Gelation in free-radical terpolymerization of poly(allyl methacrylate) crosslinked polymer nanosphere with allyl benzoate and vinyl benzoate

Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel.     

Novel amphiphilic network polymers consisting of nonpolar,short primary polymer chains and polar,long crosslink units: Influence of characteristic dangling chains on swelling behavior of resulting amphiphilic gels

Novel amphiphilic network polymers consisting of nonpolar, short primary polymer chains and polar, long crosslink units were prepared, and the swelling behavior of resulting amphiphilic gels is discussed by focusing on the influence of characteristic dangling chains; that is, benzyl methacrylate (BzMA) was copolymerized with tricosaethylene glycol dimethacrylate [CH₂?C(CH₃)CO(OCH₂CH₂)₂₃OCOC(CH₃)?CH₂, PEGDMA‐23] in the presence of lauryl mercaptan as a chain‐transfer agent because BzMA forms nonpolar, short primary polymer chains and PEGDMA‐23 as a crosslinker contains a polar, long poly(oxyethylene) unit. The enhanced incorporation of dangling chains into the network polymer was brought by shortening the primary polymer chain length, and copolymerization with methoxytricosaethylene glycol methacrylate, a mono‐ene counterpart of PEGDMA‐23, enforced the incorporation of flexible dangling poly(oxyethylene) chains into the network polymer, although the former dangling chains as terminal parts of primary poly(BzMA) chains were rather rigid. Then, the influence of characteristic dangling chains on the swelling behavior of amphiphilic gels was examined in mixed solvents consisting of nonpolar t‐butylbenzene and polar methanol. The profiles of the solvent‐component dependencies of the swelling ratios were characteristic of amphiphilic gels. The introduction of dangling poly(oxyethylene) chains led not only to an increased swelling ratio but also to sharpened swelling behavior of amphiphilic gels. The swelling response of amphiphilic gels was checked by changing the external solvent polarity. The dangling chains with freely mobile end segments influenced the swelling response of gels. The amphiphilic gels with less entangled, collapsed crosslink units exhibited faster swelling response than the ones with more entangled, collapsed primary polymer chains. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2192–2201, 2004     

Colorimetric determination of lipid hydroperoxides in oils and fats with microperoxidase

The use of the peroxidase-like activity of microperoxidase for the calorimetric determination of lipid hydroperoxides in oils and fats has been investigated. The principle of the determination is that 4-aminoantipyrine and N,N-diethylaniline are coupled oxidatively by the hydroperoxides through the action of microperoxidase, yielding a violet colour with maximum absorbance at 554 nm. The response of the microperoxidase system is enhanced by the presence of acetonitrile. The method has been successfully applied to the determination of methyl linoleate hydroperoxide, tert-butyl hydroperoxide and the hydroperoxides in oil and fat samples (soybean oil, linseed oil, olive oil, salad oil, butter and lard). The results agreed closely with those obtained by the iodometric method. The proposed method permitted the determination of the hydroperoxides at 0.5-0.05 mumole levels, with the same sensitivity regardless of sample type tested, with satisfactory reproducibility compared with that obtained by the conventional assay methods.     

Photochemical vapor deposition of amorphous silicon through 185 nm excitation of monosilane

Photochemical vapor deposition of a-Si films at a high rate using SiH₄ and a 185 nm low pressure mercury lamp is described. A maximum rate of 1 nm/sec was attained using the 185 nm lamp. This rate was about ten times higher than that using a 254 nm lamp. Assuming that there is no interaction between the effects of the two wavelengths, the deposition rate per light output power of 184.9 nm light is 160 times larger than that for 253.7 nm light. The absorption cross-section of the 184.9 nm light is ten times greater than that for the 253.7 nm light.     

Characterization of resulting network polymer precursors in stepwise crosslinking diepoxide/diamine polymerization

Our previous mechanistic discussion of network formation in chainwise crosslinking multiallyl polymerization was extended to stepwise crosslinking diepoxide/diamine polymerization, typically including bisphenol‐A diglycidyl ether (BADGE) and 4,4′‐diaminodiphenylmethane (DDM). In allyl polymerization a monomer chain transfer is an essential termination reaction, providing only oligomeric primary polymer chains. Therefore, crosslinking multiallyl polymerization could be in the category of a classical gelation theory. Thus, the gelation behavior was discussed by comparing the actual gel point with the theoretical one. Then the resulting network polymer precursors (NPPs) were characterized by size‐exclusion chromatography‐multiangle laser light scattering‐viscometry to clarify the stepwise crosslinking BADGE/DDM polymerization mechanism. Notably, the intrinsic viscosity ratio [η]_NPP/[η]_Linear tended to decrease with the progress of crosslinking and finally, it reached less than 0.2. This suggests that the structure of resulting NPP becomes dendritic at a conversion close to the gel point. These dendritic NPPs can collide with each other to form crosslinks between NPPs, eventually leading to gelation as a reflection of the high concentration of NPP. The dilution effect on gelation was marked in polar solvent; no gelation was observed at a dilution of 1/5. However, in nonpolar solvent the gelation was promoted by dilution; this is ascribed to enhanced crosslink formation between NPPs through hydrogen bonding due to abundant hydroxyl groups in the NPP generated by the polyaddition reaction. Finally, the subject of “Is cured epoxy resin inhomogeneous?” is briefly discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011