Synthesis, solution properties, and glass transition temperatures of polymethacrylates with alicyclylmethyl side groups

Abstract

The synthesis, solution properties, and glass transition temperatures of polymethacrylates having alicyclic rings connected to the ester linkage via methylene spacers are reported. The rings cover the range in size from cyclobutyl to cycloundecyl. An attempt was also made to prepare and study poly(cyclopropylmethy1 methacrylate), but free radical solution polymerization led to gels. Solution and thermal properties of these polymers are compared to those previously reported for polymethacrylates with both alicyclyl and n-alkyl substituents. The introduction of themethylene spacer between the ester linkage and the ring results, for small rings, in diminished characteristic ratios relative to those obtained for the alicyclyl materials. Chain flexibilities of poly(alicycly1-methyl methacrylates) are instead found to be identical to those of poly(n-alkyl methacrylates) having the same number of carbons. The glass transition temperatures of the poly(alicyclylmethy1 methacrylates) are generally intermediate to those observed for alicyclyl and n-alkyl methacrylates, but are closer to the former.

Poly(tetrahydropyranyl-2-methyl methacrylate): Comparative study in solution and at the air/water interface

“…Conformational parameters, glass transition, and/or crystallization temperatures have been reported for this type of polymers and the effect of the lateral chain on the rigidity of polymer has been studied [1][2][3][4]. However, there is no information, to our knowledge, about the behavior of this type of polymer at the air/water interface.…”

Prediction of the Glass Transition Temperature of Multicyclic and Bulky Substituted Acrylate and Methacrylate Polymers Using the Energy, Volume, Mass (EVM) QSPR Model

“…Our recent interest in the incorporation of polycyclic and bulky substituents onto polymer backbones − has led to the need for a method to estimate the effects on properties that result from these substituents (Figure ). These substituents have primarily been studied as glass transition temperature ( T g ) modifiers. − T g is known to increase with substituent size for rigid substituents, probably due to the increased barrier to rotation about the backbone bonds. Bulky and inflexible substituents lead to steric constraints that couple appreciably with the backbone to increase the dynamics constraints imposed on local segmental motion.…”

“…These substituents have primarily been studied as glass transition temperature (T g ) modifiers. [5][6][7][8][9][10][11] T g is known to increase with substituent size for rigid substituents, probably due to the increased barrier to rotation about the backbone bonds. Bulky and inflexible substituents lead to steric constraints that couple appreciably with the backbone to increase the dynamics constraints imposed on local segmental motion.…”

DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

“…Additionally, the introduction of a linear aliphatic hydrocarbon spacer between methacrylate and DOPO moieties was a structural parameter for modifying the thermal behavior as well as fire resistance of the material. Indeed on the one hand, the length of aliphatic spacer has been shown to decrease the T g of homopolymers by separating the backbone and the bulky side groups . On the other hand, an optimal number of carbon atoms has been evidenced regarding thermal stability in the case of phosphorus‐containing additives .…”