Synthesis and properties of novel organosoluble copoly(arylene ether nitriles) containing thioether moiety

In this work, a series of novel organosoluble copoly(arylene ether nitriles) containing thioether moiety (PENS) were synthesized via nucleophilic aromatic substitution polymerization of 2,6-dichlorobenzonitrile with bisphenol A and sodium sulfide nonahydrate, using N-Methyl-2-Pyrrolidone as solvent in the presence of anhydrous potassium carbonate. The chemical structures of PENS were characterized by FTIR and ¹H NMR. The derived copolymers showed high glass transition temperatures in the range of 167–178 °C and excellent thermal stability with the 5% weight loss temperatures ranging from 465 °C to 503 °C. Meanwhile, all of the PENS were amorphous and can be readily cast into transparent films with a tensile strength exceeding 77 MPa and a breaking elongation over 4.8%.In addition, the dielectric constant of all the PENS copolymers showed weak frequency dependence, the dielectric loss showed slight decrease with increasing frequency over the range of 100 Hz to 200 kHz. Therefore, this kind of organosoluble copoly(arylene ether nitriles) containing thioether moiety could be a good candidate as matrix resins for high-performance polymeric materials.     

Novel poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s from bis‐(4‐aminobenzyl) hydrazide and aromatic diacid chlorides: Synthesis and characterization

A new aromatic diamine, viz., bis‐(4‐aminobenzyl) hydrazide (BABH), which contains preformed hydrazide and methylene linkage, was synthesized starting from α‐tolunitrile. The BABH and intermediates involved in its synthesis were characterized by spectroscopic methods. Novel poly(amide‐hydrazide)s were synthesized by low temperature solution polycondensation of BABH with isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC). Furthermore, two series of copoly(amide‐hydrazide)s, based on different mol % of BABH and bis‐(4‐aminophenyl) ether (ODA) with IPC/TPC were also synthesized. Poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s were characterized by inherent viscosity [η_inh], FTIR, solubility, X‐ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polycondensation proceeded smoothly and afforded the polymers with inherent viscosities in the range of 0.18–0.93 dL/g in (NMP + 4% LiCl) at 30°C ± 0.1°C. These polymers dissolved in DMAc, NMP or DMSO containing LiCl. The solubility of copolymers was considerably improved in line with less crystalline nature due to random placement of constituent monomers during the copolymerization. XRD data indicated that poly(amide‐hydrazide)s from BABH alone and IPC/TPC had higher crystallinity than the corresponding copoly(amide‐hydrazide)s derived from a mixture of BABH and bis‐(4‐aminophenyl) ether (ODA). Polymers showed initial weight loss around 160°C which is attributed to the cyclodehydration leading to the formation of corresponding poly(amide‐oxadiazole)s. Copolyamide‐hydrazides showed T_max between 400 and 540°C which is essentially the decomposition of poly(amide‐oxadiazole)s. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups for proton‐exchange membrane materials

A series of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups were synthesized via a nucleophilic aromatic substitution reaction from phenolphthalein, hydroquinone sulfonic acid potassium salt, and 2,6‐difluorobenzonitrile in N‐methyl pyrrolidone (NMP) with K₂CO₃ as a catalyst. The synthesized copolymers had good solubility in common polar organic solvents and could be easily processed into membranes from solutions of dimethyl sulfoxide, NMP, N,N′‐dimethyl acetylamide, and dimethylformamide. Typical membranes in acid form were gained, and the chemical structures of these membranes were characterized by Fourier transform infrared analysis. The thermal properties, fluorescence properties, water uptake, ion‐exchange capacity, and proton conductivities of these copolymers were also investigated. The results indicate that they had high glass‐transition temperatures in the range 151–187°C and good thermal stability, with the 10 wt% loss temperatures ranging from 330 to 351°C under nitrogen. The copolymers showed characteristic unimodal ultraviolet–visible (UV–vis) absorption and fluorescence emission, and the UV–vis absorption, fluorescence excitation, and emission peaks of the copolymers were obvious. Moreover, the copolymer membranes showed good water uptake and proton conductivities at room temperature and 55% relative humidity because of the introduction of both sulfonic acid groups and carboxyl groups into the copolymers, whose contents were in ranges 18.45–67.86 and 3.4 × 10^?4 to 3.0 × 10^?3 s/cm, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40213.     

