【作者】 邢宏龙；

【导师】 陈水林；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2012， 博士

【摘要】 涂料印染因其工艺流程简单、低碳和环保等优点而得到了广泛的应用,但是涂料印染还存在着印染织物手感和摩擦牢度的矛盾。涂料印染黏合剂的性能是决定涂料印染质量的主要因素。互穿聚合物网络是由两种或两种以上的共混聚合物,分子链相互贯穿,并至少有一种聚合物分子链以化学键的方式交联而形成的网络结构。由于互穿聚合物网络形态结构的特点和两相之间贯穿,其力学性能也存在一些独特之处,利用互穿聚合物网络技术改善涂料印花黏合剂的性能也具有重要的意义。论文首先制备具有第一网络结构的聚丙烯酸酯乳液,该乳液能在低温固化成膜,应用于织物涂料印染,手感柔软；其次选择线性大分子聚乙烯醇(PVA)和交联单体乙二醛(Glyoxal)为形成第二网络的组分；最后把具有第一网络结构的聚丙烯酸酯乳液和PVA、乙二醛混合,在一定条件下PVA、乙二醛交联并与第一网络随机互穿,形成互穿网络聚合物膜。(1)以丙烯酸正丁酯(n-BA)、甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-AEH)、苯乙烯(St)为共聚单体,双官能团的单体为交联单体,十二烷基硫酸钠(SDS)、辛基酚聚氧乙烯醚(TX-30)为复合乳化剂,a-甲基丙烯酸(MAA)为助乳化剂,过硫酸铵(APS)为引发剂,微乳液聚合制备了具有第一网络结构的聚丙烯酸酯乳液。用表面张力仪和Zetasizer Nano粒度仪进行了表征,研究了复合乳化剂的量与质量比、助乳化剂的量和反应温度对微乳液粒径、Zeta电位、转化率和稳定性的影响。结果表明,SDS与TX-30复配质量比为1：2,且量为体系总质量的3.0-3.5wt%;MAA的用量为单体总质量的5wt%,反应温度为75-80℃,制得的微乳液单体转化率达96%,聚合物乳液较稳定。(2)制备具有第一网络结构的聚丙烯酸酯乳液,在基本配方中改变交联单体在共聚单体中的比例。研究了交联单体种类及交联单体在共聚单体中的含量对聚合物膜的外观、力学性能、Tg和表面形貌的影响。用强力仪、DSC和扫描探针显微镜进行了表征。研究结果表明：(a)不加交联单体和加入较多交联单体,乳液的成膜性能均不好,交联单体在共聚单体中质量比为2wt%左右时,成膜性能最好。(b)交联单体在共聚单体中含有相同比例时,选择分子链相对较长的交联单体A,在应力-应变曲线上,聚合物膜在应变250%之前,能保持较小的应力不变；而选择分子链相对较短的交联单体B,应力随应变一直在线性增加。根据实验设计要求,实验选择交联单体A。(c)共聚单体中加入交联单体A的比例在1-5wt%之间逐渐增加时,聚合物膜的Tg也升高。当共聚单体中A含量超过5wt%后,聚合物膜的Tg却几乎不变。(d)扫描分子探针对聚合物胶膜表面形貌及粗糙度的观测表明,交联单体在共聚单体中比例增加,其聚合物膜的表面粗糙度也增加。(3)以制备的具有第一网络结构的聚丙烯酸酯乳液为组分Ⅰ(AⅠ),聚乙烯醇-乙二醛体系为组分Ⅱ(AⅡ),制备互穿聚合物网络膜。研究了AⅠ中交联单体的比例、AⅠ和AⅡ的比例以及膜的焙烘温度等对互穿网络聚合物膜的力学性能、吸水率、溶失率和Tg的影响。用红外光谱仪、强力仪和DSC等进行了表征。研究结果表明：(a)在AⅠ中,加入适量交联单体,能使第一网络膜在应变250%之前,应力基本保持不变,应变250%之后,应力急剧上升。说明,第一网络膜柔软,但强度不够。形成的第一网络交联密度小,网格大,才能有利于第二网络互穿。(b)形成互穿聚合物网络膜后,在应变约250%之前,应力随应变基本保持不变,应变在250%之后,应力也快速升高,但比之第一网络膜应变250%后的应力变化要小。说明,互穿聚合物网络膜既保持了第一网络膜的柔软,同时也增加了膜的“韧性”。(c)形成互穿聚合物网络膜后,膜的吸水率、溶失率降低。(d)AⅠ中交联单体含量为2%,AⅡ组分中m(PVA):m(Glyoxal)为1：0.2-1：0.4,m (AⅡ)/m(AⅠ)为1-3wt%,互穿网络聚合物膜的综合性能最佳。(4)以AⅠ和AⅡ为涂料印染黏合剂,按照涂料印染配方制备印染涂料。研究了AⅠ组分中交联单体含量、AⅡ组分中PVA、乙二醛的质量比、AⅠ和AⅡ组分之间比例、焙烘温度等条件对织物印染性能的影响。研究结果表明：AⅠ组分中交联单体含量为2-3wt%,AⅡ组分中m(PVA):m(Glyoxal)为1：0.2,m (AⅡ)/m(A1)为2wt%,m(AⅠ+AⅡ)为印花色浆的15wt%,于120℃焙烘3min,织物涂料印染的综合性能最好。(5)以苯乙烯、丙烯酸正丁酯和a-甲基丙烯酸为单体,二乙烯基苯为交联单体,辛基酚聚氧乙烯醚(TX-30)和十二烷基磺酸钠为复合乳化剂,过硫酸铵(APS)为引发剂,通过乳液聚合制备了聚丙烯酸酯反应性微凝胶。把微凝胶加入到涂料印染黏合剂中,研究了微凝胶对黏合剂的流变性能、流平性、力学性能和涂料印染性能的影响。用红外光谱仪表征了微凝胶的结构,透射电镜表征了微凝胶的粒子形态,流变仪表征了涂料印染黏合剂的流变性,摩擦色牢度测试仪表征了涂料印花的色牢度,强力仪表征了黏合剂胶膜的力学性能。研究结果表明：微凝胶加入涂料印染黏合剂中能改善黏合剂的触变性、流平性和力学性能,提高涂料印染的质量。更多还原

【Abstract】 With its low-carbon, environmental-friendly and simple process, coating printing has been widely used in dyeing of cotton. However, rubbing fastness of dyeing fabric is dissatisfied, and the hand feeling of dyeing fabric is hard. The main factor which determines the coating quality is the performance of coating dyeing adhesive. Interpenetrating polymer network is composed of two or more kinds of polymer blends, the molecular chain interconnected, and at least one polymer chain formed cross-linked network structure with chemical bonds. Because of interpenetrating polymer network structure characteristics and interconnected phases, it also has some unique mechanical properties. Therefore, using interpenetrating polymer network technology has important significance to improve performance of adhesive.According to the requirements of the adhesive coating printing, polyacrylate microemulsion latex with the first network structure was first prepared. This emulsion can cure to film at low temperature, which can be applied to fabric printing and dyeing. As a result, the soft fabric was obtained. To solve the first network film’s problem of low friction fastness, adding linear macromolecules of PVA and glyoxal cross-linking monomer composition of the second component was designed. PVA and glyoxal cross-link between each other, and interpenetrate with the first network, therefore, interpenetrating polymer network membranes was formed.