Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Copolymer hydrogels based on N-isopropylacrylamide and itaconic acid

In this study, the swelling behaviour of copolymer hydrogels of N-isopropylacrylamide (NIPAM) and itaconic acid (IA) in response to temperature and pH value of the external media was studied. The equilibrium degree of swelling for PNIPAM and PNIPAM/IA copolymers was greater at 25 °C than at 37 °C. The degree of swelling was low at low pH values. As the degree of ionization increased above the nominal pK_a values of IA, the increased hydrophilicity resulted in larger degrees of swelling. At 37 °C, the PNIPAM hydrogel and some copolymers show anomalous swelling behaviour, i.e. the overshooting effect, in buffered solutions of certain pH values. A swelling-deswelling study showed that the deswelling process of the hydrogels was faster then the swelling process. According to dynamic swelling studies, the diffusion exponent and the diffusion coefficient both increase with increasing content of IA.     

Formulation design,optimization, characterization and swelling behaviour of a cationic superabsorbent based on a copolymer of [3‐(methacryloylamino)propyl]trimethylammonium chloride and acrylamide

A series of crosslinked copolymers with cationic nature have been prepared based on acrylamide (AAm) and [3‐(methacryloylamino)propyl]trimethyl ammonium chloride (MAPTAC) using N,N′ methylene‐bis‐acrylamide (MBA) as crosslinking agent. Taguchi's method has been employed for the purpose of formulation design and optimization as well as investigating the effects of various compositional parameters, such as total monomer concentration, cationic monomer and crosslinking agent concentration. The swelling behaviour of the synthesized gels in electrolyte solutions composed of ions with different valency has been studied and compared with an anionic‐based superabsorbent. The swelling capacity and absorbency were found to be enhanced with increase of the MAPTAC moieties of the copolymer chains, and therefore increase of their cationic character. All the cationic hydrogels prepared had greater swelling capacity, with less change in their swelling behaviour, when immersed into aqueous solutions containing multivalent cations. The anionic‐based hydrogels collapsed in similar ionic solutions with moderate‐to‐high ionic strength and did not show any tendency to re‐swell. The complex modulus (G*) of the crosslinked copolymers in the equilibrium swollen state was measured by rheomechanical spectroscopy and was correlated with the chemical composition of the network. Thermogravimetric analysis of the dry cationic superabsorbent showed more bound water but similar thermal behaviour to crosslinked polyacrylamide Copyright © 2003 Society of Chemical Industry     

Rapid pH‐dependent phase transition and elasticity of stimuli‐responsive cationic poly(N,N‐dimethylaminoethyl methacrylate) hydrogels prepared with a dimethacrylate crosslinker

Stimuli‐responsive hydrogels prepared from poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) and its copolymers have attracted much interest to serve in biomedical and pharmaceutical applications. To investigate pH‐dependent swelling and elasticity, a series of cationic hydrogels based on N,N‐dimethylaminoethyl methacrylate were prepared by free radical crosslinking copolymerization at 60 °C in the presence of tetraethylene glycol dimethacrylate as the crosslinker. The equilibrium swelling and the mechanical properties of the PDMAEMA hydrogels were investigated as a function of the gel preparation concentration. To explain the effect of pH on the equilibrium swelling of the hydrogels, pH‐dependent swelling studies were carried out in solutions of pH ranging from 2.1 to 10.7. It was found that the PDMAEMA hydrogels exhibit a rapid pH‐dependent phase transition in aqueous solutions; that is, the gels first remain in the swollen state at acidic pH then collapse in a very narrow range of pH. The results showed that the volume of PDMAEMA hydrogels in acidic conditions is about 10‐ to 40‐fold larger than that in the basic pH region. By using the Flory–Rehner theory, the characteristic network parameters of the PDMAEMA hydrogels were calculated and good agreement obtained between the swelling equilibria of hydrogels and their mechanical properties over the whole range of gel preparation concentration. © 2012 Society of Chemical Industry     

Swelling behavior of poly(acrylamide‐co‐N‐vinylimidazole) hydrogels under different environment conditions

