Elasticity of model poly(oxypropylene) networks

The equilibrium stress-strain properties and the swelling behavior of moderately cross-linked model networks of poly(oxypropylene) were studied. Results were in general agreement with the theory of rubber elasticity due to Flory. However, data on the highly cross-linked networks (M?_c ≈ 725) could not be satisfactorily described by the recent theories of elasticity or swelling. This is believed to be primarily due to the marked non-Gaussian character of the very short network chains and the substantial chemical modification of the polymer by the cross-linking moiety which inevitably occurs at high cross-link densities.     

Dynamic - mechanical properties of poly(oxypropylene)di-amine-diepoxide and poly(oxypropylene)triamine-diepoxide networks and their relationship to the structure of elastically active network chains

The effect of the initial mole ratio of reactive components on the shape and position of dynamic mechanical functions in the main transition and rubbery region was investigated for two series of networks made from poly(oxypropylene)diamine (D-400)-diglycidyl ether of Bisphenol A (DGEBA) and poly(oxypropylene)-triamine (T-403)-DGEBA. The networks were prepared with an excess of amine groups up to the highest conversion of epoxy groups; the ratio ^rH = 2 [ NH₂ ]₀/ [E]₀ ranged from unity to 2,1 for networks from D-400 and from unity to 3,5 for networks from T-403. By using the theory of branching processes, structural parameters of these networks were calculated, in particular, the molecular weights of elastically active network chains (EANC's) including dangling chains, of backbone EANC's and of dangling chains. A comparison between theory and experiment led to the following conclusions: (a) the mechanical behaviour in the rubberlike region can be described either by using an affine deformation model (front factor A = 1), or by means of a phantom model (A = (f_e-2)/f_e, f_e being functionality of the crosslink) with the contribution of permanent interchain interactions; (b) the temperature and frequency position of viscoelastic functions in the main transition region is conclusively affected by the concentration of EANC's; (c) the shape of visco-elastic functions, especially of retardation spectra in the main transition and rubbery region, depends on the detailed structure of EANC's, but it cannot be decided from the result which structural parameter has the strongest effect on the shape of the functions.     

Stress-optical properties of bimodal polymer networks

The optical properties of bimodal poly(dimethylsiloxane) (PDMS) networks were studied with special emphasis on the non-linear stress optical properties exhibited by these materials. In particular the effect of chain length, and junction functionality on the strain induced birefringence was investigated. It is shown that for the non-linear properties to clearly manifest themselves a critical concentration of short chains is essential and that the junctions are tetra-functional. However, all bimodal compositions studied were found to exhibit a non-linear variation of birefringence with strain irrespective of the junction functionality. The optical properties of the unimodal networks were found to vary linearly with stress and strain as expected. The transition from non-linear to linear optical behavior on increasing the molecular weight of the short chains is also established.     

Stress-optical behavior of poly(cis/trans-1, 4-cyclohexane dimethanol-alt-formaldehyde) (PCDO) networks

Two samples of poly(cis/trans-1,4-cyclohexane dimethanol-alt-formaldehyde), having fractions of trans configuration of cyclohexylene rings F_t = 0.1 and 0.7, were synthesized by polycondensation of the appropriate mixtures of glycols with paraformaldehyde. These two samples were crosslinked by a chemical reaction using 2,4-bis(p-isocyanatebenzyl) phenylisocyanate as the crosslinking agent. The stress-optical behavior of the resulting networks was studied at several temperatures in the range 10–80°C. The values of the optical configuration parameter Δα were 9.9 and 7.2 in units of 10^?24 cm³ for F_t = 0.7 and 0.1, respectively. The temperature coefficient of this quantity was roughly zero. Theoretical analysis, performed using the rotational isomeric state model, proved that the only parameters that have an appreciable effect on the calculated values of Δα are those concerning the cyclohexane ring (i.e., F_t and the optical parameter Γ_CC = Δα_CC ? 2Δα_CH). Conformational energies, geometrical parameters, and contributions to the optical anisotropies from the oxymethylene oxide have no noticeable effect on the value of Δα calculated for the polymer. In fact, values of Δα calculated for the polymer at F_t = 0 and 1 are very close to those obtained, respectively, for cis and trans cyclohexane dimethylene. The theoretical values of Δα are roughly one order of magnitude lower than the experimental results; however, the theory reproduces satisfactorily both the variation of Δα with F_t and its temperature coefficient.     

