几种聚醚胺改性蒙脱土对环氧树脂固化过程的影响

首先制备了五种聚醚胺改性蒙脱土(MMT), 并将这五种聚醚胺改性蒙脱土加入到双酚A 型环氧树脂E51 和聚醚胺D400体系中, 采用差示扫描量热法(DSC)考察了五种聚醚胺改性MMT对环氧树脂升温固化进程的影响. 随后, 优选一种EP/MMT 混合体系即EP/D400-T500-MMT 混合体系, 系统地研究了该体系与纯环氧树脂体系在130, 140, 150 及160 ℃等几个温度下的等温固化过程, 考察了等温固化时间对固化度和固化度变化速率的影响以及固化度与固化度变化速率之间的关系, 并利用Kamal 模型进行拟合计算了固化动力学参数. 研究结果表明, 与纯环氧树脂相比, 几种聚醚胺改性MMT 的固化放热峰均向高温迁移, 同时聚醚胺D400 协同插层MMT 降低了高分子量聚醚胺插层MMT 所导致的环氧树脂DSC 曲线的畸变情况; EP/D400-T500-MMT 混合体系和纯环氧体系的等温固化反应过程符合Kamal 模型;在相同的固化温度下, EP/D400-T5000-MMT 混合体系的反应速率常数k₁ 和k₂ 值以及反应级数m 均比纯EP 体系小, 而反应级数n 以及总反应级数m+n 值比纯EP 体系大, 表明两种聚醚胺协同插层的改性蒙脱土D400-T5000-MMT 的加入降低了环氧体系固化反应速率. 另外, EP/D400-T5000-MMT 混合体系的活化能E_a1 和E_a2 与纯EP 体系的相比也略有升高.     

4,4'-二氨基二苯醚二苯酮固化环氧树脂/粘土纳米复合材料的研究

采用离子交换法, 用十六烷基三甲基溴化铵处理钙基蒙脱土(MMT), 使蒙脱土的层间距由1.49 nm扩大到2.21 nm, 制备了环氧树脂/ BADK/MMT纳米复合材料, 并用XRD等手段研究了有机蒙脱土在环氧树脂中的插层及剥离行为. 研究结果表明, 蒙脱土含量及环氧树脂与有机土的混合温度和时间均对固化后复合材料的剥离产生影响, 只有在特定条件下才能得到剥离型纳米复合材料.     

苯并噁嗪/蒙脱土插层体系和苯并噁嗪体系的动态固化行为比较

比较了苯并噁嗪单体(BZ)和插层于蒙脱土层间的苯并噁嗪单体(BZ/MMT)两种体系的动态固化特性.实验发现,经有机化处理的蒙脱土在BZ/MMT体系的固化行为中起着重要的作用,使该体系存在催化聚合和热聚合两类固化单元反应.结果造成两种体系在特征固化温度、固化速率、反应热、反应级数以及表观活化能上存在明显的差别.     

Avrami法研究环氧树脂/蒙脱土/咪唑纳米复合材料的固化动力学

运用Flory凝胶化理论和Avrami法研究环氧树脂／有机蒙脱土／咪唑插层型纳米复合体系在不同温度及不同有机蒙脱土用量时的固化动力学。实验表明,随固化温度的提高,Avrami速率常数k值增大,凝胶化时间tg缩短,凝胶点后的t1/2降低,固化速率加快,当固化温度低于90℃时,Avrami指数n值为3左右,而固化温度高于90℃时,n值为2左右。有机蒙脱土的加入,使固化速率加快,但并不改变固化反应的机理,Avrami方程可以很好地描述凝胶点后的固化动力学。     

酚醛树脂/蒙脱土纳米复合材料的制备及固化反应动力学研究

利用自制的有机蒙脱土 ,采用浇模固化成型法制备酚醛树脂 /六次甲基四胺 /蒙脱土纳米复合材料 ,并用XRD观察有机蒙脱土分别在热塑性和热固性酚醛树脂中复合行为 .研究发现 ,由于两种树脂的固化反应机理不同 ,热固性酚醛树脂与蒙脱土复合 ,可得插层型纳米复合材料 ;而采用热塑性酚醛树脂进行固化 ,则得到部分剥离的纳米复合材料 .通过DSC进一步研究热塑性酚醛树脂 /蒙脱土复合体系的固化反应动力学 .运用Kissinger ,Flynn Wall Ozawa ,Crane方法求出活化能和反应级数等动力学参数 .结果发现 ,加入蒙脱土使固化反应活化能下降 ,反应级数减小 ,从而有利于固化工艺的实现 ,便于纳米复合材料实际应用 .     

