Sorption of sulfur mustard and its oxygen analog in black and nonblack-filled butyl rubber membranes

Butyl rubber (IIR) membranes containing a 0–50% volume fraction of carbon black (GPF N660) or nonblack fillers (talc/precipitated CaCO₃/fullers earth) were prepared by solution casting and evaluated for permeation resistance to the vesicant, bis(2-chloroethyl)sulfide, or sulfur mustard (SM) and its oxygen analog (OA), bis(2-chloroethyl)ether. The diffusivity of the chemicals was determined from the breakthrough time (BTT), obtained using the spot disc test and a gravimetric method. The permeation parameters, calculated from the sorption data, were used to determine an optimum filler content for maximum protection against SM. To investigate the effect of carbon loading on the permeation properties of IIR, the permeation of SM and OA in carbon-loaded black membranes was compared with nonblack membranes and interpreted in terms of the dispersion of carbon in the membranes. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 503–511, 1998     

Development of butyl rubber nanocomposites in presence and absence of compatibiliser

Abstract

Chlorobutyl rubber nanocomposites containing organically modified nanoclay (CI-C) were prepared by solution mixing. The nanoclay used in this study was Cloisite 20A. The obtained nanocomposites were incorporated in butyl rubber (IIR) with sulphur as a curing agent. Morphology, curing characteristics, mechanical and gas barrier properties of the nanocomposites were analysed. The morphological studies proved the partial exfoliation along with agglomeration of nanoclay platelets in chlorobutyl rubber, and further incorporation of CI-C in IIR matrix enhance the exfoliation of the nanoclay platelets. Curing study demonstrated shorter scorch time, cure time and increase in maximum torque for the nanoclay loaded IIR compound in the presence of chlorobutyl rubber as a compatibiliser compared to pure and IIR-nanoclay compound without compatibilisers. Dynamic mechanical thermal analysis results showed tremendous improvement in storage modulus and decrease in tan?δ value for the one containing a compatibiliser. This particular compound exhibited substantial improvement in mechanical and gas barrier properties.     

Segmented and nonsegmented polyurethanes: Polyaddition products of 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether and 1,6‐hexanediisocyanate

New linear polyurethanes (PUs) derived from 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether (4‐HEDE) and 1,6‐hexanediisocyanate (HDI) were synthesized by either melt or solution polymerization. We found that the properties of PUs obtained are dependent mainly on the kind of organic solvent, contribution of the catalyst, and concentration of the monomers used. Good results are obtained using aprotic solvent‐N,N‐dimethylformamide, ∼ 30 wt % concentration of monomers, dibutyltin dilaurate as a catalyst, and conducting the process at 90–100°C for 4 h. This article presents basic properties of the series of PUs obtained. Thermal properties of the polymers were investigated by means of thermal gravimetric analysis and differential scanning calorimetry. Molecular weight distribution was determined by gel permeation chromatography. Shore hardness and tensile test results are also presented. The structure of the resulting products was confirmed by elemental analysis, Fourier transform infrared spectroscopy and X‐ray diffractometry. We also present the properties of copolyurethanes type 4‐HEDE/HDI/1,6‐hexanediol or 4‐HEDE/HDI/polytetramethylene oxide containing variable amounts of 1,6‐hexanediol or polytetramethylene oxide (M _n ∼ 650) synthesized in the optimal conditions established earlier for PU 4‐HEDE/HDI. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 83–91, 1999     

Sorption and diffusion of n-alkanes into bromobutyl rubber membranes

Sorption and diffusion of n-alkanes into bromobutyl rubber membranes were investigated in the temperature interval 25–60°C by a sorption gravimetric method. The Fickian diffusion equation was used to calculate the diffusion coefficients, which were dependent on the size of the alkanes, their interactions with the chain segments of the polymer and temperature. The diffusion coefficients varied from 0.34×10^?7 cm²/s (n-hexadecane) to 9.94×10^?7 cm²/s (n-hexane). The activation energy for diffusion varied from 14kJ/mol (n-hexane) heptane to 2.0kJ/mol for n-hexadecane. The sorption/swelling results are discussed in terms of first and second order kinetic equations. The molar mass between chain-entanglement-crosslinks was estimated from swelling data. The experimental and calculated results showed a systematic dependence on the increasing size of the alkanes. None of the solvents showed any degradative effects on the polymer.     

