Counterion association to cationic polyelectrolytes in methanol/water mixtures

The effect of the nature of the medium on the chloride and bromide condensation to a cationic polyelectrolyte was studied. Methanol/water mixtures were used as solvent in order to vary continuously the properties of the medium. The counterion–polyion interaction was studied by the determination of the Eisenberg interaction parameter (f^*) by means of electrical conductivity measurements. Results indicate that f^* parameters increase while the limiting electrical conductivity is rapidly decreasing. This apparently anomalous phenomenon is interpreted as a preferential solvation of the polyelectrolyte which brings about a conformational change, as revealed by the intrinsic viscosity behavior of the solutions. This change could induce an increase in the average distance between charges without further dissociation, which could explain the observed behavior of the f^* parameter. It is concluded that the actual dielectric constant which governs the polyion–counterion interaction in the polyelectrolyte domain is not the bulk dielectric constant.     

Sulfonated N‐Heterocyclic Carbenes for Pd‐Catalyzed Sonogashira and Suzuki–Miyaura Coupling in Aqueous Solvents

The reactions of the N,N′‐diarylimidazolium and N,N′‐diarylimidazolinium salts with chlorosulfonic acid result in the formation of the respective disulfonated N‐heterocyclic carbene (NHC) precursors in reasonable yields (46–77%). Water‐soluble palladium catalyst complexes, in situ obtained from the respective sulfonated imidazolinium salt, sodium tetrachloropalladate (Na₂PdCl₄) and potassium hydroxide (KOH) in water, were successfully applied in the copper‐free Sonogashira coupling reaction in isopropyl alcohol/water mixtures using 0.2 mol% catalyst loading. The preformed (disulfonatedNHC)PdCl(cinnamyl) complex was used in aqueous Suzuki–Miyaura reactions at 0.1 mol% catalyst loading. The coupling protocol reported here is very useful for Sonogashira reactions of N‐ and S‐heterocyclic aryl bromides and chlorides with aryl‐ and alkylacetylenes.     

Effective biosynthesis of poly(3‐hydoxy‐ butyrate‐co‐4‐hydroxybutyrate) with high 4‐hydroxybutyrate fractions by Wautersia eutropha in the presence of α‐amino acids

BACKGROUND: Biopolymers produced by microbes are in demand as their biodegradable and biocompatible properties make them suitable for disposable products and for potential use as biomaterials for medical applications. The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate(4HB) with high molar fractions of 4HB unit by a wild‐type Wautersia eutropha H16 was investigated in culture media containing 4‐hydroxybutyric acid (4HBA) and different carbon substrates in the presence of various α‐amino acids. RESULTS: The addition of carbon sources such as glucose, fructose and acetic acid to the culture medium containing 4HBA in the presence of α‐amino acids resulted in the production of random poly(3HB‐co‐4HB) with compositions of up to 77 mol% 4HB unit, but the yields of copolyesters with 60–77 mol% 4HB units were less than 15 wt% of dried cell weights. In contrast, when carbon sources such as propionic acid and butyric acid were used as the co‐substrates of 4HBA in the presence of α‐amino acids, poly(3HB‐co‐4HB) copolyesters with compositions of 72–86 mol% 4HB were produced at maximally 47.2 wt% of dried cell weight (11.3 g L^?1) and the molar conversion yield of 4HBA to 4HB fraction in copolyesters was as high as 31.4 mol%. Further, poly(3HB‐co‐4HB) copolyesters with compositions of 93–96 mol% 4HB were isolated at up to 35.2 wt% of dried cell weights by fractionation of the above copolymers with chloroform/n‐hexane. CONCLUSION: The productivity of copolyesters with over 80 mol% 4HB fractions was as high as 0.146 g L^?1 h^?1 (3.51 g L^?1 for 24 h) by flask batch cultivation. Copyright © 2007 Society of Chemical Industry     

Synthesis and chiroptical properties of liquid crystalline copolymers containing azobenzene chromophores

