催化剂对IPDI的异氰酸酯基选择性的影响

分别以三乙胺(TEA)、1,4-二氮杂二环[2.2.2]辛烷(DABCO)、二月桂酸二丁基锡(DBTDL)、辛酸亚锡(SO)作催化剂,在甲苯溶液中进行了异佛尔酮二异氰酸酯(IPDI)与苯甲醇的反应,对比了IPDI中不同异氰酸酯基的反应活性,并探讨了催化剂、温度等对其活性差异的影响。结果表明,TEA、DABCO作催化剂时,IPDI中异氰酸酯基的活性差异并不明显;DBTDL、SO作催化剂时,则存在明显的活性差异,仲脂环异氰酸酯基的活性大于伯异氰酸酯基的活性,而且SO作催化剂时活性差异更加显著。此外,根据不同温度的反应速率常数计算了各异氰酸酯基的活化能:DBTDL作催化剂时,伯仲异氰酸酯基的活化能分别为62.68 kJ/mol和53.02 kJ/mol;SO作催化剂时,伯仲异氰酸酯基的活化能分别为63.60kJ/mol和57.01 kJ/mol。     

RIM聚氨酯体系锡／胺类催化剂作用机理的研究

用自行研制的绝热流变仪和FTIR方法研究三种催化剂:三乙撑二胺(TD)、辛酸亚锡(SO)、二丁基锡二月桂酸酯(DBTOL),在RIM聚氨酯反应中的作用机理,着重探讨了锡/胺混合催化体系的协同效应。发现DBTDL/TD体系有协同效应,而SD/TD体系不表现协同效应。提出了存在这种差别的原因。     

PHA与TDI本体聚合反应动力学

用滴定法测定了甲苯二异氰酸酯(TDI),聚酯多元醇(聚己二酸己二醇酯PHA)在无催化剂和有催化剂时的本体聚合反应动力学。结果表明,TDI和PHA为二级反应,无催化剂时反应活化能为41.58 kJ/mol,在二月桂酸二丁基锡(DBTDL)催化下,活化能降为34.02 kJ/mol,说明催化剂能有效降低反应的活化能,提高反应速率。但无论有无催化剂,反应后期体系黏度均升高,反应逐步转为扩散控制而偏离二级动力学规律。     

聚氨酯封端反应动力学研究

利用傅里叶红外光谱技术研究了催化剂及反应温度对聚氨酯封端反应动力学的影响,研究表明三乙胺能加快对甲基苯酚封端聚氨酯预聚物反应的速度;加入0.2%三乙胺催化时,该反应活化能由不加催化剂时的15.16kJ/mol降低到5.4kJ/mol。未加催化剂时,该封端反应为二级反应,加入三乙胺催化剂后,该封端反应为一级反应。     

二甲基二烯丙基氯化铵与丙烯酰胺的共聚动力学

采用膨胀计法研究了以过硫酸铵-亚硫酸氢钠为引发剂的二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)的水溶液共聚合动力学,测定了相应的聚合速率方程、聚合表观活化能和单体竞聚率。结果表明,聚合反应温度为45℃,当DMDAAC与AM物质的量比分别为1∶9,2∶8和3∶7时,共聚速率方程分别为Rp1=k[M]2.61[IO]0.51[IR]0.52,Rp2=k[M]2.70[IO]0.50[IR]0.53和Rp3=k[M]2.73[IO]0.50[IR]0.56,表观活化能分别为Ea1=79.10 kJ/mol,Ea2=81.39 kJ/mol和Ea3=85.15 kJ/mol,两单体的竞聚率分别为rDMDAAC=0.14,rAM=6.11。上述实验结果可从动力学角度为不同阳离子度PDA聚合速率差别及产物特征黏度值差异进行解释。     

D4/D4Vi阴离子开环乳液共聚动力学及乳胶粒径

采用阴离子开环乳液聚合法制备了聚硅氧烷共聚乳液,研究了反应条件对共聚动力学及乳胶粒径的影响。结果表明,初始恒速阶段的表观动力学方程为Rp=k[E]0.18[KOH]0.59[M]0.75,表观活化能为52.77 kJ/mol。乳胶粒径随反应温度升高而变小,粒径分布在80℃出现最小值。随[KOH]的增大,乳胶粒径变大,粒径分布变宽。复合乳化剂质量浓度[E]在不同范围内对乳胶粒径及其分布的影响不同,当[E]<0.0572 g/mL时,随[E]增大,乳胶粒径变小,粒径分布变窄;当[E]>0.0572 g/mL时,乳胶粒径反而变大。     