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

The preparation of new compounds, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene, is described. 1,1‐Bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α‐bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α‐bis(oxazolyl) polystyrene follows first‐order rate kinetics with respect to monomer consumption. α,ω‐Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post‐ATRP chain‐end‐functionalization reaction which involves the direct addition of 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene to the ω‐terminus of the α‐bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α‐Bis(carboxyl) and α,ω‐tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain‐end‐functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using ¹H NMR and ¹³C NMR spectrometry and Fourier transform infrared spectroscopy, size‐exclusion and thin‐layer chromatography and non‐aqueous titration measurements. © 2014 Society of Chemical Industry     

Synthesis and properties of novel phosphorus‐containing poly(ether ether ketone ketone)s

A novel monomer, bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide, was synthesized through the reaction of bis(4‐chloroformylphenyl) phenyl phosphine oxide with fluorobenzene. Three poly(ether ether ketone ketone)s derived from bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide and different aromatic bisphenols were prepared by aromatic nucleophilic substitution reactions. The resulting polymers had inherent viscosities in the range of 0.55–0.73 dL/g. The structures of the poly(ether ether ketone ketone)s were characterized with Fourier transform infrared and ¹H‐NMR. Thermal analysis indicated that the glass‐transition temperatures of the poly(ether ether ketone ketone)s were higher than 200°C, and the 5% weight loss temperatures in nitrogen were higher than 463°C. All the polymers showed excellent solubility in polar solvents such as N‐methyl‐2‐pyrrolidone, dimethylformamide, and dimethylacetamide and could also be dissolved in chlorinated methane. The polymers afforded transparent and flexible films by solvent casting. Organic phosphorous moieties also imparted good flame‐retardancy to the polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of Cyclic Deformations on the Dynamic‐Mechanical Properties of Silica‐Filled Butyl Rubber

The effect of the chemical modification of the silica surface by the silane coupling agent (Si69) on both the real and the imaginary parts of the shear compliance (J′, J″) on silica‐filled butyl rubber vulcanizates was investigated in a wide temperature and frequency range, ?70 to 120 °C and 10^?4 to 10 Hz, respectively. In addition, the stress‐strain measurements, DSC, and TEM were carried out. Moreover the effect of stress‐strain cyclic deformation up to ten times with maximum deformation 80% of the elongation at break on J′, J″ is also studied. It was found that the filler network recovers after cyclic stress‐strain in a time scale of one year at room temperature.

Transmission electron photographs of the butyl rubber [IIR] vulcanizates: (a) IIR, unfilled, (b) IIR, filled with 20 phr SiO₂, (c) IIR,filled with 20 phr SiO₂ + 1.6 phr Si69.     

Iminodiacetic acid‐containing polymer brushes grafted onto silica gel for preconcentration and determination of copper(II) in environmental samples

Silica gel has been modified by silylation with 3‐mercaptopropyltrimethoxysilane followed by graft polymerization of dimethylacrylamide and (N,N‐bis‐carboxymethyl)amino‐3‐allylglycerol‐co‐dimethylacrylamide, synthesized via the reaction of allyl glycidyl ether with iminodiacetic acid. The sorbent, poly(AGE/IDA‐co‐DMAA)‐grafted silica gel, has been characterized by FTIR, elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy and studied for the preconcentration and determination of trace amounts of Cu(II) ion in environmental water samples. The optimum pH value for quantitative sorption of Cu(II) in batch mode was 5.5 and desorption was achieved, using 0.5 mol L^?1 nitric acid. The sorption capacity of functionalized sorbent is 32.3 mg g^?1. The chelating sorbent was reused for 15 sorption–desorption cycles without any significant change in sorption capacity. The profile of copper uptake by the sorbent reflected good accessibility of the chelating sites in the poly(AGE/IDA‐co‐DMAA)‐grafted silica gel. Scatchard analysis demonstrated homogeneous nature of binding sites. The equilibrium adsorption data of Cu(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.0665, 4.26, and 8.34, respectively, at pH 5.5 and 20°C. Adsorption isotherms were analyzed at different temperatures to obtain free energy, enthalpy, and entropy of adsorption. The method was applied for Cu(II) determination in sea water samples. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Membranes based on polyimide–polyaniline nanocomposites for pervaporation of organic mixtures

