环氧树脂/液晶固化剂固化反应动力学研究

通过差热分析 (DSC)研究了非等温过程环氧树脂 /液晶固化剂体系的固化反应动力学 ,研究了不同配比对固化反应的影响 ,固化反应转化率与固化温度的关系 ,计算了固化反应的活化能 ,确定了环氧树脂 /液晶固化剂的固化工艺条件 ,用偏光显微镜观察了环氧树脂 /液晶固化剂 / 4 ,4′ -二氨基二苯砜 (DDS)体系在不同温度下固化时的形态。结果表明 :液晶固化剂的加入量越大 ,固化反应速度越快 ;环氧树脂 /液晶固化剂体系固化反应的活化能为 71 5kJ/mol;偏光显微镜观察表明 :随着固化起始温度的增加 ,固化体系的形态由原来的具有各向异性的丝状结构变化为各向同性 ,液晶丝状条纹消失。     

双酚A型环氧树脂/芳香胺固化体系的固化动力学研究

分别以4,4‘-二氨基二苯甲烷（DDM）和4,4‘-二氨基二苯砜（DDS）为固化剂，采用非等温差示扫描量热法（DSC）研究了E-44和E-51两种双酚A型环氧树脂的固化反应动力学。收集与分析了在25～350℃范围内分别以5、10、15、20℃/min的升温速率进行固化的反应参数，然后采用Starink法计算得到不同环氧固化体系的表观活化能。同时，借助各固化体系的动态流变性能，分析了双酚A型环氧树脂/芳香胺固化体系的固化反应机理，并选用双参数自催化模型计算了各固化体系的反应速率方程。研究结果表明：当环氧固化体系的固化剂不同时，采用DDM作为固化剂的环氧固化体系（E-44/DDM、E-51/DDM），其表观活化能均低于添加DDS固化剂的环氧体系；选用同种固化剂（DDM或DDS）时，E-51树脂体系的表观活化能均低于E-44树脂固化体系。反应速率方程结果显示，该双参数自催化模型与实际试验结果的吻合性良好，可用于描述双酚A型环氧树脂/芳香胺固化体系的固化历程。     

腰果酚缩醛胺与环氧树脂的固化反应动力学的研究

在不同升温速率下,用差示扫描量热分析(DSC)研究了腰果酚缩醛胺固化剂(PCD)与环氧树脂的固化反应动力学。通过Kissinger、Crane方程和等转化率的方法求得了其表观活化能E=39.89kJ/mol,固化反应级数n=0.906。     

环氧树脂固化用腰果酚型酚醛胺的制备及其固化动力学研究

以腰果酚、甲醛和二乙烯三胺为原料通过曼尼希反应合成了腰果酚醛胺固化剂,通过红外光谱和凝胶渗透色谱分别对其化学结构和相对分子质量进行了分析,并研究了腰果酚醛胺固化剂对环氧树脂的固化动力学。结果表明：制备的腰果酚醛胺固化剂的数均、重均相对分子质量均在 1 250左右,且相对分子质量分布较窄。通过将非等温 DSC曲线数据拟合 Kissinger方程、 Ozawa方程、 Crane方程,得到环氧树脂 /二乙烯三胺固化体系表观活化能为 71. 40 kJ/mol,环氧树脂 /腰果酚醛胺固化剂的表观活化能低于前者为 56. 72 kJ/mol,固化反应级数没有变化,均为 0. 93。因此,相比于传统固化剂二乙烯三胺,腰果酚型酚醛胺能使得环氧树脂在更低的温度下,更快地进行固化,符合研究预期结果。     

