硼含量对改性酚醛树脂性能的影响

以硼酸作为高羟甲基低游离酚PF(酚醛树脂)的改性剂,制备相应的BPF(硼改性酚醛树脂)及其模塑料。采用红外光谱(FT-IR)法对BPF的结构进行了表征,并对其凝胶化时间、固化工艺条件、热性能和模塑料的性能等进行了探讨。研究结果表明:当w(B)=9%时,BPF及其模塑料的综合性能相对最好,其固化工艺为160℃/20 min,后处理工艺为"140℃/1 h→160℃/1 h→180℃/2 h";与纯PF模塑料相比,BPF模塑料的马丁耐热温度(196℃)提高了42℃、弯曲强度(111.8 MPa)提高了21.9 MPa且冲击强度(18.50 kJ/m2)也有所提高。     

硼酚醛树脂的制备和研究进展

由于在酚醛树脂(PF)的分子结构中引入了无机硼元素,故硼酚醛树脂(BPF)具有优异的抗氧化性、高温稳定性、力学性能和高残炭率等特点,并且在热解时不会释放出有毒气体,因而已成为目前最成功的PF改性品种之一,在汽车、军事装备和航空航天等领域中应用广泛。总结了国内外近年来有关制备BPF的各种方法,简要介绍了BPF的性能及应用研究,并对该领域的研究方向作了展望。     

高残炭耐烧蚀树脂基体研究进展

综述了近年来氨酚醛树脂、钡酚醛树脂等广泛使用的传统酚醛树脂(PF),硼改性酚醛树脂(BPF)、苯并恶嗪树脂(BZ)和酚三嗪树脂(PT)等部分改性PF,以及以聚芳基乙炔树脂(PAA)为代表的新型高残炭树脂的研究进展。分析了传统PF不能满足先进热防护材料发展需求的原因。着重介绍了BPF主要的合成方法和热分解机理、BZ的分子改性设计和共混共聚改性以及PAA的改性和固化过程中存在的主要问题。对比介绍了不同耐烧蚀基体在高温热环境下的残炭率,以及其在制备工艺、实际应用等方面所存在的问题,并且展望了树脂基耐烧蚀复合材料未来在纳米改性方面的发展趋势。     

BPR/PF复合材料的热性能和动态力学性能

采用硼酚醛树脂(BPR)与普通酚醛树脂(PF)熔融共混挤出制备BPR/PF树脂,通过模压成型工艺制备BPR/PF复合材料。利用热失重(TG)、动态力学性能(DMA)研究不同BPR含量对复合材料热性能、动态力学性能、蠕变和应力松弛性能的影响。结果表明,BPR能显著增强树脂的热性能。700℃,BPR加入质量分数50份时,BPR/PF的残炭率达到了58%,而PF的残炭率只有38.29%,共混复合材料的储能模量提高了28%;玻璃化转变温度提高了18.3℃;复合材料的蠕变和应力松弛性能也得到了提高。     

硼-腰果酚改性酚醛树脂的制备及固化动力学

针对酚醛树脂(PF)耐热性和韧性不足的缺点,采用硼、腰果酚对酚醛树脂进行改性,考察了硼酸用量和腰果酚用量等对改性酚醛树脂性能的影响。红外(FT-IR)分析结果表明,硼酸与酚醛树脂中的酚羟基发生了反应,生成了新的交联键。通过热重(TG)分析,结果表明经硼改性的酚醛树脂耐热性能明显提高。通过非等温差示扫描量热法(DSC)分析了改性酚醛树脂在不同升温速率下的固化行为,采用Ozawa法和Crane方程建立了改性酚醛树脂的固化动力学模型,确定了其固化工艺参数。     

