光-热双重固化MAP-POSS改性水性环氧树脂/聚氨酯丙烯酸酯涂料的制备与性能

为了使聚氨酯丙烯酸酯(PUA)涂料具有更加优异的性能,本文通过合成二苯基碘鎓盐(DPI·PF6),制备了甲基丙烯酰氧基硅笼(MAP-POSS)改性环氧树脂(ER)/聚氨酯丙烯酸酯(PUA)复合涂料,用二苯基碘鎓盐为光引发剂研究了涂料的光-热混杂固化反应,动态力学和热降解过程。结果表明,涂料有良好的光固化性能,光-热混杂固化可进一步提高材料刚性;紫外光和热固化均可以很好地使体系进行固化成膜反应,并且热固化能提高体系的玻璃化转变温度,使体系的Tg增加50℃左右,当MAP-POSS含量达到12%时,体系的Tg达到最高98.5℃。通过Friedman研究体系的热降解动力学,可以看出在光固化和热固化过程中不同含量的MAP-POSS的加入均随着β的增加Ea明显提高,当MAP-POSS含量达到3%时,Ea值均达到一个高点,但在热固化中,随着反应的进一步进行,在MAP-POSS含量达到12%后,Ea值又继续增加。     

含芳醚芴二胺/环氧树脂固化反应动力学及性能研究

以9,9-双[4-4-氨基苯氧基苯基]芴(BAOFL)作为固化剂,采用非等温DSC技术,研究了BAOFL/环氧树脂(E-51、TDE-85和芴基环氧树脂)体系的固化反应动力学,利用动态热机械分析仪(DMA)和热重分析仪(TGA)测试了固化树脂的力学性能和热稳定性。结果表明,固化反应活化能与环氧树脂和固化剂的结构密切相关,芳醚的引入提高了氨基与环氧基的反应性,固化树脂呈现出优良的热性能和力学性能,其玻璃化转变温度(T)达到206~248℃,贮能模量为2.54~2.94 GPa,初始热分解温度312~375℃,700℃g时的残炭率达到15.2%~31.7%。()     

松香基环氧树脂/马来海松酸酐固化反应动力学与热稳定性研究

松香与马来酸酐进行Diels-Alder反应合成马来海松酸酐(MPA),与环氧氯丙烷进一步反应生成松香基环氧树脂,以马来海松酸酐（MPA）做固化剂固化松香环氧树脂,利用差示扫描量热仪、动态力学谱仪、热重分析仪等分析手段,对该体系固化产物进行固化动力学和热降解动力学研究。结果表明,质量比为5∶5的环氧树脂/马来海松酸酐体系固化后玻璃化转变温度达53.2 ℃,平均固化反应活化能为52.29 kJ/mol;固化物在10 ℃/min时初始分解温度为211.9 ℃,最大分解温度为347.7 ℃,最终分解温度为639.0 ℃。     

苯并噁嗪/二苯基碘鎓六氟磷酸盐体系的催化固化研究

以二苯基碘鎓六氟磷酸盐(PF)为催化剂实现了对双酚A型苯并噁嗪(BA)的催化固化。通过差示扫描量热仪(DSC)和动态机械热分析仪(DMA)研究了PF对BA固化行为以及热力学性能的影响,并采用Kissinger和Ozawa方法研究了体系的固化动力学参数。研究表明,当PF添加量(质量分数)为1%时,BA的起始固化温度(T_i)和峰值固化温度(T_p)分别下降了41℃和25℃;PF添加量提升到3%时,T_i和T_p分别下降了43℃和31℃。BA在200℃固化30 min时的固化度为72%,而BA/PF-1%和BA/PF-3%体系在相同条件下固化度分别达到91%和99%。DMA测试表明,当添加1%的PF时,树脂的玻璃化转变温度(T_g)提升至213℃,比纯聚苯并噁嗪高13℃,且体系在25℃时的储能模量达到7 069 MPa,比纯聚苯并噁嗪树脂提高了近50%(25℃)。动力学研究结果表明,BA以及BA/PF体系的固化过程符合自催化固化模型。     

