Colloidal crystal assembly film was prepared by using monodispersed colloidal particles of cross-linked random copolymer of methyl methacrylate and ethyl acrylate prepared by soap-free emulsion polymerization. The colloidal crystal film exhibited structural color when swollen with ethyl acrylate monomer. The structural color was maintained even after polymerization of the swelling monomer and cross-linker, suggesting the colloidal crystalline order was successfully fixed and embedded in the matrix of poly(ethyl acrylate) elastomer. Stretching deformation of the structural colored elastomer induced a sensitive change to shorter wavelength color. Peak wavelength of the UV-vis absorption spectrum of the stretched elastomer revealed an excellent proportional relationship with film thickness. In the swollen colloidal crystal film, ethyl acrylate was absorbed in the colloidal particle; therefore, poly(ethyl acrylate) chain should be penetrating into the colloidal particle after the polymerization of the matrix elastomer. This interpenetrated polymer network structure was considered to be effective for the rubber-like elasticity and sensitive strain-responsive color-changing phenomena of the structural colored elastomer.
Graft copolymers consisting of amorphous main chain, poly(methyl methacrylate) (PMMA), or poly(methyl acrylate) (PMAc), and crystalline side chains, poly(ethylene glycol) (PEG), have been prepared by copolymerization of PEG macromonomers with methyl methacrylate or methyl acrylate (MMAx or MACx, respectively). Because of the compatibility of PMMA/PEG and PMAc/PEG, from small-angle X-ray scattering results, the main and side chains in graft copolymers were suggested to be homogeneous in the molten state. Differential scanning calorimetry (DSC) cooling scans revealed that PEG side chains for graft copolymers with large PEG fractions were crystallized when the sample was cooled, with a cooling rate of 10°C/min. The spherulite pattern observed by a polarized optical microscope suggested the growth of PEG crystalline lamellae. Crystallization of PEG in MMAx was more restrained than in MACx. From these results, we have concluded that the crystallization behavior of the grafted side chains is strongly influenced by the glass transition of a homogeneously molten sample as well as dilution of the crystallizable chains. Domain spacings for isothermally crystallized graft copolymers were described by interdigitating chain packing in crystalline-amorphous lamellar structure.
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