Synthesis of cellulose derivative based superabsorbent hydrogels by radiation induced crosslinking

Hydrogels with high water uptake were prepared by ionizing radiation induced crosslinking in aqueous solutions of four cellulose derivatives (carboxymethylcellulose sodium salt—CMC-Na, methylcellulose—MC, hydroxyethylcellulose—HEC and hydroxypropylcellulose—HPC). The gel fraction increased with absorbed dose, while water uptake decreased. At high polymer concentrations lower gel fractions were found due to the lower polymer chain mobility and inhomogeneity at low water content. The swelling rate gradually slowed down after 4–5 h. CMC and HEC gels reached equilibrium after 24 h, while HPC and MC gels required longer immersion times. Gels showed second-order swelling kinetics in water. The mechanism of the water diffusion proved to be anomalous. In pure water, CMC gels showed the highest, while HPC and MC gels the lowest water uptake. The derivatives had different sensitivities to ionic strength in the swelling solution. The salt type also proved to be a significant factor at uniform ionic strength. Thus different cellulose derivative based gels may be preferred at various applications depending on the environment.     

Preparation of homogeneous polyacrylamide hydrogels by free-radical crosslinking copolymerization

Network microstructures of acrylamide (AAm)-based hydrogels were investigated by static and dynamic light scattering techniques. The hydrogels were prepared by free-radical crosslinking copolymerization of the monomers acrylamide (AAm), N,N-dimethylacrylamide (DMA) and N-isopropylacrylamide (NIPA) with N,N′-methylenebis(acrylamide) as a crosslinker in aqueous solutions. It was observed that the addition of DMA or NIPA into the comonomer feed suppresses the extent of frozen concentration fluctuations in polyacrylamide (PAAm) hydrogels. The cooperative diffusion coefficient increases while both the static and dynamic correlation lengths decrease as the amount of DMA in the comonomer feed is increased. Formation of homogeneous PAAm hydrogels by introduction of hydrophobic moieties was explained as a result of the steric effect of the bulky side groups on DMA or NIPA segments.     

Electron-beam initiated crosslinking in poly(N-isopropylacrylamide) aqueous solution

The reactions between the OH, H and e_aq⁻ transients of water radiolysis and a linear poly(N-isopropylacrylamide) were identified by the spectral and kinetic properties of intermediates. The radical responsible for crosslink formation is the isopropyl-centered radical that forms mainly in OH radical attack on the polymer. Below pH 3 this radical undergoes reversible protonation with pK_a≈2.1. The radical decay is composed of fast and slow parts. The initial fast decay is attributed to intramolecular reactions of radicals on the same chain (loop formation), the following slow decay to competition between further intramolecular and intermolecular (H-type crosslinks) termination processes. The differences in the network formation during irradiation of aqueous monomer and polymer solutions are discussed.     

Determination of the radiation yield of hydrogels crosslinking

The ability of polymer to crosslink or exposure to radiation is frequently represented by a G value, the number of crosslinks per 100 eV absorbed. Several methods are available for its determination, the most frequent being the dose D_g required to form an incipient network since (with many systems) this corresponds to one crosslinked unit per weight average molecular (δ = 1). Its determination therefore depends on a knowledge of the molecular weight of the starting polymer. An alternative method, far less frequently used, is to measure the degree of swelling of a crosslinked network. This involves a knowledge of the Flory-Huggins interaction parameter μ and of the initial number average M_n(0). However if the concentration V_e of effective chains (deduced from swelling) is plotted against dose D, the slope gives G(X) directly, independent of M_n(0). This applies only when the system is very largely crosslinked. It may also be used to determine G(X) even when starting from the monomer itself (i.e. combining polymerization and crosslinking). It is shown that, for a series of polymers, irradiated either as liquids or in solution, the theoretical relation between swelling and crosslink density is followed, and the G(X) values derived from swelling compare well with those given in the literature, and based on gel fraction.     

