Polyketone Research Articles

자외선/오존 조사에 의한 Poly Ketone의 광산화와 염색성

Poly ketone (PK) was photo-oxidized by UV/ozone irradiation and the effect of UV energy on the surface properties of the UV-irradiated PK film was investigated by the measurement of reflectance, surface roughness, contact angles, ESCA, and ATR. Reflectance, particularly at the wavelength of 380nm, decreased with increasing UV energy. And the irradiation produced nano-scale roughness on the surface uniformly. The maximum surface roughness increased from 25.3nm for the unirradiated sample to 104.9nm at the irradiation of <TEX>$42.4J/cm^2$</TEX>. The improvement in hydrophilicity was caused by the introduction of polar groups such as C-O and C=O bonds resulting in higher <TEX>$O_{1s}/C_{1s}$</TEX>. The surface energy of PK film increased from <TEX>$43.3mJ/m^2$</TEX> for the unirradiated sample to <TEX>$71.9mJ/m^2$</TEX> at the irradiation of <TEX>$31.8J/cm^2$</TEX>. The zeta potential of the UV-irradiated PK decreased with increased UV energy and the dyeability to cationic dyes increased accordingly, resulting from the photochemically introduced anionic and dipolar dyeing sites on the PK films surfaces.

Influence of formic acid and water on the [Pd(OAc)2(dppp)] catalyzed ethene–carbon monoxide copolymerization carried out in aprotic organic solvents

The copolymerization of ethene with carbon monoxide catalyzed by [Pd(OAc)2(dppp)] in an aprotic solvent such as 1,4-dioxane or nitromethane is efficiently promoted both by H2O and HCOOH and yields a perfectly alternating polyketone (PK). The influence of the concentration of the promoters, pressure and temperature on the catalyst productivity and the limiting viscosity number (LVN) has been studied. The productivity increases with the increase of temperature and pressure. The LVN increases upon increasing the pressure and lowering the temperature. At 363K and 9.0MPa, in HCOOH/H2O/1-4,dioxane (2.7/1.35/1 molar ratio), the productivity is 37.50kgPK(gPdh)−1 (LVN 2.77dLg−1).LVN lowers upon increasing the concentration of the acid, suggesting that it is involved in the protonolysis chain-transfer process.

Ethylene and carbon monoxide copolymerization catalyzed by supported palladium catalyst

The kinetics of the copolymerization of ethylene with carbon monoxide catalyzed by (dppp)Pd(TsO) 2 ( I) has been investigated under homogeneous conditions and in slurry with supported catalyst I/ P ( P: polymer support polyketone (PK)), at different catalyst concentrations. The specific rate reduced to gram of Pd of the initial stage of reaction is going up with increasing catalyst concentration, and the specific rate of the second macro-kinetic stage decreases with increasing catalyst loading. The productivity of supported catalysts I/ P and I/ SiO 2 has been analyzed in terms of the PK yield per gram of supported catalyst per hour. The specific copolymer yield increases with the increase in catalyst loading in I/ P to 2 × 10 −4 mol of Pd per 1 g of the supported catalyst and attains the maximum value of 27 g PK/(g sup.cat. h) when copolymerization is carried out in the heptane–toluene mixture.

Preparation and characterization of polyketone (PK) fibrous membrane via electrospinning

In this study, the aliphatic polyketone (PK) fibrous membrane was successfully prepared from the solution by electrospinning process at room temperature. As solvents for PK polymer, the mixed solvents of trifluoroacetic acid (TFA) and dichloromethane (MC) were used. Electrospun PK fibrous membrane was characterized by scanning electron microscope (SEM), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), Fourier transform infrared spectrophotometer (FT-IR), and Raman spectroscopy, and compared to the corresponding cast PK film. The crystal structures of electrospun PK fiber and solvent cast PK film were characterized by WAXD. The result indicated that the crystal structure of cast PK film was assigned to α-form, while the crystal structure of PK fibrous membrane corresponded to β-form, which was attributed to fast crystallization during electrospinning process. Accordingly, the crystallinity of electrospun PK fibrous membrane was lower than that of solvent cast PK film. To confirm further these crystalline structures, FT-IR and Raman spectroscopy were employed.

