本文關(guān)鍵詞： 阻燃硬質(zhì)聚氨酯泡沫 抑煙減毒 過渡金屬 羥基錫酸鹽 超支化磷氮阻燃劑　出處：《中國科學(xué)技術(shù)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：本論文專注于硬質(zhì)聚氨酯泡沫(RPUF)燃燒毒性的研究,以經(jīng)典的聚磷酸銨/二甲基膦酸二甲酯(APP/DMMP)為阻燃體系,配合實(shí)驗(yàn)室制備的一系列過渡金屬類助劑,成功制備了多個(gè)系列的復(fù)合RPUF材料,并采用多種技術(shù)手段對(duì)其燃燒毒性進(jìn)行了系統(tǒng)評(píng)估,初步揭示了各類助劑的抑煙減毒機(jī)理。為了改進(jìn)阻燃體系對(duì)RPUF的燃燒毒性的影響,在原有傳統(tǒng)阻燃體系的基礎(chǔ)上,設(shè)計(jì)合成了兩種超支化磷氮系阻燃劑,并將其引入到RPUF體系中。此外,為了探究兩種超支化阻燃劑應(yīng)用于其他基體的可能性,將其引入到聚苯二甲酸丁二醇酯(PBT)和聚丙烯(PP)中。本論文的研究工作共劃分為四個(gè)部分,現(xiàn)簡要分述如下:1)通過濕化學(xué)的方法,制備了具有規(guī)則八面體形貌的Cu_2O顆粒及其雜化物Cu_2O@CNT、Cu_2O@GO。將其引入到阻燃RPUF體系中得到復(fù)合RPUF材料。錐形量熱測(cè)試表明,Cu20及其系列雜化物均使得熱釋放速率(HRR)和產(chǎn)煙速率(SPR)明顯下降。煙密度箱測(cè)試表明,Cu_2O及其系列雜化物能夠有效抑制APP/DMMP帶來的增煙效應(yīng),而且使復(fù)合RPUF材料的產(chǎn)煙低于純樣品。在火災(zāi)毒性測(cè)試平臺(tái)(FTTP)的測(cè)試中,825℃比650℃更能使Cu_2O發(fā)揮抑煙減毒作用。熱重紅外分析表明,Cu20使材料的氣相逸出強(qiáng)度明顯減弱,而且使CO的逸出速率明顯降低。激光拉曼分析顯示,Cu_2O及其系列雜化物使材料殘?zhí)康氖潭忍岣?可知其改變了材料熱解、炭化的歷程,有利于煙氣的抑制。2)通過水熱的方法,制備了一系列炭包裹微球Fe_20_3@C、Cu@C和Cu20@Fe_2O_3@C。將其引入阻燃RPUF體系,制得了一系列復(fù)合RPUF材料。錐形量熱測(cè)試發(fā)現(xiàn),三種微球都使HRR和SPR顯著降低,其中Fe_20_3@C效果最佳。煙密度箱給出的結(jié)果表明,在產(chǎn)煙方面三種微球都在一定程度上抑制了 APP/DMMP的消極影響,但是均未能達(dá)到純RPUF的水平。FTTP的測(cè)試發(fā)現(xiàn),在650℃時(shí)無論通風(fēng)狀態(tài)如何,各微球都未能抑制RPUF的產(chǎn)煙;而通風(fēng)條件不好時(shí)使CO的產(chǎn)率降低。熱重紅外分析顯示,各微球都使材料的氣相逸出強(qiáng)度下降,其中尤以Cu@C的效果最佳。拉曼分析表明,各微球也都使得材料殘?zhí)康氖潭忍岣?其中尤以Fe_2O_3@C的表現(xiàn)最好,可見微球?qū)τ跓煔獾淖韪粢种瓢l(fā)揮了積極作用。3)采用溶液共沉淀的方法,制備了一系列形貌各異的羥基錫酸鹽:羥基錫酸鋅(ZHS)、羥基錫酸銅(CHS)和羥基錫酸鐵(IHS)。將其引入到阻燃RPUF體系中,制備了一系列復(fù)合RPUF材料。熱重分析發(fā)現(xiàn),各羥基錫酸鹽使RPUF的殘?zhí)棵黠@增加,使降解溫度區(qū)間變窄而初始降解提前。錐形量熱儀的測(cè)試結(jié)果顯示,ZHS、CHS以及IHS抑制HRR的效率都偏低,但都能夠顯著抑制SPR。在煙密度箱的測(cè)試中,三種羥基錫酸鹽也表現(xiàn)出了優(yōu)良的抑煙效率。FTTP的測(cè)試結(jié)果表明,在抑制產(chǎn)煙上三種鹽均不理想,但使CO產(chǎn)率有了明顯降低。熱重紅外分析表明,ZHS、CHS和IHS抑制氣相產(chǎn)物的效率依次升高,拉曼分析也發(fā)現(xiàn),IHS最能夠提高材料殘?zhí)康氖潭取?)為了避免傳統(tǒng)阻燃劑帶來的增煙效應(yīng),自主合成了超支化磷氮系阻燃劑CEPO和HBP。將其應(yīng)用到RPUF中并配合各類助劑,制得了一系列復(fù)合RPUF材料。錐形量熱的測(cè)試結(jié)果顯示,10份的HBP代替5份APP和5份HBP后,材料的HRR有了顯著下降,SPR更是降到了接近于零的水平。煙密度箱的測(cè)試結(jié)果顯示,RPUF/HBP的產(chǎn)煙量遠(yuǎn)低于RPUF/APP/HBP,加入Cu20、Fe_20_3@C或ZHS后,產(chǎn)煙又有了進(jìn)一步降低。在FTTP的測(cè)試中,RPUF/10HBP的產(chǎn)煙已經(jīng)接近純樣的水平,加入5份ZHS后光透過率已接近100%。5)為了初步探究CEPO和HBP在其他聚合物基體中的阻燃表現(xiàn),將APP/CEPO體系應(yīng)用于PBT中,將APP/HBP體系應(yīng)用于PP中,發(fā)現(xiàn)兩體系均具有非常高的阻燃效率,其中尤以比例為1:1時(shí)最好。熱重紅外分析、掃面電子顯微鏡(SEM)以及拉曼分析等證明了 APP/CEPO體系氣、固兩相的阻燃機(jī)理,而APP/HBP體系主要在凝聚相中發(fā)揮作用。
[Abstract]:This thesis focuses on the rigid polyurethane foam (RPUF) on combustion toxicity, using classical ammonium polyphosphate / two methyl phosphonic acid methyl ester (APP/DMMP) as the two flame retardant system, with a series of transition metal compounds prepared in the lab, the RPUF composite material of many series were successfully prepared, and its combustion toxicity evaluation system using a variety of techniques, revealing the attenuated mechanism of smoke suppression of various additives. In order to improve the combustion toxicity of flame retardant system of RPUF, based on the original traditional flame retardant system, two kinds of hyperbranched nitrogen phosphorus flame retardant was synthesized, which was introduced into the RPUF system. In addition, in order to explore the possibility of two kinds of hyperbranched flame retardants used in other matrix, it will be introduced to the two poly terephthalate (PBT) and polypropylene (PP). The research work of this thesis is divided into four parts, the paper points as follows : 1) by wet chemical method, with rule eight surface morphology of Cu_2O particles and Cu_2O@CNT hybrids were prepared, Cu_2O@GO. introduced to the flame retardant RPUF system to obtain RPUF composite material. The cone calorimeter test showed that Cu20 and its hybrid makes heat release rate (HRR) and smoke production rate (SPR) decreased significantly. The smoke density test showed that Cu_2O and its hybrids can effectively inhibit the growth of tobacco effect brought by APP/DMMP, and the RPUF composite material is lower than that of the pure smoke samples. The fire toxicity test platform (FTTP) test, 