Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO2‐in‐water emulsions

Poly(vinyl acetate‐alt‐dibutyl maleate)‐block‐poly(ethylene glycol) (PVDBM‐b‐PEG) copolymers were synthesized via reversible addition–fragmentation chain transfer radical polymerization and used as emulsifiers to form stable CO₂‐in‐water high internal phase emulsions (C/W HIPEs). Then, highly interconnected cellular polyacrylamide (PAM) and poly(acrylamide‐co‐N‐hydroxymethyl acrylamide) [P(AM‐co‐HMAM)] poly‐HIPEs with enhanced mechanical strength were prepared based on the stable C/W HIPEs. The porous structures of the PAM poly‐HIPEs, as well as morphology and compressive modulus, could be influenced by the surfactant concentration and the length of the CO₂‐philic tails of the surfactants. PAM poly‐HIPEs with the smallest average pore diameter (11.12 ± 0.62 μm) and the highest compressive modulus (22.65 ± 0.10 MPa) could be obtained by using the short CO₂‐philic chains of the PVDBM‐b‐PEG surfactant at a high concentration (1.0 wt %). Moreover, with the copolymerization of N‐hydroxymethyl acrylamide (HMAM) comonomers with acrylamide, the compressive modulus of the obtained P(AM‐co‐HMAM) poly‐HIPEs was three times higher than that of PAM poly‐HIPEs. Both PAM and P(AM‐co‐HMAM) poly‐HIPEs were employed as scaffolds to guide H9c2 cardiac muscle cellular growth. Fluorescence images showed that a smaller average pore size and a narrower pore‐size distribution were helpful for cell growth and proliferation on these materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46346.     

Recovery and Recycling of CO2/N2‐Switchable Anionic Surfactants in Emulsions

To develop a mild, effective, and clean strategy for recovery and recycling of anionic surfactants in CO₂/N₂‐switchable emulsions, a CO₂/N₂‐switchable anionic surfactant, which is a combination of dodecyl seleninic acid (DSA) and N,N,N′,N′‐tetramethyl‐1,2‐ethylenediamine (TMEDA), here referred to as DSA–TMEDA, was used to stabilize an oil‐in‐water (O/W) emulsion. Upon stimulation with CO₂, DSA–TMEDA was switched off to form insoluble DSA and the water‐soluble TMEDA bicarbonate. Upon N₂ bubbling and heating, the OFF state of DSA–TMEDA was restored to the surfactant of DSA–TMEDA. In this manner, O/W emulsions stabilized by DSA–TMEDA can be switched reversibly between demulsification (phase separation) and re‐emulsification (recovered emulsion) by triggering with CO₂/N₂ over ten times. After breakage of the emulsion, nearly all of the OFF state surfactant could be separated conveniently away from the oil phase, thus facilitating recovery and recycling of the surfactant afterward in emulsifying oil. No obvious adverse changes in the dispersed oil particles size and the relative stability of the regenerated emulsions were observed over five cycles, and the surfactant loss can be neglected during the recycling.     

Dye‐containing nonaqueous dispersions derived from methanol‐soluble polymers stabilized by block–random copolymer surfactant

In this study, nonaqueous emulsion solvent evaporation was utilized to prepare nonaqueous dispersions derived from various methanol‐soluble polymers, such as polyvinylpyrrolidone (PVP), polyethylene glycol, polyvinyl acetate (PVAC), and poly(acrylic acid), using a block–random copolymer surfactant; the block–random copolymer poly(SMA)₈₈‐b‐poly(DEAGMA₁₅‐r‐SMA₁₄), composed of stearyl methacrylate, and diethanolamine‐modified glycidyl methacrylate, was used to stabilize the nonaqueous emulsions of methanol containing the polymers and an isoparaffin solvent, Isopar M. In the cases without dye, all emulsions and dispersions obtained after the evaporation of methanol exhibited nanometer‐sized particles as well as good stability. For emulsions consisting of dye‐containing methanol phases, particle sizes and stability of the obtained dispersions were dependent on the nature of the methanol‐soluble polymers. The dispersions derived from PVP and PVAC, which possibly interact weakly with the block–random copolymer and dye, exhibited good stability and a small particle size, which can be applied for inkjet printing. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44671.     

