PC/纳米SiO2复合材料的热降解行为

采用熔融共混法制备了聚碳酸酯(PC)/纳米二氧化硅(SiO2)复合材料。采用X射线衍射和扫描电子显微镜研究了PC和PC/纳米SiO2复合材料的结构,采用热重分析了PC和PC/纳米SiO2复合材料的热降解行为,用Kissinger-Akahira-Sunose法研究了PC和PC/纳米SiO2复合材料的热降解动力学。结果表明:PC的内部结构没有发生变化,且纳米SiO2在基体中分散均匀;加入纳米SiO2能显著改善PC的热稳定性,且PC和PC/纳米SiO2复合材料的热降解温度均随升温速率提高呈线性增加;PC和PC/纳米SiO2复合材料的热降解活化能均随转化率升高而增加,且PC/纳米SiO2复合材料的活化能明显高于PC。     

氮化硼杂化环保型酚醛树脂的研究

采用硅烷偶联剂对氮化硼(BN)微米粒子进行表面处理,并在酚醛树脂(PF)的聚合反应过程中将其加入,制备出一种新型的有机/无机BN杂化环保型PF。采用红外光谱(FT-IR)、扫描电镜(SEM)和热重分析(TGA)等手段对杂化树脂的结构与性能进行了研究,并运用Kissinger、Ozawa和Crane方法计算其热分解反应的动力学参数。结果表明:杂化树脂的活化能和频率因子分别为126.1kJ/mol和1.64×108s-1(Kissinger法),反应级数为0.929(Crane法),其热分解反应机理比较复杂;经偶联剂处理过的BN粒子在PF中的分散性较好,BN杂化PF的耐热性略有提高;采用玻璃纤维增强杂化树脂制备BN杂化PF复合材料,其力学强度和电性能明显提高,拉伸强度由476.6MPa提高到610.5MPa,表面电阻率由2.88×1012Ω增加到1.92×1015Ω。     

环境友好含氟乳液功能型氟树脂涂料的研究及应用

氟树脂由于其特殊的结构特点比其他传统的树脂表现出优良的耐候性和耐久性,含氟聚合物涂料优异的力学性能、耐候性、抗污性、耐化学品性等使其获得越来越广泛的应用。本文介绍了氟树脂及相关涂料的研究进展及其应用,强调溶剂型氟树脂涂料功能特点与含氟乳液涂料的环境友好性,特别指出,当今涂料的发展应朝着环境友好、高性能和多功能的方向发展。     

环保可发性甲阶酚醛树脂的合成及性能研究

采用多聚甲醛代替37%甲醛溶液与苯酚逐步加成聚合,合成可发性甲阶酚醛树脂。通过粘度、固含量、游离苯酚和甲醛含量及凝胶时间测定以及IR,GPC和TG分析研究了多聚甲醛-苯酚物质的量比为1.8∶1条件下,缩聚反应温度及催化剂加入量对可发性甲阶酚醛树脂性能的影响。结果表明,缩聚反应温度为90℃,催化剂质量分数为5%(以苯酚质量计)时,可得到性能优良的可发性甲阶酚醛树脂,其性能如下:粘度2.6 Pa·s,游离甲醛质量分数1.23%,游离苯酚质量分数5.13%,热失重质量残留率50%以上。     

快固型钛酸酯杂化酚醛树脂的合成

通过钛酸四丁酯与热塑性酚醛树脂(Novolac树脂)的酯交换反应合成了一类快速固化型杂化酚醛树脂,可加入六亚甲基四胺进行固化。通过红外、核磁、凝胶时间和粘度等测试研究了树脂的分子结构和理化性能。结果表明:随着钛酸四丁酯用量增大,杂化酚醛树脂的分子质量明显增大,凝胶时间缩短,杂化酚醛树脂溶液的粘度增大,并基本呈线性关系。钛酸酯键有效改进了酚醛树脂的粘接性。固化速率的加快来源于改性树脂分子质量的增大和钛酸酯结构对于固化反应的催化作用;而杂化酚醛树脂粘接性的提高是由于酚醛树脂中的钛酸酯结构起到了偶联剂作用。     

