Thermal behavior of blends based on a thermoplastic-modified epoxy resin with a crosslinking density variation

The thermal behavior of blends based on a polystyrene (PS) and several epoxy-amine systems where amino groups were provided by a monoamine (MA) and a diamine (DA) mixed in different proportions was investigated. This way, the crosslinking density of epoxy-amine polymer was controlled and continuously changed from a linear polymer (epoxy-MA) to a highly crosslinked polymer (epoxy-DA). The effect of the MA–DA proportion and PS modifier on the thermal stability, glass transition, and polymerization reaction was studied by differential scanning calorimetry and thermogravimetric analysis. The MA–DA ratio and modifier proportion did not affect the reaction heat but affected the reactivity. The thermal stability and glass transition temperature increased by increasing the DA proportion in the blend as a result of the higher degree of crosslinking. A study of miscibility of blends based on glass transitions was performed. The thermoplastic-modified materials generally showed two glass transitions with values close to the those of the pure materials, indicating that the mixtures were separated into phases.     

Simulation of molecular fractionation and species distributions in phase separation of polystyrene-modified epoxy/monoamine–diamine blends

Molecular fractionation occurred at the beginning of phase separation in blends based on a polystyrene modifier and an epoxy system undergoing polymerization with a monoamine and a diamine mixed in different proportions was studied thermodynamically. The study was conducted by simulating in each separated phase the species distributions of components of the blend, the stoichiometric ratio, and the proportion of monoamine–diamine at cloud-point conditions. A model based on Flory–Huggins theory described in a previous paper Rico et al. [1] where the interaction parameters were dependent on temperature, composition, and conversion, χ(T,?,p), and where the polydispersity of the components was taken into account, was used for simulation. The effect of modifier proportion, monoamine–diamine ratio and polymerization temperature on molecular fractionation and species distribution was determined and analyzed. Explanations of the estimated trends were given on the basis of the thermodynamic model used.     

Controllable preparation of epoxy‐functionalized magnetic polymer latexes with different morphologies by modified miniemulsion polymerization

The synthesis of functional magnetic polymer latexes (MPLs) with epoxy groups introduced via a modified miniemulsion polymerization route was described. The epoxy group content on the surface could be controlled by seed emulsion followed and characterized by FTIR and zeta potential measurements. We also developed a novel approach to achieve manipulation of the morphology of the MPLs based on kinetic control of the polymerization system. MPLs with different morphologies were obtained ranging from core–shell microstructures, dispersed microstructures to asymmetric microstructure, which were characterized by TEM, DLS, and TGA. The mechanisms of the contribution of kinetic factors such as polymerization rate, reaction time, and temperature contributing to the formation of the different morphologies were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2284–2293, 2010     

BSA denaturation in the absence and the presence of urea studied by the iso-conversional method and the master plots method

The effect of cure temperature and modifier proportion on the miscibility of an epoxy–amine system with a thermoplastic modifier was studied by analysis of phase diagrams, morphologies, and glass transitions. Phase diagrams for the system before and during reaction were obtained from a thermodynamic analysis of phase separation using a model based on Flory–Huggins theory. Different types of morphologies were observed and analyzed in function of cure temperature and modifier proportion. The validity of the thermodynamic model was checked by comparing with observed morphologies. Two glass transitions were observed for most of the modified systems indicating that a phase separation was occurred.     

Production of organometallic polymers by the interfacial technique. X. Influence of the nature of base employed on the synthesis of polysilylalkylene (arylene) diamines

The influence of base type on polymerization and on polymer properties in the synthesis of polysilylalkylene(arylene)diamines by a modified interfacial system was investigated. The modified system utilizes 2,5-hexanedione or acetonitrile in place of the usual aqueous solvent. Protonation of both diamine and amine groups in the polymer chain is important when NaOH or diamine itself is employed as the base. Protonation is unimportant when triethylamine is used. In triethylamine systems the highest yield is formed with the silane containing the most electron-deficient silicon, and the highest molecular weight products are formed with the least sterically hindered silane. When NaOH or diamine itself is employed there is no apparent correlation between silane and amine electronic or steric nature and any of the measured polymer properties. As diamine solubility decreases, polymer yield increases.     

