Hydrogels for biomedical applications.

The use of photoinitiated polymerization is continuously growing in industry as reflected by the large number of applications in not only conventional areas such as coatings, inks, and adhesives but also high-tech domains, optoelectronics, laser imaging, stereolithography, and nanotechnology. In this Perspective, the latest developments in photoinitiating systems for free radical and cationic polymerizations are presented. The potential use of photochemical methods for step-growth polymerization is also highlighted. The goal is, furthermore, to show approaches to overcome problems associated with the efficiency, wavelength flexibility, and environmental and safety issues in all photoinitiating systems for different modes of activation. Much progress has been made in the past 10 years in the preparation of complex and nano-structured macromolecules by using photoinitiated polymerizations. Thus, the new and emerging applications of photoinitiated polymerizations in the field of biomaterials, surface modific...

Photoinitiated Polymerization: Advances, Challenges, and Opportunities

Photochemical reactions, particularly those involving photoinduced electron transfer processes, establish a substantial contribution to the modern synthetic chemistry, and the polymer community has been increasingly interested in exploiting and developing novel photochemical strategies. These reactions are efficiently utilized in almost every aspect of macromolecular architecture synthesis, involving initiation, control of the reaction kinetics and molecular structures, functionalization, and decoration, etc. Merging with polymerization techniques, photochemistry has opened up new intriguing and powerful avenues for macromolecular synthesis. Construction of various polymers with incredibly complex structures and specific control over the chain topology, as well as providing the opportunity to manipulate the reaction course through spatiotemporal control, are one of the unique abilities of such photochemical reactions. This review paper provides a comprehensive account of the fundamentals and applications ...

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Polymer modified clay minerals: A review

We have studied the morphology of blends of PS/PMMA, PC/SAN24, and PMMA/EVA and compared the morphologies with and without modified organoclay Cloisite 20A or Cloisite 6A clays. In each case we found a large reduction in domains size and the localization of the clay platelets along the interfaces of the components. The increased miscibility was accompanied in some cases, with the reduction of the system from multiple values of the glass transition temperatures to one. In addition, the modulus of all the systems increased significantly. A model was proposed where it was proposed that in-situ grafts were forming on the clay surfaces during blending and the grafts then had to be localized at the interfaces. This blending mechanism reflects the composition of the blend and is fairly nonspecific. As a result, this may be a promising technology for use in processing recycled blends where the composition is often uncertain and price is of general concern.

Compatibilizing Bulk Polymer Blends by Using Organoclays

In situ synthesis of poly(methyl methacrylate) (PMMA) nanocomposites by photopolymerization using organophilic montmorillonite (MMT) as the layered clay is reported. MMT clay was ion exchanged with N-phenacyl, N,N-dimethylanilinium hexafluoro phosphate (PDA) which acts as both suitable intercalant- and photo-initiator. These modified clays were then dispersed in methyl methacrylate (MMA) monomer in different loading degrees to carry out the in situ photopolymerization. Intercalation ability of the photoinitiator and exfoliated nanocomposite structure were evidenced by both X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.

Clay-PMMA nanocomposites by photoinitiated radical polymerization using intercalated phenacyl pyridinium salt initiators

A series of polyacrylamide nanocomposite hydrogels were synthesized by in situ free radical polymerization of acrylamide (AAm) with ethylene glycol dimethacrylate (EGDMA) as a crosslinker in the presence of sodium montmorillonite (NaMMT) and organically modified montmorillonite (OrgMMT) clays. Modification of MMT was carried out with a quaternary salt of coco amine as intercalant having a styryl group whose contribution to both polymerization and crosslinking reactions via its reactive double bond was confirmed by solid state NMR. Exfoliation success was checked with X-ray diffraction (XRD) and atomic force microscopy (AFM) techniques whereas mechanical performance was followed with uniaxial compression experiment. It has been found that exfoliated PAAm nanocomposites having 0.5% OrgMMT had both the maximum equilibrium swelling in water and compression strength as well as improved thermal stability due to the special and beneficial morphology observed via scanning electron microscopy (SEM).

High strength poly(acrylamide)-clay hydrogels

Uncured and cured state properties of fly ash filled unsaturated polyester composites

Polymeric nanocomposites were synthesized from functionalized soybean-oil-based polymer matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Acrylated epoxidized soybean oil combined with styrene was used as the monomer. Organophilic MMT (OrgMMT) was obtained using a quaternized derivative of methyl oleate, which was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized using X-ray diffraction and atomic force microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated using thermogravimetric analysis and dynamic mechanical analysis. It was found that the desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt%, whereas a partially exfoliated or intercalated nanocomposite was obtained for 3 wt% loading. All the nanocomposites were found to have improved thermal and mechanical properties as compared with virgin acrylated epoxidized soybean-oil-based polymer matrix. The nanocomposite containing 2 wt% OrgMMT clay was found to have the highest thermal stability and best dynamic mechanical performance. Copyright © 2010 Society of Chemical Industry

Synthesis of bio‐based polymeric nanocomposites from acrylated epoxidized soybean oil and montmorillonite clay in the presence of a bio‐based intercalant

Sinan Şen

Papers

Clay-PMMA nanocomposites by photoinitiated radical polymerization using intercalated phenacyl pyridinium salt initiators

High strength poly(acrylamide)-clay hydrogels

Uncured and cured state properties of fly ash filled unsaturated polyester composites

Synthesis of bio‐based polymeric nanocomposites from acrylated epoxidized soybean oil and montmorillonite clay in the presence of a bio‐based intercalant

Tuning of final performances of unsaturated polyester composites with inorganic microsphere/platelet hybrid reinforcers