Synthesis and Characterization of Poly(3‐azidomethyl‐3‐methyl oxetane) by the Azidation of Poly(3‐mesyloxymethyl‐3‐methyl oxetane)

Poly(3‐azidomethyl‐3‐methyl oxetane) (PAMMO) was prepared by the azidation reaction of poly(3‐mesyloxymethyl‐3‐methyl oxetane) (PMMMO), which was synthesized by cationic ring‐opening polymerization of MMMO for the first time. Two azidation reaction methods of PMMMO were considered to obtain PAMMO securely and efficiently. The thermal decomposition performance of PAMMO was studied by TG/FTIR/MS. The result of TG showed that the thermal decomposition of PAMMO involved two steps. Combined with FT‐IR and MS of the escaping gases to investigate the decomposition products of PAMMO, it is found that the first step was mainly corresponding to the thermal decomposition of azide group ( N₃), and the second step was mainly corresponding to the thermal decomposition of the polyether backbone.     

Effect of α‐, γ‐, and δ‐tocopherol on the distribution of volatile secondary oxidation products in fish oil

The relative ability of α‐, γ‐ and δ‐tocopherol (TOH) to influence the distribution of volatile secondary oxidation products in fish oil was studied, with particular emphasis on oxidation products expected to be important for adverse flavour formation. Purified fish oil samples with 100 ppm or 1000 ppm of the different tocopherols were analysed by dynamic headspace analysis of the volatiles formed after 2, 5 and 8 d of storage at 30 �C. The tocopherol type and concentration affected not only the overall formation of volatile secondary oxidation products, but also the composition of this group of oxidation products. Principal component analysis of the data obtained suggested that high tocopherol hydrogen‐donating power, i.e. a high tocopherol concentration or the use of αTOH as opposed to γTOH or δTOH, directs the formation of hydrocarbons, unsaturated carbonyl compounds of relatively high molecular weight, as well as the formation of cis, trans isomers of unsaturated aldehydes. Although an active inhibitor of overall volatile formation, αTOH at a high concentration thus appears to direct the formation of the more flavour‐potent aldehydes, such as those linking the carbonyl group with ethylenic conjugated unsaturation.     

Influence of γ‐irradiation on poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was γ‐irradiated (5–20 kGy) by a ¹³⁷Cs source at room temperature in air. The changes in the molecular structure attributed to γ‐irradiation were studied by mechanical testing (flexure and hardness), size‐exclusion chromatography, differential scanning calorimetry, thermal gravimetric analysis, and both Fourier transform infrared and solution ¹³C‐NMR spectroscopy. Scanning electron microscopy was used to investigate the influence of the dose of γ rays on the fracture behavior of PMMA. The experimental results confirm that the PMMA degradation process involves chain scission. It was also observed that PMMA presents a brittle fracture mechanism and modifications in the color, becoming yellowish. The mechanical property curves show a similar pattern when the γ‐radiation dose increases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 886–895, 2002     

Kinetics of antioxidant action of α‐ and γ‐toco‐pherols in sunflower and soybean triacylglycerols

A kinetic analysis was performed to evaluate the antioxidant behavior of α‐ and γ‐to‐copherols (5—2000 ppm) in purified triacylglycerols obtained from sunflower oil (TGSO) and soybean oil (TGSBO) at 100 °C. Different kinetic parameters were determined, viz. the stabilization factor as a measure of effectiveness, the oxidation rate ratio as a measure of strength, and the antioxidant activity which combines the other two parameters. In the low concentration range (up to 400 ppm in TGSBO and up to 700 ppm in TGSO) α‐tocopherol was a more active antioxidant than γ‐tocopherol whereas the latter was more active at higher concentrations. It has been found that the different activity of the tocopherols is not due to their participation in chain initiation reactions, but that the loss of antioxidant activity at high tocopherol concentrations is due to their consumption in side reactions. The rates of these reactions are higher in TGSBO than in TGSO. Both α‐tocopherol itself and its radicals participated more readily in side reactions than γ‐tocopherol and its radicals. Both α‐ and γ‐tocopherol reduce lipid hydroperoxides, thus generating alkoxyl radicals which are able to amplify the rate of lipid oxidation by participating in chain propagation reactions.     