Phase separation and mechanical properties of polyketone/polyamide polymer alloys

AbstractWe have investigated polyketone (PK)/polyamide 6 (PA) polymer alloys having enhanced Charpy impact energy greater than that of polycarbonate (PC) as a result of moisture absorption. From the results of differential scanning calorimetry (DSC), Raman spectroscopy, and transmission electron microscope (TEM) observation of the polymer alloys, it was found that PK‐rich and PA‐rich phases exist at the nanometer level in the polymer alloys; however, a microscopic interaction phase formed between the two phases. 3D‐TEM observations, electron energy loss spectroscopy, and small‐angle X‐ray scattering measurements revealed that a co‐continuous nanolayer formed from the PA‐rich phase and lamella network of the PK‐rich phase. Moreover, the interaction and mobility of PK and PA molecular chains were investigated by using a 13C cross polarization/magic angle sample spinning NMR technique. It was found that moisture absorption markedly enhances the mobility of PA molecular chains in PK/PA alloys. This suggests that the wet (moisture‐absorbed) PA phase of PK/PA alloys allows quick deformation upon impact stimulation. On the other hand, the results of Charpy impact tests showed that the total impact energy (Etotal) of the wet polymer alloy was much higher than that of the dry one. An examination of the load‐displacement curves revealed that the wet samples showed a pronounced increase in displacement compared with the dry ones. From these results, it was concluded that the lamella network of the PK‐rich phase sustains the maximum stress and that the large displacement of the PA‐rich phase increases the impact energy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

CO–ethene copolymerisation catalysed by [PdCl 2(PPh 3) 2]/PPh 3/HCl in MeOH

The system [PdCl 2(PPh 3) 2]/PPh 3/HCl catalyses the carbonylation of ethene in MeOH as a solvent to give methyl propanoate (MP) or a polyketone (PK). The influence of temperature, Pd/P, CO/ethene and Pd/HCl ratios, and concentration of H 2O on the catalytic activity has been studied. The catalytic system is active only in the presence of HCl and is stable when P/Pd is ≥6/1 up to 110 °C. At 100 °C, with Pd/P/HCl = 1/6/1600 (HCl initially added), under 6.0 MPa total pressure, the main product is MP at 1.0 MPa of ethene, whereas is PK when the pressure of the olefin is higher than 4.0 MPa. Water, which forms in the solvent, because of the reaction of MeOH with HCl, has a minor effect. The PK product presents a 2.5–4/1 ratio between the keto and ester end groups. The proposed catalytic cycle takes into account the results.

Selective alternating copolymerisation of carbon monoxide and ethene catalysed by [PdCl 2(dppf)] in acetic acid–water as a solvent [dppf = 1,1′-bis(diphenylphosphino)ferrocene

The title complex is highly active and selective for the alternating copolymerisation of carbon monoxide and ethene in CH 3COOH–H 2O as a solvent. Under typical reaction conditions, 90 °C, 4.5 MPa, CO/ethene = 1/1, the productivity passes through a maximum of 15,500 gPK (gPd h) −1 when the concentration of the acid is 40% (mol mol −1), whereas the limiting viscosity number (LVN) increases upon increasing the acid concentration. Under the above conditions, but in the presence of sodium acetate, a polyketone (PK) of higher molecular weight is obtained, though at the expense of the productivity. Under higher pressure of ethene both productivity and LVN increase; under higher pressure of CO the productivity slightly decreases, whereas the LVN increases. These results are discussed taking into account the factors relevant to the chain growing and the termination processes.

A new catalytic system for copolymerization of styrene with CO:PdCl 2/bipy/M(CF 3SO 3) n

A new three-component catalytic system, PdCl 2/bipy/M(CF 3SO 3) n , was studied for copolymerization of styrene with CO to prepare alternating polyketone (PK). It is found that the PdCl 2/bipy/CF 3SO 3H catalytic system had a very low catalytic activity for copolymerization of CO with styrene, but when M(CF 3SO 3) n was introduced instead of CF 3SO 3H, the PdCl 2/bipy/M(CF 3SO 3) n catalytic system exhibited high activity. The copolymer was characterized by elemental analysis, FTIR, 1H NMR, DSC and TGA. The results indicated that the copolymer is a linear alternating copolymer of carbon monoxide and styrene with glass transition temperature, melting point, and decomposition temperature of 275, 350, and 400 °C, respectively. The effects of M(CF 3SO 3) n , ligands, p-benzoquinone/PdCl 2 ratio, solvents, and reaction temperatures on the reaction have been discussed in detail. The results showed that this novel catalytic system exhibited high activity, especially when Cu(CF 3SO 3) 2 was used. The corresponding productivity was 20,000 gPK/molPd h when the reaction was carried out at 338 K for 4 h under 3.0 MPa of CO.

