含氟双氨基邻苯二甲腈树脂合成及性能研究

采用2,2-双（3-氨基-4-羟基苯基）六氟丙烷和4-硝基邻苯二甲腈为原料,通过亲核取代反应制备了一种含氟元素的双氨基邻苯二甲腈树脂（FPN-p）。通过傅里叶红外光谱（FT-IR）和核磁氢谱（1H-NMR）对其化学结构进行表征,通过差示扫描量热法（DSC）和FT-IR考察了树脂的固化行为,并研究了树脂的热稳定性、热机械性能以及耐湿热性能。研究结果表明：FPN-p树脂在不加促进剂的情况下可实现自催化聚合,产物结构以三嗪环和酞菁环为主;树脂的玻璃化转变温度和质量分数5%热分解温度均超过400℃,耐温等级较高;树脂的耐湿热性能良好,高温水煮168 h后吸水率小于1%。该树脂有望用于耐高温涂层、树脂基复合材料以及高性能胶粘剂等领域。     

聚芳醚腈改性双邻苯二甲腈树脂及其玻纤复合材料制备

采用聚芳醚腈(PEN)对双邻苯二甲腈树脂(BPH)进行改性,并采用熔融共混粉末法制备PEN/BPH/玻纤复合材料。研究了PEN/BPH树脂体系的反应特性和流变行为,对PEN/BPH/玻纤复合材料的力学性能以及耐热性进行了表征。结果表明:随着PEN用量的增加,PEN/BPH树脂体系的固化反应速率有所提升,而且PEN的引入没有引起BPH耐热性的降低;当PEN的质量分数为10%时,复合材料的力学性能得到了有效的提升。     

含二茂铁的双邻苯二甲腈-苯并恶嗪树脂的合成

以联苯二酚,4-氨基苯氧基邻苯二甲腈,二茂铁甲醛为原料,采用缩聚反应制备了含二茂铁的双邻苯二甲腈-苯并恶嗪树脂(FPNBZ)。通过核磁共振(1HNMR,13CNMR)、红外光谱(FTIR)、DSC、TGA对合成的含二茂铁的双邻苯二甲腈-苯并恶嗪单体的结构、热行为及固化物(FPNBZR)的热性能进行了研究。结果表明,FPNBZ的加工温度窗较宽,达到74℃,FPNBZR具有较好的耐热性,初始分解温度为353.38℃,600℃残重达到45%。     

含芳醚腈链段的双邻苯二甲腈树脂的合成与性能

合成了一系列含芳醚腈链段的双邻苯二甲腈,以2,6-二-4-氨基苯氧基苯甲腈为交联剂获得了相应的预聚树脂。采用FTIR,1H NMR和13C NMR对合成的双邻苯二甲腈的结构进行了表征,并通过DSC及TGA分析研究了预聚物的固化性能和耐热性。结果表明,该类树脂熔融流动温度在60℃左右,固化反应温度在220℃左右,加工温度范围得以有效提高。其固化物在空气和氮气气氛下的起始分解温度均高于460℃,表明固化物具有较高的热稳定性和热氧稳定性。     

固化工艺对双酚AF型邻苯二甲腈树脂性能的影响

采用六氟双酚A(BPF)和4-硝基邻苯二甲腈为原料,通过亲核取代反应制备了一种双酚AF型邻苯二甲腈树脂(AFPN)。通过傅里叶红外光谱(FT-IR)、核磁氢谱(1H-NMR)、时间飞行质谱(TOF-MS)对其化学结构进行表征。考察了不同固化工艺对AFPN热稳定性、热机械性能和粘接性能的影响。研究结果表明：AFPN的熔点为230℃,1,3-双(3-氨基苯氧基)苯(TPE-M)可以加速其聚合过程;当固化温度为375℃时,AFPN聚合物质量分数为5%时的热分解温度(T_5%)为501℃,T_10%为522℃,玻璃化转变温度(T_g)为327℃;AFPN树脂具有较好的阻燃性能和高温粘接性能以及潜在的应用前景。     

新型耐高温材料-酞腈树脂

酞菁树脂是一种新型结构树脂,具有优异的高温力学性能、热氧稳定性。对由美国海军研究室研制的系列酞菁树脂做出了概述：首先综述了具有多种桥链结构的酞菁树脂的类型,包括单体的结构、合成方法、树脂的耐热能力;然后探讨了树脂的固化机理、固化剂的类型、特点;最后,介绍了树脂的应用领域,包括热熔胶、与环氧树脂组成混合物、纤维增强材料,指出我国科研工作者制备出具有独立知识产权的新型的双邻苯二甲腈单体至关重要,且应拓宽树脂在耐高温领域的应用范围。     

POSS改性邻苯二甲腈树脂制备及性能

为探究不同结构笼型聚倍半硅氧烷(POSS)对邻苯二甲腈(PN)树脂综合性能的影响,以PN树脂为基体,分别添加了三硅烷醇苯基POSS、氨基丙基异丁基POSS、缩水甘油基异丁基POSS、三硅醇异丁基POSS及环氧环己基异丁基POSS 5种POSS,利用溶液共混法制备了改性PN浇铸体试样,并制备了PN/石英布复合材料。开展了热重分析、动态热机械分析、透波率测试、介电性能测试等多种试验,研究了不同结构POSS对PN树脂热稳定性以及复合材料透波性能和介电性能的影响。结果表明,POSS的引入提升了PN树脂的耐热性能及热分解起始温度,同时,POSS的引入提高了PN树脂的玻璃化转变温度,提高了材料的可用温度范围,也提升了PN复合材料在12～18 GHz及26.5～40GHz两个波段下的透波性能。除环氧环己基异丁基POSS使PN复合材料的介电损耗有所增大外,其余4种POSS对复合材料的介电性能影响较小。综合分析5种改性后的试样表明,使用三硅醇异丁基POSS改性的PN树脂及复合材料具有最优的综合性能。该改性PN复合材料在12～18 GHZ频率下的平均透波率可达74.21%,在26.5～40 GHz频率下的...     

高耐热聚芳醚酮固化邻苯二甲腈树脂

以4-(4-羟基苯基)-2,3-二氮杂萘-1-酮、4,4’-二氟二苯甲酮和4-氨基苯酚为原料，通过两步一锅法合成了一种新型的氨基封端杂萘联苯聚芳醚酮(A-PPEK)，采用差示扫描量热法(DSC)探究了其对间苯二酚基邻苯二甲腈(DPPH)的固化性能。相比于常用的芳香二胺固化剂4,4’-二氨基二苯砜(DDS),A-PPEK的5%热失重温度(T_d5%)提高了69.3℃。另外，与DDS在400℃时快速升华不同，A-PPEK在相同温度下的质量保留率仍>95%，说明A-PPEK可以有效解决小分子固化剂高温下分解，容易在邻苯二甲腈树脂中形成缺陷的问题。一系列实验表明，以A-PPEK固化DPPH，体系具有优异的耐热性和加工流动性，当A-PPEK含量为DPPH质量的10%时，固化树脂的T_d5%可达553.2℃，玻璃化转变温度高于实验测试范围380℃，最低黏度可达0.167 Pa·s。     

聚邻苯二甲腈树脂研究进展

介绍了聚邻苯二甲腈树脂(PN)的热聚合行为和机理,加工特性,综述了近年来在其热性能,力学性能,吸水性,导电性研究及树脂改性、应用开发方面的进展,并指出了该树脂未来的研究方向。     

含苯并恶嗪单元的双邻苯二甲腈树脂的粘接性能

采用含苯并恶嗪单元的双邻苯二甲腈树脂(BZ-BPH)粘接经过处理表面为新鲜铝合金层及氧化物的铝合金基片,对粘接样的室温及高温热处理后(400℃,30 min)的拉伸性能进行了测试并采用SEM观察了断面的形貌。以上述表面不同的2种铝合金粉体为模型,采用差热扫描(DSC)研究了不同界面对BZ-BPH固化反应的影响。研究结果表明,表面为氧化物的试片室温力学性能远大于表面为铝合金的试片;经过高温热处理后,后者的拉伸剪切强度有较大提高,而前者稍有降低,这表明BZ-BPH具有较好的高温粘接性能。     

氰酸酯树脂及其胶粘剂（续）

５　改性氰酸酯树脂氰酸酯树脂与其他热固性树脂相比虽然具有较好的韧性,但如作为结构用复合材料和胶粘剂的基体,仍然较脆。与其他热固性树脂的增韧相似,它可采用热塑性塑料（ＴＰ）和橡胶增韧。这类增韧改性氰酸酯树脂许多已商品化。另一类是氰酸酯分别与环氧、ＢＭＩ共混改性,以达到取长补短的目的。这２种共混树脂也已商品化。５．１　ＴＰ增韧氰酸酯氰酸酯树脂可与许多无定形的ＴＰ共混。固化后形成半互穿网络（Ｓｅｍｉ－ＩＰＮ）［１５,１６］。所用ＴＰ主要有：聚砜（ＰＳＵ）、聚醚砜（ＰＥＳ）、聚醚砜亚胺（ＰＥＩ）和聚碳酸…     

