Hybrid free radical/cationic frontal photopolymerizations

The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

Hydrogel‐like elastic membrane consisting of semi‐interpenetrating polymer networks based on a phosphorylcholine polymer and a segmented polyurethane

To obtain a hydrogel‐like elastic membrane, we prepared semi‐interpenetrating polymer networks (IPNs) by the radical polymerization of methacrylates such as 2‐methacryloyloxyethyl phosphorylcholine (MPC), 2‐hydroxyethylmethacrylate, and triethyleneglycol dimethacrylate diffused into segmented polyurethane (SPU) membranes swollen with a monomer mixture. The values of Young's modulus for the hydrated semi‐IPN membranes were less than that for an SPU membrane because of higher hydration, but they were much higher than that for a hydrated MPC polymer gel (non‐SPU). According to a thermal analysis, the MPC polymer influenced the segment association of SPU. The diffusion coefficient of 8‐anilino‐1‐naphthalenesulfonic acid sodium salt from the semi‐IPN membrane could be controlled with different MPC unit concentrations in the membrane, and it was about 7 × 10² times higher than that of the SPU membrane. Fibroblast cell adhesion on the semi‐IPN membrane was effectively reduced by the MPC units. We concluded that semi‐IPNs composed of the MPC polymer and SPU may be novel polymer materials possessing attractive mechanical, diffusive‐release, and nonbiofouling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 68–75, 2003     

Interpenetrating polymer networks of poly(dimethyl siloxane–urethane) and poly(methyl methacrylate)

Simultaneous IPNs of poly(dimethyl siloxane-urethane) (PDMSU)/poly(methyl methacrylate) (PMMA) and related isomers have been prepared by using new oligomers of bis(β-hydroxyethoxymethyl)poly(dimethyl siloxane)s (PDMS diols) and new crosslinkers biuret triisocyanate (BTI) and tris(β-hydroxylethoxymethyl dimethylsiloxy) phenylsilane (Si-triol). Their phase morphology have been characterized by DSC and SEM. The SEM phase domain size is decreased by increasing crosslink density of the PDMSU network. A single phase IPN of PDMSU/PMMA can be made at an M_c = 1000 and 80 wt % of PDMSU. All of the pseudo- or semi-IPNs and blends of PDMSU and PMMA were phase separated with phase domain sizes ranging from 0.2 to several micrometers. The full IPNs of PDMSU/PMMA have better thermal resistance compared to the blends of linear PDMSU and linear PMMA. © 1993 John Wiley & Sons, Inc.     

Optically clear simulataneous interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and epoxy. II. Kinetic study

Simultaneous interpenetrating polymer networks (SINs) based on diglycidyl ether of bis-phenol A (DGEBA) and poly(ethylene glycol) diacrylate (PEGDA) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using benzoyl peroxide (BPO) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 45, 55, 63, and 70°C. Concentration changes for both the epoxide and C?C bond were monitored with FTIR. A rate expression for DGEBA cure kinetics was established with a model reaction of phenyl glycidyl ether (PGE) and benzylamine. Experimental results revealed that lower rate constants and higher activation energy for the SIN were found, compared with those for the constituent DGEBA and PEGDA network formation. A model of network interlock was proposed to account for this phenomenon. During simultaneous cure of DGEBA and PEGDA, the interlock (mutual entanglement) between DGEBA and PEGDA networks provided a sterically hindered environment, which subsequently increased the activation energy and reduced cure rates for both DGEBA and PEGDA. © 1993 John Wiley & Sons, Inc.     

Interpenetrating polymer networks of poly(carbonate-urethane) and polyvinyl pyridine

Simultaneous interpenetrating polymer networks (IPN's), pseudo IPN's, and liner blends of aliphatic poly(carbonate-urethane) (PCU) and polyvinyl pyridine (PVP) have been prepared and characterized by DSC, DMA, and TEM. The full IPN's of PCU and PVP had a single phase morphology only above 50 wt % PCU, as determined by both DSC and DMA and confirmed by transmission electron microscopy (TEM). However, in both pseudo IPN's of PCU and PVP and in their linear blends there exist multiple glass transitions and melting points seen by DSC and DMA indicating phase incompatibility. The full IPN's exhibited superior ultimate mechanical properties and solvent resistance as compared to the pseudo IPN's, liner blends, and the pure crosslinked PCU and PVP networks.     