聚氨酯/脲RIM用新原料

三洋化成工业公司开发并出售一种通用于聚氨酯RIM及今后可能普及的聚氨酯/脲RIM、R—RIM的高反应性多元醇,商品名为“FA-947”。聚氨酯反应注射成型(RIM)是将高反应性多元醇和聚异氰酸酯进行快速混合,注入密闭模内使其反应固化的成型方法。这种方法是目前用聚氨酯制造保险杆、方向盘等汽车外装及内装材料的主要成型方法。但该方法存在许多问题,①注射成型时间比热塑性树脂长;②涂装时在耐热性方面存在影     

AM/SA反相微乳液聚合反应动力学研究

以油酸失水山梨醇酯Span80和壬基酚聚氧乙烯醚OP-10为乳化剂，白油为连续介质，高活性过氧化二碳酸（2-乙基已基）酯（EHP）为引发剂，进行了丙烯酰胺/丙烯酸钠（AM/SA）反相微乳液共聚合反应。研究了单体总浓度[M]，引发剂浓度[I]，乳化剂浓度[E]对AM/SA反相微乳液聚合速率Rp和共聚物分子量M^-v的影响规律，得到Rp∞[M]^m[I]^0.65[E]^0.34,M^-v∞[M]^n[I]^-0.30[E]^-1.08，其中当[M]=3.21mol/L-6.42mol/L时，m=2.34,n=0.68，当[M]=1.28mol/L-3.33mol/L时，m=1.61,n=0.58,比较了不同单体浓度范围内AM/SA反相微乳液聚合速率。     

酯交换法合成聚氨酯的预聚反应动力学

熔融酯交换法是合成聚氨酯材料的一种全新工艺方法。文中基于熔融酯交换法,并根据其特点,对预聚动力学进行了研究。利用液相色谱法研究了1,6-六亚甲基二氨基甲酸甲酯(HDU)与聚乙二醇(PEG)在110℃,115℃,120℃和125℃熔融酯交换合成聚氨酯的预聚表观反应动力学;计算了这4个温度的正逆反应速率常数与平衡常数;按照Arrhenius计算了该反应的表观活化能为99.62 k J/mol,指前因子为2.51×1012m L/(mol·min);按照Van’t Hoff方程计算了该反应的表观反应焓为101.34 k J/mol。     

熔体反应法制备Al-4.5Cu/TiB2复合材料的热力学

用冶金热力学理论计算出TiO2-H3BO3-Na3AlF6-Al-4.5Cu体系的起始反应温度,为950℃,并根据溶液热力学分析了TiB2颗粒形成的可能性.当熔体中[Ti]、[B]的摩尔比为1/2时,在熔体中形成TiB2颗粒;当熔体中[Ti]、[B]的摩尔比大于1/2时,熔体中除生成TiB2颗粒外,还形成TiAl3组织.     

Investigation of effects of dibutyltin dilaurate on reaction injection molding polyurethane-urea kinetics,morphology and mechanical properties by FTIR

The bulk catalyst effect of dibutyltin dilaurate (DBTDL) on the reaction of NCO respectively with OH and NH₂ was investigated in detail. The results showed that DBTDL had specific catalyst effect on the reaction of NCO with OH and no measurable effect on the reaction of NCO with NH₂. In situ Fourier transform infrared spectroscopy (FTIR) used in the reaction injection molding (RIM) process showed that with increasing the concentration of DBTDL, the formation rate of the soft segment became fast, and the order degree of urea carbonyls became worse. Meanwhile, more arrange manners of urea carbonyl were present. The bands at 1653, 1647 and 1637 cm^-1 were able to be detected at the low conversion. No hydrogen-bonded urea carbonyl available in the spectra at the beginning. The tensile-stress behavior showed that, with the increase of the DBTDL content, the interaction between polar groups became weak, while the virtual crosslinks also became weak. Although the break stress (?), 300%? and the hardness of elastomers decreased obviously, however, the tear strength, associated with the morphology of polyurethane-urea (PUU), showed the maximum when the DBTDL content was 2.63‰.     