聚苯醚改性高固含量热塑性PF的制备与性能研究

合成了高固含量(>85%)的线性PF(酚醛树脂)和聚苯醚(PPO)改性高固含量线性PF。采用红外光谱(FT-IR)法、差示扫描量热(DSC)法和热重分析(TGA)法等,分析了PPO改性前后线性PF的结构、固化反应和热降解过程,并对两者的玻璃纤维增强复合材料的力学性能进行了研究。结果表明:PPO的引入,既增强了PF的固化反应活性,又提高了PF的耐热性能;PPO改性线性PF基玻璃纤维增强复合材料的力学性能得到了有效提升,其拉伸强度、剪切强度和弯曲强度分别提高了17.8%、73.0%和21.4%。     

硼、钼双改性酚醛树脂的制备与表征

采用硼、钼双改性酚醛树脂,制备具有耐高温性能的酚醛树脂,并利用红外光谱仪、热重分析和冲击试验等方法对其性能进行分析。结果表明:硼和钼元素已经接枝到酚醛树脂的分子链中;硼、钼双改性酚醛树脂耐热性能和抗冲击性能明显优于传统的热塑性酚醛树脂PF。     

BPR含量对BPR/SF/PF复合材料摩擦磨损性能和力学性能的影响

将硼酚醛树脂(BPR)与普通酚醛树脂(PF)熔融共混,再加入经过碱处理的剑麻纤维(SF),通过模压成型工艺制备BPR/SF/PF复合材料。利用定速式摩擦试验机和电子万能试验机研究了BPR含量对复合材料摩擦磨损性能及力学性能的影响,采用扫描电镜观察了复合材料磨损表面的形貌。结果表明:在BPR/PF=50/100时,与普通PF/SF复合材料相比,BPR/SF/PF复合材料在300℃下的磨损率降低了42%,冲击强度提高了14%,弯曲强度和弯曲模量分别提高了25%和36%;复合材料磨损面形貌显示,加入BPR后,复合材料由疲劳磨损转变为磨粒磨损。     

NBR改性硼酚醛树脂的性能研究

研究：NBR用量对：NBR改性硼酚醛树脂冲击性能的影响，并利用傅立叶转换红外光谱、差示扫描量热法和热重法对改性前后硼酚醛树脂的结构和热性能进行分析。结果表明，硼酚醛树脂的冲击强度随NBR用量的增大而呈上升趋势，当NBR用量为6．7份时，其冲击强度达到最大值，NBR与硼酚醛树脂之间不是简单的物理共混，而是发生了共聚反应，改性硼酚醛树脂的固化峰顶温度下降，耐热性(低于430℃时)提高。     

PHET/PF原位复合材料力学、动态力学和热性能研究

自行合成了端羟基的热致性聚酯液晶(PHET),采用原位复合的方法制备了热致性聚酯液晶(PHET)/酚醛树脂(PF)原位复合材料,研究了PHET的用量对PHET/PF原位复合材料的冲击强度、弯曲强度、动态力学性能、热性能等的影响。结果表明,PHET的加入可以提高PHET/PF原位复合材料的力学性能、动态力学性能和热性能,当PHET质量分数为7.5%时,原位复合材料的冲击强度、弯曲强度和玻璃化转变温度(Tg)分别提高了44.69%、44.68%和22.9℃。在200℃时,PHET/PF共混物中液晶丝状织态结构明显且分布连续。     

N-(4-羟基苯基)马来酰亚胺改性酚醛树脂的制备与表征

采用N-(4-羟基苯基)马来酰亚胺(4-HPM)改性酚醛树脂(PF),改性后PF的耐热性能明显优于传统的热塑性PF。质量分数2%的4-HPM改性PF的热分解温度比纯PF提高104.6℃,冲击强度提高130%。改性PF的固化过程分为两个固化阶段:第一阶段是少量羟甲基的缩合;第二阶段为马来酰亚胺的双键打开进行自交联。     

Enhanced mechanical properties,thermal stability of phenolic‐formaldehyde foam/silica nanocomposites via in situ polymerization

