本文關(guān)鍵詞： 聚甲醛 包覆改性 聚磷酸銨 阻燃　出處：《安徽大學》2017年碩士論文　論文類型：學位論文

【摘要】：聚甲醛(POM,又名"奪鋼"、"賽鋼"),是五大工程塑料之一。因其高強度、高模量的性能特點,經(jīng)常被用來替代銅、鐵、鋁等金屬材料。此外聚甲醛還具有很好的耐疲勞性、自潤滑性和尺寸穩(wěn)定性,這使得聚甲醛被廣泛應用于工業(yè)機械、汽車、電子電氣、運動器械等行業(yè)。聚甲醛樹脂結(jié)晶度高,缺口極為敏感缺口沖擊強度低,且聚甲醛熱穩(wěn)定性差,極限氧指數(shù)僅為15%,易燃燒,燃燒釋放大量有毒甲醛氣體。因其以上兩個特點(脆性大和易燃燒)極大的限制了聚甲醛在生產(chǎn)中的發(fā)展,特別是近年來我們化工廠火災不斷,對阻燃性能的要求也是越來越高。迄今為止國內(nèi)外的研究工作者們從未停止對聚甲醛的阻燃的探索,但聚甲醛阻燃的問題卻一直未能得到很好的解決。本文主要研究聚磷酸銨阻燃的改性及其改性阻燃劑阻燃聚甲醛,研究APP粒子的包覆改性過程以及改性粒子的阻燃效果。本課題主要研究內(nèi)容包括以下幾個方面:首先,研究了阻燃劑聚磷酸銨(APP)包覆改性的合成過程,分別制備以熱塑性聚氨酯和熱固性聚氨酯為囊材的PUAPP粒子。對PUAPP粒子采用紅外吸收分析、透射電子顯微鏡電鏡(TEM)等表征方法研究其結(jié)構(gòu)特點,PUAPP的紅外吸收峰有明顯的羰基吸收峰,說明PUAPP中具有聚氨酯成分。此外通過透射電鏡觀察PUAPP粒子形貌,可以觀察到PUAPP粒子具有明顯的核殼結(jié)構(gòu)。研究了 PUAPP粒子的水溶性和疏水性,表明PUAPP粒子較APP粒子具有更低的水溶性和較強的疏水性。較強的疏水性表明PUAPP阻燃粒子與聚甲醛基體有更好的相容性。此外還對比了 PUAPP粒子的熱穩(wěn)定性能,通過熱穩(wěn)定分析,可知PUAPP的熱穩(wěn)定性更好。在兩種不同的聚氨酯包覆改性聚磷酸銨粒子有著不同的效果,其中以熱固性聚氨酯樹脂改性聚磷酸銨粒子具有更好的疏水性、熱穩(wěn)定性。APP粒子的表面改性使得APP粒子和聚合物之間有更好的相容性,使得APP阻燃粒子的應用范圍更加的廣泛,在這拓展APP阻燃劑應用方面具有一定的現(xiàn)實意義。其次,研究了不同改性聚磷酸銨粒子阻燃POM的阻燃效果。結(jié)果表明:包覆改性的聚磷酸銨粒子阻燃性能明顯優(yōu)于未改性聚磷酸銨粒子,在使用相同配比情況下,使用PUAPP粒子阻燃的POM復合材料的UL-94可以達到V-0級別(APP阻燃復合材料為V-1),極限氧指數(shù)(LOI)可達到66.5%。在相同阻燃劑比例的提前下,PUAPP粒子的阻燃效果明顯優(yōu)于APP的阻燃效果。PUAPP粒子表面的PU層可以充當成炭劑,增強復合材料的成炭能力。此外所形成炭層還可以有效隔離酸性物質(zhì)和聚甲醛基體的接觸,減緩酸性物質(zhì)對POM基體分解的催化作用;包覆改性聚磷酸銨粒子在阻燃POM復合材料的燃燒過程中具有更低熱釋放速率(HRR)、總熱釋放量(THR)以及更高的成炭率。兩種改性的PUAPP在阻燃方面均表現(xiàn)優(yōu)于APP;熱固型PUAPP在阻燃方面比熱塑性PUAPP表現(xiàn)更佳;對比未改性APP時,在使用包覆改性APP阻燃聚甲醛復合材料在力學性能方面表現(xiàn)更加的優(yōu)異。其中在拉伸強度方面表現(xiàn)突出,可以達到37.0 MPa,缺口沖擊強度為4.1 kJ/m2力學性能基本保留優(yōu)于未改性APP阻燃復合材料。PUAPP是以PU為囊材料的微膠囊粒子,其表面的PU與POM的結(jié)合力明顯優(yōu)于無機粒子和POM之間的結(jié)合力,而在宏觀表現(xiàn)出較好的物理力學性能。對比兩組不同囊材料的PUAPP在復合材料中的效果,以熱固性PUAPP表現(xiàn)更加突出。聚甲醛(P O M)因為其特點的結(jié)構(gòu)特點,使其成為為難阻燃的復合材料之一。研究阻燃聚甲醛復合材料時,在加工過程少量的酸、堿即會引發(fā)聚甲醛基體的大量分解,此外聚甲醛基體也對溫度非常敏感,加工溫度區(qū)間約20℃左右。聚磷酸雖然具有較好的阻燃效果,但聚磷酸銨在燃燒過程中分解產(chǎn)生出的酸性物質(zhì)會催化聚甲醛基體的分解,加速聚甲醛的燃燒。這就使得APP在阻燃POM時有兩方面表現(xiàn),一方面可以對POM進行脫水成炭,有效降低熱釋放速率提高阻燃性能;另一方面,在燃燒過程中APP粒子產(chǎn)生的酸性物質(zhì)加速POM分解,不利于阻燃性能的提高。
[Abstract]:Polyoxymethylene (POM, also known as "seize steel", "steel"), is one of the five major engineering plastics. Because of its high strength, high modulus characteristics, are often used to replace copper, iron, aluminum and other metal materials. In addition, POM has good fatigue resistance, self lubrication and size the stability, which makes the POM is widely used in industrial machinery, automobile, electronic and electrical, sports equipment and other industries. The poly formaldehyde resin with high crystallinity, the gap is extremely sensitive to the low impact strength, and thermal stability of polyoxymethylene, limit oxygen index is only 15%, easy combustion, combustion release toxic formaldehyde gas. Because of the above two characteristics (brittleness and easy combustion) greatly limits the development of POM in production, especially in recent years, our chemical plant fire, the flame retardancy of the requirements is also more and more high. So far the domestic and foreign research workers never stop to POM resistance Gas exploration, but the flame retardant polyoxymethylene problem has not been solved well. This paper mainly studies the polyphosphate flame modification and modification of flame retardant POM, APP particle coating process and flame retardant effect of modified particles. The main contents of this paper include the following: first of all, the flame retardant ammonium polyphosphate (APP) synthesis process modification, were prepared with thermoplastic polyurethane and thermosetting polyurethane as capsule material. PUAPP particles of PUAPP particles by infrared absorption analysis, transmission electron microscope electron microscope (TEM) to study the structural characteristics of the infrared characterization method, PUAPP the absorption peak has obvious carbonyl absorption peak, indicating the polyurethane components of PUAPP. In addition to observe PUAPP particle morphology can be observed by transmission electron microscope, PUAPP particle