桐油制备C_(21)聚酰胺环氧固化剂的性能及固化反应动力学研究

以桐油的甲醇酯交换产物桐酸甲酯和丙烯酸为原料,通过Diels-Alder加成反应合成了C21二元酸单甲酯(TMAA),桐酸甲酯和丙烯酸的加成温度为180℃,反应时间3 h,比通用C21二元酸的合成反应温度低70℃。然后用C21二元酸单甲酯和不同多元胺酰胺化制备了3种不同胺值的C21二酸聚酰胺环氧固化剂。机械性能测试显示,C21二元酸聚酰胺和双酚A环氧树脂(DGEBA)的环氧固化物和C36二聚酸聚酰胺650C的DGEBA固化物相比,具有更高的机械强度和模量。胺值为496 mg/g的C21二元酸聚酰胺与DGEBA的固化产物拉伸强度达58.63 MPa,断裂伸长率为3.27%,弹性模量达2 635.84 MPa,弯曲强度达99.9 MPa。差示扫描热分析法(DSC)测得C21二元酸聚酰胺的DGEBA固化物的玻璃化温度分别为108、109和116℃,比C36二聚酸聚酰胺的DGEBA固化物的玻璃化温度高出50℃左右。n级反应机理求取的3种固化剂与DGEBA的固化反应活化能分别为62.179、56.551和59.761 kJ/mol,比C36二聚酸聚酰胺与DGEBA的固化反应活化能高出约10 kJ/mol。固化反应动力学得出固化剂与DGEBA的凝胶温度、固化温度和后固化温度分别为40、90和150℃左右。     

环氧树脂／液晶固化剂固化反应动力学研究

通过差热分析（DSC）研究了非等温过程环氧树脂／液晶固化剂体系的固化反应动力学,研究了不同配比对固化反应的影响,固化反应转化率与固化温度的关系,计算了固化反应的活化能,确定了环氧树脂／液晶固化剂的固化工艺条件,用偏光显微镜观察了环氧树脂／液晶固化剂／4,4－二氨基二苯砜（DDS）体系在不同温度下固化时的形态。结果表明：液晶固化剂的加入量越大,固化反应速度越快;环氧树脂／液晶固化剂体系固化反应的活化能力为71.5kJ/mol,偏光显微镜观察表明：随着固化起始温度的增加,固化体系的形态由原来的具有各向异性的丝状结构变化为各向同性,液晶丝状条纹消失。     

环氧树脂增韧固化剂固化反应的FT-IR研究

使用环氧-三乙烯四胺缩聚物G(Epon828-TETA)及其环氧油酸辛酯改性物(G1)作为环氧树脂(Epon828)的固化剂,通过傅立叶变换红外光谱(FT-IR)法,比较研究了G/Epon828和G1/Epon828两个固化体系的动态等温固化过程,并能进一步对两个固化体系固化初期的固化反应进行了动力学研究.结果表明:两个固化体系的环氧基转化率都在较短时间内达到较高水平,随时间的延长,转化率上升缓慢并逐渐趋于恒定;固化温度越高,转化率越高;固化反应的反应速率在开始时很快达到最高,随反应时间的延长,反应速率逐渐下降并趋于稳定,并且固化温度越高,反应速率越高;但在相同的固化温度下,G/Epon828固化体系的转化率始终高于G1/Epon828固化体系.前者的固化反应速率在初期也大于后者;G/Epon828和G1/Epon828固化体系的固化反应均属一级反应,在相同的环氧基转化率时,前者的反应活化能和指前因子均小于后者.     

促进剂对低温固化剂-环氧树脂体系性能的影响

分别选用二乙烯三胺和间二甲苯二胺与甲醛、腰果酚按照不同比例反应制得13种改性胺环氧低温固化剂,通过剪切强度,反应活化能和固化度测定以及红外光谱分析研究了不同促进剂DMP-30用量对环氧树脂及上述胺体系的物理性能、固化过程及固化产物性能的影响。结果表明:DMP-30与环氧树脂/胺体系具有一定的匹配性,促进剂具有正负效应。对于环氧和改性胺反应配比n(腰果酚)∶n(间二甲苯二胺)∶n(醛)=1.0∶1.0∶1.0的体系而言,促进剂的最佳添加质量分数为2%。     

