Nanosphere formation in copolymerization of methyl methacrylate with poly(ethylene glycol) macromonomers

Polymeric nanospheres consisting of poly(methyl methacrylate) (PMMA) cores and poly(ethylene glycol) (PEG) branches on their surfaces were prepared by free radical copolymerization of methyl methacrylate (MMA) with PEG macromonomers in ethanol/water mixed solvents. PEG macromonomers having a methacryloyl (MMA‐PEG) and p‐vinylbenzyl (St‐PEG) end group were used. It has become clear that the obtained polymer dispersions form three kinds of states, particle dispersion (milky solution), clear solution, and gel/precipitation. It was found that the reaction parameters such as MMA concentration, molecular weight, and concentration of PEG macromonomers, and water content can affect nanosphere formation in a copolymerization system. The water volume fraction of mixed ethanol/water solvents affected the particle size of the nanospheres. These differences in the formation of nanospheres were due to the solvophilic/solvophobic balance between the copolymers and solvents during the self‐assembling process of the copolymers. The sizes of nanospheres can be controlled by varying concentration of PEG macromonomer and water content in solvents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1811–1817, 2000     

Terpolymerization of methyl methacrylate, poly(ethylene glycol) methyl ether methacrylate or poly(ethylene glycol) ethyl ether methacrylate with methacrylic acid and sodium styrene sulfonate: determination of the reactivity ratios

Materials bearing ionic monomers were obtained through free radical terpolymerization of methyl methacrylate (MMA), poly(ethylene glycol) methyl ether methacrylate (PMEM) or poly(ethylene glycol) ethyl ether methacrylate (PEEM) with methacrylic acid (MA) and sodium styrene sulfonate (NaSS). The reactions were carried out in dimethyl sulfoxide using azobis(isobutyronitrile) as initiator. The reactivity ratios of the different couple of monomers were calculated according to the general copolymerization equation using the Finnemann-Ross, Kelen-Tüdos and Tidwell-Mortimer methods. The values of the reactivity ratios indicate that the different monomer units can be considered as randomly distributed along the chains for terpolymerizations of MMA, PMEM or PEEM with MA and NaSS. The average composition of the comonomers in the different terpolymers were calculated, showing a good agreement between the experimental and theoretical compositions. The instantaneous compositions are constant until about 70% of conversion. For higher conversions, the insertion of ionic monomers increases or decreases according to the system studied.     

Ion conductivity studies of blends of poly(methyl methacrylate)-g-poly(ethylene glycol) and poly(ethylene glycol) complexed with LiCF3 SO3

Polymer electrolytes which are adhesive, transparent, and stable to atmospheric moisture have been prepared by blending poly(methyl methacrylate)-g-poly(ethylene glycol) with poly(ethylene glycol)/LiCF₃ SO₃ complexes. The maximum ionic conductivities at room temperature were measured to be in the range of 10⁻⁴ to 10⁻⁵ s cm⁻¹. The clarity of the sample was improved as the graft degree increased for all the samples studied. The graft degree of poly(methyl methacrylate)-g-poly(ethylene glycol) was found to be important for the compatibility between the poly(methyl methacrylate) segments in poly(methyl methacrylate)-g-poly(ethylene glycol) and the added poly(ethylene glycol), and consequently, for the ion conductivity of the polymer electrolyte. These properties make them promising candidates for polymer electrolytes in electrochromic devices. © 1996 John Wiley & Sons, Inc.     