has obvious core-shell structure of PUAPP particles. The water solubility and hydrophobicity, showed that the PUAPP particles with APP particles with lower water solubility and strong hydrophobicity. Strong hydrophobic shows have better compatibility with the POM matrix PUAPP flame retardant particles. In addition, compared to the thermal stability of PUAPP particles, the thermal stability analysis, the better thermal stability PUAPP. In two different polyurethane coating modified ammonium polyphosphate particles have different effects, the modified hydrophobic poly ammonium phosphate particles has better thermosetting polyurethane resin, the thermal stability of.APP particle surface modification which have better compatibility between APP particle and polymer, making the application of flame retardant APP the particle becomes more widespread, has a certain practical significance in the development of APP flame retardant application. Secondly, study the different modified ammonium polyphosphate particles of flame retardant POM flame retardant effect. The results show that the coating The flame retardant ammonium polyphosphate particles has better performance than the unmodified poly ammonium phosphate particle, with the same proportion of cases, the use of PUAPP flame retardant POM composite particles of UL-94 can reach V-0 level (APP Flame Retardant Composites of V-1), the limiting oxygen index (LOI) can reach 66.5%. In the same proportion of flame retardant in advance under the PU layer of flame retardant effect of.PUAPP particle surface of PUAPP particles in flame retardant effect is obviously better than that of APP can act as a charring agent, reinforced carbon composites. In addition to the ability of the formation of carbon layer can effectively isolate the acidic substances and the POM matrix contact, slow acid catalytic effect on the decomposition of the POM matrix; coating modified poly ammonium phosphate particle in the combustion process of flame retardant POM composite has more low heat release rate (HRR), total heat release (THR) and char yield higher. Two kinds of modified PUAPP were excellent in flame retardant. APP; PUAPP in flame retardant thermosetting plastic PUAPP on heat performance better; compared with unmodified APP, the use of modified APP flame retardant POM composite performance in mechanics performance more excellent. The outstanding performance in terms of tensile strength, can reach 37 MPa, the notched impact strength is 4.1 kJ/m2 mechanical properties the basic reserve is better than that of the unmodified APP composite flame retardant.PUAPP is microencapsulation with PU as capsule material, combined with the surface of the PU and POM of the binding force between the force is obviously better than that of inorganic particles and POM, and better physical mechanical properties in macro performance. Compared the effects of the two groups of different materials in PUAPP capsule in the composite, thermosetting PUAPP performance more prominent. Polyoxymethylene (P O M) because of its structure characteristics, make it become one of difficult flame retardant composites. Study on flame retardant POM Composites, processed in A small amount of acid alkali process, which will lead to a large number of decomposition of the POM matrix, in addition the POM matrix is very sensitive to temperature, processing temperature of about 20 DEG C. Poly phosphoric acid has good flame retardant effect, but ammonium polyphosphate in the combustion process of acid decomposition will produce catalytic decomposition of POM matrix and accelerate POM combustion. This makes the APP has two aspects in flame retardant POM, on the one hand, POM can be dehydrated into carbon, reduce the heat release rate and improve the flame retardant performance; on the other hand, acidic substances of APP particles in the combustion process to accelerate the decomposition of POM, is not conducive to flame retardant performance.

