含苯并恶嗪及联苯结构双邻苯二甲腈共聚树脂

将联苯结构的双邻苯二甲腈树脂(4,4'-二-3,4-二腈基苯氧基联苯,简称BPH)熔融后与含有苯并恶嗪单元的双邻苯二甲腈树脂(简称BZ-BPH)共混。通过示差扫描量热法(DSC)、流变测试研究了共混树脂的固化工艺性能,通过热重分析(TGA)研究了共混树脂固化物的耐热性能。此外采用SEM观察了浇注样的断面结构。结果表明,通过调节BZ-BPH的加入量可实现对固化工艺的调控。经过240℃/4 h+280℃/4 h+320℃/4 h+375℃/6 h的固化,产物在空气和氮气下5%热失重温度均高于500℃(高于BPH固化物)。BZ-BPH与BPH之间共聚形成了均相的交联网络。     

4,4''''-二炔丙氧基二苯醚与二乙炔基苯共聚合及其共聚物性能研究

通过4,4'-二炔丙氧基二苯醚与二乙炔基苯共聚制备改性聚芳基乙炔树脂(MPAA),并对工艺性能、浇铸体热性能及其复合材料的力学性能进行研究,DSC研究表明,MPAA有效降低了PAA树脂的固化热,MPAA具有良好的工艺性能;TGA、DMA结果表明,固化MPAA与PAA相比,脆性得到改善,仍具有较好的热稳定性,MPAA在800℃时的残碳率为76%.MPAA树脂基复合材料的力学性能比PAA树脂有明显提高,230℃下弯曲强度保留率为82%.     

基于双马来酰亚胺树脂的高耐热电子封装模塑料制备北大核心CSCD

采用双马来酰亚胺树脂(BMI70)、2,2′-二烯丙基双酚A(DBA)、多官环氧树脂(EPPN501H)和芳烷基型酚醛树脂(MEH78004S)制备了BDEP四元树脂共混物,研究了不同BMI含量对共混物固化行为和热稳定性的影响。以BDEP四元树脂为基体制备了电子封装模塑料,测试了所得模塑料的热性能、力学性能、耐老化性及介电性能,并与商用环氧模塑料(EMC)进行对比。结果表明,选用质量分数1%的2-乙基-4-甲基咪唑作固化促进剂时,BDEP四元树脂的固化放热峰温约为150℃,可在较低温度下成型。通过优化配方,BDEP模塑料固化物的玻璃化转变温度可达242℃,与商用EMC相比提高了约60℃,最大热分解温度可达455℃,同时具有良好的力学强度和介电性能,在高功率电子元器件封装领域具有良好的应用前景。     

双马来酰亚胺树脂基电子封装模塑料研究

以双马来酰亚胺树脂为基体树脂,2,2′-二烯丙基双酚A为改性剂,研究了树脂/改性剂比例、固化促进剂及其用量对体系固化行为的影响,然后将树脂体系用于电子封装模塑料制备,并将产品性能与环氧模塑料进行了对比。结果表明,以咪唑作为固化促进剂,用量为体系总质量的3%时,不同树脂/改性剂比例体系的非等温固化放热峰均在200℃以下,满足现行环氧模塑料固化工艺要求。通过配方设计得到的双马来酰亚胺树脂基模塑料固化物的玻璃化转变温度(Tg)可达256℃,热分解温度(T_(d1%))可达415℃,与环氧模塑料相比,T_g和T_(d1%)分别提高了109℃和21℃,固化物耐热性能优异,同时具有较好的粘附强度和介电性能,在高功率器件封装领域具有良好的应用前景。     

4，4＇-二炔丙氧基二苯醚与二乙炔基苯共聚合及其共聚物性能研究

通过4,4＇-二炔丙氧基二苯醚与二乙炔基苯共聚制备改性聚芳基乙炔树脂（MPAA）,并对工艺性能、浇铸体热性能及其复合材料的力学性能进行研究。DSC研究表明,MPAA有效降低了PAA树脂的固化热,MPAA具有良好的工艺性能;TGA、DMA结果表明,固化MPAA与PAA相比,脆性得到改善,仍具有较好的热稳定性,MPAA在800℃时的残碳率为76％。MPAA树脂基复合材料的力学性能比PAA树脂有明显提高,230℃下弯曲强度保留率为82％。     