A series of new liquid crystalline copolymers, poly[((S)‐2‐methyl‐1‐butyl methacrylate)‐co‐(6‐(4‐(4‐cyanophenylazo)phenoxy)hexyl methacrylate)], with different contents of chiral units of 17, 36, 54 and 78 mol% were synthesized. The structures and properties of the copolymers were characterized and evaluated using infrared, ¹H NMR and UV spectroscopy, differential scanning calorimetry, gel permeation chromatography and circular dichroism (CD). The CD results suggested that absorptions of azobenzene chromophores were observed in films of copolymer containing 17, 36 or 54 mol% chiral units, but not in the film of copolymer containing 78 mol% chiral units. Also, CD values of the copolymeric films decreased with increasing chiral content. After irradiation with linear polarized light at 442 nm, CD values were changed in all the copolymeric films, and the CD values increased with decreasing chiral content in a nonlinear way, while the photoinduced change of chirality of the copolymers increased in a linear way with decreasing chiral content. The results are discussed in terms of interactions between structures and chiroptical properties. Copyright © 2007 Society of Chemical Industry     

Boiling points of the propylene glycol + glycerol system at 1 atmosphere pressure: 188.6–292 °C without and with added water or nicotine

Abstract

In electronic cigarettes (“electronic nicotine delivery systems”, ENDS), mixtures of propylene glycol (PG) and/or glycerol (GL; aka “vegetable glycerin”, VG) with nicotine are vaporized to create a nicotine-containing aerosol. For a given composition, the temperature required to boil the liquid at 1 atmosphere must be at least somewhat greater than the boiling point (BP). The use of ENDS is increasing rapidly worldwide, yet the BP characteristics of the PG?+?GL system have been characterized as the mixtures; here we re-do this, but significantly, also study the effects of added water and nicotine. BP values at 1 atmosphere pressure were measured over the full binary composition range. Fits based on the Gibbs–Konovalov theorem provide BP as a function of composition (by mole-percent, by weight-percent, and by volume-percent). BPs of PG?+?GL mixtures were then tested in the presence of additives such as water (2.5 and 5?mol% added) and nicotine (3?mol%). Water was found to decrease the BP of PG?+?GL mixtures significantly at all compositions tested, and nicotine was found to decrease the BP of PG?+?GL mixtures containing ～75 GL: 25?PG (by moles) or more. The effect of added water (5, 10, and 15?mol% added) on electronic cigarette degradation production (some aldehydes and formaldehyde hemiacetals) was examined and found to have no significant impact on solvent (PG or GL) degradation for the particular device used.     

Solvent engineering applied to lipase-catalyzed glycerolysis of triolein

Solvent engineering was applied to lipase-catalyzed glycerolysis of triolein for the selective synthesis of monoolein and diolein. The effect of different binary mixtures of n-hexane and 2-methyl-2-butanol (2M2B) on the selective production of mono- or diacylglyceride was established. Conditions for high selectivity toward monoolein synthesis were enhanced from 10.6 mol% in pure n-hexane to 64 mol% in 2M2B. On the contrary, the highest production of diolein, corresponding to 62 mol%, was achieved in n-hexane. Concerning triolein conversion, the best results were obtained in 100% 2M2B, with a conversion of 75%. The effect of the n-hexane/2M2B ratio on diolein regioisomer production during triolein glycerolysis was also evaluated. Two different profiles of diolein regioisomers were observed as a function of solvent composition: Although the production of the 1,2-diolein isomer was favored as the proportion of 2M2B in n-hexane was increased, the 1,3-isomer was preferentially synthesized in reactions where n-hexane was the predominant solvent. When 100% n-hexane was used as a solvent, 1,3-diolein comprised 72 mol% of the total diolein population (58 mM). On the contrary, when the reaction was carried out in 100% 2M2B, the total concentration of diolein was lower (21 mM) but the 1,2-diolein regioisomer was preferentially formed (89%). These results were explained as a consequence of the different extents of hydrolysis-synthesis reactions involved in the glycerolysis process, which are strongly dependent on solvent mixtures and water concentration. Finally, some advantages of the use of binary mixtures of solvents compared with other strategies applied to glycerolysis reactions are discussed.     

