Morphology of Fractured Polymer‐Polymer Interfaces Bonded at Ambient Temperature as Studied by Atomic Force Microscopy

The amorphous polymer surfaces of polystyrene (PS, M _n=200 kg/mol, M _w/M _n=1.05) and poly(methyl methacrylate) (PMMA, M _n=51.9 kg/mol, M _w/M _n≤1.07) were brought into contact at 21°C to form PS‐PS (for 54 days) and PMMA‐PMMA auto‐adhesive joints (for 11 days). After contact at that temperature corresponding to T _g‐bulk ?81°C for PS and to T _g‐bulk–88°C for PMMA, where T _g‐bulk is the calorimetric glass transition temperature of the bulk sample, the bonded interfaces were fractured and their surfaces were analyzed by atomic force microscopy (AFM). The surface roughness, R _q, of the fractured interfaces was larger by a factor of 3–4 than was that of the free PS and PMMA surfaces aged for the same period of time. A similar increase in R _q was found by comparison of the free PS surface aged at T _g‐bulk+15°C for 1 h and of the surface of the PS‐PS interface fractured after healing at T _g‐bulk+15°C for 1 h. These observations, indicative of the deformation of the fractured interfaces, suggest the occurrence of some mass transfer across the interface even below T _g‐bulk ?80°C.     

Autoadhesion of High‐Molecular‐Weight Monodisperse Glassy Polystyrene at Unexpectedly Low Temperatures

Abstract

Healing of symmetric interfaces of amorphous anionically polymerized high‐ and ultrahigh‐molecular weight (HMW and UHMW, respectively) polystyrene (PS) in a range of the weight‐average molecular weight M _w from 102.5 (M _w/M _n = 1.05) to 1110 kg/mol (M _w/M _n = 1.15) was followed at a constant healing temperature, T _h, well below the glass transition temperature of the polymer bulk [T _g‐bulk = 105–106°C as measured by differential scanning calorimeter (DSC)]. The bonded interfaces were shear fractured in tension on an Instron tester at ambient temperature. Autoadhesion at symmetric HMW PS–HMW PS and UHMW PS–UHMW PS interfaces was detected mechanically after healing at T _h = 38°C for 107 hr, and even at 24°C (for longer healing times). The occurrence of autoadhesion between the surfaces of the UHMW PS with M _w = 1110 kg/mol at 24°C implies that the glass transition temperature at the interface, T _{g‐interface}, of this polymer was a least lower: by 82°C than its DSC T _g‐bulk, by 30–40°C than the Vogel temperature, T _∞—the lowest theoretical value of a kinetic T _g‐bulk at infinite long time—and by 20°C than T ₂ (a “true” thermodynamic T _g‐bulk corresponding to a second‐order phase transition temperature). To our knowledge, this is the first observation of such nature, which gives further evidence of the lowering of the T _g at polymeric surfaces and the persistence of this effect at early stages of healing of polymer–polymer interfaces.     

Reaction‐Induced Phase Separation in Polyoxyethylene/Polystyrene Blends. I. Ternary Phase Diagram

Abstract

Reaction‐induced, phase separation has been studied in polymer blends. A model crystalline‐amorphous system consisted of semicrystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was used as a reactive solvent to ease processing. When the styrene was polymerized to polystyrene (PS) in the mold, phase separation and phase inversion are induced, and a polymer blend was formed. Polyoxyethylene was selected with a molar mass, M _n  = 8578 g mol^?1 and a polydispersity of 1.19, as determined by using gel permeation chromatography. The polymerization of styrene was initiated by using 1 wt% benzoin methyl ether and 0.2 wt% 2,2′‐azobisisobutyronitrile under ultraviolet light. The polymerization kinetics were determined by monitoring the reduction in the intensity of the C?C stretching vibration band at 1631 cm^?1 in the Raman spectrum of styrene. The onset times for the liquid–solid (L–S) phase separation and crystallization of POE from styrene/PS were observed by using simultaneous small‐angle x‐ray scattering (SAXS) and wide‐angle x‐ray scattering. Onset times for L–S phase separation determined from the SAXS data were combined with the styrene polymerization kinetics to plot the L–S phase separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45°C and 50°C.     