混杂固化MAP-POSS改性水性聚氨酯丙烯酸酯/邻甲酚醛环氧树脂的制备与性能

制备了水性邻甲酚醛环氧树脂（o-CFER）和聚氨酯丙烯酸酯（PUA）,并以甲基丙烯酰氧基丙基笼型倍半硅氧烷（MAP-POSS）改性了PUA/o-CFER。通过UV-阳离子混杂固化制备了热固性高分子材料,用红外光谱仪、动态力学谱仪和热重分析仪进行了表征。结果表明,体系有很好的相容性,MAP-POSS的加入量为16 ％（质量分数,下同）时,材料的玻璃化转变温度达到122.3 ℃,提高了19.7 ℃;热重分析表明,当 MAP-POSS加入量为12 ％时,热降解所需的活化能最高,为41.44 kJ/mol,反应级数n为1.38;同时,玻璃钢复合材料的拉伸强度和弹性模量分别达到201.15 MPa和8.17 MPa,涂膜的硬度达到3 H,冲击性能达到50 kg·cm,并具有良好的附着力。     

耐高温拉挤环氧树脂及其复合材料性能研究

本文研究了改性多元缩水甘油胺型耐高温环氧树脂的固化动力学,分析了该树脂体系的浇注体性能,制备了碳纤维拉挤复合材料,并通过热机械分析(DMTA)考察了树脂浇注体及其复合材料的动态热机械性能.结果表明,树脂体系的凝胶化温度与固化温度相差较小,固化反应放热集中,适合于快速拉挤成型;其复合材料具有优良的耐高温性能,玻璃化温度(Tg)达到210℃以上.     

环氧灌封料固化反应动力学及其性能研究

采用非等温示差扫描量热法(DSC)研究了环氧树脂(E-51)/甲基四氢苯酐/DMP-30/球形SiO2体系的固化反应动力学,采用Kissinger法和Crane公式对体系的DSC数据进行了处理,获得了固化反应动力学参数,确定了固化工艺。同时通过力学性能和热性能测试研究了球形SiO2添加量对复合材料性能的影响。结果表明,SiO2质量分数为10%的体系其起始固化温度为109.7℃,峰顶固化温度为134.8℃,终止固化温度为154.3℃;较好的固化工艺为100℃/2 h+140℃/2 h+160℃/2 h。该体系反应级数n=0.917,表观活化能Ea=78.52 kJ/mol。当SiO2添加量为30%时,其弯曲强度达到最大值97 MPa,同时热分解温度达到最大值332℃,试样热膨胀系数也明显降低。     

苯酐固化邻甲酚醛环氧的热性能与热分解动力学

研究了邻甲酚醛环氧树脂(o CFER)与邻苯二甲酸酐固化物的热分解动力学,用动态力学谱仪测定了玻璃化温度(Tg)。讨论了固化剂用量、固化时间等因素对玻璃化转变温度(Tg)的影响。结果表明,固化体系的玻璃化温度随反应程度的增加而升高,当达到一定程度后,趋于一定值。利用热重分析仪(TGA)研究了完全固化产物的热分解动力学,说明热分解反应分2步进行。     

端羟基聚丁二烯改性氰酸酯体系固化反应动力学

采用示差扫描量热法(DSC)研究了端羟基聚丁二烯(HTPB)改性双酚A型氰酸酯树脂(BADCy)体系的固化反应动力学,根据Arrhenius方程对固化过程动力学参数进行了求解,建立了固化反应动力学模型。结果表明,随着HTPB含量的增大,动态DSC固化反应放热峰向低温方向移动,说明HTPB可以催化固化反应并降低体系的反应温度。纯BADCy和BADCy/15%HTPB体系等温固化符合自催化反应模型。纯BADCy体系以及BADCy/15%HTPB体系的表观反应活化能分别为59.67 kJ/mol、56.91 kJ/mol。     

一种紫外光固化树脂的合成及性能表征

以羟丙基硅油MOK-7800、异氟尔酮二异氰酸酯IPDI和甲基丙烯酸羟丙酯HPMA为原料,合成了一种紫外光固化树脂HPSACR。通过红外光谱(FT-IR)跟踪反应进程,通过动态热机械分析仪(DMA)、拉伸试验机和热重分析仪(TGA)研究HPSACR与三羟甲基丙烷三丙烯酸酯(TMPTA)以不同比例共混紫外光固化样品的热机械性能、力学性能和热稳定性。最终确定,HPSACR与TMPTA以10∶7.5比例共混所得紫外光固化样品较优,储能模量在-40℃,25℃和40℃分别为668.3MPa,542.5MPa和434.6MPa,玻璃化转变温度为91.65℃;常温弹性模量为677.85MPa,断裂伸长率为95.295%;氮气气氛下初始降解温度T5%和T10%分别为292.06℃和301.90℃,残炭率为2.082%。     