Thermoresponsive copolymers of methacrylic acid and poly(ethylene glycol) methyl ether methacrylate

Copolymers of methacrylic acid (MAA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) were prepared and their cloud points in aqueous solution were studied as a function of comonomer ratio, solution pH, and presence of hydrophobic comonomers. Under acidic conditions, the cloud point falls below 0 °C for copolymers with between 25% to 60% ether content, because of the formation of hydrophobic H‐bonded ether–acid complexes. The cloud point also decreases with solution pH. For equivalent ether to acid ratios, the cloud point decreases with decreasing PEG chain length, because of the presence of a larger number of hydrophobic methyl and methacrylate groups. Similarly, the cloud point decreases upon incorporation of hydrophobic comonomers such as butyl, lauryl, or glycidyl methacrylates. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6095–6104, 2005     

Synthesis of densely branched poly(methyl methacrylate)s via ATR copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Densely branched poly(methyl methacrylate)s have been synthesized by copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) using atom transfer free radical polymerization (ATRP). By employing the phenyl and benzyl esters of 2-bromo-2-methylpropionic acid as the initiators with 2,2-bipyridyl and Cu(I)Cl it has been possible to use high field ¹H nuclear magnetic resonance spectroscopy to evaluate in some detail the composition and structure of the branched PMMAs obtained. Parallel molar mass size exclusion chromatographic analysis using a multi-angle light scattering detector with a refractive index detector (MALS/SEC) has allowed the branched architecture of the products to be confirmed. Rather remarkably, high yields of branched PMMAs can be obtained without crosslinking using MMA/EGDMA molar feed ratios of up to 5/1 by appropriate adjustment of the molar feed of initiator. In particular by maintaining the EGDMA/initiator molar feed ratio ∼1/1 fully soluble products can be obtained that are densely branched since this feed ratio ensures that on average each living primary chain initiated contains on average only one branching EGDMA segment. As might be expected this controlled free radical process offers better control in the synthesis of branched polymer than the corresponding system we have reported using conventional free radical polymerization, and unlike the latter which requires the use of a chain transfer agent, the ATRP system requires no additional chain regulating component. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2375–2386, 2007     

Synthesis and characterization of poly(ethylene glycol) grafted poly(L-lactide)

Poly(ethylene glycol) grafted poly(L -lactide) was prepared by ring opening polymerization of L -lactide and epoxy-terminated poly(ethylene glycol) methyl ether (PEGME). Stannous octoate and Al(Et)₃·0.5 H₂O were tested as polymerization catalysts, and Al(Et)₃·0.5 H₂O was found to be more effective for the ring-opening of the epoxy group of the modified PEGME monomer. The synthesized polymers were characterized by NMR and the efficiency of the incorporation of epoxy-terminated PEGME in the copolymer was determined.     

Competition between poly(methyl methacrylate) and poly(ethylene glycol) during their interaction with poly(silicic acid) in an organic solvent

It is shown that the interpolymer complex of poly(silicic acid) and poly(ethylene glycol) formed in the organic solvent benzene is thermodynamically more stable than the corresponding complex with PMMA. Therefore, poly(silicic acid) prepared via template polycondensation conducted in the presence of poly(ethylene glycol) contains a smaller amount of defects (branches and crosslinks) than the same polymer obtained in the presence of PMMA. To provide evidence for the interaction between poly(silicic acid) and PMMA, the dynamic light-scattering method with the use of “invisible” macromolecules has been applied for the first time.     

Synthesis and characterization of poly(ethylene glycol) methyl ether endcapped poly(ethylene terephthalate)

Linear and branched poly(ethylene terephthalate) (PET) copolymers with polyethylene glycol) (PEG) methyl ether (700 or 2000 g/mol) end groups were synthesized using conventional melt polymerization. DSC analysis demonstrated that low levels of PEG end groups accelerated PET crystallization. The incorporated PEG end groups also decreased the crystallization temperature of PET dramatically, and copolymers with a high content of PEG (>17.6 wt%) were able to crystallize at room temperature. Rheological analysis demonstrated that the presence of PEG end groups effectively decreased the melt viscosities and facilitated melt processing. XPS and ATR-FTIR revealed that the PEG end groups tended to aggregate on the surface, and the surface of compression molded films containing 34.0 wt% PEG were PEG rich (85 wt% PEG). PEG end-capped PET (34.0 wt% PEG) and PET films were immersed into a fibrinogen solution (0.7 mg/mL BSA) for 72 h to investigate the propensity for protein adhesion. XPS demonstrated that the concentration of nitrogen (1.05%) on the surface of PEG endcapped PET film was statistically lower than PET (7.67%). SEM analysis was consistent with XPS results, and revealed the presence of adsorbed protein on the surface of PET films.     

