Polymeric nanocomposites containing polyhedral oligomeric silsesquioxanes prepared via frontal polymerization

Frontal polymerization (FP) has been successfully applied, for the first time, to obtain polymeric nanocomposites containing polyhedral oligomeric silsesquioxanes (POSS) in an amine‐cured epoxy matrix. Variations of maximum temperature (T_max) and front velocity (V_f) have been studied. A comparison of these products with the corresponding materials, obtained by the classical batch polymerization technique, demonstrated that FP allows a higher degree of conversion than batch polymerization. The products have been characterized in terms of their thermal behavior with DSC analysis. SEM and X‐ray analyses revealed the morphology and the structures of the nanocomposites. The nanocomposites obtained by FP have the same characteristics of those synthesized, in much longer times, by batch polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4514–4521, 2007     

First solvent‐free synthesis of poly(N‐methylolacrylamide) via frontal free‐radical polymerization

We report the first synthesis of poly (N‐methylolacrylamide) (PNMA) via free‐radical frontal polymerization (FP) with solid monomers at ambient pressure. The appropriate amounts of reactants (N‐methylolacrylamide) (NMA) and initiator (ammonium persulfate) were mixed together at ambient temperature without solvent. FP was initiated by heating the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self‐propagate throughout the reaction vessel. Once initiated, no further energy was required for polymerization to occur. To suppress the fingers of molten monomer, a small amount of nanosilica was added. We also produced PNMA with dimethyl sulfoxide (DMSO) or N‐methyl‐2‐pyrrolidone, as solvent by FP, to study the macrokinetics in FP of PNMA without fillers. The front velocity and front temperature dependence on the ammonium persulfate and N‐methyl‐2‐pyrrolidone concentration were investigated. The polymer was analyzed by thermogravimetric analysis. Results show that without postpolymerization solvent removal, waste production can be reduced. Solvent‐free FP could be exploited as a means for preparation of PNMA with the potential advantage of higher throughput than solvent‐based methods. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4322–4330, 2007     

Facile synthesis of fluorescent quantum dot‐polymer nanocomposites via frontal polymerization

We report an available approach for quickly fabricating CdS QD‐polymer nanocomposites via frontal polymerization (FP). First, we synthesized (3‐mercaptopropyl)‐1‐trimethoxysilane (MPS)‐capped CdS quantum dots (QDs). With these MPS‐capped CdS QDs containing mercapto groups, MPS‐capped CdS QDs can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP. A variety of features for preparing QD‐polymer nanocomposites, such as initiator concentration and CdS concentration, were thoroughly investigated. The fluorescence properties of QD‐polymer nanocomposites prepared via FP are comparatively investigated on the basis of ultraviolet–visible (UV–vis) spectra and photoluminescence (PL) spectra. Results show that the PL intensity of QD‐polymer nanocomposites prepared via the FP method is superior to that obtained by the traditional batch polymerization (BP) method. In addition, by measuring the changes of PL intensity of the samples immersed in different concentrations of copper acetate solution, we found the QD‐polymer nanocomposites can be ultrasensitive to copper ions. This FP process can be exploited as a facile and rapid way for synthesis QD‐polymer nanocomposites on a large scale, avoiding the fluorescence quenching of nanocrystals during incorporation nanocrystals into polymer matrices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2170–2177, 2010     

Facile synthesis of amphiphilic gels by frontal free‐radical polymerization

We report a new facile strategy for quickly synthesizing poly(2‐hydroxyethyl acrylate‐co‐vinyl versatate) amphiphilic gels with excellent physicochemical properties by frontal free‐radical polymerization. The appropriate amounts of 2‐hydroxyethyl acrylate, vinyl versatate (VeoVa 9) and ammonium persulfate initiator were mixed together at ambient temperature in the presence of N‐methyl‐2‐pyrrolidone as the solvent medium. Frontal polymerization (FP) was initiated by heating the wall of the tube with a soldering iron. Once initiated, no further energy was required for the polymerization to occur. The dependence of the front velocity and front temperature on the initiator concentration was investigated. The front temperatures were between 132 and 157 °C, depending on the initiator concentration. The morphology, swelling rate, and swelling behavior of amphiphilic gels prepared via FP were comparatively investigated on the basis of scanning electron microscopy, water contact angle, and swelling measurements. Results show that the amphiphilic gels prepared via FP behave with good swelling capacity both in water and organic solvents. The FP can be exploited as an alternative means for synthesis of amphiphilic gels with additional advantages of fast and efficient way. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 823–831, 2010     