Semi-aromatic copoly(ether ether amide): Synthesis and properties

A series of semi-aromatic copoly(ether ether amide)s (hydroquinone (HQ) (0%)-HQ (100%)) were synthesized by 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BHPPE), 1,4-benzenediol (HQ) and 1,6-N,N′-bis(4-fuorobenzamide) hexane (BFBH) in this work. The inherent viscosities of copoly(ether ether amide)s were in the range of 0.487–0.769 dl g⁻¹. Following with increase of the content of HQ, the resultant polymers were converted from amorphous to crystalline. The copolymers were found to have high glass transition temperatures (T_g) of 141.4–155.6°C and weight-loss temperature (T_5%) of 423.3–434.3°C. They can be hot-pressed into films with tensile strength of 63.3–87.6 MPa, and storage modulus over 0.8 GPa at about 150°C, indicating good thermal and mechanical property of the obtained copolymers. The results of rheological property showed that the copolymers had good melt flowability and thermal stability. Additionally, the introduction of HQ improved the corrosion resistance of copolymers, the obtained polymers HQ (60%), HQ (80%) and HQ (100%) exhibited better corrosion resistance than that of HQ (0%). Especially, HQ (80%) and HQ (100%) were insoluble in organic polar solvents such as DMSO, DMF because of their crystalline nature, indicating that they had potential to be applied to the corrosion-resistant materials.     

Processable high Tg high strength fluorinated new poly(arylene ether)s containing imido aryl group

A series of poly(arylene ether)s ( 7a–7f ) were successfully synthesized by aromatic nucleophilic substitution reactions of imidoaryl biphenol (5), 4,9‐bis‐(4‐hydroxy‐phenyl)‐2‐phenyl‐benzo[f]isoindole‐1,3‐dione with six different trifluoromethyl substituted bisfluoro monomers ( 6a–6f ). The weight‐average molar masses of the polymers were up to 280 kD as measured by GPC. These poly(arylene ether)s exhibited glass transition temperatures up to 361°C in DSC. These polymers showed very high thermal stability up to 558°C for 10% weight loss under synthetic air in TGA. Except 7d–7f, remaining polymers 7a–7c were soluble in a wide range of organic solvents. Transparent thin films of these polymers cast from DCM or NMP exhibited tensile strengths up to 75 MPa and elongation at break up to 41% depending on their exact repeating unit structures. These poly(arylene ether)s showed cut‐off wavelength in between 400 and 450 nm except 7d and water absorption were in the range of 0.4 to 0.6%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of organic soluble semicrystalline poly(aryl ether ketone)s copolymers containing phthalazinone moieties

A series of poly(aryl ether ketone)s (PAEK) copolymers containing phthalazinone moieties were synthesized by modest polycondensation reaction from 4‐(4‐hydroxyl‐phenyl)‐(2H)‐phthalazin‐1‐one (DHPZ), hydroquinone (HQ), and 1,4‐bis(4‐fluorobenzoyl)benzene (BFBB). The T_g values of these copolymers ranged from 168 to 235°C, and the crystalline melting temperatures varied from 285 to 352°C. By introducing phthalazinone moieties into the main chain, the solubility of these copolymers was improved in some common polar organic solvents, such as chloroform (CHCl₃), N‐methyl‐2‐pyrrolidinone (NMP), nitrobenzene (NB) and so on. The values of 5% weight loss temperatures were all higher than 510°C in nitrogen. The crystal structures of these copolymers were determined by wide‐angle X‐ray diffraction (WAXD), which revealed that they were semicrystalline in nature, and the crystal structure of these copolymers was orthorhombic, equal to poly(ether ether ketone ketone)s. As phthalazinone content in the backbone varied from 0 to 40 mol % (mole percent), the cell parameters of these copolymers including the a, b, and c axes lengths ranged from 7.76 to 7.99 Å, 6.00 to 6.14 Å, and 10.10 to 10.19 Å, respectively. The degree of crystallinity (via differential scanning calorimetry) decreased from 37.70% to 16.14% simultaneously. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1744–1753, 2007     

Synthesis and characterization of soluble copoly(arylene ether sulfone phenyl-s-triazine)s containing phthalazinone moieties in the main chain

