Morphology, photopolymerization

Finally, block copolymers have been made in a two-step process. First a mixture of chloroprene and -xylenebis-Ai,Ar-diethyldithiocarbamate is photopolymerized to form a dithiocarbamate terminated polymer which is then photopolymerized with styrene to give the block copolymer. The block copolymer has the expected morphology, spheres of polystyrene domains in a polychloroprene matrix (46). 

The need for increased stabilities and for controllable permeabilities and morphologies led to the development of polymerized surfactant vesicles [55, 158-161]. Vesicle-forming surfactants haw been functionalized by vinyl, methacrylate, diacetylene, isocyano, and styrene groups in their hydrocarbon chains or headgroups. Accordingly, SUVs could be polymerized in their bilayers or across their headgroups. In the latter case, either the outer or both the outer and inner surfaces could be polymerized separately (Fig. 38). Photopolymerization links both surfaces selective polymerization of the external SUV surface is accomplished by the addition of a water-soluble initiator (potassium persulfate, for example) to the vesicle solution. 

Morphological consequences of the photopolymerization of vesicles prepared from (C18H37)2N+(CH3)CH2C6H4-p-CH=CH2Cl were investigated by using pyranine [100], It was seen to bind appreciably to the surface of the vesicle. Changes in the relative intensities of neutral and anionic form fluorescence were... 

Photo-DSC on the other hand, is a much more recent technique which has been developed thanks to technological developments in thermal analysis and coupled techniques. Until very recently, it has been used mainly to study photopolymerization or photocuring reactions by measuring the heat of reaction. We proposed the use of this powerful technique to study polymer photo-aging, using the photo-DSC as an accelerated aging device and coupled in situ analysis of the modification of the morphology of the materials. In this case, the crystallizability of the polymer is used as an indicator of the structural modifications. 

It was first reported that the topochemical photopolymerization of diolefin crystals gave rise to cracks and deformation [7]. An atomic force microscopic (AFM) study made possible the observation that the photodimerizations of trans-cinnamic acids and anthracenes in the crystalline state induced surface morphological changes at the tens and hundreds of nanometers level by the transportation and rebuilding of the surface molecules [8]. The appearance of a surface relief grating on the single crystal of 4-(dimethylamino)azobenzene was demonstrated by repeated irradiation with two coherent laser beams [9]. 

A polyurethane (PU)/poly(n-butyl methacrylate) (PBMA) system has been selected for an investigation of the process of phase separation in immiscible polymer mixtures. Within this system, studies are made of the XX, lx, xl, and the 11 forms. In recognition of the incompatibility of PBMA with even the oligomeric soft segment precursor of the PU, no attempt was made to equalize the rates of formation of the component linear and network polymers. Rather, a slow PU formation process is conducted at room temperature in the presence of the PBMA precursors. At suitable times, a relatively rapid photopolymerization of the PBMA precursors is carried out in the medium of the slowly polymerizing PU. The expected result is a series of polymer mixtures essentially identical in component composition and differing experimentally only in the time between the onset of PU formation and the photoinitiation of the acrylic. This report focuses on the dynamic mechanical properties cf these materials and the morphologies seen by electron microscopy. 

A new class of liquid crystal/polymer network composite with very small amounts of polymer network (3 Wt%) is described. These composites are formed by photopolymerization of the monomers in-situ from a solution of monomer dissolved in low-molar-mass liquid crystals. Several techniques have proven useful to characterize these polymer networks. This review describes polymer network structure and its influence on electro-optic behavior of liquid crystals. Structural formation in these composites begins with the phase separation of polymer micronetworks, which aggregate initially by reaction-limited, and then by diffusion-limited modes. The morphology can be manipulated advantageously by controlling the crossover condition between such modes, the order of the monomer solution prior to photopolymerization, and the molecular structure of monomers or comonomers. 

To understand this new class of materials requires an interdisciplinary approach free-radical photopolymerization chemistry, low-molar-mass liquid crystals physics, materials science of thermosets and display technology. This short review will touch on aspects of understanding of the morphology of these polymer networks formed in liquid crystal media. 

Diara, H. Takafuji, M. Hirayama, C. O Brien, D J. Effect of photopolymerization on the morphology of heDcal supra-molecular assembUes. Langmuir 1992, 8, 1548. 

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