MAP-POSS改性PMMA非等温聚合反应动力学及物理性能

通过共聚将甲基丙烯酰氧丙基笼型倍半硅氧烷（MAP-POSS）引入到聚甲基丙烯酸甲酯（PMMA）中,制备了有机/无机纳米杂化复合材料。用非等温差示扫描量热法研究了MAP-POSS与MMA共聚反应动力学,测定了反应动力学参数,建立了反应动力学数学模型,并测试了其力学、热学及电学性能。结果表明,MAP-POSS与MMA可以共聚,在不降低电性能的情况下,其冲强度提高了约30 kJ/m2,热分解温度提高了34 ℃。     

UV-Curable Coating of Unsaturated Polyester/Epoxy Resins Containing Polyhedral Oligomeric Silsesquioxanes

UV-curable coating of unsaturated polyester/epoxy resin (UP-ER) modified with methylacryloylpropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) was prepared. The UV-cured process, kinetics, and some properties of coating were investigated. The results show that this coating has a better UV-curing property. The curing reaction can be described by a two-parameter autocatalytic ?esták-Berggren (S-B) model. The mechanical loss peak temperature T _p of curing coating nanocomposites increased with increasing MAP-POSS content and has a highest value when MAP-POSS content is 12%, which is 121.8°C, and higher, about 18.3°C, than a pure UP-ER system. The coating film has lower volume shrinkage than pure UP-ER.     

Non-isothermal crystallization kinetics of polypropylene/MAP-POSS nanocomposites

Non-isothermal crystallization kinetics of polypropylene (PP)/methylacryloypropy polyhedral oligomeric silsesquioxanes (MAP-POSS) nanocomposites (PP/MAP-POSS) were investigated by DSC at various cooling rates. Jeziorny and Mo method were used to study the non-isothermal crystallization kinetics. The results show that the Jeziorny and Mo method are all successful in describing the non-isothermal crystallization kinetics of PP/MAP-POSS nanocomposites. The MAP-POSS can act a role of heterogeneous nucleation and increase the crystallization rate constant Z _c and decrease crystallization half time t _1/2, and the spherulite crystal size decreases, the inter-spherulitic action or crosslinking structure each other appear at the appropriate content. The DSC peak temperature T _p increase about 5 °C, t _1/2 reduce 0.21 min at 6 % content of MAP-POSS and heating rate of 10 °C/min. The MAP-POSS can also increase the mechanical property of PP/MAP-POSS nanocomposites, the tensile strength and impact strength increase from 12.97 to 19.93 MPa and from 33.2 to 52.6 kJ/m², respectively, at 4 % content of MAP-POSS. But the spherulitic crystal becomes larger and boundaries become clearer again; the macrophase separation will occur and mechanical properties decrease when more and more MAP-POSS was added. The nanocomposite has the best mechanical property at 4 % content of MAP-POSS.     

Synthesis and properties of waterborne epoxy acrylate nanocomposite coating modified by MAP-POSS

In this paper, waterborne epoxy acrylate (EA) coating modified with methylacryloylpropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) was prepared. The cure kinetics of the coating was investigated by differential scanning calorimetry (DSC). The curing process, thermal and mechanical properties of the coating were investigated by FTIR, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). These results show that the non-isothermal curing process can be described by Kissinger method and a two-parameter autocatalytic Šesták–Berggren (S–B) model. The kinetic equations of curing reaction were obtained. The UV-curing property of MAP-POSS/EA nanocomposite coating is better than that of pure epoxy acrylate system. The glass transition temperature (T_g) increases with increasing MAP-POSS content. When MAP-POSS content is 12 wt%, the T_g reaches the maximum 54.3 °C which is 9.5 °C higher than that of pure epoxy acrylate.     