A series of new poly(arylene ether sulfone phenyl-s-triazine) copolymers containing phthalazinone moieties in the main chain (PPESPs) were prepared by a direct solution polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HPPZ) with 2-phenyl-4,6-bi(4-fluorophenyl)-1,3,5-triazine (BFPT) and 4,4′-dichlorodiphenyl sulfone (DCS). Model reactions monitored by HPLC indicated that BFPT had slightly higher reactivity than DCS in nucleophilic displacement reactions. The obtained random copolymers were characterized by FTIR, NMR, elemental analysis and GPC. The presence of sulfone and phthalazinone in the polymer chain results in an improvement in the solubility of poly(arylene ether phenyl-s-triazine)s in common organic solvents, such as N-methylpyrrolidone, N,N-dimethyl acetamide (DMAc), chloroform, sulfolane and pyridine. Thermal analysis reveal that the copolymers exhibit high glass transition temperatures (T_gs) ranging from 271–300 °C, and excellent thermal stability associated with decomposition temperatures for 5% mass-loss exceeding 503 °C. All copolymers are amorphous except PPESP28 as evidenced by WAXD. Their T_gs and solubility increase with an increase in sulfone content in the polymer backbone, while the crystallinity and overall thermal stability appear to decrease. This kind of phthalazinone-based copoly(arylene ether sulfone phenyl-s-triazine)s may be considered a good candidate for using as high-performance structural materials.     

Synthesis and properties of poly(arylene ether)s based on 3‐pentadecyl 4,4'‐biphenol

A new biphenol, 3‐pentadecyl 4,4′‐biphenol, was synthesized starting from 3‐pentadecylphenol and was polycondensed with 4,4′‐difluorobenzophenone, 1,3‐bis(4‐fluorobenzoyl)benzene and bis(4‐fluorophenyl)sulfone to obtain poly(arylene ether)s with biphenylene linkages in the backbone and pendent pentadecyl chains. Inherent viscosities and number‐average molecular weights (M_n) of the poly(arylene ether)s were in the range 0.50 ? 0.81 dL g^?1 and 2.2 × 10⁴ ? 8.3 × 10⁴, respectively. Detailed NMR spectroscopic studies of the poly(arylene ether)s indicated the presence of constitutional isomerism which existed because of the non‐symmetrical structure of 3‐pentadecyl 4,4′‐biphenol. The poly(arylene ether)s readily dissolved in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran and could be cast into tough, transparent and flexible films from their chloroform solutions. The poly(arylene ether)s exhibited T_g values in the range 35–60 °C which are lower than that of reference poly(arylene ether)s without pentadecyl chains. The 10% decomposition temperatures (T₁₀) of the poly(arylene ether)s were in the range 410–455 °C indicating their good thermal stability. A gas permeation study of poly(ether sulfone) containing pendent pentadecyl chains revealed a moderate increase in permeability for helium, hydrogen and oxygen. However, there was a large increase in permeability for carbon dioxide which could be attributed to the internal plasticization effect of pendent pentadecyl chains. © 2016 Society of Chemical Industry     

Synthesis and Characterization of Sulfonated Cardo Poly(Arylene Ether Sulfone)s for Fuel Cell Proton Exchange Membrane Application

Sulfonated cardo poly(arylene ether sulfone)s ( SPPA ‐ PES ) with various degrees of sulfonation (DS) were prepared by post‐sulfonation of synthesized phenolphthalein anilide ( PPA ; N‐phenyl‐3,3′‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrolidone) poly(arylene ether sulfone)s ( PPA ‐ PES ) by using concentrated sulfuric acid. PPA ‐ PES copolymers were synthesized by direct polycondensation of PPA with bis‐(4‐fluorophenyl)‐sulfone and 4,4′‐sulfonyldiphenol. The DS was varied with different mole ratios of PPA (24, 30, 40, 50 mol.%) in the polymer. The structure of the resulting SPPA ‐ PES copolymers and the different contents of the sulfonated unit were studied by Fourier transform infrared (FT‐IR) spectroscopy, ¹H NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity of SPPA ‐ PES were evaluated according to the increase of DS. The water uptake (WU) of the resulting SPPA ‐ PES membranes was in the range of 20–72%, compared with 28% for Nafion 211®. The SPPA ‐ PES membranes showed proton conductivities of 23–82 mS cm^–1, compared with 194 mS cm^–1 for Nafion 211®, under 100% relative humidity (RH) at 80 °C.     