On oxygen diffusion in poly(methyl methacrylate) films

ESR spectroscopy has been used to follow the kinetics of decay of radicals produced by UV-radiation in PMMA films upon exposure to oxygen in the temperature range 160-210 K. In the same films and at the same conditions, decay kinetics of phenanthrene phosphorescence has been studied at 180-220 K. Both types of the experiments give the same values for diffusion coefficients of oxygen in PMMA. Thus, from the oxygen diffusion standpoint, the sites of the radical stabilization and phenanthrene molecule localization in the polymer matrix do not differ.     

Bacterial polyesters grafted with poly(ethylene glycol): Behaviour in aqueous media

An easy method for grafting of poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate) (PHOU) was developed. Oxidation of the pendant double bonds of PHOU into carboxyl groups to yield poly(3-hydroxyoctanoate-co-3-hydroxy-9-carboxydecanoate) (PHOD) and the esterification of the carboxyl side groups with poly(ethylene glycol) (PEG) were carried out in a single reaction solution. The grafting yield is dependent on the molar mass of the PEG graft. The maximum carboxyl group conversion (52%) was obtained with PEG M_n = 350 and decreased with increasing molar mass of PEG (19% for PEG M_n = 2000). Yields were determined by ¹H and ¹³C NMR. Short PEG grafts lowered the glass transition temperature (PHOD-g-PEG 350 −57 °C) compared to PHOD (−19 °C) and PHOU (−39 °C). This effect depends on the COOH conversion and PEG chain length. Grafting enhanced the hydrophilic character of the modified polymers making them soluble in polar solvents, such as alcohols and water/acetone mixtures. PHOD-g-PEG films were more stable towards hydrolytic degradation as PHOD films. No obvious modification of films was observed after more than 200 days at pH 7.2 and 37 °C. The molar mass of the grafted polymers decreased only slightly during this period, while PHOD films were hydrolyzed into soluble fragments.     

Grafting of poly(ethylene oxide) on poly(methyl methacrylate) by transesterification

The grafting of the potassium alkoxide derivative of poly(ethylene oxide) on poly(methyl methacrylate) in homogeneous solution in toluene was studied. The alkoxide was prepared by reaction with potassium metal with methanolic potassium methoxide, or with potassium naphthalene. The last was the most suitable for the systematic investigation of the grafting process. Soluble graft polymers were formed, and essentially the initial poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) participated in the production of graft polymer. The composition of the graft polymers and the frequency of grafting of the side chains were determined by NMR. The solubility of the graft polymers in methanol and water increased with increasing PEO contents, while the melting ranges decreased. Fractionation of the crude graft polymers showed that the grafting reaction was random, and graft polymers containing one PEO side chain per about 10–170 MMA units were obtained.     

Polymer blend/organoclay nanocomposite with poly(ethylene oxide) and poly(methyl methacrylate)

A series of polymer blend/organoclay nanocomposite at a fixed blending ratio was prepared using equal ratio of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) via solvent casting method. With respect to nanoscale internal structure, we found that PMMA chains have better affinity with organoclay than PEO, based on the results from X-ray diffraction. Direct visualization via transmission electron microscopy (TEM) also supported the better affinity of PMMA with organoclay by indicating the existence of hybrid structures of mainly intercalated but with some exfoliated forms. The miscible nature of the blend and homogeneous dispersion state of layered silicate in the blend system were investigated via the microscopic fractured surface morphologies. From rheological measurements (storage and loss modulus), we discovered the role of the physical network structure between polymer and organoclay to be a main factor for the enhancement of elastic properties.     

