一种改性双马来酰亚胺共聚树脂体系及其粘接性能的研究

以二苯甲烷双马来酰亚胺和二烯丙基双酚A为共聚单体，在适当的催化剂等作用下，制备了一种改性双马来酰亚胺共聚树脂。本文对这种改性的双马来酰亚胺共聚树脂的溶解性能、固化反应动力学和固化机理进行了讨论；对体系固化物的机电热性能及其胶粘剂的高低温粘接性能也进行了研究。     

双马来酰亚胺树脂固化的催化体系及催化机理

综述了目前国内外用于催化双马来酰亚胺树脂(BMI)固化以降低树脂固化温度的方法及机理,包括热引发固化,自由基引发剂、阴离子催化剂及纳米颗粒催化剂引发固化等。     

晶须改性二苯甲烷型双马来酰亚胺树脂体系的研究

以硼酸铝晶须、钛酸钾晶须为增强剂，以N，N′-二胺基二苯甲烷型双马来酰亚胺(BMI)／O，O′-二烯丙基双酚A(BA)体系作为基体，采用浇注成型工艺制备了晶须增强二苯甲烷型双马来酰亚胺树脂基复合材料。研究了晶须对树脂体系凝胶特性的影响，晶须对体系固化反应性的影响；晶须的种类、表面处理方法、含量对树脂体系力学性能和热性能的影响；树脂体系的固化工艺材料对性能的影响。结果表明，晶须对树脂体系固化工艺影响不大；硼酸铝晶须增强效果优于钛酸钾晶须；偶联剂以丙酮作溶剂处理的效果优于乙醇水溶液，酸化溶剂的效果更好；晶须可明显改善体系的力学性能和耐热性，在晶须添加量为15％左右时，所得体系的综合性能较好；改进的固化工艺有助于树脂体系性能的改善。在本研究中，弯曲强度最大提高了约18％，热变形温度最大提高了12％。     

烯丙基酚氧树脂改性双马来酰亚胺树脂基体的研究

以新型烯丙基酚氧树脂作为BMI(双马来酰亚胺)树脂的改性剂,制备相应的改性树脂,并采用红外光谱(FT-IR)法跟踪了该改性树脂的固化反应过程;探讨了活性稀释剂D和后固化工艺等对该改性树脂的黏度、凝胶时间、力学性能和热性能等影响。结果表明:当n(活性稀释剂D):n(BMI)=10:100时,改性树脂的综合性能相对最好,其冲击强度为30.52 kJ/m²、弯曲强度为157.1 MPa和HDT(热变形温度)为224℃;加入适量的活性稀释剂D,可明显降低体系的黏度、提高改性树脂的韧性;后处理工艺可以明显提高改性树脂的耐热性,当后处理工艺为"220℃/2 h→240℃/2 h"时,改性树脂的HDT达到了314℃。     

共聚改性氰酸酯树脂及其性能

利用环氧树脂和双马来酰亚胺树脂做改性剂,对氰酸酯树脂进行共聚改性,通过对粘度的测量描述了共聚树脂的固化反应情况。性能测试表明内聚改性氰酸酯树脂的冲击强度比纯氰酸酯树脂自聚体提高了2倍多,可达12.3kJ/cm^2,热变形温度高达235℃,并具有优异的介电性能,如10kHz 介电常数为2.25,介电损耗角正切＜10^-4。共聚树脂中的配比和固化条件对性能有影响。     

改性双马来酰亚胺基体树脂及其复合材料的研究

以二苯甲烷双马来酰亚胺与二烯丙基双酚Ａ为共聚单体，在适当的催化剂等作用下，制备了一种改性双马来酰亚胺树脂。本文对这种改性的双马来酰亚胺树脂体系的溶解性能、固化反应动力学和固化反应机理进行了研究。对这种基体树脂及其玻璃纤维复合材料的力学、电学和耐热性能也进行了考察。     

