Porous Superabsorbent Hydrogel Composites: Synthesis,Morphology and Swelling Rate

Summary: Novel porous hydrogel composites with very high swelling capacity and enhanced rate of water absorption were synthesized in aqueous media at room temperature under normal atmospheric conditions. The porosity was induced through either foaming conducted in the course of polymerization or non‐solvent dewatering of the as‐synthesized gels. Kaolin was incorporated as an inorganic component in the polymerization process. The foaming technique was used to form porosity using three systems of different porogens (porosity generators), i.e. sodium bicarbonate, acetone and their combination. The as‐synthesized gels were dried through oven drying and non‐solvent dewatering. Morphology and swelling rate of the superabsorbent hydrogel composites (SHCs) were studied versus either the porogen system or the drying method. It was found that the simultaneous polymerization‐foaming technique had great influence on the improvement of porosity, morphology of the porous structure and the rate of water absorption. It was also shown that the drying procedure had remarkable influence on preserving the preformed porosity. Methanol as a dewatering solvent produced SHCs with higher porosity and swelling rate in comparison with the porosity of the hydrogels dewatered in acetone. Our invented methodology including simultaneous polymerization and foam formation using dual‐porogen system and the subsequent methanol‐dewatering approach was found to be the most efficient, highly practical, and cost‐effective route for preparing improved superabsorbing hydrogel materials.

     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Study on Superabsorbent Composite, 14

Summary: Organo‐attapulgite (organo‐APT) was prepared by modifying APT using four quaternary ammonium salts with various lengths of the alkyl group, including (octyl)trimethylammonium bromide (OTMABr) and (stearyl)trimethylammonium chloride (STMACl), etc. A series of composite hydrogels, poly(acrylic acid)/organo‐APT, from acrylic acid (AA), and organo‐APT was prepared by aqueous polymerization, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification and organification degree of APT as well as the corresponding composites were characterized by FTIR, TGA, and XRD. The effects of the length of the alkyl group for different quaternary ammonium salts, organification degree of APT, and organo‐APT content on water absorbency and swelling behaviors in various electrolyte solutions were investigated in this study. Equilibrium water absorbency strongly depends on chain length of the alkyl group of quaternary ammonium salts, organification degree of APT as well as organo‐APT content. Longer alkyl group, higher organification degree, and proper organo‐APT content are of benefit for the improvement of equilibrium water absorbency. Equilibrium water absorbency in distilled water for PAA/APT was enhanced from 350.1 to 562.1 g · g^?1 after 10 wt.‐% organo‐APT, modified with STMACl for the highest degree, was introduced. The kind of cation is the key factor influencing equilibrium water absorbency of these composite hydrogels in electrolyte solutions. Organification of APT could enhance responsiveness of the corresponding composite hydrogel to electrolyte solutions.

Schematic structure of PAA/organo‐APT composite in a dry state (left) and in a swollen state (right).     

Thermosensitive Poly[(2‐(diethylamino)ethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] Cryogels Prepared by a Two‐Step Polymerization Method

Summary: Temperature‐sensitive P(DEAEMA‐co‐DMAAm) cryogels with five different DMAAm contents were synthesized via a two‐step polymerization method, the initial polymerization being conducted for various times at 22 °C, followed by polymerization at ?26 °C for 24 h. The influence of the first‐step time and the content of DMAAm on the swelling ratio and network parameters such as the polymer/solvent interaction parameter, the average molecular mass between crosslinks, and the mesh size of the cryogels were reported and discussed. The swelling studies indicated that the swelling increased in the following order: 22C45 > 22C30 > 22C15 > 22C0. The cryogels exhibited swelling/deswelling transitions (reentrant phenomena) in water depending on temperature. These properties were attributed to the macroporous and regularly arranged network of the cryogels. Scanning electron microscope graphs reveal that the macroporous network structure of the cryogels can be adjusted by applying a two‐step polymerization.

Chemical structure of the P(DEAEMA‐co‐DMAAm) cryogels.     

A Novel N‐Succinylchitosan‐graft‐Polyacrylamide/Attapulgite Composite Hydrogel Prepared through Inverse Suspension Polymerization

A novel N‐succinylchitosan‐graft‐polyacrylamide/attapulgite composite hydrogel was prepared by using N‐succinylchitosan, acrylamide and attapulgite through inverse suspension polymerization. The result from FTIR spectra showed that ? OH of attapulgite, ? OH and ? NHCO of N‐succinylchitosan participated in graft polymerization with acrylamide. The introduced attapulgite could enhance thermal stability of the hydrogel. Scanning electron microscopy observation indicates that the composite hydrogel has a microporous surface. The volume ratio of heptane to water, weight ratio of acrylamide to N‐succinylchitosan and attapulgite content have great influence on swelling ability of the composite hydrogel. The composite hydrogel shows higher swelling rate and pH‐sensitivity compared to that of without attapulgite.