Thermal degradation kinetics and lifetime estimation for polycarbonate/polymethylphenylsilsesquioxane composite

The thermal degradation behaviors of polycarbonate/polymethylphenylsilsesquioxane (FRPC) composites were investigated by thermogravimetric analysis (TGA) under isothermal conditions in nitrogen atmosphere. The isothermal kinetics equation was used to describe the thermal degradation process. The results showed that activation energy (E), in the case of isothermal degradation, was a quick increasing function of conversion (α) for polycarbonate (PC) but was a strong and decreasing function of conversion for FRPC. Under the isothermal condition, the addition of polymethylphenylsilsesquioxane (PMPSQ) retardanted the thermal degradation and enhanced the thermal stability of PC during the early and middle stages of thermal degradation. It also indicated a possible existence of a difference in nucleation, nuclei growth, and gas diffusion mechanism in the thermal degradation process between PC and FRPC. Meanwhile, the addition of PMPSQ influenced the lifetime of PC, but the composite still met the demand in manufacturing and application.     

对苯二甲醛酚醛树脂的制备及其固化动力学研究

基于酚醛树脂原料中甲醛的危害性与不可再生性,使用安全、可再生的对苯二甲醛代替甲醛,合成了一种新型的酚醛树脂——对苯二甲醛酚醛树脂。采用核磁、红外、GPC和流变仪等分析手段对此类树脂的结构与性能进行了表征。为了进一步提高该树脂的热性能,使用二茂铁甲醛对其进行改性。采用Kissinger方程、等转换法及双参数自催化模型对改性前后树脂的固化动力学进行了研究,明确了二茂铁甲醛在树脂固化中的作用机理。最后通过MDSC和TG研究了改性前后树脂固化物的热性能,结果表明：在加入15%的二茂铁甲醛后,改性树脂呈现出优异的热性能,其玻璃化转变温度为319.3℃,起始分解温度为397.7℃,在800℃氮气气氛下质量保持率高达76.07%。     

氧化铝/环氧树脂/聚氨酯导热复合材料的制备及表征

采用硅烷偶联剂KH550对氧化铝表面进行改性,并以改性氧化铝为导热填料,以环氧树脂为基体树脂,自制的聚氨酯预聚体为柔性改性剂,制备了氧化铝/环氧树脂/聚氨酯导热复合材料。采用红外光谱对KH550改性氧化铝的结构进行了表征,探讨了影响复合材料热导率的主要因素,研究了改性氧化铝用量对复合材料力学性能的影响,并利用扫描电镜对复合材料的微观结构进行了观察。结果表明,KH550已通过化学键接枝在氧化铝表面。随着KH550改性氧化铝用量的增加,复合材料的拉伸强度逐渐增大,而导热率和断裂伸长率呈现先上升后下降的趋势。当改性氧化铝的用量为150 phr时,复合材料的导热率达到最大值0.66 W/(m·K),拉伸强度和断裂伸长率分别为37.2 MPa和1.62%。随着m(PUA)/m(EP)的增大,复合材料的导热率相应下降,适宜的m(PUA)/m(EP)为15/85。     

Thermal degradation of a phenolic resin,vegetable fibers,and derived composites

The thermal degradation behavior of resol, several vegetable fibers (two types of cotton fibers, sisal and sugar cane bagasse) and derived polymer composites have been investigated using thermogravimetric analysis (TGA). The initial thermal degradation temperature T_ONSET, the temperature at the maximum degradation rate TD_M, and the char left at 500°C corresponding to the crosslinked resol were higher than the values measured for the fibers and their composites. Thus, the addition of the fibers reduced the thermal resistance of the phenolic thermoset. The polymer and the fiber‐composites showed a complex degradation involving different thermal decomposition processes. For that reason, the DTG curves were deconvoluted and a phenomenological kinetic expression was found for each individual peak. The overall thermal decomposition curve was recalculated adding each degradation process weighted according to its contribution to the total weight loss. An increase in the activation energy corresponding to the cellulose degradation was observed in the composites, highlighting the protective action of the resin encapsulating the fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

