Morphology and mechanical properties of poly(ether-imide)-modified polycyanurates

A high temperature thermosetting bisphenol A dicyanate (BADCy) was modified with a novel thermoplastic poly(ether-imide) (PEI) at various compositions. Fourier transform infrared spectroscopy was used to measure the conversion of BADCy. Curing kinetics of the BADCy/PEI blend were studied by the dynamic differential scanning calorimeter method. Morphologies of PEI-modified polycyanurates were investigated by scanning electron microscopy (SEM). It was found that the phase structures of the blends changed dramatically with the PEI content and molecular weight. The tensile results showed that the mechanical properties could be correlated with the morphologies. The blend with cocontinuous morphology had the highest tensile strength and elongation at break while the blend with ribbon-like morphology had the lowest one despite PEI molecular weight.     

Relation between chemical structure of amino acids and their thermal decomposition

The influence of substituents on the thermal decomposition of monomeric organic compounds was studied. For this purpose the thermal destruction of dozen or so α-amino acids of the diversified chemical constitution, among others compounds containing the second amine group, additional carboxyl group, amino acids containing hydroxyl or sulfhydryl groups and amino acids connected with five-member heterocyclic ring or existing in the form of hydrates or hydrochlorides were investigated. The analyses were performed using a derivatograph in an air atmosphere, sample sizes were from 50 to 200 mg and heating rate from 3 to 15 K min^-1. It has been established that the thermal decomposition of studied compounds occurs in three stages. The temperature ranges, in which the analyzed compounds undergo thermal transformations were established. For evaluation of the thermoanalytical results an advanced multivariate data processing method, principal component analysis (PCA), was used. By this method the influence of the specific functional groups on the thermal decomposition of α-amino acids was determined. The stage of decomposition, in which the thermoanalytic data are the best correlated to the chemical constitution of the compound, is the second stage. It has also been recognized, that better discrimination among the analyzed compounds was obtained for the data set of the DTA.     

Preparation and thermal properties of polyquinazolones: Effect of the chemical structure of bisbenzoxazinones on the thermal properties

Four kinds of polyquinazolones were synthesized from 4,4′-diaminodiphenylether and bisbenzoxazinones having different central aromatic nuclei (benzene, biphenyl, benzophenone, diphenylmethane). All the polymers were prepared by solution polycondensation at 190°C at a concentration of 15% solid in m-cresol, and were obtained with intrinsic viscosities in the range of 0.3–0.8 dL/g in 97–98% yield. Their thermal properties were studied by using dynamic thermogravimetry and isothermal weight loss. All the polymers were found to produce high char yields (55–75%) in nitrogen. Oxidative thermal stability of the polymers was dependent on the chemical structure of bisbenzoxazinone and was governed by the stability of the bonds in the quinazolone units. The following order of oxidative thermal stability of the quinazolone units was determined from this study: diphenylmethane < benzophenone < biphenyl < benzene.     

Processing of poly(lactic acid): Characterization of chemical structure, thermal stability and mechanical properties

The processing of poly(lactic acid) (injection and extrusion/injection) as well as annealing of processed materials were studied in order to analyze the variation of its chemical structure, thermal degradation and mechanical properties. Processing of PLA was responsible for a decrease in molecular weight, as determined by GPC, due to chain scission. The degree of crystallinity was evaluated by means of differential scanning calorimetry and X-ray diffraction. It was found that mechanical processing led to the quasi disappearance of crystal structure whereas it was recovered after annealing. These findings were qualitatively corroborated by means of FTIR. By analyzing ¹H NMR and ¹³C NMR chemical shifts and peak areas, it was possible to affirm that the chemical composition of PLA did not change after processing, but the proportion of methyl groups increased, thus indicating the presence of a different molecular environment. The thermal stability of the various materials was established by calculating various characteristic temperatures from thermograms as well as conversion and conversion derivative curves. Finally, the mechanical behaviour was determined by means of tensile testing (Young modulus, yield strength and elongation at break).     

Effects of chemical modification on the structure and mechanical properties of starch-based biofilms

Abstract  

In this work, chemically modified corn starch and plasticized corn starch biofilms were obtained and characterized in four steps: (1) preparation of corn starch microparticles, (2) preparation of malic acid-modified corn starch microparticles (MA–SM), (3) preparation of corn starch biofilms and MA–SM-plasticized corn starch biofilms, and (4) characterization of the biofilms. The effects of MA–SM concentration (4, 8, and 12% based on the amount of corn starch) on the structural characteristics and mechanical properties of the biofilms were investigated. Changes in the starch granules after chemical modification were studied by X-ray diffraction, FT-IR spectroscopy, and scanning electron microscopy. The presence of ester carbonyl group stretching vibration at 1,720 cm⁻¹ in FT-IR spectra was evidence of reaction of the starch microparticles with malic acid. The tensile yield strength and Young’s modulus of the films increased with increasing MA–SM content. Water uptake decreased from 69.8% for biofilm without MA–SM to 52.7% for biofilm with MA–SM. The improvement of these properties in the plasticized product could be attributed to the good interaction between the MA–SM filler and the corn starch.     