Self‐Aggregation and Emulsifying Properties of Methyl Ester Sulfonate Surfactants

Methyl ester sulfonate (MES) anionic surfactants made from natural resources are of particular interest as sustainable surfactants. They offer good physicochemical properties for applications as detergents and emulsifiers. The liquid crystal structures of MES surfactants synthesized in a previous work were determined by polarizing optical microscopy (POM) and small‐angle X‐ray scattering (SAXS). The emulsifying activity for each surfactant was also measured, and the stability of emulsions was estimated and compared to that induced by sodium dodecyl sulfate (SDS). The POM micrographs showed the presence of birefringent textures. Several factors, including temperature and hydration, influenced the stability of the phases and their structure. SAXS confirmed the structure of the phases formed by dry and hydrated ф‐MES surfactants at 25 °C, giving the position of peaks corresponding to the ratio 1:2:3 and revealing the phase transitions of lamellar to double lamellar or the reverse. Also, the Bragg distance (d) decreased with an increase in chain length from 13 to 17 carbon atoms and an increase in the area per molecule of surfactant. The geometric packing parameters were also determined, and suggest that surfactants are tilted. The stability of surfactant emulsions is around 60%, which is comparable to that of SDS. The micrographs show that the emulsions formed are O/W, and an increase in chain length gives rise to a decrease in the size of the emulsion droplets. These results are confirmed by the values of hydrophilic‐lipophilic balance (HLB) which reveals the hydrophilic nature of these surfactants.     

Carbon dioxide‐in‐water foams stabilized with nanoparticles and surfactant acting in synergy

Synergistic interactions at the interface of nanoparticles (bare colloidal silica) and surfactant (caprylamidopropyl betaine) led to the generation of viscous and stable CO₂‐in‐water (C/W) foams with fine texture at 19.4 MPa and 50°C. Interestingly, neither species generated C/W foams alone. The surfactant became cationic in the presence of CO₂ and adsorbed on the hydrophilic silica nanoparticle surfaces resulting in an increase in the carbon dioxide/water/nanoparticle contact angle. The surfactant also adsorbed at the CO₂–water interface, reducing interfacial tension to allow formation of finer bubbles. The foams were generated in a beadpack and characterized by apparent viscosity measurements both in the beadpack and in a capillary tube viscometer. In addition, the macroscopic foam stability was observed visually. The foam texture and viscosity were tunable by controlling the aqueous phase composition. Foam stability is discussed in terms of lamella drainage, disjoining pressure, interfacial viscosity, and hole formation. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3490–3501, 2013     

Effect of lipid type on water‐in‐oil‐emulsions stabilized by phosphatidylcholine‐depleted lecithin and polyglycerol polyricinoleate

Water‐in‐oil (W/O, 30:70) emulsions were prepared with phosphatidylcholine‐depleted lecithin [PC/(PI,PE) = 0.16] or polyglycerol polyricinoleate (PGPR) as emulsifying agents by means of pressure homogenization. The effect of lipid type (medium‐chain triacylglycerols, sunflower, olive, butter oil, or MCT‐oil/vegetable fat blends) was investigated in relation to particle size distribution, coalescence stability and the sedimentation of the water droplets. A significant correlation (p <0.05) was observed between the interfacial pressure caused by the addition of lecithin to the pure lipids and the specific surface area of the emulsion droplets (r_s = 0.700), and between the viscosity of the lipids used as the continuous phase (reflecting the fatty acid composition) and the specific surface area of the emulsion droplets (r_s = 0.8459) on the other hand. Blends of vegetable fat and MCT‐oil led to reduced coalescence stability due to the attachment of fat crystals to the emulsion droplets. Lecithin‐stabilized W/O emulsions showed significantly higher viscosities compared to those stabilized with PGPR. It was possible to adjust the rheological properties of lecithin‐stabilized emulsions by varying the lipid phase.     

Hydrophilic modification of poly(vinylidene fluoride) membrane with poly(vinyl pyrrolidone) via a cross‐linking reaction

A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (J_v) was constant as ～ 600 L m^?2 hr^?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚乙烯吡咯烷酮对聚醋酸乙烯酯共聚乳液性能的影响

以醋酸乙烯酯(VAc)和丙烯酸丁酯(BA)为聚合单体、聚乙烯醇(PVA)为保护胶体、聚乙烯吡咯烷酮(PVP)为分散剂、十二烷基硫酸钠(SDS)为表面活性剂及羟丙基甲基纤维素(HMPC)为增稠剂等,制备出一种低黏度聚醋酸乙烯酯(PVAc)乳液胶粘剂。考察了PVP用量对PVAc乳液胶粘剂的黏度、粘接性能、稳定性能及单体转化率等影响。结果表明:红外光谱(FT-IR)证实,PVP参与了VAc和BA的接枝共聚反应;适量的PVP可使乳液黏度明显降低;当w(PVP)=0.15%时,PVAc乳液胶粘剂的综合性能相对最好。     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

Mechanochemical modification of silica with poly(1‐vinyl‐2‐pyrrolidone) by grinding in a stirred media mill