Microemulsion polymerization of methyl methacrylate initiated with γ ray

Polymerization of methyl methacrylate was studied in an oil and water microemulsion stabilized with styrene 12-butinoyloxy-9-octadecenoic acid. During the polymerization the size change of the monomer-swollen particles with conversion was measured with photon correlation spectroscopy, and the hydrodynamic diameter of the final polymer latex was about 50 nm. The polymerization kinetics in this microemulsion were also investigated. The apparent plateau of the polymerization rate was observed at a low dose rate and high emulsifier content. The mechanism leading to this plateau was discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2621–2626, 1999     

Reaction of 3-methyl phenol with methyl α-eleostearate

The aromatic ring substitution reaction of 3-methyl phenol with methyl α-eleostearate under acidic conditions was carried out. The product was analyzed to find out if 3-methyl phenol was subjected to the ring substitution reaction with methyl α-eleostearate at its conjugated double bonds. Up to two molecules of 3-methyl phenol were addition-reacted with the conjugated triene of the eleostearyl group of methyl α-eleostearate. The 4-position of 3-methyl phenol was preferentially subjected to the cresol's ring substitution. When 3-methyl phenol was reacted with a relatively large amount of methyl α-eleostearate, the substitution reaction occurred at the 6- as well as 4-position of 3-methyl phenol, to yield a methyl α-eleostearate dimer having 3-methyl phenol units in its molecule. The above results were confirmed by infrared (IR), nuclear magnetic resonance (NMR), and high-speed liquid chromatographic (HLC) analyses, and the results of a previous paper connected with reaction of 3-methyl phenol were supported by the results of this paper.     

α‐, γ‐ and δ‐ Tocopherols as inhibitors of isomerization and decomposition of cis,trans methyl linoleate hydroperoxides

The effects of α‐, γ‐ and δ‐tocopherols on the stability and decomposition reactions of lipid hydroperoxides were studied. Isomerization and decomposition of cis,trans methyl linoleate hydroperoxides (cis,trans ML‐OOH) in hexadecane at 40 °C were followed by high‐performance liquid chromatography. Due to its higher hydrogen donating ability, α‐tocopherol was more efficient than γ‐ and δ‐tocopherols in inhibiting the isomerization of cis,trans ML‐OOH to trans,trans ML‐OOH. α‐Tocopherol stabilized hydroperoxides into the cis,trans configuration, whereas γ‐ and δ‐tocopherols allowed hydroperoxides to convert into trans,trans isomers. Thus, the biological importance of α‐tocopherol as compared to other tocopherols may be partly due to its better efficacy in protecting the cis,trans configuration of hydroperoxides formed, for example, in the enzymatic oxidation of polyunsaturated fatty acids. The isomeric configuration of hydroperoxides has an impact on biological activities of further oxidation products of polyunsaturated fatty acids. Paradoxically, the order of activity of tocopherols with regard to hydroperoxide decomposition was different from that obtained for hydroperoxide isomerization. γ‐ and δ‐tocopherols were more efficient inhibitors of ML‐OOH decomposition when compared to α‐tocopherol. A loss of antioxidant efficiency, observed as the tocopherol concentration increased from 2 to 20 mM, was highest for α‐tocopherol but was also evident for γ‐ and δ‐tocopherols. Thus, the differences in the relative effects of tocopherols at differing concentrations seem to result from a compromise between their radical scavenging efficiency and participation in side reactions of peroxidizing nature.     

γ‐radiation‐induced preparation of polyamidoxime resins and their adsorption of methyl violet

Poly(acrylic acid–amidoxime) [P(AA–AO)] and poly(maleic acid–amidoxime) [P(MA–AO)] resins were prepared by the γ‐radiation‐induced copolymerization of acrylonitrile with acrylic acid and maleic acid, respectively. The obtained resins were amidoximated by reaction with hydroxylamine. The prepared resins were used for the removal of methyl violet (MV) dye from aqueous solutions. Batch adsorption studies were made by the measurement of the effects of pH, the amount of adsorbent, the contact time, and the adsorbate concentration. The adsorption isotherm of MV onto P(AA–AO) and P(MA–AO) was determined at 25°C with initial MV dye concentrations of 10–70 mg/L. The equilibrium data were analyzed with the Langmuir and Freundlich isotherm models. The equilibrium process was described well by the Langmuir isotherm model with maximum adsorption capacities of 398.4 and 396.8 mg/L for P(AA–AO) and P(MA–AO), respectively. The kinetics of adsorption of MV onto P(AA–AO) and P(MA–AO) are discussed. The pseudo‐second‐order kinetic model described the adsorption of MV onto P(AA–AO) and P(MA–AO) very well. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Copolymerization of γ-methacryloxy propyl trimethoxy silane and methyl methacrylate

Copolymerization of methyl methacrylate (MMA) with low mole fractions of γ-methacryloxypropyl trimethoxy silane (MTS) was investigated with an aim to synthesize copolymers which can be cross-linked by hydrolytic cleavage of methoxy groups. Several copolymer samples were prepared by changing the molar ratios of two monomers in the initial monomer feed. Rate of copolymerization depended on the concentration of monomers and increased with an increase in MTS concentration. The copolymers were characterized by infrared (IR) and ¹H nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and intrinsic viscosity determination. The effect of structure on thermal behavior was investigated by using dynamic thermogravimetry in nitrogen atmosphere. An attempt was made to identify products of degradation using mass spectrometry. Copolymers were also hydrolyzed in water and cross-linked. The effect of MTS in copolymers on percentage gel formation was determined.     