Molecular-weight dependence of the glass transition temperature of freely-standing poly(methyl methacrylate) films

We have used transmission ellipsometry to measure the glass transition temperature, T_g, of freely-standing films of atactic and syndiotactic poly(methyl methacrylate) (PMMA). We have prepared films with different molecular weights, MW, (159×10³ < M _w < 1.3×10⁶) and film thicknesses, h, ( 30nm < h < 200 nm). For the high-MW ( M _w > 509×10³) atactic PMMA films, we find that T_g decreases linearly with decreasing h, which is qualitatively similar to previous results obtained for high-MW freely-standing polystyrene (PS) films. However, the overall magnitude of the T_g reduction is much less (by roughly a factor of three) for the high-MW freely-standing PMMA films than for freely-standing PS films of comparable MW and h. The observed differences between the freely-standing PMMA and PS film data suggest that differences in chemical structure determine the magnitude of the T_g reduction and we discuss the possible origins of these differences. Our analysis of the MW-dependence of the T_g reductions suggests that the mechanism responsible for the MW-dependent T_g reductions observed in the high-MW freely-standing films is different than that responsible for the MW-independent T_g reductions observed in the low-MW freely-standing and supported films.     

Neutron scattering from PEEK

An alkali‐soluble polysaccharide, GM5‐1, from the mycelium of Ganoderma tsugae, was fractionated by the nonsolvent addition method. The weight‐average molecular mass (M _w) and intrinsic viscosity ([η]) of fractions were studied by laser light scattering and viscometry with dimethylsulfoxide (DMSO) containing 0.25M LiCl (0.25M LiCl/DMSO) as the solvent at 30°C. The dependences of [η] and the radius of gyration (?S ²?_z ^1/2) on M _w were found to be [η]=9.8×10^?2 M _w ^0.57 (cm³g^?1) and ?S ²?_z ^1/2=1.65×10^?2 M _w ^0.58 (nm) in the M _w range from 8.6×10⁵ to 2.6×10⁶. The analysis based on current theories for a wormlike chain showed that the chain conformational parameters of GM5‐1 were 4.2 nm for persistence length (q) and 833 nm^?1 for linear mass density (M_L) with an obvious excluded volume effect. The results suggested the alkali‐soluble polysaccharide behaves like a semiflexible chain in 0.25M LiCl/DMSO at 30°C.     

Thermal Cross‐Linking of Poly(Vinyl Methyl Ether). I. Effect of Cross‐Linking Process on the Viscoelastic Properties

Abstract

Thermal cross‐linking of poly(vinyl methyl ether) (PVME) in the absence of cross‐linking agent, was detected rheologically. The linear viscoelastic properties of PVME were found to be greatly changed by the onset of the cross‐linking process. The viscoelastic material functions, such as dynamic shear moduli, G′ and G″, complex shear viscosity, η*, and loss tangent, tan δ, were found to be sensitive to the structure changes during the cross‐linking process and the formation of a three‐dimensional polymer network. At the onset temperature of the cross‐linking process, an abrupt increase in G′, G″, and η* (several orders of magnitude) during dynamic temperature ramps (2°C/min heating rate) was observed with some frequency dependence. The temperature dependence of tan δ was found to be frequency independent at the gel‐point, T _gel, that is, the crossover in tan δ regardless of the value of frequency can be taken as an accurate method for determination of T _gel. The coincidence of G′ and G″ at the gel‐point cannot be considered a general method for evaluation of T _gel due to its high frequency dependence, that is, T _gel determined from the crossover of G′ and G″ in the dynamic temperature ramp at 1 rad/sec is about 20°C less than at 100 rad/sec. Furthermore, a dramatic increase in η₀ above the minimum (“v” shape) was observed at T = T _gel in agreement with the value obtained from tan δ vs. T (190°C). The time–temperature‐superposition principle was found to be valid only for temperatures lower than the T _gel (190°C); the principle failed at T ≥ 190°C. This was clearly seen in the low‐frequency region as a deviation from the terminal slope in the G′ curve. Similar behavior was observed in the modified Cole–Cole analyses (G″ vs. G′) that is, the curves start to deviate at 190°C.     

