环氧树脂/玻璃纤维模压预浸料固化反应动力学研究

采用非等温DSC方法研究了一种模压预浸料（环氧树脂/玻璃纤维）的固化动力学,应用Kissinger和Crane方程拟合求得固化动力学参数,并建立了该预浸料固化动力学唯象模型。通过无转子硫化仪测试预浸料在不同温度下的凝胶时间,通过线性拟合得到固化温度与凝胶时间的函数关系,并对预浸料的固化工艺进行优化。结果表明,通过Kissinger和Crane方法算得该预浸料的固化反应动力学表观活化能为89.9 kJ/mol,指前因子为1.17×10¹¹ min^-1,反应级数为0.93;预浸料在模具温度为150 ℃下预热40 s,环氧树脂具有一定的流动性,并在2 MPa压力下固化300 s,可制备综合性能良好的复合材料制品。     

非等温DSC法研究VAc-BA-AM共聚乳液固化反应动力学

以醋酸乙烯酯、丙烯酸丁酯、丙烯酰胺为单体,通过半连续乳液聚合方法制备PVC皮革用胶黏剂,借助非等温DSC法(差示扫描量热法)研究共聚乳液的固化过程。使用Kissinger方程、Crane方程和T-β(温度-升温速率)外推法,计算共聚乳液体系固化反应的动力学参数和固化温度。结果表明,共聚乳液体系固化反应的表观活化能为51.71 k J/mol,指前因子为2.79×106S^(-1),反应级数为0.889,最佳固化温度为295.4 K。     

液体乙烯基硅树脂的制备及固化反应动力学

合成了一种液体乙烯基硅树脂,并用FT-IR、GPC、¹H NMR和²⁹Si NMR等手段对其结构进行表征。采用非等温差示扫描量热法（DSC）研究了乙烯基硅树脂/苯基含氢硅油体系的固化反应动力学,用Kissinger方程和高级等转化率法（Vyazovkin方法）分别计算了该体系的表观活化能E_a,用Málek法进行模型拟合动力学分析,通过T-β外推法确定该体系的固化工艺参数。结果表明：Kissinger法和Vyazovkin法得到的活化能分别为85.3 kJ·mol^-1和84.0 kJ·mol^-1,二者所得结果的差别较小;乙烯基硅树脂体系固化动力学符合Šesták-Berggren（m,n）模型,m和n分别为0.092、1.440,拟合曲线与实验的DSC曲线吻合;该树脂体系的近似凝胶化温度为89.1℃,固化温度为127.8℃,后处理温度157.6℃。     

聚酯树脂粉末涂料的固化行为

用差示扫描量热法(DSC)对固态条件下聚酯/TGIC(triglycidyl isocyanurate)体系的非等温固化反应动力学进行了研究。根据DSC和热重（TG）的分析结果,对聚酯粉末的固化过程及热稳定性进行了探讨,通过温度-升温速率图外推法确定了该体系的凝胶温度、固化温度和后固化温度分别为113、146和195℃。采用Kissinger方程、Doyle-Ozawa方程和Crane方程对DSC数据进行分析,得到了固化反应的平均表观活化能65.71 kJ·mol^-1,频率因子8.50×106 min^-1、反应级数0.95,建立了该树脂体系的固化动力学模型。讨论了固化反应速率、固化度、固化温度与时间等关系的变化规律及影响因素,为优化铝型材用粉末涂料聚酯体系的固化工艺提供了理论基础。     