Fast fabrication of superabsorbent polyampholytic nanocomposite hydrogels via plasma‐ignited frontal polymerization

We report the facile synthesis of poly(VI‐co‐MAA) superabsorbent polyampholytic hydrogels (VI = N‐vinylimidazole, MAA = methacrylic acid) via plasma‐ignited frontal polymerization (PIFP). On igniting the top surface of the reactants with air plasma, frontal polymerization occurred and poly(VI‐co‐MAA) hydrogels were obtained within minutes. The preparation parameters were investigated, along with swelling capacity, morphology, and chemical structures of poly(VI‐co‐MAA) hydrogels. Interestingly, the hydrogels are superabsorbent in water and show ampholytic characteristic toward pH. Moreover, the hydrogels are able to capture cationic dyes through electrostatic interaction, offering the potential for further development as dye adsorbents for water purification. In addition, nanocomposite hydrogels were obtained by embedding quantum dots (carbon dots or CdS nanocrystals) into the polymer matrix, which endows the nanocomposite hydrogels with favorable fluorescence and potential applications in bioimaging and biosensing. The results indicate that FP can be applied as an alternative means for facile synthesis of multifunctional hydrogels with additional efficiency and energy‐saving. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 912–920     

E-beam radiation synthesis of xanthan-gum/carboxymethylcellulose superabsorbent hydrogels with incorporated graphene oxide

In this study the electron beam (e-beam) radiation synthesis in “paste-like condition” and characterization of the network structure of acrylic acid (AA) sodium salt/xanthan gum (XG)/carboxymethylcellulose (CMC) superabsorbent hydrogels incorporating graphene oxide (GO) was investigated. The effects of the AA concentration on gel fraction, sol-gel analysis, swelling degree and network parameters, as well as the relationship between these parameters and radiation dose was also established.

Gel fraction exceeds 90%, and the p₀/q₀ ratio shows a moderate degradation process. The swelling kinetic data were used to determine, first the swelling degree, second the diffusion characteristics, and third the average molecular weight between crosslinks (Mc), as well as. The diffusion data revealed a Fickian mechanism transport, for each hydrogel compositions. The network parameters (Mc and ξ) increased with absorbed dose, while cross-linking density and the radiation-chemical yields were decreased.     

Poly(N-vinylpyrrolidone) hydrogels: 1.Radiation polymerization and crosslinking of N-vinylpyrrolidone

POLY(N-VINYLPYRROLIDONE) HYDROGELS: 1 RADIATION POLYMERIZATION AND CROSSLINKING OF N-VINYLPYRROLIDONE). The effects of irradiation dose on the conversion of vinylpyrrolidone (VP) with various concentration and other characteristics such as Gelation Dose (Dg), Degree of Swelling (DS) and Equilibrium Water Content (EWC) have been investigated. Aqueous solution of vinylpyrrolidone with several concentrations such as 5, 10, 20, 40, 60, 80 and 100 Wt % were irradiated by using gamma rays of Cobalt-60 source with a dose rate of 0. 139 Gy/s. After irradiation, parameters such as conversion of vinylpyrrolidone, gelation dose, degree of swelling, and equilibrium water content were analyzed. Results show that the conversion of VP to PVP was almost 100% at a dose of 2 kGy. The gelation dose of PVP depends on initial content of monomer. Degree of swelling of gels with concentration of 10 % was 55 at the dose of 10 kGy and 30 at the dose of 40 kGy. The lowest value of degree of swelling is 15. At the range of irradiation dose of 10 to 40 kGy the EWC of gel was found to be 98 to 94 %.     

Preparation of polymeric nanocapsules by radiation induced miniemulsion polymerization

In this research, polystyrene (PSt) nanocapsules with liquid cores were prepared by ⁶⁰Co γ-ray radiation induced miniemulsion polymerization, in which N-vinyl pyrrolidone (NVP) was used as the polar monomer. The characterization of polymer was carried out by ¹H NMR. It was verified that during polymerization, graft copolymerization between poly (pyrrolidone) (PVP) and PSt had taken place instead of random copolymerization. The interfacial tension between polymer and water was reduced because of the grafting reaction that had occurred, which was helpful to form nanocapsules. The influence of the ratio of St to NVP, the type and amount of the surfactant and the monomer/dodocane ratio on the particle morphology was studied by TEM. Finally, the releasing process of the synthesized nanoparticles was monitored by UV-vis measurement.     

海藻酸钠与丙烯酰胺微波共聚制备高吸水树脂

高吸水性树脂是近年来得到迅速发展的一类新型的功能性高分子材料,由于其能吸收自身质量数百倍至数千倍的水,且具有优良的保水性能,因此被广泛应用于农业、林业、卫生用品材料、工业用脱水剂,医用材料、水凝胶材料等。反相悬浮聚合法是目前制备高吸水性树脂较先进的方法,具有制备工艺简单,树脂的物理形态和吸水性能较好等优点。海藻酸钠是从褐藻中提取得到,由于其良好的生物降解性和生物相容性,     

Branching and crosslinking in emulsion polymerization

The seeded semibatch emulsion polymerization of butyl acrylate (BA) with allyl methacrylate (AMA) and butanediol diacrylate (BDA) was used to study the influence of the crosslinkers on the kinetics, branching and crosslinking density, gel fraction and sol MWD produced during the experiments carried out at 80°C using potassium persulfate as initiator. Surprisingly, the most reactive crosslinker, BDA, produced the less crosslinked, branched and gel containing polymer. These results were explained with the help of a mathematical model in terms of cyclization reactions and diffusion controlled propagation and termination reactions.     