Investigation of effects of dibutyltin dilaurate on reaction injection molding polyurethane-urea kinetics, morphology and mechanical properties by in situ FTIR

The bulk catalyst effect of dibutyltin dilaurate (DBTDL) on the reaction of NCO respectively with OH and NH₂ was investigated in detail. The results showed that DBTDL had specific catalyst effect on the reaction of NCO with OH and no measurable effect on the reaction of NCO with NH₂. In situ Fourier transform infrared spectroscopy (FTIR) used in the reaction injection molding (RIM) process showed that with increasing the concentration of DBTDL, the formation rate of the soft segment became fast, and the order degree of urea carbonyls became worse. Meanwhile, more arrange manners of urea carbonyl were present. The bands at 1653, 1647 and 1637 cm⁻¹ were able to be detected at the low conversion. No hydrogen-bonded urea carbonyl available in the spectra at the beginning. The tensile-stress behavior showed that, with the increase of the DBTDL content, the interaction between polar groups became weak, while the virtual crosslinks also became weak. Although the break stress (d), 300‰δ and the hardness of elastomers decreased obviously, however, the tear strength, associated with the morphology of polyurethane-urea (PUU), showed the maximum when the DBTDL content was 2.63‰.     

Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads

The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).     

硅烷接枝聚乙烯的催化机理与交联动力学研究

为了进一步探讨硅烷接枝聚乙烯水解交联反应机理及动力学,通过酸、碱和盐催化作用原理,说明了羧酸锡对交联反应的作用,用凝胶含量(G%)指标表征了交联反应程度,讨论了反应条件(温度、催化剂用量、水分扩散速度等)对该反应动力学的影响.结果表明:交联反应程度随催化剂浓度升高和环境湿度增大而增大;利用Arrhenius方程可表征该反应动力学的特征,并可求出交联反应的活化能(39.46 kJ/mol);提高水解温度,可加快水在聚乙烯中的扩散速度,因此,也加快了交联反应.硅烷接枝聚乙烯水解交联反应是关于催化剂和水分浓度的一级反应.     

反应性聚碳酸酯增韧改性环氧树脂体系固化反应动力学的研究

对环氧树脂／胺化聚碳酸酯体系的固化反应动力学进行了研究，借助Ozawa t ASTME698动力学方法，利用差示扫描量热仪对该体系的固化动力学参数，包括活化能E，指数前因子A，速率常数k和60min的半周期温度进行了分析，并对不同胺化聚碳酸酯含量时的固化行为，放热峰和动力学参数进行了探讨。     

Cr/SiO_2界面还原反应研究

利用俄歇电子能谱研究了Cr／SiO2薄膜在热处理过程中的界面扩散反应机理、界面反应动力学过程及界面反应产物。研究结果表明，Cr／SiO2体系的界面还原反应主要是Cr与SiO2的反应，其还原反应产物是CrSix和Cr2O3物种。界面还原反应的速度与反应时间的平方根成正比，其界面还原反应过程受Cr向SiO2层的扩散过程所控制，界面还原反应的表观活化能为72．5kJ／mol（约0．75eV）。     

酰胺扩链剂对聚脲扩链反应动力学的影响

采用红外光谱(FT-IR)技术研究了新型位阻型酰胺扩链剂二乙酰乙二胺(MEDA)和二乙酰己二胺(MHAD)与4,4′-二苯甲烷二异氰酸酯(MDI)的扩链反应。考察了酰胺扩链剂对聚脲凝胶时间的影响,得出酰胺扩链剂能大大延长聚脲的凝胶时间,有利于反应动力学分析。扩链反应动力学研究结果表明,脂肪族酰胺扩链剂合成聚脲的扩链反应中,在反应初期低转化率时,反应均遵循二级动力学关系,得出MEDA和MHAD合成聚脲反应的活化能Ea分别为36.81 kJ/mol和43.99kJ/mol;MEDA反应活性高于MHAD.