Adhesion,morphology, and heat resistance properties of polyurethane coated poly(methyl methacrylate)/fullerene-C60 composite films

Novel polyurethane (PU) adhesive was prepared and coated on poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/fullerene (PMMA/Full-C₆₀) composite. Dip-coating technique was employed as facile and cost-effective procedure to coat polyurethane on film substrate. The properties of PU/PMMA and PU/PMMA/Full-C₆₀ composite were studied using Fourier transform infrared spectroscopy, Field Emission Scanning Electron Microscopy, tensile, adhesion, thermal and flammability measurement. Testing polyurethane-coated PMMA exhibited crumpled surface while fullerene addition formed unique pattern of dispersed spherical structures. Fullerene nanofiller loading improved the adhesion and mechanical properties of composite films due to polymer–carbon interaction. In PU/PMMA/Full-C₆₀ 0.5 composite with 0.5 wt.% nanofiller, tensile strength (71.4 MPa) was increased by 18.6% while tensile modulus was increased by 143.85% compared with PU/PMMA. In PU/PMMA/Full-C₆₀ 0.5, T₀ of 473 °C and T_max of 655 °C were observed. Increasing the fullerene content up to 0.5 wt.% decreased the peak heat release rate to 131 kW/m². Novel polyurethane-coated PMMA/Full-C₆₀ composite have potential applications as adhesive coatings in electronic and automotive appliances.     

Dielectric anomalous response of water at 60 °C

Recently, the paraelectric response of water was investigated in the range 0–100 °C. It showed an almost perfect Curie–Weiss behaviour up to 60 °C, but a slight change in slope of 1/ε_d versus T at 60 °C was overlooked. In this work, we report optical extinction measurements on metallic (gold and silver) nanoparticles dispersed in water, annealed at various temperatures in the range from 20 to 90 °C. An anomalous response at 60 °C is clearly detectable, which we associate to a subtle structural transformation in the water molecules at that temperature. This water anomaly is also manifested by means of a blue shift in the longitudinal surface plasmon resonance of the metallic nanoparticles for the solutions annealed at temperatures higher than about 60 °C. A reanalysis of 1/ε_d (T) for water in the whole temperature range leads us to conclude that the water molecule undergoes a subtle transformation from a low temperature (0–60 °C) configuration with a dipole moment μ₁ = 2.18 D (close to the molecular dipole moment of ice) to a high temperature (60–100 °C) configuration with μ₂ = 1.87 D (identical to the molecular dipole moment in water vapour).     

The Evolution of Interfacial Strength as a Way to Characterize a Low-Temperature Limit of the Surface Glass Transition of an Amorphous Polymer

The evolution of autoadhesive strength, σ, with healing temperature, T _h, at the symmetric amorphous polystyrene (PS)?PS interfaces of the samples with vitrified bulk has been used to characterize a low-temperature limit of the surface glass transition temperature T _g ^surface(low). The existence of a linear relationship between the square root of σ and T _h has been found for both polydisperse and monodisperse polymers. By the extrapolation of straight lines σ ^1/2 ? T _h to σ ^1/2 = 0, the values of T _g ^surface(low) have been determined and compared with those of a high-temperature limit of T _g ^surface, T _g ^surface(high), measured earlier. The differences between T _g ^surface(low) and T _g ^surface(high) have been found to be insignificant, 10–20°C. Using an average value of the shift of T _g ^surface(low) with healing time, t _h, the quasi-equilibrium value of the surface glass transition temperature of amorphous PS T _∞ ^surface has been estimated to be 10–15°C.     

Reactive Compatibilization of Poly(trimethylene terephthalate)/Polypropylene Blends by Polypropylene‐graft‐Maleic Anhydride. Part 2. Crystallization Behavior

The crystallization behavior of uncompatibilized and reactive compatibilized poly(trimethylene terephthalate)/polypropylene (PTT/PP) blends was investigated. In both blends, PTT and PP crystallization rates were accelerated by the presence of each other, especially at low concentrations. When PP content in the uncompatibilized blends was increased to 50–60 wt%, PTT showed fractionated crystallization; a small PTT crystallization exotherm appeared at ～135°C besides the normal ～175°C exotherm. Above 70 wt% PP, PTT crystallization exotherms disappeared. In contrast, PP in the blends showed crystallization exotherms at 113–121°C for all compositions. When a maleic anhydride‐grafted PP (PP‐g‐MAH) was added as a reactive compatibilizer, the crystallization temperatures (T _c ) of PTT and PP shifted significantly to lower temperatures. The shift of PTT's T _c was larger than that of the PP, suggesting that addition of the PP‐g‐MAH had a larger effect on PTT's crystallization than on PP due to reaction between maleic anhydride and PTT.

