摘要
目前市场上聚酯聚醚型亲水整理剂大多是以DMT,EG和PEG为原料缩聚而成,聚合物分子结构规整,结晶度高,导致其水溶性差,分散在水中易聚集,影响其使用及应用效果,并且不宜与染色同浴,难以满足印染行业节水、节能的要求。
为此,本课题采用DMT、EG和PEG为原料,以SIPM代替部分DMT,通过酯交换和缩聚反应两步法合成一种新型的聚酯聚醚共聚型亲水整理剂。通过SIPM的间位结构破坏共聚物分子结构的规整性,降低共聚物的结晶度,同时SIPM分子上磺酸钠基团的引入,进一步增加了聚酯聚醚共聚物的水溶性,使整理剂在不影响其亲水性和耐洗性的情况下,具有良好的水溶性,同时满足与分散染料同浴染色整理涤纶织物的要求。具体研究内容及其结果如下:
第一部分:以间苯二甲酸二甲酯-5-磺酸钠(SIPM)为改性单体,采用DMT、EG和PEG为原料,并以SIPM代替部分DMT,通过酯交换和缩聚反应两步法合成一种新型的聚酯聚醚共聚型亲水整理剂。研究了PEG的分子量、n(DMT)/n(PEG)和PEG加料次序、SIPM添加量、缩聚反应温度、时间、催化剂用量和反应体系真空度对整理剂水溶性和亲水性的影响,优化合成工艺条件;研究缩聚反应温度、时间和催化剂用量对整理剂酸值的影响,考察整理剂酸值与亲水性的相关性;用FTIR、热重分析仪和X-射线衍射仪对整理剂结构和性能进行分析研究;并将其与市场上常规聚酯聚醚型亲水整理剂进行性能比较。研究发现:当PEG在缩聚反应阶段加入,PEG分子量为1500且n(DMT)/n(PEG)为3:1时,SIPM摩尔用量为二元酯(DMT和SIPM的总量)的30%,缩聚反应温度260℃、时间45min,催化剂用量为二元酯质量的0.20%时,合成的新型亲水整理剂具有良好的水溶性和亲水性;酸值与整理剂的亲水性存在较好的相关性;红外分析表明整理剂具有酯醚结构;TG分析表明整理剂具有良好的热稳定性,满足涤纶织物热定型对整理剂热稳定性要求,XRD分析表明整理剂为非结晶化合物,整理剂具有良好的水溶性;整理剂的亲水性和耐洗性与常规聚酯聚醚型亲水整理剂相当,但其水溶性和浊点得到明显提高,理论上应适宜和分散染料同浴染色。
第二部分:采用浸渍法,用自制的新型聚酯聚醚共聚型亲水整理剂对涤纶织物进行亲水整理,研究整理剂用量、焙烘温度和焙烘时间对整理织物亲水性的影响,优化了整理工艺条件;测试了整理织物的亲水性、耐洗性、抗静电性和柔软性,并与国内同类产品进行应用性能比较,并考察了整理涤纶织物机械性能的变化。结果表明:整理剂浸渍整理优化工艺条件为:整理剂用量4%(owf),焙烘温度150℃,焙烘时间70s;整理涤纶织物的亲水性和抗静电性得到了极大的改善,且耐洗性佳,同时具有一定的柔软性能;在一定程度上,其应用性能优于国内同类产品,而且整理织物断裂强力还有所提高。
第三部分:为缩短染整工序,降低能耗,提高生产效率,染色的同时赋予涤纶织物一定的亲水性。本章采用高温高压和载体染色法,将自制新型聚酯聚醚共聚型亲水整理剂与分散染料同浴上染涤纶织物。研究不同整理剂用量对低温型、中温性和高温型分散染料上染涤纶织物的上染率、K/S值、染色色光、亲水性和色差的影响,优化整理剂用量;研究整理剂的加入对分散染料上染涤纶织物各项牢度的影响;研究高温高压染色法整理剂的加入对分散染料上染涤纶织物升温上染速率曲线和染料提升性的影响。研究结果表明:无论是采用高温高压染色法还是载体染色法,低温型分散染料上染涤纶织物的上染率和K/S值几乎不受整理剂添加的影响,而中温型和高温型分散染料上染涤纶织物的上染率和K/S值却随着整理剂用量的增加而呈现一定的下降趋势,且高温型分散染料的上染率和K/S值受亲水整理剂用量增加的影响较中温型分散染料大;分散染料上染涤纶织物染色色光和各项牢度不仅未受整理剂添加的影响,而且某些染料的染色牢度还会有一定程度的改善;对低温型和中温型分散染料而言,整理剂的用量为6%(owf),同浴染色织物亲水性好,耐洗性佳,且与未加整理剂的染色织物相比无明显色差;对于高温型染料来说,整理剂用量需控制在4%(owf),才能同时满足亲水性和不产生明显色差的要求;采用高温高压染色法,同浴染色上染速率递增缓慢,但染料提升性未受影响。
In present market, the polyester polyether hydrophilic finishing agent was synthesized with DMT、EG and PEG by polycondensation, it has regular structure, high crystallinity, and poor water solubility, and is easy to aggregate when being dispersed in water. The hydrophilic performance of the finishing agent was influenced by finishing agent’s poor water solubility, and the finishing agent is not suited for hydrophilic finishing of polyester fabric in dyeing bath with disperse dyes, and don’t meet the requirements of saving water and energy in dyeing industry. In view of this. A new type polyester polyether copolymer hydrophilic finishing agent was
synthesized with DMT, EG, SIPM(being used to replace section of DMT)and PEG as raw materials by means of two-step reaction including transesterification and polycondensation. The interoposition structure of SIPM could destroy the regularity of the copolymer’s structure and decrease the crystallinity of the copolymer; meanwhile, the introduction of soluble groups–SO3Na of SIPM could further improve the water solubility of the copolymer. the hydrophilic and washing durability of the new polyester polyether copolymer hydrophilic finishing agent are not effected, the water solubility of the finishing agent can be improved greatly, and this hydrophilic finishing agent can be suited for using with disperse dyes in one bath to polyester fabric. Specific research and results are as follows.