A series of random copolymers of acrylamide and N‐vinylimidazole, poly(AAm‐co‐NVI), with various compositions were prepared using redox copolymerization. The influence of environmental conditions such as pH, temperature, and ionic strength on the swelling behavior of the copolymeric hydrogels was investigated. The hydrogels exhibited the highest equilibrium swelling in basic medium at high temperature. Equilibrium swelling decreased with rising ionic strength at pH 5.0. As pH increased, equilibrium swelling of the hydrogels increased at pH 11.0 and I = 0.20 M. Swelling kinetics of the hydrogels was found to be non‐Fickian at 25°C. The process tended to be Fickian at higher pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1783–1788, 2005     

Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and swelling behavior of pH- and temperature-sensitive poly[2-(dimethylamino)ethyl methacrylate-co-2-acrylamido-2-methylpropane-1-sulfonic acid] hydrogels

Summary Poly[2-(dimethylamino)ethyl methacrylate-co-2-acrylamido-2-methylpropane-1-sulfonic acid], poly(DMAEMA-co-AMPS), hydrogels were prepared by chain polymerization in water at 60 °C in the presence of tetraethyleneglycol diacrylate (TEGDA) as crosslinking agent. Ammonium persulfate (APS) and N,N,N’,N’-tetramethylethylenediamine (TEMED) were used as initiator and accelerator, respectively. Hydrogels with different feed compositions were prepared by keeping the total monomer concentration constant at 1 or 0.5 M. The concentration of TEGDA in the feed was adjusted so that it made for 3 or 2 mol % of the total monomer content while it was 1% for APS. In order to observe the effects of pH and ionic strength of the medium on swelling, the equilibrium swelling behavior of these hydrogels were investigated both in distilled water at various temperatures between 30 and 90 °C and in different buffer solutions with pH of 2.8, 5.3, 7.0, 10.0, and 12.4 at constant ionic strength (I=0.08 mol/l) at room temperature. The effects of temperature and co-monomer AMPS content on the swelling behavior of poly(DMAEMA-co-AMPS) in distilled water were also investigated. The copolymers with equimolar contents of DMAEMA and AMPS displayed minimum swelling both in distilled water and in buffer solutions due to ionic complex formation. Their swelling values in distilled water between 30 and 90 °C were constant. While equilibrium swelling values of copolymers in buffer solutions with pH between 2.8 and 7 were almost constant, they increased with increasing pH. The increase in the AMPS content and decrease in initial monomer concentration increased the equilibrium swelling values of copolymers.     

Influence of the swelling history on the swelling kinetics of stimuli-responsive poly[(N-isopropylacrylamide)-co-(methacrylic acid)] hydrogels

The influence of the swelling history on the swelling behavior of poly[(N-isopropylacrylamide)-co-(methacrylic acid)] P[(N-iPAAm)-co-(MAA)] random copolymers hydrogels synthesized by free radical polymerization in solution of N-iPAAm and MAA comonomers crosslinked with tetraethylene glycol dimethyl acrylate (TEGDMA) has been studied. The swelling behavior under pH 7 at 18, 29, 39 and 49 °C of this series of copolymers, previously soaked either at pH 2 or 7 has been investigated. The swelling kinetics of these two series of samples displays different behavior as function of the composition and temperature. However, the equilibrium swelling values only show slight dependences on the previous soaking pH and temperature. When samples are soaked at pH 7, then the swelling at pH 7 follows a first order kinetics, irrespective of the copolymer composition or the temperature at which the experiment has been carried out. In this case, the swelling process is very fast and depends only slightly on temperature. The first order rate constant increases with the MAA content in the hydrogel. Furthermore, the swelling rate of copolymer hydrogels soaked at pH 2, show strong dependence on composition and temperature. They follow an autocatalytic swelling kinetics due to the disruption of hydrogen bond arrangements. An initial slow water uptake is followed by an acceleration process, in which water molecules inside the gel help the next water molecules to come in. Two rate constants, a first-order rate constant and an autocatalytic one have been obtained from the kinetics analysis. They have revealed different temperature dependence which may be due to a balance between hydrophobic and hydrogen bond interactions. The temperature dependence of the swelling kinetics is stronger and more complex for copolymers treated under pH 2 than for copolymers soaked under pH 7.     

pH/temperature-responsive poly(dimethylaminoethyl methacrylate) grafted κ-carrageenan copolymer: Synthesis and physicochemical properties