环氧基POSS/PAMAM杂合材料的制备及性能研究

以3-缩水甘油基氧丙基三甲氧基硅烷(EPTMS)为原料,合成得到了八官能团缩水甘油醚-多面体低聚倍半硅氧烷(简称POSS-EP)。采用4代树型端氨基聚酰胺-胺(PAMAM)作为POSS-EP和双酚A型环氧树脂(DGEBA)共混物的固化剂,制备了5个环氧基POSS/PAMAM杂化材料。通过动态差示扫描量热仪(DSC),研究了环氧和PAMAM的固化反应动力学。通过DSC、热重分析(TGA)、拉力和冲击测试,对环氧基POSS/PAMAM杂化材料的热性能和力学性能进行了研究。结果表明,该环氧基POSS/PAMAM杂化材料具有优良的热性能和力学性能。     

EP结构胶用腰果酚改性混胺低温固化剂的合成与表征

以腰果酚作为脂肪胺/脂环胺混胺的曼尼希改性剂,合成了一种EP(环氧树脂)结构胶用新型可低温固化的固化剂。研究结果表明:含不同脂肪胺/脂环胺配比的固化剂,其胺值、低温固化程度及固化度(α)均随脂肪胺掺量增加而增大;当w(脂肪胺)≥70%(相对于混胺质量而言)时,结构胶的剪切强度(14 MPa)仍可满足低温固化的要求;全脂肪胺体系与全脂环胺体系相比,前者的表观活化能(Ea)明显低于后者;混胺体系的固化反应兼具自催化和扩散控制的特征。     

Curing of DGEBA epoxy resin by low generation amino‐group‐terminated dendrimers

Low generation amino‐group‐terminated poly(ester‐amine) dendrimers PEA1.0 (NH₂)₃ and PEA1.5 (NH₂)₈, and poly(amido‐amine) dendrimer PAMAM1.0 (NH₂)₄ were used as diglycidyl ether of bisphenol A (DGEBA) epoxy resin hardeners. Thermal behavior and curing kinetics of dendrimer/DGEBA systems were investigated by means of differential scanning calorimetry (DSC). Compared with ethylene diamine (EDA)/DGEBA system, the dendrimer/DGEBA systems gradually liberated heat in two stages during the curing process, and the total heat liberated was less. Apparent activation energy and curing reaction rate constants for dendrimer and EDA/DGEBA systems were estimated. Thermal stabilities and mechanical properties of cured thermosetting systems were examined as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3902–3906, 2006     

树形分子的制备及对量子点荧光性能的影响

采用发散法合成了以乙醇胺为初始核的扇形树枝状化合物PAMAM,用核磁共振法（^1H NMR和^13C NMR）对G1．0—NH2,G1．0-SH进行了表征,证实了其结构;并用荧光分光光度计检测了PAMAM对CdTe量子点水溶液的荧光性质的影响。发现PAMAM树形分子可增强CdTe—TGA量子点的荧光,不同浓度的PAMAM对量子点荧光性能的影响不同。     

Synthesis and antioxidant activities in polyolefin of dendritic antioxidants with hindered phenolic groups and tertiary amine