     

Extensional Flow and Relaxation of Semi‐dilute Solutions of Schizophyllan

Capillary thinning experiments of semi‐dilute solutions of schizophyllan in water and DMSO are performed to determine the relaxation behavior in extensional flows as experienced, for example, in the flow through porous media in enhanced oil recovery. The extensional relaxation time λ_E is found to scale with concentration following a dissimilar power‐law dependency for the two solvents, λ_E ∝ c^1.52 in water and λ_E ∝ c^0.90 in DMSO. It is shown that the extensional flow fields are strong enough to break, and prevent the rebuilding of, intermolecular structures, due to hydrogen bonding that was observed to alter the viscoelastic response in shearing flows of aqueous schizophyllan solutions.

     

Temperature and pH‐Sensitive Swelling Behavior of Binary DMAEMA/4VP Grafts on Poly(propylene) Films

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) is a polymer or hydrogel that is both thermosensitive and pH sensitive, with a low critical solution temperature (LCST) around 38 °C and a pH critical point of 2.5. Poly(4‐vinylpyridine) (P4VP) shows pH sensitivity with a critical point of 5.1. Grafting of stimuli‐sensitive polymers onto mechanically durable poly(propylene) (PP) substrates was used in this study. We have focused on the influence of temperature and pH on the response of binary graft films produced by gamma irradiation in one and two steps. An LCST‐type hydration transition in the grafts was observed by measuring swelling of the films and water contact angle at different temperatures and pH. An upper critical solution temperature (UCST)‐type behavior was also observed by swelling PP‐g‐DMAEMA and DMAEMA/4VP binary grafting onto PP films at pH 2.2.

     

Copolymers of Poly(2,5‐benzimidazole) and Poly[2,2′‐(p‐phenylene)‐5,5′‐bibenzimidazole] for High‐Temperature Fuel Cell Applications

Copolymers of poly(2,5‐benzimidazole) (ABPBI) and poly[2,2′‐(p‐phenylene)‐5,5′‐bibenzimidazole] (pPBI) were synthesized for use as fuel cell membranes to take advantage of the properties of both constituents. The composition of the copolymers were controlled by changing the feed ratio of 3,4‐diaminobenzoic acid and terephthalic acid with 3,3′‐diaminobenzidine in the polycondensation reaction. The copolymer membranes showed higher conductivities, better mechanical properties, and larger acid absorbing abilities than commercial poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] membranes.

     

Effects of Temperature and Surfactants on the Equilibrium Swelling Behavior of Poly[acrylamide‐co‐(itaconic acid)] Hydrogels

Summary: The swelling equilibrium of poly(acrylamide) [PAAm] and poly[acrylamide‐co‐(itaconic acid)] [P(AAm/IA)] hydrogels was studied as a function of temperature and IA content in aqueous solutions of surfactants: sodium dodecyl sulfate (SDS, anionic) and hexadecyltrimethylammonium bromide (HTAB, cationic). P(AAm/IA) hydrogels in water exhibited reentrant conformational transitions depending on temperature, whereas PAAm hydrogels were not affected with the change of temperature. The equilibrium‐volume‐swelling ratio of P(AAm/IA) hydrogels increased sharply in SDS solutions, with an increase of the mole percent of IA. However, in HTAB solution, the equilibrium‐volume‐swelling ratio of these hydrogels decreased with an increase of IA content.

The equilibrium volume‐swelling ratios of the hydrogels in water shown as a function of temperature.     

Tubular Polymer Nanoobjects with a Crosslinked Shell and Inward‐Grafted Polymer Brushes

A simple route for preparing robust polymer nanotubes by SI‐ATRP within porous anodic aluminum oxide membranes and subsequent removal of the templates is presented. The nanotubes are composed of a crosslinked poly(styrene‐co‐divinylbenzene) shell and an inwardly grafted functional P4VP or PGMA brush‐like internal surface. The crosslinked skin endows the nanotubes with stability against organic solvents while the inwardly grafted polymer brushes supply the nanotubes with reactivity and functionalities. The inward PGMA hairs are post‐modified with sodium azides to introduce azido groups along tubular internal surfaces which are further reacted with propargyl alcohol. Structure and properties of the nanotubes are studied by SEM, TEM, LSCM, and FT‐IR spectroscopy.