The nonisothermal crystallization kinetics was analyzed by a modified Avrami equation. The results confirmed that PTT's and PP's crystallization was accelerated by the presence of each other and the effect varied with blend compositions. When the PP content increased from 0 to 60 wt%, PTT's Avrami exponent n decreased from 4.35 to 3.01; nucleation changed from a thermal to an athermal mode with three‐dimensional growths. In contrast, when the PTT content increased from 0 to 90 wt% in the blends, changes in PP's n values indicated that nucleation changed from a thermal (0–50 wt% PTT) to athermal (60–70 wt% PTT) mode, and then back to a thermal (80–90 wt% PTT) mode. When PP‐g‐MAH was added as a compatibilizer, the crystallization process shifted considerably to lower temperatures and it took a longer crystallization time to reach a given crystallinity compared to the uncompatibilized blends.     

Structure and electrical properties of Sb2Te3 and Bi0.4Sb1.6Te3 metastable phases obtained by HPHT treatment

We have obtained the metastable phase of the thermoelectric alloy Bi_0.4Sb_1.6Te₃ with electron type conductivity for the first time using the method of quenching under pressure after treatment at P=4.0 GPa and T=400–850 °C. We have consequently performed comparative studies with the similar phase of Sb₂Te₃. The polycrystalline X-ray diffraction patterns of these phases are similar to the known monoclinic structure α-As₂Te₃ (C2/m) with less monoclinic distortion, β ≈ 92°. We have measured the electrical resistivity and the Hall coefficient in the temperature range of T=77?450 K and we have evaluated the Hall mobility and density of charge carriers. The negative Hall coefficient indicates the dominant electron type of carriers at temperatures up to 380 K in the metastable phase of Sb₂Te₃ and up to 440 K in the metastable state of Bi_0.4Sb_1.6Te₃. Above these temperatures, the p-type conductivity proper to the initial phases dominates.     

SOLUTION PROPERTIES OF PACHYMAN FROM PORIA COCOS MYCELIA IN DIMETHYL SULFOXIDE

A linear β-(1→3)-d-glucan PCM3 (pachyman), a major polysaccharide in Poria cocos mycelia, formed aggregates in aqueous solution or dimethyl sulfoxide (DMSO) with absorbed moisture, thereby considerably complicating its fractionation and study of solution properties. In this work, the pachyman PCM3 having narrow polydispersity (M _w/M _n = 1.9) was carefully fractionated by a preparative size exclusion chromatography (SEC) using dehydrated DMSO as the mobile phase. The weight-average molecular mass M _w and intrinsic viscosity [η] of the fractions were measured by static and dynamic laser light scattering, SEC combined with light scattering, and viscometry in DMSO at 25°C, thus eliminating the aggregation. The Mark-Houwink equation for the pachyman in DMSO is established to be: [η] = 6.79 × 10^?4 M _w ^0.95 (mL/g) in the M _w range from 1.2 to 3.5 × 10⁵. The characteristic ratio C _∞ of the PCM3 in DMSO at 25°C, from light scattering by using Flory theory, was obtained to be 10.1, thus indicating that it behaves as a relatively expanded, flexible coil. In addition, the M _w of the pachyman from Poria cocos mycelia was 1.68 × 10⁵, obviously larger than that from the sclerotium (8.9 × 10⁴).     

Variety of LaSrMnO structures induced by growth conditions and laser irradiation

Crystallographic phase transitions in perovskite-like LaSrMnO metallic oxides are studied. The transitions are induced when internal stresses generated during film synthesis (at temperatures between 450 and 730°C) vary (decrease or increase) upon subsequent irradiation by a KrF laser emitting in the UV range. As the synthesis temperature T _s grows, the rhombohedral-to-orthorhombic phase transition occurs at 650–670°C. The resistivity is shown to be either temperature-independent, ρ(T)=const, at T<T _crit, or varies and reaches a maximum, ρ(T)=ρ_max, at the Curie temperature T _c. Optical transmission spectra taken at photon energies ℏω=0.5–2.5 eV exhibit both a high (0.8–0.9) and low (0.1–0.3) transmission coefficient t, depending on the synthesis temperature. As follows from X-ray diffraction data, the laser irradiation causes a phase transition only in LaSrMnO films grown at T _s<650°C. Phases of different size scales appear: the long-range-order orthorhombic matrix and mesoscopic-range-order rhombohedral clusters are observed in the films grown at T _s=450–550°C and the rhombohedral matrix with orthorhombic clusters, in the films grown at T _s=550–650°C.     