(1) Polyacrylate emulsion with first network structure was prepared by the way of micro-emulsion polymerization using n-butyl acrylatestyrene (n-BA), methyl methacrylate (MMA), iso-octyl acrylate (2-AEH), styrene (St) as comonomer, bifunctional monomer as crosslinking monomer. Sodium dodecyl sulfate (SDS), polyoxyethylene octylphenol ether (TX-30) as emulsifier, a-methacrylic acid (MAA) as the emulsifier and ammonium persulfate (APS) as initiator. The amount of emulsifier, the mass ratio of monomers, the amount of assistant emulsifier and reaction temperature impacted on the micro-emulsion particle size, Zeta potential, conversion rate and stability were studied by surface tension meter and Zetasizer Nano particle size analyzer. The results showed that when the mass ratio of SDS to TX-30was1:2(the amount was3.0-3.5wt%for the total latex system), the amount of MAA monomer was5wt%for the total monomer mass, the reaction temperature was75-80℃, the monomer conversion of microgel emulsion could reach96%, and the prepared polymer latex was stable.(2)Series of polyacrylate emulsion with the first network structure which changed proportion of cross-linking monomer in the comonomer were prepared. The effect of cross-linking monomer type and content in copolymer monomer on the appearance, mechanical properties, Tg and surface morphologies of the prepared polymer films were studied by using strength tester, DSC and scanning probe microscope. The results as below,(a) Adding more cross-linking monomer or nothing, the film-forming properties of the prepared films were poor. When the mass ratio of cross-linking monomer in the comonomer was about2wt%, the film-forming properties of the prepared films were the best.(b) When proportion of cross-linking monomer was the same in the comonomer, chosen cross-linking monomer A which has relatively long molecular chains. In the stress-strain curve, before strain reached250%, it could maintain the less stress and not changed. However, when chosen cross-linking monomer B with relatively short molecular chains. Stress raised in the uniform linear with strain. According to the experimental design, the cross-linking monomer A was chosen in the experiments(c) As the content of cross-linking monomer A increased form1to5wt%in the co-monomers, the Tg of the prepared polymer membrane was also increased, however, when the content of cross-linking monomer A was added above5wt%, the Tg of the polymer film was not increased.(d) The observation of the polymer film surface morphology and roughness with scanning molecules probe indicated that, as the content of cross-linking monomer in the comonomer increased, the roughness of the polymer membrane also increased.