层层自组装阻燃涂层的设计及其涤纶后整理的研究

发布时间：2018-01-12 00:12

本文关键词：层层自组装阻燃涂层的设计及其涤纶后整理的研究　出处：《中国科学技术大学》2017年博士论文　论文类型：学位论文

【摘要】：本文在综述了层层自组装技术的最新研究进展及涤纶织物阻燃现状的基础上,针对涤纶织物的传统后整理阻燃方法阻燃效率低、缺乏阻燃耐久性以及对织物的服用性能损害等缺点,开发了基于生物基原料和层层自组装技术的新型涤纶织物后整理生物基阻燃涂层技术。进一步结合纳米复合和催化成炭的原理,制备了一系列含无机纳米粒子、金属离子络合海藻酸、多聚磷酸/植酸以及次磷酸结构的生物基层层自组装涂层,研究了这些涂层对涤纶织物性能的影响,同时考察了这几种涂层修饰后的织物的阻燃耐水洗性。获得的具体研究结果如下:1.将四种不同的纳米金属氧化物(ZnO、TiO2、CeO2和NiO)和海藻酸钠混合后,与带正电的聚电解质聚乙烯亚胺通过层层自组装技术在涤纶P、涤棉A(90/10)和涤棉B(80/20)三种织物基体上制备涂层,四种由金属氧化物组成的涂层在不同基体上的涂层增重情况相似,不同的基体对于涂层的增重影响较小。研究四种由金属氧化物组成的涂层对涤纶P以及两种涤棉A和B的热分解过程的影响发现,对于涤纶纤维,这些金属氧化物组成的涂层在高温阶段有较为明显的降低其热失重速率的作用,含CeO2的涂层尤为明显。与修饰前的涤纶P相比,8 BL含CeO2的涂层修饰后的涤纶P-CeO2-8在700 ℃下的成炭量提高了 11.1 wt%。水平燃烧测试中,含ZnO和TiO2的涂层修饰后的B-ZnO-8和B-TiO2-8所剩炭渣的量明显多于修饰前涤棉B的炭渣量。在锥形量热仪测试中,4 BL含TiO2的涂层使涤棉B-TiO2-4的热释放速率峰值(PHRR)和总热释放(THR)与修饰前的涤棉B相比分别降低了 23%和30%。2.首先在三种织物基体——涤纶P、涤棉A(90/10)和涤棉B(80/20)上以海藻酸作为负聚电解质、聚乙烯亚胺为正聚电解质通过层层自组装技术制备涂层,然后将这种含海藻酸的涂层通过浸泡在四种不同的二价金属离子(Ca2+、Ba2+、Ni2+、Co2+)溶液中使其与海藻酸络合,形成含离子交联结构的涂层。在燃烧测试中,Ca2+和Ba2+交联涂层修饰的涤棉B-Ca与B-Ba可使涤棉B基体的燃烧时间分别延长了 13%和8%,且B-Ca与B-Ba在燃烧测试后的炭渣保留十分完整。同时,与修饰前涤棉B相比,B-Ba的PHRR与THR分别降低了 26%和36%。通过对炭渣的形貌以及拉曼光谱的分析发现钙离子与钡离子交联的涂层在燃烧过程中可以形成石墨化程度较高的炭层更好地保护了基体。此外,经过标准洗涤测试前后的B-Ca和B-Ba样品在水平燃烧测试中所获得的炭渣以及燃烧数据差别较小,说明离子交联的涂层表现出了良好的耐水洗性。3.采用两种不同结构的酸源——植酸与多聚磷酸作为负聚电解质,聚乙烯亚胺和三聚氰胺复配溶液作为正聚电解质,通过层层自组装技术,分别在三种织物基体——涤纶P、涤棉A(90/10)和涤棉B(80/20)上制备两种不同的膨胀型阻燃涂层。膨胀型阻燃涂层的组装可明显提高涤棉基体在高温下的成炭量,2 BL含植酸的涂层修饰后的涤棉B-PT-2在氮气条件下700 ℃的成炭量与修饰前相比提高了 6.2 wt%。水平燃烧测试中,两种涂层修饰后的涤纶以及涤棉织物均表现出优异的阻燃性能,涤棉在经过1BL-2BL组装层修饰后即可达到自熄。此外在锥形量热仪的测试中,与修饰前织物相比,2 BL含植酸的涂层修饰后的涤棉B-PP-2的PHRR和THR分别降低了 55%和46%,说明在燃烧过程中形成的膨胀型涂层可以有效的促进基体成炭。在耐水洗性测试中,洗涤之后的样品不能达到洗涤前样品自熄的效果,说明直接通过层层自组装制备的涂层耐水洗性较差。4.首先合成了氧化海藻酸钠(OSA),然后将OSA与聚乙烯亚胺(PEI)分别作为负聚电解质和正聚电解质通过层层自组装技术分别在三种织物基体——涤纶P、涤棉A(90/10)和涤棉B(80/20)上构建涂层;最后将OSA/PEI修饰后的织物在次磷酸的作用下使涂层交联,从而获得次磷酸交联的OSA/PEI修饰的涤纶织物。次磷酸交联的涂层均匀的覆盖在涤纶纤维和棉纤维表面,并且不影响织物中纤维本身的结构。在空气条件下涂层的存在可使基体在高温条件下的最大分解温度提高近80 ℃并提高了基体在高温下的残炭量。水平燃烧测试中,对于涤棉B来说,当涂层仅为5 BL时,织物在燃烧4s内便可达到自熄。此外锥形量热仪的结果中,与修饰前涤棉B相比,10 BL的次磷酸交联结构的涂层修饰的涤棉B-10的PHRR与THR分别降低了 77%和75%。研究结果表明,涂层的存在可以有效的促进基体成炭并减少可燃性气体的释放。最后,通过织物的耐水洗性研究发现,经过标准洗涤测试的B-10样品仍然可以使基体达到自熄的效果,且洗涤前后涂层的形貌差别较小,说明此涂层具有良好的耐水洗性能。5.针对涤纶织物在燃烧过程中的熔融滴落问题,首先将丙烯酰胺通过紫外光接枝的方法在涤纶表面进行修饰,再通过层层自组装的方法在接枝后的涤纶表面组装OSA/PEI的涂层,最后通过次磷酸交联,从而获得丙烯酰胺接枝与次磷酸交联自组装涂层的复合涂层修饰的涤纶织物。与修饰前涤纶相比,这种复合涂层使涤纶在空气中高温下的最大热分解温度提高了超过30 ℃,残炭量也有明显的提升。水平燃烧测试中,15 BL的次磷酸交联自组装涂层与丙烯酰胺的接枝相结合之后,P-UV-15可以在不滴落的情况下3s内发生自熄。与未经修饰的涤纶P相比,P-UV-15的PHRR与THR分别降低了 44%和29%,这种复合涂层在燃烧过程中可以形成石墨化程度较高的炭层从而更好地保护基体。此外,经过标准洗涤测试前后的P-UV-15样品在水平燃烧测试中的滴落及自熄情况差别较小,说明离子交联的涂层表现出了良好的耐水洗性。
[Abstract]:Based on present situation of flame retardant fabric and polyester in the latest research reviewed self-assembly techniques, for polyester fabric after finishing the traditional flame retardant methods of low efficiency, lack of durability and flame retardant performance of the fabric damage and other shortcomings, development of coating technology of bio based polyester raw material of flame retardant finishing model based on self assembled materials and technology layers of fabric. Based on further integration of nano composite and catalytic charring principle, preparation of a series of inorganic nanoparticles, metal ion complexation of alginate, poly phosphoric acid / phytic acid and biological base layer structure hypophosphite self-assembly coating, to study the effect of these coatings on polyester fabric the performance of the coating was also investigated, several modified flame retardant fabric washability. Specific results were as follows: 1. four kinds of nano metal oxides (ZnO, TiO2, CeO2 And mixed NiO) and sodium