Synthesis and characterization of the new high pressure phases ACu3 V4O12(A=Gd,Tb, Er)

New ACu₃V₄O₁₂ (A=Gd, Tb, Er) phases have been prepared at high pressure and high-temperature conditions (P～8–9 GPa, T～1000°C) in a toroid-type high pressure cell. These compounds crystallize in the cubic symmetry with a perovskite-like structure. At ambient pressure, they are paramagnetic and have activation-type conductivity. The effect of high pressure (10–50 GPa) on the electrical properties of the materials was analyzed in the temperature range from 78 to 300 K. Pressure ranges of the transition from activation type to metallic conductivity have been determined. The crystal structure of ACu₃V₄O₁₂ (A=Gd, Tb, Er) was found to be stable up to 50 GPa.     

Influence of synthesis conditions on structural,optical and magnetic properties of iron oxide nanoparticles prepared by hydrothermal method

The iron oxide nanoparticles were synthesized by a simple hydrothermal method at different heating temperatures and pH conditions. The synthesized materials were characterized by X-ray diffractometer, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV–visible spectrometer and vibrating sample magnetometer. With increment in pH of the synthesized materials were resulted in orthorhombic (goethite) and cubic (magnetite) structures at pH 6 and 12, respectively. The banding nature of synthesized materials was analyzed by infrared spectra. The synthesized powders at 130?°C showed higher percent of nanorods (length = 90–120 nm) in addition to lower percentage of nanoparticles. The material at pH 12 consisted of maximum nanoparticles with size = 10–60 nm with small agglomerations. Band gap energy of synthesized materials was 2.2–2.8 eV. Herein, the reaction conditions tuned the saturation magnetization (M_S). The maximum M_S (59.38 emu/g) was obtained at pH 12 and lower M_S (0.65 emu/g) was observed at pH 6 due to intrinsic property of goethite phase.     

Confinement effects on glass transition temperature,transition breadth,and expansivity: Comparison of ellipsometry and fluorescence measurements on polystyrene films

Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T _gof supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: T_g(bulk)-T_g(23 nm) = 10 ^°\ensuremath T_{{\rm g}}({\rm bulk})-T_{{\rm g}}(23{\,\mbox{nm}})= 10 ^{\circ} C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T _g where expansivity slowly decreases with decreasing T . As determined from expansivities, the T _g breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T _g reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T _g ’s from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T _g(bulk) - T _g(23 nm) = 15^° C via fluorescence. This small difference in the T _g confinement effect reflects differences in how fluorescence and ellipsometry report “average T _g ” with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution.     

Composite coatings of polyamide/graphene: microstructure,mechanical, thermal,and barrier properties

This effort reports on novel fluorinated polyamide (FPA) and polyamide 1010 (PA1010)-based blends and graphene reinforced nanocomposite. PA1010/FPA (80:20) blend was opted as matrix material on the basis of molecular weight, thermal, and shear stress performance. Graphene was obtained through in situ chemical method of graphene oxide reduction. PA1010/FPA/Graphene nanocomposites was developed using various graphene loadings (up to 5 wt.%). Thin film coatings were prepared on glass substrate. Consequently, the PA1010/FPA/Graphene attained regular spongy morphological pattern. PA1010/FPA/Graphene 3 also showed improved T₀ and T_max of 534 and 591 °C relative to the neat blend (T₁₀ 423 °C; T_max 551 °C). Limiting oxygen index measurement indicated better non-flammability of PA1010/FPA/Graphene 1–3 nanocomposite series (57–60%) relative to the blend series (28–31%). UL94 tests also showed V-0 rating for nanocomposites. Furthermore, PA1010/FPA/Graphene 3 nanocomposite revealed significantly high tensile strength (62 MPa), flexural modulus (1690 MPa), and adhesive properties to be utilized as coating materials. The nanocomposite coatings also displayed outstanding barrier properties against O₂ and H₂O compared with neat blends.     