Polyimide–polyaniline nanocomposites were obtained by mixing poly{[4,4′‐bis(4″‐N‐phenoxy)diphenylsulfone]imide‐1,3‐bis(3,4‐dicarboxyphenoxy)benzene} (PI) and polyaniline (PANI) solutions in N‐methylpyrrolidone. These solutions were used for the preparation of homogeneous and composite membranes. Uniform distribution of PANI particles in the membranes, resulted from interactions between macromolecules, was confirmed by transmission electron microscopy. Membranes based on PI and PI–PANI were tested in pervaporation of binary organic mixtures: methanol/toluene and methanol/cyclohexane and showed a remarkable selectivity with respect to methanol. In both pervaporation processes, selectivity was improved in PANI‐containing membranes. Interactions between membrane polymers and liquid penetrants (methanol, toluene, and cyclohexane) were studied by measurements of surface tension, sorption, and pervaporation parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(ether urethane)s from aromatic diisocyanates based on lignin‐derived phenolic acids

A series of new bio‐based aromatic diisocyanates, namely bis(4‐isocyanato‐2‐methoxyphenoxy)alkane and bis(4‐isocyanato‐2,6‐dimethoxyphenoxy)alkane, were synthesized starting from lignin‐derived phenolic acids, namely vanillic acid and syringic acid, via the Curtius rearrangement. The diisocyanates were employed to synthesize poly(ether urethane)s by reacting them with potentially bio‐based aliphatic diols, namely 1,10‐decanediol and 1,12‐dodecanediol. The chemical structures of diisocyanates and poly(ether urethane)s were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. Inherent viscosities and number‐average molecular weights of the poly(ether urethane)s were in the ranges 0.58–0.68 dL g^?1 and 32 100–58 500 g mol^?1, respectively, indicating the formation of reasonably high molecular weight polymers. The poly(ether urethane)s exhibited 10% weight loss in the temperature range 304–308 °C. The glass transition temperatures of the poly(ether urethane)s were in the range 49–74 °C and were dependent both on the number of methylene units in the diols and on the number of methoxy substituents on the aromatic rings of the diisocyanate component. © 2017 Society of Chemical Industry     

Synthesis and characterization of novel poly(arylene ether)s based on 9,10‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) anthracene and 2,7‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) fluorene

Two new bisfluoro monomers 9,10‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) anthracene and 2,7‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) fluorene have been synthesized by the cross‐coupling reaction of 2‐fluoro‐3‐trifluoromethyl phenyl boronic acid with 9,10‐dibromo anthracene and 2,7‐dibromo fluorine, respectively. These two bisfluoro compounds were used to prepare several poly(arylene ether)s by aromatic nucleophilic displacement of fluorine with various bisphenols; such as bisphenol‐A, bisphenol‐6F, bishydroxy biphenyl, and 9,9‐bis‐(4‐hydroxyphenyl)‐fluorene. The products obtained by displacement of the fluorine atoms exhibits weight‐average molar masses up to 1.5 ×10⁵ g mol^?1 and number average molecular weight up to 6.8 × 10⁴ g mol^?1 in GPC. These poly(arylene ether)s show very high thermal stability even up to 490°C for 5% weight loss occurring at this temperature in TGA in synthetic air and showed glass transition temperature observed up to 310°C. All the polymers are soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP, and DMF. Films cast from DMF solution are brittle in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Novel poly(ether ketone)arylates: Synthesis,characterization and properties

In order to reduce the melt temperature (T_m) of the thermotropic crystalline polyarylate and improve its compatibility with poly(ether ether ketone) (PEEK), a series of poly(ether ketone)arylates (PEKARs) containing aryl ether ketone units (AEK) are synthesized through melt transesterification reaction from p‐acetoxybenzoic acid, 1,3‐bis(4′‐carboxylphenoxy)benzene and 4,4′‐bis(p‐acetoxyphenoxy)benzophenone. The inherent viscosities of these polymers are in the range 0.35–0.81 dL/g. The morphologies and properties of PEKARs are characterized by polarized optical microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, thermal gravimetric analysis, etc. The results show that all PEKARs are semi‐crystalline polymers, and the introduction of AEK units can reduce the symmetry of the main chains, leading to decreasing the crystallizability and changing the crystalline form. The PEKARs with AEK less than 30% can exhibit thermotropic liquid crystalline state. The initial and the maximum decomposition temperatures increase with the increase in AEK content. These PEKARs are expected to act as processing agents for PEEK to reduce its processing viscosity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Organosoluble and light‐colored fluorinated polyimides based on 1,1‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐1‐phenylethane and various aromatic dianhydrides

