本文主要研究内容
作者袁尧（2019）在《反应型磷氮化合物及其阻燃硬质聚氨酯泡沫设计与抑烟减毒的研究》一文中研究指出：硬质聚氨酯泡沫(RPUF)是一种通过多元醇和异氰酸酯的聚加成反应生成的多功能化商业材料。RPUF由于自身具有显著的机械性能和独特的隔热等性能,广泛用于居家和建筑等行业,例如作为建筑隔热材料,以及家具的重要组成部分。然而,RPUF材料点火后,由于其特殊的多孔的结构和它易燃的组成部分,可在短时间内产生大量的热和有毒烟气,例如有害的烟颗粒及CO,NOx和HCN等毒性气体。这些有毒烟气会对人体造成的伤害,是绝大多数火灾伤亡的真凶,危害超过了其燃烧产生的热危害。近年来,不断增加的高层建筑火灾事件给人类造成了巨大的损失。因此,对RPUF保温材料的阻燃和有毒烟气的抑制工作是必不可少的,这对人类社会和环境的和谐健康发展至关重要。在本论文的研究中,试图利用分子设计手段解决硬质聚氨酯泡沫高火灾危险性等难题,从以下几个方面着手:首先在聚氨酯分子结构中引入含磷、氮等阻燃元素的阻燃单元,并改变聚氨酯的热解机制,从而加快炭化速度,提高成炭量,制备出具有优异综合性能的本征型阻燃硬质聚氨酯泡沫材料,这样可以有效减少聚合物燃烧热的释放,使之具有良好的阻燃效果和耐热性;其次,为了降低RPUF材料在燃烧过程中释放的有毒烟气,成功合成了几种含过渡金属元素的纳米氧化物颗粒,它们不仅具有物理阻隔效应,而且可以催化聚氨酯的热解产物从而形成稳定的多孔炭质层;与此同时,具有二维形貌、比表面积大和优异物理性能的层状化合物也可以作为一种新型载体,提高催化剂的催化效率,将片层阻隔作用与过渡金属化合物的催化成炭与催化减毒作用结合起来,不仅如此,负载在层状化合物片层上的无机纳米粒子可以有效限制片层结构的叠聚效应。基于以上研究,本文拟将分子设计、纳米复合、协效阻燃、催化成炭及催化减毒相结合,将有望制备出性能优异的阻燃硬质聚氨酯泡沫材料。详细研究工作如下:1.首先系统研究了含磷多元醇(BHPP)和含氮多元醇(MADP)在提高EG/RPUF复合材料的阻燃性方面的协同作用。阻燃多元醇BHPP和MADP分别是通过脱氯化氢和曼尼希反应合成的。通过热重分析(TGA)和极限氧指数(LOI)等测试研究了BHPP和MADP的重量比对性能的影响。结果表明,BHPP和MADP在阻燃EG/RPUF体系中的最佳质量比为1:1。此外,可膨胀石墨(EG)与BHPP和MADP复配使用可以大大提高RPUF复合材料的阻燃性能。当EG含量为15wt%时,RPUF复合材料的LOI值可达到33.5%。此外,与纯RPUF相比,热释放峰值(PHRR)降低了52.4%。在实验和分析的基础上,提出了一种凝聚相阻燃机理。2.通过自由发泡技术制备出含有含氮阻燃多元醇(MADP)和含磷阻燃剂DOPO的阻燃硬质聚氨酯泡沫。并通过热重分析(TGA),极限氧指数(LOI)和锥形量热仪(CONE)研究RPUF的热稳定性和燃烧行为。与单独添加阻燃成分(MADP或DOPO)的结果相比,RPUF/MADP-DOPO阻燃体系显示出更高的压缩强度,这是由于异氰酸酯(-NCO)与DOPO的P-H之间的反应赋予了界面粘合从而达到增强效果。此外,RPUF/MADP-DOPO体系赋予RPUF更稳定的结构,并增加了LOI数值和减少了热释放量。通过扫描电子显微镜(SEM),X射线光电子能谱分析(XPS)和炭残留物的拉曼光谱(Raman)表明了RPUF复合材料燃烧后形成了致密而连续的炭层。通过实验和分析,提出了可能的阻燃机理,RPUF/MADP-DOPO体系促进了凝聚相中富含磷的残余物的生成,从而形成保护性炭层,并在气相中稀释可燃性气体。在分析和讨论的基础上,可以根据两相阻燃机理,MADP/DOPO的引入赋予RPUF优异的阻燃性能。然而,改性RPUF材料燃烧释放的有毒气体和烟颗粒产生明显增加,这对环境有害并增强了RPUF的火灾危险性。3.大量的聚氨酯泡沫塑料(RPUF)消耗给社会带来了两个严峻的挑战:火灾热危害和火灾毒性危害。为了解决这些问题,合成了不同种类的用于降低RPUF燃烧产生有毒烟气的过渡金属氧化物和双金属氧化物。首先通过X射线衍射(XRD)和透射电子显微镜(TEM)确认了其结构和形貌。然后通过热重分析表明,由于其催化偶联效应,掺入2wt%NiO显著提高了RPUF纳米复合材料的残余产率,提高量达到63.8%。此外,通过对挥发性和凝聚相产物的充分分析,研究得到RPUF在热解和燃烧过程中的烟气毒性的抑制机理,发现通过将CO转化为CO2的氧化还原的循环体系,其中包括通过CO还原Ni2+成为Ni0,通过O2氧化Ni0成为Ni2+等过程。在所有纳米添加剂中,金属氧化物NiO和Cu2O是降低RPUF材料在热解和燃烧过程中产生有毒气体的有效催化剂。4.作为一种降低有毒气体释放和抑制烟颗粒产生的活性催化剂,不同尺寸的Cu20颗粒被成功合成并得到充分的表征,并通过LOI测试和锥形量热方法评估其RPUF复合材料的阻燃和烟气抑制性能。结果表明,随着Cu2O微米颗粒的加入不会使RPUF/Cu20-1μm复合材料的HRR曲线出现太大变化。然而,RPUF/Cu20-100nm纳米复合材料的PHRR降低为262 kW/nm2,这可能是由于Cu2O纳米颗粒在RPUF基体中起到明显的催化成炭作用和促进网络结构的形成,从而形成更多和更致密的炭层,显著提高了对基体的保护作用。特别有趣的是,当加入尺寸为5nm的Cu2O纳米颗粒,PHRR值反而升高了,这是由于随着纳米粒子粒径的减少,其比表面积越大,从而得到更好的催化氧化的效果,充分分解了更多的RPUF复合材料。这些结果都表明了越小纳米尺寸的Cu2O具有越大的催化氧化作用。虽然没有得到很好的阻燃效果,但是可以对RPUF基体热降解过程的催化减毒效应起到很好的作用。对于RPUF复合材料热降解过程中释放的毒性气体CO的释放量,不同尺寸的Cu2O纳米颗粒均具有很好的减毒的效果,这与Cu2O纳米颗粒在RPUF基体中的催化成炭和催化氧化的过程有关。5.