新型含硅聚三唑树脂及其复合材料的制备与性能

通过格式试剂法合成了低分子量的含硅芳炔(LPSA),并以LPSA和二叠氮(A2)为原料制备出加工性能较好的新型含硅聚三唑树脂(Si-PTA树脂),采用模压方法制备了单向T700碳纤维/Si-PTA树脂复合材料。用FT-IR、流变、DSC、DMA、TGA等分析测试方法表征了Si-PTA树脂及其固化物的结构与性能,研究了炔基和叠氮基团配比对树脂热性能的影响,测定了复合材料的力学性能。结果表明,Si-PTA树脂可以在80℃下固化,固化后树脂的玻璃化温度(Tg)能达到310℃,在氮气气氛中的5%热失重温度(Td5)在340℃以上。单向T700碳纤维/Si-PTA树脂复合材料常温下弯曲强度为1622MPa,弯曲模量为132GPa,层间剪切强度为58.2MPa,200℃下弯曲强度保留率为70.8%。     

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%。     

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(Tg)超过180℃,高者达251℃,热分解温度可达360℃。     

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℃。     

RTM成型工艺用改性硅炔杂化树脂性能研究

采用间二乙炔基苯(PAA)改性硅炔杂化树脂(PSA),制备了适用于RTM成型工艺的耐高温聚合物(H树脂)。通过差示扫描量热(DSC)法、流变分析、傅里叶变换红外光谱(FT-IR)法探索H树脂的固化行为。研究结果表明:随着PAA含量增加,H树脂的DSC固化峰值温度从235℃降到208℃;H-0、H-2、H-3和H-4的凝胶温度分别为194、162、136和132℃;采用Kissinger法和Ozawa法计算得到H-2树脂固化的表观活化能分别为122.7和124.6 kJ/mol,属于一级固化反应;玻璃纤维增强H-2树脂复合材料的常温弯曲强度为208 MPa,经700℃热处理7 min后常温弯曲强度为105 MPa。     

碳纤维增强环氧树脂基复合材料的性能研究

研究了WBS-3环氧树脂固化体系的反应特性,分析了该固化体系浇铸体的性能;并以碳纤维(T-700S)为增强材料,采用手糊成型螺栓加压工艺制备了WBS-3/T-700S复合材料,研究了复合材料的常温力学性能、高温力学性能、水煮后力学性能和动态力学性能,并对弯曲断面进行分析。研究结果表明,WBS-3树脂基体黏度低、适用期长且韧性好,适合于手糊成型、缠绕成型等低成本制造工艺;由此制得的WBS-3/T-700S复合材料具有优良的力学性能和耐高温性能,其弯曲强度为1434MPa,拉伸强度为1972MPa,剪切强度为76.1MPa,玻璃化温度(Tg)超过210℃;该WBS-3/T-700S复合材料具有很好的界面粘接性(树脂对纤维的浸润性良好)、较低的空隙率且纤维分布均匀。     

一种耐高温双酚A型2H-苯并吡喃树脂作为复合材料基体的评价

引入红外辐射加热技术,将二炔丙基双酚A醚(BPA单体)在185℃下加热3h,成功制备了双酚A型2H-苯并吡喃(BCA)树脂,并使用该树脂基体制备了玻璃纤维增强复合材料。用差示扫描量热技术(DSC)评价了BCA树脂的固化行为,研究表明其固化放热焓为620J/g。热重分析(TGA)结果表明,BCA树脂具有较好的热稳定性。与环氧树脂基复合材料相比,BCA树脂复合材料力学性能优异,其弯曲强度、弯曲模量及层剪强度分别达到580MPa、24.7GPa和40MPa。另外,动态热机械性能分析(DMTA)结果表明其复合材料具有优良的热性能。     

不同双马树脂制备预浸料对复合材料单向板力学性能的影响

采用热熔预浸技术,对TR525型树脂和改性BMI型树脂制备了两种规格的东丽T700预浸料,测试了预浸料的物理性能,并且用DSC法测出了两种树脂的固化曲线,确定了树脂的固化制度。对东丽T700/TR525型预浸料和东丽T700/改性BMI型预浸料分别制备了复合材料单向板,对单向板力学性能进行了测试。结果表明,东丽T700/改性BMI型复合材料单向板0°拉伸强度、90°拉伸强度和层间剪切强度比东丽T700/TR525型复合材料单向板分别高出15.00%、87.39%和27.72%,达到了2391.22MPa、24.38MPa和84.86MPa。     

含苯炔基侧链的聚酰亚胺树脂及其复合材料

采用联苯酐(3,4′-BPDA)与4,4′-二氨基二苯醚(4,4-ODA),3,5-二氨基-4′-苯炔基二苯甲酮(DPEB),苯炔基苯酐(PEPA)制备了不同分子质量的聚酰亚胺树脂。通过流变分析,热重分析,红外光谱,动态热力学分析及静态力学性能测试等研究了分子结构,分子质量等因素对聚酰亚胺树脂耐热性和力学性能的影响。结果表明,合成的聚酰亚胺树脂具有优异耐热性能和较高的韧性,固化后树脂的玻璃化转变温度为379℃,5%热失重温度高于550℃,并且浇注体的拉伸强度是61 MPa,断裂伸长率是6.2%.碳纤维复合材料的室温弯曲强度为1 850 MPa,层间剪切强度为84 MPa,316℃时弯曲强度为946 MPa,剪切强度为46 MPa,具有良好的高温力学保持率。     

