环氧树脂/氧化石墨纳米复合物的等温固化行为研究

用示差扫描分析仪(DSC)研究了氧化石墨(GO)对N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷环氧树脂(TGDDM)/4,4'-二氨基二苯基砜(DDS)体系的等温固化反应的影响,用X射线光电子能谱仪(XPS)和傅里叶变换红外光谱仪(FTIR)研究了GO上存在的官能团及其对TGDDM/DDS体系固化行为的影响,用热失重分析仪(TGA)研究了天然石墨和GO的热力学稳定性.XPS、FTIR和TGA结果表明,GO上存在的大量羟基、羧基、环氧基等官能团能够影响环氧树脂的固化行为.DSC研究发现,环氧树脂/氧化石墨纳米复合物的固化反应属于自催化类型,随着GO含量的增加,达到最大反应速率的时间不断减小,初始反应速率不断增大,这说明GO对环氧树脂的固化反应有促进作用.Kamal模型计算得到的结果表明,随着GO含量的增加自催化反应初期阶段表观活化能E1先减小再增大,而自催化反应结束后表观活化能E2略微减小.经Kamal模型扩散控制函数修正后,整个固化过程中拟合得到的结果与实验数据相当吻合.以上结果说明,少量的GO对TGDDM/DDS体系的固化反应起着催化作用.     

基于TGA-FTIR联用技术研究ABS树脂的热氧降解行为

采用热失重-傅立叶变换红外光谱(TGA-FTIR)联用技术研究了空气气氛下ABS树脂的热稳定性及热氧降解失重情况。研究了ABS在4个不同升温速率下的失重情况;采用TGA-FTIR联用技术对10℃/min等速升温下ABS失重过程的逸出气体进行分析;采用热分解动力学方法分析ABS的热氧降解过程,计算热分解活化能。结果表明,ABS的TGA曲线有两个失重区间:第一区间是ABS的急剧氧化降解过程,活化能(Ea)为191.8~262.8 kJ.mol-1,第二区间是成炭产物的氧化,Ea约为139.7 kJ.mol-1;升温速率越小,ABS热氧降解速率越慢,交联成炭产物越多,有利于抑制ABS的降解;由FTIR测试和Ea变化发现,热氧降解反应为多步复杂反应,初期时氧化反应和氧化断链同时进行,并以氧化断链反应为主,随着分子链上产生的双键增多发生交联反应,失重率大于80%时开始炭化反应,最终交联炭层发生氧化反应生成CO2。     

N,N′-二苯胺基己二酰胺β-晶型成核剂的热分解动力学分析

基于热重分析、微商热重分析及示差热分析研究了N,N′-二苯胺基己二酰胺β-晶型成核剂在空气气氛中的热分解动力学;通过利用Friedman方程和Flynn-Wall-Ozawa(FWO)方程对其热分解过程进行动力学分析求得了其热分解表观活化能;同时利用Achar-Brindly-Sharp方程和Coats-Redfern方程研究了其热分解机理,用等温热重分析法测得了失重10%时的寿命方程.结果表明,N,N′-二苯胺基己二酰胺β-晶型成核剂的表观活化能为138.66kJ.mol-1,其热分解反应的机理函数符合Mample法则,反应级数n=3/2,动力学方程为G(α)=α3/2,寿命方程为:lnτ=-51.877+2.922 2×104/T.     

新型阻燃聚丙烯腈共聚物在空气中的非等温热分解动力学

用O,O-二乙基-O-烯丙基硫代磷酸酯(DATP)与丙烯腈共聚合成了新型阻燃聚丙烯腈共聚物(FR-PAN), 对其在空气中的非等温动力学通过TG-DTG技术进行了研究, 并通过极限氧指数法(LOI)考查了FR-PAN的阻燃性能; 利用Kissinger方法和Flynn-Wall-Ozawa (FWO)方法计算出了FR-PAN热降解过程中的表观活化能; 采用Satava-Sestak方法通过对不同机理模型的选取, 确定了FR-PAN的热降解机理. 结果表明, 由Kissinger法和FWO法所计算得到的FR-PAN的表观活化能分别为119.62和123.99 kJ•mol－1; FR-PAN的热降解反应属于随机成核和随后增长机理, 其机理函数为G(α)＝－ln(1－α), 反应级数n＝1.     