Synthesis and properties of copolymers of poly(ether ether sulfone)/semiaromatic polyamides (PEES/PA)

Poly(ether ether sulfone) (PEES) containing semi‐aromatic polyamides with methylene units and ether linkage were synthesized through the copolymerization of m‐dihydroxybenzene, 4,4‐dichlorodiphenylsulfone (DCDPS) and 1,6‐N, N′‐bis(4‐fluorobenzamide) hexane (BFBH) by the method of nucleophilic polymerization. The inherent viscosities of the resultant different proportion of copolymers were in the range of 0.39–0.78 dL/g. These copolymers were found to have excellent thermal properties with glass transition temperatures (T_g) of 121–177°C, and initial degradation temperatures (T_d) of 417.5–432.5°C. These copolymers showed good mechanical properties with tensile strengths of 45–83 MPa, storage modulus of 1.8–2.6 GPa. The complex viscosities of pure Poly(ether ether sulfone) (PEES) was in the range of 176,000–309.8 Pas from 0.01 to 100 Hz, the complex viscosities of the copolymers decreased significantly with the increase of semi‐aromatic amide content, the copolymers of 20% decreased from 4371 to 142.4 Pas (from 0.01 to 100 Hz), and the copolymers of 70% dropped from 634.6 Pas to 55.97 Pas (from 0.01 Hz to 100 Hz). All copolymers exhibited non‐Newtonian and shear‐thinning behavior. These results suggested the resultant copolymers possess better melt flowability that is beneficial for the materials’ melt processing. POLYM. ENG. SCI., 56:44–50, 2016. © 2015 Society of Plastics Engineers     

Copolymers of poly(arylene sulfide sulfone)/poly(ether sulfone): Synthesis,structure, and rheology properties

In order to overcome the poor flowability of poly(arylene sulfide sulfone) (PASS), we introduced ether bonds into the polymer main chain. A series poly(arylene ether sulfide sulfone) copolymers (PAESS) containing different proportion of ether bonds were synthesized with 4,4′‐dichlorodiphenyl sulfone (DCDPS), sodium sulfide (Na₂S·xH₂O), and 4,4′‐dihydroxydiphenyl ether (DHDPE). The copolymers were characterized by Fourier transform infrared (FTIR), ¹H‐nuclear magnetic resonance (NMR), differential scanning calorimetry, dynamic mechanical analysis (DMA), and rheometer. The results of FTIR and ¹H‐NMR indicate the copolymers are synthesized successfully. PAESS were found to have excellent thermal properties with glass transition temperature (T_g) of 175.7–219.1 °C and 5% weight lost temperature were all above 420 °C. The tensile and DMA test indicates that these resultant copolymers have good mechanical properties with tensile strength of 60 MPa and storage modulus of 1.5 GPa. From the results of rheology properties testing, we found that the melt stability and melt flowability of PASS were improved distinctly from 25,470 Pa s down to 355 Pa s with the incorporation of ether bonds. That will be quite beneficial to the processing of PASS, especially for the thermoforming of precision products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46534.     

Synthesis and characterization of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s for optical waveguides

A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm^?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry     

Synthesis of aromatic poly(urea‐imide) with heterocyclic side‐chain structure

The poly(urea‐imide) copolymers with inherent viscosity of 0.81–1.08 dL/g were synthesized by reacting aryl ether diamine or its polyurea prepolymer with various diisocyanate‐terminated polyimide prepolymers. The aryl ether diamine was obtained by first nucleophilic substitution of phenolphthalein with p‐chloronitrobenzene in the presence of anhydrous potassium carbonate to form a dinitro aryl ether, and then further hydrogenated to diamine. The polyimide prepolymers were prepared by using 4,4′‐diphenylmethane diisocyanate to react with pyromellitic dianhydride, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride, or 3,3′,4,4′‐sulfonyldiphthalic anhydride by using the direct one‐pot method to improve their solubility, but without sacrificing thermal property. These copolymers are amorphous and readily soluble in a wide range of organic solvents such as N‐methyl‐2‐pyrrolidone, dimethylimidazole, N,N‐dimethylacetamide, dimethyl sulfoxide, N,N‐dimethylformamide, m‐cresol, and sulfolane. All the poly(urea‐imides) have glass transition temperatures in the range of 205–240°C and show a 10 wt % loss at 326–352°C in nitrogen and 324–350°C in air. The tensile strength, elongation at break, and initial modulus of these copolymer films range from 42 to 79 MPa, 5 to 16%, and 1.23 to 2.02 GPa, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1719–1730, 1999     

