammonium chloride (EDAC) was prepared by the reaction between epichlorohydrin and long-chain alkyl dimethyl tertiary amine (C8, C12, C14, C16 and C18). In the second step, HPE (H20 or H30) was modified by EDAC to transfer the hydroxyl terminals to the ammonium functional groups. A series of water-soluble QHPEs was obtained by adjusting the molar ratio of EDAC to HPE. QHPEs were written as H20CxN or H30CxN, where x= 8,12,14,16, and 18, is the lengths of the alkyl chain in the quaternary ammonium groups. All compounds were characterized and confirmed by FTIR,1H NMR,13C NMR, EA, and TG
The results showed that all of the QHPEs were soluble in common polar solvents like water with poor solubility in non-polar or weak polar solvents. With increasing length of the alkyl groups in the quaternary ammonium salt part, the solubility of the QHPEs increased at first, and then decreased because of the hydrophobicity of the long alkyl chain. In addition, with increasing molar ratio of EDAC to HPE, QHPEs showed better solubility in polar solvents.
The thermal degradation properties of QHPEs were changed after modification because of the introduction of the quaternary ammonium groups. We have noted indeed that all of the QHPEs began to degrade at 175-230℃, whereas the unmodified hyperbranched polyester had high degradation temperature.
The foaming properties of QHPE solutions indicated surface activity. The surface activity of QHPE was evaluated by critical micelle concentration (CMC). As expected, a decrease in the CMC values was observed with increasing length of the alkyl chain modified on HPE (H20 or H30).
2. Application of QHPEs on the alkaline hydrolysis of PET fabrics
Alkaline hydrolysis (or "silk-like") treatment is an important method for modifying chemical and physical properties of PET fabrics. It improves the handling, wettability, resistance to abrasion damage, and soil resistant properties of the fabrics. A series of QHPEs with different lengths of the alkyl chain (H30C8N, H30C12N, H30C16N and H30C18N) was used as the polycationic accelerator for the alkaline hydrolysis of PET fabrics to impart silk-like handling.
The effects of the structure and concentration of the accelerator QHPE, NaOH concentration, and hydrolysis time and temperature on the weight loss of PET fabrics were discussed. The results indicated that the length of the alkyl chain of the accelerators influenced their catalytic performance. Accelerators with longer lengths of the alkyl chain showed higher hydrolysis rates. With increasing length of the alkyl chain, the reduction of the surface tension became greater, the accelerators were more easily absorbed onto the fiber surface, and the hydrolysis reaction occurred more rapidly. The equilibrium concentration of the accelerator was on the order of H30C18N< H30C16N< H30C12N.
Satisfactory linear relationship was obtained between the weight loss and the hydrolysis time. The presence of the accelerators changes the activation energy (Ea). Ea= 52.98 kJ/mol for the system without accelerators. For the system containing 8 g/L NaOH and 0.16 g/L accelerators (H30C12N, H30C16N, and H30C18N), Ea was 84.43,58.78, and 69.96 kJ/mol, respectively. Moreover, SEM images indicated that the addition of accelerator did not change the basic mechanism of the hydrolysis reaction of PET fabrics in alkaline solution.
The catalytic ability of alkaline hydrolysis between hyperbranched polyester quaternary ammonium salt (H30C16N) and cetyltrimethylammonium bromide (HTAB) were compared. The results showed QHPE has greater effectiveness for alkaline hydrolysis of PET fabrics compared with conventional ammonium compound with the same alkyl chain length. There were two possible reasons. First, the synergistic effect of multiple quaternary ammonium groups in the polycationic compound H30C16N showed greater electrostatic attractions to OH-in solution than HTAB. Second, compared with HTAB, H30C16N had a stronger affinity with PET fabrics because of its high film-forming properties and weaker interaction with combined OH- on the surface of the fiber because of its bigger molecular volume.
As a result, QHPE was demonstrated as a kind of novel efficient accelerator for alkaline hydrolysis of PET fabric.
3. Study on the flocculability of the dye wastewater with QHPEs
Dye wastewater is one of the most difficult constituents in textile wastewater to treat. Large quantities of dye effluents are discharged from the dyeing process with strong high chroma value that is environmentally unfriendly. The application of QHPEs (H20C1N-8, H20C1N, H30C1N and H20C12N) as novel flocculants for single and binary system dye removal was investigated. Acid Black 24 and Acid Blue 80 were used as model acid dyes and Disperse Red 73 and Disperse Blue 60 were used as model disperse dyes.
