Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction

High‐molecular‐weight poly(phthalazinone)s with very high glass‐transition temperatures (T_g's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers ( 7a–e ) were synthesized from 2‐(4‐chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited T_g's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4‐flurophenyl) sulfone demonstrated the highest T_g of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4′‐isopropylidenediphenol and 4,4′‐(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly‐(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481–2490, 2003     

Preparation of HPEEK by Oligomer A2+B3 Approach

A series of hyperbranched poly(ether ether ketones) with different chain length between branching point (L) were prepared using a A₂+B₃ methodology, in which the A₂ is hydroxyl‐terminated PEEK oligomer. The L affects the properties of the polymers such as the inherent viscosity, the degree of crystallinity, the thermal properties of the polymers etc. The polymer with a L₂≈8 had T _g (122.4°C), T _c (200.2°C), and broad T _m (247.4°C). With the increment of L, up to the point L₂≈20 and L₂≈35, the polymers become semi‐crystalline, with a melting point of 300.9°C and 317.9°C, respectively. Their wide angle X‐ray scattering (WAXS) pattern indicated that their crystal structure is exactly the same as that of the linear homopolymer.     

Facile Synthesis of Well‐Defined Branched Sulfur‐Containing Copolymers: One‐Pot Copolymerization of Carbonyl Sulfide and Epoxide

Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well‐defined branched poly(monothiocarbonate)s in a “grafting through” manner by copolymerizing carbonyl sulfide (COS) with epichlorohydrin (ECH), where the side‐chain forms in situ. The lengths of the side‐chains are tunable based on reaction temperatures. More importantly, enhancement in thermal properties of the branched copolymer was observed, as the T_g value increased by 22 °C, compared to the linear analogues. When chiral ECH was utilized, semicrystalline branched poly(monothiocarbonate)s were accessible with a T_m value of 112 °C, which is 40 °C higher than that of the corresponding linear poly(monothiocarbonate)s. The strategy presented herein for synthesizing branched polymers provides efficient and concise access to topological polymers.     

Synthesis and characterization of novel poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate

The melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L‐proline (N‐CBz‐Hpr) with cyclic carbonate [trimethylene carbonate (tri‐MC) or tetramethylene carbonate (tetra‐MC)] at a wide range of molar fractions in the feed produced new degradable poly(ester‐carbonate)s. The influence of reaction conditions such as polymerization time and temperature on the yield and inherent viscosity of the copolymers was investigated. The polymerizations were carried out in bulk at 140 °C with 1.5 wt % stannous octoate as a catalyst for 30 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, gel permeation chromatography, and Ubbelohde viscometry. The copolymers synthesized exhibited moderate molecular weights with rather narrow molecular weight distributions. The values of the glass‐transition temperature (T_g) of the copolymers depend on the molar fractions of cyclic carbonate. For the poly(N‐CBz‐Hpr‐co‐tri‐MC) system, with a decreased tri‐MC content from 93 to 16 mol %, the T_g increased from ?10 to 60 °C. Similarly, for the poly(N‐CBz‐Hpr‐co‐tetra‐MC) system, when the tetra‐MC content decreased from 80 to 8 mol %, the T_g increased from ?18 to 52 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐tri‐MC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐tri‐MC)s was evaluated from weight‐loss measurements. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1435–1443, 2003     

Syntheses and properties of novel fluorinated polyamides based on a bis(ether‐carboxylic acid) or a bis(ether amine) extended from bis(4‐hydroxyphenyl)phenyl‐2,2,2‐trifluoroethane

Two series of novel fluorinated aromatic polyamides were prepared from 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic diamines or from 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic dicarboxylic acids with the phosphorylation polyamidation technique. These polyamides had inherent viscosities ranging from 0.51 to 1.54 dL/g that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 36,200–80,000 and 17,200–64,300, respectively. All polymers were highly soluble in aprotic polar solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide, and some could even be dissolved in less‐polar solvents like tetrahydrofuran. The flexible and tough films cast from the polymer solutions possessed tensile strengths of 76–94 MPa and initial moduli of 1.70–2.22 GPa. Glass‐transition temperatures (T_g's) and softening temperatures of these polyamides were observed in the range of 185–268 °C by differential scanning calorimetry or thermomechanical analysis. Decomposition temperatures (T_d's) for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. Almost all the fluorinated polyamides displayed relatively higher T_g and T_d values than the corresponding nonfluorinated analogues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 420–431, 2003     

