Studies on Cure Kinetics of Diglycidyl Ether of 4,4′-Bisphenol/4,4′-Diaminobiphenyl Using the Advanced Isoconversional Method

The cure kinetics of a rigid-rod epoxy monomer, diglycidyl ether of 4,4′-bisphenol (DGEBP), and the curing agent with the similar rigid-rod group, 4,4′-diaminebiphenyl (DABP), was studied using an advanced isoconversional method (AICM). DGEBP/DABP curing system was carried out by means of differential scanning calorimetry (DSC). Three exothermic peaks were depicted by nonisothermal DSC studies: the first two peaks were attributed to the curing reaction, and the last peak was attributed to the decomposition of the cured epoxy resin. The LC phase transformation of the curing process was observed by PLM. Using AICM, the largest activation energy of the curing reaction of DGEBP/DABP system was obtained as 108 kJ/mol. It can also be learned that LC phase transformation of the curing process affects the reaction significantly.     

Synthesis and characterization of curable methacrylate‐based monomers

The synthesis of new methacrylate‐based, curable macromonomers, 4,4′‐bis[2‐hydroxy‐3‐aminopropylmethacrylate] diphenyl ether (BHAPE) and 4,4′‐bis[2‐hydroxy‐3‐aminopropylmethacrylate] diphenyl methane (BHAPM), is reported. BHAPE and BHAPM were prepared by the reaction of glycidyl methacrylate (GMA) with 4,4′‐diaminodiphenyl ether and 4,4′‐diaminodiphenyl methane, respectively. The progress of the reaction was monitored by thin‐layer chromatography (TLC), and the structure of the monomers was characterized by Fourier transform infrared (FTIR) and ¹H‐NMR spectroscopy. Thermal curing of the monomers was conducted in a differential scanning calorimeter (DSC) with peroxide as the initiator. Thermal curing of the monomers showed the highest rate at 100°C with the activation energy value in the range 80–90 kJ distilled/mol. The water absorption properties of the cured samples in water, acidic, and basic solutions were studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Cure kinetics and catalyzed effect of hydroxyl group of LC diglycidyl ether of bisphenol‐S with aromatic diamines

The curing reactions of liquid crystalline 4,4′‐bis‐(2,3‐epoxypropyloxy)‐sulfonyl‐bis(1,4‐phenylene) (p‐BEPSBP) with 4,4′‐diaminodiphenylmethane (DDM) and 4,4′‐diaminodiphenylsulfone (DDS) were investigated by nonisothermal differential scanning calorimeter (DSC). The relationships of E_a with the conversion α in the curing process were determined. The catalyzed activation of hydroxyl group for curing reaction of epoxy resins with amine in DSC experiment was discussed. The results show that these curing reactions can be described by the autocatalytic ?esták‐Berggren model. The curing technical temperature and parameters were obtained, and the even reaction orders m, n, and ΔS for p‐BEPSBP/DDM and p‐BEPSBP/DDS are 0.35, 0.92, ?81.94 and 0.13, 1.32, ?24.45, respectively. The hydroxyl group has catalyzed activation for the epoxy–amine curing system in the DSC experiment. The average E_a of p‐BEPSBP/DDM is 67.19 kJ mol^?1 and is 105.55 kJ mol^?1 for the p‐BEPSBP/DDS system, but it is different for the two systems; when benzalcohol as hydroxyl group was added to the curing system, the average E_a of p‐BEPSBP/DDM decreases and increases for p‐BEPSBP/DDS. The crystalline phase had formed in the curing process and was fixed in the system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,Characterization, and Conducting Properties of Poly(thiourea azomethines)

Three new polyazomethines having phenylthiourea groups were synthesized through solution polycondensation of terephthalaldehyde with 4,4′-bis(thiourea)biphenyl ether, 4,4′-bis(thiourea)biphenylmethane, and 4,4′-bis(thiourea)biphenyl sulphone. For comparison purposes, simple polyazomethines were prepared by the polycondensation of terephthalaldehyde with 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl sulphone. Poly(imine)s having phenylthiourea groups were characterized through IR and ¹H-NMR spectroscopic methods and the thermal stability of the polymers were evaluated through TGA analysis. Conductivity of polyaniline synthesized in aqueous p-toluenesulfonic acid was found to be 3.83 Scm^?1. The conductivity of the polymeric blends with polyaniline dopped with p-toluenesulfonic acid and HCl (20% by weight) were found to be in the range 0.16 × 10^?3 ? 5.7 × 10^?3 Scm^?1.     