Lignin organosolvolysis from autohydrolyzed corn (Zea mays) stalks: Ozonation of both solvolytic solid and juice

The solubility of lignin from autohydrolyzed corn (Zea mays) stalks in different organic solvent–water mixtures and conditions was studied. The best lignin solvent was selected according to its lignin extraction capacity and its low reactivity to ozone. Both the organosolvolytic solid and juice obtained in optimal conditions, 75/25 (v/v) acetone–water mixture at 210°C for 45 min, and the autohydrolyzed material were treated with ozone, and the reaction products were determined by gas chromatography–mass spectrometry and gas chromatography–flame ionization detection. The concept of the solubility parameter (δ-value) was applied to explain the effect of the solvent-to-water ratio on lignin solubility. The δ-value of the lignin dissolved was 13.8 (cal/cm³)^1/2. The δ-value of the various solvent–water mixtures was also calculated. The experimental delignification capacity of the aqueous organic solvents clearly reflects the proximity of their δ-value to that of lignin. In other words, the closer the δ-value of the aqueous organic solvent to that of lignin, the more effective it is; the hydrogen-bonding capacity of the solvent–water mixtures was also taken into account. The following acids were identified during ozonation: glycolic, oxalic, malonic, glyoxylic, butanedioic, malic, p-hydroxybenzoic, vanillic, and syringic. In addition, syringaldehyde, vanillin, p-hydroxybenzaldehyde, and hydroquinone were identified. Ozonation of theorganosolvolytic juice led to the formation of the oxyaromatic compounds, which were destroyed during treatment. This destruction was accompanied by the generation of aliphatic acids. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1867–1876, 1998     

Separation of organic solvent from dilute aqueous solutions and from organic solvent mixtures through crosslinked acrylate copolymer membranes by pervaporation

The composite membranes of acrylate polymers and porous substrate were prepared. The separation of the organic solvent–water mixtures and the organic solvent–organic solvent mixtures through these membranes by pervaporation was investigated. The acrylate copolymer membrane showed the organic solvent permselectivity for the separation of the organic solvent–water mixture, especially for the chlorinated hydrocarbon–water mixture separation. The high organic solvent permselectivity should be governed by solubility selectivity. The influence of the ester residue of acrylate on the phenol–water mixture separation was observed. The copolymerization of the macromonomers containing the polystyrene, poly(methyl methacrylate), and polydimethylsiloxane chain had a small effect on the separation of the chlorinated hydrocarbon–water mixture. High flux and low selectivity of organic solvent were observed in the case of the organic solvent mixture separation through the n-butylacrylate membrane. The difference of permeability of organic solvent was observed for the acrylate copolymer which has various structures of ester residue. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 1483–1494, 1998     

Lipase‐catalyzed esterification of cinnamic acid and oleyl alcohol in organic solvent media

The esterification of cinnamic acid (CA) and oleyl alcohol (OA) in organic solvent media by immobilized lipase Novozym 435 was optimized in terms of selected parameters, including the logarithm of the 1‐octanol/water partition coefficient of the organic solvent (log P, 0.29–4.5), initial water activity (a_w, 0.05–0.75), agitation speed (0–200 rpm), temperature (35–65 °C) and ratio of substrates (CA/OA, 1.0:0.5–1.0:6.0). The results showed that the more hydrophobic solvent mixtures and lower initial a_w values resulted in a higher enzymatic activity and bioconversion yield. The most appropriate solvent medium and initial a_w value was the mixture of iso‐octane/2‐butanone (85:15, v/v) and 0.05, respectively. The results also showed that an agitation speed of 150 rpm and a reaction temperature of 55 °C were optimal for the reaction system. The activation energy (E_a) of the esterification reaction was calculated as 43.6 kJ mol^?1. The optimal ratio of CA to OA was 1.0:6.0, with the absence of any inhibition by OA. Using the optimized conditions, the maximum enzymatic activity was 390.3 nmol g^?1 min^?1, with a bioconversion yield of 100% after 12 days of reaction. In addition, the electrospray ionization‐mass spectroscopy analysis confirmed that the major end product of the esterification reaction was oleyl cinnamate. Copyright © 2005 Society of Chemical Industry     

Temperature and light sensitive copolymers containing azobenzene moieties prepared via a polymer analogous reaction

Four different series of polyacrylamides containing different amounts of azobenzene moieties have been synthesized via a polymer analogous reaction of poly(pentafluorophenylacrylate) (PPFPA). All copolymers were designed to exhibit a lower critical solution temperature (LCST) in aqueous solution, which was dependent on (i) the amount of incorporated chromophoric azobenzene groups and (ii) the isomerization state of the respective azobenzene group. Higher LCST values were measured for UV-irradiated solutions of the copolymers in comparison to the non-irradiated copolymer solutions. A maximum difference in the LCST of up to 7 °C was found for the copolymer poly(N,N-dimethylacrylamide) containing 8.5 mol% of azobenzene groups. Within this temperature range, a reversible solubility change of the copolymer could be induced by irradiation with light.     

