Facile modifications of a polyimide via chloromethylation. I. Novel synthesis of a new photosensitive polyimide

A soluble aromatic polyimide was chloromethylated via a reaction with chloromethyl methyl ether in the presence of tin(IV) chloride to produce a new starting material for the modification of aromatic polyimides. The chemical structure of the resulting polymer was confirmed by ¹H NMR and Fourier transform infrared spectroscopy. The maximum number of chloromethyl groups per repeat unit was 1.81. The chloromethylated polyimide was stable up to 250 °C and soluble in both chloroform and tetrahydrofuran. So that its utilization for further modification could be demonstrated, cinnamic acid was reacted with the formed polyimide, and it produced a new photosensitive polyimide with a cinnamoyl side chain. The photosensitivity of the resulting polyimide was investigated with ultraviolet spectroscopic methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 22–29, 2003     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Fracture toughening of epoxy matrices with blends of resins of different molecular weights and other modifiers

The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004     

Depth profile analysis of polyimide film treated by potassium hydroxide

The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003     

Ring‐opening grafting polymerization of cyclic monomers onto human hair

Natural human hair was successfully modified by the graft polymerization of trimethylene carbonate, β‐propiolactone, ε‐caprolactone, glycidol, ε‐caprolactam, and 5,5‐dimethyl‐1,3‐dioxane‐2‐thione. In contrast, we could not modify natural human hair by the graft polymerization of oxetane under similar conditions. The model reaction suggested that the main initiating species in these polymerizations were the amino, thiol, and hydroxyl groups in hair, which could induce ring‐opening polymerization. Among the tested monomers, β‐propiolactone was most effective for hair modification with its graft polymer, whose concentration was as high as 0.5 g/g of hair though polymerization under mild conditions. The effects of the hair pretreatment and polymerization temperature on the weight ratio of the grafted polymers were also investigated. Hair modified by grafted polymers was characterized with scanning electron microscopy and Fourier transform infrared measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 736–744, 2007     

UV curing of a novel resin derived from poly(ethylene terephthalate)

The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007     

Local chain‐configuration dependence of the mechanisms of the chemical reaction of poly(vinyl chloride). IX. Novel results on stereoselectivity of chlorination reaction

A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by ¹³C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Reinforcement effect of MAA on nano‐CaCo3‐filled EPDM vulcanizates and possible mechanism

Methacrylic acid (MAA) was used as in situ surface modifier to improve the interface interaction between nano‐CaCO₃ particle and ethylene–propylene–diene monomer (EPDM) matrix, and hence the mechanical properties of nano‐CaCO₃‐filled EPDM vulcanizates. The results showed that the incorporation of MAA improved the filler–matrix interaction, which was proved by Fourier transformation infrared spectrometer (FTIR), Kraus equation, crosslink density determination, and scanning electron microscope (SEM). The formation of carboxylate and the participation of MAA in the crosslinking of EPDM indicated the strong filler–matrix interaction from the aspect of chemical reaction. The results of Kraus equation showed that the presence of MAA enhanced the reinforcement extent of nano‐CaCO₃ on EPDM vulcanizates. Crosslink density determination proved the formation of the ionic crosslinks in EPDM vulcanizates with the existence of MAA. The filler particles on tensile fracture were embedded in the matrix and could not be observed obviously, indicating that a strong interfacial interaction between the filler and the matrix had been achieved with the incorporation of MAA. Meanwhile, the presence of MAA remarkably increased the modulus and tensile strength of the vulcanizates, without negative effect on the high elongation at break. Furthermore, the ionic bond was thought to be formed only on filler surface because of the absolute deficiency of MAA, which resulted in the possible structure where filler particles were considered as crosslink points. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1226–1236, 2006     

Electroless preparation and electrochemical behavior of a platinum-doped nickel hexacyanoferrate film–zinc modified electrode: catalytic ability of the electrode for electrooxidation of methanol

The use of a zinc substrate as an electrode and the modification of its surface by means of a thin film of platinum-doped nickel hexacyanoferrate (Pt-NiHCF) were developed. The modification conditions of the zinc surface including the electroless deposition of metallic nickel on the electrode surface from NiCl₂ solution, chemical derivatization of the deposited nickel to the NiHCF film in 0.5 M K₃[Fe(CN)₆] solution, and electrochemical penetration of metallic platinum into the modified film are described. The modified zinc electrodes prepared under optimum conditions show a well-defined redox couple due to the [Ni^IIFe^III/II(CN)₆]^1–/2– system. The effects of pH, the alkali metal cation, and the anion of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied in detail. The diffusion coefficients of hydrated alkali metal cations in the film (D), the transfer coefficient (), and the transfer rate constant for the electron (k_s) were calculated in the presence of some alkali metal cations. The electrocatalytic activity of the modified electrode for methanol oxidation was demonstrated. The stability of the modified electrode under various experimental conditions was investigated.