Complex new materials from simple chemistry: Combining an amino‐substituted polysiloxane and carboxylic acids

Changes in rheological, adhesive, and swelling properties of quaternary salts, made by adding one of eight mono‐ or six α,ω‐alkanedioic acids (the latter with two to six or nine carbon atoms) to 6‐7PSil (a polysiloxane with 6%–7% of the monomer units contain a 3‐aminopropyl group) have been correlated with the salt structures. The simple acid‐base chemistry initiates drastic changes in the bulk properties of the materials that depend on the amount and type of the added acid. Thus, the quaternized forms of the 6‐7PSil have significantly enhanced viscoelastic and adhesive properties compared to those of the initial polysiloxane, and they can swell selectively liquids based on their polarity. Also, interpenetrating networks have been made in situ by photopolymerization of salts with vinylic carboxylic acids. DFT calculations on model systems consisting of dimethylammonium α,ω‐alkanedioate salts with two to six carbon atoms provide insights into the interactions responsible for the unexpected dependence of the properties of the 6‐7PSil salts on the chain lengths of the diacids. The potential for applying the methodologies described here to systems with other amino‐substituted polymers and other acid types is noted. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3851–3861     

Morphological study of an intrinsically stretchable photovoltaic bulk heterojunction

Thin‐film polymer solar cell consisting of [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) and poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7) demonstrates elastic stretchability with the aid of a high boiling point additive, 1,8‐diiodooctane (DIO). The usage of DIO not only helps to form uniformly distributed nanocrystalline grains, but may also create free volumes between the nano‐grains that allow for relative sliding between the nano‐grains. The relative sliding can accommodate large external deformation. Large dichroic ratios of the optical absorption of both PC₇₁BM and PTB7 were observed under large‐strain deformation, indicating reorientation of the nanocrystalline PC₇₁BM and PTB7 polymer chains along stretching direction. The dichroic ratio decreases to nearly 1.0 as the blend was relaxed to 0% strain. Therefore, the nanometer‐size grain blending morphology provides an approach to impart stretchability to organic semiconductors that are otherwise un‐stretchable. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 814–820     

Side chain engineering of naphthalene diimide–bithiophene‐based polymer acceptors in all‐polymer solar cells

Two novel polymeric acceptors based on naphthalene diimide (NDI) and 2.2′‐bithiophene, named as P(NDI2THD‐T2) and P(NDI2TOD‐T2), were designed and synthesized for all polymer solar cells application. The structural and electronic properties of the two acceptors were modulated through side‐chain engineering of the NDI units. The optoelectronic properties of the polymers and the morphologies of the blend films composed of the polymer acceptors and a donor polymer PTB7‐Th were systemically investigated. With thiophene groups introduced into the side chains of the NDI units, both polymers showed wider absorption from 350 nm to 900 nm, compared with the reference polymer acceptor of N2200. No redshift of absorption spectra from solutions to films indicated reduced aggregation of the polymers due to the steric hindrance effect of thiophene rings in the side chains. The photovoltaic performance were characterized for devices in a configuration of ITO/PEDOT:PSS/PTB7‐Th:acceptors/2,9‐bis(3‐(dimethylamino)propyl)anthra[2,1,9‐def:6,5,10‐def]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDIN)/Al. With the addition of diphenyl ether as an additive, the power conversion efficiencies (PCEs) of 2.73% and 4.75% for P(NDI2THD‐T2) and P(NDI2TOD‐T2) based devices were achieved, respectively. The latter showed improved J_sc, Fill Factor (FF), and PCE compared with N2200 based devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3679–3689     

Mechanical,Thermal and Morphological Behaviors of Castor Oil Based PU/PS Interpenetrating Polymer Network-Metakaolin Composites

The meta kaolin (MK) clay particulate filler with different weight ratios viz., 0, 5, 10, 20 and 30 wt% were incorporated into castable polyurethane (PU)/polystyrene (PS) (90/10) interpenetrating polymer network (IPN). The effects of MK particulate filler loading on the mechanical and thermal properties of PU/PS (90/10) IPN composites have been studied. From the tensile behavior, it was noticed that a significant improvement in tensile strength and tensile modulus as an increase in MK filler content. Thermogravimetric analysis (TGA) data reveals the marginal improvement in thermal stability after incorporation of MK filler. TGA studies of the IPN composites have been performed in order to establish the thermal stability and their mode of thermal degradation. It was found that degradation of all composites takes place in two steps. Degradation kinetic parameters were obtained for the composites using three mathematical models. Tensile fractured composite specimens were used to analyze the morphology of the composites by scanning electron microscopic (SEM) technique.