Preparation and characterization of cyclic poly(oxypropylene)

Poly(propylene glycol) [α-hydro-ω-hydroxypoly(oxypropylene)] of number-average molar mass M̄_n ≈ 2000 g · mol⁻¹ (PPG2000) was cyclised with high conversion (ca. 75%) by reaction with dichloromethane in the presence of powdered KOH. The cyclic product was separated from chain extended polymer by preparative GPC, giving an overall yield of polymer (M̄_n ≈ 2000 g · mol⁻¹, narrow molar mass distribution) in excess of 50%. Characterisation by analytical GPC and ¹³C NMR spectroscopy confirmed cyclisation. DEPT and ¹H-coupled NMR spectra were used to show that the links in cyclic poly(oxypropylene) were 77% single acetal, 12% double acetal and 11% triple acetal (or higher). This complexity probably results from competitive reaction with water introduced with KOH.     

Birefringence of amorphous polyoxides: Stress-optical behavior of poly(3-methyltetrahydrofuran)

The stress-optical behavior of an unswollen elastomeric network of poly(3-methyltetrahydrofuran) was measured for elongation ratios a in the range 1.182–1.549, at several temperatures between 20 and 60°C. No evidence of strain-induced crystallization was found; moreover, the dependence of birefringence Δn on true stress f/A was linear in the interval of α investigated. Values of Δa ranged from 2.4 to 2.8 in units of 10^?24 cm³, in the temperature range studied, with a temperature coefficient 3.1 × 10^?3 K^?1. Theoretical calculations carried out with the rotational-isomeric-state model gave values of Δa noticeably smaller than the experimental results; however, a small increase in the backbone valence angles θ improved the theoretical result of Δa without worsening that of the dipole ratio. Analysis of the Δa results seems to corroborate the conclusion obtained through the study of dipole moments concerning the preference for nucleophilic attack on the less hindered α carbon in the monomer. Theoretical and experimental values of the temperature coefficient of Δa were in clear disagreement; a qualitative explanation for this discrepancy is discussed.     

Self-assembly of gold nanoparticles induced by poly(oxypropylene)diamines

A series of poly(oxypropylene)diamines D230, D400, D2000, and D4000, having molecular weights of hydrophobic segments of 230, 400, 2000, and 4000, were used as ligands to synthesize self-organized gold nanocrystals. Ligand exchange significantly reduced the average particle size and the polydispersity of nanocrystals, and this effect was more remarkable as the molar ratio of amine groups to Au3+ ions ([N]/[Au3+] ratio) was increased. Under the same [N]/[Au3+] ratio of 100, D2000 generated an ordered 2D-monolayer; however, D230 and D400 colloids formed mainly a densely packed 3D structure with minor 2-D layers, and D4000 presented disordered 3D and 2D structures. The gap among the nanoparticles was found to be increased with the increasing molecular weight of the hydrophobic segment of ligands, accompanied by the decreasing wavelength of UV-vis absorption bands. This increased gap can be interpreted as the ligand thickness calculated from the equation of steric force increasing with increasing molecular weight of the hydrophobic segment. The potential energies obtained from the calculated ligand thickness according to the soft sphere model show more steep potential wells for D230 and D400 colloids than that for the D2000 colloid. This explains why the aggregation hardly occurred for the gold nanoparticles obtained under D2000, where the nanoparticles are single crystals having face center crystal structure with a lattice constant of 2.36 A and have grain sizes close to the average particle sizes, evidenced from the results of transmission electron microscopy and X-ray diffraction spectroscopy.     

Synthesis and interfacial behaviors of amphiphilic poly(oxypropylene) amidoacids

A series of hydrophobic poly(oxypropylene) (POP)‐backboned and hydrophilic poly(oxyethylene)‐backboned amidoacids and imidoacids were prepared through the reaction of poly(oxyalkylene) diamines and trimellitic anhydride (TMA) under mild conditions. The synthesized copolymers were characterized with nuclear magnetic resonance and Fourier transform infrared. Their ability to lower the water surface tension and toluene/water interfacial tension was measured and correlated with the hydrophobic/hydrophilic balance with multiple sodium carboxylate functionalities. The specific POP2000/TMA copolymers, consisting of a 2000 g/mol POP segment and multiple amidoacid functionalities, enabled the demonstration of a strong surfactant tendency and a critical micelle concentration at 0.1 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 646–652, 2006     

Structure,equilibrium and viscoelastic mechanical behaviour of polyurethane networks based on triisocyanate and poly(oxypropylene)diols