FPC用改性丙烯酸酯胶粘剂的固化研究

改性丙烯酸酯类胶粘剂应用于挠性印制电路板(FPC)及其基材时,其固化程度对性能有着决定性的影响。本文以自制的环氧树脂改性的丙烯酸酯类胶粘剂为例,通过动态差示扫描量热仪(DSC)从理论上分析其非等温固化的动力学行为,以研究其在室温时的储存稳定性和高温固化的工艺条件。然后通过傅里叶变换红外光谱仪(FT-IR)研究其在室温以及125～300℃温度范围内的固化反应历程,以保证该胶粘剂应用于FPC的热固性胶膜/片的固化性能或效果。研究结果表明：(1)通过非等温DSC测试,确定了改性丙烯酸酯胶粘剂的固化动力学方程,由此推算其在10～50℃的常规储存温度下的反应速率常数K值低至10^-5 min^-1级别及以下,具有优异的B阶稳定性;同时在180℃及以上的K值达到10^-1 min^-1级别,可以满足其高温烘烤迅速固化的使用要求。(2)由动态DSC测试得到的三种特征温度,进而推算本胶膜的理论固化温度为182℃,且在此温度下实现100%固化需时约100 min,并通过DSC测试进行了验证。(3)通过FT-IR对比验证了以上...     

臭氧/过硫酸氢钾体系降解酮洛芬的动力学研究

利用臭氧/过硫酸氢钾体系降解酮洛芬模拟废水,考察了不同反应温度、初始浓度、初始p H值下酮洛芬的降解动力学,并拟合表观动力学方程;采用竞争法,以硝基苯和苯甲酸为分子探针,测定酮洛芬与硫酸根自由基的二级反应速率常数。结果表明,不同实验条件下酮洛芬降解符合准一级动力学,通过对实验数据进行拟合得到表观动力学方程k=494296exp（-31494/RT） C₀^-0.3677[OH^-]^0.1478,酮洛芬与硫酸根自由基的二级反应速率常数为1.49×10⁹M^-1s^-1。     

环氧树脂和环氧/环硫树脂与胺的固化反应动力学

采用非等温DSC法对低黏度体系CY184/IPDA环氧树脂体系及对CY184/ES184/IPDA环氧/环硫树脂体系的固化反应动力学进行了研究。用高级等转化率Vyazovkin积分法求取活化能E_a,通过Málek法确定了固化反应机理函数和动力学参数,得到固化反应动力学方程。结果表明:CY184/IPDA环氧树脂体系的平均活化能为47.04 kJ·mol^-1;CY184/ES184/IPDA环氧/环硫树脂体系的活化能为48.97 kJ·mol^-1。两种体系的模型拟合曲线与实验得到的DSC曲线吻合得较好,均符合esták-Berggren(m,n)模型。     

GAP与炔丙基三嗪的固化反应动力学研究

采用动态差示扫描量热法(DSC)研究了炔丙基三嗪类新型多功能固化交联剂TPC与叠氮黏合剂GAP的固化反应动力学。根据所测量的不同升温速率的DSC曲线,采用Kissinger和Crane方程计算了GAP/TPC体系的动力学参数,建立了GAP/TPC体系的固化动力学方程。结果表明:TPC与GAP的固化反应为一级反应,反应级数n=0.935,表观活化能Ea=97.30 kJ/mol,表观频率因子A=2.38×1012min–1。     

柔性UPR树脂/粉煤灰非等温固化动力学

用差示扫描量热法(DSC)研究了柔性不饱和聚酯树脂/粉煤灰体系的非等温固化过程,利用T-β外推法确定了体系的固化工艺温度:凝胶温度257.625K、固化温度374.275K、后处理温度406.565K。用Flynn-Wall-Ozawa法和Friedman-Reich-Levi法获得了柔性UPR固化反应表观活化能为Ea=83.94kJ·mol-1。由ASTME698-79标准方法求得指前因子,lnA=25.27;结合Crane方程分析知,复合体系的固化反应接近于一级反应。最终建立了复合体系固化反应动力学方程为ln(ddαt)=25.27-10096.22T+ln(1-α)0.9126。     

TGDDM/1,4-二(4-氨基苯-1-氧)正丁烷非等温固化反应动力学

合成了一种新型环氧树脂固化剂1,4-二(4-氨基苯-1-氧)正丁烷(DDBE),并采用FTIR、¹H NMR手段对其结构进行表征和确认。采用非等温差示扫描量热法(DSC)研究了N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯甲烷(TGDDM)/DDBE体系的固化反应动力学,根据Kissinger方程计算体系的活化能为58.5 kJ·mol^-1;采用Málek法进行模型拟合动力学分析,结果表明:其中的Šesták-Berggren模型的拟合曲线与实验的DSC曲线吻合,确定了体系的固化反应动力学参数和方程。DSC测试TGDDM/DDBE固化物玻璃化转变温度为195℃。     

