Development of highly ionic conductive cellulose acetate-g-poly (2-acrylamido-2-methylpropane sulfonic acid-co-methyl methacrylate) graft copolymer membranes

A novel cellulose acetate-g-poly (2-acrylamido-2-methylpropane sulfonic acid-co- methyl methacrylate) copolymer was prepared via free radical polymerization for the first time. The chemical structure of the graft copolymer was confirmed using FT-IR, ¹H NMR and EDX. The TGA and DSC investigated the thermal changes. Factors affecting the grafting process were studied and various grafting characteristic parameters such as grafting efficiency (%), grafting yield (%) and add-on value (%) were determined. Flexible membranes based on different graft copolymer compositions were fabricated by simple solution casting. Physicochemical properties including ion exchange capability (IEC), water uptake (WU) and proton conductivity (σ) were evaluated. These membranes demonstrated higher IEC, WU and conductivity than the pristine CA. The maximum proton conductivity of the CA-g-poly (2-acrylamido-2-methylpropane sulfonic acid-co- methyl methacrylate) copolymer membrane (68%; Add-on %) was found to be 6.44 × 10⁻³ S/cm compared with 0.035 × 10⁻³ S/cm of the pristine CA. Thus, the appropriate graft copolymer composition will allow fine-tuning of the physical characteristics and led to several potential applications, such as polyelectrolyte fuel cells membranes or biodiesel production.     

Synthesis of Poly(ϵ-caprolactone) Grafted Poly(2-hydroxyethyl methacrylate) Functionalized Hydroxyapatite by RAFT and ROP

Poly(?-caprolactone) grafted poly(2-hydroxyethyl methacrylate) functionalized hydroxyapatite (HAP@PHEMA-g-PCL) nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). The RAFT agent was anchored on the surface of hydroxyapatite nanocrystals (HAPs) through the silane condensation process of 3-chloropropyltrimethoxysilane followed by reaction with potassium xanthogenate. Poly(2-hydroxyethyl methacrylate) (PHEMA) was covalently functionalized on the surface of HAPs by RAFT polymerization. Then, poly(?-caprolactone) (PCL) was grafted on HAPs by ROP based on the hydroxyl groups of PHEMA to afford HAP@PHEMA-g-PCL. The structure and composition of HAP@PHEMA-g-PCL nanocomposites were characterized by FT-IR, XRD, and TGA analyses. The morphology and formation of the polymer encapsulating HAPs were demonstrated from SEM and TEM images, while the ¹H MNR analysis of the cleaved PHEMA-g-PCL confirmed the grafting.     

Steric effects upon transition states of radical addition polymerizations

Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (E_as) show good correlations with experimental values. Calculated activation entropies (−ΔS^‡s) are found to be well proportional to E_as. The entropy terms play an important role as well as E_a in radical additions. E_a depends on the angle (θ_rs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc.     

Reactive polymers incorporating silyl enol ether groups. I. synthesis by radical polymerization of 2-(trimethylsiloxy)-butadiene and 2-(tert)-butyldimethylsiloxy butadiene

2-(Trimethylsiloxy)butadiene (TMSBD) and 2-(tert-butyldimethylsiloxy)butadiene (TBMSBD) were copolymerized with styrene (St) and methyl methacrylate (MMA) under free-radical conditions. The obtained polymers were found to contain reactive silyl enol ether groups in a ratio identical to the TMSBD or TBMSBD molar fraction in the copolymer. All investigated samples displayed only 1,4- and 3,4-microstructures. The influence of several experimental factors on the yields, rates of polymerization, microstructures, and copolymer compositions were examined. Monomer reactivity ratios r₁ and r₂ at 60°C were determined from copolymer composition curves at low conversions. The homopolymerization of TBMSBD was also investigated and results were compared with those previously obtained for TMSBD. A slight increase in rates was observed and was rationalized on the basis of the higher viscosity resulting from the structural change in the monomer. Thermal stabilities of the synthesized polymers were investigated by TGA and their glass transition temperatures were determined by DSC. All measurements are compatible with a possible use of TMSBD and TBMSBD copolymers as reactive polymers. © 1996 John Wiley & Sons, Inc.     