Synthesis and characterization of thermo-sensitive poly (N-isopropylacrylamide) hydrogel with fast response rate

Thermo-sensitive poly (N-isopropylacrylamide) (PNIPA) hydrogel with fast response rate was prepared by polymerizing N-isopropylacrylamide (NIPA) in an aqueous hydroxyl-propyl-methyl cellulose solution. The volume phase transition temperature of PNIPA hydrogels was characterized by differential scanning calorimetry (DSC), and the surface morphology was observed by scanning electron microscopy (SEM). The swelling ratios of the hydrogels at different temperatures were measured. Furthermore, the deswelling kinetics of the hydrogels was also studied by measuring their water retention capacity. In comparison with a conventional PNIPA hydrogel prepared in water, the hydrogel synthesized in aqueous hydroxyl-propyl-methyl cellulose solution has higher swelling ratios at temperatures below the lower critical solution temperature and exhibits a much faster response rate to temperature changes. For example, the hydrogel made in aqueous hydroxyl-propyl-methyl cellulose solution lost 89% water within 1 min and about 93% water in 4 min, whereas the conventional hydrogel lost only about 66% water in 15 min from the deswelling measurement in similar conditions. Translated from Chinese Journal of Applied Chemistry, 2006, 23(6): 581–585 (in Chinese)     

Reversible addition-fragmentation chain transfer polymerization of N-isopropylacrylamide: a comparison between a conventional and a fast initiator

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was studied to determine the reasons for deviation of experimental molecular weights to lower molecular weight at high monomer conversion when S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAm) and S,S-bis(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAd) were used as RAFT agents at 65 degrees C. For this purpose, experiments were performed in N,N'-dimethylformamide (DMF) at the NIPAM/CTA ratio of 200 with initiators capable of yielding fast and slow initiation, respectively by photochemical and thermal process, either at ambient temperature or at 65 degrees C. When the polymerization of NIPAM was conducted under these conditions with Irgacure-2959 (IRGC) as photoinitiator, a continuing supply of primary radicals by incremental initiator addition was required to achieve reasonably high conversion. This effect was also apparent by the loss of linearity of the first-order kinetic plot with a conventional initiator (4,4-azobis(4-cyanovaleric acid) (ACVA) as azo-initiator, 10h (t1/2) decomposition at 65 degrees C) indicating that steady-state concentration of the macroradical decreases significantly with the initiator consumption. Nevertheless, polymers with predictable number-average molecular weight Mn (i.e., based on [monomer]/([CTA] + [initiator]) ratio) and narrow polydispersities were obtained (PDIs < 1.2) with CTAm indicating that the process of chain growth was controlled. When CTAd was used, instead of CTAm, the polymers obtained were characterized by a larger polydispersity (1.2 < PDIs < 1.3). The so-called "living steady-state concentration" in chain equilibration together with the linear dependence of Mn vs conversion was observed only when the 200/1 NIPAM/CTA mixture in DMF was subjected to a permanent photoirradiation at 65 degrees C. With ACVA, the deviation of the experimentally measured molecular weights at high conversion was accounted for by the simultaneous self-initiated polymerization of NIPAM with the controlled process in the presence of CTA at 65 degrees C. Similar drift from the linear dependence Mn vs conversion was also observed at 65 degrees C when a significant number of low molecular weight polymer chains were generated intentionally by photodecomposition of IRGC.     

