Synthesis and properties of novel conjugated poly(silylacetylene silazane)s

A series of novel conjugated polymers, poly(silylacetylene silazane)s having different substituents, were prepared by ammonolysis of the corresponding α,ω‐dichlorosilyleneacetylene oligomers. The structures and properties of the poly(silylacetylene silazane)s were characterized by Fourier transform infrared, ¹H, ¹³C, ²⁹Si NMR, and elemental analyses, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and spectrofluorophotometry. The resulting polymers had good thermal properties and were moderately fluorescent. Their thermal stability was improved, and obvious red shift was observed when a phenyl substituent was attached on a silicon atom of polymers in the emission spectra. These polymers have the potential to be used as light‐emitting materials with good thermal stability. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2897–2903, 2004     

Synthesis and thermal analysis of branched and “kinked” poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) was synthesized by self-condensation of bis-(2-hydroxyethyl) terephthalate (BHET). Copolymerization of BHET with ethyl, bis-3,5-(2-hydroxyethoxy) benzoate (EBHEB) and ethyl, 3-(2-hydroxyethoxy) benzoate (E3HEB) yielded copolymers that contain varying amounts of branching and kinks, respectively. Copolymers of BHET with ethyl, 4-(2-hydroxyethoxy) benzoate (E4HEB), in which only the backbone symmetry is broken but without disruption of the linearity, were also prepared for comparison. The composition of the copolymers were established from their ¹H-NMR spectra. The intrinsic viscosity of all the copolymers indicated that they were of reasonably high molecular weights. The thermal analysis of the copolymers using DSC showed that both the melting temperatures (T_m) and the percent crystallinity (as seen from the enthalpies of melting) (ΔH_m) decreased with increasing comonomer (defect concentration) content, although their glass transition temperatures (T_g) were less affected. This effect was found to be most pronounced in the case of branching, while the effects of kinks and linear disruptions, on both T_m and ΔH_m, were found to be similar. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 309–317, 1998     

Mixed iridium(III) and ruthenium(II) polypyridyl complexes containing poly(ε‐caprolactone)‐bipyridine macroligands

A hydroxy‐functionalized bipyridine ligand was polymerized with ε‐caprolactone utilizing the controlled ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate. The resulting poly(ε‐caprolactone)‐containing bipyridine was characterized by ¹H NMR and IR spectroscopy, and gel permeation chromatography, as well as matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, revealing the successful incorporation of the bipyridine ligand into the polymer chain. Coordination to iridium(III) and ruthenium(II) precursor complexes yielded two macroligand complexes, which were characterized by NMR, gel permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight MS, cyclic voltammetry, and differential scanning calorimetry. In addition, both photophysical and electrochemical properties of the metal‐containing polymers proved the formation of a trisruthenium(II) and a trisiridium(III) polypyridyl species, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4153–4160, 2004     

Thermal analysis of the double-melting behavior of poly(L-lactic acid)

The melting and crystallization behavior of poly(L -lactic acid) (PLLA; weight-average molecular weight = 3 × 10⁵) was studied with differential scanning calorimetry (DSC). DSC curves for PLLA samples were obtained at various cooling rates (CRs) from the melt (210 °C). The peak crystallization temperature and the exothermic heat of crystallization determined from the DSC curve decreased almost linearly with increasing log(CR). DSC melting curves for the melt-crystallized samples were obtained at various heating rates (HRs). The double-melting behavior was confirmed by the double endothermic peaks, a high-temperature peak (H) and a low-temperature peak (L), that appeared in the DSC curves at slow HRs for the samples prepared with a slow CR. Peak L increased with increasing HR, whereas peak H decreased. The peak melting temperatures of L and H [T_m(L) and T_m(H)] decreased linearly with log(HR). The appearance region of the double-melting peaks (L and H) was illustrated in a CR–HR map. Peak L decreased with increasing CR, whereas peak H increased. T_m(L) and T_m(H) decreased almost linearly with log(CR). The characteristics of the crystallization and double-melting behavior were explained by the slow rates of crystallization and recrystallization, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 25–32, 2004     

Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

New light‐colored poly(ether imide)s based on 2,5‐di‐tert‐butylhydroquinone bis(ether anhydride) and aromatic diamines

