耐高温邻苯二甲腈树脂研究进展

邻苯二甲腈树脂是以邻苯二甲腈结构封端的高性能耐高温热固性树脂,具有优异的热氧稳定性、阻燃性、力学强度、低吸水率、低热膨胀系数和介电常数,可用于制备先进复合基体材料、涂料、粘接剂等,在航空技术、电子、机械、军事等领域得到广泛应用.本文综述了邻苯二甲腈树脂结构、邻苯二甲腈单体类型、邻苯二甲腈的固化剂、自催化邻苯二甲腈、生物...     

钇掺杂锆酸钡中空微球的发光性能

采用水热法合成了不同钇掺杂量的BaZrO3中空微球,并通过TEM,XRD和SEM等手段对样品进行了表征.结果表明,样品均为中空微球,钇掺杂进入BaZrO3晶格,产物均具有立方钙钛矿型结构.中空微球的粒径随钇掺杂量的增加由180 nm增大到300 nm.钇掺杂量小于3%时,可得到纯相.不同掺杂量的中空微球在410 nm光...     

中空TiO_2微球的制备及对聚丙烯酸酯薄膜性能的影响

采用阳离子聚苯乙烯微球作为模板,钛酸四丁酯为钛源,氨水为催化剂,制备了中空TiO_2微球.采用X射线衍射、扫描电镜及比表面测定仪对其形貌和结构进行了表征,并考察了模板粒径、钛源用量以及催化剂用量对中空TiO_2微球形貌的影响.通过物理共混法将其引入至聚丙烯酸酯乳液中并成膜,研究了复合薄膜的保温性能、抗紫外性能及力学性能.结果表明,锐钛矿相中空TiO_2微球模板粒径、钛源用量以及催化剂用量影响中空TiO_2微球的空心尺寸、壁厚及壳层致密性.中空TiO_2微球可显著提升聚丙烯酸酯薄膜的保温性能、抗紫外性能和力学性能.采用不同粒径的模板制备的中空TiO_2微球对复合薄膜的各项性能均有影响,其中模板粒径为140 nm时复合薄膜性能最优,光反射率提升63%,导热系数降低27%,且在波长小于360 nm范围内,紫外透过率几乎为0,抗张强度增加100%,断裂伸长率提升62%.     

乙酸基和羟基对固化的环氧树脂吸水性能的影响

应用称重法、差示扫描量热法和腐蚀测试法研究固化的环氧树脂的吸水行为。实验结果表明,该树脂中的羟基改为乙酸基后可降低树脂的饱和吸水率,并增大水在树脂中的扩散能力。邻甲酚环氧树脂用乙酸线型酚醛酯树脂固化后所得的树脂(EPA)在30℃时饱和吸水率为0.84%(质量分数),而用线型酚醛树脂固化所得的树脂(EP)的则为1.97%;水在EPA和EP中的扩散活化能分别为40和48kJ.mol^-1.这可归因于乙酸基中的甲基的憎水性,降低了吸水率,却因乙酸基的弱相互作用增强了链的柔顺性,而有利于水在链空间中的扩散。EPA涂层/金属铝界面的特殊结构降低了该界面的吸水率,从而提高了该涂层的防护性能。     

芳氧基取代酞菁锌的合成及光物理化学性质

合成得到3-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、4-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、3-联苯氧基邻苯二甲腈(C20H12N2O)及4-联苯氧基邻苯二甲腈(C20H12N2O)4种未见报导的取代邻苯二甲腈,以此为前躯体合成了四[α-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[β-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[α-(联苯氧基)]酞菁锌(C80H48N8O4Zn)和四[β-(联苯氧基)]酞菁锌(C80H48N8O4Zn)4种未见报导的芳氧基取代酞菁锌配合物。通过测定它们的紫外-可见吸收光谱、荧光发射光谱,获得其最大吸收波长及其摩尔消光系数、最大发射波长、荧光量子产率(ΦF)、单线态氧量子产率(ΦΔ)及光降解速率常数并与其类似物进行了比较,探讨了它们的光物理光化学性质的构效关系。研究结果表明四[α-(联苯氧基)]酞菁锌在红光区具有大的摩尔消光系数,且具有较高的ΦΔ,有望开发成为光动力治疗用光敏剂。     

含芳基均三嗪环耐高温低聚酰亚胺的合成与性能

通过调控聚合单体的摩尔配比,合成了一系列新型的不同分子链长度的邻苯二甲腈封端含二氮杂萘酮联苯结构低聚酰亚胺,通过FTIR、1H-NMR、WAXD和元素分析对其结构进行表征.以4,4′-二氨基二苯砜为催化剂,低聚物经常压下固化交联后,得到含芳基均三嗪环结构的热固性聚酰亚胺.低聚物表现了良好的溶解性能,可溶于N-甲基-2-...     