κ-Carrageenan-graft-poly(dimethylaminoethyl methacrylate) (CRG-g-PDMA) was synthesized via free-radical copolymerization under microwave irradiation. ¹³C-Nuclear magnetic resonance spectroscopy (¹³C-NMR), fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD) methods were used for characterization of the CRG-g-PDMA structure. The effect of reaction variables including the concentrations of the initiator and dimethylaminoethyl methacrylate (DMA) as well as the microwave irradiation time and power on graft ratio and conversion was investigated, and their highest values were obtained to be 179 and 76%, respectively. The lower critical solution temperatures (LCSTs) of the CRG-g-PDMA copolymers were determined at various pH conditions, and their value in distilled water was found as 47°C. Besides, the swelling capacity of the copolymers under different pH levels was investigated and it was seen that the swelling capacity of the copolymer increased with the decrease in the pH value of the medium. The CRG-g-PDMA copolymer exhibited excellent swelling performance in acidic pH conditions and possessed responsiveness to pH and temperature stimuli.     

具有pH及温度敏感性的共聚物Poly(NIPAm-co-IA)水凝胶的合成及其性能研究

用自由基聚合合成了具有两水亲性的异丙基丙烯酰胺与衣康酸共聚物 ,对它们水溶液及其水凝胶的 p H及温敏性进行了研究。结果表明 ,在一定的范围内 ,随衣康酸含量增加、水溶液浓度减少和 p H值增大 ,共聚物水溶液的低临界溶解温度随之升高。共聚物水凝胶的溶胀率随温度升高呈下降趋势 ,并且 p H值低时的溶胀率随温度的升高而下降的趋势比 p H高时的要快 ,而且表现出明显的溶胀 -退胀可逆过程。     

Interpolymer complexes of novel linear and crosslinked acrylic acid–Schiff base copolymers

Novel linear and crosslinked copolymers of acrylic acid and Schiff base, containing the amine groups in the main chain and the carboxylic groups in the side chain, have been synthesized by the Michael addition reaction followed by radical copolymerization. The copolymers that exhibited poly(ampholyte–electrolyte) behaviour were used to prepare complexes by reaction with anionic (poly(acrylic acid), poly(styrene sodium sulfonate)), cationic (polyethyleneimine, poly(hexamethylene guanidine)) and non‐ionic (poly(N‐vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol)) polymers. The influence of external factors, such as solvent quality, temperature, pH and ionic strength, on phase (coil–globule) and volume (swelling–collapse) transitions has been studied. © 2003 Society of Chemical Industry     

Drug diffusion in hydrophobically modified N,N-dimethylacrylamide hydrogels

The use of hydrophobically modified hydrogels for drug release was investigated. Copolymers of N,N-dimethylacrylamide and 2-(N-ethyl-perfluorooctanesulfonamido) ethyl acrylate (FOSA) were prepared by free-radical polymerization. The drug release rates, dynamic swelling behavior, and pH sensitivities of copolymers ranging in composition from 0 to 30 mol% FOSA were studied. Pheniramine maleate, an ocular antihistamine, was used as the model drug substance. Hydrogels of DMA produced with increasing amounts of FOSA had a decreased equilibrium media content and exhibited a slower drug release rate. Early-time, late-time and Etters approximation drug diffusion coefficients ranged from 0.4×10⁻³ to 12.3×10⁻³ mm²/min. The diffusion of the drug model was less sensitive to pH of the buffered media over the range of pH 4-8, but increasing the media pH slowed the permeability slightly by decreasing the swellability of the hydrogel. The power law exponent (n≈0.5) and the swelling interface number (Sw?1) suggested that the drug release mechanism from these hydrogels was Fickian and not swelling controlled. These novel thermoprocessible hydrogels have potential to be used as controlled ocular drug delivery devices (e.g. contact lenses or ocular inserts).     