Oxidative degradation of poly(isophthaloylhydrazine‐1,2‐diyl)s

The condensation polymerization of isophthalodihydrazide and diphenyl isophthalate affords poly(isophthaloylhydrazine‐1,2‐diyl). High‐molecular‐weight poly(5‐tert‐butylisophthaloylhydrazine‐1,2‐diyl) is prepared by the polycondensation of 5‐tert‐butylisophthalodihydrazide and bis(4‐nitrophenyl) 5‐tert‐butylisophthalate in NMP at 100 °C. T_d of the poly(diacylhydrazine) is observed above 300 °C. No T_g is observed below T_d. The high‐molecular‐weight poly(diacylhydrazine) exhibits a film‐forming ability. The poly(diacylhydrazine) decomposes on treatment with an oxidant such as sodium hypochlorite solution to obtain the corresponding carboxylic acid and nitrogen. However, poly(diacylhydrazine) was stable to oxygen and hydrogen peroxide even in the presence of transition metal ions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6255–6262, 2008     

Thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) modified with divinyl benzene and vinyltrimethoxysilane

The effect of butyl acrylate (BA), divinyl benzene (DVB) and vinyltrimethoxysilane (TMVS) on the thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) was investigated. Glass transition temperature (T_g), melting temperature (T_m) and specific heat capacity of the copolymers were investigated using Differential Scanning Calorimetry. Thermal stability of the copolymers which is associated with the degradation temperature (T_d) was studied by Thermogravimetric Analysis. Polyacrylates with T_g ranges between -19°Cand 19°C were obtained. With the incorporation of >7 wt% of DVB, the T_g of the copolymer increases from about ?17°C to ?10°C even though they have not undergone UV irradiation. Gel content results prove that crosslinking has occurred in the copolymers. With increasing amount of TMVS from 0 wt% to 7 wt%, the T_m of the copolymers prepared at acidic pH is about 40-60°C higher than that at the alkaline pH. However, the addition of TMVS gives no significant effect to the T_g and T_d of the copolymer films. The thermal stability of the copolymer has improved with increasing amount of BA and DVB, with DVB being more effective. The highest T_d of 425°C with 8% of DVB has been obtained. Consequently, a polyacrylate copolymer with a T_g of about ?13°C, a T_m of 170 °C and a T_d of about 424°C has been successfully synthesized. Hence, the soft polyacrylate with its relatively high T_m and T_d could serve as a superb material especially to be applied in the areas that require high melting temperature and good thermal stability.     

Preparation and Thermal Properties of Polycarbonates/esters Catalyzed by Using Dinuclear Salph‐Al from Ring‐Opening Polymerization of Epoxide Monomers

A dinuclear Salph‐Al complex/bis(triphenylphosphine)iminium chloride catalyst system was synthesized and employed for cyclohexene oxide (CHO) and CO₂ copolymerization. The catalyst system had an excellent selectivity of 99 % for carbonate linkages and the resultant poly(cyclohexene carbonate) (PCHC) had a high glass transition temperature (T _g) of 123.8 °C and a thermal decomposition temperature (5 % weight loss; T _{d 5 %}) of 265 °C. Furthermore, this catalyst system was active in the polymerization of phthalic anhydride (PA) and epoxides. Poly(CHO‐alt ‐PA) was completely alternating, and had improved thermal properties (T _g=142.7 and T _{d 5 %}=295 °C) compared with PCHC. The T _g values of the polyesters could be adjusted by addition of PO to the CHO/PA reaction system. For the CHO/PO/PA terpolymerization, CHO and PO participated concurrently and proportionally in the chain growth and the obtained terpolyesters had tunable T _g values from 62.8 to 142.7 °C depending on the CHO/PO feed ratio.     