聚碳酸亚丙酯马来酸酐的热分解动力学(英文)

通过热重分析研究了新型三元共聚物聚碳酸亚丙酯马来酸酐(PPCMA)在不同升温速率下的热分解动力学.设计并引入一种新的计算方法,非线性约化法(NLA),对共聚物热分解过程中的表观活化能进行了计算.研究发现,虽然用非线性约化法计算的表观活化能相对误差值稍大于用传统计算方法Flynn-Wall-Ozawa(FWO),Tang和Kissinger-Akahira-Sunose(KAS)计算的相对误差值,但其分析合理且计算过程更为简便.此外,固态反应模型拟合方法计算结果表明,共聚物的热分解过程对应多个反应机理.整个热分解过程,表观活化能值处于70-135kJ·mol-1之间,指前因子处于5.24×104-9.89×107min-1之间.同时,通过对表观活化能值的比较,初步解释了聚碳酸亚丙酯(PPC)与PPCMA热解温度差异的原因.     

双酚A二炔丙基醚与4,4′-联苯二苄叠氮的合成及聚合反应研究

合成了两种单体双酚A二炔丙基醚与4,4′联苯二苄叠氮,研究了一种新的低温聚合体系———双酚A二炔丙基醚与4,4′联苯二苄叠氮在烘箱中的本体聚合行为.通过红外、核磁共振以及质谱、元素分析等表征了单体的结构.利用傅立叶红外技术(FTIR)跟踪了聚合反应过程中特征基团的变化,采用差示扫描量热技术(DSC)研究了聚合反应工艺及其动力学,热失重分析(TGA)考察了聚合产物的热稳定性能.通过Kissinger法和0zawa法获得了反应的一些动力学参数.结果表明,双酚A二炔丙基醚与4,4′联苯二苄叠氮易发生1,3偶极环加成聚合反应,在聚合物结构中形成三唑五元环,它们的聚合起始温度在70℃左右,聚合反应的主反应是一级反应,表观活化能ΔE=84.6kJmol,指前因子A=4.865×1010min-1.同时发现,聚合物具有较好的热稳定性能.     

膨胀型无卤阻燃HIPS热分解动力学及阻燃机理研究

利用动态热失重法(TGA)研究了一种新型的膨胀型无卤阻燃高抗冲聚苯乙烯(HIPS)热降解反应动力学及阻燃机理, 通过对Kissinger模型和Coat-Redern (C-R)模型求解的热降解反应的动力学参数对比, 最终确定反应的动力学参数. 其中, 反应级数n的确定是通过一般反应对Ea/RTmax取值范围的限定, 利用最大热降解速率所对应的失重率αmax与n的关系, 确定其取值. 并采用TGA-FTIR及Py-GC/MS对材料气相产物及热裂解产物进行了阻燃机理的研究. 研究表明, 两种反应的热降解反应动力学参数基本一致, 其中阻燃HIPS的平均表观活化能小于纯HIPS, 说明在HIPS分解之前, 无卤阻燃剂已经开始分解, 释放的难燃气体(氨气及其衍生物、水蒸气等)在气相中起到阻燃的作用. 同时阻燃剂的添加, 促使反应向链转移反应飘移, 使燃烧产物中非单体化合物增加, 而在凝聚相中形成的致密的炭层结构也起到阻燃的效果.     

聚甲基丙烯酸甲酯热氧化降解的化学动力学研究

使用质谱、热分析手段研究了PMMA热解反应.结果表明,在氮气中,PMMA-CH=CH2有两个失重阶段,分别对应于主链末端双键引发的断链和主链无规则断链反应,转折点的失重率约为26%.其中,第一阶段的失重速率受扩散过程控制,平均表观活化能E为158.5 kJ/mol, lnA为27.69;第二失重阶段为1.5级化学反应,平均表观活化能E为214.79 kJ/mol, lnA为40.46.在空气中, PMMA也有两个失重阶段,反应机理为1级化学反应,转折点处的失重率约为70%.其中在第一失重阶段平均表观活化能E为130.32 kJ/mol, lnA为24.81,在此阶段中, 过氧化基团的分解反应对PMMA的失重速率有重要影响; 在空气中第二失重阶段平均表观活化能E为 78.25 kJ/mol, lnA为13.97.     

BMI/DDE/F-51 环氧树脂的固化及其热稳定性

以双马来酰亚胺(BMI)/二氨基二苯醚(DDE)组合固化剂对酚醛环氧树脂(F-51)进行固化,得到了BMI/DDE/F-51 固化体系,将该体系与单一固化剂固化的 BMI/F-51、DDE/F-51 体系进行比较,探求其固化机理和热稳定性.用差示扫描量热仪(DSC)研究了BMI/DDE/F-51 的固化反应动力学,求得固化反应表观活化能 Ea=60.86 kJ/mol、碰撞因子 A=2.04×106s-1和反应级数 n=0.89;用傅里叶变换红外光谱(FT-IR)对反应历程进行了探讨;用热失重分析仪(TGA)研究BMI/DDE/F-51 固化树脂的热分解动力学,确定了热稳定性能良好的耐高温环氧树脂新体系,其热分解反应表观活化能为 BMI/F-51 或 DDE/F-51 固化体系的3倍以上,达 166.08 kJ/mol.     