Surface covalent encapsulation of multiwalled carbon nanotubes with poly(acryloyl chloride) grafted poly(ethylene glycol)

Multiwall carbon nanotube (MWNT) was grafted with polyacrylate‐g‐poly (ethylene glycol) via the following two steps. First, hydroxyl groups on the surface of acid‐treated MWNT reacted with linear poly(acryloyl chloride) to generate graft on MWNT; secondly, the remaining acryloyl chloride groups were subjected to esterification with poly(ethylene glycol) leading the grafted chains on the surface of MWNTs. Thus obtained grafted MWNT was characterized using Fourier transform infrared spectrometer, transmission electron microscopy, and X‐ray photoelectron spectroscopy. Thermogravimetric analysis showed that the weight fraction of grafted polymers amounted to 80% of the modified MWNT. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6880–6887, 2006     

Photopolymerization mechanisms of acrylates in poly(methyl methacrylate) films

Photoinitiation processes for photopolymer coating layers have been investigated with respect to quenching rates by a laser flash photolysis using a total reflection cell, as well as to the decomposition‐quantum yield of a sensitizer dye and a radical‐generating reagent by a gel permeative chromatographic analysis (GPC); the sensitizer dye,2‐[p‐(diethylamino)styryl]naphtho[1,2‐d]‐thiazole (DNT) and the radical‐generating reagent, 2,2′‐bis(2‐chlorophenyl)‐4,4′,5,5′‐tetraphenyl‐1,1′‐bi‐1H‐imidazole (BI). From experiments using flash photolysis, strong fluorescence was observed at excitation of 355 nm laser pulse, though no transient absorption was observed. The fluorescence was statically quenched by BI with a quenching distance, R = 11 Å. From the experiments using GPC, the high‐quantum yield of decomposition (Φ) was obtained as Φ (DNT) = 3 and Φ (BI) = 9 for DNT and BI in the presence of acrylate monomers, trimethyrolpropanetri‐acrylate (TMPTA), at 488 nm exposure of 3.36 mJ cm which was required to form a photo‐hardened image, however no decomposition of DNT and BI was detected in the absence of TMPTA. The results imply that the photoinitiator system undergoes efficient static‐dye sensitization and efficient polymerization of the acrylate monomers accompanied with the chain decomposition of DNT and BI. Copyright © 1999 John Wiley & Sons, Ltd.     

Compatibility in poly(ethylene oxide)–poly(methyl methacrylate) blends

The compatibility of poly(ethylene oxide)-poly(methyl methacrylate) (PEO-PMMA) blends were examined covering the complete composition range. Up to 20% of PEO content films were transparent and glass transition temperatures were determined by DSC and by refractive index vs. temperature measurements. Only one T_g was obtained for these samples and the relationship between T_g and composition has been evaluated. At higher PEO content crystallization took place and the films were opaque. Melting temperatuures of PEO in blends were determined by DSC. Melting point depression was observed for increasing proportion of PMMA and the binary interaction parameter has been calculated.     

Thermoresponsive oligo(ethylene glycol) methacrylate colloids with antifouling surface properties

Thermoresponsive polymeric colloids attract great attention in several biotechnological applications owing to their ability to manipulate drug release characteristics in a controlled manner. Majority of these applications utilized N‐isopropylacrylamide (NIPAM)‐based particles for controlled drug release. Despite its advantages, such as easy chemical modification and well‐documented literature, a potentially important bottleneck for NIPAM in biological applications is its tendency for nonspecific protein adsorption. Herein, we report a simple way to prepare novel thermoresponsive colloids composed of oligo(ethylene glycol) side chains via precipitation polymerization technique. In addition to displaying highly reversible thermal response, these particles also have considerably low nonspecific protein adsorption when compared with NIPAM counterparts. These crosslinked poly(ethylene glycol) ethyl ether methacrylate particles were characterized using dynamic light scattering and transmission electron microscopy. The effects of co‐monomer, crosslinker and initiator on particle characteristics were investigated. Finally, particle toxicity studies were carried out using 3T3 fibroblast cell lines in MTT cytotoxicity assay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Flow properties of poly(methyl methacrylate) solutions