Notch sensitivity of aliphatic polyketone terpolymers

AbstractThe notch sensitivity of aliphatic polyketone (PK) terpolymers was investigated in this article. The notch‐tip radius was varied between the size of an actual propagating crack tip of 1–2 μm and the largest notch tip of 1000 μm radius. The larger notch‐tip radii (1000–15 μm) were milled into the polymer. The smallest notch‐tip radii of 2 and 15 microns were made with a novel technique with the aid of an Eximer laser. The fracture behavior of the PK‐terpolymer was found to be sensitive toward changes in notch‐tip radius. The fracture energy decreased strongly with decreasing notch‐tip radius even when fractured ductile. Sharper notches were not as effectively blunted as were larger notches in the ductile region. The brittle‐to‐ductile transition temperature (Tbd) was increased with decreasing notch‐tip radius for the larger notches (1000–100 μm). For sharper notches (2 and 15 μm) the Tbd decreased again. This behavior could be explained by the decreasing amount of elastic energy release with sharper notches. The energy release proved to be very important for this material. A mixed‐mode fracture behavior was found to occur with larger notches because of the elastic energy present in the sample before fracture. The notch sensitivity was reduced considerably by the addition of a 10% core‐shell rubber phase. For the blend material the notch‐tip radius had almost no influence on the Tbd. The fracture energy on the other hand was still lowered with a sharper notch. This was attributed to the difference in the crack initiation process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2558–2575, 2004

Preparation and Characterization of Polyketone/Clay Nanocomposites

Nanocomposites of Polyketone (PK)/Cloisite 30B clay were prepared by the melt intercalation technique. The nanocomposites were characterized for their microstructure using wide-angle x-ray diffraction (WAXD), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). An increase in the “d” spacing of silicate layers, as revealed by WAXD analysis, indicated the intercalated structure of the nanocomposites. A uniform dispersion of clay layers in polymer matrix was confirmed by TEM micrographs. The DMA analysis indicates improved storage modulus over the temperature range studied and an increase in the glass transition temperature of the nanocomposites.

Morphology and structures of polypropylene-aliphatic polyketone blends

Aliphatic polyketone (PK) contains both non-polar aliphatic units and polar carbonyl groups, which make it an ideal and unique candidate for modifying non-polar polymer systems containing purely alkyl chains,such as polyalkenes. A new polymer blend system based on polypropylene (PP) and aliphatic polyketone has been prepared; PP-PK blends containing 5 and 8 wt-% PK were prepared by the melt blending method. The morphology and structures of the blends were characterised using SEM, DSC, WAXS, FTIR, and TGA. The SEM study indicates that the blends are immiscible in this composition range. They have typical island-sea morphology and the size of the droplets increases as the PK concentration increases. On the fractured surfaces of the blend samples some droplets are partially connected to the matrix, which implies that the interface between the two phases has relatively high strength. The DSC study shows that the blending significantly reduces the crystallinity of both PP and PK. The WAXS result indicates that the crystal size of PP along the b axis is largely reduced in the blends, which implies that a small amount of PK chains may have been incorporated into the matrix,interrupting the growth of the PP crystals. Both FTIR and TGA studies suggest that there are chemical reactions between PP and PK during compounding, which may contribute to the partial miscibility and to the relatively strong interface observed.

Morphology and fracture behavior in aliphatic polyketones

Morphological features and fracture mechanisms in aliphatic polyketone (PK) samples, prepared via compression molding and injection molding processes, were investigated using differential scanning calorimetry, dynamic mechanical spectroscopy, transmitted optical microscopy and transmission electron microscopy techniques. The PK samples studied are found to have a crystallinity of about 38%. The fracture mechanisms observed in the PK samples are found to be sensitive to strain rate, notch, and stress state. Upon double-notch four-point-bend fracture, the PK fails in a brittle fashion under impact condition and fails in a ductile manner when the testing rate is low. Crazing is the dominant fracture mechanism under the low-rate test conditions, even in the region close to the surface (plane stress region) of the sample. The dominant fracture mechanisms under uniaxial tension are found to be shear yielding and voiding due to debonding of the less-compliant sub-micrometer particles in the PK matrix. No sign of crazing is observed in uniaxial tensile specimens.