Synthesis and tunable thermoresponsive solution morphologies of 2,2‐bis‐methylolpropionic acid dendron–azobenzene–poly(N‐isopropyl acrylamide) copolymers

Amphiphilic temperature‐ and photoresponsive linear–dendritic block copolymers comprising second‐generation acetonide‐2,2‐bis‐methylolpropionic acid‐based polyester dendron and linear poly(N‐isopropyl acrylamide) (PNIPAM) linked by an azobenzene unit were synthesized using atom transfer radical polymerization (ATRP) followed by click chemistry. Linear PNIPAM precursor was prepared from an azide‐functionalized azobenzene containing ATRP initiator. Two polymers obtained by varying the chain length of the PNIPAM block showed different morphologies and lower critical solution temperature (LCST) values in aqueous solution. Complete change in morphology of the two polymers into large spherical aggregates and nanotubes, respectively, was observed upon heating the micellar solution above LCST. The azobenzene unit was found to undergo trans–cis photoisomerization in the assemblies and caused a change in the microenvironment of an encapsulated hydrophobic dye without any release. Acetonide groups on the dendron were deprotected to afford hydroxylated polymer that showed well‐defined morphologies above the LCST and after heating–cooling cycle while significant dye encapsulation was seen only above the LCST. © 2017 Society of Chemical Industry     

Coiling/uncoiling behaviour of sodium polystyrenesulfonate in 2‐ethoxyethanol–water mixed solvent media as probed using viscometry

Precise measurements of the viscosities of solutions of sodium polystyrenesulfonate in water and in 2‐ethoxyethanol–water mixtures containing varying amounts of 2‐ethoxyethanol have been performed at 308.15, 313.15, 318.15 and 323.15 K. The intramolecular contributions to the reduced viscosities of the polyelectrolyte solutions were obtained through isoionic dilution maintaining the total ionic strengths of the solutions at polyelectrolyte concentrations of 0.0033, 0.0054 and 0.0080 eq L^?1 with sodium chloride. The Huggins constants were also obtained from the experimental data. The influences of the medium and the temperature on the intramolecular contributions to the reduced viscosities as well as on the Huggins constants have been interpreted from the points of view of the conformational characteristics and polyelectrolyte–solvent and polyelectrolyte–polyelectrolyte interactions prevailing in the polyelectrolyte solutions under investigation. Polyion chains were found to coil upon addition of 2‐ethoxyethanol to water or upon an increase of temperature. Thermodynamic affinities for polyelectrolyte–solvent and polyelectrolyte–polyelectrolyte interactions were found to depend greatly on the medium. © 2014 Society of Chemical Industry     

Studies on poly(acrylic acid)/attapulgite superabsorbent composites. II. Swelling behaviors of superabsorbent composites in saline solutions and hydrophilic solvent–water mixtures

The effect of the attapulgite content on the swelling for a series of poly(acrylic acid)/attapulgite superabsorbent composites in water was studied. The effects of the temperature and pH values on the water absorbency of the superabsorbent composites were investigated. The swelling behavior of the superabsorbent composites in various saline solutions was also investigated. The water absorbency in various salt solutions decreased with an increase in the ionic strength of the solutions. At a high ionic strength (>1 × 10^?3M), the water absorbency in monovalent cationic solutions was higher than that in multivalent cation solutions. This dramatic reduction of the water absorbency in multivalent cationic solutions of high ionic strength may have been due to the complexing ability of the carboxylate groups inducing the formation of intramolecular and intermolecular complexes, which resulted in an increased crosslink density of the network. The swelling behavior of the superabsorbent composites in mixtures of water and hydrophilic solvents, including methanol, acetone, ethanol, and dimethyl sulfoxide (DMSO), was also investigated. The water absorbency decreased with an increase in the concentration of any of the four organic solvents, and two transitions were observed in the superabsorbent composite/hydrophilic solvent–water mixture systems. The main transition for the four hydrophilic solvent–water mixtures was a collapse of the swollen gel (at 50–80% methanol, 30–80% acetone, 50–80% ethanol, and 50–80% DMSO). For the methanol–water system, the magnitudes of the first and second transitions for the poly(acrylic acid)/attapulgite superabsorbent composites containing lower proportions of attapulgite were larger than those for the superabsorbent composites with higher attapulgite contents. The effect of the mixture temperature on the water absorbency of the superabsorbent composites in 10 min was also reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1869–1876, 2004     