A study on the polymer structures and electro-optical properties of epoxy-mercaptan-based polymer dispersed liquid crystal films

ABSTRACT

In this paper, polymer dispersed liquid crystal (PDLC) films based on epoxy-mercaptan system were prepared by thermal-initiated polymerization. The effects of the liquid crystal (LC) content, the proportion and the functionality of epoxy monomers on the polymer structures and electro-optical properties of the as-made PDLC films were investigated systematically. It was found that the morphologies of the polymer matrix can be altered from polymer meshes to polymer balls by increasing the LC content as well as the functionality of epoxy monomers. Accordingly, the electro-optical properties could be regulated by the morphologies of polymer networks. Especially, the as-made PDLC films with homogeneous porous structures exhibited the optimal electro-optical properties. Consequently, this work offers a meaningful approach to control the microstructures and optimize the electro-optical properties of PDLC films, which indeed can form a wonderful footstone for the wide application of PDLC.     

Novel route for synthesizing hyperbranched polyamine

A novel route for the synthesis of hyperbranched polyamine containing imidazolidine rings was developed, proceeding by the step‐growth polymerization of acrolein with ethylene diamine. The reaction kinetics and polymerization mechanism were studied with NMR and ultraviolet–visible spectroscopy. The influence of the reaction temperature and the concentration and feed ratio of the reactants on the structural characteristics of the obtained products was investigated. To obtain stable hyperbranched polyamines as analogues of hyperbranched poly(ethylene imine) or dendrimeric poly(propylene imine), sodium borohydride was used to reduce the synthesized hyperbranched polyamines to open the imidazolidine rings. The molecular weights, degrees of branching, and glass‐transition temperatures of the hyperbranched polyamines before and after reduction were compared. The polymerization behaviors of acrolein with other amines such as ethanol amine, propylene diamine, and 1,6‐hexane diamine were also investigated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 699–708, 2007     

Preparation of microcapsules containing a curing agent for epoxy resin by polyaddition reaction with the self-assembly of phase-separated polymer method in an aqueous dispersed system

To prepare cured epoxy resin particles encapsulating a curing agent (diamine), the self-assembly of phase-separated polymer (SaPSeP) method was developed to be applicable to polyaddition reaction of a stoichiometrically imbalanced system. The SaPSeP method was developed by the authors for preparation of micrometer-sized, hollow cross-linked polymer particles by radical polymerization based on the self-assembly of phase-separated polymer at the inner interface of particles. Although a polyaddition reaction, in general, requires that the reactants are in stoichiometric balance for the cure reaction to proceed well, diamine was successfully encapsulated within a cured epoxy resin shell by utilizing the SaPSeP method regardless of stoichiometric imbalance. The results provide further support of the previously proposed SaPSeP mechanism for the formation of hollow particles. Moreover, such diamine capsules can be employed in one-component epoxy adhesives.     

Morphology control in polystyrene/poly(methyl methacrylate) composite latex particles

The effect of the presence of different amounts of block copolymers [polystyrene-block-poly(methyl methacrylate)] on the morphology of polystyrene/poly (methyl methacrylate) composite latex particles was investigated. The block copolymers were produced in situ by controlled radical polymerization (CRP) through the addition of the second monomer to a seed prepared by miniemulsion polymerization with a certain amount of a CRP agent. With an increase in the amounts of the block copolymers, the particle morphology changed from a hemisphere morphology (for a latex without block copolymers, i.e., without the use of a CRP agent during the polymerization) to clear core–shell morphologies as a result of decreasing polymer–polymer interfacial tension © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2484–2493, 2007     

双模板体系中多级结构碳酸钡晶体的控制合成

在用细乳液聚合法制备聚合物微球的基础上,以此聚合物形成的不溶性自组装膜与可溶性的修饰剂聚丙烯酰胺组成的双模板为三维聚合物模板体系,成功完成了多孔、刺球等具有复杂多级结构碳酸钡晶体的制备.实验过程中发现,调节双模板的组成可精确调控碳酸钡晶体的成核与生长.同时,多孔碳酸钡晶体为典型的大孔材料,孔径为103.4 rm,BET...     