Reaction kinetics and physical properties of unsaturated polyester modified with methylacyloxylpropyl-POSS

The polyhedral oligomeric silsesquioxanes which contains methylacryloylpropyl group (MAP-POSS) was synthesized and used to modify unsaturated polyester resin (UPR). The cure kinetics was investigated by isothermal DSC technique. The mechanical and electrical properties of fiberglass-reinforced laminate were determined. The result shows that the reaction can be described by a Kamal autocatalytic model which has two reaction rate constants k ₁ and k ₂, and two apparent activation energies E _a1 and E _{a 2} are 98.12 kJ/mol and 74.01 kJ/mol, respectively. UPR and MAP-POSS can co-cure in free radical polymerization. When the MAP-POSS content is 5 wt%, the impact and tensile strength of fiberglass-reinforced laminate enhanced 10% and 6%, respectively, and has better electrical properties than no MAP-POSS. The dielectric constant ε and dielectric loss tanδ are all decrease. The surface resistance ρ _s is 4.7 times higher than pure UPR laminates     

Synthesis of Methylacryloypropyl-POSS/Poly(fluorine-acrylate) Core-Shell Nanocomposites and Effect on Thermal Properties of Materials

Core-shell nanocomposites were prepared from acrylates, fluorine- containing methacrylate monomers and methylacryloypropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) by emulsion polymerization. The properties of latex and nanocomposites were characterized by FTIR, NMR, TEM, laser particle diameter analyzer, DMA and TGA. The results showed that the particle diameter of composite latexes was about 33.5 nm, dynamic mechanical loss peak temperature T_p of the nanocomposites had the best high value at 99.6°C when 7 wt.% MAP-POSS was added, which is 7.8°C higher than the pure polyacrylates. MAP-POSS could increase the thermal stability of materials, the initial thermal decomposition temperature increases about 34°C.     

微水固相法对皂荚多糖的阳离子化改性工艺研究

以皂荚种子胚乳片为原料，以3-氯-2-羟丙基三甲基氯化铵为醚化剂，采用微水固相工艺制备了阳离子皂荚多糖，通过单因素试验考察了氢氧化钠质量分数、醚化剂质量分数、反应温度及反应时间对产物黏度和取代度的影响，确定了最优反应条件为皂荚种子胚乳片500 g、250 mL 40% NaOH溶液、500 mL 60%的3-氯-2-羟丙基三甲基氯化铵溶液、反应温度60℃和反应时间4 h。该条件下制备的阳离子皂荚多糖含水不溶物为2.81%、黏度为1 196.2 mPa·s（1%的水溶液，25℃）、阳离子取代度为0.151。红外光谱和核磁共振氢谱的表征结果均证明皂荚多糖实现了季铵型阳离子化反应，阳离子皂荚多糖的表观黏度测试结果显示其符合皂荚多糖的假塑性流体特征。     

双氯芬酸钠合成工艺研究

以2,6-二氯二苯胺(Ⅳ)和氯乙酰氯为主要原料,经过酰化、分子内付-克烷基化和水解反应,合成了非甾体消炎镇痛药双氯芬酸钠(Ⅰ)。前两步反应均采用无溶剂操作,第3步反应在水溶液中进行,符合绿色化学的原则。各步反应的最佳工艺条件为:①酰化反应,n(Ⅳ)∶n(氯乙酰氯)=1∶1.2,反应温度140℃,中间体Ⅲ的收率为96.6%;②分子内付-克烷基化反应,n(Ⅲ)∶n(A lC l3)=1∶2,反应温度150℃,中间体Ⅱ的收率为91.2%;③水解反应,n(Ⅱ)∶n(NaOH)=1∶2.5,氢氧化钠溶液的质量分数为20%,反应时间6 h,催化剂用量为Ⅱ的质量的2%,Ⅰ的收率为92.5%。三步总收率为81.5%。     

邻甲硼酚醛树脂固化双酚-A环氧树脂及其复合材料的性能

用邻甲硼酚醛树脂(BoPFR)固化双酚-A环氧树脂(BPAER),制备了含硼酚醛的高性能玻璃钢复合材料.分析了固化过程,研究了固化树脂以及玻璃纤维层压板的力学性能、热性能和电性能.当m(BoPFR)/m(BPAER)为1.0∶0.5时,复合材料的玻璃化转变温度从198.4 ℃下降到134.5℃,材料韧性提高.固化物有良好的耐热性能,当m(BoPFR)/m(BPAER)为1.0∶0.2时,材料在900℃时的残留率为25.83％,热降解动力学符合一级反应动力学;玻璃纤维层压板拉伸强度提高了一倍,而电性能变化不大.