Phenolic foam (PF) displays excellent flame, smoke, and toxicity (FST) properties and good insulation properties. Nevertheless, the friability and inferior mechanical properties of PF have critically restricted its application in many fields. A series of phenolic foam/silica nanocomposites (MPF) with different silica contents were synthesized by in situ polymerization in this study. During the in situ polymerization process, the synthesis of phenolic resin/silica nanocomposites and formation of chemical bonding between the components were generated simultaneously. The reactive principle between silica nanoparticles and prepolymer was investigated using Fourier transform infrared spectroscopy (FTIR), and the results of FTIR indicated existence of the chemical reaction between them. Meanwhile, silica can act as “bridge” to form crosslinked network structure. The mechanical, thermal, and friability properties of MPF nanocomposites were characterized. Moreover, the results of microstructure of pure PF and MPFs indicated that the cell size distributions of MPFs are narrower, the cell distributions of MPFs are more uniform, and the cell wall thickness of MPFs is thicker, compared with pure PF. When the content of silica sol was 2 wt%, the compressive strength, compressive modulus, and tensile strength were increased by a factor of 47.37%, 38.55%, and 57.14% compared with that of pure PF, respectively. Furthermore, all MPF nanocomposites exhibited better thermal stability and lower pulverization ratio than that of pure PF. POLYM. ENG. SCI., 55:2783–2793, 2015. © 2015 Society of Plastics Engineers     

异氰酸酯/可发性酚醛树脂泡沫体的制备

采用端异氰酸酯聚醚预聚物与可发性酚醛树脂制备了新型泡沫体。通过ESI-MS光谱分析和泡沫物理力学性能测试研究了异氰酸酯基团与可发性酚醛树脂比例、异氰酸酯基团和三聚体相对含量、可发性酚醛树脂分子质量对泡沫体制备及性能的影响。结果表明:异氰酸酯基团与酚醛树脂质量比为40/100、三聚体质量分数17.33%、酚醛树脂聚合时间45min时,泡沫体的体积稳定性好,收缩率低;可发性酚醛树脂分子质量增加时,泡沫体的密度从60.16kg/m3增加到63.96kg/m3,基本保持稳定;其弯曲强度为0.2MPa,弯曲应变达到15%以上,远高于纯酚醛泡沫(6%)。在150℃下烘烤2h,泡沫体的质量损失为6%左右,体积变化为-5%左右。泡沫体的热稳定性优于聚氨酯泡沫,同时又有良好的韧性。     

Synthesis and characterization of phenolic resol resin blended with silica sol and PVA

The phenolic resol resin (PF) has a wide application in industry, but its poor tensile ductility and insufficient mechanical strength have severely limited its application. To overcome these limitations, in this study, the mixtures of silica sol and poly(vinyl acohol) (PVA) were used to modify the PF. The structure, morphology, mechanical properties, and thermal stability of these hybrid materials were investigated by FTIR, SEM, tensile shear test (TSS), and TG. FTIR spectra indicated that the multiple reactive functional silanol group Si OH on the surface of SiO₂ particles reacted with PVA and PF. Compared with pure PF, the composite 50‐50‐3% exhibited the maximum shear strength which increased by 158%, whereas the elongation at break increased by 63%. Morphological results agreed well with the mechanical properties. The TG results suggested that the composite material 50‐50‐3% and pure PF had almost the same thermal stability because silica sol and PVA had opposite effects on the heat resistance of the hybrid materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

EG阻燃热固性聚苯乙烯泡沫保温板的性能

以可发性聚苯乙烯(EPS)为基材,利用酚醛树脂(PF)作为包覆剂,可膨胀石墨(EG)作为阻燃剂,利用包覆法,制备了一种无卤环保、阻燃性能好、力学性能优良的热固性PS外墙泡沫保温板。研究了PF与EG对EPS保温板阻燃及力学性能的影响,探究了阻燃机理。结果表明,使用PF作为包覆剂制得的EPS/PF泡沫保温板力学性能尤其是压缩强度明显提高,当PF用量为90份时,LOI值可由18%提升至27.9%;阻燃剂EG的加入,使得保温板的阻燃性能及压缩性能进一步提高,当添加4份的EG时,保温板的压缩强度最高,LOI值达到了29.4%,垂直燃烧等级达到V–0级,残炭率由纯EPS的10%提高到50%。     

