發(fā)布時間：2018-01-12 00:12

  本文關(guān)鍵詞：層層自組裝阻燃涂層的設(shè)計及其滌綸后整理的研究　出處：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 層層自組裝涂層 滌綸織物 阻燃性能 熱穩(wěn)定性 耐水洗性

【摘要】：本文在綜述了層層自組裝技術(shù)的最新研究進展及滌綸織物阻燃現(xiàn)狀的基礎(chǔ)上,針對滌綸織物的傳統(tǒng)后整理阻燃方法阻燃效率低、缺乏阻燃耐久性以及對織物的服用性能損害等缺點,開發(fā)了基于生物基原料和層層自組裝技術(shù)的新型滌綸織物后整理生物基阻燃涂層技術(shù)。進一步結(jié)合納米復(fù)合和催化成炭的原理,制備了一系列含無機納米粒子、金屬離子絡(luò)合海藻酸、多聚磷酸/植酸以及次磷酸結(jié)構(gòu)的生物基層層自組裝涂層,研究了這些涂層對滌綸織物性能的影響,同時考察了這幾種涂層修飾后的織物的阻燃耐水洗性。獲得的具體研究結(jié)果如下:1.將四種不同的納米金屬氧化物(ZnO、TiO2、CeO2和NiO)和海藻酸鈉混合后,與帶正電的聚電解質(zhì)聚乙烯亞胺通過層層自組裝技術(shù)在滌綸P、滌棉A(90/10)和滌棉B(80/20)三種織物基體上制備涂層,四種由金屬氧化物組成的涂層在不同基體上的涂層增重情況相似,不同的基體對于涂層的增重影響較小。研究四種由金屬氧化物組成的涂層對滌綸P以及兩種滌棉A和B的熱分解過程的影響發(fā)現(xiàn),對于滌綸纖維,這些金屬氧化物組成的涂層在高溫階段有較為明顯的降低其熱失重速率的作用,含CeO2的涂層尤為明顯。與修飾前的滌綸P相比,8 BL含CeO2的涂層修飾后的滌綸P-CeO2-8在700 ℃下的成炭量提高了 11.1 wt%。水平燃燒測試中,含ZnO和TiO2的涂層修飾后的B-ZnO-8和B-TiO2-8所剩炭渣的量明顯多于修飾前滌棉B的炭渣量。在錐形量熱儀測試中,4 BL含TiO2的涂層使滌棉B-TiO2-4的熱釋放速率峰值(PHRR)和總熱釋放(THR)與修飾前的滌棉B相比分別降低了 23%和30%。2.首先在三種織物基體——滌綸P、滌棉A(90/10)和滌棉B(80/20)上以海藻酸作為負聚電解質(zhì)、聚乙烯亞胺為正聚電解質(zhì)通過層層自組裝技術(shù)制備涂層,然后將這種含海藻酸的涂層通過浸泡在四種不同的二價金屬離子(Ca2+、Ba2+、Ni2+、Co2+)溶液中使其與海藻酸絡(luò)合,形成含離子交聯(lián)結(jié)構(gòu)的涂層。在燃燒測試中,Ca2+和Ba2+交聯(lián)涂層修飾的滌棉B-Ca與B-Ba可使滌棉B基體的燃燒時間分別延長了 13%和8%,且B-Ca與B-Ba在燃燒測試后的炭渣保留十分完整。同時,與修飾前滌棉B相比,B-Ba的PHRR與THR分別降低了 26%和36%。通過對炭渣的形貌以及拉曼光譜的分析發(fā)現(xiàn)鈣離子與鋇離子交聯(lián)的涂層在燃燒過程中可以形成石墨化程度較高的炭層更好地保護了基體。此外,經(jīng)過標準洗滌測試前后的B-Ca和B-Ba樣品在水平燃燒測試中所獲得的炭渣以及燃燒數(shù)據(jù)差別較小,說明離子交聯(lián)的涂層表現(xiàn)出了良好的耐水洗性。3.采用兩種不同結(jié)構(gòu)的酸源——植酸與多聚磷酸作為負聚電解質(zhì),聚乙烯亞胺和三聚氰胺復(fù)配溶液作為正聚電解質(zhì),通過層層自組裝技術(shù),分別在三種織物基體——滌綸P、滌棉A(90/10)和滌棉B(80/20)上制備兩種不同的膨脹型阻燃涂層。