New soluble cyano‐containing poly(arylene ether) copolymers bearing pendant xanthene groups

Homopolymers and copolymers of poly(arylene ether nitrile) (PAEN)‐bearing pendant xanthene groups were prepared by the nucleophilic substitution reaction of 2,6‐difluorobenzonitrile with 9,9‐bis(4‐hydroxyphenyl)xanthene (BHPX) and with various molar proportions of BHPX to hydroquinone (100/0 to 40/60) with N‐methyl‐2‐pyrrolidone (NMP) as a solvent in the presence of anhydrous potassium carbonate. These polymers had inherent viscosities between 0.61 and 1.08 dL/g, and their weight‐average molecular weights and number‐average molecular weights were in the ranges 34,200–40,800 and 17,800–20,200, respectively. All of the PAENs were amorphous and were soluble in dipolar aprotic solvents, including NMP, N,N‐dimethylformamide, and N,N‐dimethylacetamide and even in tetrahydrofuran and chloroform at room temperature. The resulting polymers showed glass‐transition temperatures (T_g's) between 220 and 257°C, and the T_g values of the copolymers were found to increase with increasing BHPX unit content in the polymer. Thermogravimetric studies showed that all of the polymers were stable up to 422°C with 10% weight loss temperatures ranging from 467 to 483°C and char yields of 54–64% at 700°C in nitrogen. All of the new PAENs could be cast into transparent, strong, and flexible films with tensile strengths of 106–123 MPa, elongations at break of 13–17%, and tensile moduli of 3.2–3.7 GPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of copolymers of poly(ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

Poly(aryl ether ketone)s (PAEKs) are a class of high‐performance engineering thermoplastics known for their excellent combination of chemical, physical and mechanical properties, and the synthesis of semicrystalline PAEKs with increased glass transition temperatures (T_g) is of much interest. In the work reported, a series of novel copolymers of poly(ether ketone ketone) (PEKK) and poly(ether amide ether amide ether ketone ketone) were synthesized by electrophilic solution polycondensation of terephthaloyl chloride with a mixture of diphenyl ether and N,N′‐bis(4‐phenoxybenzoyl)‐4,4′‐diaminodiphenyl ether (BPBDAE) under mild conditions. The copolymers obtained were characterized using various physicochemical techniques. The copolymers with 10–35 mol% BPBDAE are semicrystalline and have markedly increased T_g over commercially available poly(ether ether ketone) and PEKK due to the incorporation of amide linkages in the main chain. The copolymers with 30–35 mol% BPBDAE not only have high T_g of 178–186 °C, but also moderate melting temperatures of 335–339 °C, having good potential for melt processing. The copolymers with 30–35 mol% BPBDAE have tensile strengths of 102.4–103.8 MPa, Young's moduli of 2.33–2.45 GPa and elongations at break of 11.7–13.2%, and exhibit high thermal stability and good resistance to organic solvents. Copyright © 2010 Society of Chemical Industry     

Crystallinity of poly(arylene ether nitrile) copolymers containing hydroquinone and bisphenol A segments

The hydroquinone (HQ) and bisphenol A (BPA) type poly(arylene ether nitrile) (PEN) (HQ/BPA‐PEN) were synthesized through nucleophilic aromatic substitution polymerization from HQ, BPA, and 2,6‐dichlorobenzonitrile (DCBN). The prepared copolymers were characterized by intrinsic viscosity, Fourier transform infrared (FTIR), and dynamic rheological analysis. The properties of resultant copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mechanical testing. The results showed that the PEN copolymers exhibited crystallization performance with excellent thermal and mechanical properties. HQ/BPA‐PEN10 was made into films by solution‐casting process and then were treated at different temperatures (200, 260, 280, 300, 310, and 320 °C) for different times (1, 2, 3, 4, and 5 h) to investigate the crystallinity. Results showed that when isothermal treatment temperature is 310 °C and isothermal treating time is 4 h, HQ/BPA‐PEN10 showed best properties. At this condition, the melting enthalpy, crystallinity, tensile strength, and elongation at break of the sample is 17.7 J/g, 14.11%, 132.9 MPa, and 6.1%, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46412.     