The polymerization of 1‐vinyl‐2‐pyrrolidone (VP) mechanochemically initiated by grinding silica was investigated in a wet stirred media mill. The polymerization itself proceeds from the silica grinding without any additional initiator. We have found that the amount of grafted polymer increases with an increase in total ground silica surface. The suspension of polymer‐modified silica nanoparticles showed high colloidal stability in water because of the appearance of grafted hydrophilic PVP on the surface during the reactive grinding. Because the nanoparticles SiO₂‐graft‐PVP are biocompatible, the developed polymer nanocomposite material can be of particular interest for the performance of membranes and for the fabrication of biocompatible hydrogels with enhanced mechanical properties and porosity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3708–3714, 2007     

Separation of CO2 from CH4 by pure PSF and PSF/PVP blend membranes: Effects of type of nonsolvent,solvent, and PVP concentration

Complete CO₂/CH₄ gas separation was aimed in this study. Accordingly, asymmetric neat polysulfone (PSF) and PSF/polyvinylpyrrolidone (PVP) blend membranes were prepared by wet/wet phase inversion technique. The effects of two different variables such as type of external nonsolvent and type of solvent on morphology and gas separation ability of neat PSF membranes were examined. Moreover, the influence of PVP concentration on structure, thermal properties, and gas separation properties of PSF/PVP blend membrane were tested. The SEM results presented the variation in membrane morphology in different membrane preparation conditions. Atomic forced microscopic images displayed that surface roughness parameters increased significantly in higher PVP loading and then gas separation properties of membrane improved. Thermal gravimetric analysis confirms higher thermal stability of membrane in higher PVP loading. Differential scanning calorimetric results prove miscibility and compatibility of PSF and PVP in the blend membrane. The permeation results indicate that, the CO₂ permeance through prepared PSF membrane reached the maximum (275 ± 1 GPU) using 1‐methyl‐2‐pyrrolidone as a solvent and butanol (BuOH) as an external nonsolvent. While, a higher CO₂/CH₄ selectivity (5.75 ± 0.1) was obtained using N‐N‐dimethyl‐acetamide (DMAc) as a solvent and propanol (PrOH) as an external nonsolvent. The obtained results show that PSF/PVP blend membrane containing 10 wt % of PVP was able to separate CO₂ from CH₄ completely up to three bar as feed pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1139‐1147, 2013     

A Zwitterionic Surfactant Bearing Unsaturated Tail for Enhanced Oil Recovery in High‐Temperature High‐Salinity Reservoirs

High‐temperature/high‐salinity (HTHS) reservoirs contain a significant fraction of the world's remaining oil in place and are potential candidates for enhanced oil recovery (EOR). Selection of suitable surfactants for such reservoirs is a challenging task. In this work, two synthesized zwitterionic surfactants bearing a saturated and an unsaturated tail, namely 3‐(N‐stearamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate and 3‐(N‐oleamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate, respectively, were evaluated. The surfactant with the unsaturated tail showed excellent solubility in synthetic seawater (57,643 ppm) and in formation brine (213,734 ppm). However, the unsaturated surfactant with a saturated tail showed poor solubility, and therefore it was not evaluated further. The thermal stability of the synthesized unsaturated surfactant solution in seawater was evaluated by heating the solution at 90 °C in a sealed aging tube for 2 weeks. The thermal stability of the unsaturated surfactant was confirmed by FTIR and NMR analysis of the aged samples at such harsh conditions. The critical micelle concentration (CMC) of the synthesized unsaturated surfactant in seawater was 1.02 × 10^?4 mol L^?1, while the surface tension at CMC was 30 mN m^?1. The synthesized unsaturated surfactant was able to reduce the oil–water interfacial tension to ~10^?1 mN m^?1 at different conditions. A commercial copolymer of acrylamide and 2‐acrylamido‐2‐methylpropane sulfonic acid (AM‐AMPS) was tested for EOR applications in HTHS conditions. The addition of the synthesized unsaturated surfactant to the AM‐AMPS copolymer increased the viscosity of the system. The increase in oil recovery by injecting the unsaturated surfactant solution and the surfactant–polymer mixture in solution was 8 and 21%, respectively. The excellent properties of the synthesized unsaturated surfactant show that surfactants with an unsaturated tail can be an excellent choice for HTHS reservoirs.     