新型含磷酚醛树脂的合成与性能

通过亚膦酸酯与碳碳双键之间的亲电加成反应,合成了一种新型的含磷马来酰亚胺酚醛树脂。采用红外光谱(FTIR)和元素分析法对聚合物的结构进行了表征。并用此含磷酚醛树脂作为环氧树脂的固化剂制得了一含磷氮的环氧固化物。采用热分析法、极限氧指数法对相应环氧固化物的耐热性能和阻燃性能进行了表征。研究结果表明:以该含磷聚合物作为环氧树脂的固化剂,对稳定固化物骨架碳的结构和交联成炭能力的提高起到了增强作用;环氧固化物具有较高的玻璃化转变温度(145.4℃)和较高的热稳定性(T508℃),极限氧指数显示其具有较好的阻燃性能。     

粗酚部分替代苯酚制备酚醛泡沫保温材料

采用多聚甲醛、粗酚和苯酚为原料制备了酚醛泡沫保温材料,研究了聚合时间、聚合温度、醛酚[多聚甲醛与总酚(粗酚和苯酚的总称)]摩尔比、催化剂用量和粗酚替代量等合成条件对可发性酚醛树脂性能的影响。经优化的酚醛树脂合成条件:聚合时间为3.0 h,聚合温度为85℃,醛酚摩尔比为1.60,催化剂用量为0.04 mol(总酚1.00 mol),粗酚替代量为总酚质量的30%。酚醛泡沫(表观密度为45 kg/m3)的导热系数为0.028 W/(m.K),氧指数为36%,压缩强度为0.29 MPa。     

酚醛在丙烯酸树脂防火改性中的应用

以酚醛树脂为主防火剂、胺类为协效剂,研究了其种类、用量对丙烯酸树脂防火性能的影响,采用锥形量热仪和热重分析仪对酚醛改性丙烯酸树脂的燃烧性能和热稳定性进行了测试,并对燃烧后的炭层结构进行了电镜分析。结果表明,硼酚醛树脂能显著提高丙烯酸树脂的防火性能,硅酸铝、六次甲基四胺具有有良好的协效作用;当丙烯酸树脂与硼酚醛树脂质量比为50:50,硅酸铝质量分数为7%,六次甲基四胺为2%时,改性树脂耐燃时间达到39min,点燃时间(TTI)及热释放速率峰值出现时间明显延长,热释放速率明显降低,800℃时残炭率为45%,热稳定性明显提高,燃烧烧后形成了表面为致密网状、断面为微细泡孔状的炭层结构,防火性能提高。     

环保型酚醛树脂合成工艺链及其经济分析

采用多聚甲醛替代37%的甲醛水溶液,可以合成用于覆膜砂生产的热塑性酚醛树脂。以上述热塑性酚醛树脂生产中排放的全部废水、多聚甲醛、苯酚为原料可以合成多种用途的热固性酚醛树脂。这一联产工艺,彻底解决了酚醛树脂生产企业的废水排放问题。同时,热塑性酚醛树脂的成本仅增加1.24%,而热固性酚醛树脂可减少10.2%以上的支出,因此经济上也是可行的。     

双马改性酚醛树脂的耐热性及热分解动力学研究

采用二笨甲烷型双马来酰亚胺对酚醛树脂进行改性,制备出一种耐热性良好的改性酚醛树脂.采用热重分析法研究了双马来酰亚胺改性酚醛树脂的热分解动力学,并用Kissinger法、Ozawa法、Crane法计算其热分解动力学参数.结果表明,改性树脂的平均表观活化能为376.144kJ/mol,反应级数为0.940,其热分解分为3个...     