Living cationic polymerization of vinyl ethers in the presence of added bases: Recent advances

The living cationic polymerization of vinyl ethers was carried out with organoaluminum compounds in the presence of various types of esters and ethers (cyclic and acyclic), to find out the suitable added bases available for the living polymerization. The effects of the basicity and steric hindrance of added bases were investigated in detail. On the basis of these results, a fast living polymerization system was realized. To synthesize water-soluble polymers such as thermally-induced phase separating polymers and polyalcohols with well-defined polymer structure, the living polymerization of various vinyl ethers was examined. The aqueous solution of living poly(vinyl ethers) having oxyethylene units exhibited a quite sensitive (ΔT_ps=0.3–0.5°C) and reversible phase separation on heating and cooling. The effects of polymer structures (pendant substituent, polymer sequence, molecular weight, and MWD) on the phase separation behavior were investigated. PVA and block copolymers containing PVA units with a narrow MWD were also prepared via living cationic polymerization of vinyl ethers and a deprotection reaction.     

Anionic polymerization. VI. Effect of polar modifiers on alkylsodium and alkylpotassium polymerization of butadiene

It was found that N,N,N′,N′-tetramethylethylene diamine and hexamethyl phosphorus triamide minimize chain transfer reactions in the polymerization of 1,3-butadiene in hydrocarbon solvent with alkylsodium or alkylpotassium initiators. The polymers obtained with alkylsodium initiators had a high molecular weight and high vinyl content at 90–95% conversion. The molecular weight of the polybutadiene made by alkylsodium and alkylpotassium initiators was dependent on the polymerization temperatures and modifier ratios, but the vinyl contents were independent of the modifier ratios. Vinyl contents of alkylpotassium-initiated polymers showed a slight dependency on polymerization temperature; the vinyl contents of alkylsodium-initiated polymers were independent of temperature. Addition of lithium tert-butoxide and potassium tert-amylate to these initiators in the presence of the modifiers affected the molecular weight but not the microstructure.     

Comparative kinetic and active centre studies on magnesium chloride supported catalysts in propylene polymerization

Three different types of high activity magnesium chloride catalysts were prepared and used for propylene polymerization both in the absence and in the presence of external donors. The rates of polymerization were studied as functions of polymerization time, and the effects of methyl paratoluate and diphenyldimethoxysilane as external donors were investigated. Active centre concentrations (C*) were determined using tritiated methanol quenching and ¹⁴CO radio-labelling in order to assess their applicability. A relatively good agreement between values of C* evaluated by the use of these two methods was obtained. The morphologies of the supports, catalysts and polymers produced were studied using scanning electron microscopy. A model involving expanding microreactors is proposed for polymer growth.     

Effect of amines on vinyl polymerization initiated by chromous acetate–alkyl halide systems

The radical polymerization of vinyl monomers initiated by Cr²⁺–RX in the presence of various amines was studied in DMF at 30°C. Polyamines able to form the chelate complex with Cr²⁺ accelerated the rate of polymerization of styrene in the following order: ethanolamine > triethylenetetramine > diethylenetriamine > ethylenediamine. However, aliphatic monoamine, hexamethylenediamine, and aromatic diamine did not have any effect on the polymerization. These results suggest that the effect of multidentate ligands may be associated with chelating effects which affect the electron transfer ability of the metal complex. An apparent activation energy of 8.2 kcal/mole for the polymerization of styrene was obtained in the presence of ethanolamine. With the Cr²⁺–CHCl₃ system, on addition of ethanolamine, the polymerization of methyl methacrylate was accelerated, and acrylonitrile and vinyl chloride, could be polymerized.     

Synthesis and diels–alder polymerization of furfurylidene and furfuryl-substituted maleamic acids

The reactions of monomaleamic acid derived from an aromatic diamine with furfural afforded a novel class of furfurylidene-substituted maleamic acids 2a–2d . The latter were cyclodehydrated to yield maleimides 3a–3d which are AB-monomers for a Diels–Alder polymerization. In addition, N-furfurylmaleamic acid ( 4 ) was synthesized by reacting furfurylamine with maleic anhydride at ambient temperature. Cyclodehydration of 4 afforded N-furfurylmaleimide ( 5 ). The polymer precursors were characterized by IR and ¹H-NMR spectroscopy. Their curing behavior was investigated by DTA and correlated with chemical structures. Diels–Alder polymerization of monomers occurred at the temperature range of 113–210°C. Thermal stability of monomers was evaluated by TGA and isothermal gravimetric analysis (IGA). It was shown that thermal stability of the polymer derived from maleamic acid 4 was dramatically improved upon curing at high temperatures due to the formation by dehydration of a stable aromatic structure.     