通过水热法和简便的湿化学处理方法成功制备了 Cu2O纳米颗粒负载修饰的层状MoS2纳米片,应用在RPUF复合材料中,最终减少了材料在燃烧过程中的有毒气体和烟颗粒的形成。当Cu2O与MoS2的质量比较低时,所得的Cu2O-MoS2杂化物可以有效地阻止MoS2纳米片的重新堆叠。然而,Cu2O-MoS2-M杂化物是通过增加Cu2O的负载量来获得的,其具有MoS2的特征性的堆叠结构,显著降低了在基体中的分散状态。当Cu2O-MoS2纳米杂化物应用到RPUF基体中,由于MoS2的物理吸附和Cu2O的催化作用,显著降低了有害有机挥发物和有毒气体的产生(CO和NOx产物分别减少了28%和53%)。Cu2O-MoS2杂化物的添加直接增加了RPUF纳米复合材料的成炭率,这表明了该杂化体系的高效催化成炭性能。在这项工作中,使用了用于预测火灾烟气毒性的N-Gas模型,并应用到研究工作中。此外,该研究通过理论模型和实际数据验证了堆叠的MoS2结构对降低RPUF纳米复合材料的烟气毒性的负面影响的直接证据。
Abstract
ying zhi ju an zhi pao mo (RPUF)shi yi chong tong guo duo yuan chun he yi qing suan zhi de ju jia cheng fan ying sheng cheng de duo gong neng hua shang ye cai liao 。RPUFyou yu zi shen ju you xian zhe de ji xie xing neng he du te de ge re deng xing neng ,an fan yong yu ju jia he jian zhu deng hang ye ,li ru zuo wei jian zhu ge re cai liao ,yi ji jia ju de chong yao zu cheng bu fen 。ran er ,RPUFcai liao dian huo hou ,you yu ji te shu de duo kong de jie gou he ta yi ran de zu cheng bu fen ,ke zai duan shi jian nei chan sheng da liang de re he you du yan qi ,li ru you hai de yan ke li ji CO,NOxhe HCNdeng du xing qi ti 。zhe xie you du yan qi hui dui ren ti zao cheng de shang hai ,shi jue da duo shu huo zai shang wang de zhen xiong ,wei hai chao guo le ji ran shao chan sheng de re wei hai 。jin nian lai ,bu duan zeng jia de gao ceng jian zhu huo zai shi jian gei ren lei zao cheng le ju da de sun shi 。yin ci ,dui RPUFbao wen cai liao de zu ran he you du yan qi de yi zhi gong zuo shi bi bu ke shao de ,zhe dui ren lei she hui he huan jing de he xie jian kang fa zhan zhi guan chong yao 。zai ben lun wen de yan jiu zhong ,shi tu li yong fen zi she ji shou duan jie jue ying zhi ju an zhi pao mo gao huo zai wei xian xing deng nan ti ,cong yi xia ji ge fang mian zhao shou :shou xian zai ju an zhi fen zi jie gou zhong yin ru han lin 、dan deng zu ran yuan su de zu ran chan yuan ,bing gai bian ju an zhi de re jie ji zhi ,cong er jia kuai tan hua su du ,di gao cheng tan liang ,zhi bei chu ju you you yi zeng ge xing neng de ben zheng xing zu ran ying zhi ju an zhi pao mo cai liao ,zhe yang ke yi you xiao jian shao ju ge wu ran shao re de shi fang ,shi zhi ju you liang hao de zu ran xiao guo he nai re xing ;ji ci ,wei le jiang di RPUFcai liao zai ran shao guo cheng zhong shi fang de you du yan qi ,cheng gong ge cheng le ji chong han guo du jin shu yuan su de na mi yang hua wu ke li ,ta men bu jin ju you wu li zu ge xiao ying ,er ju ke yi cui hua ju an zhi de re jie chan wu cong er xing cheng wen ding de duo kong tan zhi ceng ;yu ci tong shi ,ju you er wei xing mao 