A series of poly(ether imide)s (PEIs), III _a–k , with light color and good physical properties were prepared from 1,4‐bis(3,4‐dicarboxypheoxy)‐2,5‐di‐tert‐butylbenzene dianhydride ( I ) with various aromatic diamines ( II _a–k ) via a conventional two‐stage procedure that included a ring‐opening polyaddition to yield poly(amic acid)s (PAA), followed by thermal imidization to the PEI. The intermediate PAA had inherent viscosities in the range of 1.00–1.53 dL g^?1. Most of the PEIs showed excellent solubility in chlorinated solvents such as dichloromethane, chloroform, and m‐cresol, but did not easily dissolve in dimethyl sulfoxide and amide‐type polar solvents. The III series had tensile strengths of 96–116 MPa, an elongation at break of 7–8%, and initial moduli of 2.0–2.5 GPa. The glass‐transition temperatures (T_g) and softening temperatures (T_s's) of the III series were recorded between 232 and 285 °C and 216–279 °C, respectively. The decomposition temperatures for 10% weight loss all occurred above 511 °C in nitrogen and 487 °C in air. The III series showed low dielectric constants (2.71–3.54 at 1 MHz), low moisture absorption (0.18–0.66 wt %), and was light‐colored with a cutoff wavelength below 380 nm and a low yellow index (b^*) values of 7.3–14.8. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1270–1284, 2005     

Influence of electronic effect on catalytic activity of salicylaldiminato nickel(II) complexes

A means of correlation between the activity and the net charge, the metal atom net charge correlation (MANCC), which was successful in the activity prediction of the early‐transition metal catalysts, has been used to study the catalytic activities of salicylaldiminato Ni(II) complexes, the late‐transition metal catalysts, in olefin polymerization or oligomerization. A comparison with the available quantum mechanics/molecular mechanics (QM/MM) calculation data suggests that even without a detailed mechanism, MANCC results mostly agree with QM/MM calculation data regarding insertion barrier data and enthalpy change. Eight experimental complexes were further built up by modeling; their catalytic activities predominantly increased in line with the net charges on the metal atoms. The same results were obtained for the other four complexes synthesized in the present work. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4765–4774, 2004     

Synthesis and characterization of 2,2‐bis(methylol)propionic acid dendrimers with different cores and terminal groups

Three sets of aliphatic polyester dendrimers based on 2,2‐bis(methylol)propionic acid (bis‐MPA) were synthesized. Two of the sets had benzylidene terminal groups and either a trimethylolpropane or triphenolic core moiety. The last set had acetonide terminal groups and a triphenolic core moiety. Benzylidene‐[G#1]‐anhydride and acetonide‐[G#1]‐anhydride were used as the reactive building blocks in the construction of all dendrimers. The large excess of building blocks used in the coupling reactions initially resulted in considerable material loss. This waste was eliminated through the development of a recycling method. ¹H and ¹³C NMR and matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) analysis were used to verify the purity of all compounds. Size exclusion chromatography (SEC) was used, as well as MALDI‐TOF, for molecular weight determinations. The SEC measurements were conducted with a universal calibration method and an online right‐angle laser light scattering detector. Measured dendrimer molecular weights were close to their theoretical molar masses. Observations were also made of the hydrodynamic radius and intrinsic viscosity for the different dendrimers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1758–1767, 2004     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Ethylene polymerization by bis(salicylaldiminate)nickel(II)/aluminoxane catalysts

The homopolymerization of ethylene by using different catalytic systems based on dinitro‐substituted bis(salicylaldiminate)nickel(II) precursors such as bis[3,5‐dinitro‐N(2,6‐diisopropylphenyl)]nickel(II) and bis[3,5‐dinitro‐N(phenyl)]nickel(II) in combination with organoaluminum compounds was investigated. In particular, the catalytic performances were studied as a function of the main reaction parameters, such as temperature, pressure, Al/Ni molar ratio, and duration. Methylaluminoxane resulted in the best co‐catalyst. Activities up to 200 kg polyethylene/(mol Ni × h) to give a linear high‐molecular‐weight polymer were achieved. The influence of the bulkiness of the substituents on the N‐aryl group of the aldimine ligand was also checked; it resulted in a determinant for catalytic activity rather than for polymer characteristics. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2534–2542, 2004     