Glass transition temperature of methyl methacrylate–ethyl α‐benzoyloxymethylacrylate copolymers

Poly(ethyl α‐benzoyloxymethylacrylate) (EBMA) and copolymers of methyl methacrylate (MMA) with EBMA have been prepared by free radical polymerization. Monomer precursors of ethyl α‐benzoyloxymethylacrylate have likewise been polymerized. Glass transition temperatures (T_g) of homo and copolymers have been determined by differential scanning calorimetry. The Johnston equation, which considers the influence of monomeric unit distribution on the copolymer glass transition temperature, has been used to explain the T_g behaviour. T_g12 has been calculated by the application of the Johnston equation, which gave a value markedly lower than the average value expected from the additive contribution of the T_g of the corresponding homopolymers. © 2000 Society of Chemical Industry     

Copolymerization of alkyl α-chloroacrylates with methyl methacrylate

Hexyl α-chloroacrylate (HCA) and cyclohexyl α-chloroacrylate (CCA) have been copolymerized with methyl methacrylate (MMA) in toluene at 55°C using azobisisobutyronitrile (AIBN) as initiator. Copolymer compositions have been determined both by ¹H NMR and elemental analyses. For copolymerization of MMA (M1) with HCA (M2), the reactivity ratios (RR) are r₁ = 0.47 ± 0.19 and r₂ = 0.81 ± 0.51 and with CCA the values are r₁ = 0.76 ± 0.31 and r₂ = 2.30 ± 1.73. Thermal properties of these copolymers have also been investigated.     

Studies of methyl methacrylate-methyl α-chloroacrylate,copolymers and poly(methyl α-chloroactylate) as electron sensitive positive resists

Poly(methyl α-chloroacrylate) (PMCA) and the copolymers of methyl methacrylate and methyl α-chloroacrylate (poly(MMA-co-MCA)) have been reported recently to be more susceptible to radiation degradation than poly(methyl methacrylate) (PMMA). In this paper we report our studies of PMCA and poly(MMA-co-MCA) as electron-sensitive positive resists. It has been found that both PMCA and the copolymers are more sensitive than PMMA. Using mixtures of dimethylformamide and 2-propanol as developers, the sensitivities of PMCA and poly(MMA-co-MCA) (38 mole percent MCA) have been found to be 1 × 10^?5 and 6 × 10^?6 coulomb/cm², respectively. It has also been found that crosslinking predominates in PMCA when the electron dose exceeds 6 × 10^?4 coulomb/cm².     

“Living”/controlled polymerization of methyl acrylate mediated by dithiocarbamates under γ‐ray irradiation

γ‐Ray initiated reversible addition–fragmentation chain transfer (RAFT) polymerizations of methyl acrylate (MA) were investigated in bulk using five different dithiocarbamate structures, 2‐phenyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1b ), 2‐methyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1c ), 2‐pheny‐indole‐1‐cardithioic acid benzyl ester ( 1d ), 2‐(carbazole‐9‐carbothioylsulfanyl)‐2‐methyl‐propionic acid ester ( 1e ), and carbazole‐9‐carbodithioic acid naphthalene‐1‐ylmethyl ester ( 1f ), as RAFT agents. The experiment results showed that MA polymerized in a controlled way under a low irradiation dose rate, i.e., first‐order kinetic plots, the experimental molecular weights increased linearly with monomer conversions. The polydispersity indices of polymers generally remained at a relatively low value (lower than 1.4). The effect of irradiation dose on the polymerization results was investigated. The obtained polymers were characterized with ¹H NMR and GPC. Chain‐extension reaction was also successfully carried out using the obtained polymer as the macro‐RAFT agent and styrene as the second monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1769–1775, 2007     