The effects of the treatment conditions, such as QHPE concentration, pH value and initial dye concentration were discussed. The result showed that QHPEs are good flocculants to remove dyes in dye wastewater efficiently. The dye removal enhanced with increasing flocculant dosage in the case of flocculants with short carbon chain (H20C1N-8, H20C1N, and H30C1N). However, a restabilized phenomenon was observed in the case of flocculants with long carbon chain (H20C12N), that is, dye removal increased at first and then reduced, with increasing flocculant dosage. pH value of the dye solution had a major impact on the flocculation of dyes. The decolorization under the acidic or neutral conditions was better than the alkaline condition. With the increase of the initial dye concentration, the combining weight of flocculant and dye increased at first and then decreased.
The flocculability was also influenced by the structures of the flocculants and dyes. Dye removal of the four flocculants was in the order of H20C1N-8< H20C1N < H30C1N< H20C12N. The results indicated that the higher the modification substitution is, the better the flocculation ability is; dye removal of three-generation H30C1N is higher than that of two-generation H20C1N; moreover, dye removal increased with the increasing length of the alkyl chain of QHPE. In addition, the decolorization behavior of the four kinds of eight dyes, including disperse, acid, direct and reactive dyes was compared. The results showed that dye structure had a major impact on the flocculation and flocculant QHPE had a better effect on dyes with small size and linear molecular structure.
The results indicated that QHPEs had a good potential application for treating dye wastewater. The flocculation mechanism may be due to the theory of electrostatic neutralization, hydrogen bonding, trestle bridge, and encapsulation.
The flocculation behavior of binary mixtures of acid dyes (Acid Black 24 and Acid Blue 80) and disperse dyes (Disperse Red 73 and Disperse Blue 60) by flocculant H20C1N and H20C12N was investigated. A synergistic effect for decolorization in binary dyes was observed where the decolorization efficiencies of binary dyes were greater than those in single dye wastewater samples. Moreover, the flocculation curves were different for each other because of the difference in the interaction between dye and flocculant.
4. Color fixing properties of QHPEs on direct-dyed cotton facrics
QHPEs (H30C1N and H30C16N) were used as color fixatives to improve the wash and crock fastness of the direct-dyed cotton fabrics. Direct dyes, containing sulphonic groups, were electrostatically attracted by the ammonium groups of QHPEs, forming insoluble salts, reducing the solubility of the water-soluble dyes, therefore, improving the color fastness of the dyed fabrics. The results indicated that QHPE with longer carbon chain (H30C16N) had better fixing effectiveness, especially in improving wash fastness. The crock fastness was 1 class improved by both H30C1N and H30C16N. The best improvement in wash fastness was 1 class when fixing agent H30C16N was applied and little change occurred in the case of H30C1N.
As a whole, hyperbranched polyester with hydroxyl end groups is converted into ammonium functionalities, and the product shows a great potential application on dyeing and finishing of textiles. And these studies may widen the application fields of the hyperbranched polyester and provide a new idea for the functional modification of other hyperbranched polymers.