Synthesis of carbon-polyacrylate nanocomposite materials by crosslinking polymerization

Nanocomposite materials made of carbon nanoparticles dispersed in a crosslinked polymer have been produced by light-induced polymerization of a multifunctional acrylic resin containing graphite, oxidized graphite or acetylene black. Exfoliation of graphite was achieved by sonication of the filled resin, and confirmed by sedimentation analysis. Under intense illumination the solvent-free resin was transformed within a fraction of a second into a hard and tough material, at ambient temperature. The photopolymerization was followed by infrared spectroscopy and shown to proceed effectively up to 85% conversion of the acrylate double bonds. The slowing down effect of the carbon particles by screening of the UV-radiation is becoming increasingly important as the sample thickness and the filler content are increased. A redox initiator consisting of benzoyl peroxide and a tertiary amine was used to achieve a deep through-cure of thick samples, a process which was markedly accelerated in presence of acetylene black. These carbon nanocomposite materials proved to be more flexible and resistant to shocks than the neat acrylic polymer. Electrical conductivity was found in nanocomposites containing acetylene black at concentrations above 1 wt.%.     

Effect of chemical structure on the properties of some hydrogels prepared by using gamma radiation polymerization

Several hydrogels were prepared using radiolytic polymerization of aqueous solutions of acrylamide or acrylamide containing appropriate comonomer such as acrylic acid, maleic acid, itaconic acid, and maleic anhydride. The hydrogels have been prepared at an irradiation dose of 30 kGy. The effects of the chemical structure of the monomer(s) and crosslinking agents on the yield of homopolymer(s) or copolymers have been studied. These crosslinking agents include N, N′‐methylene dimethacrylate (MDA) and N, N′‐methylene bisallyamide (MBA). The hydrogels obtained were characterized using swelling technique, thermal and spectroscopic analysis. The results obtained showed that the prepared samples are able to reject sodium ions and are not able to recover the Basic Blue Dye from their aqueous solution. © 2005 John Wiley & Sons, Ltd.     

Control of poly(N-isopropylacrylamide) microgel network structure by precipitation polymerization near the lower critical solution temperature

Poly(N-isopropylacrylamide) (pNIPAm) microgels were synthesized by precipitation polymerization at temperatures ranging from 37 to 45 °C using redox initiator system ammonium persulfate (APS)/N,N,N',N'-tetramethylethylenediamine (TEMED) or photoinitiator 2,2'-azobis(amidinopropane) dihydrochloride (V50). Photon correlation spectroscopy (PCS) and atomic force microscopy (AFM) studies revealed that spherical microgels with narrow size dispersities can be obtained with these methods and that the resultant microgels have volume phase transition behaviors expected from their compositions. Additionally, the low-temperature redox initiator strategy produces microgels devoid of self-cross-linking, thereby permitting the synthesis of completely degradable microgels when using N,N'-(1,2-dihydroxyethylene)bisacrylamide (DHEA) as a cleavable cross-linker. We also demonstrate the potential utility of the approach in bioconjugate syntheses; in this case, avidin immobilization is demonstrated by one-pot copolymerization at low temperature.     

Gelation mechanism of poly(N-isopropylacrylamide)-clay nanocomposite hydrogels synthesized by photopolymerization

The gelation process of poly-(N-isopropylacrylamide)-clay nanocomposite hydrogels (PNIPAAm-clay NC gels) was investigated by dynamic and static light scattering (DLS and SLS), as well as by fluorescence correlation spectroscopy (FCS). The photopolymerization method chosen for the radical polymerizing system ensured that, when the irradiation is removed, the reaction stopped immediately. Experiments showed that shortly before the gelation threshold is reached, no changes in the DLS autocorrelation functions appear, while the monomer conversion can be observed by 1H NMR spectroscopy. These results correspond to the formation of microparticles, in which the PNIPAAm chains are closely attached to the clay platelets. During the further polymerization process, clay clusters are developed before the sol-gel threshold is reached. FCS measurements were performed to obtain information on the motion of the clay platelets inside the NC gel. The DLS method gives only an average of the motions in the gel. In a time window between 10 micros and 1 s, the clay sheets labeled with Rhodamine B show no characteristic motions.     

Synthesis of clay nanocomposite materials by light-induced crosslinking polymerization

Different types of nanocomposite materials have been synthetized within seconds at ambient temperature, by photoinitiated crosslinking polymerization of epoxy, vinyl ether and acrylate-based resins containing a small amount (3 wt%) of an organoclay filler. The curing process was followed quantitatively by infrared spectroscopy through the decrease upon UV exposure of the IR bands characteristic of the functional groups. The silicate nanoparticles were found to have no effect on the polymerization kinetics. The UV-cured nanocomposites proved to be more flexible and impact resistant than the corresponding microcomposites. This method of synthesis of nanocomposites presents the advantages associated with the UV-curing technology, namely a solvent-free resin transformed rapidly at ambient temperature into a chemically resistant material, with a minimum consumption of energy.