常温制备形貌可控中空羟基磷灰石的研究

利用锂钙硼玻璃(LCB)微球在磷酸盐溶液中的原位转化反应,在常温下制备中空的羟基磷灰石(HA)微球,研究了玻璃微球的组分、磷酸盐浸泡液的浓度及热处理等工艺参数对微球的形貌影响。研究结果表明,常温下反应得到的产物微球为晶型较好具有中空结构的羟基磷灰石,随着玻璃微球组分中CaO含量的升高,中空微球的球壁逐渐变厚,当CaO含量达到30%时,微球变为实心结构。磷酸盐溶液浓度较低时,中空微球的球壁容易形成层状结构。     

模板法制备聚苯乙烯/聚4-乙烯基吡啶功能微球

以工业化的聚苯乙烯中空微球为模板,利用种子乳液法合成了粒径均一的功能化中空聚苯乙烯/聚4-乙烯基吡啶(PS/P4VP)微球,改变制备条件可以控制功能基团4-乙烯基吡啶(4-VP)在聚苯乙烯微球表面的分布.合成的微球在水和有机溶剂如二氯甲烷、乙醇、乙腈等中有良好的分散性,并能促进油水体系混溶.     

反应诱导相分离法制备双马来酰亚胺树脂微球

从聚醚酰亚胺(PEI)/[双马来酰亚胺(BMI)单体+烯丙基双酚A(DBA)]共混体系出发,通过反应诱导相分离,制备了约3μm尺寸的、单分散的BMI树脂微球.用扫描电镜(SEM)观察BMI树脂微球的形态,用激光粒度仪(LPS)表征BMI树脂微球的粒度及其分布,差示扫描量热法(DSC)测试BMI树脂微球的Tg.研究结果表明:PEI和聚酯酰亚胺(PEsI)的主链结构对BMI树脂微球形态有很大影响;PEI-A的用量增加,BMI树脂微球粒径减小,且粒度分布呈不均匀-均匀-不均匀变化;BMI树脂微球的Tg为215~218℃,略低于纯BMI树脂的Tg(225℃).     

二氧化硅中空微球的制备及结构调控

在St9ber法制备间苯二酚甲醛树脂(RF)微球的过程中,向体系中添加柠檬酸可以促进微球长大.以RF微球为模板,并结合酸洗除模板的方法,制备了一系列表面具有树莓状结构的中空二氧化硅微球(h-SiO_2);固定柠檬酸的浓度,同时向体系中添加三氯化铁,所得h-SiO_2的尺寸随着三氯化铁加入量的增加而减小,且微球表面逐渐变得光滑.对比实验结果表明,三氯化铁的加入有助于RF模板的去除,有利于制备具有高比表面积的产物.采用这种方法还可以制备金纳米粒子负载的中空二氧化硅微球(Au@h-SiO_2),在硼氢化钠还原亚甲基蓝的反应中显示出良好的催化活性.     

Facile synthesis of a melt-spinnable polyborazine from asymmetric alkylaminoborazine

<正>A novel asymmetric alkylaminoborazine monomer,2-propylamino-4,6-bis(methylamino)borazine,was synthesized for the first time,and directly polymerized to give a melt-spinnable polyborazine(PBN).This asymmetric alkylaminoborazine was synthesized by an aminolysis reaction of 2,4,6-trichloroborazine(TCB) with different amines under mild conditions.This route turns out to be much cheaper and simpler than the conventional routes.The chemical composition,structure,molecular weights and ceramic yield were investigated by EA,FTIR,NMR,GPC and TG analysis.The PBN exhibits suitable rheological property for melt-spinning, which suggests that it is a potential precursor for BN fibers.     