Preparation and properties of polybenzoxazine/poly(imide‐siloxane) alloys: In situ ring‐opening polymerization of benzoxazine in the presence of soluble poly(imide‐siloxane)s

Benzoxazine monomer (Ba) was blended with soluble poly(imide‐siloxane)s in various weight ratios. The soluble poly(imide‐siloxane)s with and without pendent phenolic groups were prepared from the reaction of 2,2′‐bis(3,4‐dicarboxylphenyl)hexafluoropropane dianhydride with α,ω‐bis(aminopropyl)dimethylsiloxane oligomer (PDMS; molecular weight = 5000) and 3,3′‐dihydroxybenzidine (with OH group) or 4,4′‐diaminodiphenyl ether (without OH group). The onset and maximum of the exotherm due to the ring‐opening polymerization for the pristine Ba appeared on differential scanning calorimetry curves around 200 and 240 °C, respectively. In the presence of poly(imide‐siloxane)s, the exothermic temperatures were lowered: the onset to 130–140 °C and the maximum to 210–220 °C. The exotherm due to the benzoxazine polymerization disappeared after curing at 240 °C for 1 h. Viscoelastic measurements of the cured blends containing poly(imide‐siloxane) with OH functionality showed two glass‐transition temperatures (T_g's), at a low temperature around ?55 °C and at a high temperature around 250–300 °C, displaying phase separation between PDMS and the combined phase consisting of polyimide and polybenzoxazine (PBa) components due to the formation of AB‐crosslinked polymer. For the blends containing poly(imide‐siloxane) without OH functionalities, however, in addition to the T_g due to PDMS, two T_g's were observed in high‐temperature ranges, 230–260 and 300–350 °C, indicating further phase separation between the polyimide and PBa components due to the formation of semi‐interpenetrating networks. In both cases, T_g increased with increasing poly(imide‐siloxane) content. Tensile measurements showed that the toughness of PBa was enhanced by the addition of poly(imide‐siloxane). Thermogravimetric analysis showed that the thermal stability of PBa also was enhanced by the addition of poly(imide‐siloxane). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2633–2641, 2001     

Synthesis of repeating sequence copolymers of lactic,glycolic, and caprolactic acids

Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with M_ns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (T_gs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent T_gs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited T_gs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Syntheses and properties of new aromatic polybenzoxazoles bearing ether and phenylethylidene or 1‐phenyl‐2,2,2‐trifluoroethylidene linkages

Two new bis(ether acyl chloride)s, 1,1‐bis[4‐(4‐chloroformylphenoxy)phenyl]‐1‐phenylethane and 1,1‐bis[4‐(4‐chloroformylphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane, were prepared from readily available reagents. Aromatic polybenzoxazoles with both ether and phenylethylidene or 1‐phenyl‐2,2,2‐trifluoroethylidene linkages between phenylene units were obtained by a conventional two‐step procedure including the low‐temperature solution polycondensation of the bis(ether acyl chloride)s with three bis(o‐aminophenol)s, yielding poly(o‐hydroxyamide) precursors, and subsequent thermal cyclodehydration. The intermediate poly(o‐hydroxyamide)s exhibited inherent viscosities of 0.39–0.98 dL/g. All of the poly(o‐hydroxyamide)s were amorphous and soluble in polar organic solvents such as N,N‐dimethylacetamide, and most of them could afford flexible and tough films via solvent casting. The poly(o‐hydroxyamide)s exhibited glass‐transition temperatures (T_g's) of 129–194 °C and could be thermally converted into corresponding polybenzoxazoles in the solid state at temperatures higher than 300 °C. All the polybenzoxazoles were amorphous and showed an enhanced T_g but a dramatically decreased solubility with to respect to their poly(o‐hydroxyamide) precursors. They exhibited T_g's of 216–236 °C through differential scanning calorimetry and were stable up to 500 °C in nitrogen or air, with 10% weight‐loss temperatures being recorded between 538 and 562 °C in nitrogen or air. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 914–921, 2003     