Glycidyl Azide Polymer Crosslinked Through Triazoles by Click Chemistry: Curing,Mechanical and Thermal Properties

Glycidyl azide polymer (GAP) was cured through “click chemistry” by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3‐dipolar cycloaddition reaction to form 1,2,3‐triazole network. The properties of GAP‐based triazole networks are compared with the urethane cured GAP‐systems. The glass transition temperature (T_g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T_g in comparison to the GAP‐urethane system (T_g−20 °C) and the networks exhibit biphasic transitions at 61 and 88 °C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)‐based theoretical calculations implied marginal preference for 1,5‐addition over 1,4‐addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP‐triazole and the mechanism of decomposition was elucidated using pyrolysis GC‐MS studies. The higher heat of exothermic decomposition of triazole adduct (418 kJ ⋅ mol⁻¹) against that of azide (317 kJ ⋅ mol⁻¹) and better mechanical properties of the GAP‐triazole renders it a better propellant binder than the GAP‐urethane system.     

高热流低流速条件下超临界CO2在小圆管内的对流传热特性

为获取高热流、低流速条件下超临界CO₂的传热规律，开展了超临界CO₂在内径2 mm水平小圆管内对流传热试验研究，并重点探讨了变物性、浮升力和热加速等效应对传热过程的影响。试验参数范围：系统压力7.6~8.4 MPa，质量流速400~500 kg/(m²?s)，热通量0~200 kW/m²，流体温度20~60℃，Reynolds数1.2×10⁴~4.3×10⁴。分别采用Gr/Re ²和Kv作为浮升力效应和热加速效应的判别因子。结果显示，在高热流低流速工况下，浮升力效应显著（Gr/Re ² > 10^-3），同一个截面处的上壁面传热系数始终小于下壁面传热系数。浮升力效应是高热流低流速工况下传热恶化的主要诱发因素。试验中热加速因子较小（Kv < 8.5×10^-7），其效应可以忽略。将试验数据与典型的传热经验关联式作对比，结果表明Liao-Zhao关联式的计算结果与试验结果最吻合。     

酸功能化离子液体催化合成仲丁醇的反应动力学(英文)

The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4 as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a ho-mogeneous kinetic model was established. The results show that the reaction heatΔH is 10.94 × 103 J·mol?1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea?are 60.38 × 103 and 49.44 × 103 J·mol?1, respectively.     

Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis ...     

Study on Curing Reaction Thermokinetics of Azide Binder/Bispropargyl Succinate by Microcalorimetry

The thermokinetics of the curing reactions between poly‐(3‐azidomethyl‐3‐methyloxetane) (PAMMO) and bispropargyl succinate (BPS) were studied using a microcalorimeter. On the basis of experimental and calculated results, three thermodynamics parameters (the activation enthalpies, the activation entropies, the activation free energies), the rate constant, three thermokinetic parameters (the activation energies, the pre‐exponential constant, and the reaction order) and the enthalpies of the curing reactions between PAMMO and BPS in the temperature range of 50–65 °C were obtained, showing that the main reaction leading to a triazole structure easily took place in the studied temperature range. The linear relationship between lnk and the molar ratio of triple bonds to azide groups was found. Furthermore, the corresponding kinetic equation describing the curing reaction between PAMMO and BPS was dα/dt=10^−4.48(1−α)^0.962 at 333.15 K.     