Synthesis and thermal behavior of new poly(ethylene terephthalate‐imide)s

Copoly(ethylene terephthalate‐imide)s (PETIs) were synthesized by the melt copolycondensation of bis(2‐hydroxyethyl)terephthalate with a new imide monomer, N,N′‐bis[p‐(2‐hydroxyethoxycarbonyl)phenyl]‐biphenyl‐3,3′,4,4′‐tetracarboxydiimide (BHEI). The copolymers were characterized by intrinsic viscosity, Fourier transform infrared, ¹H NMR, differential scanning calorimetry, and thermogravimetric analysis techniques. Although their crystallinities decreased as the content of BHEI units increased, the glass‐transition temperatures (T_g) increased significantly. When 5 or 10 mol % BHEI units were incorporated into poly(ethylene terephthalate), T_g increased by 10 or 24 °C, respectively. The thermal stabilities of PETI copolymers were about the same as the thermal stability of PET, whereas the weight loss of PETIs decreased as the content of BHEI units increased. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 408–415, 2001     

Segmented block copolymers of poly(ethylene glycol) and poly(ethylene terephthalate)

A new series of segmented copolymers were synthesized from poly(ethylene terephthalate) (PET) oligomers and poly(ethylene glycol) (PEG) by a two‐step solution polymerization reaction. PET oligomers were obtained by glycolysis depolymerization. Structural features were defined by infrared and nuclear magnetic resonance (NMR) spectroscopy. The copolymer composition was calculated via ¹H NMR spectroscopy. The content of soft PEG segments was higher than that of hard PET segments. A single glass‐transition temperature was detected for all the synthesized segmented copolymers. This observation was found to be independent of the initial PET‐to‐PEG molar ratio. The molar masses of the copolymers were determined by gel permeation chromatography (GPC). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4448–4457, 2004     

Miscibility,melting, and crystallization of poly(butylene‐2,6‐naphthalate)/poly(ether imide) blends

We prepared blends of poly(butylene‐2,6‐naphthalate) (PBN) and poly(ether imide) (PEI) by solution‐casting from dichloroacetic acid solutions. The miscibility, crystallization, and melting behavior of the blends were investigated with differential scanning calorimetry (DSC) and dynamic mechanical analysis. PBN was miscible with PEI over the entire range of compositions, as shown by the existence of single composition‐dependent glass‐transition temperatures. In addition, a negative polymer–polymer interaction parameter was calculated, with the Nishi–Wang equation, based on the melting depression of PBN. In nonisothermal crystallization investigations, the depression of the crystallization temperature of PBN depended on the composition of the blend and the cooling rate; the presence of PEI reduced the number of PBN segments migrating to the crystallite/melt interface. Melting, recrystallization, and remelting processes occurring during the DSC heating scan caused the occurrence of multiple melting endotherms for PBN. We explored the effects of various experimental conditions on the melting behavior of PBN/PEI blends. The extent of recrystallization of the PBN component during DSC heating scans decreased as the PEI content, the heating rate, the crystallization temperature, and the crystallization time increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1694–1704, 2004     

Poly(ether imide)s derived from phthalazinone‐containing dianhydrides

An unsymmetrical and noncoplanar heterocyclic dianhydride was synthesized from a bisphenol‐like phthalazinone, 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, and a series of novel poly(ether imide)s based on it, with intrinsic viscosities of 0.67–1.42 dL/g, were obtained by one‐step solution polymerization in m‐cresol at 200 °C for 20 h. The polymers were readily soluble in N‐methyl‐2‐pyrrolidinone and m‐cresol. The poly(ether imide)s derived from 4,4′‐oxydianiline and 4,4′‐methylenedianiline were also very soluble in chloroform, 1,1′,2,2′‐tetrachloroethane, and N,N‐dimethylacetamide. The glass‐transition temperatures were 289–326 °C, as determined by differential scanning calorimetry. All the degradation temperatures for 5% weight loss occurred above 482 °C in nitrogen. The tensile strength of thin films of some of the polymers varied from 103.1 to 121.4 MPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6089–6097, 2004     

Thermal,crystallization, mechanical,and rheological characteristics of poly(trimethylene terephthalate)/poly(ethylene terephthalate) blends