Preparation of poly(methyl acrylate)/phosphate/composites and its possible use as storage medium for radioactive isotopes

The distribution of ¹³⁷Cs, ¹⁵²Eu, ²³⁸U, and ⁸⁵Sr in a solid/aqueous system (poly(methyl acrylate)/phosphate/composite in contact with groundwater, was investigated using γ-Spectrometry and flourometry. The results were compared with earlier results with mineral phosphate in the solid phase. The effect of contact time, pH and the concentration of concurrent element were studied. The ability of the prepared polymer composites to keep the studied radioisotopes in the solid phase is much higher than mineral phosphate. The used polymer composites have been prepared consisting of natural phosphate powder and the monomer methyl acrylate using gamma irradiation. The yield of polymerization was followed up with respect to the irradiation dose using thermogravimetric analyzer (TGA). A thermomechanical analyzer (TMA) was used to locate the area of the glass transition temperatures (T _g ) using the mode with alternative variable force; the mode with constant force was used to determine the T _g of the pure polymer and the polymer composite prepared at the same irradiation dose. The T _g of the pure poly(methyl acrylate) is 13 ± 3 °C, and the T _g of poly(methyl acrylate)/phosphate/composites is 8 ± 3 °C. The T _g were also determined using the DSC technique, and similar values were found.     

Nanostructured latexes made by a sequential multistage emulsion polymerization

A series of linear and lightly crosslinked nanostructured latices was prepared by a sequential multistage semicontinuous emulsion polymerization process alternating styrene (S) and n‐butyl acrylate (BA) monomer feeds five times, that is ten stages, and vice versa, along with several control latices. Transmission electron micrographs of the RuO₄‐stained cross sections of nanostructured and copolymer latex particles and films showed that their particle morphologies were not very different from each other, but the nanostructured latex particles were transformed into a nanocomposite film containing both polystyrene (PS) and poly(n‐butyl acrylate) (PBA) nanodomains interconnected by their diffuse polymer mixtures (i.e. interlayers). The thermal mechanical behaviors of the nanostructured latex films showed broad but single T_gs slightly higher than those of their counterpart copolymer films. These single T_gs indicated that their major component phases were the diffuse interlayers and that they behaved like pseudopolymer alloys. The minimum film formation temperatures of nanostructured latices capped with PBA and PS, respectively, were 15 °C lower than and equal to those of their counterpart copolymer latices, but their T_gs were about 10 °C higher. Consequently, nanostructured latices enabled us to combine good film formation with high strengths for adhesives and coatings applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2826–2836, 2006     

Effect of supercritical CO2 on the copolymerization behavior of cyclohexene oxide/CO2 and copolymer properties with DMC/Salen‐Co(III) catalyst system

The copolymerization of cyclohexene oxide (CHO) and carbon dioxide (CO₂) was carried out under supercritical CO₂ (scCO₂) conditions to afford poly (cyclohexene carbonate) (PCHC) in high yield. The scCO₂ provided not only the C1 feedstock but also proved to be a very efficient solvent and processing aid for this copolymerization system. Double metal cyanide (DMC) and salen‐Co(III) catalysts were employed, demonstrating excellent CO₂/CHO copolymerization with high yield and high selectivity. Surprisingly, our use of scCO₂ was found to significantly enhance the copolymerization efficiency and the quality of the final polymer product. Thermally stable and high molecular weight (MW) copolymers were successfully obtained. Optimization led to excellent catalyst yield (656 wt/wt, polymer/catalyst) and selectivity (over 96% toward polycarbonate) that were significantly beyond what could be achieved in conventional solvents. Moreover, detailed thermal analyses demonstrated that the PCHC copolymer produced in scCO₂ exhibited higher glass transition temperatures (T_g ～ 114 °C) compared to polymer formed in dense phase CO₂ (T_g ～ 77 °C), and hence good thermal stability. Additionally, residual catalyst could be removed from the final polymer using scCO₂, pointing toward a green method that avoids the use of conventional volatile organic‐based solvents for both synthesis and work‐up. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2785–2793     