湿法缠绕成型T700碳纤维/氰酸酯树脂复合材料力学性能研究

研究了湿法缠绕成型的T700碳纤维/氰酸酯树脂复合材料NOL环及单向板力学性能。测试了树脂配方的粘度-温度特性,T700碳纤维/氰酸酯树脂复合材料NOL环的拉伸及剪切性能,采用SEM对NOL环拉伸试样破坏形貌进行了观察。测试了T700碳纤维/氰酸酯树脂单向板复合材料的常温拉伸性能、弯曲性能、层间剪切性能和高温弯曲性能。结果表明,树脂配方在25℃下的粘度为800 cps,可以直接在室温条件下用于复合材料湿法缠绕成型,并具有充分的使用期。NOL环的拉伸强度为2220 MPa,剪切强度为56. 8 MPa,树脂基体对碳纤维具有良好的浸润性,能够较好地发挥出碳纤维的高强度特性。T700碳纤维氰酸酯树脂单向板复合材料的高温力学性能优异,200℃下弯曲强度保留率高达60. 4%,250℃下弯曲强度保留率高达45. 0%。     

酚醛型氰酸酯的性能

表征了采用"改进的卤化氰-酚法"合成得到的酚醛型氰酸酯未固化树脂的粘度、反应性和凝胶特性,固化树脂及其复合材料的力学性能、耐热性、耐烧蚀性能等。结果表明,固化气氛对酚醛型氰酸酯的反应活性有着显著的影响,在空气气氛中的凝胶时间远小于惰性气氛的凝胶时间。固化树脂及其复合材料具有优异的耐热性和烧蚀残留率,力学性能优于酚醛树脂。     

Synthesis and characterization of a novel silicon‐containing polytriazole resin

4,4′‐Diazidomethylbiphenyl (DAMBP) and poly(dimethylsilylene‐ethynylenephenyleneethynylene) (PDMSEPE) were thermally polymerized to form a novel silicon‐containing polytriazole resin (PDMSEPE‐DAMBP) by 1,3‐dipolar cycloaddition. Differential scanning calorimetry, FTIR, and ¹³C‐NMR were used to characterize the curing behaviors of PDMSEPE‐DAMBP resins. The results indicated that the resins could cure at temperatures as low as 80°C. Dynamic mechanical analysis showed that there was a glass transition at 302°C for the cured PDMSEPE‐DAMBP resin. The carbon fiber (T700) reinforced PDMSEPE‐DAMBP composites exhibited excellent mechanical properties at room temperature and high property retention at 250°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

光照条件对可见光固化乙烯基酯树脂固化物性能的影响

本文通过对不同光照条件下得到的可见光固化及过氧化物固化的乙烯基酯(VLC)树脂的弯曲、拉伸性能和玻璃化转变温度及残留苯乙烯含量的比较研究,发现只要保证可见光照射的照度和光照量,VLC树脂可见光固化物性能和过氧化物固化物性能相当,高照度光源照射下双酚型VLC-760浇铸体的断裂伸长率及玻璃化转变温度会有明显提高。     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

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。     

Preparation and properties of dipropargyl ether of bisphenol A‐modified bismaleimide resins and composites

A kind of modified bismaleimide resin, with good heat resistance and processing properties for advanced composites, was developed. The modifier, dipropargyl ether of bisphenol A (DPBPA), was prepared by a phase‐transfer catalyzing procedure, characterized by FTIR, ¹H NMR, and elementary analysis, and used to modify 4,4′‐bismaleimidodiphenylmethane (BMDPM). The thermopolymerization of a DPBPA‐modified BMDPM resin was followed up by FTIR. The curing of the resin was investigated by differential scanning calorimeter and gelation characterization. The relation of viscosity and temperature was used to characterize the processability of the resin. The results of DMA analysis showed that the cured DPBPA‐modified BMDPM resins had a glass transition temperature higher than 320°C. The carbon fiber (T700) reinforced composites showed excellent flexural properties at ambient temperature and at 250°C. DPBPA could effectively improve mechanical properties without deteriorating heat resistance of the BMDPM resin a lot. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Preparation and properties of a new polytriazole resin made from dialkyne and triazide compounds and its composite

A new kind of polytriazole resins were prepared from a triazide and a dialkyne compounds and characterized. These resins can be cured at 80 °C. The curing process for a resin was traced by FT-IR. The glass transition temperature T_g and thermal decomposition temperature T_d5 of the cured resin with the molar ratio of azide group to alkyne group [a]/[b]=1.0:1.0 reach 216 °C and 360 °C, respectively. The flexural strength of the cured resin and its glass fiber reinforced composite arrive at 183.6 MPa and 963.4 MPa, respectively. The resin would be a good candidate for the matrices of advanced composites.     

Synthesis of epoxy‐functionalized hyperbranched poly(phenylene oxide) and its modification of cyanate ester resin

High curing temperature is the key drawback of present heat resistant thermosetting resins. A novel epoxy‐functionalized hyperbranched poly(phenylene oxide), coded as eHBPPO, was synthesized, and used to modify 2,2′‐bis (4‐cyanatophenyl) isopropylidene (CE). Compared with CE, CE/eHBPPO system has significantly decreased curing temperature owing to the different curing mechanism. Based on this results, cured CE/eHBPPO resins without postcuring process, and cured CE resin postcured at 230°C were prepared, their dynamic mechanical and dielectric properties were systematically investigated. Results show that cured CE/eHBPPO resins not only have excellent stability in dielectric properties over a wide frequency range (1–10⁹Hz), but also show attractively lower dielectric constant and loss than CE resin. In addition, cured CE/eHBPPO resins also have high glass transition temperature and storage moduli in glassy state. These attractive integrated performance of CE/eHBPPO suggest a new method to develop high performance resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012