中温固化树脂基体的研究

4,4'-二胺基二苯甲烷(DDM)是一种性能良好的固化剂,但其熔融温度较高,对中温固化的使用期及工艺性能产生不良效果.本研究利用一种新型的液体固化剂二甲硫基甲苯二胺(DADMT)与其共混以降低其熔融温度,改变树脂体系的工艺性能.利用DSC研究了不同促进剂对树脂体系的促进效果,在此基础上对两种固化剂的加入比例及体系的反应性、使用期、粘度及浇铸体的性能等进行了初步研究.研究发现,两种固化剂共混比例在1:1(摩尔比)时40℃左右即可熔融,而且固化产物的性能相对较高.     

PAA用量对PA6/PAA共混物性能的影响

采用摩尔比为1.02的均苯四羧酸二元酐(PMDA)、4,4'-二氨基二苯醚(ODA)为单体,N-甲基吡咯烷酮(NMP)为溶剂合成出了高黏度的聚酰胺酸(PAA),并以共混挤出的方式制备了不同PAA含量的PA6/PAA共混物。研究了PAA用量对共混物的力学性能、热变形温度、结晶性能的影响。结果表明:当PAA用量小于5%时,PAA的羧基与PA6间的反应以及小分子的增塑作用明显,从而使PA6的结晶速率和结晶度降低;用量大于5%时,PAA高温酰亚胺化成为第二相占主导,其固化的聚酰亚胺可能能够起到异相成核作用,促使力学性能和热变形温度的提升。     

动态固化增容聚丙烯/长玻璃纤维复合材料的研究

将动态固化技术应用于热塑性树脂/热固性树脂体系,制备动态固化聚丙烯(PP)/Jg氧树脂(EP)/长玻璃纤维(LGF)共混物.研究动态固化聚丙烯/环氧树脂/玻璃纤维共混物的力学性能和热性能,并用电子扫描显微镜考察共混物的微观形态.试验结果表明:当EP质量含量为4%时,试样的拉伸强度和弯曲强度达到最大值,共混物的弯曲模量随EP含量的增加而增加;在体系中加入EP会降低维卡软化点温度.     

取代苯胺对含烯丙基的苯并恶嗪的性能影响

以甲基苯胺和苯胺与多聚甲醛、烯丙基双酚A合成了含烯丙基的苯并恶嗪(BA),采用红外及核磁氢谱对其结构进行了表征。其与单官能度苯并恶嗪(PAF)在溶液中共混并加热固化。通过DSC,TGA及DMA对BA及共混物、固化物的热性能进行了研究。结果表明,BA固化峰值温度>250℃,与PAF共混后固化温度下降,且随PAF加入量的增加而下降。共混后固化后热稳定性较好,其中含间位取代苯胺的烯丙基苯并恶嗪与PAF共混树脂的热稳定和弯曲强度最高,热失重5%和10%时的温度分别为308℃、384℃,玻璃化转变温度为171℃,弯曲强度24 MPa。     

中温预固化高性能环氧树脂复合材料性能研究

主要介绍了一种中温预固化耐热环氧树脂玻璃布复合材料,对树脂进行理化性能分析,采用热熔法制备预浸料,对玻璃布复合材料层压板进行性能测试.该树脂具有良好的耐热性和阻燃性,其预浸料可在125℃预固化,玻璃化温度达到155℃,完全固化后能达到245℃,耐热性能较好,该复合材料氧指数高,具有阻燃性.适合模具用复合材料或中温预固化...     