Conformational and Structural Analysis of 6‐(4‐Methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one

Abstract

The cis stereochemistry of 6‐(4‐methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one was studied by use of a PM3 semi‐empirical quantum mechanical model, and x‐ray crystallographic analysis. It crystallizes in the monoclinic space group P2 ₁ /n with a = 10.812(1) Å, b = 16.464(2) Å, c = 13.379(1) Å, α = 90.00°, β = 98.39(1)°, γ = 90.00°, V = 2356.07(4) Å³, Z = 4, D _calc = 1.3067 g cm^?3, F(0 0 0) = 976.41, and μ = 0.086 mm^?1. The structure was solved by direct methods and refined to R = 0.066 for 1257 independent reflections [I > 4σ (I)]. The results from x‐ray diffraction were seen to be generally consistent with the results from previously reported spectroscopic investigations, beside theoretical calculations, except for conformations of five‐membered fused heterocycles. Two inter‐ and intramolecular weak interactions in addition to carbon atoms (C1 and C3) with different chiralities were found in the structure. The conformational study was performed by randomly scanning the potential energy surface belonging to the title compound with respect to selected torsion angles.     

Microhardness Studies of the Interphase Boundary in Rubber‐Softened Glassy Polymer Blends Prepared with/without Compatibilizer

Abstract

The interphase boundary of incompatible polymer blends such as poly(methyl methacrylate) (PMMA)/natural rubber (NR) and polystyrene (PS)/NR, and of compatible blends such as PMMA/NR/epoxidized NR (ENR) and PS/NR/styrene–butadiene–styrene (SBS) block copolymer, where ENR and SBS were used as compatibilizers, was studied by means of microindentation hardness (H) and microscopy. Cast films of neat PMMA and PS, and blended films of PMMA/NR, PS/NR, PMMA/NR/ENR, and PS/NR/SBS were prepared by the solution method using a common solvent (toluene). Hardness values of 178 and 173 MPa were obtained on the surfaces of the neat PMMA and PS, respectively. After the inclusion of soft phases, the binary (incompatible) and the ternary (compatible) blend surfaces show markedly lower H‐values. Scanning electron and optical microscopy reveal a clear difference at the phase boundary of the surface of compatible (smooth boundary) and incompatible (sharp boundary) blends. The compatibilized blends were characterized by using microhardness measurements, as having the thinnest phase boundary (～30 µm), while incompatible blends were shown to present a boundary of about 60 µm. The hardness values indicate that the compatibilizer is smoothly distributed across the interface between the two blend components. Results highlight that the microindentation technique, in combination with microscopic observations, is a sensitive tool for studying the breadth and quality of the interphase boundary in non‐ or compatibilized polymer blends and other inhomogeneous materials.     

Fluorene-Based Poly(imino ketone) with Fluorine Atoms on the Side Chains as an Intelligent High-Performance Polymer

Abstract

Fluorene-based poly(imino ketone) with fluorine atoms in the side chains (PIKF-F), as an intelligent, high-performance polymer, was synthesized by the reaction of 4,4′-dibromobenzophenone and 9,9-bis(3-F-4-aminophenyl) fluorene via a palladium catalyzed C-N cross-coupling reaction. Its structure was characterized by means of FT-IR and ¹H NMR spectroscopy. The results showed a good agreement with the proposed structure. The molecular weights of the PIKF-F were measured by GPC (calibrated by polystyrene standards). The M_n and M_w values were 64,800 and 153,300, respectively. Thermogravimetric analysis and differential scanning calorimetry measurements showed that the polymer possessed good thermal stability with a high 10% decomposition temperature (450?°C) and a high glass transition temperature (T_g = 250?°C). The PIKF-F exhibited UV (ultra violet) absorption bands at 340–370?nm in NMP solution, while the fluorescence spectra showed maximum emission of PIKF-F at 498?nm in NMP solution. Both optical properties indicate the PIKF-F is of potential use as an organic photoelectric material. Additionally, due to its special conjugated system and the intramolecular hydrogen bonding (N–H···F), it was endowed with significantly strong photonic luminescence and the change of fluorescent intensity was reversible as the temperature was changed.