Swelling behavior, mechanical properties and network parameters of pH- and temperature-sensitive hydrogels of poly((2-dimethyl amino) ethyl methacrylate-co-butyl methacrylate)

In this study, swelling behavior and mechanical properties of polyelectrolyte cationic hydrogels of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA), and poly((2-dimethylamino) ethyl methacrylate-co-butyl methacrylate) (P(DMAEMA-co-BMA)), were investigated. Hydrogels were prepared by free-radical solution copolymerization of DMAEMA and BMA using ethylene glycol dimethacrylate (EGDMA) as the crosslinking agent. Compression-strain measurements were used to analyze the mechanical properties of the hydrogels. It was found that increasing the amount of BMA comonomer in the gel structure increases the compression modulus of the material. The results of mechanical measurements were used to characterize the network structure of the hydrogels, namely the effective crosslinking density (. It was found that exceeds the theoretical crosslinking density (ν_t) calculated from the initial amount of EGDMA used for hydrogel synthesis. These hydrogels demonstrated dual sensitivity to both pH and temperature. It was shown that the pH-sensitive or temperature-sensitive phase transition behavior of the gels can be changed by changing the temperature or pH of the swelling medium at constant hydrogel composition. Increasing the temperature decreased the transition pH of the pH-sensitive phase transition. On the other hand, increasing the pH of the surrounding medium decreased the transition temperature of the temperature-sensitive phase transition. Incorporation of BMA in the gel structure has a significant effect on the transition point of the gel. Increasing the BMA content reduced the transition pH and temperature of the pH- and temperature-sensitive phase transition, respectively. The similar effect of increasing temperature or BMA content can be explained by the role of hydrophobicity in the phase transition behavior of hydrogels. Finally, the results of equilibrium swelling and compression-strain measurements were used to calculate the polymer-solvent interaction parameters of these hydrogels using the Flory-Rehner equation of equilibrium swelling.     

Photopolymerization of enzymatically synthesized methacrylated poly(caprolactone) with poly(ethylene glycol) macromonomer

Polycaprolactone (PCL) based α,ω-methacrylated macromonomer (DMPCL) was synthesized via enzymatic ring-opening polymerization (eROP) by using Novozyme 435 as the enzyme immobilized catalyst. DMPCL was further photopolymerized with monofunctional poly(ethylene glycol) methyl ether methacrylate (PEGMA-950) macromonomer and trimethylolpropane triacrylate (TMPTA) as tri-functionalized crosslinking agent in glass vials when CHCl₃ was the solvent and Irgacure 819 was the photoinitiator. Ultraviolet (UV) Light Emitting Diode (LED) bulbs enabled photoinduced reactions at room temperature with low heat generation and high reaction efficiency. The obtained gels were characterized with Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC). DMPCL participated as an effective crosslinking agent in the photopolymerization of PEGMA-950. Combined usage of DMPCL and PEGMA-950 resulted in significantly more effective polymerization than the separate photopolymerizations of these macromonomers.     

Photoinitiated polymerization of methacrylates comprising phenyl moieties

Investigation of photopolymerization kinetics of 4-(4-methacryloyloxyphenyl)-butan-2-one (1) in comparison with 2-phenoxyethyl methacrylate (2) and phenyl methacrylate (3) using a UV-LED emitting at 395 nm shows significantly faster polymerization of 1 compared to both 2 and 3 at 40°C. Vitrification affects photopolymerization kinetics of all methacrylates under investigation. Interestingly, quantitative final conversion is observed during photoinitiated polymerization of 1 and 2 whereas 3 shows limited conversion at about 80%. Furthermore, higher degree of polymerization is obtained by photoinitiated polymerization of 1 compared to 2 and 3. This shows that the 3-oxobutyl substituent at the phenyl ring of 1 significantly affects both polymerization kinetics and final conversion of the photoinitiated polymerization. Moreover, an additional higher molecular weight fraction is observed in case of polymerization of 1 at 85°C that is above the glass transition temperature of the polymer formed during photoinitiated polymerization. As a thermal polymerization at 85°C in the absence of light results in a high molecular weight polymer as well, an additional thermal process may be discussed as reason for the higher molecular weight polymer fraction in case of the photopolymer made at 85°C.     

Novel study on the liquid crystalline behavior of poly(methacrylate)s with biphenyl side groups

We report the synthesis and characterization of a series of liquid crystalline polymers substituted with the 4′-methoxybiphenyl-4-yloxy group. The spacer length is varied from 4–8 methylene units. The materials are characterized by polarized light microscopy, differential scanning calorimetry, and X-ray analysis. All homologues show highly ordered phases. Additionally, the butylene polymer shows a broad nematic mesophase. For the first time, the narrow nematic phase of the hexylene homologue could be confirmed experimentally. X-ray analysis of the polymers made exact assignments of the low temperature phases possible, thus giving access to the analysis of the arrangement of the mesogenes within the layers. The pentylene homologue shows a distinct deviation from the behavior of the other polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2669–2679, 1998     

Chemical surface modifications of microfibrillated cellulose

Microfibrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization. The surface of the MFC was modified using different chemical treatments, using reactions both in aqueous- and organic solvents. The modified MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium (IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate, followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC surface as a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC.