双马来酰亚胺—三嗪树脂改性研究进展

综述了国内外对双马来酰亚胺–三嗪树脂(BT树脂)改性的研究进展,包括新型结构单体共混改性,烯丙基化合物改性、环氧树脂改性、苯并噁嗪改性、聚苯醚改性和无机填料改性等。指出BT树脂在航空、航天及电子工业领域有很大的应用前景,应加速BT树脂的工业化进程,以满足高性能复合材料的需求。     

烯丙基双酚A改性双马来酰亚胺-三嗪树脂的热性能

以4,4′-二苯甲烷双马来酰亚胺、双酚A型氰酸酯和2,2-二烯丙基双酚A为基本原料制备了改性双马来酰亚胺-三嗪（BT）树脂。系统地研究了2,2-二烯丙基双酚A对BT树脂固化动力学、BT树脂的溶解性能和BT树脂固化物的热性能的影响。研究结果表明：烯丙基双酚A有效地降低了BT树脂的固化反应温度并提高了BT树脂的溶解性能。当烯丙基双酚A的加入量为20%（质量分数）时,BT树脂的固化反应峰值降至233.1 ℃;并且,其固化物的玻璃化转变温度仍然达到239.4 ℃,5%热失重温度为372.9 ℃,显示了良好的耐热性能。     

烯丙基化合物改性双马来酰亚胺

介绍了烯丙基化合物改性双马来酰亚胺树脂(BMI)的反应机理,综述了二烯丙基双酚A、含硼烯丙基化合物、烯丙基醚、烯丙基酚氧树脂等改性BMI体系的研究进展。     

烯丙基苯并恶嗪改性BT树脂的研究

采用熔融缩聚法合成了烯丙基苯并恶嗪(Boz-allyl),并利用傅立叶变换红外光谱,磁共振氢谱对其表征。用动态扫描量热与热重分析研究了其固化过程及热性能,随后用其对双马来酰亚胺–三嗪树脂(BT树脂)改性,并分析了改性树脂的力学性能。结果表明,Boz-allyl存在两种固化机理,固化物5%和10%热失重温度分别为325,385℃,在800℃时质量保持率仍可达34%,说明其具有优良的热稳定性和耐烧蚀性,用其改性后BT树脂韧性明显提高,当Boz-allyl质量分数为8%时冲击和弯曲强度达到最大值,分别为11.32 kJ/m2和127.11 MPa。     

缠绕用无溶剂低温固化双马来酰亚胺树脂体系

在乙烯基苄基化合物改性双马来酰亚胺树脂体系中添加烯丙基苯酚活性稀释剂,得到了粘度小于1000 mPa·s,加工适用期大于8 h,在150～155℃完成固化与后固化、适用于缠绕成型工艺的树脂体系。增韧改性后,该树脂的玻璃化转变温度达到261℃,拉伸强度和弯曲强度分别为73 MPa和133 MPa。     

DAIP改性双马来酰亚胺三嗪树脂的性能研究

本文采用间苯二甲酸二烯丙酯(DAIP)和二烯丙基双酚A(DBA)对双马来酰亚胺三嗪树脂(BT)进行改性,制得了一系列改性BT树脂.研究了改性BT树脂的工艺性及其浇铸体的力学性能、热性能和介电性能.结果表明,经DAIP改性后的BT树脂粘度降低,工艺性更佳,浇铸体的拉伸强度和玻璃化转变温度(Tg)均有所提高,介电常数(ε)也稍有减小,且ε有良好的热稳定性;另外,动态热机械分析(DMA)曲线仅显示单个损耗峰,表明DAIP与BT树脂体系有良好的相容性.     

双马来酰亚胺/氰酸酯共固化树脂的研究进展

介绍了双马来酰亚胺/氰酸酯(BMI/CE)树脂的固化机制及其应用范围,特别综述了BMI/CE树脂的改性研究(如新型结构树脂单体改性、环氧树脂改性、烯丙基化合物改性和聚苯醚改性等)。最后对BMI/CE树脂今后的研究与发展方向进行了展望。     

烯丙基化合物改性双马来酰亚胺树脂的研究进展

双马来酰亚胺(BMI)树脂以其优异的机械和热稳定性能广泛用于航空航天等领域,但纯BMI熔点高、韧性和溶解性差,不能满足实际使用要求,必须对其进行改性。探讨了烯丙基化合物改性BMI的反应机理,包括"Ene"反应、Diels-Alder反应以及体系中可能存在的其他反应;并分别概述了二烯丙基双酚A(DABPA)、含硼烯丙基化合物、烯丙基酚醛树脂、烯丙基酚氧树脂及其他烯丙基化合物改性BMI体系的研究进展和改性效果。     