Synthesis of polyisocyanurates by thermal rearrangement of polycyanurates

Polyisocyanurates have been successfully prepared by the thermal rearrangement of polycyanurates, which were obtained from 2,4‐dichloro‐6‐methoxy‐1,3,5‐triazine and bisphenol monomers. The thermal rearrangement was carried out in the presence of a small amount of tetrabutylammonium bromide (TBAB) as a catalyst at 200 °C for 30 or 60 min in an argon atmosphere, and the degree of arrangement was greater than 95%. Transparent and amorphous polyisocyanurate films were obtained and showed a good thermal stability with a 5% weight loss temperature above 340 °C in nitrogen and the glass transition temperature above 210 °C. Films with a 10‐µm thickness exhibited an excellent transparency above 90% at 400 nm. Furthermore, the thermal rearrangement of 2,6‐bis(4‐methoxyphenyl)‐6‐methoxy‐1,3,5‐triazine to 1,3‐bis(4‐methoxyphenyl)‐5‐methyl‐1,3,5‐triazinane‐2,4,6‐trione was investigated in detail. It was found that the complete thermal rearrangement was successfully accomplished in the presence of 2 wt % TBAB at 150 °C for 20 min in an argon atmosphere. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 692–698     

Randomly branched polycyanurates - modification of the network structure

Polycyanurates (poly(2,4,6-trisaroxy-1,3,5-triazines)) are built up through a step-growth polycyclotrimerization of difunctional aromatic cyanic acid esters and form an ideally trifunctional randomly branched network, where all initial cyanato groups are linked with the triazine branching units at full conversion. Results on modifications of the high network density of pure polycyanurates are reported for three types of comonomers: monofunctional cyanic acid esters, difunctional phenols and difunctional aromatic glycidyl ethers. Using the coreaction of mono- and difunctional aromatic cyanic acid esters, additional chain segments, dangling ends and low molecular weight compounds are built, the fractions of which are dependent on the initial admixture of the monofunctional compound and its relative reactivity. Therefore, the critical conversion at the gel point is shifted to higher values and the network density at full conversion decreases. The abstraction of phenols from intermediately formed iminocarbonic ester structures is utilized for the modification of the polycyanurate network through the coreaction of difunctional aromatic cyanic acid esters with phenols. It was found that the critical conversion and the network structure are dependent on all the initial amount of phenols, their reactivity and functionality. The modification with the help of glycidyl ethers is characterized by an insertion of the oxirane ring into the cyanurate and the succeeding reactions into isocyanurates and oxazolidinones. Depending on the initial mixture and the reaction conditions, a large spectrum of chemical and topological network structures can be obtained, what is demonstrated by both experimental and theoretical investigations.     

Synthesis of transparent and thermally stable polycyanurates and their thermal rearrangement

Transparent and thermally stable polycyanurates, whose solubility can be changed by thermal rearrangement, have been synthesized as functional films used in the multilayer coating process. Before the synthesis of polycyanurates, the model compound, 2,6‐bis(4‐methoxyphenyl)?6‐methoxy‐1,3,5‐triazine as a cyanurate is prepared and rearranged to an isocyanurate, 1,3‐bis(4‐methoxyphenyl)?5‐methyl‐1,3,5‐triazinane‐2,4,6‐trione in an excellent yield by thermal treatment. Based on this result, polycyanurates are prepared by the phase‐transfer‐catalyzed polycondensation of 2,4‐dichloro‐6‐methoxy‐1,3,5‐triazine with bisphenol monomers in the presence of quaternary ammonium salts. The polycyanurate obtained from 9,9‐bis(hydroxyphenyl)fluorene exhibits a high glass transition temperature at 251 °C. The solubility of polycyanurate films containing 1 wt % of tetrabutylammonium bromide can be changed by thermal rearrangement. The partially rearranged films keep high transparency and low birefringence. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3950–3955     

Influence of chemical structure on nonelastic mechanical properties in polystyryl-pyridine resins

We propose a micromechanical characterization of the chemical structure (i.e., the state of cure) of polystyryl-pyridine (PSP) resin. The nonelastic work-hardening rate K is measured in the preyield stage during compression tests at constant strain rate. The nonelastic deformation is analyzed from a metallurgical point of view; the parameter K varies as the inverse of the nucleation rate for dislocations and thus is a measure of the ability of the material to deform plastically. The comparison with high-resolution solid-state carbon-13 NMR experiments shows that, at room temperature, the ability of PSP resin to deform plastically depends mainly on the degree of crosslinking, whatever the length of prepolymer molecule; however, at high temperatures (T = 200°C) it is affected by the length of prepolymer molecule during curing, whatever the degree of crosslinking. Plastic deformation of PSP resin is easier at 200°C than at room temperature. The longer the duration of curing, the better the mechanical properties at high temperatures; PSP resin readily deforms plastically and has a sufficiently high elastic modulus.     