Using the theory of branching processes, the detailed structure of polyurethane networks from poly(oxypropylene)diols (PPDs), monofunctional alcohol (cyclohexanol) and triisocyanate prepared at various initial ratios of the reactive groups r_HD ≡ [OH]_PPD/[NCO] = 0·5−1·7 was characterized in terms of the number, size and structure of elastically active network chains (EANCs), backbone and dangling chains. From an analysis of the dependence of the critical molar ratio at gelation r_HD^c on dilution it follows that PPD samples are composed of molecules bearing primary and secondary hydroxy groups. The branching theory, in which the presence of both primary and secondary hydroxy groups in PPDs is accounted for, adequately describes the dependence of the mass fraction of the sol w_s on r_HD when no side reactions occur in the system (networks in the range r_HD ≥ 1 or networks with monofunctional alcohols). The equilibrium photoelastic behaviour can be described by the junction-fluctuation theory with front factor A = 1 without entanglement contribution. The frequency-temperature superposition can be performed for all networks; the temperature dependence of the horizontal shift factor satisfies the WLF equation. While the position of the main transition region of viscoelastic functions on temperature or frequency depends on the content of the polar triisocyanate component, the shape of these functions at the end of the transition is determined predominantly by the concentration of EANCs.     

Random-coil configurations of aromatic polyesters: Stress-optical behavior of poly(diethylene glycol terephthalate)

The stress-optical behaviour of an elastomeric network of poly(diethylene glycol terephthalate) (PDET) was measured over a wide range of elongation ratios α (up to 5) and temperatures (293-353K). No evidence of strain -induced crystallization was found;on the contrary, the plot of birefringence versus stress exhibits negative deviations from linearity at values of α over 2.6. Values of the optical configuration parameter Δα of the order of 20 × 10^?24cm³ with relative temperature coefficients of -1.1 × 10^?3K^?1 were found for the unswollen sample. The introduction of tricresylphosphate as diluent roughly doubles the birefringence of the network, presumably because of an increase in intermolecular interactions. Theoretical calculations carried out with the RIS model give values of Δα about one order of magnitude smaller than the experimental ones and temperature coefficients of about 4.1 × 10^?3K^?1. No reasonable modification of conformational energies or contributions to the anisotropic part of the polarizability tensor would achieve agreement between theory and experiments. The discrepancy between theoretical and experimental results may be qualitatively explained by intermolecular interactions.     

Stress-optical coefficients of swollen polymer networks

Stress-optical coefficients have been determined for crosslinked samples of polyethylen (PE) and polystyrene (PS) at high temperatures, i.e., in the rubberlike state, and when swollen in a variety of liquids. For PE, swelling liquids with long straight molecules gave large values of optical anisotropy whereas liquids with more symmetrical molecules gave minimum values, as found previously for cis- polyisoprene and trans-polyisoprene. This solvent effect is attributed to short-range orientational order in molecularly asymmetric media. Sizes of the equivalent random link for unperturbed molecules of these three polymers were deduced from the minimum values of optical anisotropy. Measures of shape asymmetry were also obtained by matching the optical anisotropy of samples when unswollen with that observed when swollen with a liquid of known molecular asymmetry. Reasonable agreement was found to hold between the two methods. In contrast, the optical anisotropy of swollen PS was found to be substantially independent of the swelling liquid. The apparent absence of a molecular ordering effect in this case is attributed to the bulky nature of the PS molecule. A marked reduction in optical anisotropy on swelling is ascribed to increased phenyl group motion.     

Analysis of the mechanical behavior of amorphous atactic poly(oxypropylene) by atomistic modeling

The mechanical behavior of amorphous atactic poly(oxypropylene) was simulated using a molecular mechanics technique. The elastic properties obtained from the well‐defined structure were found to be comparable with those obtained from theory and experiment. A simulated stress‐strain curve shows a yield point at about ε = 0.13 after the linear elastic region. In order to elucidate the relationship of yielding with change in cell structure, various factors, such as dihedral angle distribution, pair correlation, bond orientation, and free volume distribution were analyzed. As a result, yielding and plastic deformation require no specific change in structure. From the stress decomposition into two components, namely, enthalpic and entropic, the thermodynamic yield point was defined as a point where the enthalpic contribution to the total stress vanishes and the entropic contribution is exclusively dominant.     

Synthesis of poly(oxypropylene)-lithium bis(trifluoromethyl-sulfonylimide) polymer electrolytes. Diffusion study by NMR techniques

High molecular weight polymers have been prepared by ring-opening polymerization of propylene oxide PO using a Vandenberg initiator. Polymer electrolytes based on this polymer and an imide salt LiTFSI have been investigated. We present the results concerning the synthesis of the polymer and the glass transition temperatures evolution of the complexes with respect to salt composition. Diffusion constants of ¹⁹F and ⁷Li nuclei are determined by NMR techniques and a value of the cationic transport number t⁺ = 0.1 is obtained.     

Polyacrylamide conjugated with poly(oxyethylene)-block-poly(oxypropylene)-block-poly(oxyethylene): a self-assembling material

A novel one-step synthesis of hydrophobically modified polyacrylamide (PAAm) is described. Triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PEO-PPO-PEO) are grafted onto PAAm in melts of acrylamide in the presence of benzoyl peroxide. The resulting PEO-PPO-PEO-g-PAAm graft copolymers are capable of self-assembly in response to temperature changes in aqueous media.     