【學位授予單位】：安徽大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ326.51;TB332

【參考文獻】

相關(guān)期刊論文 前10條

1 王文玲;;高分子材料的阻燃方法分析[J];工程技術(shù)研究;2016年06期

2 韓悅;李姣;劉娟;胡博淵;桑曉明;;微膠囊化聚磷酸銨的制備及其性能[J];工程塑料應用;2016年10期

3 王偉;錢立軍;陳雅君;;磷腈化合物阻燃高分子材料研究進展[J];中國科學:化學;2016年08期

4 石延超;王國建;;有機磷阻燃劑的合成及在阻燃高分子材料中的應用研究進展[J];高分子材料科學與工程;2016年05期

5 蔡欣;潘明珠;;原位聚合法制備聚磷酸銨微膠囊及其應用的研究進展[J];高分子通報;2016年01期

6 翟金國;許肖麗;尹亮;;硅烷微膠囊包覆聚磷酸銨的制備及其阻燃TPU的研究[J];聚氨酯工業(yè);2015年06期

7 王鑒;馮思喬;;包覆紅磷協(xié)效微膠囊聚磷酸銨對聚丙烯阻燃和力學性能的影響[J];塑料工業(yè);2015年06期

8 劉成娟;陳葵;紀利俊;朱家文;;環(huán)氧樹脂包覆聚磷酸銨微膠囊的制備及其對聚丙烯的阻燃效果[J];復合材料學報;2015年03期

9 李備戰(zhàn);;高分子材料的阻燃技術(shù)探析[J];化工管理;2014年23期

10 李清艷;王學良;雷明輝;;高分子材料PP和PET阻燃性能分析[J];輕工科技;2014年08期

相關(guān)會議論文 前3條

1 王琪;陳學;郭丹;白時兵;劉淵;李莉;;新型無鹵阻燃高分子泡沫材料的研究[A];2012年全國高分子材料科學與工程研討會學術(shù)論文集（上冊）[C];2012年

2 胡小平;趙國明;楊冰;王玉忠;;膨脹型阻燃聚乙烯/MWNT復合材料的阻燃性及燃燒性能研究[A];2005年全國阻燃學術(shù)年會論文集[C];2005年

3 王琪;陳英紅;劉淵;;反應性擠出加工制備無鹵阻燃高分子材料[A];中國化學會第28屆學術(shù)年會第7分會場摘要集[C];2012年

相關(guān)碩士學位論文 前4條

1 楊甜甜;碳納米管高分子阻燃材料的阻燃特性及機理研究[D];沈陽航空航天大學;2015年

2 解學霞;新型N-P協(xié)同阻燃高分子材料的合成與表征[D];山東農(nóng)業(yè)大學;2012年

3 趙魁敏;微膠囊化聚磷酸銨在聚氨酯彈性體中阻燃及協(xié)效性的研究[D];中國科學技術(shù)大學;2011年

4 胡志榮;無機阻燃劑超細硼酸鋅的制備研究[D];廣東工業(yè)大學;2003年

，

本文編號：1514921