Cure kinetics of ternary blends of epoxy resins studied by nonisothermal DSC data

The curing kinetics of blends of diglycidyl ether of bisphenol A (DGEBA), cycloaliphatic epoxy resins, and carboxyl‐terminated butadiene‐acrylonitrile random copolymer (CTBN) in presence of 4,4′‐diamino diphenyl sulfone (DDS) as the curing agent was studied by nonisothermal differential scanning calorimetry (DSC) technique at different heating rates. The kinetic parameters of the curing process were determined by isoconversional method given by Malek for the kinetic analysis of the data obtained by the thermal treatment. A two‐parameter (m, n) autocatalytic model (Sestak‐Berggren equation) was found to be the most adequate selected to describe the cure kinetics of the studied epoxy resins. The values of E_a were found to be 88.6 kJ mol^?1 and 61.6 kJ mol^?1, respectively, for the studied two sample series. Nonisothermal DSC curves obtained using the experimental data show a good agreement with that theoretically calculated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of fluorinated biphenyl‐type epoxy resin

A novel fluorinated biphenyl‐type epoxy resin (FBE) was synthesized by epoxidation of a fluorinated biphenyl‐type phenolic resin, which was prepared by the condensation of 3‐trifluoromethylphenol and 4,4′‐bismethoxymethylbiphenyl catalyzed in the presence of strong Lewis acid. Resin blends mixed by FBE with phenolic resin as curing agent showed low melt viscosity (1.3–2.5 Pa s) at 120–122°C. Experimental results indicated that the cured fluorinated epoxy resins possess good thermal stability with 5% weight loss under 409–415°C, high glass‐transition temperature of 139–151°C (determined by dynamic mechanical analysis), and outstanding mechanical properties with flexural strength of 117–121 MPa as well as tensile strength of 71–72 MPa. The thermally cured fluorinated biphenyl‐type epoxy resin also showed good electrical insulation properties with volume resistivity of 0.5–0.8 × 10¹⁷ Ω cm and surface resistivity of 0.8–4.6 × 10¹⁶ Ω. The measured dielectric constants at 1 MHz were in the range of 3.8–4.1 and the measured dielectric dissipation factors (tan δ) were in the range of 3.6–3.8 × 10^?3. It was found that the fluorinated epoxy resins have improved dielectric properties, lower moisture adsorption, as well as better flame‐retardant properties compared with the corresponding commercial biphenyl‐type epoxy resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of Curing and Thermal Degradation of POSS Epoxy Resin/DDS System

Polyhedral oligomeric silsesquioxanes epoxy resin (POSSER) was prepared from 3-glycidypropyl-trimethoxysilane (GTMS) and tetramethylammonium hydroxide (TMAH) by hydrolytic condensation. POSSER was characterized using Fourier-transformed infrared spectroscopy (FTIR), ¹H-NMR, and liquid chromagraphy/mass spectrometry (LC/MS). The epoxy value of POSSER is 0.50 mol/100 g. The LC/MS analysis indicated that T₁₀ is the majority and contain some amount of T₈, besides, a trace T₉ also exists. The curing kinetics of POSSER with 4,4′-diaminodipheny sulfone (DDS) as a curing agent was investigated by means of differential scanning calorimetry (DSC). The curing reaction order n is 0.8841 and the activation energy Ea is 61.06 kJ/mol from dynamic DSC analysis. Thermal stability and kinetics of thermal degradation were also studied by thermal gravimetric analysis (TGA). TGA results indicated that the temperature of POSSE/DDS system 5% weight loss is approximately 377.0°C, which is higher by 12.6°C than that of pure POSSER, and the primary degradation reaction (300–465°C) followed first order kinetics; the activation energy of degradation reaction is 75.81 kJ/mol.     