Two novel primary antioxidants with dendritic structure and hindered phenolic groups were synthesized using 3‐(3,5‐diter‐butyl‐4‐hydroxyphenyl) propionic acid as raw material and dendritic poly(amidoamine) (PAMAM) as linker in chloroform. The antioxidant activities of the dendritic antioxidants were evaluated in polyolefin by melt flow index (MFI), yellowness index (Y.I.), and oxidation induction time (OIT). The dendritic antioxidants had excellent processing property and oxidation resistance behavior in polyolefin. At the same weighed amount of antioxidant, the MFI and Y.I. values of mulitiple‐extruded polyethylene (PE) stabilized with the dendritic antioxidants were smaller than those of the commercial antioxidants, as well as the OIT values of polyethylene (PE) stabilized with the dendritic antioxidants were larger. Applying to polypropylene, the antioxidant ability of the second‐generation dendritic antioxidant (G2.0 dendritic antioxidant) with larger molecular weight was superior to the commercial antioxidants and that of the first‐generation dendritic antioxidant (G1.0 dendritic antioxidant) was equal to the commercial antioxidants. The dendritic antioxidants can prevent polyolefin from breaking of macromolecular chain in processing and had stabilizing effect in polyolefin in service life by donating H‐atoms and electron to free radicals. The dendritic antioxidants combined with Irgafos 168 had improvement of antioxidant activities of the dendritic antioxidants in polyolefin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of Ag nanoparticles in the presence of low generational poly(ester‐amine) dendrimers

Stable Ag nanoparticles of 10–20 nm were prepared by reduction of AgNO₃ with NaBH₄ in water solution in the presence of low generational hydroxyl‐ terminated poly(ester‐amine) dendrimer G1.0 (OH)₁₆ and amino‐terminated poly(ester‐amine) dendrimer G1.5 (NH₂)₈ by optimizing preparation conditions. UV–vis absorption spectra and transmission electron microscopy were adopted to characterize absorption properties of Ag⁺/dendrimer complex, Ag/dendrimer nanocomposite aqueous solutions, and the morphology of the formed Ag nanoparticles, respectively. The results showed that the size of the Ag particles increased with Ag⁺/dendrimer molar ratio, and the size of Ag nanoparticles in Ag/G1.0 (OH)₁₆ system was larger than that of Ag nanoparticles in Ag/G1.5 (NH₂)₈ system, while the polydispersities of two systems were similar. Moreover, the Ag/G1.5 (NH₂)₈ nanocomposite system was more stable than the Ag/G1.0 (OH)₁₆ one. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 422–426, 2007     

Polyamidoamine dendrimers as curing agents: The optimum polyamidoamine concentration selected by dynamic torsional vibration method and thermogravimetric analyses

Polyamidoamine (PAMAM) dendrimers were investigated as curing agents in bisphenol A epoxy resin systems. The cure behavior of epoxy resin/PAMAM at varying components was investigated by a dynamic torsional vibration method (DTVM); the thermal behavior of the materials was characterized by means of thermogravimetric (TGA) analyses. The DTVM results show that 10/100 parts of the resin (phr) PAMAM was the optimum concentration for 1.0, 3.0, and 5.0 G PAMAM dendrimers/resin systems in our experiment. Also, the TGA results agreed with the conclusions made by the DTVM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1430–1434, 2007     

Curing behavior and viscoelastic properties of pine and wattle tannin-based adhesives studied by dynamic mechanical thermal analysis and FT-IR-ATR spectroscopy

This study investigated the curing behavior and viscoelastic properties of two types of tannin-based adhesives, wattle and pine, with three hardeners: paraformaldehyde, hexamethylenetetramine and TN (tris(hydroxylmethyl)nitromethane), by FT-IR-ATR spectroscopy and dynamic mechanical thermal analysis (DMTA). Using FT-IR-ATR spectroscopy, the chemical structures of tannin-based adhesives were determined and the degrees of curing as a function of temperature and time were compared with the conversion degrees of the hydroxyl groups. Paraformaldehyde was shown to be more reactive with wattle tannin than the other hardeners, while hexamethylenetetramine was the most reactive with the pine tannin. As the quantity of hardener was increased, the conversion degree also increased. The storage modulus (E′), loss modulus (E′′) and loss factor (tan δ) of each adhesive system were obtained by DMTA. With increasing temperature, as the tannin-based adhesives hardened, the storage modulus (E′) increased in all adhesive systems. The curing behavior results obtained by DMTA showed a similar tendency as seen from the FT-IR-ATR spectroscopy results. The curing behavior of the tannin-based adhesives was successfully determined using FT-IR-ATR spectroscopy in combination with DMTA.     