Collapse of acrylamide‐based polyampholyte hydrogels in water

The swelling behavior of balanced acrylamide (AAm)‐based polyampholyte hydrogels in water and in aqueous salt (NaCl) solutions was investigated. Equimolar ratio of the ionic comonomers 4‐vinylpyridine (cationic monomer) and acrylic acid (anionic monomer) were used together with the nonionic monomer AAm in the hydrogel preparation. The variations of the hydrogel volume in response to changes in pH were measured. It was found that the hydrogels are in a collapsed state not only at the pH of the isoelectric point pH_IEP but also over a wide range of pH including pH_IEP. The width of the collapsed plateau increased and the hydrogels assumed a more compact state as the ionic group content is increased. The antipolyelectrolyte behavior was observed along the collapsed plateau region, where the gel occupies a larger volume in salt solution. The experimental swelling data were compared with the predictions of the Flory‐Rehner theory of swelling equilibrium including the ideal Donnan equilibria. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of the anionic‐group/cationic‐group ratio on the swelling behavior and controlled release of agrochemicals of the amphoteric,superabsorbent polymer poly(acrylic acid‐co‐diallyldimethylammonium chloride)

A series of amphoteric, superabsorbent polymers [poly(acrylic acid‐co‐diallyldimethylammonium chloride)] with different molar ratios of anionic groups to cationic groups were prepared by solution polymerization to investigate their swelling behaviors and the controlled release of agrochemicals. Various factors, including the solution pH, the concentrations of different salt solutions, and the temperature, were studied. The dynamic parameters of hydrogels at different temperatures suggested that diffusion was Fickian at lower temperatures, whereas non‐Fickian diffusion prevailed at higher temperatures. A copolymer hydrogel with a low anionic‐group/cationic‐group ratio showed a higher swelling capacity in water and higher salt tolerance. Also, the anionic‐group/cationic‐group ratio was not the dominant factor in determining the water retention. A poly(acrylic acid‐co‐diallyldimethylammonium chloride) hydrogel could control the release of agrochemicals effectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 986–991, 2006     

Preparation of a novel pH-sensitive hydrogel based on acrylic acid and polyhedral oligomeric silsesquioxane for controlled drug release of theophylline

Hydrogels based on pH-sensitive polymers are of great interest as potential biomaterials for the controlled delivery of drug molecules. In this study, a novel pH-sensitive copolymer hydrogel based on acrylic acid (AA) monomer by free-radical solution polymerization were synthesized with organic–inorganic cross-linking agent of octavinyl polyhedral oligomeric silsesquioxane (OVPOSS). And its properties were compared with conventional hydrogels using N,N′-methylenebisacrylamide (MBA) as cross-linking agent. The copolymers were characterized by Fourier transform infrared spectra and differential scanning calorimetry. The morphology after swelling was presented by scanning electron microscopy. Swelling behaviors in different pH and potential applications in controlled drug delivery of the hydrogels were also examined. The results showed that both hydrogels were pH sensitive. However, as the addition of OVPOSS limited the movement of the molecular chain segment, the swelling ratio and the drug-release rate of theophylline in SGF decreased obviously when using OVPOSS as cross-linking agent, comparing with P(MBA-co-AA) hydrogels. The results in this study suggested that P(OVPOSS-co-AA) could serve as potential candidate for theophylline drug delivery.     

Swelling of porous copolymers based on alkyl methacrylate esters in water

Porous copolymers based on alkyl methacrylate esters (AMA) were prepared in the presence of toluene as the inert diluent, and their swelling properties in water were investigated by measuring the water uptake of the copolymers with or without being pretreated with methanol. With ethylene glycol dimethacrylate (EGDM) being used as the crosslinking agent, the obtained AMA/EGDM copolymers, regardless of their inherent hydrophobic nature, were found to be able to swell in water directly. The swelling was negligible in the lower degree of crosslinking region. However, once it increased to a value beyond a certain EGDM percentage, the swelling transition occurred, and the water uptake, which was measured by direct contact of the copolymers with water for all three kinds of AMA/EGDM copolymers based on methyl MA (MMA), ethyl MA (EMA), and butyl MA (BMA), reached very high values. The direct swelling of highly crosslinked AMA/EGDM copolymers in water was very fast at the beginning of the swelling with the swelling rate order of MMA/EGDM > EMA/EGDM > BMA/EGDM, but thereafter it progressed very slowly with most swelling being achieved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 250–258, 2000     