(3)The interpenetrating polymer network membranes were prepared by polyacrylate emulsion with the first network structure as component Ⅰ (AⅠ) and polyvinyl alcohol-glyoxal system as component Ⅱ (AⅡ). The effects of the content of cross-linking monomer in AⅠ, the ratio of AⅠ to AⅡ, curing temperature of membranes, etceteras on the mechanical properties, water absorption, dissolution-loss rate and Tg of the IPNs film were studied and characterized by infrared spectrometer, strength tester and DSC. The results showed that:(a) Adding appropriate cross-linking monomer into A I made the stress of the film remaining basically unchanged before strain250%and the stress increasing dramatically after250%, the results shows that the first network membrane was flexible, but strength was not enough. In addition, the small density and large grid of first network membrane could be conducive to the second network interpenetrating.(b) After interpenetrating polymer network membrane being formed, stress evenly increased with strain before the strain reached250%, the stress rapidly increased after strain reached250%, but was smaller than changes of the first network film after the strain250%, which showed that interpenetrating polymer network membranes maintained softness of the first network membrane, and also increased the "toughness" of the membrane.(c) After interpenetrating polymer network membrane being formed, the water absorption and dissolution-loss rate reduced, but Tg increased.(d) When the cross-linking monomer content was2%in AI, the ratio of m (PVA) and m (Glyoxal) was from1:0.2to1:0.4, the ratio of m (AⅡ) and m (AⅠ) was from1%to3%in A I, IPNs polymer film achieved the highest overall performance.(4)The paint dyeing coating was prepared according to coat-dyeing formulations with pigment printing binder AⅠand AⅡ. The effects of cross-linking monomer content in component AI, the mass ratio of polyvinyl alcohol and glyoxal in component AⅡ, the proportion of component AI and component AⅡ as well as the curing temperature on the dyeing properties of cotton fabrics were studied. The results show that:when the cross-linking monomer content in the component AI was2-3wt%, m(PVA)/m(Glyoxal) was1:0.2, m (AⅡ)/m(AⅠ)was2:100, the weight percent of total amount of component AⅠand AⅡ was15%for total amount of printing paste, as well as curing temperature and time was120℃and3min, The coating dyeing fabric could reach the optimum performance.(5) Polyacrylate reactive microgel was prepared by a emulsion polymerization method using styrene, a-n-butyl acrylate and methyl methacrylate as monomer, polyoxyethylene octylphenol ether (TX-30) and sodium dodecyl sulfate(SDS) as emulsifier, divinyl benzene and ammonium persulfate (APS) as cross-linking monomer and initiator, respectively. Microgels were put into coating dyeing adhesive. The effects of microgels on the rheological properties, leveling, mechanical properties and pigment printing performance of the prepared adhesives were studied. The microgel structure, particle morphology of microgel emusion and rheology of pigment printing binder were characterized respectively by infrared spectroscopy, TEM and rheometer. The color fastness of pigment printing and mechanical properties of adhesive film were characterized by friction color fastness test instruments and strength tester. The results showed that: the thixotropy, leveling and mechanical properties of adhesive printing binder as well as quality of pigment printing were improved when the microgel was added.更多还原