PEGDA‐based luminescent polymers prepared by frontal polymerization

Frontal polymerization (FP) of poly(ethylene glycol) diacrylate (PEGDA) was carried out using benzoyl peroxide (BPO) as radical initiator. In addition, a pyrene containing monomer, 1‐pyrenebutyl acrylate (PyBuAc), was incorporated as a fluorescent probe in order to obtain luminescent materials with different chromophore contents. The resulting polymers were characterized by FT‐IR spectroscopy in the solid state and their thermal properties were determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Moreover, the optical properties of these materials were studied by absorption and fluorescence spectroscopy. The maximum amount of the incorporated pyrene‐containing monomer into the polymer matrix was limited to 1 wt % by the polymerization process. The obtained labeled polymers poly(PEGDA‐co‐PyBuAc) exhibited a broad absorption band at 345 nm. The fluorescence spectra of these polymers exhibited mainly “monomer emission” so that no excimer emission was observed. It is possible to tune the color of the emitted light by varying the pyrene content in the samples. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2890–2897     

Preparation,Tg improvement,and thermal stability enhancement mechanism of soluble poly(methyl methacrylate) nanocomposites by incorporating octavinyl polyhedral oligomeric silsesquioxanes

The soluble poly(methyl methacrylate‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PMMA–POSS) hybrid nanocomposites with improved T_g and high thermal stability were synthesized by common free radical polymerization and characterized using FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA. The POSS contents in the nanocomposites were determined based on FTIR spectrum, revealing that it can be effectively adjusted by varying the feed ratio of POSS in the hybrid composites. On the basis of the ¹H NMR analysis, the number of the reacted vinyl groups on each POSS molecules was determined to be about 6–8. The DSC and TGA measurements indicated that the hybrid nanocomposites had higher T_g and better thermal properties than the pure PMMA homopolymer. The T_g increase mechanism was investigated using FTIR, displaying that the dipole–dipole interaction between PMMA and POSS also plays very important role to the T_g improvement besides the molecular motion hindrance from the hybrid structure. The thermal stability enhances with increase of POSS content, which is mainly attributed to the incorporation of nanoscale inorganic POSS uniformly dispersed at molecular level. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5308–5317, 2007     

Polymerization of cyclic imino ethers: From its discovery to the present state of the art

Topics concerning the cationic ring‐opening polymerization of cyclic imino ethers and functional material production based on the resulting polymers are reviewed. Cyclic imino ethers are readily subjected to isomerization polymerization via cationic initiators. Mechanistic studies have provided a new concept, electrophilic polymerization. Double isomerization polymerization and no‐catalyst alternating copolymerization are interesting examples that show characteristics of the ring opening of cyclic imino ethers. The living polymerization of these monomers affords precisely controlled polymeric materials. Through the use of the unique properties of the product polymers, various functional polymeric materials, such as polymeric nonionic surfactants, compatibilizers, hydrogels, stabilizers for dispersion polymerization, biocatalyst modifiers, and supramolecular assemblies, have been developed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 192–209, 2002     

Synthesis and self‐assembly of tadpole‐shaped organic/inorganic hybrid poly(N‐isopropylacrylamide) containing polyhedral oligomeric silsesquioxane via RAFT polymerization

Aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) was used to prepare a POSS‐containing reversible addition‐fragmentation transfer (RAFT) agent. The POSS‐containing RAFT agent was used in the RAFT polymerization of N‐isopropylacrylamide (NIPAM) to produce tadpole‐shaped organic/inorganic hybrid Poly(N‐isopropylacrylamide) (PNIPAM). The results show that the POSS‐containing RAFT agent was an effective chain transfer agent in the RAFT polymerization of NIPAM, and the polymerization kinetics were found to be pseudo‐first‐order behavior. The thermal properties of the organic/inorganic hybrid PNIPAM were also characterized by differential scanning calorimetry. The glass transition temperature (T_g) of the tadpole‐shaped inorganic/organic hybrid PNIPAM was enhanced by POSS molecule. The self‐assembly behavior of the tadpole‐shaped inorganic/organic hybrid PNIPAM was investigated by atomic force microscopy and dynamic light scattering. The results show the core‐shell nanostructured micelles with a uniform diameter. The diameter of the micelle increases with the molecular weight of the hybrid PNIPAM. Surprisingly, the micelle of the tadpole‐shaped inorganic/organic hybrid PNIPAM with low molecular weight has a much bigger and more compact core than that with high molecular weight. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7049–7061, 2008     