825 C can make Cu_2O play smoke attenuated effect more than 650 degrees Celsius. Thermal infrared analysis showed that the Cu20 material gas escaping strength decreased significantly, and the CO removal rate decreased significantly. Laser Raman analysis showed that Cu_2O and its hybrids to the degree of graphitization of carbon residue materials increased, the change Change of material pyrolysis, carbonization process, the inhibition of.2 for flue gas) through hydrothermal method, a series of carbon encapsulated Fe_20_3@C microspheres were prepared by Cu@C and Cu20@Fe_2O_3@C., the introduction of flame retardant RPUF system, prepared a series of RPUF composite. The cone calorimeter test found that three kinds of microspheres are HRR and SPR decreased significantly, and Fe_20_3@C has the best effect. The smoke density box are presented and the results show that in the tobacco producing three kinds of microspheres are to some extent inhibited the negative effects of APP/DMMP, but failed to reach the level of.FTTP pure RPUF test found at 650 DEG C regardless of ventilation state, each microsphere failed to inhibit RPUF smoke; ventilation condition is not good. The yield of CO decreased. The thermal infrared analysis showed that the microspheres are the material of gas phase evolution intensity decreased, especially in Cu@C is the best. The Raman analyses show that the microspheres are the material The graphitization degree of carbon material increased, especially Fe_2O_3@C was the best, the flue gas barrier suppression of visible microspheres has played a positive role in.3) by solution co precipitation, hydroxy stannate a series of different morphologies were prepared: zinc Hydroxystannate (ZHS), hydroxyl radical (acid copper tin CHS) and hydroxystannates iron (IHS). It will be introduced to the flame retardant RPUF system, a series of RPUF composite materials were prepared. The thermogravimetric analysis showed that the hydroxyl stannate makes the carbon residue of RPUF significantly increased, the degradation temperature intervals and the initial degradation in advance. The test results of cone calorimeter display, ZHS, CHS and IHS HRR inhibition efficiency is low, but it can significantly inhibit SPR. in smoke density test box, three hydroxy stannate also showed.FTTP inhibition efficiency of the smoke test results showed excellent, three kinds of smoke in the inhibition of salt are not ideal, but to make the CO the yield of Ming Dynasty Significantly reduced. Thermal infrared analysis showed that ZHS, CHS and IHS inhibition efficiency of the gas products increased and Raman analysis also found that IHS can improve the degree of graphitization of carbon materials.4) in order to avoid the increasing effect of traditional flame retardant smoke caused by self synthesized hyperbranched nitrogen phosphorus flame retardant and CEPO HBP. applied in RPUF and with various additives, prepared a series of RPUF composite. Test results of cone calorimeter showed 10 HBP instead of 5 APP and 5 HBP, material HRR had significantly decreased, SPR is reduced to a level close to zero. The test results the smoke density display box, smoke production of RPUF/HBP is much lower than that of RPUF/APP/HBP, joined the Cu20, Fe_20_3@C or ZHS after smoke have been further reduced. In FTTP test, RPUF/10HBP smoke is close to pure kind of level, adding 5 phr of ZHS light transmittance is close to 100%.5) for preliminary exploration The CEPO and HBP flame retardant in other polymer matrix in the performance of the APP/CEPO system can be used in PBT, the APP/HBP system can be used in PP, found that two system has a very high flame retardant efficiency, especially when the proportion is 1:1. The best thermal infrared analysis, scanning electron microscopy (SEM) and Raman analysis the proof system of APP/CEPO gas, flame retardant mechanism of solid phase, while the APP/HBP system mainly play a role in condensed phase.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ328.3