超支化聚合物种类众多,其中超支化聚酯已实现商业化,是目前研究较为成熟的一类超支化聚合物,其分子末端为活性较强的羟基,容易进行功能化改性。季铵盐类表面活性剂在纺织印染中的优势明显,应用广泛。本论文旨在探索超支化聚酯的季铵化改性,研究季铵化改性产物的结构与性能,探讨超支化聚酯季铵盐在涤纶碱减量、印染废水处理及其固色方面的应用。具体研究内容和结果如下：
1.超支化聚酯季铵盐的合成、表征及其性能
以环氧丙基三烷基氯化铵为阳离子改性剂,对超支化聚酯Boltorn H20和H30进行改性,利用H20和H30端羟基的活性和环氧基反应得到H20和H30的季铵盐衍生物。
以环氧丙基三甲基氯化铵(GTA)和超支化聚酯H20的合成为例,研究了超支化聚酯与环氧丙基三烷基氯化铵的反应条件,探讨了溶剂、催化剂种类(NaOH、Ba(OH)2、三乙胺、吡啶等)、反应物摩尔比、温度、时间等因素对反应产率的影响,找到一种切实可行的反应条件。结果表明,当n(H20)/n(GTA)=1:16, n(NaOH)/n(H20-OH)=0.5,反应温度为50℃的条件下反应24h,反应产率最高为61.1%。采用FTIR、1HNMR、13CNMR、元素分析(EA)等手段对产物的结构与性能进行表征。研究发现,增加催化剂的用量,升高反应温度和延长反应时间,均可提高反应产率,但过量的催化剂,过高的温度和过长的反应时间却可能导致GTA水解或使副反应加剧,使得反应产率有所下降。
为了得到具有更广泛用途的季铵盐类表面活性剂,在上述研究的基础上,选用两步法合成了端基含不同长链烷基的超支化聚酯季铵盐QHPE (H20CxN和H30CxN。其中x=8,12,14,16和18,为季铵盐改性端基中除环氧丙基和二甲基后烷基链的长度)。首先以环氧氯丙烷和多种长链叔胺(C8,C12,C14,C16和C18)为原料,得到了一系列含不同长链烷基的缩水甘油三烷基氯化铵(EDAC);然后以DMF为溶剂,在NaOH催化条件下,将得到的EDAC作为阳离子醚化剂对超支化聚酯进行改性,调节反应物的投料比合成了一系列水溶性的端基含长链的QHPE。采用FTIR、1HNMR、13CNMR、EA、TG等手段对产物结构进行表征,并探讨了其溶解性、热性能及水溶液性能等。
研究发现,超支化聚酯季铵盐在极性溶剂(如H2O、甲醇、乙醇、DMF、DMSO等)中溶解性很好,但在一些非极性溶剂和弱极性溶剂(如丙酮、THF、乙醚等)中溶解性较差。相同改性程度下,随着碳链的增长,聚合物在多数溶剂(如丙酮、THF等)中的溶解度逐渐增加,但由于长烷基链本身的疏水性质,碳链长度超过16后,溶解性能下降。此外,改性程度的差异也会影响聚合物的溶解性,一般随着反应物摩尔比的增加,季铵含量增加,在极性溶剂中的溶解性能增强。
与原料超支化聚酯相比,改性后QHPE的热性能发生了很大的变化,由于季铵盐的引入,所有改性产物的热分解温度均有所下降,其中H30C1N和H30C12N的初始分解温度在230℃左右,H30C16N和H30C18N的初始分解温度在175℃左右,均能满足纺织加工的要求。
季铵盐端基含长烷基链的QHPE水溶液具有表面活性,随着改性端基烷基链的增长,临界胶束浓度(CMC)迅速下降,其变化规律与常规季铵盐类表面活性剂相同。
2.超支化聚酯季铵盐在涤纶碱减量中的应用
碱减量(或称“仿真丝”)处理是改善涤纶织物吸湿性、舒适性,获得柔软手感的重要方法。因此研究了四种自制的季铵盐端基含不同长度碳链的QHPE (H30C8N、H30C12N、H30C16N和H30C18N)对涤纶碱减量处理的促进作用,分析了超支化促进剂的结构对涤纶织物碱减量的影响,并对影响碱减量的各种因素进行了探讨。
研究表明,促进剂QHPE对碱减量处理的促进作用与其季铵盐端基的碳链长度有关,其中季铵盐端基含8个碳的QHPE的促进效果不明显,而碳链长度超过12以后,促进作用迅速增加。减量率随促进剂浓度的增加而增大,碱减量达到平衡时,三种促进剂的浓度顺序为H30C18N
此外,超支化聚酯季铵盐作为碱减量促进剂,对织物白度影响较小,强力损失率比常规季铵盐类阳离子表面活性剂略低,是一种新型高效的碱减量促进剂。
3.超支化聚酯季铵盐对染料的絮凝脱色作用研究
印染废水是目前我国主要有害、难处理的工业废水之一,其特点是排放量大、色度深、有机污染物含量高、水质变化频率大,其中尤以染料的污染最为严重。本文合成得到的QHPE是一种聚阳离子高分子,具有良好的稳定性,分子结构中含有多种官能团,预计在水溶液中有很好的絮凝和螯合等作用。因此,研究了4种不同结构的QHPE (H20C1N-8、H20C1N、H30C1N和H20C12N)对以酸性黑24和酸性蓝80为代表的阴离子染料和以分散红73和分散蓝60为代表的非离子染料的絮凝脱色,探讨了影响絮凝效果的主要因素,初步分析了絮凝脱色效果与染料结构的关系以及超支化絮凝剂的絮凝机理。并在此基础上,研究了超支化絮凝剂QHPE对二元混合染料的脱色作用。
研究了絮凝剂的结构与浓度浓度、pH值以及染料初始浓度对脱色率的影响。结果表明,这四种絮凝剂对阴离子染料和非离子染料都有一定的絮凝性能。脱色效果与絮凝剂的结构有关,相同核心的QHPE,季铵盐取代程度越高,絮凝效果越好,即H2OC1N-8
通过研究絮凝剂浓度、染液pH值以及絮凝剂和染料的结构与脱色率的关系可知,超支化絮凝剂与染料之间的相互作用主要包括静电中和、氢键、架桥连接以及包覆作用。