烯丙基酚醛改性双马来酰亚胺树脂的制备与性能

合成并表征了烯丙基酚醛树脂,再将其与双马来酰亚胺共聚制备了烯丙基酚醛改性双马树脂。通过DSC和FTIR分析了该树脂的固化行为,研究了其工艺性,利用TGA和DMA评价了其固化物的耐热性。结果表明,烯丙基酚醛树脂改性双马树脂可用于RTM等成型工艺,其固化物Tg约为330℃,初始热分解温度约400℃,5%失重温度达410℃,10%失重温度423℃。该树脂耐热性优异,可用作耐高温先进复合材料的基体树脂。     

烯丙基化合物对双马来酰亚胺树脂的改性研究

为了得到综合性能更好的双马来酰亚胺(BMI)树脂,本文以二烯丙基双酚A(BA)和二烯丙基双酚S(BS)为共改性剂,对BMI树脂进行了改性,考察了共改性剂配比、固化后处理时间对改性BMI树脂体系的影响.采用动态力学分析(DMA)对改性后的BMl树脂浇铸体的热性能进行了初步分析.结果表明,BA/BS(摩尔比)为7/3的浇铸体的玻璃化转变温度(Tg)高达349.5℃,延长固化后处理时间可使浇铸体的Tg大幅提高.     

Thermal and dielectric properties of bismaleimide‐triazine resins containing octa(maleimidophenyl)silsesquioxane

Octa(maleimidophenyl)silsesquioxane (OMPS) was synthesized, characterized, and employed to modify the BT resin which composed of 4,4′‐bismaleimidodiphenylmethane (BMI) and 2,2′‐bis(4‐cyanatophenyl)propane (BCE). The curing reaction between OMPS and BT resin was first investigated. It was found that OMPS accelerate the curing reaction of BCE, and the onset temperature of the cyclotrimerization was reduced up to 95.5°C (by DSC). As demonstrated by DSC and FTIR, there was no evidence that indicated the coreaction between maleimide and cyanate ester. 2,2′‐diallyl bisphenol A (DBA) and diglycidyl ether of bisphenol A (E‐51) (Wuxi Resin Factory, Jiangsu Province, China) were also used to enhance the toughness of BT resin, and the formulated BTA (containing DBA) and BTE (containing E‐51) resins were obtained. The thermal properties of BT, BTA, and BTE resins incorporated with OMPS were then investigated. The results of DMA and TG showed that the BT, BTA, and BTE resins containing 1 wt % of OMPS exhibit enhanced thermal properties in comparison with their pristine resins respectively, while more contents of OMPS may impair the thermal properties of the polymer matrix, though the effect of OMPS was slight. Finally, the dielectric constant of these hybrid materials were detected, and their dielectric constant were distinctly reduced by the incorporation of OMPS, while overmuch contents of OMPS were disadvantageous for dielectric constant because of the aggregation of OMPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

E-51环氧树脂改性双酚A型氰酸酯树脂的研究

采用示差扫描量热法(DSC)、傅里叶变换红外光谱(FTIR)研究了E-51环氧树脂改性双酚A型氰酸酯树脂(BADCy)体系的反应活性、反应机理及固化工艺,通过TGA分析了不同含量E-51环氧树脂改性BADCy后固化物的热性能,并测定了体系的吸水率及力学性能。结果表明,随着E-51环氧树脂用量的增加,BADCy改性体系的反应活性逐渐提高,固化温度逐渐降低;用环氧树脂改性BADCy生成了恶唑烷酮等芳杂环结构,降低了氰酸酯树脂体系的三嗪环交联密度,增加了体系的韧性;改性后材料的起始热分解温度均在380℃以上,吸水率均低于2%。     

Investigation of the curing mechanism and properties of bismaleimide-triazine resins containing phenolphthalein and cyano group

A series of bismaleimide-triazine (BT) resins with and without O, O′-diallyl bisphenol A (DABPA) were produced by mixing 2, 2-bis (4-cyanatophenyl) propane (BADCy) and MCBMI (2,6-bis(4-(1-(4-(4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)phenoxy)-3-methylphenyl)-3-oxo-1,3-dihydroisobenzofuran-1-yl)-2-methylphenoxy)benzonitrile). The resins show just one glass-transition temperature (T _g) and enhanced flexural properties as well as superior fracture toughness compared with commercial BDM/BADCy system, in which BDM is (N,N′-bismaleimido-4,4′-diphenylmethane). Introduction of DABPA can decrease the curing temperature of bismaleimide-triazine (BT) resins but increase its impact strength. When the mole of DABPA reach up to 1.2, the impact strength was increased by 1.34 times in comparison with BDM/ BADCy system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 136, 47420.     