Foaming of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) and their blends with carbon dioxide

Poly(ethylene‐co‐vinyl acetate) (EVA‐25) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) (EVACO‐2410) and their blends with EVACO:EVA ratios of 80:20, 60:40, 40:60, and 20:80 were foamed using CO₂. These foams are of interest for applications ranging from footwear to medical devices. Foaming experiments were carried out using 1 mm thick melt‐extruded films in CO₂ at a range of pressures (100, 200, and 300 bar) and temperatures (30, 40, 50, and 60 °C). Foamability of the polymers was explored both under isothermal and gradient temperature conditions. Foams of EVACO‐2410 displayed high initial expansions followed by postfoaming relaxation and shrinkage while foams generated from EVA‐25 showed more dimensional stability. Blending EVACO‐2410 with EVA‐25 was explored as an approach to reduce postfoaming relaxation and shrinkage. The surfaces of the foamed samples displayed blistering that was linked to CO₂ bubble entrapment and coalescence at the surface. Scanning electron micrographs of the foams generated from blends displayed distinct morphologies reflecting whether the sections were representing the machine‐ or cross‐machine direction of extruded films. In going from EVACO‐2410 to EVA‐25, the cell densities ranged from about 10⁶ to 10¹⁰ cells/cm³. Foams with low bulk densities of about 0.11 g/cm³ could be generated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45841.     

Processability and characterization of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) prepared by living radical polymerization of vinyl chloride. Comparison with a flexible commercial resin formulation prepared with PVC and dioctyl phthalate

This work reports the synthesis and processing of a new flexible material based on PVC produced by living radical polymerization. The synthesis was carried out in a two‐step process. In the first step the macroinitiator α, ω‐di(iodo)poly(butyl acrylate) [α, ω‐di(iodo)PBA] was synthesized in water by single electron transfer/degenerative chain transfer mediated living radical polymerization (SET‐DTLRP) catalyzed by Na₂S₂O₄. In the second step this macroinitiator was reinitiated by SET‐DTLRP of vinyl chloride (VC), thereby leading to the formation of the block copolymer poly(vinyl chloride)‐b‐poly(butyl acrylate)‐b‐poly(vinyl chloride) [PVC‐b‐PBA‐b‐PVC]. This new material was processed on a laboratory scale. The DMTA traces showed only a single glass transition temperature, thus indicating that no phase segregation was present. The copolymers were studied with regard to their processing, miscibility, and mechanical properties. The first comparison with commercial formulations made with PVC and dioctyl phthalate (DOP) is presented. J. VINYL ADDIT. TECHNOL., 12:156–165, 2006. © 2006 Society of Plastics Engineers     

Synthesis,characterization, and application of novel amphiphilic poly(D‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐ poly(D‐gluconamidoethyl methacrylate) triblock copolymers

Novel amphiphilic ABA‐type poly(D ‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐poly(D ‐gluconamidoethyl methacrylate) (PGAMA‐b‐PU‐b‐PGAMA) tri‐block copolymers were successfully synthesized via the combination of the step‐growth and copper‐catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO‐PU‐OH) was synthesized by the step‐growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA‐b‐PU‐b‐PGAMA block copolymers were synthesized via copper‐catalyzed ATRP of GAMA in N, N‐dimethyl formamide at 20°C in the presence of 2, 2′‐bipyridyl using Br‐PU‐Br as macroinitiator and characterized by ¹H‐NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by ¹H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo‐gravimetric analysis, and differential scanning calorimetric study. Spherical Ag‐nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri‐block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of PBMA‐b‐PSt‐b‐PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate)‐b‐polystyrene‐b‐poly(n‐butyl methacrylate) (PBMA‐b‐PSt‐b‐PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end‐groups were prepared by ATRP of styrene (St) with CCl₄ as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen‐1 nuclear magnetic resonance (¹HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported. POLYM. ENG. SCI., 45:1508–1514, 2005. © 2005 Society of Plastics Engineers     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Preparation and characterization of biodegradable polymer blends from poly(3‐hydroxybutyrate)/poly(vinyl acetate)‐modified corn starch

Biodegradable polymer blends prepared by blending poly(3‐hydroxybutyrate) (PHB) and corn starch do not form intact films due to their incompatibility and brittle behavior. For improving their compatibility and flexibility, poly(vinyl acetate) (PVAc) was grafted from the corn starch to prepare the PVAc‐modified corn starch (CSV). The resulting CSV consisted of 47.2 wt% starch‐g‐PVAc copolymer and 52.8 wt% PVAc homopolymer and its structure was verified by FT‐IR analysis. In comparison with 35°C of the neat PVAc, the glass transition temperature (T_g) of the grafted PVAc chains on starch‐g‐PVAc was higher at 44°C because of the hindered molecular mobility imposed from starch on the grafted PVAc. After blending PHB with the CSV, structure and thermal properties of the blends were investigated. Only a single T_g was found for all the PHB/CSV blends and increased with increasing the CSV content. The T_g‐composition dependence of the PHB/CSV blends was well‐fitted with the Gordon‐Taylor equation, indicating that the CSV was compatible with the PHB. In addition, the presence of the CSV could raise the thermal stability of the PHB component. It was also found that the presence of the PHB and PVAc components would not hinder the enzymatic degradation of the corn starch by α‐amylase. POLYM. ENG. SCI., 55:1321–1329, 2015. © 2015 Society of Plastics Engineers