Synthesis and Properties of Random Copolymers of Functionalised Polybenzimidazoles for High Temperature Fuel Cells

A series of polybenzimidazoles (PBIs) incorporating main chain sulphonic acid groups were synthesised as random copolymers with p‐PBI in varying ratios using polyphosphoric acid (PPA) as both the polymerisation solvent and polycondensation reagent. The PPA process was used to produce high molecular weight phosphoric acid (PA) doped PBI gel membranes in a one‐step procedure. These membranes exhibit excellent mechanical properties (0.528–2.51 MPa tensile stress and 130–300% tensile strain) even at high acid doping levels [20–40 mol PA/PRU (polymer repeat unit)] and high conductivities (0.148–0.291 S cm^–1) at elevated temperatures (>100 °C) with no external humidification, depending on copolymer composition. Fuel cell testing was conducted with hydrogen fuel and air or oxygen oxidants for all membrane compositions at temperatures greater than 100 °C without external feed gas humidification. Initial studies showed a maximum fuel performance of 0.675 V for the 25 mol% s‐PBI/75 mol% p‐PBI random copolymer at 180 °C and 0.2 A cm^–2 with hydrogen and air, and 0.747 V for the same copolymer at 180 °C and 0.2 A cm^–2 with hydrogen and oxygen.     

Preparation,photoisomerization, and microfabrication with two‐photon polymerization of crosslinked azo‐polymers

We report the preparation, photoisomerization properties, and three‐dimensional (3D) microstructure fabrication with two‐photon polymerization of crosslinked azo‐polymers. A series of bi‐acrylate‐substituted azobenzene derivatives were designed and synthesized as the monomers and/or crosslinkers of the crosslinked azo‐polymers. The doping concentration of the derivatives in pre‐polymer resins was significantly increased due to the introduction of bulky tert‐butyl and flexible alkyl chains. The double‐exponential dynamics of trans‐to‐cis photoisomerization of the azo‐polymers indicated the coexistence of different processes for the azobenzene moieties in the polymeric crosslinked networks. The crosslinked azo‐polymers exhibited ideal “on–off” switching performance in the highly reversible trans–cis–trans isomerization cycles. Furthermore, we prepared a photoresist containing the azobenzene derivative for 3D microstructure fabrication based on two‐photon polymerization. A woodpile photonic crystal with a photonic bandgap at telecommunication wavelength region was successfully fabricated with the azobenzene‐containing photoresist, which would open the way for the design and manufacturing of miniature optical communication devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2947–2956, 2013     

Syntheses and optical properties of hybrid materials containing azobenzene groups via sol–gel process for reversible optical storage

We focused on the synthesis and optical properties of new organic–inorganic hybrid materials containing azobenzene groups for rewritable optical recording media. Hybrid material (SGUR19‐n's) design has the structure of azobenzene group with urethane bonds in the silica network. The structures of the synthesized monomers and precursors were confirmed by FTIR and ¹H NMR spectrophotometer. Also, we reported on the effects of the direction of the polarized beam, the intensity of the induced beam, and the structures of SGUR19‐n's materials on the diffraction efficiency of SGUR19‐n's films. It was revealed that SGUR19‐n's films prepared by the sol–gel process have adequate writing–erasing–rewriting properties when used as a reversible optical storage material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4811–4818, 2006     

Network formation and swelling behavior of photosensitive poly(vinyl alcohol) gels prepared by photogenerated crosslinking

Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained. The proportion of the free water to the bound water in PVA-SbQ gels was 3.3?2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27?0.58. The water uptake after swelling of the gels in water increased 6–27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2?5.8) × 10^?5 cm² S^?1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.     