Study on Novel Epoxy Based Poly (Schiff Reagent)s

Abstract

Novel poly(schiff reagent)s from diketo derivative of epoxy resin were synthesised and characterised. A series of epoxy resin based poly(schiff reagent)s were synthesised by reacting an epoxy resin, diglycidyl ether of bisphenol-A (DGEBA) with 4-amino acetophenone (4-AAP) in a 1:2 mole ratio to afford the corresponding diketo derivative, and subsequent reaction with various aliphatic diamines in a presence of a triethyl amino as a catalyst. The resultant poly(schiff reagent)s were characterised by infrared spectroscopy (IR) and number average molecular weight (Mn) of PSs were estimated by non-aqueous conductometric titration. As produced, PSs having amine groups may act for curing of epoxy resins. Differential scanning calorimetric (DSC) curing kinetics of the epoxy resins viz. diglycidyl ether of bisphenol-A(DGEBA) and triglytidyl-p-amino phenol (TGPAP) have been investigated using PSs as a curing agent and triethyl amine as a catalyst. Thermal stability of the cured epoxy systems were studied by thermogravimetric analysis (TGA). The glass fiber reinforced composites of the produced PSs-epoxy system have been fabricated and were characterised by their mechanical properties and chemical resistance.     

Poly(amidoamine) dendrimers with phenyl shells: fluorescence and aggregation behavior

The fluorescence and aggregation behavior of poly(amidoamine) (PAMAM) dendrimers modified with phenyl groups at the periphery (PAMAM-P) were investigated. For comparison, the third generation (G3) PAMAM dendrimer with a shell of positive charge (PAMAM-PA) was also synthesized. PAMAM-P G3, G4 and G5 show dual fluorescence emission due to the fluorescence emission of phenyl ring and its excimer. By increasing the generation number from G2 to G4, the fluorescence intensity of phenyl ring decreases, and the fluorescence of phenyl excimer appears and becomes obvious. The three-dimensional geometry arrangement or dendrimer architecture was found to have a strong effect on their fluorescence behavior. This result is further supported by the solvent effect and model compound studies. The lower generations (PAMAM-P G0 to G3) were self-organized into spherical aggregates. However, no aggregation behavior was observed for the higher generations (>G3). The critical aggregation concentration (CAC) values measured by fluorescence spectroscopy were found to decrease gradually with increasing generation number from G0 to G3.     

Confocal microscopy study of phase morphology evolution in epoxy/polysiloxane thermosets

The morphology of stoichiometric initially immiscible reactive blends of DGEBA epoxy resin and poly(3-aminopropylmethylsiloxane) has been characterized by laser scanning confocal microscopy. Observations were done on samples cured isothermally at different curing temperatures in the range 20-120 °C as well as in situ and in real time at 60 °C. Three different processes were revealed: coalescence, which occurs primarily at very low conversion, diffusion of DGEBA through polysiloxane-rich domains and chemical reaction, which occurs at the interphase between both phases. The interphase-thickness and compositional gradients were characterized by laser scanning confocal microscopy (LSCM). Results show that as curing temperature increases within the studied range, the material becomes more homogeneous although the interphase thickness remains almost constant.     

Studies on Mechanical Properties of Imide-Amine Cured Expoxy-Glass Fiber Laminates

Epoxy (DGEBA)-glass fiber laminates were cured with different hardeners. Imide-amine hardeners were synthesized with different chemical groups in their backbone structure. Higher curing and postcuring temperatures were required for epoxy-glass fiber laminates cured with imide-amine hardeners. Compared to epoxy cured with aromatic amine (DADPM), tensile and flexural strength increased by 38.5% and 23.1%, respectively, in the laminates cured with imide-amine with sulfone groups in the backbone structure. Fracture surface of the laminates showed good bonding between the fiber and matrix.