酚醛树脂/蒙脱土纳米复合材料的制备及其性能研究

利用原位聚合法制备了酚醛树脂/蒙脱土（PF/MMT）纳米复合材料,通过对其力学性能和电学性能的研究发现,当MMT含量为5 %（质量分数,下同）时,复合材料的综合性能最好,拉伸强度是未改性PF的2.33倍,体积电阻率提高了4个数量级,热失重速率最大时所对应的温度提高了15.24 ℃,线烧蚀率为未改性PF的80 %。并通过扫描电子显微镜对复合材料烧蚀面的观察,建立了耐烧蚀复合材料的烧蚀模型。     

蔗糖八乙酸酯改性酚醛树脂的研究

首次将蔗糖八乙酸酯(SOA)引入到酚醛树脂(PF)体系中,并采用傅里叶红外光谱(FT-IR)、差示扫描量热法(DSC)、热重分析(TGA)和扫描电镜(SEM)等对改性PF的性能进行了表征。结果表明:当w(SOA)≤9.1%时,PF的热分解温度和800℃时的残炭率都有所提高;加入SOA后,PF的固化温度提高,并且由一步固化转变为二步固化;SOA与PF具有良好的相容性,可以有效抑制树脂固化中产生的气泡,有利于降低材料的内部缺陷;当w(SOA)≈7%时,玻璃纤维增强SOA改性PF复合材料的冲击强度提高了9.5%。     

Preparation and characterisation of phenolic foam/HTAB-ATP nanocomposites

Abstract

Attapulgite (ATP), which was modified with hexadecyl trimethyl ammonium bromide (HTAB), was introduced into phenolic foam (PF), and HTAB modified ATP (HTAB-ATP) reinforced PF nanocomposites (PF/HTAB-ATP nanocomposites) were first synthesised. The HTAB-ATP was well dispersed in phenolic resin, and a simultaneously good compatibility between HTAB-ATP and phenolic resin was observed. Compared with neat PF, PF/HTAB-ATP nanocomposites exhibited improved compressive properties, including compressive strength and modulus, and this could be ascribed to the finer cell structure and higher curing degree of PF/HTAB-ATP, which were verified by SEM and DSC. Besides, HTAB-ATP improved the friability of PF. What is more, thermogravimetric analysis indicated that thermal stability of PF/HTAB-ATP was improved, and initial weight loss temperature increased by ～30°C at the loading of 1 wt-%HTAB-ATP.     

Bio‐oil from whole‐tree feedstock in resol‐type phenolic resins

Renewable chemicals are of growing importance in terms of opportunities for environmental concerns over fossil‐based chemicals. Lignocellulosic biomass can be converted into energy and chemicals via thermal and biological processes. Among all the transformation processes available, fast pyrolysis is the only one to produce a high yield of a liquid‐phase product called bio‐oil or pyrolysis oil. Bio‐oil is considered to be a promising substitute for phenol in phenol formaldehyde (PF) resin synthesis. In this work, bio‐based phenolic resins have been formulated, partially substituting phenol by bio‐oils from two Canadian whole‐tree species. The new resins are produced by replacing 25, 50, and 75% of phenol with bio‐oil for each species (three bioresins per species). The aim of this study is to synthesize renewable resins with competitive price and satisfactory quality. The results obtained have shown that substitution degree up to 50% provided reactivity and performance equal or superior to the pure PF resin. They also present a good storage stability, improved shear strength, and thermal stability comparable to the pure PF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40014.