Effective microbial production of poly(4‐hydroxybutyrate) homopolymer by Ralstonia eutropha H16

The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate (4HB) with high mole fractions of 4HB units by a wild‐type strain of Ralstonia eutropha H16 was investigated in culture solutions containing 4‐hydroxybutyric acid (4HBA) and various carbon substrates in the presence of a nitrogen source such as ammonium sulfate. The addition of glucose or acetic acid to the culture solution containing 4HBA in the presence of ammonium sulfate resulted in the production of random copolymers of P(3HB‐co‐4HB) with compositions of up to 82 mol% 4HB, but the yield of copolymers was less than 7 wt% of dried cell weights. In contrast, when n‐alkanoic acids such as propionic acid, butyric acid, valeric acid and hexanoic acid, being subject to β‐oxidation metabolism in the cell, were used as the co‐substrates of 4HBA in the presence of ammonium sulfate, a mixture of copolymers with two different 4HB compositions was produced, and copolyesters with compositions of 93–100 mol% 4HB were isolated from chloroform–n‐hexane insoluble fractions in the mixture of copolymers. Especially, when this wild‐type Ralstonia eutropha H16 was cultivated in a medium containing 4HBA (15 g litre⁻¹), propionic acid (5 g litre⁻¹) and ammonium sulfate (5 g litre⁻¹), namely C/N (mol/mol) = 10, the P(4HB) homopolymer was produced at maximally 34 wt% of dry cell weight (7.8 g litre⁻¹), and the conversion yield of 4HBA to P(4HB) homopolymer resulted in values as high as 21 mol%. © 1999 Society of Chemical Industry     

Torlon® hollow fiber membranes for organic solvent reverse osmosis separation of complex aromatic hydrocarbon mixtures

Defect-free polyamide-imide (Torlon®) hollow fiber membranes were fabricated to investigate the potential for polymer-based organic solvent reverse osmosis (OSRO) separations. The quality of the membranes was assessed by gas permeation, and the membranes were found to be defect-free. Low molecular weight cut-offs of ~180 g/mol were obtained using a complex mixture of aromatic hydrocarbons relevant to refinery separations. We demonstrate bulk OSRO-type separations of 80/20 (mol%) mixtures of toluene and 1,3,5-triisopropylbenzene (TIPB, 204 g/mol). At an upstream pressure of 80–90 bar, we find that the permeate concentration was approximately 98.5–99.0 mol% toluene and that the TIPB rejection coefficient was approximately 90% in the permeate. We observed low solvent permeances of 0.01 L/m² hr bar, which can be attributed to the low OSRO driving forces and the low permeability of Torlon®. The membranes were found to provide stable performance up to pressures of 95 bar and temperatures of 60°C.     

Graft polymerization of styrene onto starch by simultaneous cobalt-60 irradiation

Starch-g-polystyrene copolymers have been prepared by the simultaneous ⁶⁰Co-irradiation of starch–styrene mixtures, and copolymers have been characterized with respect to weight per cent polystyrene (% add-on) and also the molecular weight and molecular weight distribution of polystyrene grafts. In a typical polymerization, 4 g each of starch and styrene were blended with 1 ml water and 1.5 ml of an organic solvent; the resulting semisolid paste was irradiated to a total dose of 1 Mrad. With ethylene glycol, acetonitrile, ethanol, methanol, acetone, and dimethylformamide as the organic solvent, values for % add-on ranged from 24% to 29%. The highest % add-on (43%) and the highest conversion of styrene to grafted polymer (76%) were obtained when the organic solvent was omitted, and water alone was used. When water was also omitted, polymerization of styrene was negligible; however, graft copolymer was formed in the absence of water when either ethylene glycol or ethanol was added. Attempts were unsuccessful to achieve a % add-on greater than 43% by doubling the amount of styrene in the polymerization recipe. Mixtures of equal weights of starch and styrene are relatively nonvicious, but these mixtures thicken when either water or ethylene glycol is blended in. Reasons for this thickening action and the possible influence of thickening on the graft polymerization reaction were explored.