在二元酸性(酸性黑24和酸性蓝80)和二元分散(分散红73和分散蓝60)混合染料的絮凝脱色体系中,通过测定混合体系各组分的脱色率,发现絮凝过程中存在协同效应,即二元混合染料的脱色率比单染料存在时更高。由于絮凝剂与染料之间的结合力不同,混合染料的脱色还存在不同步现象,酸性黑24优先于酸性蓝80絮凝,分散红73优先于分散蓝60絮凝。
4.超支化聚酯季铵盐对直接染料的固色性能研究
超支化聚酯季铵盐QHPE与阴离子染料之间存在较强烈的相互作用(如静电、包覆等),预计能与染料形成不溶性盐,降低染料的水溶性,从而提高染色织物的色牢度。本文初步探讨了超支化聚酯季铵盐(H30C1N和H30C16N)对直接染料的固色性能。结果表明,超支化固色剂对直接染料具有较好的固色效果,其中H30C16N的固色增深作用比H30C1N强,即改性端基的碳链越长,固色性能越好,这种差异主要表现在皂洗牢度上。两者均能使湿摩擦牢度提高1级,但H30C1N对染色织物的皂洗牢度影响不大,而H30C16N能使沾色和褪色牢度分别提高1级和0.5级。
总之,本研究对超支化聚酯进行季铵盐改性,改性产物结合了超支化聚合物和季铵盐类化合物的优点,在印染领域显示了巨大的应用前景,拓宽了超支化聚酯的应用领域,同时也为其他超支化聚合物的功能化改性和应用提供了一种新的研究思路。
Hyperbranched polymers are torispherical irregular macromolecules with highly branched architecture, a large number of terminal functional groups and inner cavities, showing low viscosity, high solubility and chemical reactivity. Due to their unique chemical and physical properties, interest in hyperbranched polymers is growing rapidly. A great progress has been made in the synthesis and characterization methods during the past two decades. Investigations on the modification of hyperbranched polymers to obtain various functional materials become a new research direction.
A number of hyperbranched polymers have been synthesized, among which hyperbranched polyester is commercially available. Hyperbranched polyester is one of the most widely used hyperbranched polymers because of the activity of the terminal hydroxyl groups. Quaternary ammonium surfactants are widely used in dyeing and finishing of textiles because of their excellent performance. In this dissertation, a series of quaternary ammonium functionalized hyperbranched polyesters (QHPEs) with different lengths of the alkyl chain were synthesized. In addition, the applications of QHPEs on the alkaline hydrolysis of polyethylene terephthalate (PET) fabrics, dye wastewater treatment and color fixing effectiveness on direct-dyed cotton fabrics were studied. The details and key conclusions are described as follows:
1. Synthesis, characterization and properties of QHPEs
A novel kind of macromolecule, QHPE was synthesized by the reaction of hyperbranched polyester (HPE) and 2,3-epoxypropyl alkyl dimethyl ammonium chloride. Aliphatic hyperbranched polyester Boltorn H20 or H30 was chosen in this study. After modification, the hydroxyl terminal group of hyperbranched polyester was converted into ammonium functional group.