Preparation,Acid Curing,and Thermal Stability of Various Formulated Phenolic Resole Resins: Unfilled and Nanocomposites

Several phenol-formaldehyde resole resins were prepared with variety in monomers ratio, catalyst type, and content, having different nanoclay levels; then they were cured using various acids in the wide range of concentration. The acid-curing process was studied, considering gel time (t_G) and cure time (t_C). In addition, the thermal stability was investigated before and after cure for all samples. With increasing F/P ratio, t_G, t_C and t_G-t_C decreased and also C_C (critical concentration). By using more catalyst in the synthesizing step, the curing was done more rapidly in the order of NaOH, Ba(OH)₂ and NH₃. Stronger acids having smaller pK_a made a more realizable cure. However, the weak boric acid had no curing effect. Nanocomposites had shorter t_G and t_C, mainly at lower acid concentration. The structure peak of nanoclay shifted to the lower angles in nanocomposites, especially in the cured state. Crosslinked samples had higher degradation temperature (T_D) and lower weight decrease (Δ_w) related to the primary resoles. For uncured resins, thermal stability increased with decreasing of F/P ratio, and the inverse effect was found for the cured resins. Resins cured with HCL had higher T_D and lower Δ_w. However, at 30% concentration the sample cured by H₂SO₄ was more stable. With increasing catalyst amount and reactivity, T_D increased and Δ_w decreased. In all acid concentrations, at the presence of nanoclay the better thermal resistance was observed. T_D increased and Δ_w decreased as the nanoclay level increased.     

Improving the curing process and thermal stability of phthalonitrile resin via novel mixed curing agents

High curing temperature (including post‐curing temperature) and long curing time of phthalonitrile resins make them thermally stable but difficult to process. In this paper, novel mixed curing agents (CuCl/4,4′‐diaminodiphenylsulfone (DDS) and ZnCl₂/DDS) were firstly designed for solving these problems. Bisphenol‐based phthalonitrile monomer (BP‐Ph; melting point: 228–235 °C) was synthesized and used as the curing precursor. Differential scanning calorimetry results indicated that BP‐Ph cured with CuCl/DDS and ZnCl₂/DDS exhibited curing temperatures close to the melting point of BP‐Ph with curing ending temperatures of 225.4 and 287.1 °C, respectively. Rheologic investigations demonstrated obvious curing reactions of BP‐Ph occurred with the mixed curing agents at 220 °C. Thermogravimetric analysis showed that BP‐Ph cured by CuCl/DDS or ZnCl₂/DDS maintained 95% mass at 573 or 546 °C, respectively, at a post‐curing temperature of 350 °C for 2 h. Reasonable long‐term thermo‐oxidative stability was also demonstrated. When the post‐curing temperature decreased to 290 °C, char yield at 800 °C of BP‐Ph cured by CuCl/DDS was 77.0%, suggesting the curing procedure can be milder when using mixed curing agents. © 2017 Society of Chemical Industry     

Thermal Stability and Mechanical Properties of Organo-Soluble and Processable Polyimides for High-Temperature Materials

A new series of organo-soluble polyimides with pendant groups of methoxy or methyl of azomethine diamine were synthesized through two-step process by chemical imidization. Such polyimides were tested for thermal and mechanical properties. Their thermal stability was studied in terms of temperature at 10% weight loss which ranged between 475 and 498°C with T_g around 240–278°C. Activation energy, enthalpy of the polyimides were calculated and ranged 31.12–43.59?kJmol^?1 and 29.46–41.93?kJmol^?1. Thermal, mechanical, and thermodynamic parameters demonstrated that the resulting polyimides can hold excellent application in the fields of high-performance, advanced composites, and high-temperature microelectronics.     

双酚A型双邻苯二甲腈/酚醛树脂共混体系研究

双酚A型双邻苯二甲腈(BAPh)与酚醛树脂(novolac)通过熔融共混形成了预聚物(BAPh/novolac),经后续热处理制备了BAPh/novolac固化物。通过DSC,FTIR,TGA及流变性能测试研究了该共混体系的固化反应特性,固化物的热稳定性和热氧化稳定性。结果表明:该共混体系可以在无外加固化剂的条件下进行固化反应,固化物的玻璃化转变温度(Tg)达241℃。其固化物在空气和N2气氛中的起始分解温度为380～449℃,且在氮气下800℃残炭率达71%,表现出良好的热稳定性和热氧稳定性。     

Copolymerization modification: improving the processability and thermal properties of phthalonitrile resins with novel comonomers