Effect of structure of aromatic imide–amines on curing behavior and thermal stability of diglycidyl ether of bisphenol‐A

The curing behavior of diglycidyl ether of bisphenol‐A (DGEBA) with aromatic imide–amines having aryl ether, sulfone, and methylene linkages was studied using differential scanning calorimetry (DSC). Six imide–amines of varying structure were synthesized by reacting 1 mol of naphthalene 1,4,5,8‐tetracarboxylic dianhydride (N) or 4,4′‐oxodiphthalic anhydride (O) with excess (>2 mol) of 4,4′‐diaminodiphenylether [E] or 4,4′‐diaminodiphenyl methane [M] or 4,4′‐diaminodiphenyl sulfone [S]. The imide–amines prepared by reacting O or N with S, M, and E have been designated as OS/NS; OM/NM, and OE/NE, respectively. Structural characterization of imide–amines was done using FTIR, ¹H NMR, ¹³C NMR, and elemental analysis. The curing behavior of DGEBA in the presence of stoichiometric amount of imide–amines was investigated by recording DSC scans. A broad exothermic transition was observed and the peak exotherm temperature was found to be dependent on the structure of imide–amines. The peak exotherm temperature (T_p) was lowest in case of imide–amines OE and highest in case of imide–amines NS/OS. Thermal stability of isothermally cured DGEBA in the presence of imide–amines was evaluated by dynamic thermogravimetry. The char yield was highest for resin cured with imide–amines NE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

联苯酚醛环氧树脂固化动力学及热性能研究

以4,4'-二氨基二苯砜(DDS)为固化剂,采用非等温示差扫描量热法(DSC)研究了联苯酚醛环氧树脂(BPNE)的固化动力学。通过外推法确定了体系的固化工艺。采用Kissinger、Ozawa法计算出固化体系的表观活化能,根据Crane理论计算得到该体系的固化反应级数。采用DSC,热重分析(TGA)研究了固化物的耐热性。结果表明:BPNE的固化工艺为160℃/2h+200℃/2h+230℃/2h;固化反应的活化能约为61.86kJ/mol,指前因子为5.27×105min-1,反应级数为1.1;玻璃化转变温度(Tg)为167℃,其10%热失重温度为398.1℃,800℃残炭率为29.37%,与双酚A环氧树脂/DDS固化物相比,分别提高了22℃,11.71%。     

Studies on the kinetics of free-radical bulk polymerization of multifunctional acrylates by dynamic differential scanning calorimetry

The course and kinetics of nonisothermal bulk polymerization of multifunctional acrylates were studied by dynamic differential scanning calorimetry (DSC). Measurements were carried out for four straight-chain monomers, diethylene glycol diacrylate (DEGDA), triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and poly(ethylene glycol)diacrylate (PEGDA) (mol. wt. 600), to study the effect of the backbone chain length, atmosphere, and type of initiator on the crosslinking kinetics. 4,4′-Azobis(4-cyanovaleric acid) (1.0%, w/w) was used as a free-radical initiator. From the dynamic scanning of polymerization of DEGDA at five heating rates (2–30°C/min), the average heat of polymerization (ΔH_p) was found to be 524.2 J/g. An activation energy of 108.8 kJ/mol and preexponential factor 5.34 × 10¹² s^?1 were obtained from the Arrhenius plot, In dα/dt. The rate of polymerization was found manyfold greater at 20–60% conversion than at the initial stage (2–8% conversion). Polymerization was studied under both nitrogen and air atmosphere. The results corresponded well with the theory of oxygen inhibition. Different types of initiators, e.g., 4,4′-azobis(4-cyanovaleric acid) (ABCVA), 2,2′-azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO) were used for polymerization and ABCVA was found to be the most efficient among all. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of novel borosiloxane‐containing aromatic copolyimides with excellent thermal stability and low coefficient of thermal expansion