Synthesis and study of new polyamides with side oxadiazole rings

A series of six new aromatic polyamides with side oxadiazole rings has been synthesized by polycondensation reaction of aromatic diamines containing pendent substituted oxadiazole groups with a silicon‐containing diacid chloride [namely, bis(p‐chlorocarbonyl‐phenylene)diphenylsilane] or with a fluorine‐containing diacid chloride [namely, hexafluoroisopropylidene‐bis(p‐benzoyl chloride)]. All polymers were easily soluble in amidic solvents, such as N‐methylpyrrolidinone and dimethylformamide, and gave thin transparent films by casting such solutions. Very thin coatings were deposited onto silicon wafers and exhibited smooth, pinhole‐free surfaces in atomic force microscopy investigations. The polymers showed high thermal stability, with decomposition temperature >400°C. Some of them did exhibit a glass transition, in the range 152–276°C, with a reasonable interval between glass transition and decomposition. Four of these polymers showed blue photoluminescence, in the range 460–480 nm, which makes them promising candidates for future use as high‐performance materials in the construction of light‐emitting devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 714–721, 2003     

Synthesis and characterization of poly(ether sulfone)‐graft‐polydimethylsiloxane copolymers

Novel poly(arylene ether sulfone) (PAES) polymers containing polydimethylsiloxane (PDMS) side chains were synthesized and characterized with NMR and Fourier transform infrared spectroscopy. The thermal properties of the copolymers were evaluated with differential scanning calorimetry and thermogravimetric analysis. The polymers showed perfect thermal stability, as the decomposition temperatures were all above 380°C, and exhibited glass‐transition temperatures in the range 130–188°C. Furthermore, the surface properties of the copolymers were evaluated by X‐ray photoelectron spectroscopy and contact angle analysis. The results show that the hydrophobic abilities of the graft copolymer surfaces were improved significantly compared to PAES through the introduction of the PDMS chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride,m‐aminobenzoic acid,and 4,4″‐oxydianiline and various aromatic diamines

A series of new, organosoluble, and light‐colored poly(amide imide imide)s were synthesized from tetraimide dicarboxylic acid ( I ) and various aromatic diamines by direct polycondensation with triphenyl phosphite and pyridine as condensing agents. I was prepared by the azeotropic condensation of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, m‐aminobenzoic acid, and 4,4′‐oxydianiline at a 2/2/1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP)/toluene. The thin films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 400 nm (365–394 nm) and color coordinate b* values between 13.10 and 36.07; these polymers were lighter in color than the analogous poly(amide imide)s and isomeric polymers. All of the polymers were readily soluble in a variety of organic solvents, including NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even less polar dioxane and tetrahydrofuran. The cast films exhibited tensile strengths of 90–104 MPa, elongations at break of 7–22%, and initial moduli of 1.9–2.4 GPa. The glass‐transition temperatures of the polymers were recorded at 274–319°C. They had 10% weight losses at temperatures beyond 520°C and left more than a 50% residue even at 800°C in nitrogen. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 669–679, 2003     

Synthesis and characterization of poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain

Soluble and heat‐resistant polymers have great potential for use as processable, high‐temperature polymeric materials. In this study, four types of new poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain were prepared through direct solution polycondensation of 2,4‐bis(4‐fluorophenyl)‐6‐phenyl‐s‐triazine with each of methyl‐, phenyl‐ and chloro‐substituted phthalazinones. A key feature of these polymers is the incorporation of phthalazinone and side groups into the poly(arylene ether s‐triazine) backbone to endow them with good solubility while maintaining other attractive properties. The polymers were obtained in high yields, and had inherent viscosities ranging from 0.38 to 0.55 dL g^?1. Their structure was characterized using Fourier transform infrared and NMR spectra and elemental analysis. The polymers were almost amorphous, and soluble in N‐methyl‐2‐pyrrolidone, pyridine, N,N‐dimethylacetamide, hot N,N‐dimethylformamide and sulfolane. Tough and nearly transparent films obtained by direct solution casting exhibited good mechanical properties. The resulting polymers displayed glass transition temperatures ranging from 255 to 265 °C and thermal decomposition temperatures for 10% mass loss ranging from 476 to 599 °C, according to differential scanning calorimetry and thermogravimetric analysis, respectively. The reactivity of substituted phthalazinones in nucleophilic displacement reactions and the effect of the side groups on the physical properties of the polymers were also investigated. The results obtained revealed that such s‐triazine‐containing polymers possessed good solubility while maintaining acceptable thermal stability and high mechanical strength with the incorporation of alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties into their backbones, which makes them an attractive series of high‐performance structural materials. Copyright © 2010 Society of Chemical Industry