A Study on the Triazole Crosslinked Polymeric Binder Based on Glycidyl Azide Polymer and Dipolarophile Curing Agents

Instead of using urethane curing systems, which have long been used as solid propellants, a triazole curing system has been introduced into a new binder recipe in which azide groups in the polymer react with triple bonds of a dipolarophile curing agent. Commercially available glycidyl azide polymers (GAP) were used and an aliphatic curing agent, bispropargyl succinate (BPS), as well as an aromatic curing agent, 1,4‐bis(1‐hydroxypropargyl)benzene (BHPB), were synthesized as dipolarophile curing agent. Together with networks prepared under the triazole curing system, the networks under dual curing systems, which consist of an isocyanate curing agent and a dipolarophile curing agent, were prepared. Through swelling experiments, solubility parameters and crosslinking densities of the triazole crosslinked networks were determined by using Gee’s theory and Flory–Rhener theory. The mechanical properties of the triazole crosslinked networks were also investigated with different contents of the dipolarophile curing agent, along with the type of dipolarophile curing agent. The networks prepared under the triazole curing system did not show good mechanical properties. However, GAP‐based networks prepared under a dual curing system showed excellent mechanical properties with only a small amount of dipolarophile curing agent used. The effects of BPS and BHPB on the mechanical properties of the networks were much more distinguishable in networks prepared under a dual curing system rather than a single curing system.     

圆管束中导流器对其自然对流换热的影响

对无限大空间中5根同规格圆管组成的圆管束在管间放置导流器的自然对流换热进行了数值模拟研究。考虑了Ra在10³～10⁴范围内,导流器偏转角为0°～60°,圆管间距为2～4倍圆管直径的自然对流换热,分析了5根圆管的局部Nusselt数（Nu_loc）和平均Nusselt数（Nu_ave）。研究结果表明,导流器对管束结构的自然对流换热影响体现在两方面：一是对导流器下方圆管而言相当于障碍物削弱其换热,二是对导流器上方圆管而言隔绝了下方羽状流的影响,从而增强系统的整体换热。在圆管间距较大时,与无导流器的圆管束相比,C1～C4各圆管换热下降趋势明显放缓,并且从C4、C5圆管换热趋势上升,系统整体换热增强。圆管间距S=2D,Ra=10³,导流器主要起障碍物的作用,削弱C1～C4各圆管换热,导致系统整体换热下降。当导流器偏转角度为45°时系统换热达到最大值,较无导流器时换热最多有着21%的提升。     

石墨烯导电粉末涂料的制备与研究

将石墨烯邦定至粉末底粉的表面,在固化过程中,石墨烯可迁移至涂层表层,成膜后制备导电型石墨烯粉末涂料(邦定法)。作为对比,将石墨烯通过挤出机混炼后,完全分散在涂层中,制备导电型石墨烯粉末涂料(内挤法)。结果发现:石墨烯用量同样为0.3%时,内挤法涂层表面电阻为10 ¹² Ω,而邦定法可降低至10 ⁶ Ω。邦定技术可大大降低石墨烯的用量,降低成本。采用红外光谱对粉末涂料的化学结构进行表征,通过差示扫描量热仪(DSC)测定其固化过程,并探讨了石墨烯的添加量对涂层表面电阻的影响。     

降冰片烯酰亚胺型双苯并嗪的合成及性能

首先用降冰片烯二酸酐、对氨基苯酚为原料合成降冰片烯酰亚胺（NI）,然后用合成的NI、4,4-二氨基二苯醚（ODA）和多聚甲醛为原料进行Mannich反应合成出降冰片烯酰亚胺型双苯并嗪（NI-BOZ）,经高温固化后形成热固性树脂。用FTIR、¹H NMR、¹³C NMR分析了NI和NI-BOZ的化学结构,证实了所得的目标产物;用DSC对NI-BOZ的固化动力学进行研究;用DMA和TGA分析了NI-BOZ的固化物的热性能。结果表明：NI-BOZ的固化反应活化能为86.27 kJ·mol^-1,反应级数为0.91;poly（NI-BOZ）树脂空气条件下的玻璃化转变温度为215℃,氮气条件下失重5%的温度为445℃,失重10%的温度为467℃,在800℃的残碳率为63%。