ESR spectroscopic studies on the microheterogeneity of crosslinked polymers, 3. Attempt to a detailed evaluation of void parts in monomethacrylate/dimethacrylate resins by ESR measurements at lower temperatures

Abstract

ESR spectroscopic studies on the microheterogeneity of crosslinked polymers were extended to the attempt on a detailed void evaluation of microheterogeneously crosslinked monomethacrylate/dimethacrylate resins by measuring ESR spectra at lower temperatures, utilizing the interactions between spin probes and side chains. That is, the mobility of copper(II) tetraphenylporphyrin (CuTPP), a spin probe useful for the evaluation of void parts in crosslinked resins, excluded from densely crosslinked network parts to void ones was found to be much restricted at lower temperatures; this provides a useful tool to allow a detailed evaluation of the void parts. Thus, methyl methacrylate (MMA)/ethylene dimethacrylate (EDMA) (mole ratio 70/30) solution copolymerization in toluene at a dilution of 2/3 was chosen as a standard copolymerization system to provide the cured resin with void parts. The effect of introducing polar poly(oxyethylene) units was explored to clarify their interaction with the polar central part of the CuTPP molecule leading to the restricted mobility of CuTPP. The detailed evaluation of void sizes was done by changing the crosslinker content. The polar interaction was prevented by changing the CuTPP spin probe to a nonpolar one; the nonpolar interaction was verified by adding docosyl methacrylate having a long‐chain alkyl group to the MMA/EDMA copolymerization.

Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free‐radical crosslinking monomethacrylate/dimethacrylate copolymerizations

“…Moreover, the occurrence of intramolecular crosslinking should be preceded by intermolecular crosslinking, whereas intramolecular cyclization would occur during the growth of a propagating radical, regardless of the occurrence of intermolecular crosslinking, and it always competes with intermolecular propagation with two monomer types as a lengthening reaction of the primary polymer chain. In addition, the locally extensive occurrence of intramolecular crosslinking would induce microgelation, leading not only to delayed gelation4–17 but also to the inhomogeneity of the network structures of three‐dimensional crosslinked polymers, being closely related to their properties 18–28…”

Copolymerization of Poly(allyl methacrylate) Crosslinked Polymer Microspheres with Allyl Benzoate

“…The clarification of polymerization characteristics of microgel is considered to be significant because microgelation leads not only to delayed gelation, [3][4][5][6][7][8][9][10][11][12][13][14][15][16] but also to the inhomogeneity of network structures of three-dimensional crosslinked polymers as closely related to their properties. [17][18][19][20][21][22][23][24][25][26] EXPERIMENTAL ABz, supplied by Daiso Co., Ltd., as monomer was purified by vacuum distillation under nitrogen. Benzoyl peroxide (BPO) was purified by repeated precipitation from a chloroform solution with methanol.…”