新型烯丙基化合物改性双马来酰亚胺树脂的制备及研究

利用环氧树脂和二烯丙基双酚A (DP)合成了一种新型烯丙基化合物(改性剂A),然后用该化合物改性双马来酰亚胺树脂(BMI),通过差示扫描量热法研究了BMI/DP/改性剂A体系的固化反应动力学,确定了固化工艺参数,并测试了该体系的力学性能、热性能和溶解性能。结果表明,该体系固化反应的表观活化能为88.512 kJ/mol,反应级数为0.91,为非整数,表明固化反应机理较为复杂;该体系较佳的固化工艺为150℃/1 h+170℃/2 h+200℃/2 h;相对于DP,改性剂A对BMI的增韧效果更为优异,当改性剂A用量为70份时,BMI/DP/改性剂A体系的力学性能最好,其冲击强度为23.31 kJ/m2,弯曲强度为155.8 MPa,热变形温度为224℃,质量损失5%时的温度为389.4℃,可溶于丙酮,具有良好的韧性、热性能和溶解性能。     

二元胺型苯并噁嗪/双马来酰亚胺共混树脂及其玻璃布增强的层压板

苯并噁嗪(BZ)和双马来酰亚胺(BMI)按照不同的配比进行共混固化。用FTIR、DSC、凝胶化时间、DMA、TGA、万能电子拉力机分别研究了BZ/BMI共混体系的固化行为以及BZ/BMI固化树脂的热性能和剪切强度等。结果表明BZ和BMI除了发生均聚反应,还发生苯并噁嗪开环生成的酚羟基和双马来酰亚胺的双键生成醚键的反应。BZ和BMI共混后,固化温度比各自的固化温度都低。BMI的加入提高了共混树脂的热性能,BZ/BMI固化树脂的T_g达289℃,T_d5达387℃,T_d10达422℃,800℃的残炭率达55.3%。另外,BMI的加入提高了BZ/BMI固化树脂的剪切强度,当BMI的含量为60％时,BZ/BMI固化树脂的剪切强度为12.44 MPa。进一步,制备了玻璃布增强的BZ/BMI层压板,并对其力学性能和断面形貌进行了研究。结果表明,当BMI用量为40%时,BZ/BMI层压板的拉伸强度、弯曲强度、冲击强度分别达394 MPa、490 MPa、160 kJ·m^-2。     

聚醚酰亚胺对共聚双马来酰亚胺树脂的增韧作用

采用二烯丙基双酚A、烯丙基酚醛改性4,4'-二氨基二苯甲烷双马来酰亚胺共聚制备了一类新型的双马来酰亚胺树脂(简称ABD)。以ABD为基体,选用热塑性树脂聚醚酰亚胺(PEI)为增韧剂,采用共混法制备了共聚双马来酰亚胺/聚醚酰亚胺(PEI)树脂体系。采用DSC和流变仪对ABD树脂的固化行为进行了研究,结果表明,该树脂粘度较低,室温下为液态,树脂的冲击强度为8.99 kJ/m2。通过DMA、TGA和扫描电镜对PEI加入量对树脂热性能和微观形貌的影响表明,添加质量分数为15%聚醚酰亚胺时,树脂冲击强度达到16.9 kJ/m2,比基体树脂提高了88%。     

低温固化改性BMI树脂基体动力学研究

采用催化剂、3,3′-二烯丙基双酚A(DP)和多官能团单体C改性4,4′-二氨基二苯甲烷双马来酰亚胺(BMI)树脂,制取低温固化、高温性能优良的改性BMI树脂。采用差示扫描量热法(DSC)研究了改性BMI树脂的固化反应动力学,计算了固化反应体系的动力学参数,进而提出了该改性BMI树脂固化成型过程的动力学模型,并结合傅里叶红外光谱(FT-IR)对反应机理进行了探讨。研究结果表明,催化剂对固化反应的进行有重要的促进作用,改性BMI树脂的固化温度由259℃降为178℃;烯丙基与马来酰亚胺基的"ene"反应非常显著,且改性剂C与DP的"ene"反应历程相似;改性BMI树脂的固化工艺确定为120℃×6h+140℃×2h+160℃×2h+180℃×2h,后处理工艺为200℃×6h。     

纳米SiO_2改性EP/BMI/CE树脂体系固化动力学研究

采用非等温差示扫描量热(DSC)法对纳米二氧化硅/环氧树脂/双马来酰亚胺/氰酸酯(nano-SiO2/EP/BMI/CE)树脂进行了固化反应动力学和固化工艺研究。通过Kissinger法和Ozawa法求得了nano-SiO2/EP/BMI/CE树脂体系固化反应动力学的表观活化能。结果表明:改性CE树脂体系的固化工艺参数为凝胶温度112℃、固化温度195℃及后处理温度213℃,进而确定了改性CE树脂体系的最佳固化工艺条件为"150℃/3 h→180℃/3 h→200℃/2 h";改性CE树脂体系的平均表观活化能为59.90 kJ/mol。     

