前线聚合研究及应用进展(上)

前线聚合(Frontal Polymerization,FP)是一种以自身反应热为推动力,通过反应区域连续移动,最终实现整体聚合转化的聚合反应模式。本文综述介绍了前线聚合的定义、反应机理、基本形成条件及主要特点。     

波聚合制备淀粉接枝丙烯酸钠-丙烯酰胺高吸水性树脂

高吸水树脂是一种新型功能高分子材料,广泛应用于卫生用品、农林业和生物医药等领域．将淀粉接枝改性制备吸水树脂不仅可以减少对石油产品的依赖性,而且还可以使吸水树脂具有可生物降解性,从而避免出现环境问题．     

Frontal copolymerization synthesis and property characterization of starch-graft-poly(acrylic acid) hydrogels

Recently, a considerable amount of research has centered on uniquely structured polymers synthesized through self-propagating frontal polymerization. The obtained polymer materials have better features than those obtained by using the classical batch route. The additional advantages are short reaction times and low cost. This work describes the first frontal polymerization synthesis of a graft copolymer superabsorbent hydrogel of acrylic acid onto starch at high monomer and initiator concentration. The effects of varying the relative amounts of the reaction components on the most relevant parameters relating to frontal polymerization were explored. The front velocity dependence on initiator concentration could be fit to a power function. The temperature profiles were found to be very sharp with a maximum temperature below 150 degrees C, which was responsible for high monomer conversion. The ultimate properties of the product appear to depend on the polymerization front velocity and the temperature. The high-temperature and rapid temperature increase at the polymerization front led to products with interconnected porous structures caused by the evaporation of water. So, a fast-swelling, highly absorbing hydrogel with respect to batch polymerization was obtained.     

Online-Analysis on Acoustically Levitated Droplets

Summary: Aqueous solutions of acrylic acid were levitated in a 40 kHz acoustic levitator. The monomer amount in the levitated droplets was monitored by Raman spectroscopy relating to an internal standard. Thus evaporation of the monomer as well as polymerization reactions initiated by a redox system were investigated by Raman spectroscopy and resultant data were compared to HPLC data. Decreases in monomer amount due to evaporation can be clearly distinguished from polymerization reactions. Additionally, temperature measurement within the droplet throughout a polymerization reaction shows the typical temperature course originating from the heat of polymerization.     

前线聚合研究及应用进展(下)

综述了单体性质、压力、引发剂、反应容器等因素对前线聚合的影响,并对影响前线稳定性的诸多因素进行了讨论,简要介绍了光引发前线聚合近年来最新发展,综述了前线聚合在制作梯度材料、聚氨酯合成、不饱和聚酯及环氧固化、双环戊二烯开环异位聚合、互穿网络结构制备及微孔材料填充固化保护等方面的应用状况。     

Free‐Radical Frontal Copolymerization: The Dependence of the Front Velocity on the Monomer Feed Composition and Reactivity Ratios

Frontal copolymerization is a process in which a spatially localized reaction zone propagates into a mixture of two monomers, converting them into a copolymer. In the simplest case of free‐radical copolymerization, a mixture of monomers and initiator is placed into a test tube. Reaction is initiated at one end of the tube, and a self‐sustained thermal wave, in which chemical conversion occurs, develops and propagates through the tube. We develop a mathematical model of the frontal copolymerization process and analytically determine the structure of the polymerization wave, the propagation velocity, maximum temperature, and degree of conversion of the monomers. Specifically, we examine their dependence on reactivity ratios as well as other kinetic parameters, monomer feed composition, and exothermicity of the reactions. Our analytic results are in good quantitative agreement with both direct numerical simulations of the model and experimental data, which are also presented in the paper.

Dependence of front velocity on monomer feed composition for different heat release parameters.     