、bi biao mian ji da he you yi wu li xing neng de ceng zhuang hua ge wu ye ke yi zuo wei yi chong xin xing zai ti ,di gao cui hua ji de cui hua xiao lv ,jiang pian ceng zu ge zuo yong yu guo du jin shu hua ge wu de cui hua cheng tan yu cui hua jian du zuo yong jie ge qi lai ,bu jin ru ci ,fu zai zai ceng zhuang hua ge wu pian ceng shang de mo ji na mi li zi ke yi you xiao xian zhi pian ceng jie gou de die ju xiao ying 。ji yu yi shang yan jiu ,ben wen ni jiang fen zi she ji 、na mi fu ge 、xie xiao zu ran 、cui hua cheng tan ji cui hua jian du xiang jie ge ,jiang you wang zhi bei chu xing neng you yi de zu ran ying zhi ju an zhi pao mo cai liao 。xiang xi yan jiu gong zuo ru xia :1.shou xian ji tong yan jiu le han lin duo yuan chun (BHPP)he han dan duo yuan chun (MADP)zai di gao EG/RPUFfu ge cai liao de zu ran xing fang mian de xie tong zuo yong 。zu ran duo yuan chun BHPPhe MADPfen bie shi tong guo tuo lv hua qing he man ni xi fan ying ge cheng de 。tong guo re chong fen xi (TGA)he ji xian yang zhi shu (LOI)deng ce shi yan jiu le BHPPhe MADPde chong liang bi dui xing neng de ying xiang 。jie guo biao ming ,BHPPhe MADPzai zu ran EG/RPUFti ji zhong de zui jia zhi liang bi wei 1:1。ci wai ,ke peng zhang dan mo (EG)yu BHPPhe MADPfu pei shi yong ke yi da da di gao RPUFfu ge cai liao de zu ran xing neng 。dang EGhan liang wei 15wt%shi ,RPUFfu ge cai liao de LOIzhi ke da dao 33.5%。ci wai ,yu chun RPUFxiang bi ,re shi fang feng zhi (PHRR)jiang di le 52.4%。zai shi yan he fen xi de ji chu shang ,di chu le yi chong ning ju xiang zu ran ji li 。2.tong guo zi you fa pao ji shu zhi bei chu han you han dan zu ran duo yuan chun (MADP)he han lin zu ran ji DOPOde zu ran ying zhi ju an zhi pao mo 。bing tong guo re chong fen xi (TGA),ji xian yang zhi shu (LOI)he zhui xing liang re yi (CONE)yan jiu RPUFde re wen ding xing he ran shao hang wei 。yu chan du tian jia zu ran cheng fen (MADPhuo DOPO)de jie guo xiang bi ,RPUF/MADP-DOPOzu ran ti ji xian shi chu geng gao de ya su jiang du ,zhe shi you yu yi qing suan zhi (-NCO)yu DOPOde P-Hzhi jian de fan ying fu yu le jie mian nian ge cong er da dao zeng jiang xiao guo 。ci wai ,RPUF/MADP-DOPOti ji fu yu RPUFgeng wen ding de jie gou ,bing zeng jia le LOIshu zhi he jian shao le re shi fang liang 。tong guo sao miao dian zi xian wei jing (SEM),Xshe xian guang dian zi neng pu fen xi (XPS)he tan can liu wu de la man guang pu (Raman)biao ming le RPUFfu ge cai liao ran shao hou xing cheng le zhi mi er lian xu de tan ceng 。