【參考文獻(xiàn)】

相關(guān)期刊論文 前7條

1 周順;寧敏;王孝峰;何慶;張亞平;徐迎波;佘世科;朱棟梁;陳剛;汪華;田振峰;;基于氧消耗原理和可控等值比法實(shí)時(shí)分析煙草燃燒熱釋放[J];中國煙草學(xué)報(bào);2015年03期

2 Shou-song Xiao;Ming-jun Chen;Liang-ping Dong;鄧聰;Li Chen;王玉忠;;Thermal Degradation, Flame Retardance and Mechanical Properties of Thermoplastic Polyurethane Composites Based on Aluminum Hypophosphite[J];Chinese Journal of Polymer Science;2014年01期

3 許冬梅;丁飛;郝建薇;杜建新;;改性可膨脹石墨的制備及在硬質(zhì)聚氨酯泡沫中的阻燃性能[J];高等學(xué)校化學(xué)學(xué)報(bào);2013年11期

4 周代營;劉建生;李偉善;譚春林;許夢(mèng)清;趙靈智;;Performance of electrolyte with dimethyl methyl phosphonate as flame-retardant additive[J];Transactions of Nonferrous Metals Society of China;2007年S1期

5 石秋杰;劉寧;梁義;;MgO負(fù)載Cu_2O催化劑的制備及其催化環(huán)己醇脫氫[J];催化學(xué)報(bào);2007年01期

6 劉華道,曹毅,朱建華,馬麗麗;Fe_2O_3改性NaY沸石上吡咯烷亞硝胺的降解[J];催化學(xué)報(bào);2003年07期

7 ;Comparative study of the effect of Cu_2O and MoO_3 on flame retardance and smoke emission of PVC by Cone and TGA[J];Chinese Science Bulletin;1998年13期

相關(guān)碩士學(xué)位論文 前2條

1 張強(qiáng)俊;火災(zāi)煙氣毒性分析測(cè)試平臺(tái)的組建及其用于聚丙烯復(fù)合材料燃燒煙氣的研究[D];中國科學(xué)技術(shù)大學(xué);2015年

2 汪正軍;錫酸鹽微/納米材料的結(jié)構(gòu)調(diào)控與氣敏性能研究[D];上海師范大學(xué);2011年

，

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