The properties of borosiloxane‐containing copolyimides with borosiloxane in the main chain and in the side chain were studied. Two series of borosiloxane‐containing copolyimides were synthesized by the reaction of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA ) and 2,3′,3,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA ) with p ‐phenylenediamine (PDA ), 4,4′‐oxydialinine (4,4′‐ODA ) and different borosiloxane diamine monomers (BSiAs ). The synthesized borosiloxane‐containing copolyimides exhibited better solubility than borosiloxane‐free copolyimides and showed high glass transition temperatures (320–360 °C), excellent thermal stability (570–620 °C for T ₁₀), great elongation at break (10% ? 14%) and a low coefficient of thermal expansion (14–24 ppm °C^?1). More specifically, the copolyimides containing BSiA‐2 formed nano‐scale protrusions and the copolyimides containing BSiA‐1 formed micro‐scale protrusions. The contact angles of the copolyimides increased from 72° for neat copolyimide to 96° for 5% of borosiloxane in the main chain of the copolymer up to 107° for 10% of borosiloxane in the side chain of the copolymer. © 2017 Society of Chemical Industry     

Resistive switching characteristics of polyimides derived from 2,2′‐aryl substituents tetracarboxylic dianhydrides

2,2′‐Position aryl‐substituted tetracarboxylic dianhydrides including 2,2′‐bis(biphenyl)‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride and 2,2′‐bis[4‐(naphthalen‐1‐yl)phenyl)]‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride were synthesized. A new series of aromatic polyimides (PIs) were synthesized via a two‐step procedure from 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride and the newly synthesized tetracarboxylic dianhydrides monomers reacting with 2,2′‐bis[4′‐(3″,4″,5″‐trifluorophenyl)phenyl]‐4,4′‐biphenyl diamine. The resulting polymers exhibited excellent organosolubility and thermal properties associated with T_g at 264 °C and high initial thermal decomposition temperatures (T_5%) exceeding 500 °C in argon. Moreover, the fabricated sandwich structured memory devices of Al/PI‐a/ITO was determined to present a flash‐type memory behaviour, while Al/PI‐b/ITO and Al/PI‐c/ITO exhibited write‐once read‐many‐times memory capability with different threshold voltages. In addition, Al/polymer/ITO devices showed high stability under a constant stress or continuous read pulse voltage of ? 1.0 V. Copyright © 2011 Society of Chemical Industry     

Blue‐light‐emitting poly(arylene ethynylenes) containing alternating sequences of biphenylene or fluorenediyl and p‐phenylene moieties linked through triple bonds

Two new poly(arylene ethynylenes) were synthesized by the reaction of 1,4‐diethynyl‐2.5‐dioctylbenzene either with 4,4′‐diiodo‐3,3′‐dimethyl‐1,1′‐biphenyl or 2,7‐diiodo‐9,9‐dioctylfluorene via the Sonogashira reaction, and their photoluminescence (PL) and electroluminescence (EL) properties were studied. The new poly(arylene ethynylenes) were poly[(3,3′‐dimethyl‐1,1′‐biphenyl‐4,4′‐diyl)‐1,2‐ethynediyl‐(2,5‐dioctyl‐1,4‐phenylene)‐1,2‐ethynediyl] (PPEBE) and poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐1,2‐ethynediyl‐(2,5‐dioctyl‐1,4‐phenylene)‐1,2‐ethynediyl] (PPEFE), both of which were blue‐light emitters. PPEBE not only emitted better blue light than PPEFE, but it also performed better in EL than the latter when the light‐emitting diode devices were constructed with the configuration indium–tin oxide/poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonic acid) (50 nm)/polymer (80 nm)/Ca:Al. The device constructed with PPEBE exhibited an external quantum efficiency of 0.29 cd/A and a maximum brightness of about 560 cd/m², with its EL spectrum showing emitting light maxima at λ = 445 and 472 nm. The device with PPEFE exhibited an efficiency of 0.10 cd/A and a maximum brightness of about 270 cd/m², with its EL spectrum showing an emitting light maximum at λ = 473 nm. Hole mobility (μ_h) and electron mobility (μ_e) of the polymers were determined by the time‐of‐flight method. Both polymers showed faster μ_h values. PPEBE revealed a μ_h of 2.0 × 10^?4 cm²/V·s at an electric field of 1.9 × 10⁵ V/cm and a μ_e of 7.0 × 10^?5 cm²/V·s at an electric field of 1.9 × 10⁵ V/cm. In contrast, the mobilities of the both carriers were slower for PPEFE, and its μ_h (8.0 × 10^?6 cm²/V·s at an electric field of 1.7 × 10⁶ V/cm) was 120 times its μ_e (6.5 × 10^?8 cm²/V·s at an electric field of 8.6 × 10⁵ V/cm). The much better balance in the carriers' mobilities appeared to be the major reason for the better device performance of PPEBE than PPEFE. Their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels were also a little different from each other. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 299–306, 2006     