Viscosity and normal stress behavior were measured for poly(methyl methacrylate) samples of various average molecular weights in diethyl phthalate solution at 30 and 60°C. All samples conformed approximately to the most probable distriution (M?_w/M?_n = 2). Concentrations ranged from 0.113 to 0.38 g/ml, and M?_w from 53,800 to 1,620,000. Despite considerable evidence in the literature of unusual linear viscoelastic behavior for this polymer, its nonlinear properties appear to be rather conventional. The viscosity–shear rate master curve was similar to that found earlier for concentrated solutions of polystyrene and poly(vinyl acetate) of comparable molecular-weight distribution. The viscosity time constant τ_o parallels τ_R, the characteristic time of the Rouse model, although the residual dependence of τ_o/τ_R on concentration and molecular weight appears to be slightly different from that for polystyrene and poly(vinyl acetate). Similar conclusions apply to the recoverable compliance J_e,^o estimated from the normal stress behavior of each solution, and its relationship to the Rouse model compliance J_R.     

Studies on copolymerization of N-isopropylacrylamide with poly(ethylene glycol) methacrylate

The paper describes the preparation and characterization of cross-linked homopolymers and copolymers of N-isopropyl acrylamide (NIPAAm) with poly(ethylene glycol) methacrylate (PEGMA, M_n = 526 g/mol). Several copolymer samples were prepared by taking varying amounts of monomers i.e. NIPAAm and PEGMA in the initial feed using hydrophilic (IRGACURE-2959) and hydrophobic (DURACURE-1173) photoinitiator. In order to investigate the effect of reaction conditions, copolymers were prepared below or above the lower critical solution temperature (LCST) using water or water:ethanol (50:50) as solvent and by varying the amounts of cross-linker. Hydrogels prepared under varying reaction conditions were characterized for its swelling behaviour (using optical microscope), phase transition temperature (using DSC) and morphology (using SEM). As expected LCST increased from 35 to 39 °C as PEGMA content in copolymers increased from 1 to 20% (w/w). However, the morphology of hydrogels was found to be independent on the reaction conditions.Copolymer films having an optimum combination of swelling and performance properties were evaluated as switchable cell culture membranes. Hepatic cancer cell lines (Hep G-2) was used to study the cell growth and detachment. Cell growth and detachment were found to be dependent on the copolymer composition. Cell viability was found comparable to trypsin which also supports application of these films as cell culture membrane.     

Thermal oxidation of blends of poly(ethylene oxide) and poly(methyl methacrylate)

Thermal oxidation of poly(ethylene oxide) (PEO) and its blends with poly(methyl methacrylate) (PMMA) were studied using oxygen uptake measurements. The rates of oxidation and maximum oxygen uptake contents were reduced as the content of PMMA was increased in the blends. The results were indicative of a stabilizing effect by PMMA on the oxidation of PEO. The oxidation reaction at 140°C was stopped at various stages and PMMA was separated from PEO and its molecular weights were measured by gel permeation chromatography (GPC). The decrease in the number-average molecular weight of PMMA was larger as the content of PEO increased in the blends. The visual appearance of the films suggested that phase separation did not occur after thermal oxidation. The activation energy for the rates of oxidation in the blends was slightly increased compared to pure PEO. © 1992 John Wiley & Sons, Inc.     

Thermoresponsive poly(poly(ethylene glycol) methylacrylate)s grafted cellulose nanocrystals through SI-ATRP polymerization

We report a series of thermoresponsive cellulose nanocrystals (CNCs) decorated with poly(poly(ethylene glycol) methylacrylate) copolymers (poly(PEGMA)-g-CNCs) synthesized by surface initiated-atom transfer radical polymerization (SI-ATRP). The chemical structures and surface morphologies were subsequently confirmed by FT-IR, XPS, and AFM measurements. With regard to thermally responsive behavior, poly(PEGMA)-g-CNCs show tunable lower critical solution temperature (LCST) values in the range of 34–66 °C by varying the feeding ratios of comonomers. The reversible morphological transformation from individual nano-rod structures to larger globule aggregates was further verified by AFM during the LCST transition. These functionalized CNCs have potential as smart film filters and biosensors.