New monomers and polymers derived from α‐hydroxymethyl methyl vinyl ketone

2‐Hydroxymethyl‐but‐1‐ene‐3‐one [α‐hydroxymethyl methyl vinyl ketone (HMVK)] was synthesized from methyl vinyl ketone using paraformaldehyde and a tertiary amine catalyst. Free‐radical polymerization of this monomer created transparent, tough polymers that were insoluble in organic solvents. HMVK was converted to trimethylsilyl, acetate, and chloride derivatives. When the hydroxyl group was thus protected or removed, all these monomers could be free radically polymerized in bulk to make soluble polymers. The chlorination reaction is complicated by the formation of 1,1‐bischloromethylacetone, which dehydrohalogenated unexpectedly to the desired α‐chloromethyl methyl vinyl ketone. HMVK will self‐condense to an ether dimer in the presence of a catalytic acid. This reagent is capable of crosslinking many alkene monomers through hydrolytically stable ether bonds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 509–516, 2000     

Modeling of the copolymerization,with depropagation,of α‐methyl styrene and methyl methacrylate at an elevated temperature

We propose a dynamic model for the copolymerization of α‐methyl styrene (α‐MS) and methyl methacrylate (MMA) in a batch reactor. The parameters are based on data from the literature and our own laboratories over the full conversion range. A two‐parameter model with constant reactivity ratios shows the most reasonable results. The dynamic model depicts the reaction kinetics and reactor behavior more clearly. Termination occurs mainly by the cross reaction of unlike radicals, and its rate increases with the molar ratio of α‐MS to MMA. The model enables us to predict the instantaneous and cumulative properties of the copolymer and also provides us with a basic tool for the optimization and control of industrial reactors. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 261–270, 2004     

Intestinal digestion of fish oils and ω‐3 concentrates under in vitro conditions

A comparative study of the in vitro bioaccesibility of ω‐3‐oils (salmon oil, SO; tuna oil, TO; enriched‐ω‐3 oil as triacylglycerols (TAGs), ω‐3‐TAG; and enriched‐ω‐3 oil as ethyl esters (EEs), ω‐3‐EE) was performed after treatment with pancreatin (pancreatic lipase as major lipolytic enzyme) at pH 7.5. Aliquots were taken at different times of digestion for analyzing the evolution of lipid products. The micellar phase (MP) formed at 120 min of digestion was isolated, its total lipid content was extracted and its composition in lipid products was analyzed. The rate of hydrolysis of ω‐3‐TAG concentrates was continuous throughout the time of reaction (51% hydrolysis of TAGs at 120 min), whereas the digestion of SO and TO was initially faster but stopped after 10 min of reaction (35 and 38% hydrolysis of TAGs at 120 min of SO and TO, respectively). A poor hydrolysis of EEs took place for the ω‐3‐EE oil (around 7% hydrolysis of EEs at 120 min). The MP of ω‐3‐TAG oil, SO, and TO mainly consisted of free fatty acids (FFAs) and MAGs. The MP from digested ω‐3‐EE oil consisted of FFAs and undigested EEs. Therefore, the highest degree of hydrolysis and inclusion of lipid products in the micellar structure was found for the ω‐3‐TAG oil, but compared to fish oils long times of digestion were required. This experience also shows for the first time the MP composition from ω‐3‐concentrates in the form of EEs. Practical applications: Commercial ω‐3 sources can be found as purified fish oil or concentrates in the form of TAGs, FFAs, and EEs. Despite differences exist regarding their intestinal metabolism, there is lack of information about the specific composition in lipolytic products of the absorbable fraction (MP) from ω‐3‐TAG or ω‐3‐EE concentrates. This comparative study showed that (i) the in vitro bioaccesibility of ω‐3‐polyunsaturated fatty acid (PUFA) seems to be better as ω‐3‐TAG concentrates than purified fish oils, but after long times of digestion; and (ii) the in vitro hydrolysis of ω‐3‐PUFA as EEs seems to be poor, at least after the activity of the major lipolytic enzyme of pancreatin, namely pancreatic lipase. Furthermore, the inclusion of EEs within micellar structures seems to be limited. These results contribute to the knowledge of the intestinal lipolysis of ω‐3 sources by showing the composition of the MP on lipid products for the first time.     

Homogeneous graft copolymerization of chitosan with methyl methacrylate by γ‐irradiation via a phthaloylchitosan intermediate

The graft copolymerization of methyl methacrylate (MMA) onto chitosan was tried via a new protection‐graft‐deprotection procedure. Because the intermediate phthaloylchitosan was soluble in organic solvents, the graft copolymerization was carried out in a homogeneous system. Grafting was initiated by γ‐irradiation. The graft percentage extent was dependent on the irradiation dose and the concentration of MMA monomer, and copolymers with grafting above 100 % were readily prepared. The graft copolymers exhibited a high affinity not only for aqueous acid but also for some organic solvents. Differential scanning calorimetry measurements revealed the presence of a glass transition phenomenon, which could be ascribed to the poly(methyl methacrylate) side‐chains. Copyright © 2004 Society of Chemical Industry