液晶环氧树脂/蒙脱土纳米复合材料的制备和固化反应动力学研究

用带有介晶基元的联苯二酚二缩水甘油醚 (BP)、4 氨基苯基磺酰胺 (SAA)和有机化蒙脱土 (93A)采用浇铸成模固化成型的方法制备出液晶环氧树脂 蒙脱土纳米复合材料 .WRXD结果表明 93A含量是 2 %时可形成剥离型纳米材料 ,而当 10 %时形成插层型纳米材料 ,5 %时则形成剥离和插层混合型的纳米材料 ;POM结果表明蒙脱土的存在能够破坏原有的扇形近晶相液晶织构 .DSC研究表明体系的固化反应动力学 ,可用变形的Kissinger Akahira Sunose法 (VKAS)表征 ,从求出的反应活化能和转化率关系 ,发现反应初期 ,蒙脱土使反应活化能降低 ,能够促进液晶环氧树脂的固化 .     

苯并恶嗪／蒙脱土插层体系和苯并恶嗪体系的动态固化行为比较

比较了苯并恶嗪单体（BZ）和插层于蒙脱土层间的苯并恶嗪单体（BZ／MMT）两种体系的动态固化特性。实验发现，经有机化处理的蒙脱土在BZ／MMT体系的固化行为中起着重要的作用，使该体系存在催化聚合和热聚合两类固化单元反应，结果造成两种体系在特征固化温度、固化速率、反应热、反应级数以及表观活化能上存在明显的差别。     

高抗冲聚苯乙烯/蒙脱土复合材料的阻燃性研究

用经十六烷基三甲基溴化铵有机化改性的蒙脱土 (OMMT)与高抗冲聚苯乙烯 (HIPS)通过熔融插层法制备了HIPS OMMT复合材料 ,用X ray衍射技术对材料结构进行了表征 ,发现钠基蒙脱土 (Na+ MMT)和有机蒙脱土的层间距分别为 1 5 1nm和 2 18nm ,HIPS OMMT(5phr)复合材料中蒙脱土的层间距因聚合物大分子的插入扩大为 3 4 4nm ;而HIPS与Na+ MMT形成的复合材料的层间距与Na+ MMT的层间距相比却没有变化 ,表明未有机化处理土没有形成插层结构 .锥形量热仪的研究结果表明HIPS OMMT复合材料的热释放速率、质量损失速率以及生烟速率等燃烧特性参数均显著降低 ,具有较明显的阻燃性和抑烟性 ,而HIPS Na+ MMT非插层型复合材料只有在Na+ MMT很高填充量下 (>2 0phr)才有一定阻燃效果 .比较了铵盐对HIPS阻燃性的影响 ,结果表明铵盐自身的阻燃作用很小 ,主要是插层复合结构起阻燃作用 .     

环氧基笼型倍半硅氧烷/4,4'-二氨基二苯砜体系的等温固化动力学

应用等温差示扫描量热法研究了4,4'-二氨基二苯砜(DDS)固化笼型倍半硅氧烷环氧树脂(POSSER)体系的反应动力学,测定了固化反应热,得出了不同温度下固化反应程度与反应时间、固化反应速率与反应时间的关系曲线,通过非线性拟合得到固化反应速率与反应程度的关系曲线.结果表明,固化反应在体系的玻璃化转变温度以上进行,等温固化反应遵从自催化反应机理,用Kamal方程可很好地描述不同温度下固化反应的自催化过程,拟合得到其反应动力学参数k1、k2、m、n,k1和k2对应的固化反应的表观活化能分别为79.67和59.84 kJ/mol.     