UV光引发的丙烯酰胺反相乳液聚合

报道了不透明丙烯酰胺反相乳液体系的UV光引发聚合新方法 .使用普通中压汞灯并辅以适当搅拌 ,UV光引发丙烯酰胺 水 煤油 Span80 +OP 10反相乳液聚合可在 2 0min左右完成 ,所得聚合物分子量达千万 ;聚合过程中不存在恒速期 ,扫描电镜未观察到聚合前后乳胶粒径有数量级的变化 ,表明聚合反应以单体液滴成核为主 .此外 ,考察了光引发剂类型及浓度、单体浓度、乳化剂用量、反应温度等对聚合反应的影响 ,结果表明不同光引发剂的引发活性为Irgacure 2 95 9>(ITX +EDAB) >BDK ,引发剂浓度增加 ,反应速度先增加而后降低 ,存在一最大值 ;单体浓度增加 ,反应速度加快 ,聚合物分子量提高 ;乳化剂用量增加 ,反应速度加快而分子量变化不明显 ;聚合表观活化能为 13 34kJ mol.     

PU/纳米SiO2溶胶杂化材料的前端聚合研究

前端聚合(FP)是通过在单体前端区域引发增长聚合将单体合成为聚合物的一种不同于传统的反应模式．它是一种通过局部反应区域在聚合物单体中的移动而将聚合物单体转变为聚合物的一种反应模式,主要运用在放热反应中,在反应初始阶段进行短时间的加热,然后停止加热,借助放热反应的热自催化完成单体的聚合。根据反应机理的不同,     

Segmented polyurethane synthesized by frontal polymerization

Frontal polymerization (FP) is a mode of converting a monomer into a polymer via a localized reaction zone that propagates through the monomer. In this study, segmented polyurethane was successfully prepared by FP. The reactants, poly (propylene oxide) glycol, 2, 4-toluene diisocyanate and 1,4-butanediol and the catalyst stannous caprylate, were mixed together at an initial temperature in the presence of dimethylbenzene (as the solvent). The reactions were thermally ignited at one end of the tubular reactor, and the resultant hot fronts propagated throughout the reaction reactor. No further energy was required for polymerization to occur. The effect factors of front velocity, stannous caprylate concentration and temperature on the FP, along with comparison of FP with bulk polymerization, were thoroughly investigated. Fourier transform infrared and differential scanning calorimetry were employed to characterize polyurethane (PU). The polymer materials obtained by FP displayed features similar to those obtained by batch polymerization. The reaction time of FP for preparing PU was lower than that of BP.     

Thermal transport and chemical effects of fillers on free-radical frontal polymerization

Frontal polymerization (FP) is a process in which a front propagates in a localized reaction zone, converting monomer into polymer through the coupling of thermal diffusion with the Arrhenius kinetics of an exothermic reaction. Fillers are added to control the rheological properties of the formulation and to enhance the mechanical properties of the product. However, the thermal and chemical effects of these fillers on the front propagation have not been thoroughly explored. Herein we report the thermal and chemical effects of fillers on free-radical frontal polymerization. It was found that fillers with high thermal diffusivities, such as milled carbon fiber and boron nitride increased the front velocity. Despite their high thermal diffusivities, fillers such as aluminum and alumina decreased the front velocity. This is likely due to the radical-scavenging ability of aluminum oxide, which was explored with clay minerals. It was found that the presence of water within clay fillers can also decrease the front velocity. To probe the chemical effects, acid-activated clay minerals were utilized. The results demonstrate that some fillers can increase front velocity through their high thermal diffusivities while others decrease it by acting as radical scavengers.     

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA–propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA–triacetin and HEMA–isoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore, in the HEMA–dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA–poly(methyl methacrylate) system were also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate.     