The optimum reaction conditions of the synthesis of QHPE were determined by the reaction of H20 and (2,3-epoxypropyl)trimethyl ammonium chloride (GTA). The reaction conditions, such as the solvent, catalyst, the molar ratio of the reactants, and reaction time and temperature were investigated, and feasible conditions were indicated for the synthesis of QHPE. FTIR,1H NMR,13C NMR, and elemental analysis (EA) were used to characterize the products. The results showed that under the conditions of n(H20)/n(GTA)=1:16, n(NaOH)/n(H20-OH)=0.5, reaction temperature 50℃and reaction time 24 h, the product was obtained in yield of 61.11%.
In order to obtain a novel kind of quaternary ammonium surfactant, a series of amphiphilic QHPEs with different lengths of the alkyl chain was synthesized. The synthesis of QHPE was carried out in two steps. In the first step, long chain alkyl epoxypropyl dimethyl ammonium chloride (EDAC) was prepared by the reaction between epichlorohydrin and long-chain alkyl dimethyl tertiary amine (C8, C12, C14, C16 and C18). In the second step, HPE (H20 or H30) was modified by EDAC to transfer the hydroxyl terminals to the ammonium functional groups. A series of water-soluble QHPEs was obtained by adjusting the molar ratio of EDAC to HPE. QHPEs were written as H20CxN or H30CxN, where x= 8,12,14,16, and 18, is the lengths of the alkyl chain in the quaternary ammonium groups. All compounds were characterized and confirmed by FTIR,1H NMR,13C NMR, EA, and TG
The results showed that all of the QHPEs were soluble in common polar solvents like water with poor solubility in non-polar or weak polar solvents. With increasing length of the alkyl groups in the quaternary ammonium salt part, the solubility of the QHPEs increased at first, and then decreased because of the hydrophobicity of the long alkyl chain. In addition, with increasing molar ratio of EDAC to HPE, QHPEs showed better solubility in polar solvents.
The thermal degradation properties of QHPEs were changed after modification because of the introduction of the quaternary ammonium groups. We have noted indeed that all of the QHPEs began to degrade at 175-230℃, whereas the unmodified hyperbranched polyester had high degradation temperature.
The foaming properties of QHPE solutions indicated surface activity. The surface activity of QHPE was evaluated by critical micelle concentration (CMC). As expected, a decrease in the CMC values was observed with increasing length of the alkyl chain modified on HPE (H20 or H30).
2. Application of QHPEs on the alkaline hydrolysis of PET fabrics
Alkaline hydrolysis (or "silk-like") treatment is an important method for modifying chemical and physical properties of PET fabrics. It improves the handling, wettability, resistance to abrasion damage, and soil resistant properties of the fabrics. A series of QHPEs with different lengths of the alkyl chain (H30C8N, H30C12N, H30C16N and H30C18N) was used as the polycationic accelerator for the alkaline hydrolysis of PET fabrics to impart silk-like handling.
The effects of the structure and concentration of the accelerator QHPE, NaOH concentration, and hydrolysis time and temperature on the weight loss of PET fabrics were discussed. The results indicated that the length of the alkyl chain of the accelerators influenced their catalytic performance. Accelerators with longer lengths of the alkyl chain showed higher hydrolysis rates. With increasing length of the alkyl chain, the reduction of the surface tension became greater, the accelerators were more easily absorbed onto the fiber surface, and the hydrolysis reaction occurred more rapidly. The equilibrium concentration of the accelerator was on the order of H30C18N< H30C16N< H30C12N.
Satisfactory linear relationship was obtained between the weight loss and the hydrolysis time. The presence of the accelerators changes the activation energy (Ea). Ea= 52.98 kJ/mol for the system without accelerators. For the system containing 8 g/L NaOH and 0.16 g/L accelerators (H30C12N, H30C16N, and H30C18N), Ea was 84.43,58.78, and 69.96 kJ/mol, respectively. Moreover, SEM images indicated that the addition of accelerator did not change the basic mechanism of the hydrolysis reaction of PET fabrics in alkaline solution.