ZnAc2·2H2O在空气中的热分解动力学研究

用TG/DTA,DSC和XRD技术研究了固态物质ZnAc2.2H2O在空气中的热分解过程.结果表明,ZnAc2.2H2O在空气中发生两步分解,其失重率与理论计算失重率相符.XRD结果表明,ZnAc2.2H2O分解的最终产物为ZnO.用Friedman法和Flynn-Wall-Ozawa(FWO)法求得分解过程的活化能E,并通过多元线性回归方法给出了可能的机理函数.ZnAc2.2H2O在空气中两步分解的活化能分别为119.82和66.82kJ/mol.     

Preparation and Properties of Non-ionic Polyurethane Crosslinkers from 2-Ethoxyethanol/ϵ-caprolactam-Blocked Diisocyanate

A series of novel water-based non-ionic blocked polyurethane crosslinker (n-BPUC) dispersions have been synthesized by the reaction of toluene 2,4-diisocyanate (TDI), isophorone diisocyanate (IPDI), polyethylene glycol (PEG), 1,1,1-trimethylolpropane (TMP), 2-Ethoxyethanol (2-Et) and ?-caprolactam (CL). The physical properties of prepared n-BPUC dispersions such as viscosity, pH, and storage stability are measured and compared. The chemical structure of the prepared n-BPUC dispersions is confirmed by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Deblocking temperatures of the n-BPUC dispersions are analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) techniques. The thermal analysis reveals that deblocking temperature obtained by DSC and TGA techniques is compared and found to be in the order DSC < TGA. Based on DSC and TGA data, it is shown that deblocking of n-BPUC dispersions based on 2-Et start at lower temperatures compared to that of the ones based on CL. The TDI-based n-BPUCs show higher reactivity than the ones based on IPDI. Hydroxyl-terminated polyurethane (HPU) is introduced to estimate the crosslinking effect of the prepared n-BPUCs. The better tensile properties and water resistance of n-BPUC modified HPU films compared to pure HPU film demonstrate the good crosslinking effect of the prepared n-BPUCs.     

Crystalline properties and decomposition kinetics of cellulose fibers in wood pulp obtained by two pulping processes

In this study two cellulose fibers, Eucalyptus grandis (CEG) and Pinus taeda (CPT), obtained through the kraft and sulfite pulping processes, respectively, were characterized. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were carried out. From the XRD analysis the interplanar distance, crystallite size and crystallinity index were calculated and the degradation kinetics parameters were determined by TGA at heating rates of 5, 10, 20 and 40 °C min⁻¹ using the Avrami, Flynn-Wall-Ozawa (FWO) and Criado methods. The results obtained by FTIR showed that the composition of the fibers is similar, while from the XRD analysis slight differences in the crystallinity were observed. The thermogravimetric analysis showed higher thermal stability for CPT than CEG while the values for the activation energy (E_a) were higher for CEG than CPT. The results obtained by Avrami and Criado methods showed that the degradation mechanism in the CEG samples involves a diffusion process while in the case of CPT the degradation process is a phase boundary controlled reaction. The degradation mechanisms demonstrated that the difference between thermal stability and E_a may be due to differences in the type of crystalline structure of the samples obtained through the two pulping processes.     

二氧化碳-环氧丙烷-丙交酯三元共聚物的合成与表征及其热解动力学研究

通过二氧化碳(CO2)、环氧丙烷(PO)与D,L-丙交酯(D,L-LA)的三元开环共聚,得到一种新型热塑性脂肪族聚碳酸酯(PPCLA).对PPCLA结构进行了FTIR、1H-NMR、13C-NMR及1H-1H COSY表征,表明D,L-LA开环嵌入PO-CO,分子链中,并对共聚过程聚合机理进行了初步探讨.同时设计并引入...     

Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007     

氧离子导体La2Mo2O9中α→β相变非等温动力学的研究

以差热分析(differential thermal analysis,DTA)为手段研究了La2Mo2O9中α→β相变的非等温动力学。采用Flynn-Wall-Ozawa法计算了不同转化分数下的相变活化能E,并用Ozawa迭代法对E值进行了修正。应用Criado-Ortega法获得了α-La2Mo2O9→β-La2Mo2O9相变各温度区间的动力学机理函数,并用譒atava-譒esták法进行了验证。结果表明:La2Mo2O9中α→β相变的表观活化能与转化分数有关,说明该相变不属于一步简单反应。不同温度区间α→β相变的动力学机理函数不同,836～840K、842～848 K和850～853 K的动力学机理函数G(x)可依次表示为:-ln(1-x)、[-ln(1-x)]2/3、[-ln(1-x)]3/4。     

