Aa-Bb,Cc共缩聚型固化理论

本文用几率方法研究了A_a-B_b,C_c型共缩聚体系的溶胶凝胶分配问题,得到了参加反应的各种官能团的反应程度、溶胶反应程度与溶胶分数的关系式。以此为基础,确定了B基和C基具有不同相对活性时的固化区和非固化区。用己二酸、丁二醇和三羟甲基丙烷进行了热固化反应并测定了固化树脂的溶解行为。实验结果与固化区的理论曲线基本相符。     

凝胶化理论的新概念——一种新的划环方法

本文用分子作为划环单位,与Flory等用官能团作为划环单位不同,得到∑A_(ai)与∑_(bj)型分子间反应凝胶生成的临界条件,用数均官能度或分子的数量分数,不用重均官能度或官能团的数量分数表示,更与Flory的实验结果一致.从理论分析,化学反应是分子反应,用分子比用官能团作为划环单位更合理.     

A_a_1,A_a_2-B_b_1B_b_2缩聚反应的固化理论

本文讨论了A_(a_1),A_(a_2)-B_(b_1)B_(b_2)型缩聚反应的固化理论。给出了溶胶-凝胶分配公式、凝胶化条件、分布函数及适合固化全过程的高分子矩的循环公式和k次矩的解析表示式。     

高分子固化理论中的几个问题——A_α的交联反应

本文对A_α交联反应的固化理论进行了全面讨论。内容包括凝胶点的几种形式、溶胶分数、凝胶分数、重均和Z-均聚合度在固化全过程的变化情况以及固化的标度问题。     

一般的A_aB_b缩聚反应的固化理论——Ⅰ.溶胶分数和凝胶化条件

本文讨论了最一般的A_aB_b缩聚反应,包括A基和A基、B基和B基、以及A基和B基的反应,给出了溶胶-凝胶分配公式和相应的凝胶化条件。     

苯乙烯-双烯A交联共聚凝胶、溶胶的生成与转化

本文结合提取、凝胶色谱等方法测定了苯乙烯-双烯A交联共聚过程的转化率曲线。通过研究发现,凝胶在交联共聚一开始就产生,且整个反应过程都在不断地生成;转化率40％以前几乎无溶胶生成,此后生成的溶胶仍不断地向凝胶转化;刚生成溶胶时其分子量高、分布窄,其后分子量变低、分布变宽;T_g以上温度的热处理发生进一步聚合反应,当双烯A摩尔浓度<3.3×10~(-4)时,溶胶分数增加,A-MA摩尔浓度>5.0×10~(-4)时,凝胶分数增加,这是双烯A悬吊双键及单体苯乙烯进一步反应的结果。     

A_a-B_b(B′)_b型缩聚反应在热固化反应过程中的溶、凝胶分配

Flory、Gordon和唐敖庆从相同的基本假定出发,用不同的几率方法提出了凝胶化理论,统称为经典的凝胶化理论,对A_a-B_b(B′)_b体系,汤心颐等曾研究过其凝胶化范围,但只得到了临界反应程度,我们用经典的统计方法,以甘油和丁二酸酐为模型化合物,研究了溶胶分数与反应程度的关系,并导出了酸/醇摩尔比r_b与r_b′的关系式。     

一种测定微量铀的新方法——协萃反应放射性元素置换法的研究

本文提出了一种测定微量铀的新方法,它利用了协萃反应的放射性元素置换作用,其反应式如下:UO_2~(2+)+CeA_3B_(2(0))+H~+(?)UO_2A_2B_((O))+HA_((O))+B_((O))+Ce~(3+)此处HA为1-苯基-3-甲基-4-苯酰基-吡唑啉酮-5,B为磷酸三丁酯。由于UO_2A_2B的萃取常数大于CeA_3B_2的萃取常数,因此在CeA_3B_(2(O))中的Ce~(3+)离子能被UO_2~(2+)离子所置换,从~(144)Ce的计数率可以间接测定微量铀。     

A_(a_1)B_(b_1)—A_(a_2)B_(b_2)缩聚反应的分布函数和高分子矩

本文用概率统计方法,得到了A_(a1)B_(b1)—A_(a2)B_(b2)缩聚反应的分布函数。应用分布函数定义了高分子各类矩。用直接微商法,得到了计算矩的循环公式。解决了用矩表征这类反应的问题。本文也得到了凝胶化条件。     

随机支化过程理论与分子量分布函数

本文运用随机支化过程理论于多元反应体系,应用矢量变量、矢量概率再生函数及关于函数Lagrange多元展开的一项定律,简捷地推导了A_(a_1)+A_(a_2)+…+A_(a_i)及A_(a_1)+A_(a_2)+…+A_(a_i)+B_(b_1)+B_(b_2)+…+B_(b_i)两种一般化反应类型的分子量分布函数,结果与Stockmayer用组合理论所得结果相同。本文所用方法较之采用图论的推导方法为简便。     

Crosslink Density from Sol-Gel Contents

Experimental results showed that the crosslink density of polymeric stocks may be calculated from values of the gel content based on the reactive portion of the stocks, that is, exclusive of plasticizers and fillers. Where entanglements may be neglected, the crosslink density is directly proportional to functions of the gel and sol contents. Four such functions were found. Three of these were theoretically derived relations in the literature and these were modified to provide equations connecting crosslink density and the weight fraction of gel W_g and connecting extent of reaction and W_g for condensation polymers.