     

Copolymerization of 2‐Acrylamido‐2‐methyl‐1‐propanesulfonic Acid and 1‐Vinylimidazole in Ethanol

Polymerization rate and copolymerization parameters of the free‐radical copolymerization of AMPS with 1‐VIm was studied as a function of the monomer feed and the pH value in ethanol. It was found that neutral and basic monomer mixtures containing the sodium salt of AMPS polymerized faster and led to polymers with a higher proportion of NaAMPS incorporated than those monomer mixtures containing the free acid. Additionally, based on the experimental data, copolymerization parameters of r_AMPS = 0.3 and r_1‐VIm = 0.13 were calculated for polymerization in acidic solution and r_AMPS = 4.1 and r_1‐VIm = 0.1 for polymerization in basic and neutral solutions. Finally, the thermal stability, rheological behavior, and intrinsic viscosity were determined for the polymers.

     

The Effect of Clay Loading on the Morphology and Properties of Poly(styrene‐co‐butyl acrylate)/Clay Nanocomposites

This paper investigates the effect of both the clay loading and the monomer feed rate on the morphology and properties of poly(styrene‐co‐butyl acrylate)‐clay nanocomposites prepared in emulsion polymerization. Analysis by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) of the nanocomposites prepared by batch polymerization showed that the polymer clay nanocomposites (PCNs) with 1–3 wt.‐% clay loading resulted in intercalated structures, while exfoliated structures were obtained at 10 wt.‐% clay loading. The polymerization was also carried out with semi‐batch polymerization. The morphology, thermal stability, and mechanical properties of nanocomposites obtained were found to be more strongly dependent on the clay/polymer ratio than the monomer feed rate.

     

Synthesis of Poly(methyl methacrylate)‐Grafted Poly(ethylene‐co‐1‐octene) Copolymers by a “Grafting from” Melt Process

Graft copolymers with a poly(ethylene‐co‐1‐octene) backbone and poly(methyl methacrylate) random polymer branches are successfully synthesized by the grafting‐from technique in the molten state. The in situ radical polymerization of methyl methacrylate from the polyolefin backbone is investigated with two different peroxide initiators at 135 and 150 °C, respectively. The number of PMMA grafts per polyolefin chain is varied from 0.08 to 1.07 with PMMA polymerization degrees of 500 and 18, respectively, depending on the experimental conditions. The effect of a nitroxyl‐based radical scavenger (i.e., DEPN) on competition between the grafting of PMMA from the polyolefin backbone and MMA homopolymerization is also explored.

     

Tunable PLGA‐Based Nanoparticles Synthesized Through Free‐Radical Polymerization

A new class of PLGA‐based materials suitable for the production of biodegradable NPs via free‐radical polymerization is proposed. ROP of lactide and glycolide using HEMA is carried out; macromonomers (HEMA‐L_xG_yA) with short PLGA chain ends are successfully produced. Afterwards, monomer‐starved semi‐batch emulsion polymerization of these HEMA‐L_xG_yA macromonomers is performed to obtain NPs with a low polydispersity index and a controlled size. The stability and degradability of NPs is confirmed from degradation studies that verify the possibility of tuning the degradation time by changing macromonomer characteristics such as chain length and composition.

     

Effect of hydrophobic monomer on the synthesis and swelling behaviour of a collagen‐graft‐poly[(acrylic acid)‐co‐(sodium acrylate)] hydrogel

BACKGROUND: Graft polymerization of vinylic monomers onto natural backbones is an efficient approach for the synthesis of natural‐based superabsorbents. The nature of the monomers will affect the swelling behaviour of the superabsorbents. Here, a novel superabsorbent was synthesized through grafting of acrylic acid onto collagen in the presence of hydrophobic styrene as co‐monomer. Subsequently, the effect of styrene on the swelling behaviour of the superabsorbent was studied. RESULTS: The highly swelling superabsorbent was prepared by introducing styrene into a collagen‐graft‐poly(acrylic acid) hydrogel. By inclusion of styrene monomer, the swelling capacity of the hydrogel was increased; this is discussed according to the network composition. The effect of swelling media (salt solutions and various pH values) was investigated. The results of absorbency under load showed that hydrogels containing phenyl groups exhibit better behaviour; however, by introducing styrene, the rate of water uptake and resistance to water holding under heating was reduced. Scanning electron micrographs of hydrogels revealed a decrease in porosity on using styrene. CONCLUSION: Inclusion of styrene monomer in the ionic superabsorbent caused high swelling capacity with better absorbency under load. This can be used to prepare highly swelling superabsorbents with good mechanical properties. The pH reversibility of the synthesized superabsorbent makes it a candidate for use in the controlled release of drugs and in agrochemicals. Copyright © 2008 Society of Chemical Industry     