Electromechanical properties of poly(vinylidene fluoride‐trifluoroethylene) networks

Random copolymers of 65% vinylidene fluoride and 35% trifluoroethylene were reacted with an organic peroxide, in combination with a free‐radical trap, to yield networks of high crosslink density. Crystallization subsequent to the crosslinking yielded ferroelectric materials exhibiting large electrostrictive strains. The magnitude of the electromechanical response increased with an increasing degree of crosslinking, even though this reduced the crystallinity. For the most crosslinked sample, longitudinal (thickness) strains as high as 12% were induced at an electric field of 9 MV/m. This electrostrictive performance exceeded that obtained to date with any poly(vinylidene fluoride) material. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1975–1984, 2002     

DSC study of cure kinetics of DGEBA-based epoxy resin with poly(oxypropylene) diamine

Summary A kinetic study of cure kinetics of epoxy resin based on a diglycidyl ether of bisphenol A (DGEBA), with poly(oxypropylene) diamine (Jeffamine D230) as a curing agent, was performed by means of differential scanning calorimetry (DSC). Isothermal and dynamic DSC characterizations of stoichiometric and sub-stoichiometric mixtures were performed. The kinetics of cure was described successfully by empirical models in wide temperature range. System with sub-stoichiometric content of amine showed evidence of two separate reactions, second of which was presumed to be etherification reaction. Catalytic influence of hydroxyl groups formed by epoxy-amine addition was determined.     

Formation of hierarchical molecular assemblies from poly(oxypropylene)-segmented amido acids under AFM tapping

Molecular self-aligning of amphiphilic molecules into bundles with a constant width of 7-13 nm was observed under tapping-mode atomic force microscopy (TM-AFM). The requisite amphiphile, a poly(oxypropylene)-trimellitic amido acid sodium salt, is constituted of a symmetric amido acid structure with potential noncovalent forces of ionic charges, hydrogen bonds, pi-pi aromatic stacking, and hydrophobic interactions for intermolecular interaction. The amphiphiles are able to self-align into orderly hierarchical assemblies after simply being dissolved in water and dried under spin-coated evaporation. Under the TM-AFM tapping process, the bundles increased their length from an initial 20 to 600 nm. A sequential TM-AFM scanning and interval heating process was designed to probe the morphological transformations from the molecular bundles to lengthy strips (nearly micrometer scale) and to columns (with 5-7 nm spacing between the parallel strips). The formation of hierarchical arrays via molecular stretching, aligning, and connecting to each other was simultaneously observed and accelerated under the TM-AFM vibration energy. The molecular self-alignment caused by vibrations is envisioned to be a potential methodology for manipulating molecules into assembled templates, sensors, and optoelectronic devices.     

Enhanced stabilization and deposition of Pt nanocrystals on carbon by dumbbell-like polyethyleniminated poly(oxypropylene)diamine

Pseudo-dendritic polyethyleniminated poly(oxypropylene)diamine (D400(EI)(20)) was used as a stabilizer and promoter to prepare Pt nanoparticles in aqueous solution, which was then deposited on carbon surface followed by calcination. After being deposited on carbon surface, no Pt(0) could be detected in the solution phase. In all steps, the increasing molar ratio of the amino groups of D400(EI)(20) to H(2)PtCl(6) ([N]/[Pt]) drastically reduced the size and the polydispersity and kept a constant low value after [N]/[Pt] = 20. Under a [N]/[Pt] ratio of 20, the particle sizes obtained from transmission electron microscopy (TEM) were very small in solution (2.7-2.4 nm) and remained the same after being deposited on carbon surface (2.7-2.4 nm), and were only slightly increased to 3.6-3.0 nm after calcination. The stabilizing ability of D400(EI)(20) to Pt on carbon surface before and after calcination can be interpreted by the existence of binding energy between Pt and amine nitrogen. The X-ray diffraction (XRD) pattern together with the TEM image reveals that the obtained Pt nanoparticles exist in single-crystal form. The results of photoelectron spectroscopy (XPS) evidence that the metallic Pt(0) rather than the oxidized Pt is the predominant species in the Pt/C catalysts. The electrochemical active surface (EAS) area of the Pt/C catalyst is only slightly higher than that of the E-TEK Pt/C catalyst, but the utilization factor (93.4%) is remarkably higher than the latter (62.8%). The increasing time of thermal treatment increases the crystallinity of Pt(0) on carbon, accompanied by the increasing EAS areas, which corresponds to its enhanced electrocatalytic performance to methanol oxidation.