Relation between the network structure and dynamic mechanical properties of a typical amine-cured epoxy polymer

The dynamic mechanical properties of a series of epoxy polymers of known network structure have been investigated. It was shown that the distance between crosslinks could be predicted from either the shift in the glass transition temperature T_g or by use of the dynamic modulus above T_g. The front factor in the equation of state for rubber elasticity was near unity for stoichiometric equivalence of epoxy and amine and increased slowly with excess of either component.     

Relationship of hierarchical structure to mechanical properties

The mechanical properties in complex systems are explained based on the hierarchical structures present in the system. Hierarchical structures designed for specific mechanical responses are best exemplified by examples from biology. Collagen, a main component in soft connective tissues, is organized into hierarchical structures in the form of tendons or intervertebral discs as examples. Understanding these structures is vital in relating the structures to the intended properties. This approach is also used to characterize organic/inorganic natural composites such as human bone, reindeer antler and nacre. Another example of a hierarchical structure in biology with excellent mechanical properties is that of cellulose, when organized into wood. The importance of hierarchical structures also applies to synthetic polymers for a clearer understanding of the structure-property relationships. Solid-state biaxially oriented polypropylene has excellent tensile and impact properties, which are explained by the hierarchical structure induced during the processing. Thermotropic liquid crystalline polymers develop a hierarchical structure during injection molding that influence the final properties. Furthermore, the impact modification of polycarbonate is more easily understood when the system is explained in a hierarchical manner. It is also now possible to create or force hierarchical structures in synthetic polymers by microlayering technology. Several systems are outlined in which a hierarchical structure is created to enhance specific properties. SAN, a brittle polymer, can be microlayered with PC to create tough materials due to the scale, interaction and architecture of the microlayered composite. Another example is the effect of microlayered composite of PC/SAN on the interfacial adhesion mechanisms. Furthermore, toughening mechanisms in filled microlayers are examined based on the hierarchical structure.     

Influence of chemical composition of amide block on the thermal properties and structure of terpolymers

Multiblock terpolymers -(PBT-b-PTMO-b-PA12.10)_n- comprising the polymer systems in which one of the three blocks (PBT) is not soluble in the hard phase of PA12.10 blocks but is slightly soluble in the soft phase of PTMO blocks have been obtained. The DSC and DMTA method was applied to investigate the thermal properties of these polymers and it was found that the PBT block acts as an element that produce stiffness of -(PBT-b-PTMO-b-PA12.10)_n- structure. The terpolymers were compared with the previously described [5] -(PBT-b-PTMO-b-PA12)_n- elastomers, in which the rigid PBT block (DP > 7) dissolves in the hard phase of PA12 blocks and partly dissolves in the soft phase. It was found that even a small change in the chemical structure of the amide block influences significantly on the structure, phase separation and the properties of terpolymers. This revised version was published online in July 2006 with corrections to the Cover Date.     

The influence of chemical structure on thermal properties and surface morphology of polyurethane materials

The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes.     

From chemical structure to viscoelastic properties of polymers

The basic result of the coupling model consists of a cross-over from exp-(t/τ_o) to exp-(t/τ*)^1-n at a temperature insensitive microscopic time t_c. We indicate how this basic result can be derived from chaotic, interacting Hamiltonian systems which include densely packed polymer molecules. Recent quasielastic neutron scattering experiments and molecular dynamics simulations are discussed and the results are shown to support this result as well. An application of the coupling model to find how the viscoelasticity of a polymer depends on the chemical structure of the monomer through the coupling parameter of the local segmental motion is given to illustrate the utility of the model.     

On the evolution of the viscoelastic properties and its microstructural/chemical origin in filled NBR subjected to coupled thermal and mechanical loads

This study deals with the effect of coupled thermal and cyclic mechanical loadings on the viscoelastic response of carbon black filled nitrile rubber. For this purpose, cyclic loading tests were performed at different temperatures by means of Dynamic Mechanical and Thermal Analysis (DMTA). The type and level of the thermomechanical loadings applied were chosen in order to determine the relative contribution of each of the mechanical and thermal loadings (and their coupling) to the viscoelastic response during the cyclic tests. X-ray Photoelectron Spectroscopy (XPS) and Fourier Transformed Infrared spectroscopy (FTIR) analyses were also carried out to track the change in the chemical structure corresponding to the evolution in the viscoelastic response. First, results obtained show that due to the crosslink increase, the storage modulus increases with the number of cycles. It is also observed that temperature amplifies this phenomenon. Second, the cyclic mechanical loading is found to significantly amplify the effect of temperature.     