To investigate the CF₃ group affecting the coloration and solubility of polyimides (PI), a novel fluorinated diamine 1,1‐bis[4‐(4‐amino‐2‐ trifluoromethylphenoxy)phenyl]‐1‐phenylethane (2) was prepared from 1,1‐ bis(4‐hydrophenyl)‐1‐phenylethan and 2‐chloro‐5‐nitrobenzotrifluoride. A series of light‐colored and soluble PI 5 were synthesized from 2 and various aromatic dianhydrides 3a–f using a standard two‐stage process with thermal 5a– f(H) and chemical 5a–f(C) imidization of poly(amic acid). The 5 series had inherent viscosities ranging from 0.55 to 0.98 dL/g. Most of 5a–f(H) were soluble in amide‐type solvents, such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐ dimethylacetamide (DMAc), and N,N‐dimethylformamide (DMF), and even soluble in less polar solvents, such as m‐Cresol, Py, Dioxane, THF, and CH₂Cl₂, and the 5(C) series was soluble in all solvents. The GPC data of the 5a–f(C) indicated that the Mn and Mw values were in the range of 5.5–8.7 × 10⁴ and 8.5–10.6 × 10⁴, respectively, and the polydispersity index (PDI) Mw /Mn values were 1.2–1.5. The PI 5 series had excellent mechanical properties. The glass transition temperatures of the 5 series were in the range of 232–276°C, and the 10% weight loss temperatures were at 505–548 °C in nitrogen and 508–532 °C in air, respectively. They left more than 56% char yield at 800°C in nitrogen. These films had cutoff wavelengths between 356.5–411.5 nm, the b* values ranged from 5.0–71.1, the dielectric constants, were 3.11–3.43 (1MHz) and the moisture absorptions were in the range of 011–0.40%. Comparing 5 containing the analogous PI 6 series based on 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐ phenylethane (BAPPE), the 5 series with the CF₃ group showed lower color intensity, dielectric constants, and better solubility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2399–2412, 2005     

Synthesis,properties and pyrolysis of siloxane‐ and imide‐modified epoxy resin cured with siloxane‐containing dianhydride

Hydrosilylation of nadic anhydride with tetramethyl disiloxane yielded 5,5′‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboxylic anhydride (I), which further reacted with 4‐aminophenol to give N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide (II). Epoxidation of II with excess epichlorohydrin formed a siloxane‐ and imide‐modified epoxy oligomer (ie diglycidyl ether of N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide) (III). Equivalent ratios of III/I of 1/1 and 1/0.8 were prepared and cured to produce crosslinked materials. Thermal mechanical and dynamic mechanical properties were investigated by TMA and DMA, respectively. It was noted that each of these two materials showed a glass transition temperature (T_g) higher than 160 °C with moderate moduli. The thermal degradation kinetics was studied with dynamic thermogravimetric analysis (TGA) and the estimated apparent activation energies were 111.4 kJ mol^?1 (in N₂), 117.1 kJ mol^?1 (in air) for III/I = 1/0.8, and 149.2 kJ mol^?1 (in N₂), 147.6 kJ mol^?1 (in air) for III/I = 1/1. The white flaky residue of the TGA char was confirmed to be silicon dioxide, which formed a barrier at the surface of the polymer matrix and, in part, accounted for the unique heat resistance of this material. Copyright © 2005 Society of Chemical Industry     

EPDM–chlorobutyl rubber blends in γ‐radiation and hydrocarbon environment: Mechanical,transport, and ageing behavior

In nuclear applications, ethylene propylene diene monomer (EPDM) rubber is the material of choice as gaskets and O‐rings due to its radiations resistance. In nuclear fuel reprocessing, in addition to radiation, the elastomeric components have to withstand paraffinic hydrocarbons as well. But, EPDM has poor resistance to hydrocarbons. To enhance the durability of EPDM in such environments, EPDM–chlorobutyl rubber (CIIR) blends of varying compositions were developed and characterized for mechanical, thermal, dielectric, and solvent sorption behavior. Spectroscopic and morphological analysis was used to evaluate the compatibility of blends. Due to synergistic effect, the optimal composition of blends with superior mechanical properties and solvent resistance were found to be 60% to 80% EPDM and 20% to 40% CIIR. The optimized blends were irradiated with gamma rays at cumulative doses up to 2 MGy. Based on spectroscopic, morphological, mechanical, thermogravimetric, and sorption properties, blend containing 80% EPDM was found to have superior retention of properties after irradiation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45195.     