Although followed up to moderate degrees of cure, the Flory relation was shown not to be in proper form. A fourth but simpler relation, based on an empirical correlation, was found between crosslink density and gel content, namely, that the crosslink density was directly proportional to the square of the gel fraction divided by the first power of the sol fraction. The constant of proportionality was 0.0065 meq/g for three-functional networks. When placed in terms of extent of reaction, this equation was found to yield nearly the same gel content relative to extent of reaction as that of Charlesby and there was a smaller coefficient of variation of experimentally determined proportionality constants.     

Mechanical relaxations in episulfide network polymers

A variety of condensation network polymers have been prepared by the reaction between amine, episulfide, and epoxide monomers. The mechanical relaxations occurring in these systems have been examined using a torsion pendulum and the role of hydrogen bonding in the mechanism of the β relaxation is shown to be insignificant. The chemical reaction between amine and episulfide groups has been investigated by IR spectroscopy and is shown to parallel the reaction between amine and epoxide groups. However, steric and electronic factors are suggested to decrease the extent of reaction when aromatic amines are involved. In the case of networks prepared from blends of episulfide and epoxide monomers, measurements of the gel time, together with the mechanical behavior around the glass transition, indicate that either interpenetrating or two-phase networks are formed. This is postulated to be a consequence of the high reactivity of the episulfide ring compared to the epoxide ring. The blending of small amounts of episulfide monomer with the epoxide monomer prior to curing may provide an effective method for lowering gel times without reducing the crosslink density and its dependent physical properties.     

NiO晶粒尺寸对SOFC阳极电化学性能的影响

用溶胶凝胶法合成了具有高比表面积的纳米粒子NiO,用固相合成法制备了NiO-YSZ复合材料.阻抗谱测试表明,含纳米尺寸NiO的复合材料的极化电阻更小,电导率更高.以质量分数为55%的NiO-YSZ为阳极材料,并将其封接成单电池.结果表明,含纳米尺寸NiO的复合阳极制成的单电池,其输出功率更高,短路电流更大.通过减小NiO晶粒尺寸,可增大阳极三相反应界面长度,并获得性能优良的阳极材料.     

Real-Time NMR. How Fast Can We Do It?

Network structure development during cross-linking photopolymerization of polyethylene glycol di-acrylate and its mixture with a mono-functional 2-ethylhexyl acrylate was studied using real-time proton NMR T₂ relaxation analysis. The time resolution of the method is typically in the order of seconds. The results reveal largely heterogeneous origin of network build up at the intermediate stages of photocuring. Domains of nano-gel are already formed on initial stages of UV-curing where hardly any change in viscosity is observed. Upon increasing curing time the fraction of gel increases at the expence of sol, the molar mass of network chains decreases and the molar mass of sol increases. The presence of mono-acrylate slows down the curing rate. The curing continues after UV-illumination causing a significant increase in the amount of gel and cross-link density in the gel. Thus, the NMR method is a valuable tool for characterization of the kinetics of photopolymerization, the development of molecular structure and the resultant molecular scale heterogeneity during photocuring.     

Monte Carlo simulation of diepoxides and monoepoxides cured with amines

The diepoxide–monoepoxide–diamine curing systems are investigated with a Monte Carlo simulation. The dependence of the molecular weight distribution (MWD), gel fraction, and cycle rank of the polymers on the differences in the epoxy reactivities and the contents of the monoepoxide as a reactive diluent are discussed. Before gelation, the MWD of the curing systems with a lower content of the monoepoxide is broader than the MWD of the curing systems with a higher content, and it leads to a lower critical conversion. The gel fraction and cycle rank of the polymers decrease with an increasing amount of the diluent. Even fully cured, the system with a 0.6 epoxy molar fraction of the monoepoxide still has a large fraction of sol, about 49%. Although the various reactivities of the monoepoxide result in different ways of forming gels during curing, the final gel fractions are always near 100% as long as the epoxy molar fraction of the diluent is no more than 0.2. The profiles of the molecular weights of the polymers calculated by the model are in agreement with the experimental data. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1857–1868, 2002     

NOVEL CERAMER MATERIALS BASED ON JEFFAMINE® POLY(PROPYLENE OXIDE) OLIGOMERS AND TETRAMETHOXYSILANE

Novel hybrid organic–inorganic network materials have been generated based on poly(propylene oxide) (PPO) and tetramethoxysilane (TMOS). The PPO source chosen for this study was the family of JEFFAMINE®s often employed as epoxy curing agents. These materials were end–functionalized with trialkoxysilane groups which later were exploited in the sol–gel reaction. The sol–gel variables of water and acid catalyst concentration had little influence on the final structure and properties of the resulting network materials for the ranges probed. Increasing the TMOS content, however, generated a structure that angle X-ray scattering revealed a correlation length associated with a silicate phase separated by PPO chains, which increased with PPO molecular weight, as expected.     

Actuation design for high‐performance shape memory polyurethanes

A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (M_c) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000M_c with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479     

Chemically Fueled Autonomous Sol→Gel→Sol→Gel→Sol Transitions

Complex non-equilibrium phase behaviors are a hallmark of natural self-assembling systems. Here we show how intricate phase transitions can be achieved through a chemically fueled reaction cycle to yield autonomous sol→gel→sol→gel→sol transitions. A relay of chemical transformations based on thiazinane metathesis leads to two consecutive transient gelations in a closed system. Within seconds of fuel addition to deactivated thiazinane monomers, an imine-based hydrogel forms that consists of fibrillar microspheres. This gel quickly loses its mechanical strength and forms a solution, from which a second aldehyde-based gel nucleates and remains stable for over one day. Overall, our reaction cycle gives rise to two consecutive re-entrant phase transitions without any experimental intervention.