Branched phenyl‐s‐triazine moieties to enhance thermal properties of phthalonitrile thermosets

Heat‐resistant materials have made tremendous progress in marine, aerospace and microelectronic fields. Herein, a new class of phthalonitrile resins, branched poly(biphenyl ether triphenyl‐s‐triazine) phthalonitriles, were successfully synthesized via a two‐step, one‐pot reaction, on the basis of 2,4,6‐tris(4‐fluorophenyl)‐1,3,5‐triazine and 4,4′‐biphenol. 4,4′‐Diaminodiphenylsulfone was employed to facilitate the curing reaction, and successful realization of curing behavior was concluded from rheological and differential scanning calorimetric studies, indicating the obtained resins possess favorable processability. The relationship between concentration of reactants and properties of the resins was systematically studied. After thermal curing, the E‐glass fiber‐reinforced composite, prepared with a concentration of reactants of 0.15 g mL^?1, shows an admirable glass transition temperature of 480 °C and commendable thermal stability with 5% weight loss temperature in nitrogen of 563 °C, suggesting that the improvement of the thermal properties stems from the branched structure and the phenyl‐s‐triazine units. © 2017 Society of Chemical Industry     

New Nonlinear Polyurethane: Synthesis and Optical Properties

The compound 3,4-di-(2′-hydroxyethoxy)-4-diphenyl-hydrazonomethyl was synthesized from the reaction of 3,4-dihydroxy-4-diphenyl-hydrazonomethyl with 2–chloro–1–ethanol in a 1:2 mole ratio, and subsequent reaction with methylene–4,4′–diphenyldiisocyanate (MDI) to produce the new nonlinear polyurethane. The chemical structures of the resulting monomers and polymer were characterized by CHN analysis, FT-IR, ¹H-NMR, and UV-Vis spectroscopy. The nonlinear optical properties of new polyurethane have been studied via second harmonic generation (SHG). The values of electro-optic coefficient d₃₃ and d₃₁ of the poled polyurethane film were 6.62 × 10^?8 and 3.05 × 10 ^?8 esu, respectively. Thermal behavior of this polyurethane was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Thermal degradation and kinetic study for different waste/rejected plastic materials

A kinetic analysis based on thermal decomposition of rejected polypropylene, plastic film and plastic pellets collected from different industrial outlet has been carried out. Non-isothermal experiments using different heating rates of 5, 10, 20, 30, 40 and 50 °C min^?1 have been performed from ambient to 700 °C in a thermo-balance with the objective of determining the kinetic parameters. The values of activation energy and frequency factor were found to be in the range of 107–322 kJ/mol, 85–331 kJ/mol, 140–375 kJ/mol and 3.49E+07–4.74E+22 min^?1, 3.52E+06–2.88E+22min^?1, 7.28E+13–1.17E+25 min^?1 for rejected polypropylene, plastic film and plastic pellets, respectively, by Coats-Redfern and Ozawa methods including different models. Kissinger method, a model free analysis is also adopted to find the kinetic parameters. Activation energy and frequency factor were found to be 108 kJ/mol, 98 kJ/mol, 132 kJ/mol and 6.89E+03, 2.12E+02, 8.06E+05 min^?1 for rejected polypropylene, plastic film and plastic pellets, respectively, by using the Kissinger method.     

