Synthesis of Poly(decahydro-2-naphthyl methacrylate)s with Different Geometric Structures and Effects of Side-Group Dynamics on Polymer Properties Investigated by Thermal and Dynamic Mechanical Analyses and DFT Calculations

Abstract

We prepared the geometric isomers of decahydro-2-naphthols as the source materials for the synthesis of poly(decahydro-2-naphthyl methacrylate)s [poly-(DNMA)-I, -II, -III, and -IV] including alicyclic ester groups with different geometric structures. The geometry and conformational dynamics of the decahydro-2-naphthyl moieties were investigated by NMR spectroscopy and DFT calculations. We synthesized each isomer of the methacrylic monomers, polymerized them, and investigated the optical, thermal, and mechanical properties of poly(DNMA)s with different isomer compositions. The T g values of the poly-(DNMA)s were in the following order: 139.3 °C for poly(DNMA)-II < 142.7 °C for poly(DNMA)-I < 146.2 °C for poly(DNMA)-III < 152.9 °C for poly(DNMA)-III/IV. On the basis of the dynamic motion of the alicyclic substituents determined by dynamic mechanical analysis, the tan δ peaks due to the β-relaxation for the a conformation change of the side group were observed for poly(DNMA)-I, while no peak was observed for poly(DNMA)-III. The activation energies for the β-relaxation were 65 kJ/mol for poly(DNMA)-I and 56−63 kJ/mol for the poly(DNMA)s including the four isomeric ester groups with various compositions. An increase in the DNMA-II content in the repeating units accelerated a dynamic conformation change, resulting in a decrease in the tan δ peak temperature and the activation energy value, as well as the glass transition temperature of the polymers. The optical property of the resulting polymers as the transparent polymer materials was also investigated. The density, refractive index value, and Abbe number of poly(DNMA)s were 1.04−1.10 cm 3 /g, 1.489, and 42−44, respectively.

Synthesis and Characterization of Thermoresistant Maleimide Copolymers and their Crosslinked Polymers

“…Recent years, transparent polymers with a high T g and excellent properties are one of the key materials for electronic and photonic applications, and therefore, various types of polymers and their composites have been developed as highperformance transparent materials. [16,[28][29][30][31] It is noted that the radical copolymerization of the RMIs and the postpolymerization using thiol/ene reactions are useful as the method for high-performance polymer materials production. …”

Sequence-Controlled Radical Copolymerization of N-Substituted Maleimides with Olefins and Polyisobutene Macromonomers To Fabricate Thermally Stable and Transparent Maleimide Copolymers with Tunable Glass Transition Temperatures and Viscoelastic Properties

“…These values were comparable to those for a commodity transparent polymer, e.g., n D = 1.49−1.51 and ν D = 42−53 for poly(methyl methacrylate) and other polymethacrylates. 47 The poly(RMI-co-olefin)s were also revealed to have an optical property superior to that for the previously reported poly(RMI-alt-styrene)s and poly(RMI-altBCm)s (n D = 1.53−1.56 and ν D = 38−44). 39,40 The wavelength dispersion of the refractive indicies (n λ ) is shown in Figure 8 with a fitted curve using the simplified Cauchy's formula (eq 20).…”

“…39,40 The wavelength dispersion of the refractive indicies (n λ ) is shown in Figure 8 with a fitted curve using the simplified Cauchy's formula (eq 20). 21,47 The estimated refractive index at the infinite wavelength (n ∞ ) and the dispersion coefficient (D) are listed in Table 6. The larger the N-substituents of the RMIs and the α-substituents of the olefins, the lower the n D values of the copolymers.…”

Synthesis and thermal, optical, and mechanical properties of sequence-controlled poly(1-adamantyl acrylate)-block-poly(n-butyl acrylate) containing polar side group

“…The copolymers were soluble in organic solvents, such as toluene, chloroform, 1,2‐dichloroethane, and THF, and the transparent films were obtained by casting the solutions. The block copolymers were highly transparent as well as PAdA and the other polymethacrylates including PMMA and poly(1‐adamantyl methacrylate) . The transmittance of visible light (at 380 nm) was more than 90% for the block copolymers.…”