Order in amorphous di‐n‐alkyl itaconate polymers,copolymers, and blends

The presence of a main‐chain correlation distance (d_II) in the poly(di‐n‐alkyl itaconate)s was confirmed with small‐angle X‐ray scattering/wide‐angle X‐ray scattering measurements taken over the temperature range of 293–478 K. Data for a series of alkyl acrylate polymers were also obtained for comparison. The intensity of the itaconate d_II peak was significant and indicated a greater level of nanophase formation than in analogous systems. In the lower members of the series, nanophase formation appeared to be further enhanced in the temperature range above the glass‐transition temperature (T_g). This was ascribed to the rapidly increasing main‐chain mobility in this region. Macroscopically phase‐separated itaconate blends displayed the individual d_II nanospacings of each homopolymer component. Copolymers, on the other hand, showed more interesting behavior. Poly(methyl‐co‐di‐n‐butyl itaconate) followed an average behavior in which the d_II spacing and T_g changed progressively with the comonomer content. In contrast, the side‐chain pairing in poly(methyl‐co‐di‐n‐octyl itaconate) generated d_II spacings characteristic of separate methyl and octyl nanodomains. The observation of the dioctyl nanodomains, along with the dioctyl side‐chain lower T_g relaxation event, confirmed the concept of independent side‐chain‐domain relaxation in these polymers. The temperature behavior of the poly(methyl‐co‐di‐n‐octyl itaconate) small‐angle X‐ray scattering profiles and scattering correlation lengths indicated that the two nanodomains were not completely structurally independent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4000–4016, 2004     

High‐pressure rheology and viscoelastic scaling predictions of polymer melts containing liquid and supercritical carbon dioxide

High‐pressure rheological behavior of polymer melts containing dissolved carbon dioxide (CO₂) at concentrations up to 6 wt % were investigated using a high‐pressure extrusion slit die rheometer. In particular, the steady shear viscosity of poly(methyl methacrylate), polypropylene, low‐density polyethylene, and poly(vinylidene fluoride) with dissolved CO₂ were measured for shear rates ranging from 1 to 500 s^?1 and under pressure conditions up to 30 MPa. The viscosity of all samples revealed a reduction in the presence of CO₂ with its extent dependent on CO₂ concentration, pressure, and the polymer used. Two types of viscoelastic scaling models were developed to predict the effects of both CO₂ concentration and pressure on the viscosity of the polymer melts. The first approach utilized a set of equations analogous to the Williams–Landel–Ferry equation for melts between the glass‐transition temperature (T_g) and T_g + 100 °C, whereas the second approach used equations of the Arrhenius form for melts more than 100 °C above T_g. The combination of these traditional viscoelastic scaling models with predictions for T_g depression by a diluent (Chow model) were used to estimate the observed effects of dissolved CO₂ on polymer melt rheology. In this approach, the only parameters involved are physical properties of the pure polymer melt that are either available in the existing literature or can be measured under atmospheric conditions in the absence of CO₂. The ability of the proposed scaling models to accurately predict the viscosity of polymer melts with dissolved high‐pressure CO₂ were examined for each of the polymer systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3055–3066, 2001     

Solid‐state complexes of poly(L‐histidine) with metal chlorides from the first row of the d‐block

Solid‐state characterization of poly(L ‐histidine) was obtained via differential scanning calorimetry, thermogravimetric analysis, optical microscopy, and infrared spectroscopy. The glass transition temperature of poly(L ‐histidine) is 169°C. This thermal transition has not been reported previously. Poly(L ‐histidine)'s T_g increases when complexes are produced with the following divalent transition metal chlorides: cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate, and anhydrous zinc chloride. At 10 mol % salt, nickel chloride increases T_g by 69°C. The enhancement in poly(L ‐histidine)'s T_g correlates well with ligand field stabilization energies for pseudo‐octahedral dⁿ complexes (n = 7, 8, and 10) from the first row of the d‐block. However, d⁹ copper(II) complexes do not conform to this empirical correlation. Infrared spectroscopic evidence indicates that these metal chlorides form complexes with the imidazole ring in the histidine side group and the amide group in the main chain of the polymer. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 301–309, 1999     