Process for purifying polyketones

Process for purifying polyketones

The effect of shear controlled orientation in injection moulding on the mechanical properties of an aliphatic polyketone

This article relates to an investigation of injection moulding a new commercial polymer, an aliphatic polyketone (PK). A terpolymer and a 30% glass-filled grade were used as study materials together with an isotactic polypropylene that was used as a basis for comparison. Both conventional injection moulding and shear-controlled orientation injection moulding (SCORIM) were employed in processing. Tensile testing was carried out at 80°C as well as at room temperature. Polarized light microscopy and wide-angle x-ray diffraction were used in the characterization of the mouldings. An increase of up to 30% in Young's modulus and 35% in ultimate tensile strength, and a 70–90% increase in strain at peak were gained for the terpolymer (PK) at room temperature, as a result of SCORIM processing. A substantial improvement at 80°C was also recorded for unfilled SCORIM PK mouldings, and is attributed to the pronounced molecular alignment that was induced in SCORIM mouldings, as shown by Debye patterns. It is notable that the SCORIM mouldings of PK exhibit a greater tensile strength at 80°C than the SCORIM mouldings of isotactic polypropylene at 23°C. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 415–430, 1997

US 5,066,701 Stabilized polyketone

US 5,066,701 Stabilized polyketone

Copolymerization of carbon monoxide with ethylene in the presence of palladium phosphine complexes

We have already reported the possibility of the carbonylation of olefins, in particular, of ethylene, under mild conditions in the presence of a catalyst system consisting of a palladium phosphine complex and p-toluenesulfonic acid (PTSA) [I]. In expanding the pressure range, we unexpectedly found that copolymerization occurs in acetic acid solution beginning at 0.5-1.5 MPa. In this case, refractory polyketones (PK) are formed, which are insoluble in ordinary solvents. Elemental analysis, PMR, 13C NMR, and IR spectroscopy showed that these products are i:I alternating copolymers of carbon monoxide and ethylene. According to Enikolopyan et al. [2], PK are promising polymer materials with a set of interesting new properties. An induction period T 0 is observed during the copolymerization followed by a stationary segment and a reduction in rate, which is probably due to deactivation of the catalyst. The reaction rate, yield and mp of the PK, and the T 0 value and duration of the stationary segment depend on the concentration and nature of the phosphine ligand, concentration of PTSA, synthesis conditions, and other parameters. In a typical experiment, a mixture of 0.0125 mmole (PPh3)4Pd , 0.05 mmole PPh3, i mmole PTSA, and 25 ml acetic acid is added to a steel reactor and flushed with argon. Then, a I:I mixture of CO and ethylene was added to 4.4 MPa and strongly agitated at 90~ In this case, r 0 = 25 min. The stationary activity of the catalyst a 16.2 g PK/(g Pd.min). The yield = 700 g PK/g Pd, mp 217-221~ The following results were obtained for other phosphine ligands: P(C6H4CH3-p)3) T 0 ~ 15 min, a 15.7 g PK/(g Pd.min), ~ 864 g PK/g Pd, mp 222-226~ PPhzEt) T o = 5 min, a = 8.8 g PK/(g Pd.min), a 2450 g PK/g Pd, mp 226-237~ PPhEt2) T o 0 min, a = 5.9 g PK/(g pdomin), ~ = 1500 g PK/g Pd, mp 220-224~ In accord with Sen [3], the catalytically active intermediate in this case may be a cationic palladium phosphine complex.

Synthesis of polyketones by direct polycondensation of dicarboxylic acids with diaryl compounds using phosphorus pentoxide/methanesulfonic acid as condensing agent and solvent

Reaction modele: diphenyl ether plus acide benzoique. Polycondensation pendant plusieurs termes entre 50 et 100°C

Syntheses and Reactions of Cyclic vicinal Polyketones

Syntheses and Reactions of Cyclic vicinal Polyketones