Development of high‐definition aqueous polyvinylpyrrolidone photoresists for cathode ray tubes

Aqueous photoresists that are capable of higher resolutions than are currently employed by the cathode ray tube (CRT) industry were developed by combining photoactivators, which activate at shorter UV wavelengths with polyvinylpyrrolidone (PVP). Two photoactivators were synthesized: 4,4′‐diazido‐2,2′‐biphenyl disodium disulfonate (DABP), which has a maximum absorbance at 264 nm, and 4,4′‐diazido‐2,2′‐biphenylethane disodium disulfonate (DABPE), which has a maximum absorbance at 258 nm. The PVP/DABP and PVP/DABPE photoresists successfully imaged a pattern with resolution as small as 4.4 μm with photoactivator concentrations greater than 20% of the PVP concentration. Addition of silane and emulgen greatly improved the performance of the photoresists with more uniform coatings of thicknesses of up to 1.4 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1637–1644, 2006     

Synthesis and characterization of some aromatic polyimides

The diamine 2‐methyl‐1,3‐bis(4‐aminophenyloxy)benzene was prepared via a nucleophilic substitution reaction and was characterized with Fourier transform infrared, elemental analysis, and ¹H‐ and ¹³C‐NMR spectroscopy. The prepared diamine was also characterized with single‐crystal analysis. The geometric parameters of C₁₉H₁₈N₂O₂ were in the usual ranges. The dihedral angles between the central phenyl ring and the two terminal aromatic rings were 88.9 and 91.6°. The crystal structure was stabilized by N? H···N hydrogen bonds. The diamine was then polymerized with 3,3′,4,4′‐benzophenone tetracarboxylic acid dianhydride, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10‐perylenetetracarboxylic acid dianhydride, and pyromellitic dianhydride by either a one‐step solution polymerization reaction or a two‐step procedure. These polymers had inherent viscosities ranging from 0.61 to 0.85 dL/gm. Some of the polymers were soluble in most common organic solvents even at room temperature, and some were soluble on heating. The degradation temperatures of the resultant polymers fell in the range of 260–500°C in nitrogen (with only 10% weight loss). The specific heat capacity at 200°C ranged from 1.0 to 2.21 J g^?1 K^?1. The temperatures at which the maximum degradation of the polymer occurred ranged from 510 to 610°C. The glass‐transition temperatures of the polyimides ranged from 182 to 191°C. The activation energy and enthalpy of the polyimides ranged from 44.44 to 73.91 kJ/mol and from 42.58 to 72.08 kJ/mol K, respectively. The moisture absorption was found in the range of 0.23–0.71%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

On the primary processes of sensitized photopolymerization of vinylmonomers. Laser flash photolysis studies and stationary polymerization experiments

The absorption spectra of the triplets of aromatic ketones used as photosensitizers for the polymerization of unsaturated compounds — benzophenone (BP), 3,3′,4,4′-tetramethoxycarbonylbenzophenone (TMCB) and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) — were recorded after irradiation of benzene or acetone solutions of the ketones with 25 ns flashes from a frequency doubled ruby laser (λ = 347,1 nm) at room temperature. Furthermore, the spectra of the respective ketyl radicals were measured. Rate constants of the reaction of triplets with various monomers were measured. Very high rate constants (> 10⁹ 1 · mol^?1 s^?1) were found for styrene (St) and N-vinylpyrrolidone (VP). The triplet energy E_T of these monomers is smaller than E_T of the sensitizers, except the case BP/VP. Other monomers — vinylacetate (VAc), methylmethacrylate (MMA), acrylonitrile (AN) — react relatively slowly with sensitizer triplets (5 × 10⁶ to 1.4 × 10⁸ l · mol^?1 s^?1). It is assumed that these monomers have E_T values higher than the E_T values of the sensitizers. The rate of polymerization v was determined in tetrahydrofuran solutions containing monomer (5 mol/1) and sensitizer (6–7 × 10⁴ mol/1) from stationary experiments with irradiation of light with λ > 320 nm. The probabilities, α_R, for the initiation of polymerization derived from the rate constants of triplet quenching by the monomers were correlated with the measured rates of polymerization. In accordance with expectation it was found that St and VP did not polymerize and that in the cases of VAc, MMA and AN a significant polymerization takes place (in the absence of sensitizer the rates v were negligibly small). For MMA v is proportional to α.