Effects of POSS nanoparticles on glass transition temperatures of ultrathin poly(t‐butyl acrylate) films and bulk blends

As a model system, thin films of trisilanolphenyl‐POSS (TPP) and two different number average molar mass (5 and 23 kg mol^?1) poly(t‐butyl acrylate) (PtBA) were prepared as blends by Langmuir–Blodgett film deposition. Films were characterized by ellipsometry. For comparison, bulk blends are prepared by solution casting and the samples are characterized via differential scanning calorimetry. The increase in T_g as a function of TPP content for bulk high and low molar mass samples are in the order of ～10 °C. Whereas bulk T_g shows comparable increases for both molar masses (～10 °C), the increase in surface T_g for higher molar mass PtBA is greater than for low molar mass (～22 °C vs. ～10 °C). Nonetheless, the total enhancement of T_g is complete by the time 20 wt % TPP is added without further benefit at higher nanofiller loads. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 175–182     

Aromatic polybenzoxazoles containing ether–sulfone linkages

A series of poly(o‐hydroxy amide)s having both ether and sulfone linkages in the main chain were synthesized via the low‐temperature solution polycondensation of 4,4′‐[sulfonylbis(1,4‐phenylene)dioxy]dibenzoyl chloride and 4,4′‐[sulfonylbis(2,6‐dimethyl‐1,4‐phenylene)dioxy]dibenzoyl chloride with three bis(o‐aminophenol)s including 4,4′‐diamino‐3,3′‐dihydroxybiphenyl, 3,3′‐diamino‐4,4′‐dihydroxybiphenyl, and 2,2‐bis(3‐diamino‐4‐hydroxyphenyl)hexafluoropropane. Subsequent thermal cyclodehydration of the poly(o‐hydroxy amide)s afforded polyethersulfone benzoxazoles. Most of the poly(o‐hydroxy amide)s were soluble in polar organic solvents such as N‐methyl‐2‐pyrrolidone; however, the polybenzoxazoles without the hexafluoroisopropylidene group were organic‐insoluble. The polybenzoxazoles exhibited glass‐transition temperatures (T_g) in the range of 219–282 °C by DSC and softening temperatures (T_s) of 242–320 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 450 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 474–593 °C in air and 478–643 °C in nitrogen. The methyl‐substituted polybenzoxazoles had higher T_g's but lower T_s's and initial decomposition temperatures compared with the corresponding unsubstituted polybenzoxazoles. For a comparative purpose, the synthesis and characterization of a series of sulfonyl polybenzoxazoles without the ether group that derived from 4,4′‐sulfonyldibenzoyl chloride and bis(o‐aminophenol)s were also reported. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2262–2270, 2001     

Crystalline Stereocomplexed Polycarbonates: Hydrogen‐Bond‐Driven Interlocked Orderly Assembly of the Opposite Enantiomers

Four novel crystalline stereocomplexed polymers are formed by mixing isotactic (R)‐ and (S)‐polycarbonates in 1:1 mass ratio. They show the enhanced thermal stability and new crystalline behavior, significantly distinct from the component enantiomer. Two stereocomplexed CO₂‐based polycarbonates from meso‐3,4‐epoxytetrahydrofuran and 4,4‐dimethyl‐3,5,8‐trioxabicyclo[5.1.0]octane have high melting temperatures of up to 300 °C, about 30 °C higher than the individual enantiomers. Isotactic (R)‐ or (S)‐poly(cyclopentene carbonate) and poly(cis‐2,3‐butene carbonate) are typical amorphous polymeric materials, however, upon mixing both enantiomers together, a strong interlocked interaction between polymer chains of opposite configuration occurs, affording the crystalline stereocomplexes with melting temperatures of about 200 °C and 180 °C, respectively. A DFT study suggests that the driving force forming the stereocomplex is the hydrogen‐bonding between carbonate units of the opposite enantiomers.