Cyanate ester resin modified by hydroxyl‐terminated polybutadiene: Morphology,thermal, and mechanical properties

Hydroxyl‐terminated polybutadiene (HTPB) rubber was used as a modifier for bisphenol A dicyanate ester (BADCy) to improve its toughness. The effect of catalyst on the curing behavior of the resin and the curing techniques were developed by differential scanning calorimetry. The dynamic mechanical analysis, thermogravimetry analysis, and tensile test were used to study the thermal behavior, mechanical properties, and dynamic mechanical performance of the modified BADCy resins. Results show that addition of HTPB resulted in improved toughness while maintaining relatively good thermal stability. Additional, phase separation phenomenon was confirmed by the analysis of scanning electron microscope. For the toughening of the resin, the main toughening mechanism is shear yielding and crack branching. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of the epoxy molecular weight on the properties of a cyanate ester/epoxy resin system

Bisphenol A dicyanate (BADCy) was modified by diglycidyl ether of bisphenol A epoxy resins with different molecular weights [E20 (weight‐average molecular weight = 1000) and E51 (weight‐average molecular weight = 400)] to investigate the effects of the epoxy molecular weight on the properties of the modified systems. The reactions were monitored with differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy, and the results showed that more pentacyclic oxazolidinone rings were formed in BADCy/E51 than in BADCy/E20 with the same epoxy resin weight content. DSC showed that BADCy/E20 had a lower curing temperature than BADCy/E51 because of the higher concentration of hydroxyl groups (? OH) in E20. Thermal, moisture absorption, and mechanical testing showed that E51‐modified BADCy performed better because of its lower molecular weight. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1744–1750, 2006     

环氧化端羟基聚丁二烯改性氰酸酯树脂体系研究

采用环氧化端羟基聚丁二烯(EHTPB)对双酚A型二氰酸酯树脂(BADCy)进行增韧改性。运用差示扫描量热法分析改性体系的反应性,发现EHTPB对BADCy的固化反应有一定的催化作用。采用傅立叶变换红外光谱仪、扫描电子显微镜和广角X射线衍射仪等表征共混物的结构特征,研究增韧改性机理,并对固化产物进行热重分析和力学性能测试。结果表明,EHTPB能在不显著降低体系热稳定性的同时改善体系的韧性,使得改性树脂具有较好的综合性能。     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

改性氰酸酯类耐高温胶粘剂的研究

以双马来酰亚胺(BMI)、双酚A型氰酸酯(BADCy)和苯并噁嗪(BOZ)树脂为基体树脂,纳米二氧化硅(nano-SiO2)为填料,制备耐高温胶粘剂。采用非等温差示扫描量热(DSC)法、Kissinger法和Ozawa法研究了nano-SiO2/BOZ/BMI/BADCy共聚物的固化动力学过程。结果表明:当m(BOZ)∶m(BMI)∶m(BADCy)=1∶1∶2、w(nano-SiO2)=3%时,相应BOZ/BMI/BADCy胶粘剂的表观活化能(47.82 kJ/mol)低于无nano-SiO2体系(59.17 kJ/mol),并具有良好的耐高温性能;在250℃时用该胶粘剂胶接硅钢片,胶接件经250℃老化1 000 h后,其剪切强度仍保持稳定。     

A novel cyanate ester resin/microcapsules system

Poly(urea‐formaldehyde) microcapsules filled with epoxy resins(MCEs) were applied to bisphenol A dicyanate ester (BADCy) resin to develop a novel BADCy/MCEs system. The effects of MCEs on the viscosity and the reactivity of BADCy were investigated. The mechanical properties and the hot water resistance of cured BADCy/MCEs systems were evaluated. The morphologies of the cured systems were characterized using a scanning electron microscope. The thermal property of cured systems was investigated using thermogravimetric analysis. The results indicate that MCEs may influence the reaction of BDACy. The proper addition of MCEs can significantly improve the mechanical property and the hot water resistance of cured BADCy resin. MCEs have a negative influence on the initial thermal decomposition temperature (T_d) of cured BADCy resin. POLYM. COMPOS., 2010. © 2008 Society of Plastics Engineers.     

二烯丙基双酚A催化改性酚醛型氰酸酯树脂的催化固化

研究了二烯丙基双酚A（DBA）催化改性酚醛型氰酸酯树脂（cy-5）,通过差示扫描量热法（DSC）、热重分析（TG）、冲击性能和动态热机械分析（DMA）测试,分析了改性树脂的热性能和力学性能。研究表明：DBA对cy-5有催化和增韧的双重作用,当DBA的添加量为5%（质量分数）时,催化效果最为明显,含10% DBA的改性树脂固化物的冲击强度达到7.41 kJ/m2,改性树脂固化物的玻璃化转变温度（Tg）和储能模量（E'）均有所降低,但幅度不大。