Organic–inorganic hybrid hydrogels involving poly(N‐isopropylacrylamide) and polyhedral oligomeric silsesquioxane: Preparation and rapid thermoresponsive properties

3‐Acryloxypropylhepta(3,3,3‐trifluoropropyl) polyhedral oligomeric silsesquioxane (POSS) was synthesized and used as a modifier to improve the thermal response rates of poly(N‐isopropylacrylamide) (PNIPAM) hydrogel. The radical copolymerization among N‐isopropylacrylamide (NIPAM), the POSS macromer and N,N′‐methylenebisacrylamide was performed to prepare the POSS‐containing PNIPAM cross‐linked networks. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) showed that the POSS‐containing PNIPAM networks displayed the enhanced glass transition temperatures (T_g's) and improved thermal stability when compared with plain PNIPAM network. The POSS‐containing PNIPAM hydrogels exhibited temperature‐responsive behavior as the plain PNIPAM hydrogels. It is noted that with the moderate contents of POSS, the POSS‐containing PNIPAM hydrogels displayed much faster response rates in terms of swelling, deswelling, and re‐swelling experiments than plain PNIPAM hydrogel. The improved thermoresponsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase‐separated morphology in the hydrogels, that is, the POSS structural units in the hybrid hydrogels were self‐assembled into the highly hydrophobic nanodomains, which behave as the microporogens and promote the contact of PNIPAM chains and water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 504–516, 2009     

Facile synthesis of N‐vinylimidazole‐based hydrogels via frontal polymerization and investigation of their performance on adsorption of copper ions

We report a new facile strategy for quickly synthesizing pH sensitive poly(VI‐co‐HEA) hydrogels (VI = N‐vinylimidazole; HEA = 2‐hydroxyethyl acrylate) by frontal polymerization. The appropriate amounts of VI, HEA, and ammonium persulfate (APS)/N,N,N′,N′‐tetramethylethylenediamine (TMEDA) couple redox initiator were mixed together at ambient temperature in the presence of glycerol as the solvent medium. Frontal polymerization (FP) was initiated by heating the upper side of the mixture with a soldering iron. Once initiated, no further energy was required for the polymerization to occur. The dependence of the front velocity and front temperature on the VI/HEA weight ratios were investigated. The pH sensitive behavior, morphology, and heavy metal removal study of poly(VI‐co‐HEA) hydrogels prepared via FP were comparatively investigated on the basis of swelling measurements, scanning electron microscopy, and inductively coupling plasma spectrometer. Results show that the poly(VI‐co‐HEA) hydrogels prepared via FP exhibit good pH sensitivity and adsorption capacity. The FP can be exploited as an alternative means for synthesis of pH sensitive hydrogels in a fast and efficient way. The as‐prepared hydrogels can be applied to remove heavy metals. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4005–4012, 2010     

Synthesis and self‐assembly of thermotropic block copolymer with long alkyl tethered cage silsesquioxane in the side chain

Thermotropic POSS‐containing poly(methacrylate) with long alkyl chain tethered polyhedral oligomeric silsesquioxane (POSS) in the side chain and the block copolymers (PMMA‐b‐PMAC11POSS) were developed by through living anionic polymerization. The resulting polymers indicated a phase transition temperature at 112 °C from spherocrystal to isotropic phase. The POSS‐containing polymer segments tended to form matrix of microphase‐separated nanostructures in the bulk even in the very low volume fraction, for instance, PMMA cylindrical nanostructure was obtained by PMMA₁₇₅‐b‐PMAC11POSS₁₁ (?_PMAC11POSS = 0.44). The control of thin film morphology was carried out by not only solvent annealing, but also thermal annealing, resulting in the formation of well‐ordered dot‐ and fingerprint‐type nanostructures. This is the first report in a series of POSS‐containing block polymers that are capable for thermal annealing to generate well‐ordered microphase‐separated nanostructures in thin films. The novel thermotropic POSS‐containing block copolymer offers a promising material for block copolymer lithography. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of semitelechelic POSS‐polymethacrylate hybrids by thiol‐mediated controlled radical polymerization with unusual thermal behaviors