改性BMI/苯并噁嗪树脂固化反应特性研究

以双马来酰亚胺(BMI)作为苯并噁嗪(BZ)树脂的改性剂,采用非等温差示扫描量热(DSC)法及Freeman-Carroll法研究了改性BMI/BZ树脂体系的反应特性和固化反应动力学过程。结果表明:改性BMI/BZ树脂体系的凝胶时间随BMI用量增加而缩短;改性BMI/BZ树脂体系的固化反应只有一个放热峰,其峰顶温度(230℃左右)明显低于纯BZ体系,并且与BMI用量无关;改性BMI/BZ树脂体系的固化反应近似于1级反应,当w(BMI)=30%~50%时,所建立的固化反应动力学模型在10℃/min时能较好描述改性树脂体系的固化反应过程。     

Characterization of modified bismaleimide resin

A new high-temperature resin system based on methylene dianiline bismaleimide (MDA-BMI) chemistry is studied. This is a two-component resin system which is modified by 2,2′-methylene-bis[4-methyl-6-(2-propenyl)] phenol (MBMPP) and has excellent thermal mechanical properties and good toughness characteristics. This paper discusses in detail some of the characteristics of the prepolymer by reacting the two components in addition to the cured system's properties. The prepolymer has very good stability at 100–120°C with very minimal molecular weight increase. The reaction order for curing prepolymer is almost 1. The activation energy of the curing reaction is 74.12 KJ/mol. The flexural strength and modulus of the cured modified MDA-BMI and their retention at 250°C are 124 and 3774.6 MPa and 69 and 78%, respectively. © 1996 John Wiley & Sons, Inc.     

聚醚酰亚胺对共聚双马树脂的增韧作用

采用聚醚酰亚胺(PEI)来提高共聚双马树脂的断裂韧性。实验结果表明,PEI是共聚双马树脂的有效增韧剂;分别加入10份和12.5份的PEI,可使共聚双马树脂的断裂韧性(GIC)分别提高到650J/m2和805J/m2,弯曲模量变化不大,弯曲强度则小幅度下降。用扫描电子显微镜(SEM)和动态力学分析(DMA)研究了改性树脂体系的微观结构,发现其断裂韧性主要与相态结构有关。     

POSS改性BMI树脂固化动力学及固化工艺研究

以双马来酰亚胺(BMI)、二烯丙基双酚A(BA)和七苯基倍半硅氧烷三硅醇(POSS-triol)为原料,采用非等温差示扫描量热(DSC)法研究了BMI/BA/POSS-triol体系的固化反应过程。运用Kissinger极值法、Crane法、Flynn-Wall-Ozawa(FWO)等转化率法和T-β(温度-升温速率)外推法确定了改性树脂体系的固化反应动力学参数和固化工艺参数。结果表明:改性树脂体系的固化反应活化能和反应级数(接近于1)均随POSS-triol用量增加而变化不大,说明POSS-triol的加入并没有明显改变BMI/BA体系的固化反应机理;改性树脂体系的凝胶温度为175.7℃,固化温度为226.9℃,后处理温度为271.7℃。     

聚醚酮改性BMI树脂的固化反应动力学研究

采用非等温DSC(差示扫描量热)法、FT-IR(红外光谱)法、Kissinger-Crane法、Ozawa法和T-β(温度-升温速率)外推法研究了PEK(聚醚酮)改性BMI/DBA(双马来酰亚胺/二烯丙基双酚A)树脂体系的固化动力学过程。研究结果表明:采用Kissinger-Crane法得到的动力学参数与Ozawa法的求解结果相近,PEK改性BMI/DBA的固化反应遵循1级反应机制;BMI/DBA/PEK树脂体系的固化温度为130~210℃,后处理温度为240℃。     

Properties and curing behavior of reactive blended allyl novolak with bismaleimide using dicumyl peroxide as a novel curing agent