Nonisothermal degradation kinetics for epoxy resin systems containing polymethylphenylsilsesquioxane

The thermal degradation behaviors of polymethylphenylsilsesquioxane/epoxy resin (PMPSQ/EP) systems were investigated by thermogravimetric analysis (TGA) under nonisothermal conditions in nitrogen atmosphere. During nonisothermal degradation, Kissinger's and Flynn‐Wall‐Ozawa's methods were both used to analyze the thermal degradation process. The results showed that a remarkable increase of activation energy was observed in the presence of PMPSQ, which indicated that the addition of PMPSQ retarded the thermal degradation of EP. Flynn‐Wall‐Ozawa's method further revealed that PMPSQ significantly increased the activation energy of EP thermal degradation especially in the early and final stage of thermal degradation process, which illustrated that the PMPSQ stabilized the char layer and improved the flame retardancy of EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Engineering biomass into formaldehyde‐free phenolic resin for composite materials

The use of formaldehyde to prepare phenol‐formaldehyde (PF) resins is one of the primary challenges for the world‐wide PF industry with respect to both sustainability and human health. This study reports a novel one‐pot synthesis process for phenol‐5‐hydroxymethylfurfural (PHMF) resin as a formaldehyde‐free phenolic resin using phenol and glucose, and the curing of the phenolic resin with a green curing agent organosolv lignin (OL) or Kraft lignin (KL). Evidenced by ¹³C NMR, the curing mechanism involves alkylation reaction between the hydoxyalkyl groups of lignin and the ortho‐ and para‐carbon of PHMF phenolic hydroxyl group. The curing kinetics was studied using differential scanning calorimetry and the kinetic parameters were obtained. The OL/KL cured PHMF resins were tested in terms of thermal stability, and mechanical properties for their applications in fiberglass reinforced composite materials. The results obtained demonstrated that OL/KL can be promising curing agents for the PHMF resins. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1275–1283, 2015     

Preparation of phenolic resin/organized expanded vermiculite nanocomposite and its application in brake pad

Phenolic resin (PF)/organized expanded vermiculite (OEVMT) nanocomposite was prepared via melt intercalation with EVMT organically treated using benzyldimethyloctadecylammonium. The results of the PF/OEVMT structure characterized by X‐ray diffraction and transmission electron microscopy showed that the PF/OEVMT nanocomposite formed exfoliated and intercalated mixed structure. Thermogravimetric analysis indicated that the thermal decomposition temperature of the PF/OEVMT nanocomposite (482.6°C) was higher than that of pristine PF (433.9°C) in air atmosphere. The brake pad based on PF/OEVMT nanocomposite were also prepared. The friction and wear tests illustrated that the brake pad based on PF/OEVMT had more stable friction coefficient and lower wear rate than that of the brake pad based on PF. Scanning electron microscopy also showed that the brake pad based on PF/OEVMT nanocomposite has excellent high temperature wear‐resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

硼改性酚醛树脂的合成与性能

利用半成品酚醛树脂粉与硼酸直接混合,然后固化得到硼含量不同的硼酚醛树脂,并用傅里叶红外光谱、热重分析和冲击试验等方法对其性能进行了分析。红外分析结果表明,硼酸与酚醛树脂中的酚羟基、苄羟基发生了反应,生成了新的交联键。热分析结果发现,在酚醛树脂中加入硼酸能提高树脂的耐热性,当硼酸加入量为10%时达到最高值。硼酚醛树脂的冲击强度先随硼酸加入量的增大而增加,在5%时达到最大值,然后下降。     

酚醛树脂改性石墨/天然橡胶复合材料的性能

采用酚醛树脂对石墨进行改性处理,制得改性石墨/天然橡胶(NR)复合材料,采用扫描电子显微镜对石墨的微观形貌进行了表征,并对改性石墨/NR复合材料的性能进行了研究。结果表明,改性石墨的表面粗糙度增加。改性石墨/NR复合材料在不同温度下的平均热导率高于未改性石墨/NR复合材料;随着酚醛树脂含量的增大,复合材料导热性能有所降低。与未改性石墨/NR复合材料相比,改性石墨/NR复合材料的拉伸强度、撕裂强度、定伸应力和硬度增大,扯断伸长率和永久变形降低;酚醛树脂含量高的改性石墨/NR复合材料较酚醛树脂含量低的复合材料力学性能有所降低。     

酚醛胺固化腰果酚改性酚醛树脂热降解动力学研究

研究了酚醛胺固化的腰果酚改性酚醛树脂的热稳定性,用Friedman-Reich-Levi法建立了固化产物热降解动力学模型,得出热解活化能为265.80 kJ/mol,lgA为16.73（A=5.37×1010 s-1）。