Blends of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) in the amorphous state were miscible in all of the blend compositions studied, as evidenced by a single, composition‐dependent glass‐transition temperature observed for each blend composition. The variation in the glass‐transition temperature with the blend composition was well predicted by the Gordon–Taylor equation, with the fitting parameter being 0.91. The cold‐crystallization (peak) temperature decreased with an increasing PTT content, whereas the melt‐crystallization (peak) temperature decreased with an increasing amount of the minor component. The subsequent melting behavior after both cold and melt crystallizations exhibited melting point depression behavior in which the observed melting temperatures decreased with an increasing amount of the minor component of the blends. During crystallization, the pure components crystallized simultaneously just to form their own crystals. The blend having 50 wt % of PTT showed the lowest apparent degree of crystallinity and the lowest tensile‐strength values. The steady shear viscosity values for the pure components and the blends decreased slightly with an increasing shear rate (within the shear rate range of 0.25–25 s^?1); those of the blends were lower than those of the pure components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 676–686, 2004     

Influence of carboxyl‐terminated (butadiene‐co‐acrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends

A mixture of epoxy with liquid nitrile rubber, carboxyl‐terminated (butadiene‐co‐acrylonitrile) (CTBN) was cured under various temperatures. The cured resin was a two‐phase system, where spherical rubber domains were dispersed in the matrix of epoxy. The morphology development during cure was investigated by scanning electron microscope (SEM). There was slight reduction in the glass transition temperature of the epoxy matrix (T_g) on the addition of CTBN. It was observed that, for a particular CTBN content, T_g was found to be unaffected by the cure temperature. Bimodal distribution of particles was noted by SEM analysis. The increase in the size of rubber domains with CTBN content is due probably to the coalescence of the rubber particles. The mechanical properties of the cured resin were thoroughly investigated. Although there was a slight reduction in tensile strength and young's modulus, appreciable improvements in impact strength, fracture energy, and fracture toughness were observed. Addition of nitrile rubber above 20 parts per hundred parts of resin (phr) made the epoxy network more flexible. The volume fraction of dispersed rubbery phase and interfacial area were increased with the addition of more CTBN. A two‐phase morphology was further established by dynamic mechanical analysis (DMA). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2531–2544, 2004     

Novel positive‐working and aqueous‐base‐developable photosensitive poly(imide benzoxazole) precursor

A novel positive‐working and aqueous‐base‐developable photosensitive poly(imide benzoxazole) precursor based on a poly(amic acid hydroxyamide) bearing phenolic hydroxyl groups and carboxylic acid groups, a diazonaphthoquinone (DNQ) photosensitive compound, and a solvent was developed. Poly(amic acid hydroxyamide) was prepared through the polymerization of 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane, trimellitic anhydride chloride, and 4,4′‐oxydibenzoyl chloride. Subsequently, the thermal cyclization of the poly(amic acid hydroxyamide) precursor at 350 °C produced the corresponding poly(imide benzoxazole). The inherent viscosity of the precursor polymer was 0.17 dL/g. The cyclized poly(imide benzoxazole) showed a high glass‐transition temperature of 372 °C and 5% weight loss temperatures of 535 °C in nitrogen and 509 °C in air. The structures of the precursor polymer and the fully cyclized polymer were characterized with Fourier transform infrared and ¹H NMR. The photosensitive polyimide precursor containing 25 wt % DNQ photoactive compound showed a sensitivity of 256 mJ/cm² and a contrast of 1.14 in a 3‐μm film with a 0.6 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 5 μm was obtained from this composition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5990–5998, 2004     

Aromatic poly(benzoxazole)s from multiring diacids containing (phenylenedioxy)diphenylene or (naphthalenedioxy)diphenylene groups: Synthesis and thermal properties

Poly(arylether benzoxazole)s (PAEBOs) were prepared from a series of fully aromatic dicarboxylic acids containing (phenylenedioxy)diphenylene or (naphthalenedioxy) diphenylene groups and 3,3′‐dihydroxy‐4,4′‐diaminobiphenyl (I) or 4‐4′‐(hexafluoroisopropylidene)bis(2‐aminophenol) (II) through high‐temperature direct polycondensation. A phosphorous pentoxide/methanesulfonic acid mixture or trimethylsilylpolyphosphate was used as a condensing agent. All the PAEBOs were amorphous and soluble in strong acids, and those derived from II were also readily soluble in polar organic solvents. Flexible films were cast from their chloroform solutions. The PAEBOs showed inherent viscosity values of 0.68–2.06 dL/g (CH₃SO₃H, T = 30 °C, c = 0.15 g · dL⁻¹). Thermal analysis indicated glass‐transition temperatures ranging from 236 to 270 °C and thermal stability (5% weight loss) in nitrogen up to 526 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1172–1178, 2000     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003