We have developed an efficient and versatile method for the synthesis of polyhedral oligomeric silsesquioxanes (POSS)‐polymethacrylate hybrids, such as POSS‐poly(methyl methacrylate) (POSS‐PMMA), POSS‐poly(ethyl methacrylate) (POSS‐PEMA), and POSS‐poly(benzyl methacrylate) (POSS‐PBzMA) of controllable molecular weights and low polydispersities by thiol‐mediated radical polymerization at elevated temperature (100 °C). By tuning the reactant concentrations and degree of polymerization of the grafted polymethacrylate chains, POSS content in these hybrid materials could be varied. MALDI‐TOF‐MS analysis of the hybrid molecule shows that the nanoscale POSS moiety is connected to the end of polymethacrylate chain through the sulfur atom bridge. These hybrid materials were further characterized using various techniques such as FTIR, XRD, NMR, TGA, and DSC. In all synthesized hybrids, the incorporation of POSS moiety at the end of polymethacrylate chain resulted in the decrease of glass transition temperature (T_g) compared to that of neat polymethacrylates of comparable molecular weights. Surprisingly, POSS‐PMMA hybrids only with relatively high POSS content (～ 10 and 16 wt %) showed physical aging behavior as reveled by DSC study. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1111–1123, 2008     

Polyhedral oligomeric silsesquioxane‐based fluoroether‐containing terpolymers: Synthesis,characterization and their water and oil repellency evaluation for cotton fabric

A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS‐co‐methyl methacrylate ?co‐ 4‐vinylbenzyl fluoroether carboxylate) ( P(POSS‐MMA‐VBFC) ) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X‐ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (T_d > 250 °C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133° to 159° and from 127° to 141° respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A novel use of Ti‐POSS as initiator of L‐lactide ring‐opening polymerization

The efficacy of a metal‐silsesquioxane, namely, heptaisobutyl (isopropoxyde)titanium‐polyhedral oligomeric silsesquioxanes (Ti‐POSS), as initiator of the ring‐opening polymerization of L ‐lactide (LLA) has been assessed. Indeed, as demonstrated by proton nuclear magnetic resonance (¹H NMR) spectroscopy and gel permeation chromatography (GPC) measurements, a well‐controlled polymerization occurs via a coordination‐insertion mechanism. Moreover, the above reaction leads to the direct insertion of the silsesquioxane molecule into the polymer backbone, thus producing a hybrid system. Differential scanning calorimetry measurements demonstrated that in comparison with a commercial poly‐L ‐lactide (PLLA), the polymers prepared with Ti‐POSS exhibit a higher crystallinity. Indeed, the presence of silsesquioxane molecules, attached to one end of the polymer chains, has been found to appreciably affect the crystal nucleation density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis,Assembly, and Applications

Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high‐temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono‐functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS‐based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS‐based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.     

Rapid synthesis of poly(HPA‐co‐VeoVa 10) amphiphilic gels toward removal of toxic solvents via plasma‐ignited frontal polymerization

Atmospheric air plasma was created and applied in the frontal polymerization (FP) of fabricating poly(HPA‐co‐VeoVa 10) amphiphilic gels (HPA = 2‐hydroxypropyl acrylate, VeoVa 10 = vinyl versatate) with enhanced physicochemical properties. In plasma‐ignited frontal polymerization (PIFP), once ignited by air plasma, no further energy or treatment was required for the following polymerization. In this system, the comparison between PIFP and thermal frontal polymerization (TFP) was conducted and observed that PIFP and TFP differ considerably in terms of swelling capacity, morphology and component distribution of the products. This finding is of great importance that the simultaneous generation of active radicals in the initial stage can spread throughout reactant and anchor on the synthetic polymer with the assistance of FP. More interestingly, the PIFP‐synthesized copolymer possesses remarkable selective absorption towards organic solvents, which can be facilely manipulated by varying the weight ratios of HPA/VeoVa 10. Obviously, these polymer products could serve as an “organic solvent scavenger” in the field of industrial wastewater treatment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(N,N‐dimethylacrylamide) hydrogels obtained by frontal polymerization