The catalytic ability of alkaline hydrolysis between hyperbranched polyester quaternary ammonium salt (H30C16N) and cetyltrimethylammonium bromide (HTAB) were compared. The results showed QHPE has greater effectiveness for alkaline hydrolysis of PET fabrics compared with conventional ammonium compound with the same alkyl chain length. There were two possible reasons. First, the synergistic effect of multiple quaternary ammonium groups in the polycationic compound H30C16N showed greater electrostatic attractions to OH-in solution than HTAB. Second, compared with HTAB, H30C16N had a stronger affinity with PET fabrics because of its high film-forming properties and weaker interaction with combined OH- on the surface of the fiber because of its bigger molecular volume.
As a result, QHPE was demonstrated as a kind of novel efficient accelerator for alkaline hydrolysis of PET fabric.
3. Study on the flocculability of the dye wastewater with QHPEs
Dye wastewater is one of the most difficult constituents in textile wastewater to treat. Large quantities of dye effluents are discharged from the dyeing process with strong high chroma value that is environmentally unfriendly. The application of QHPEs (H20C1N-8, H20C1N, H30C1N and H20C12N) as novel flocculants for single and binary system dye removal was investigated. Acid Black 24 and Acid Blue 80 were used as model acid dyes and Disperse Red 73 and Disperse Blue 60 were used as model disperse dyes.
The effects of the treatment conditions, such as QHPE concentration, pH value and initial dye concentration were discussed. The result showed that QHPEs are good flocculants to remove dyes in dye wastewater efficiently. The dye removal enhanced with increasing flocculant dosage in the case of flocculants with short carbon chain (H20C1N-8, H20C1N, and H30C1N). However, a restabilized phenomenon was observed in the case of flocculants with long carbon chain (H20C12N), that is, dye removal increased at first and then reduced, with increasing flocculant dosage. pH value of the dye solution had a major impact on the flocculation of dyes. The decolorization under the acidic or neutral conditions was better than the alkaline condition. With the increase of the initial dye concentration, the combining weight of flocculant and dye increased at first and then decreased.
The flocculability was also influenced by the structures of the flocculants and dyes. Dye removal of the four flocculants was in the order of H20C1N-8< H20C1N < H30C1N< H20C12N. The results indicated that the higher the modification substitution is, the better the flocculation ability is; dye removal of three-generation H30C1N is higher than that of two-generation H20C1N; moreover, dye removal increased with the increasing length of the alkyl chain of QHPE. In addition, the decolorization behavior of the four kinds of eight dyes, including disperse, acid, direct and reactive dyes was compared. The results showed that dye structure had a major impact on the flocculation and flocculant QHPE had a better effect on dyes with small size and linear molecular structure.
The results indicated that QHPEs had a good potential application for treating dye wastewater. The flocculation mechanism may be due to the theory of electrostatic neutralization, hydrogen bonding, trestle bridge, and encapsulation.
The flocculation behavior of binary mixtures of acid dyes (Acid Black 24 and Acid Blue 80) and disperse dyes (Disperse Red 73 and Disperse Blue 60) by flocculant H20C1N and H20C12N was investigated. A synergistic effect for decolorization in binary dyes was observed where the decolorization efficiencies of binary dyes were greater than those in single dye wastewater samples. Moreover, the flocculation curves were different for each other because of the difference in the interaction between dye and flocculant.
4. Color fixing properties of QHPEs on direct-dyed cotton facrics
QHPEs (H30C1N and H30C16N) were used as color fixatives to improve the wash and crock fastness of the direct-dyed cotton fabrics. Direct dyes, containing sulphonic groups, were electrostatically attracted by the ammonium groups of QHPEs, forming insoluble salts, reducing the solubility of the water-soluble dyes, therefore, improving the color fastness of the dyed fabrics. The results indicated that QHPE with longer carbon chain (H30C16N) had better fixing effectiveness, especially in improving wash fastness. The crock fastness was 1 class improved by both H30C1N and H30C16N. The best improvement in wash fastness was 1 class when fixing agent H30C16N was applied and little change occurred in the case of H30C1N.
As a whole, hyperbranched polyester with hydroxyl end groups is converted into ammonium functionalities, and the product shows a great potential application on dyeing and finishing of textiles. And these studies may widen the application fields of the hyperbranched polyester and provide a new idea for the functional modification of other hyperbranched polymers.
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