tong guo shi yan he fen xi ,di chu le ke neng de zu ran ji li ,RPUF/MADP-DOPOti ji cu jin le ning ju xiang zhong fu han lin de can yu wu de sheng cheng ,cong er xing cheng bao hu xing tan ceng ,bing zai qi xiang zhong xi shi ke ran xing qi ti 。zai fen xi he tao lun de ji chu shang ,ke yi gen ju liang xiang zu ran ji li ,MADP/DOPOde yin ru fu yu RPUFyou yi de zu ran xing neng 。ran er ,gai xing RPUFcai liao ran shao shi fang de you du qi ti he yan ke li chan sheng ming xian zeng jia ,zhe dui huan jing you hai bing zeng jiang le RPUFde huo zai wei xian xing 。3.da liang de ju an zhi pao mo su liao (RPUF)xiao hao gei she hui dai lai le liang ge yan jun de tiao zhan :huo zai re wei hai he huo zai du xing wei hai 。wei le jie jue zhe xie wen ti ,ge cheng le bu tong chong lei de yong yu jiang di RPUFran shao chan sheng you du yan qi de guo du jin shu yang hua wu he shuang jin shu yang hua wu 。shou xian tong guo Xshe xian yan she (XRD)he tou she dian zi xian wei jing (TEM)que ren le ji jie gou he xing mao 。ran hou tong guo re chong fen xi biao ming ,you yu ji cui hua ou lian xiao ying ,can ru 2wt%NiOxian zhe di gao le RPUFna mi fu ge cai liao de can yu chan lv ,di gao liang da dao 63.8%。ci wai ,tong guo dui hui fa xing he ning ju xiang chan wu de chong fen fen xi ,yan jiu de dao RPUFzai re jie he ran shao guo cheng zhong de yan qi du xing de yi zhi ji li ,fa xian tong guo jiang COzhuai hua wei CO2de yang hua hai yuan de xun huan ti ji ,ji zhong bao gua tong guo COhai yuan Ni2+cheng wei Ni0,tong guo O2yang hua Ni0cheng wei Ni2+deng guo cheng 。zai suo you na mi tian jia ji zhong ,jin shu yang hua wu NiOhe Cu2Oshi jiang di RPUFcai liao zai re jie he ran shao guo cheng zhong chan sheng you du qi ti de you xiao cui hua ji 。4.zuo wei yi chong jiang di you du qi ti shi fang he yi zhi yan ke li chan sheng de huo xing cui hua ji ,bu tong che cun de Cu20ke li bei cheng gong ge cheng bing de dao chong fen de biao zheng ,bing tong guo LOIce shi he zhui xing liang re fang fa ping gu ji RPUFfu ge cai liao de zu ran he yan qi yi zhi xing neng 。jie guo biao ming ,sui zhao Cu2Owei mi ke li de jia ru bu hui shi RPUF/Cu20-1μmfu ge cai liao de HRRqu xian chu xian tai da bian hua 。ran er ,RPUF/Cu20-100nmna mi fu ge cai liao de PHRRjiang di wei 262 kW/nm2,zhe ke neng shi you yu Cu2Ona mi ke li zai RPUFji ti zhong qi dao ming xian de cui hua cheng tan zuo yong he cu jin wang lao jie gou de xing cheng ,cong er xing cheng geng duo he geng zhi mi de tan ceng ,xian zhe di gao le dui ji ti de bao hu zuo yong 。