Frontal polymerization (FP) has been used as an alternative technique for the preparation of poly(N,N‐dimethylacrylamide) hydrogels. Samples were synthesized in bulk, water, or dimethyl sulfoxide (DMSO), and the obtained materials were characterized and compared in terms of their yield, swelling behavior, thermal properties, and morphology. It was found that their features are dependent on the presence and type of the solvent used. Samples prepared in bulk are characterized by the lowest yields and the highest front temperatures (T_max) and velocities (V_f), whereas those synthesized in water have the highest yields and the lowest values of T_max and V_f. No significant differences have been found in terms of T_g among the three series of samples. By contrast, the reaction conditions influenced the porous morphology of the samples and, consequently, their swelling capability in water. The swelling ratio ranges from about 670–700% for some samples prepared in water up to 3500% for a sample obtained in DMSO, thus indicating that this parameter can be properly tuned by using the most suitable FP conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1422–1428, 2009     

Nanocomposites through copolymerization of a polyhedral oligomeric silsesquioxane and methyl methacrylate

The mechanical properties and thermal stability of polymers can be enhanced through the formation of nanocomposites. Nanocomposites consisting of hybrid copolymers of methacrylcyclohexyl polyhedral oligomeric silsesquioxane (POSS‐1) and methyl methacrylate (MMA) with up to 92 wt % (51 mol %) POSS‐1 and with superior thermal properties were synthesized using solution polymerization. The POSS‐1 contents of the copolymers were similar to or slightly higher than those in the feeds, the polydispersity indices were relatively low, and the degree of polymerization decreased with increasing POSS‐1 content. POSS‐1 enhanced the thermal stability, increasing the degradation temperature, reducing the mass loss, and preventing PMMA‐like degradation from propagating along the chain. The mass loss was reduced in a high POSS‐1 content copolymer since the polymerization of POSS‐1 with itself reduced sublimation. Exposure to 450 °C produced cyclohexyl‐POSS‐like remnants in the POSS‐1 monomer and in all the copolymers. The degradation of these remnants, for the copolymers and for the POSS‐1 monomer, yielded 75% SiO₂ and an oxidized carbonaceous residue. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4264–4275, 2007     

Living free‐radical polymerization (reversible addition–fragmentation chain transfer) of 6‐[4‐(4′‐methoxyphenyl)phenoxy]hexyl methacrylate: A route to architectural control of side‐chain liquid‐crystalline polymers

Side‐chain liquid‐crystalline polymers of 6‐[4‐(4′‐methoxyphenyl)phenoxy]hexyl methacrylate with controlled molecular weights and narrow polydispersities were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization with 2‐(2‐cyanopropyl) dithiobenzoate as the RAFT agent. Differential scanning calorimetry studies showed that the polymers produced via the RAFT process had a narrower thermal stability range of the liquid‐crystalline mesophase than the polymers formed via conventional free‐radical polymerization. In addition, a chain length dependence of this stability range was found. The generated RAFT polymers displayed optical textures similar to those of polymers produced via conventional free‐radical polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2949–2963, 2003     

Star‐shaped polymers having side chain poss groups for solid polymer electrolytes; synthesis,thermal behavior,dimensional stability,and ionic conductivity

A series of organic/inorganic hybrid star‐shaped polymers were synthesized by atom transfer radical polymerization using 3‐(3,5,7,9,11,13,15‐heptacyclohexyl‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxane‐1‐yl)propyl methacrylate (MA‐POSS) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomers and octakis(2‐bromo‐2‐methylpropionoxypropyldimethylsiloxy)octasilsesquioxane as an initiator. Star‐shaped polymers with methyl methacrylate (MMA) and PEGMA moieties were also prepared for comparison purposes. Dimensionally stable freestanding film could be obtained from the hybrid star‐shaped polymer containing 26 wt % of MA‐POSS moieties although its glass transition temperature is very low, ?60.9 °C. As a result, the hybrid star‐shaped polymer electrolyte containing lithium bis(trifluoromethanesulfonyl)imide showed ionic conductivities (1.75 × 10^?5 S/cm at 30 °C), which were two orders of magnitude higher than those of the star‐shaped polymer electrolyte with MMA moieties. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012