alginate, and the positively charged polyelectrolyte polyethylenimine by self-assembly technique in cotton polyester P, A (90/10) and B (80/20) three kinds of polyester cotton fabrics were prepared on the surface coating, coating four is composed of metal oxide coating on different substrates of similar weight gain for different substrate, coating weight gain has little effect. Found the effects of four is composed of metal oxide coating on decomposition process of polyester P and two kinds of polyester A and B heat, for polyester fiber, coating the metal oxide composition has obvious effect to reduce the thermal loss rate at high temperature stage CeO2, containing coating obviously. Compared with the unmodified polyester P coating containing CeO2 BL 8 after the polyester P-CeO2-8 at 700 DEG C carbonresidue increased 11.1 wt%. horizontal burning test, containing ZnO and TiO2 coating modified B-ZnO-8 and B-TiO2-8 char slag was significantly more than the amount of carbon residue modification before B of cotton. In the cone calorimeter test, coating 4 BL TiO2 containing the B-TiO2-4 of cotton peak heat release rate (PHRR) and total heat release (THR) compared with the unmodified B of cotton were decreased by 23% and in the first 30%.2. of three kinds of fabrics, polyester polyester matrix P, A (90/10) and B (80/20) on cotton alginate polyelectrolyte polyethylenimine as negative, positive polyelectrolyte by self-assembly technique. The coating was prepared, and then the coating containing alginate by soaking in two valence metal ions of four different the (Ca2+, Ba2+, Ni2+, Co2+) in the solution of the alginate complexation, forming a coating containing ionic crosslinking structure. In combustion test, B-Ba Ca2+ and Ba2+ B-Ca of cotton and crosslinked coatings modified by the combustion time of B of cotton base increased by 13% and 8%, and the B-Ca and B-Ba Carbon residue in the combustion test after the reservation is complete. At the same time, compared with unmodified cotton B, PHRR and THR B-Ba were decreased by 26% and 36%. by carbon residue morphology and Raman spectroscopy analysis found that coating calcium and barium ion crosslinking in the combustion process can form a high degree of graphitization of carbon layer to better protect the matrix. In addition, after standard washing test B-Ca and B-Ba samples in the horizontal burning carbon residue obtained in the test and combustion of small data difference, that ionic crosslinking coatings exhibit good water resistance of.3. using two different acid source structure, phytic acid and polyphosphoric acid as a negative just as the polyelectrolyte, polyelectrolyte polyethylenimine and melamine compound solution, by self-assembly technique, respectively in three kinds of fabrics, polyester matrix P, polyester cotton and polyester cotton A (90/10) B (80/20) on the preparation Intumescent flame retardant coatings. Two different kinds of assembled intumescent flame retardant coating can significantly improve the carbon content of polyester substrate under high temperature, coating containing 2 BL phytic acid after B-PT-2 of cotton in the nitrogen under the condition of 700 DEG C carbonresidue and modified before improvement compared to 6.2 wt%. horizontal burning test, two a coating of modified polyester and polyester cotton fabric showed excellent flame retardant performance, polyester can achieve self extinguishing after 1BL-2BL assembled layer modified. In addition in the cone calorimeter test, compared with unmodified