Redox initiated cationic polymerization: The unique behavior of alkyl glycidyl ethers

Redox systems composed of a diaryliodonium or a triarylsulfonium salt together with a silane bearing Si? H groups were used for the in situ generation of strong Brønsted acids at room temperature in the presence of alkyl glycidyl ether monomers. Secondary oxiranium intermediates are generated with lifetimes from minutes to hours at room temperature. These systems undergo rapid, exothermic cationic chain polymerization when the temperature is raised. Metastable monomer‐redox initiator systems were also observed to undergo frontal polymerizations when a localized heat source is applied to the sample. The application of these delayed cationic ring‐opening polymerization systems for the development of one‐component structural adhesives that undergo rapid thermosetting at low temperatures are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

双官能度引发剂引发苯乙烯聚合微观动力学

采用 2 ,5 二甲基 2 ,5 二己酰基过氧化己烷 (DMDEHPH)为引发剂 ,在 5 5～ 80℃下引发苯乙烯聚合 .通过研究影响聚合速率的各种因素 ,得出了聚合速率对单体浓度和引发剂浓度的级数分别为 1 0和 0 5次、聚合活化能为 92 0kJ mol、引发效率为 0 5 5± 0 0 3.温度一定 ,引发效率随引发剂浓度的增加而减小 .求得 6 0和70℃下DMDEHPH向引发剂的链转移常数分别为 0 0 37和 0 0 4 8、向单体的链转移常数分别为 0 5 9× 10 - 4和0 75× 10 - 4.     

Using in situ rheology to characterize the microstructure in photopolymerized polyacrylamide gels for DNA electrophoresis

Photopolymerized cross-linked polyacrylamide hydrogels are attractive sieving matrix formulations for DNA electrophoresis owing to their rapid polymerization times and the potential to locally tailor the gel pore structure through spatial variation of illumination intensity. This capability is especially important in microfluidic systems, where photopolymerization allows gel matrices to be precisely positioned within complex microchannel networks. Separation performance is also directly related to the nanoscale gel pore structure, which is in turn strongly influenced by polymerization kinetics. Unfortunately, detailed studies of the interplay among polymerization kinetics, mechanical properties, and structural morphology are lacking in photopolymerized hydrogel systems. In this paper, we address this issue by performing a series of in situ dynamic small-amplitude oscillatory shear measurements during photopolymerization of cross-linked polyacrylamide electrophoresis gels to investigate the relationship between rheology and parameters associated with the gelation environment including UV intensity, monomer and cross-linker composition, and reaction temperature. In general, we find that the storage modulus G' increases with increasing initial monomer concentration, cross-linker concentration, and polymerization temperature. The steady-state value of G', however, exhibits a more complex dependence on UV intensity that varies with gel concentration. A simple model based on rubber elasticity theory is used to obtain estimates of the average gel pore size that are in surprisingly good agreement with corresponding data obtained from analysis of DNA electrophoretic mobility in gels cast under identical polymerization conditions.     

Kinetic evidence of a “matrix effect” in the bulk polymerization of acrylonitrile

The kinetics of the γ-ray-initiated polymerization of acrylonitrile in bulk are reexamined in broad ranges of temperatures and radiation dose rates. The discussion of the results coupled with an analysis of earlier data indicate that the polymerization of acrylonitrile proceeds by different mechanisms depending on the reaction temperature. Above 60°C the precipitated growing chains recombine readily; therefore, the autoaccelerated conversion curves cannot be accounted for by an “occlusion effect.” It is suggested that autoacceleration is caused by a fast propagation taking place in oriented monomer aggregates which result from dipole-dipole association of the monomer with the polymer chains formed in the early stages of the reaction (“matrix effect”). Below 10°C the precipitated growing chains are buried in the dead polymer and monomer diffusion toward the occluded chain ends is very limited (“occlusion effect”). Between 10 and 60°C the system gradually changes from one dominated by “occlusion” to one where the “matrix effect” determines the kinetic behavior. The conclusion based on kinetic data is in agreement with results obtained from studies of the postpolymerization in these various systems.     

Effect of resin staging on frontal polymerization of dicyclopentadiene

In thermal frontal polymerization (FP), ambient temperature and staging conditions highly affect the resin behavior and front properties. This study describes the effect of staging conditions and resin reactivity on frontal ring opening metathesis polymerization of dicyclopentadiene in presence of phosphite-inhibited second-generation Grubbs catalyst. An experimental setup is designed to characterize and understand the effect of inhibitor concentration, incubation time, and incubation temperature on front velocity, activation time, and front temperature of the FP reaction. The results reveal that front properties are influenced by various factors, including available energy density of resin, stability of catalyst-inhibitor complex, resin temperature, and resin viscosity. An increase in staging temperature results in lower pot lives but faster gelation process and activation of FP reaction. Additionally, increasing the inhibitor concentration leads to slower fronts, higher activation times, and longer pot lives. The results of this study can be extended to other FP systems and can be used in design of new manufacturing processes and applications using FP.     