树枝形大分子/环氧树脂体系固化反应动力学研究

用示差扫描量热仪(DSC)对树枝形大分子PAMAM/双酚-A型环氧树脂体系的固化反应动力学过程进行了分析。通过Kissinger法求得体系固化反应的表观活化能ΔE为59.78kJ/mol,通过Crane法求得体系的固化反应级数n=0.91,并计算出了反应速率常数k和不同升温速率下的频率因子A。根据动态DSC数据确定体系合适的固化反应温度为80~90℃,后固化温度为140℃。     

Investigation of cure kinetics of epoxy resin/organic montmorillonite system by differential scanning calorimetry

The cure kinetics of the epoxy resin (EP)/organic montmorillonite, with 4-diamino diphenyl methane (DDM) as curing agent, was studied by non-isothermal differential scanning calorimetry (DSC) at four linearly programmed heating rates of 5, 10, 15, and 20 deg/min, and the effects of original montmorillonite (OMMT) on cure kinetics of epoxy resin were investigated. A two parameter (m, n) autocatalytic model was used to describe the cure kinetics of the epoxy resins. The kinetic parameters were calculated with the Malek method and the curves obtained by the Málek method showed a good agreement with experimental data for EP/DDM and EP/DDM/OMMT systems. The results, based on the isoconversional method showed that the activation energy was obvious difference with the addition of OMMT in the early stages of the cure, which indicated that the OMMT have catalytic effect on the epoxy ring-opening.     

双酚-S环氧树脂与琥珀酸酐固化反应动力学

用差示扫描量热法（ＤＳＣ）研究了双酚－Ｓ环氧树脂（ＢＰＳＥＲ）与琥珀酸酐固化反应的历程。实验结果表明,固化反应主要分两个阶段,前期由化学动力学控制,服从自催化机理。实验数据利用Ｋａｍａｌ方程处理得到两个速率常数ｋ、、ｋ２及两个反应级数ｍ、ｎ、ｋ１、ｋ２的值随反应温度的升高呈增大的趋势,总反应级数ｍ＋ｎ在２～２．５之间,当转化率达到４０％左右后,由于交联程度增加,分子量迅速增长,分子间扩散较慢,进入     

Curing kinetics of o-cresol formaldehyde epoxy resin and succinic anhydride system catalyzed by tertiary amine

The kinetics of the cure reaction for system of o-cresol formaldehyde epoxy resin (o-CFER)/succinic anhydride (SA) and tertiary amine as a catalyst was investigated with a differential scanning calorimeter (DSC). Autocatalytic behavior was shown in the first stages of the cure for the system, which was well described by the model proposed by Kamal that includes two rate constants, k1 and k2, and two reaction orders, m and n. The overall reaction order, m + n, is in the range 2.1-2.6, and the activation energy for k1 and k2 was 109 and 72.0 kJ/mol, respectively. In the later stages, a cross-linked network was formed and the cure reaction is mainly controlled by diffusion. Diffusion factor, f(alpha), was introduced into Kamal's equation, then the calculated values agree very well with the experimental data. The molecular mechanism of this curing reaction was discussed.     

Influence of surface modified graphene oxide on the mechanical performance and curing kinetics of epoxy resin

In this study, the hyperbranched polyester were successfully grafted onto graphene oxide (GO). The mechanical performance and curing kinetics of epoxy resin (EP), EP/ graphene oxide (EP/GO), and EP/ hyperbranched polyester grafted GO (EP/GO‐B) were investigated by means of mechanical tests and differential scanning calorimetry (DSC). Results revealed that the presence of GO lowered the cure temperature and accelerated the curing of EP, and the addition of GO‐B exhibited a stronger effect in accelerating the cure of EP compared with GO. Activation energies were calculated using Kissinger approach, and Ozawa approach, respectively. Results revealed lowered activation energy after the addition of GO or GO‐B at low degrees of cure, indicating that GO had a large effect on the curing reaction. The presence of GO facilitated the curing reaction, especially the initial epoxy‐amine reaction. Moreover, GO‐B exhibited better performance. Related mechanism was proposed.     