Two novel tetrahydrophthalic anhydride end‐capped imide compounds (THAN and THBN) with high thermal stability were synthesized to promote the curing reaction of 1,3‐bis(3,4‐dicyanophenoxy)benzene (3BOCN), and to study the effects of comonomer structure on the curing behavior and thermal performance of phthalonitrile resins. The curing behaviors of THAN/3BOCN and THBN/3BOCN blends with various molar ratios were investigated using rheological analysis and differential scanning calorimetry, suggesting a wide processing window. Dynamic mechanical analysis and thermogravimetric analysis showed that the cured resins possessed high glass transition temperatures (> 500 °C), and superior thermal and long‐term thermo‐oxidative stabilities with weight retention of 95% ranging from about 544 to 558 °C in both nitrogen and air. All these results indicated that the processability and thermal properties of phthalonitrile resins could be improved further by modifying the structure of comonomer in this kind of curing system. © 2018 Society of Chemical Industry     

Thermal study on the copolymers of phthalonitrile and phenylnitrile‐functional benzoxazines

Ortho‐, meta‐, and para‐phenylnitrile–functional benzoxazines are polymerized at different compositions with phthalonitrile‐functional monomers providing copolybenzoxazines of high thermal stability and easy processability. The most positive effect on these properties is obtained on copolymerizing phthalonitrile‐ and ortho‐phenylnitrile–functional benzoxazines. Thermal decomposition of these polybenzoxazines is studied by thermogravimetry (TGA). It is demonstrated that only 30 mol % of phthalonitrile‐functional benzoxazine added to the ortho‐phenylnitrile–substituted monomer improves char yield significantly from 59 to 77 wt %, which is the value of neat phthalonitrile‐based polybenzoxazine. Glass transition temperature (T_g) also dramatically increases from 180°C for neat ortho‐phenylnitrile polymer to 294°C for the copolymer with 30 mol % of phthalonitrile‐functional monomer. Additionally, the high melt viscosity of phthalonitrile‐functional benzoxazines is dramatically decreased upon blending with phenylnitrile‐functional monomer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2937–2949, 1999     

有机硅改性环氧树脂的合成与性能

热熔法制备了系列聚甲基苯基硅氧烷(PMPS)改性环氧树脂,通过环氧值、红外光谱(IR)和凝胶色谱(GPC)分析表明,有机硅接枝到了环氧树脂上,且环氧基保持不变。探讨了改性方法、有机硅含量对改性树脂固化体系的微观形态、韧性及耐热性的影响。实验表明,当m(E-20)∶m(DC-3074)=7∶3时,化学改性树脂固化体系的韧性和耐热性能明显提高,玻璃化转变温度(Tg)为88.33℃,质量损失50%时的热分解温度(Td)为487.80℃,分别比物理改性环氧树脂提高了52.63℃和36.75℃,同时此改性树脂固化物还具有优良的涂膜性能。     

Curing Kinetics of Liquid Crystalline Epoxy Resins Based on Bisphenol-S Mesogen with DDE by Nonisothermal DSC Data

The curing kinetics for a system of Sulfonyl bis(4,1-phenylene)bis[4-(2,3-epoxypro pyloxy)benzoate] (p-SBPEPB) with 4,4′-diaminodiphenyl ether (DDE) were investigated by nonisothermal differential scanning calorimetry (DSC). The dependencies of the apparent activation energy Ea and the conversion α during overall curing reaction were revealed by Ozawa's method. The results shown the Ea decreased drastially from 107 to 75 KJ/mol with α in the initial stages (α = 0–20%), the average apparent activation energy Ea of p-SBPEPB/DDE is 82.81 KJ/mol and was relatively constant in the 0.5 to 0.9 conversion interval. Some parameters were evaluated using the two kinetic models of ?esták–Berggren (S-B) equation and JMA model. The liquid crystalline (LC) phase had formed and was fixed in the system during the curing process.     

Synthesis,Characterization, and Antimicrobial Properties of p-Chloroacetophenone Oxime-Based Furan Resins

A copolymer resin, p-chloroacetophenone oxime-furfuraldehyde (CAOFU), and a terpolymer resin, p-chloroacetophenone oxime-formaldehyde-benzoic acid (CAOFUBA), were synthesized in the presence of hydrochloric acid as catalyst. The structures of copolymer and terpolymer were established by FT-IR and ¹H NMR techniques. Molecular weight and polydispersity index were determined by gel permeation chromatography. The thermal stability was evaluated by thermogravimetric analyses (TGA). Softening temperatures (T_s) of these polymers were obtained from differential scanning calorimetry (DSC). All the synthesized polymers have shown reasonably good antimicrobial activities.