te bie you qu de shi ,dang jia ru che cun wei 5nmde Cu2Ona mi ke li ,PHRRzhi fan er sheng gao le ,zhe shi you yu sui zhao na mi li zi li jing de jian shao ,ji bi biao mian ji yue da ,cong er de dao geng hao de cui hua yang hua de xiao guo ,chong fen fen jie le geng duo de RPUFfu ge cai liao 。zhe xie jie guo dou biao ming le yue xiao na mi che cun de Cu2Oju you yue da de cui hua yang hua zuo yong 。sui ran mei you de dao hen hao de zu ran xiao guo ,dan shi ke yi dui RPUFji ti re jiang jie guo cheng de cui hua jian du xiao ying qi dao hen hao de zuo yong 。dui yu RPUFfu ge cai liao re jiang jie guo cheng zhong shi fang de du xing qi ti COde shi fang liang ,bu tong che cun de Cu2Ona mi ke li jun ju you hen hao de jian du de xiao guo ,zhe yu Cu2Ona mi ke li zai RPUFji ti zhong de cui hua cheng tan he cui hua yang hua de guo cheng you guan 。5.tong guo shui re fa he jian bian de shi hua xue chu li fang fa cheng gong zhi bei le Cu2Ona mi ke li fu zai xiu shi de ceng zhuang MoS2na mi pian ,ying yong zai RPUFfu ge cai liao zhong ,zui zhong jian shao le cai liao zai ran shao guo cheng zhong de you du qi ti he yan ke li de xing cheng 。dang Cu2Oyu MoS2de zhi liang bi jiao di shi ,suo de de Cu2O-MoS2za hua wu ke yi you xiao de zu zhi MoS2na mi pian de chong xin dui die 。ran er ,Cu2O-MoS2-Mza hua wu shi tong guo zeng jia Cu2Ode fu zai liang lai huo de de ,ji ju you MoS2de te zheng xing de dui die jie gou ,xian zhe jiang di le zai ji ti zhong de fen san zhuang tai 。dang Cu2O-MoS2na mi za hua wu ying yong dao RPUFji ti zhong ,you yu MoS2de wu li xi fu he Cu2Ode cui hua zuo yong ,xian zhe jiang di le you hai you ji hui fa wu he you du qi ti de chan sheng (COhe NOxchan wu fen bie jian shao le 28%he 53%)。Cu2O-MoS2za hua wu de tian jia zhi jie zeng jia le RPUFna mi fu ge cai liao de cheng tan lv ,zhe biao ming le gai za hua ti ji de gao xiao cui hua cheng tan xing neng 。zai zhe xiang gong zuo zhong ,shi yong le yong yu yu ce huo zai yan qi du xing de N-Gasmo xing ,bing ying yong dao yan jiu gong zuo zhong 。ci wai ,gai yan jiu tong guo li lun mo xing he shi ji shu ju yan zheng le dui die de MoS2jie gou dui jiang di RPUFna mi fu ge cai liao de yan qi du xing de fu mian ying xiang de zhi jie zheng ju 。
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论文作者分别是来自中国科学技术大学的袁尧，发表于刊物中国科学技术大学2019-07-12论文，是一篇关于硬质聚氨酯泡沫论文,阻燃论文,催化论文,火灾危害论文,毒性抑制论文,机理研究论文,中国科学技术大学2019-07-12论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自中国科学技术大学2019-07-12论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：硬质聚氨酯泡沫论文; 阻燃论文; 催化论文; 火灾危害论文; 毒性抑制论文; 机理研究论文; 中国科学技术大学2019-07-12论文;