呋喃/环氧/胺类固化剂共混体系的固化反应机理及性能研究

采用溶液法制备了呋喃/环氧树脂/胺类固化剂的共混物。采用粘度测试仪、DSC、FT-IR、力学测试仪、SEM对共混体系的加工性、固化反应机理及固化后样品的力学性能及机理进行了研究。研究结果揭示了共混体系的固化反应机理,发现在共混体系中呋喃树脂与部分环氧树脂可以在180℃附近反应,剩余部分环氧树脂需要在更高的温度下才能进一步完全反应。共混体系具有优异的力学性能,且随着共混体系中环氧树脂含量的增多在逐渐升高,其中弯曲强度最高达到113 MPa,弯曲模量最高达到4129 MPa,冲击强度最高达到19.1kJ/m~2。对冲击断口形貌进行观察,发现共混体系浇铸体具有相分离结构是性能优异的主要原因。     

硅烷芳炔-硅氧烷芳炔嵌段共聚物的合成与表征

合成了不同链段长度的卤代硅氧烷,并用其与间二乙炔基苯格氏试剂反应,合成了两种硅烷芳炔-硅氧烷芳炔嵌段共聚物（SiO-b-PSA）,并制成碳纤维增强树脂复合材料。利用红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、凝胶渗透色谱（GPC）、旋转流变、差示扫描量热分析（DSC）、热失重分析（TGA）和悬梁臂冲击实验对共聚物及其复合材料的结构和性能进行表征。研究结果表明所合成的共聚物具有优良的耐热性和韧性,硅烷芳炔-硅氧烷芳炔嵌段共聚物在氮气气氛下的T_d5高于513℃,1000℃残留率高于78.9%,硅烷芳炔-硅氧烷芳炔嵌段共聚物/碳纤维复合材料的冲击强度高达（30.92±0.44） kJ·m^-2。     

联苯酚醛环氧树脂固化动力学及热性能研究

以4,4'-二氨基二苯砜(DDS)为固化剂,采用非等温示差扫描量热法(DSC)研究了联苯酚醛环氧树脂(BPNE)的固化动力学。通过外推法确定了体系的固化工艺。采用Kissinger、Ozawa法计算出固化体系的表观活化能,根据Crane理论计算得到该体系的固化反应级数。采用DSC,热重分析(TGA)研究了固化物的耐热性。结果表明:BPNE的固化工艺为160℃/2h+200℃/2h+230℃/2h;固化反应的活化能约为61.86kJ/mol,指前因子为5.27×105min-1,反应级数为1.1;玻璃化转变温度(Tg)为167℃,其10%热失重温度为398.1℃,800℃残炭率为29.37%,与双酚A环氧树脂/DDS固化物相比,分别提高了22℃,11.71%。     

新型烯丙基芳香二胺的合成及其固化特性研究

以溴丙烯和芳香族二酚为原料,通过缩合、重排2步反应制备了一系列烯丙基二酚化合物。以所合成的烯丙基二酚为原料,进一步与4-溴硝基苯,通过Williamson反应和还原反应制备了一系列新型烯丙基取代二胺单体。以2,2-双[4′-(4″-氨基苯氧基)-3′-烯丙基苯基]丙烷(APAP)为例,研究了其对环氧树脂以及双马来酰亚胺树脂的固化行为。结果表明,这类二胺固化剂对于上述树脂体系均具有良好的固化效果,固化物具有良好的耐热性能以及耐溶剂稳定性。     

新型聚三唑酯和聚三唑醚树脂的合成及性能

合成了三种含酯基和三种含醚键的炔单体,通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂,可低温(60℃)固化,固化树脂的弯曲强度超过了100 MPa,可达158 MPa,玻璃化转变温度(T _g)超过180℃,高者达251℃,热分解温度可达360℃。     

Star-shaped silicon-containing arylacetylene resin based on a one-pot synthesis using zinc powder catalysis with improved processing and thermal properties

Herein, reporting a simple, sustainable, and cost-effective chemical synthesis of a star-shaped silicon-containing arylacetylene (SSA) resin via a one-pot process using zinc powder as a catalyst. The as-prepared viscous liquid resins exhibited moderate rheological behavior. The thermal curing temperature was determined to be 203 °C using differential scanning calorimetry, which is much lower than that reported for polyimide and phthalonitrile (>300 °C), indicating the SSA resins are suitable for processing at a lower temperature. Thermogravimetric analysis also revealed the excellent thermal stability and extremely high carbon residue of the cured SSA resin (the temperature at 5% mass loss and residual yield at 800 °C under N₂ were 654 °C and 93%, respectively). The results showed the excellent processability and thermal stability of SSA resin. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48248.     