For reducing the cure temperature and improving the thermal stability and mechanical properties, a thermosetting resin system composed of novolak and bismaleimide (BMI) was developed by reactive blending and using dicumyl peroxide (DCP) as a novel curing agent. Novolak was allylated and reacted with BMI to produce bismaleimide allylated novolak (BAN), and the effect of DCP on flexural, impact and heat distortion temperature of cured resin were investigated. On the basis of improved mechanical and thermal properties at 0.5% DCP contents, the curing behavior of DCP/BAN resin system was evaluated by DSC analysis. Ene, Diels‐Alder, homo‐polymerization and alternating copolymerization which occurred in DCP/BAN resin system were further verified using FTIR at sequential cure conditions from 140 to 200°C. Kissinger and Ozawa‐Flynn‐wall methods were used to optimize the process and curing reactions of DCP/BAN resin system. The results showed that the addition of 0.5% DCP in BAN reduced the curing temperature and time of the modified resin. For evaluating process ability of the modified system, composite samples using polyvinyl acetyl fiber were molded and tested for flexural properties. The resulting samples showed better flexural properties when compared with the composite made with neat BAN. The modified 0.5% DCP/BAN resin system with good mechanical properties and manufacturability can be used for making bulk molding compounds and fiber reinforced composites required in various commercial and aerospace applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41829.     

Preparation and characterization of 3,3′‐bis (maleimidophenyl)phenylphosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices

An intercrosslinked network of polysulfone (PSF)—bismaleimide (BMI) modified epoxy matrix system was made by using diglycidyl ether of bisphenol A (DGEBA) epoxy resin, hydroxyl terminated polysulfone and bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide) with diaminodiphenylmethane (DDM) as curing agent. BMI–PSF–epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, flexural strength, and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of polysulfone into epoxy resin improves the toughness to an appreciable extent with insignificant increase in stress–strain properties. DSC studies indicated that the introduction of polysulfone decreases the glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of polysulfone as well as BMI modified epoxy resin show a unimodal reaction exotherm. The thermal stability and flame retardant properties of cured epoxy resins were improved with the introduction of bismaleimide and polysulfone. Water absorption characteristics were studied as per ASTM method and the morphology of the BMI modified epoxy and PSF‐epoxy systems were studied by scanning electron microscope. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

烯丙基酚醛树脂的合成与固化特性研究

合成了烯丙基线性酚醛树脂,研究了在加热和加热/催化剂条件下的固化特性,采用烯丙基化线性酚醛树脂与双马来酰亚胺反应形成共聚物,通过FTIR和DSC分别分析了树脂在无催化剂和磷酸三苯酯(TPP)催化条件下的固化和结构,研究结果表明:烯丙基化酚醛树脂,双马来酰亚胺改性烯丙基化酚醛树脂在加热条件下不需要固化剂可以实现加成固化。     

Synthesis and characterization of siliconized epoxy-1,3-bis(maleimido)benzene intercrosslinked matrix materials

Intercrosslinked network of siliconized epoxy-1,3-bis(maleimido)benzene matrix systems have been developed. The siliconization of epoxy resin was carried out by using various percentages of (5-15%) hydroxyl-terminated polydimethylsiloxane (HTPDMS) with γ-aminopropyltriethoxysilane (γ-APS) as crosslinking agent and dibutyltindilaurate as catalyst. The siliconized epoxy systems were further modified with various percentages of (5-15%) 1,3-bis(maleimido)benzene (BMI) and cured by using diaminodiphenylmethane (DDM). The neat resin castings prepared were characterized for their mechanical properties. Mechanical studies indicate that the introduction of siloxane into epoxy resin improves the toughness of epoxy resin with reduction in the values of stress-strain properties whereas, incorporation of bismaleimide into epoxy resin improves stress-strain properties with lowering of toughness. However, the introduction of both siloxane and bismaleimide into epoxy resin influences the mechanical properties according to their percentage content. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and measurement of heat distortion temperature were also carried out to assess the thermal behavior of the matrix samples. DSC thermogram of the BMI modified epoxy systems show unimodel reaction exotherms. The glass transition temperature (T_g), thermal degradation temperature and heat distortion temperature of the cured BMI modified epoxy and siliconized epoxy systems increase with increasing BMI content and this may be due to the homopolymerization of BMI rather than Michael addition reaction. The morphology of the BMI modified epoxy and siliconized epoxy systems were also studied by scanning electron microscopy.