Supramolecular Interfacial Polymerization: A Controllable Method of Fabricating Supramolecular Polymeric Materials

A new method of supramolecular polymerization at the water–oil interface is developed. As a demonstration, an oil‐soluble supramonomer containing two thiol end groups linked by two ureidopyrimidinone units and a water‐soluble monomer bearing two maleimide end groups are employed. Supramolecular interfacial polymerization can be implemented by a thiol–maleimide click reaction at the water–chloroform interface to obtain supramolecular polymeric films. The glass transition temperature of such supramolecular polymers can be well‐tuned by simply changing the polymerization time and temperature. It is highly anticipated that this work will provide a facile and general approach to realize control over supramolecular polymerization by transferring the preparation of supramolecular polymers from solutions to water–oil interfaces and construct supramolecular materials with well‐defined properties.     

Addition Polymerization of 5-Ethylidene-2-Norbornene in the Presence of Pd N-Heterocyclic Carbene Complexes

New high-performance catalytic systems based on Pd N-heterocyclic carbene complexes for the selective addition polymerization of 5-ethylidene-2-norbornene (ENB) were proposed. With these catalysts, polymerization can be conducted at unprecedentedly high monomer/catalyst ratio (up to 5 × 10⁵/1) and gives high-molecular-weight soluble polymers with good film-forming properties. Varying the polymerization conditions (reaction temperature, monomer and catalyst concentrations, monomer/Pd ratio) makes it possible to prepare soluble ENB-based addition polymers with specified molecular weights in reasonable yields.     

Ethylene polymerization with supported bis(triphenylsilyl) chromate catalysts

Bis(triphenylsilyl) chromate is an active catalyst for ethylene polymerization without further treatment or additives. Catalytic activity is markedly increased when the compound is deposited on silica–alumina and is further increased if it is deposited on silica and then treated with an aluminum alkyl. Polymer molecular weight can be controlled by reaction temperature, hydrogen addition, support type, and reducing agent structure to give polymers ranging in melt index from essentially zero to > 100. In the supported catalysts the bis(triphenylsilyl) chromate appears to be bound to the support and to undergo a reduction step either by reaction with ethylene or with aluminum alkyl prior to polymerization. The active site is envisioned as chromium alkyl, bound to the support, with propagation occurring by insertion of the monomer into a Cr? C bond. Chain termination is by chain transfer to monomer.     

A Study of Emulsion Polymerization Kinetics by the Method of Continuous Monomer Addition

The differences in the kinetics of emulsion polymerization between nonswelling and swellable latex particles were explored in an attempt to define the locus of polymerization. The systems studied included vinylidene chloride, which forms a nonswelling particle, and mixtures of vinylidene chloride and butyl acrylate, which copolymerize to form a swellable particle. The basic experiment involved growing a seed latex by adding monomer at a constant rate. At low feed rates the rate of polymerization R_p was controlled by the rate of monomer addition R_a. The data fit the equation R_p?KR_a where the proportionality constant had an average value of 0.91. K was not dependent on monomer composition and appears to be a constant characteristic of the monomer addition process. In the range where this relationship holds, the reaction runs starved, i.e., monomer is consumed almost as fast as it enters the reactor. At higher rates of addition the reaction floods and excess monomer in the form of droplets can be detected. In this condition the rate starts out at a lower value but increases with conversion.' R_p is not controlled by R_a but does depend on monomer composition. No major differences were found between the behavior of swelling and nonswelling systems. Neither followed che kinetics expected if the Smith-Ewart theory were applicable. The results argue strongly that polymerization takes place at the particle-water interface or in a surface layer on the polymer particle.