Thermodynamic analysis of polymerization-induced phase separation of a polystyrene in epoxy/monoamine–diamine systems. Effect of monoamine–diamine proportion on the phase diagram

Polymerization-induced phase separation of a polystyrene in various epoxy-amine systems where the amino groups were provided by a monoamine and a diamine mixed in different proportions was thermodynamically studied. A model based on the Flory–Huggins theory extended by Koningsveld and Staverman approach where the interaction parameter was dependent on temperature, composition and conversion, and polydispersity of the components was considered, was used. A general equation for the evolution during polymerization of the epoxy-amine species distributions according to the monoamine–diamine ratio was derived from the Stockmayer distribution. The interaction parameters continuously decreased with conversion. Phase diagrams of the blends were obtained and the critical composition was between 5 and 6 vol.% PS in all blends.     

Phase Diagram for a System of Polydisperse Components Consisting of the Precursor of an Epoxy/Diamine Thermoset and a Thermoplastic: Analysis Based on a Lattice Theory Model

Summary: The miscibility of a thermoplastic modifier with the precursors of an epoxy/diamine thermoset without chemical reaction was studied thermodynamically. The experimental cloud point curve showed a UCST behavior. A model based on the Flory‐Huggins lattice theory and on the Koningsveld approach was used for the thermodynamic analysis, in which the polydispersity of components was taken into account and the interaction parameter was considered depending on the temperature and composition. A phase diagram for the unreacted system was obtained. Calculations of species distributions in both separated phases were realized for different compositions of the modifier. Finally, the miscibility of our system was compared with that of the same system without diamine, obtaining a greater miscibility in the system with diamine.

Phase diagram for the system formed by the precursors of an epoxy thermoset without chemical reaction modified with different amounts of polystyrene.     

Synthesis and polymerization mechanism of bisacetoacetamides

Bisacetoacetamides were prepared, and their polymerization was investigated. The acetoacetyl groups were introduced to diamines by the reaction with diketene to give bisacetoacetamides. They were polymerized under high pressure (34.5 MPa) at 200 °C for 30 min to create the crosslinked films. The polymerization mechanism was studied by a model reaction of acetoacetanilide. The model‐reaction results indicated that the polymerization of bisacetoacetamides proceeded by addition reactions of the isocyanates formed as intermediates and in part by condensation reactions between the acetoacetamido groups. The isocyanates also reacted with the urea groups on the polymer chains to form biurets, which would cause crosslinking. In the presence of a diamine, the reaction produced a soluble oligourea. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1456–1462, 2001     

Control of heterogeneous structure of porous polymer microspheres prepared from polymerization system and preformed polymer system

The studies on control of heterogeneous structure of porous polymer microspheres prepared for suspension polymerization system and preformed polymer system in author’s research group were reviewed. Firstly, the phase-separation behavior in O/W suspension polymerization system for preparation of porous poly(divinylbenzene) microspheres was quantitatively studied by combining transmittance and gelation point measurement, from which the morphology can be manipulated. The same method can be employed to study the pore size control in W/O hydrophilic polymerization system. Because the simple porous microsphere could not satisfy new applications, we developed new methods to prepare gigaporous microsphere, which possessed much larger pores than those obtained by general diluents, for chromatographic separation media, as well as hollow-porous microsphere for construction of cell-like microreactor. Furthermore, in order to overcome the difficulty of heterogeneous structure control for preformed polymer system, we developed special methods to obtain porous, hollow-porous, and hollow chitosan microspheres. Finally, some application results by utilizing special morphologies were introduced.     

Synthesis of polyacrylonitrile-block-polydimethylsiloxane-block-polyacrylonitrile triblock copolymers via RAFT polymerization

A new A-B-A type of block copolymers,polyacrylonitrile-block-polydimethylsiloxane-block-polyacrylonitrile(PAN-b-PDMSb-PAN),which comprises two polymer blocks of different polarities and compatibilities,were synthesized for the first time via reversible addition-fragmentation chain transfer polymerization.Reaction kinetics was investigated.PAN-b-PDMS-b-PAN films were prepared by spin-coating on glass chips.Significant order on the film surface morphologies was observed.