Surface chemical and mechanical properties of plasma-polymerized N-isopropylacrylamide

Surface-immobilized poly(N-isopropyl acrylamide) (pNIPAM) is currently used for a wide variety of biosensor and biomaterial applications. A thorough characterization of the surface properties of pNIPAM thin films will benefit those applications. In this work, we present analysis of a plasma-polymerized NIPAM (ppNIPAM) coating by multiple surface analytical techniques, including time-of-flight secondary-ion mass spectrometry (ToF-SIMS), contact angle measurement, atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. ToF-SIMS data show that the plasma-deposited NIPAM polymer on the substrate is cross-linked with a good retention of the monomer integrity. Contact angle results confirm the thermoresponsive nature of the film as observed by a change of surface wettability as a function of temperature. Topographic and force-distance curve measurements by AFM further demonstrate that the grafted film shrinks or swells depending on the temperature of the aqueous environment. A clear transition of the elastic modulus is observed at 31-32 degrees C. The change of the surface wettability and mechanical properties vs temperature are attributed to different conformations taken by the polymer, which is reflected on the outmost surface as distinct side chain groups orienting outward at different temperatures as measured by SFG. The results suggest that a ppNIPAM thin film on a substrate experiences similar mechanical and chemical changes to pNIPAM bulk polymers in solution. The SFG result provides evidence supporting the current theory of the lower critical solution temperature (LCST) behavior of pNIPAM.     

Synthesis of polydithiourethanes and their thermal,optical, and mechanical properties originated from monomers structure

Polyaddition of various diisothiocyanates and dithiols was achieved with triethylamine in dimethylformamide at 25 °C for 12 h under nitrogen, and then the corresponding polydithiourethanes (PDTUs) were obtained with high yield and molecular weight without depending on the monomer structures, although the dithiol monomer of the low nucleophilicity was unsuitable for polyaddition in this system. The chemical and physical properties of the obtained PDTUs such as solvent solubility, glass transition temperature, thermal stability, transparency, refractive index, and tensile strength, were analyzed in detail by gel permeation chromatography, nuclear magnetic resonance, Fourier transform infrared–attenuated total reflection, ultraviolet–visible, differential scanning calorimetry, thermogravimetric analysis, and tensile testing measurements. These results proved that PDTUs and their cast films having the aliphatic diisothiocyanate and dithiol moieties exhibited excellent chemical and physical properties compared to that of the aromatic PDTUs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2255–2262     

Influence of chemical shell structure on the thermal properties of microcapsules containing a flame retardant agent

Microcapsules containing ammonium phosphate as the acid source for an intumescent system were prepared by various processes. The microcapsules have different morphologies, load content and various types of polymeric shell. The polymers for our microcapsule shell are polymers considered as carbon source for intumescent formulations. In this paper we discuss the influence of polymeric shell and phosphate content of the microcapsules on the capacity to produce a thermally stable residue at high temperature, one of the characteristics for an intumescent formulation.     

Effect of the network structure on thermal and mechanical properties of mesogenic epoxy resin cured with aromatic amine

The epoxy resin containing a typical mesogenic group such as biphenol was cured with catechol novolak and aromatic diamines which have neighboring active hydrogens. In the biphenol-type epoxy resin cured with catechol novolak, 4,4′ diaminodiphenylmethane, and p-phenylenediamine (PPD), the glass-rubber transition almost disappeared, and thus a very high elastic modulus was obtained in the high temperature region. It is clear that the thermal motion of the network chains is significantly suppressed in these cured systems. In addition, in the PPD-cured system, a characteristic pattern like a schlieren texture was clearly observed under the crossed polarized optical microscope. Thus we conclude that the mesogenic group contained in the epoxy molecule is oriented in the networks when the mesogenic epoxy resin is cured with phenols and diamines which have neighboring active hydrogens. On the other hand, the biphenol-type resin cured with 3,3′,5,5′-tetraethyl-4,4′-diamino diphenylmethane (TEDDM) showed a well-defined glass-rubber transition and, thus, a low rubbery modulus. In this cured system, no characteristic pattern was observed under the crossed polarized light. These results show that the large branches, such as ethyl groups on the network chains, prevent the orientation of network chains which contain the mesogenic group. © 1997 John Wiley & Sons, Inc.