膨脹型阻燃涂層的組裝可明顯提高滌棉基體在高溫下的成炭量,2 BL含植酸的涂層修飾后的滌棉B-PT-2在氮氣條件下700 ℃的成炭量與修飾前相比提高了 6.2 wt%。水平燃燒測試中,兩種涂層修飾后的滌綸以及滌棉織物均表現(xiàn)出優(yōu)異的阻燃性能,滌棉在經(jīng)過1BL-2BL組裝層修飾后即可達到自熄。此外在錐形量熱儀的測試中,與修飾前織物相比,2 BL含植酸的涂層修飾后的滌棉B-PP-2的PHRR和THR分別降低了 55%和46%,說明在燃燒過程中形成的膨脹型涂層可以有效的促進基體成炭。在耐水洗性測試中,洗滌之后的樣品不能達到洗滌前樣品自熄的效果,說明直接通過層層自組裝制備的涂層耐水洗性較差。4.首先合成了氧化海藻酸鈉(OSA),然后將OSA與聚乙烯亞胺(PEI)分別作為負聚電解質(zhì)和正聚電解質(zhì)通過層層自組裝技術(shù)分別在三種織物基體——滌綸P、滌棉A(90/10)和滌棉B(80/20)上構(gòu)建涂層;最后將OSA/PEI修飾后的織物在次磷酸的作用下使涂層交聯(lián),從而獲得次磷酸交聯(lián)的OSA/PEI修飾的滌綸織物。次磷酸交聯(lián)的涂層均勻的覆蓋在滌綸纖維和棉纖維表面,并且不影響織物中纖維本身的結(jié)構(gòu)。在空氣條件下涂層的存在可使基體在高溫條件下的最大分解溫度提高近80 ℃并提高了基體在高溫下的殘?zhí)苛俊Ｋ饺紵郎y試中,對于滌棉B來說,當(dāng)涂層僅為5 BL時,織物在燃燒4s內(nèi)便可達到自熄。此外錐形量熱儀的結(jié)果中,與修飾前滌棉B相比,10 BL的次磷酸交聯(lián)結(jié)構(gòu)的涂層修飾的滌棉B-10的PHRR與THR分別降低了 77%和75%。研究結(jié)果表明,涂層的存在可以有效的促進基體成炭并減少可燃性氣體的釋放。最后,通過織物的耐水洗性研究發(fā)現(xiàn),經(jīng)過標準洗滌測試的B-10樣品仍然可以使基體達到自熄的效果,且洗滌前后涂層的形貌差別較小,說明此涂層具有良好的耐水洗性能。5.針對滌綸織物在燃燒過程中的熔融滴落問題,首先將丙烯酰胺通過紫外光接枝的方法在滌綸表面進行修飾,再通過層層自組裝的方法在接枝后的滌綸表面組裝OSA/PEI的涂層,最后通過次磷酸交聯(lián),從而獲得丙烯酰胺接枝與次磷酸交聯(lián)自組裝涂層的復(fù)合涂層修飾的滌綸織物。與修飾前滌綸相比,這種復(fù)合涂層使滌綸在空氣中高溫下的最大熱分解溫度提高了超過30 ℃,殘?zhí)苛恳灿忻黠@的提升。水平燃燒測試中,15 BL的次磷酸交聯(lián)自組裝涂層與丙烯酰胺的接枝相結(jié)合之后,P-UV-15可以在不滴落的情況下3s內(nèi)發(fā)生自熄。與未經(jīng)修飾的滌綸P相比,P-UV-15的PHRR與THR分別降低了 44%和29%,這種復(fù)合涂層在燃燒過程中可以形成石墨化程度較高的炭層從而更好地保護基體。此外,經(jīng)過標準洗滌測試前后的P-UV-15樣品在水平燃燒測試中的滴落及自熄情況差別較小,說明離子交聯(lián)的涂層表現(xiàn)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.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TS195.592

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