Poly(vinyl alcohol)/Clay‐Based Nanocomposite Hydrogels: Swelling Behavior and Characterization

Polymer/clay composite hydrogels were prepared based on PVA hydrogels containing 3–10 wt.‐% MOM. Their microstructure and morphology were studied by FT‐IR, WAXS and SEM, whereas the interactions between MOM and PVA were evaluated by thermal analyses. The swelling ratios for the PVA/MOM hydrogels decrease with increasing MOM content. WAXS results indicate that MOM was intercalates, and DSC results show a strong interaction between PVA and MOM. This interaction results in a stable network, which is confirmed by the elastic modulus and the thermal decomposition behavior of the hydrogels. Therefore, MOM acts as a co‐crosslinker, improving the stability of the network.

     

Synthesis of Fluorescent PMMA‐Based Nanoparticles

The synthesis of PMMA‐based nanoparticles (NPs) covalently labeled with a fluorescent dye is investigated for imaging applications such as cell uptake and biodistribution. Batch emulsion polymerization (BEP) and monomer‐starved semi‐batch emulsion polymerization (MSSEP) are adopted using SDS. Fluorescent properties are added to these NPs using Rhodamine‐B (RhB) as a fluorescent dye covalently bonded to 2‐hyroxyethyl‐acrylate. The resulting HEMA‐RhB monomer is copolymerized with MMA via BEP and MSSEP to synthesize fluorescent NPs. Subsequently, SDS is substituted with a biocompatible surfactant, Tween80, through ionic‐exchange resins. ζ‐Potential measurements confirmed the complete surfactant exchange that leads to biocompatible fluorescent NPs with tunable size and narrow size distribution.

     

External Stimuli‐Responsive Characteristics of Ionic Poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] Hydrogels

Summary: Polyelectrolyte hydrogels containing diprotic acid moieties sensitive to ionic strength changes of the swelling medium were synthesized from N,N‐diethylaminoethyl methacrylate (DEAEMA), N‐vinyl‐2‐pyrrolidone (VP) and itaconic acid (IA) by using ammonium persulfate (APS) as a free radical initiator in the presence of the cross‐linker, methylenebisacrylamide (MBAAm). The swelling behavior of the ionic poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] [P(DEAEMA/VP)] hydrogels were investigated in pure water; in NaCI solutions with pH 4 and 9; and in water‐acetone mixtures depending on the IA content in the hydrogel. The average molecular mass between cross‐links ( ) and polymer‐solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The pulsatile swelling behavior was also observed in response to solvent changes between the solution in water and in acetone. The equilibrium swelling ratio of these hydrogels was basically unaffected with change in temperature. The swelling variations were explained according to the swelling theory based on the hydrogel chemical structure.

Pulsatile swelling behavior of ionic P(DEAEMA/VP) hydrogels in response to solvent changes between water and acetone at 25 °C.     

Structure and Mechanical Properties of Poly(lactic acid) Filled with (Starch nanocrystal)‐graft‐poly(ε‐caprolactone)

Poly(ε‐caprolactone) (PCL) was grafted to the surface of starch nanocrystals (StN) via microwave‐assisted ROP. The resultant nanoparticles were then incorporated into a poly(lactic acid) matrix to produce fully‐biodegradable nanocomposites with good mechanical properties. A loading level of 5 wt.‐% StN‐g‐PCL resulted in simultaneous enhancements of strength and elongation. The StN‐g‐PCL self‐aggregated as rubbery microparticles to enhance the elongation by ca. 10‐fold over that of neat PLA. Meanwhile, the grafted PCL chains were miscible with PLA and formed a stress‐transferring interface to the StN, providing a reinforcing function.

     

Hybrid Organic‐Inorganic Membranes on Porous Supports by Size Exclusion and Thermal Sintering of Fluorescent Polyphenylsilsesquioxane Nanoparticles

Hybrid organic–inorganic membranes were prepared by size‐exclusion deposition and thermal sintering of fluorescent polyphenylsilsesquioxane nanoparticles on a ceramic support. Fluorescent polyphenylsilsesquioxane particles were prepared by a two‐step co‐polymerization of phenyltriethoxysilane with 0.1 mol‐% N‐(triethoxysilylpropyl)dansylamide. Because they were larger than the pores in the support, the particles formed a layer on top of the ceramic support that was sintered at 300 °C into a homogeneous, non‐porous membrane. Fluorescence of the modified polyphenylsilsesquioxane provided a valuable tool to monitor particle deposition and assist in characterization of the membranes.