PartⅠ:A new type polyester polyether copolymer hydrophilic finishing agent was synthsized with Sodium-5-sulfoisophthalic acid dimethyl ester (SIPM) as modifying monomer, through two steps of ester change raction and polycondensation. The effect of PEG molecular、mol ratio of DMT and PEG and feeding order of PEG , dosage of SIPM, temperature and time of polycondensation, amount of catalyst and vacuum degree of condensation reaction on s hydrophilic properties and solubility in water of finishing agent were researched, the synthesis reaction conditions was optimized. The effect of temperature and time of polycondensation and amount of catalyst on acid value of the finishing agent were studied in order to investigate the relativity between acid value and hydrophilicity of finishing agent. The structure and properties of finishing agent was studied by FTIR, Thermal gravimetric analyzer and X-Ray diffraction. The application properties were compared with conventional polyester polyether hydrophilic finishing agent. The results indicate that when PEG molecular is 1500, mol ratio of DMT and PEG is 3:1, and PEG is added into reaction system in polycondensation stage, the molar ratio of SIPM to ester(total amount of SIPM and DMT) is 30%, polycondensation temperature is 260℃, polycondensation time is 45min and mass fraction of catalyst to ester is 0.20%, the water solubility, hydrophilicity and washing durability of finishing agent are good. Acid value of finishing agent is good relevant with the hydrophilicity. FTIR analysis indicates that finishing agent has polyester polyether structure; TG analysis indicates thermal stability of finishing agent is good; XRD analysis indicates that finishing agent is non crystal compound. the hydrophilicity and washing durability of finished fabric with the finishing agent are equivalent with conventional polyester polyether finishing agent, and the water solubility and cloud point of finishing agent is improved obviously, and in theory, it is suited for being used with disperse dyes in one bath to dye and finish polyester fabric.
PartⅡ:Self-made new type polyester polyether copolymer hydrophilic finishing agent was applied in hydrophilic finishing of PET fabric by dipping method. The effect of these factors such as dosage of finishing agent, baking temperature and time on hydrophilicity of finished fabric were studied, and the finishing process condition was optimized. The hydrophilicity, washing durability, antistatic and softness of finished PET fabric were measured, the application properties of the hydrophilic finishing agent were compared with similar products in market. The mechanical properties of finished fabric were investigated. The results indicate that optimum dipping finishing process conditions are as follows: dosage of finishing agent is 4%(owf), baking temperature is 150℃and baking time is 70s. Finished fabrics have good hydrophilicity, antistatic property and washing durability, meanwhile, the softness of finished fabric is improved too. To some extent, the application properties are better than similar hydrophilic finishing agent products in market, and breaking strength of finished fabric was increased.
PartⅢ:In order to shorten dyeing and finishing process, reduce energy consumption, increase production efficiency, and improve the hydrophilicity of PET fabric in dyeing, self-made new type polyester polyether copolymer hydrophilic finishing agent was used to hydrophilic finish polyester fabrics in dyeing bath with disperse dyes by high temperature pressure dyeing and low-temperature carrier dyeing method. The effect of different dosage of finishing agent on dyeing uptake, K/S value, color, hydrophilicity and chromatism of polyester dyed with disperse dyes were studied, the dosage of finishing agent was optimized. The effect of finishing agent on color fastness of polyester dyed with disperse dyes was investigated. The effect of finishing agent on dyeing rate curves and dye promotion of polyester fabric dyed with disperse dyes by high temperature pressure dyeing method were studied. The results show that dyeing uptake and K/S value of polyester fabric dyed with low-temperature type dyes were not affected by finishing agent, but to intermediate-temperature and high–temperature type disperse dyes, dyeing uptake and K/S value shows some decline with the increase of amount of finishing agent, and the dosages of finishing agent have bigger effects on high-temperature dyeing than intermediate-temperature dying. The chromatism and color fastness of polyester fabric with disperse dyes were not effected by finishing agent. To low-temperature and intermediate-temperature type dyes, when the dosages of finishing agent is 6% (owf), the hydrophilicity of polyester fabric dyed with hydrophilic finishing agent and disperse dyes in one bath is good, and compared with fabric dyed with only disperse dyes, the chromatism is small. But to high-temperature type dyes, when the dosages of finishing agent are 4% (owf), the hydrophilicity is good and chromatism is small. The dyeing rate of fabric dyed in one bath is slower than that of fabric dyed with disperse dyes, but dye promotion is not effected.
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