环氧树脂/桐油酸酐/蒙脱土纳米复合材料固化动力学

环氧树脂/桐油酸酐/蒙脱土纳米复合材料固化动力学;固化反应;DSC     

Cure kinetics of epoxy resin-natural zeolite composites

The cure kinetics of epoxy resin and epoxy resin containing 10 mass% of natural zeolite were investigated using differential scanning calorimetry (DSC). The conformity of the cure kinetic data of epoxy and epoxy-zeolite system was checked with the auto-catalytic cure rate model. The results indicated that the hydroxyl group on the zeolite surface played a significant role in the autocatalytic reaction mechanism. This group was able to form a new transition state between anhydride hardener and epoxide group. The natural zeolite particles acted as catalyst for the epoxy system by promoting its curing rate.     

非等温法研究TGDDM/DDS体系固化反应动力学

采用DSC对4,4′-四缩水甘油基二氨基二苯基甲烷(TGDDM)和3,3′-二氨基二苯基砜(DDS)体系的固化反应动力学进行了研究.分别通过n级反应法和Malek的最大概然机理函数法确定了固化反应机理函数,求解了固化反应动力学参数,得到了固化反应动力学模型.结果表明,通过Kissinger,Crane方法求解动力学参数所得到的n级反应模型与实验值差别较大;而采用Malek方法判别机理,表明该固化反应按照自催化反应机理进行,实验得到的DSC曲线与模型计算所得到的曲线吻合的较好,所确立的模型在5~20K/min的升温速率下能较好地描述TGDDM/DDS体系的固化反应过程,并为工艺参数的选择和工艺窗口的优化提供了理论依据.     

Pyrolysis and fire behaviour of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS)

The pyrolysis and fire behaviour of epoxy resin (EP) composites based on a novel polyhedral oligomeric silsesquioxane containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-POSS) and diglycidyl ether of bisphenol A (DGEBA) have been investigated. The pre-reaction between the hydroxyl groups of DOPO-POSS and the epoxy groups of DGEBA at 140 °C is confirmed by FTIR, which means that DOPO-POSS molecules of hydroxyl group could easily disperse into the epoxy resin at the molecular level. The EP composites with the DOPO-POSS were prepared through a curing agent, m-phenylenediamine (m-PDA). The morphologies of the EP composites observed by SEM indicate that DOPO-POSS disperses with nano-scale particles in the EP networks, which implies good compatibility between them. The thermal properties and pyrolysis of the EP composites were analyzed by DSC and TGA, TGA-FTIR, and TGA-MS. The analysis indicates that the DOPO-POSS change the decomposition pathways of the epoxy resin and increase its residue at high temperature; moreover, the release of phosphorous products in the gas phase and the existence of Si-O and P-O structures in the residue Is noted. The fire behaviour of the EP composites was evaluated by cone calorimeter (CONE). The CONE tests show that incorporation of DOPO-POSS into epoxy resin can significantly improve the flame retardancy of EP composites. SEM and XPS were used to explore micro-structures and chemical components of the char from CONE tests of the EP composites, they support the view that DOPO-POSS makes the char strong with the involvement of Si-O and P-O structures.     

The curing kinetics and mechanical properties of epoxy resin composites reinforced by PEEK microparticles

In this paper, a polyether-ether-ketone (PEEK)/epoxy composite was prepared by using PEEK microparticles as the reinforcement. The nonisothermal differential scanning calorimetry (DSC) test was used to evaluate the curing reaction of PEEK/epoxy resin system. The curing kinetics of this system were examined utilizing nonisothermal kinetic analyses (Kissinger and Ozawa), isoconversional methods (Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) and an autocatalytic reaction model. During these analyses, the kinetic parameters and models were obtained, the curing behavior of PEEK/epoxy resin system under dynamic conditions was predicted. The results show that isoconversional methods can adequately interpret the curing behavior of PEEK/epoxy resin system and that the theoretical DSC curves calculated by the autocatalytic reaction model are in good agreement with experimental data. Furthermore, the tensile elongation at break, tensile strength, flexural strength, compression strength and compression modulus increased by 81.6%, 33.66%, 36.53%, 10.98% and 15.14%, respectively, when PEEK microparticles were added in epoxy resin composites.