Synthesis, morphology and properties of polydimethylsiloxane-modified allylated novolac/4,4′-bismaleimidodiphenylmethane

Polydimethylsiloxane was incorporated into the backbone of allylated novolac (AN) to improve the toughness of allylated novolac/4,4′-bismaleimidodiphenylmethane(AN/BDM). Polydimethylsiloxane-modified allylated novolac (PDMS-AN) was synthesized via the hydrosilylation reaction between the terminal Si-H groups of α,ω-hydrogen functional dimethylsiloxane oligomer (PDMS) and the allyl groups of allylated novolac resin (AN). The blend of PDMS-AN and 4,4′-bismaleimidodiphenylmethane (BDM) could undergo co-cure reaction at elevated temperatures, and the co-cure system was denoted PDMS-AN/BDM. PDMS-AN was characterized by Fourier transfer infrared (FTIR) spectroscopy, ¹H and ²⁹Si nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The curing behavior of PDMS-AN/BDM was evaluated by differential scanning calorimetry (DSC). The morphology of the cured resins was examined by scanning electron microscope (SEM) and dynamic mechanical analysis (DMA). The effects of the content and number-average molecular weight of the incorporated PDMS on the mechanical and thermal properties of PDMS-AN/BDM were investigated. The results indicated that the incorporation of PDMS could improve the impact toughness of AN/BDM.     

含环氧侧基酚酞聚芳醚酮的合成及其自固化

由3,3′-双(4-羟基苯基)苯并吡咯酮(HPP)和4,4′-二氟二苯酮经亲核缩聚合成聚芳醚酮(PEK-H),再经与环氧氯丙烷(ECH)的亲核取代反应,制得了一种含量可控的环氧侧基酚酞聚芳醚酮(PEK-HE)。 改变ECH的投料量,可调控环氧侧基在聚合物中的含量。 采用FTIR、1H NMR和TGA等技术对聚合物进行了结构表征与性能测试,并考察了经自固化后聚合物涂膜的性能。 涂膜热稳定性较固化前明显提高,5%热失重温度均在450 ℃以上。 涂膜具有优异的热性能和机械性能：耐温(350±20) ℃;冲击强度高于100 kg·cm。     

Introducing rigid pyrimidine ring to improve the mechanical properties and thermal‐oxidative stabilities of phthalonitrile resin

In this study, a novel phthalonitrile monomer containing pyrimidine ring, 4,6‐bis[3‐(3,4‐dicya‐ nophenoxy)phenoxy]pyrimidine (BCPM), was successfully synthesized by nucleophilic substitution reaction with resorcinol, 4,6‐dichloropyrimidine and 4‐nitrophthalonitrile. The BCPM monomer was cured by different temperature programs with 4‐(aminophenoxy)phthalonitrile (APPH) as catalyst to give the polymers. The molecular structures of the BCPM monomer and the polymers were investigated by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. Differential scanning calorimetric (DSC) analysis was performed to study the processability of the BCPM monomer, which showed a wide processing window of about 117°C. The mechanical properties and thermal‐oxidative stability of the polymer were characterized by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively, which indicated that the polymers exhibited excellent storage modulus, high glass transition temperature over 400°C, and outstanding thermal stability. The polymers also have low water absorption capacity and are suitable for humid environments.     

树状硅基大分子光引发剂的合成与表征

从Vogtle等[1]首次描述了“串级式”合成方法以来,以及Newkome[2]和Tomalia等[3]的重要贡献,具有完美的支化结构、高度对称且分子大小可精确控制的树状分子在当代化学领域中已经成为一个重要的研究方向,其新颖的结构,独特的性能吸引了众多科学工作者的兴趣[4,5].其中硅基树状分子,尤其是树状聚硅碳烷大分子由于具有可变的支化度、无论是动力学还是热力学上的高度稳定性的优点,以及Si—Cl、Si—H、Si—OH等基团的的存在使得易于根据不同的需要对树状大分子进一步功能化改性,已成为高分子领域的研究热点[6,7],例如树状硅碳烷液晶[8~10]、…     

Enhanced properties of phthalonitrile resins under lower curing temperature via complex curing agent