Synthesis and characterization of organo‐soluble poly(ether ether ketone)s and poly(ether ether ketone ketone)s containing pendant pentadecyl chains

Poly(ether ether ketone)s and poly(ether ether ketone ketone)s containing pendant pentadecyl chains were synthesized by polycondensation of each of the two bisphenol monomers viz, 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane and 1,1‐bis(4‐hydroxyphenyl)‐3‐pentadecyl cyclohexane with activated aromatic dihalides namely, 4,4′‐difluorobenzophenone, and 1,3‐bis(4‐fluorobenzoyl)benzene in a solvent mixture of N,N‐dimethylacetamide and toluene, in the presence of anhydrous potassium carbonate. Polymers were isolated as white fibrous materials with inherent viscosities and number average molecular weights in the range 0.70–1.27 dL g^?1 and 76,620–1,36,720, respectively. Poly(ether ether ketone)s and poly(ether ether ketone ketone)s were found to be soluble at room temperature in organic solvents such as chloroform, dichloromethane, tetrahydrofuran, and pyridine and could be cast into tough, transparent, and flexible films from their solutions in chloroform. Wide angle X‐ray diffraction patterns exhibited a broad halo at around 2θ = ～ 19° indicating that the polymers containing pentadecyl chains were amorphous in nature. In the small‐angle region, diffuse reflections of a typically layered structures resulting from the packing of pentadecyl side chains were observed. The temperature at 10% weight loss, obtained from TG curves, for poly(ether ether ketone)s and poly(ether ether ketone ketone)s were in the range 416–459°C, indicating their good thermal stability. A substantial drop in glass transition temperatures (68–78°C) was observed for poly(ether ether ketone)s and poly(ether ether ketone ketone)s due to “internal plasticization” effect of flexible pendant pentadecyl chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The preparation,characterization, and cure reactions of new bisbenzocyclobutene‐terminated aromatic imides

Several new bisbenzocyclobutene‐terminated aromatic imides, 2,2′‐bis(N‐4‐benzocyclobutenyl) phthalimide, 2,2′‐bis[4‐(N‐4‐benzocyclobutenylphthalimide)]‐ether, 2,2′‐bis[4‐(N‐4‐benzocyclobutenylphthalimide)]‐ketone, and 2,2′‐bis[4‐(N‐4‐benzo cyclobutenylphthalimid‐4‐oxy) phenyl]‐propane, have been synthesized in high yields and characterized by FTIR, MS, EA, and ¹H NMR spectroscopy. The polymers cured from benzocyclobutene‐terminated imides have high glass transition temperature and good thermal stabilities. The cure reaction of an imide was studied by FTIR‐ATR (attenuated total reflection) and DSC techniques. Apparent kinetic parameters of the cure reaction are obtained. The apparent cure reaction order, activation energy, and pre‐exponential factor determined by isothermal DSC method are 1, 143.4 kJ/mol, and 3.88× 10¹³ min^?1, and by nonisothermal DSC methods 1, 139.4 kJ/mol, and 2.27× 10¹³ min^?1, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1705–1719, 2006     

A novel positive‐type photosensitive polyimide based on soluble block copolyimide showing low dielectric constant with a low‐temperature curing process

A soluble block copolyimide (Bco‐PI) was prepared by direct one‐pot polycondensation of 2,2‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, and cyclohexane‐tetracarboxylic dianhydride in the presence of γ‐valerolactone and a pyridine catalyst system using γ‐butyrolactone as the solvent. The thermal transmission temperature (T_g) of Bco‐PI was 282°C. By having the curing process occur at 250°C, which was below the T_g, colorless and transparent films could be obtained. The film showed excellent optical characteristics. Such properties could not be attained by the conventional high‐temperature thermal imidization process of poly(amic acid). The hydroxy groups in the polyimide backbone gave the Bco‐PI the potential to become alkaline. To the Bco‐PI was added 15 wt % ester of 2,3,4‐trihydroxybenzophenone with 1,2‐naphthoquinone‐(2) diazide‐5‐sulfonic acid (NT200) as the photoreactive compound. The system worked as a positive‐type photosensitive polyimide (PSPI). The sensitivity and contrast of the PSPI system were 220 mJ/cm² and 1.27, respectively, when exposed to UV light, followed by development with a 5% tetramethylammonium hydroxide (TMAH) aqueous solution at room temperature. After curing at 250°C for 1 h, the average refractive index of Bco‐PI with and without NT200 was 1.5543 and 1.5563, and the optically estimated dielectric constant of the polyimides was 2.66 and 2.67, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4240–4246, 2006