Synthesis,pH sensitivity,and drug‐release behavior of acrylic acid and polyhedral oligomeric silsesquioxane copolymer

pH‐Sensitive organic–inorganic copolymers of hydrogels were developed as drug delivery systems (DDS) to improve the swelling behavior of polyacrylic acid (PAA). They were represented through FTIR, TGA and XRD characterization which revealed that the functional groups of methacryl‐phenyl polyhedral oligomeric silsesquioxane (POSS) were successfully added to the acrylic acid (AA) molecular chains through radical solution polymerization. The DSC test results indicate that the addition of POSS could improve the thermal properties of the copolymers. The swelling properties at the pH range of 1.25–8.01 exhibited the pH sensitivity of POSS/AA copolymers (POSS‐co‐AA) and the lower swelling ratio in acidic conditions indicated that the DDS had low amount of release in SGF; this phenomenon suggested that the copolymer was available as DDS of theophylline. And it was proved by drug release curve and scanning electron microscopy. Since the addition of POSS reduced the release rate of theophylline and prolonged the release time of the drug, the concentration range of theophylline could remain low for an extended duration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Paper sizing agents from micelle‐like aggregates of polystyrene‐based cationic copolymers

A series of polystyrene‐based cationic copolymers (PSCC) were synthesized by copolymerization of styrene and the cationic comonomer vinylbenzyl trimethylammonium chloride. These copolymers can be used as internal paper sizing agents in a broad pH range. The effect of the charge density on the PSCC colloid properties was investigated. It was found that at room temperature the PSCC could change from water insoluble to colloidally dispersible and finally to fully water soluble as the charge density was increased. Based on the understanding of their colloid behavior, PSCCs were applied as internal sizing agents for paper. The results showed that the hydrophobicity of handsheets could be significantly improved by PSCCs and the sizing performance was a function of copolymer addition, charge density, particle size, drying temperature, and pH conditions. The present study indicated some potential advantages of PSCC copolymers as internal sizes. PSCC can be self‐retained on the fiber surface, no hydrolysis occurs during the storage and application, and no sizing reversion occurs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2067–2073, 2000     

Delivery of bupivacaine included in poly(acrylamide‐co‐monomethyl itaconate) hydrogels as a function of the pH swelling medium

Copolymeric hydrogels of poly(acrylamide‐co‐monomethyl itaconate) (A/MMI) crosslinked with N,N′‐methylenbisacrylamide (NBA) were synthesized as devices for the controlled release of bupivacaine (Bp). Two compositions of the copolymer, 60A/40MMI and 75A/25MMI, were studied. A local anesthetic was included in the feed mixture of polymerization (2–8 mg Bp/tablet) and by immersion of the copolymeric tablets in an aqueous solution of the drug. A very large amount of Bp (36–38 mg Bp/tablet) was included in the gels by sorption due to interactions between the drug and the side groups of the hydrogels. Swelling and drug release were in accordance with the second Fick's law at the first stages of the processes. The swelling behavior of these copolymers depended on the pH of the medium. The equilibrium swelling degree (W_∞) was larger at pH 7.5 (W_∞ ≈ 90 wt %) than at pH 1.5 (W_∞ ≈ 52–64 wt %) due to the ionization of the side groups of the copolymer. Release of the drug also depended on the pH of the swelling medium; at pH 7.5, about 60% of the included drug was released, and at pH 1.5, about 80% was released. Bp release was controlled by the comonomer composition of the gels, their drug‐load, and the pH of the swelling medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 327–334, 2002     

Trisodium trimetaphosphate crosslinked xanthan networks: synthesis,swelling, loading and releasing behaviour

Xanthan (Xan) is a biocompatible and biodegradable polysaccharide with a promising potential as substrate for controlled drug delivery applications. Xan based hydrogels were synthesized in alkaline medium using trisodium trimetaphosphate (STMP) as crosslinking agent. Hydrogels with various crosslinking agent/polymer ratios were synthesized and subsequently characterized by the means of elemental analysis and dynamic swelling degree, model compound loading and releasing behaviour. Two physical parameters (crosslinking density and phosphate charge) are manifesting antagonistic actions by stiffening or disrupting the three-dimensional macromolecular ensemble. The highest swelling degree was obtained using an intermediate STMP:Xan ratio in which case the opposing effects of the two forces are well balanced. The synthesized networks are pH sensitive. In acid and alkaline media the swelling degrees are lower by comparison to neutral pH. The entrapping and releasing behaviour of the newly synthesized xanthan networks were studied using methylene blue as a cationic model molecule. The releasing kinetics present a first-order model.