High curing temperature has been restricting the application and development of phthalonitrile resin. A complex curing agent containing melamine (ME) and ZnCl₂ was developed to promote the curing reaction of resorcinol‐based phthalonitrile resin (DPPH). The thermal stability of ME can be significantly enhanced via adding ZnCl₂, which was due to the interaction between ZnCl₂ and amino group in ME. Moreover, the activities of pristine ZnCl₂ and ME were improved via mixing, especially, the curing temperature for DPPH can be effectively reduced. Even at a curing temperature of 300°C, the 5% weight loss temperature of the resulting resin cured with complex curing agent still exceeded 500°C, which was much higher than those with pristine curing agents. In addition, the good long‐term oxidation stability and relatively low water absorption can also be obtained in the resins cured with novel curing agent. This work affords a facile route for designing high‐performance curing agent to improve the curing process of phthalonitrile resin.     

Synthesis and Characterization of a Novel Curing Agent for Epoxy Resin Based on Phosphazene Derivatives

In this work, a novel amine-terminated curing agent for epoxy resin based on hexachlorocyclotriphosphazene (HCCP) was synthesized through two steps of nucleophilic substitution reactions by phenol and 4-aminophenol. Its chemical structure was characterized by ¹H-NMR, Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). This curing agent was liquid at room temperature which made it easy to disperse in the epoxy resin. The rheological test showed the viscosity of the pre-polymer fluid decreased as the proportion of the curing agent increased so it improved the process performance. The curing reaction was studied by differential scanning calorimeter (DSC). The novel curing agent had a wider range of curing temperature and relatively lower curing temperature in comparison with the widely-using curing agent 4,4′-Diaminodiphenylmethane (DDM). The wider range of curing temperature helped lower the heat accumulation which was an important factor in curing process.     

Synthesis, characterization, and cure properties of phosphorus-containing epoxy resins for flame retardance

An organophosphorus compound, 10-(2,5-dihydroxyl phenyl)-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DHPDOPO), was synthesized through the reaction of 9,10-dihydro-9-oxa-10-phosphaphnanthrene-10-oxide (DOPO) and p-benzoquinone, and characterized by elemental analysis, Fourier transform infrared spectrum (FTIR), and ¹H-NMR and ³¹P-NMR spectroscopes. Consequently, the phosphorus-containing epoxy resins with phosphorus content of 1 and 2 wt.% were prepared via the reaction of diglycidyl ether of bisphenol-A with DHPDOPO and bisphenol-A, and confirmed with FTIR and gel permeation chromatography (GPC). Phenolic melamine, novolak, and dicyanodiamide (DICY) were used as curing agents to prepare the thermosetted resins with the control and the phosphorus-containing epoxy resins. Thermal properties and thermal degradation behaviors of these the thermosetted resins were investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Phenolic melamine-cured resins exhibited higher glass transition temperatures than the other cured resins due to the high rigidity of their molecular chain. TGA studies demonstrated that the decomposition temperatures of the novolak-cured resins were higher than those of the others. A synergistic effect from the combination of the phosphorus-containing epoxy resin and the nitrogen-containing curing agent can result in a great improvement of the flame retardance for their thermosetted resins.     

FTIR法研究乙酸酚醛酯固化邻甲酚环氧树脂的反应动力学

用ＦＴＩＲ原位测量技术研究了乙酸酚醛酯与邻甲酚环氧树脂在２－甲基咪唑存在下进行恒温固化反应的动力学，测定了固化反应的动力学参数，研究结果表明，固化反应是按照一级固化反应动力学进行的，根据羰基峰在固化反应前后的变化对固化反尖机理进行了初步探讨。     

Mechanism Studies on Water Sorption and Permeation in Epoxy Resin by Impedance Spectroscopy. II. Cure Kinetics of O-Cresol Novolac Resin with Esterfied Phenol Novolac Resin

Abstract

To study the effect of water affinity of the cured epoxy resin on water sorption and permeation in the cured epoxy resin, a novel hardener (esterfied phenol novolac was synthesized and used for obtaining the cured product without free hydroxyl group. Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) were used to study the cure kinetics of o-cresol novolac epoxy resin using esterfied phenol novolac resin as curing agent in the presence of 2-methylimidazole as accelerator. Some kinetic parameters of the curing reaction such as the reaction order, activation energy, and frequency factor were obtained in the temperature range studied. The results show that this curing process is a first-order kinetic mechanism, which was different with that cured with phenol novolac resin.