fabrics, coated with phytic acid after 2 BL B-PP-2 and THR PHRR polyester cotton were decreased by 55% and 46%, that intumescent coatings formed during the combustion process can effectively promote the substrate carbon. In water resistance test, after washing the sample can not reach the effect of washing samples before self extinguishing, that directly through LBL group The preparation of the coating with poor washing.4. were first synthesized and oxidized sodium alginate (OSA), and then OSA and polyethylenimine (PEI) were used as positive and negative polyelectrolyte polyelectrolyte layer by layer self-assembly technique respectively in three kinds of fabrics, polyester matrix P, polyester cotton and polyester cotton A (90/10) B (80/20) on the construction of the OSA/PEI coating; modified fabric coating crosslinked in hypophosphite under the action of OSA/PEI modified to obtain hypophosphorous acid crosslinked polyester fabric. Coating phosphate crosslinked evenly cover on the surface of polyester fiber and cotton fiber, and does not affect the structure of fabric in the coating itself. In the presence of air can make the matrix maximum decomposition temperature under high temperature conditions increased by about 80 DEG C and increase the amount of residual carbon matrix at high temperature. The horizontal burning test, the B of cotton, when the coating is only 5 BL, the fabric in the combustion 4S Can be self extinguishing. In addition to the cone calorimeter test results, compared with unmodified cotton B, PHRR and THR 10 BL hypophosphite cross-linked structure coating modified polyester B-10 were reduced by 77% and the 75%. study showed that the presence of coating can effectively promote the substrate carbon and reduce flammability the release of gas. Finally, through the fabric washing after washing of the study found that standard test B-10 samples of the matrix can still achieve the effect of self extinguishing, and the morphology of small difference coating before and after washing, the coating has good washing performance of.5. polyester fabric for melting and dropping problems in the combustion process first of all, acrylamide modified on the surface of polyester by ultraviolet grafting method, coating and layer by layer self-assembly method on the surface of polyester graft after assembly of OSA/PEI, finally through hypophosphite crosslinking, from The obtained composite coating modified acrylamide graft and hypophosphorous acid crosslinking self-assembly coating of the polyester fabric. Compared with unmodified polyester, polyester composite coating the maximum heat in air at high temperature the decomposition temperature increased by more than 30 degrees, the amount of residual carbon has improved significantly. The level of combustion test, after grafting 15 BL hypophosphite crosslinking self-assembly coating and acrylamide combination, P-UV-15 can occur in the self extinguishing drip case 3S. With nonmodified polyester compared to P, PHRR and THR P-UV-15 were decreased by 44% and 29%, the carbon layer composite coating can be formed in the combustion process graphitization degree higher in order to better protect the substrate. In addition, after washing standard test P-UV-15 samples in the horizontal burning test in drip and self extinguishing difference is small, that ionic crosslinking coatings exhibit good Water washability.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TS195.592

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