基于含硅多芳炔化合物制备新型聚三唑树脂

以含硅多芳炔化合物(PSA)与1,3,5-三叠氮甲基-2,4,6-三甲基苯(TAMTMB)为原料,通过1,3-偶极环加成反应制备了新型含硅聚三唑树脂Si-PTA3,考察了树脂的流变性能、固化行为、热性能及单体配比对其热性能的影响。采用模压法制备了单向T700碳纤维增强的Si-PTA3树脂复合材料T700/Si-PTA3,测定了其力学性能。结果表明,Si-PTA3树脂具有良好的加工性能,可在80℃下固化,耐热性较好;炔基与叠氮基摩尔比为1.1:1.0时树脂固化物的热性能最好,玻璃化转变温度达334℃,在氮气中热失重5%时的温度达351℃;复合材料T700/Si-PTA3常温下的弯曲强度高于1670 MPa,250℃时弯曲强度保留率超过67%。     

Synthesis and characterization of melt‐processable polyimides derived from 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene

A series of molecular‐weight‐controlled imide resins end‐capped with phenylethynyl groups were prepared through the polycondensation of a mixture of 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)benzene and 1,3‐bis(4‐aminophenoxy)benzene with 4,4′‐oxydiphthalic anhydride in the presence of 4‐phenylethynylphthalic anhydride as an end‐capping agent. The effects of the resin chemical structures and molecular weights on their melt processability and thermal properties were systematically investigated. The experimental results demonstrated that the molecular‐weight‐controlled imide resins exhibited not only meltability and melt stability but also low melt viscosity and high fluidability at temperatures lower than 280°C. The molecular‐weight‐controlled imide resins could be thermally cured at 371°C to yield thermoset polyimides by polymer chain extension and crosslinking. The neat thermoset polyimides showed excellent thermal stability, with an initial thermal decomposition temperature of more than 500°C and high glass‐transition temperatures greater than 290°C, and good mechanical properties, with flexural strengths in the range of 140.1–163.6 MPa, flexural moduli of 3.0–3.6 GPa, tensile strengths of 60.7–93.8 MPa, and elongations at break as high as 14.7%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Addition‐curable propargyl‐containing novolac‐type phenolic resin: Its synthesis,characterization, cure,and thermal properties

In this article, propargyl functionalized novolac resins (PN resins), with varying propargyl contents and varying molecular weights, were synthesized conveniently. The structural characteristics were determined by ¹HNMR and FTIR methods. Thermal cure studies revealed that the uncatalyzed thermal cure was remarkably affected by propargyl extent, while it was hardly affected by molecular weight. The processability of the as‐prepared PN resins was excellent as matrix of composite materials. The cure mechanism was complicated; postcure at high temperature was required to achieve entire crosslink formation. Both dynamic mechanical analysis and thermogravimetric analysis showed that the cured PN resins had substantially improved thermal mechanical properties and thermal stability in comparison to conventional cured phenolics. High propargyl extent was preferred for high thermal stability. The results show that PN resin is one of the ideal candidates for advanced composites matrices in thermostructural and ablative applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1010–1017, 2006     

Molecular weight controlled poly(amic acid) resins end‐capped with phenylethynyl groups for manufacturing advanced polyimide films

To investigate the effect of reactive end‐capping groups on film‐forming quality and processability, a series of molecular weight‐controlled aromatic poly(amic acid) (PAA) resins functionalized with phenylethynyl end groups were prepared via the polycondensation of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), para ‐phenylenediamine (PDA), and 4‐phenylethynyl phthalic anhydride (PEPA) served as molecular‐weight‐controlling and reactive end capping agent. The PAA resins with relatively high concentrations endow enhanced wetting/spreading ability to form PAA gel films by solution‐cast method which were thermally converted to the fully‐cured polyimide (PI) films. The mechanical and thermal properties of PI films were investigated as a function of PAA molecular weights (M_n ) and thermal‐curing parameters. Mechanical property, dimensional stability and heat resistance of the fully‐cured PI films with PAA M_n > 20 ×10³ g mol^?1 are found to be better than that of their unreactive phthalic end‐capped counterparts. The covalent incorporation of chain‐extension structures in the backbones, induced by thermal curing of phenylethynyl groups, might facilitate yielding a higher degree of polymer chain order and consequently improved resistance strength and elongation at break to tensile plastic deformation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45168.