Effect of isocyanate structure on deblocking and cure reaction of N-methylaniline-blocked diisocyanates and polyisocyanates

Two series of N-methylaniline-blocked isocyanates based on monomeric diisocyanates such as 4,4′-methylene bis(phenyl isocyanate), toluene-2,4-diisocyanate, isophorone diisocyanate and 1,6-diisocyanato hexane and their NCO terminated polyurethane prepolymer (polyisocyanates) were prepared and characterized thoroughly by FTIR, ¹H NMR, ¹³C NMR and EI-Mass spectroscopic methods. The blocking reaction of N-methylaniline with aromatic isocyanates and aromatic polyisocyanates occur faster when compared to the aliphatic isocyanates. The deblocking reactions of blocked isocyanates were carried out under dynamic and isothermal conditions using hot-stage FTIR spectrophotometer. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate kinetics and thermodynamics parameters. Cure reactions of blocked isocyanates with hydroxyl-terminated polybutadiene were also followed to establish the structure-property relationship of the N-methylaniline-blocked isocyanates. The deblocking studies of blocked isocyanates reveal that the aromatic isocyanates undergo deblocking easily compared to aliphatic isocyanates. The rate of deblocking reaction of N-methylaniline-blocked aromatic polyisocyanates was found to be higher compared to N-methylaniline-blocked aromatic monomeric diisocyanate adducts. On the other hand, this trend was just reverse in the cure-reaction studies. The dissolution behavior of N-methylaniline-blocked isocyanates in Terathane-2000, polypropylene glycol-2000, polycaprolactone diol-2000 and hydroxyl-terminated polybutadiene-2500 was also studied and found that all adducts are soluble in these polyols.     

水合硼酸锶的制备及脱水热分解动力学

以氯化锶和硼酸氢铵为原料,采用液相沉淀法制备了片状水合硼酸锶（SrB6O10•5H2O）粉体,并用XRD、FT-IR及SEM进行了表征。利用热重分析法对片状纳米硼酸锶粉体的脱水热分解动力学进行了研究,分别采用 Coats- Redfern 方程和 Flynn-Wall-Ozawa（FWO）法对热重分析数据进行了处理和拟合,初步确定了水合硼酸锶的四步脱水过程及相应的热分解反应机理,得到各步反应的表观活化能和指前因子。     

Effect of a novel green modification of alumina nanoparticles on the curing kinetics and electrical insulation properties of epoxy composites

A novel green surface modification was successfully implemented on alumina nanoparticles using chitosan (CS) to prevent nanoparticles' aggregation. To evaluate the surface changes of nanoparticles, FTIR, TGA, TEM, and SEM analyses were used. The cure kinetics of the uncured samples was analyzed by DSC. Different methods such as KAS, Friedman, Starink, and FWO were applied to measure the activation energy. The activation energy of epoxy reinforced with chitosan-functionalized alumina (epoxy/[CS-EPO-alumina]) was less than that of epoxy reinforced with alumina (epoxy/alumina), which was a confirmation of the positive effect of CS on curing reaction kinetics. Using the Malek method, the Sestak-Berggren autocatalytic equation was chosen to investigate the cure kinetics of the epoxy. It was found that the Sestak-Berggren equation is well matched with the experimental data and the model was suitable to predict the epoxy curing reaction reliably. Moreover, the glass transition temperatures of all samples were approximately the same. The effect of surface modification of alumina on the electrical insulating behavior of epoxy was also studied. It was found that CS functionalized alumina (CS-EPO-alumina) increased volume resistivity of epoxy at a temperature range of 30 to 80°C more than that of alumina. Electric stability and breakdown strength of epoxy/alumina and epoxy/(CS-EPO-alumina) also enhanced, where epoxy/(CS-EPO-alumina) experienced a further increase compared to epoxy.     

多孔物质气固反应动力学研究

利用自主研制的微型流化床反应分析仪（MFBRA）在等温条件下测试了高比表面活性炭氧化反应,并根据基于固体转化的热分析动力学方法及考虑气体在微孔内扩散与反应的应用化工动力学方法求算了动力学参数．在内外扩散抑制最小化的实验条件下,粒径小于5μm的活性炭在700-1000℃的燃烧反应动力学研究表明,根据微型流化床中实验数据,采用等温热分析动力学方法求算得内扩散控制区活化能约为95kJ／mol;弓l入化工动力学方法中的随机孔模型对低温区等温燃烧数据拟合,可得孔结构参数在0．17m^-3左右,反应活化能为178kJ／mol,约为内扩散反应活化能的两倍,最为接近本征的碳燃烧反应活化能．