Investigation of swelling,drug release and diffusion behaviors of poly(N‐isopropylacrylamide)/poly (N‐vinylpyrrolidone) full‐IPN hydrogels

The synthesis of sequential full interpenetrating polymer networks (IPNs) based on poly (N‐isopropylacrylamide) (PNIPAAm) and negatively charged poly(N‐vinyl‐2‐pyrrolidone) (PNVP) was described and their swelling, drug release, and diffusion studies were investigated. PNIPAAm was used as a host network. According to swelling experiments, IPNs gave relatively lower swelling ratios compared to PNIPAAm hydrogel due to the higher cross‐linking density. Lidocaine (LD) was used as a model drug for the investigation of drug release behavior of IPNs. LD uptake of the IPNs were found to increase from 24 to 166 (mg LD / g dry gel) with increasing amount of PNIPAAm and AMPS contents in the IPN structure. It was observed that the specific interaction between drug and AMPS co‐monomer influenced the drug release profile. In the diffusion transport mechanism study in water, the results indicated that the swelling exponents n for all IPNs are in the range from 0.50 to 0.72. This implies that the swelling transport mechanism was transferred from Fickian to non‐Fickian transport, with increasing AMPS content and NIPAAm character in the IPN structure. In addition, diffusion of LD within the IPNs showed similar trend. The incorporation of AMPS leads to an increase in electrostatic interaction between charge sites on carboxylate ions and cationic LD molecules. Therefore, the highest diffusion coefficient (D) of drug was found for IPN2 sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Analysis of the thermodynamic compatibility of interpenetrating networks during their synthesis

A thermodynamic analysis of interpenetrating polymer networks (IPNs), at any extent of reaction during their synthesis, is presented for both simultaneous and sequential procedures. A model IPN is assumed to be built up by the independent stepwise homopolymerization of two monomers: a tetrafunctional one, A₄, and a trifunctional one, A₃. No reaction of copolymerization or grafting is allowed between the two types of polymers. For the case of semi-IPNs, A₃ is replaced by A₂, i.e., a bifunctional monomer leading to a linear polymer. The free energy of mixing is described by a Flory-Huggins lattice model, whereas the elastic contribution is calculated by assuming affine deformation of an ideal elastic network. Results show that a sequential polymerization gives a more incompatible system (i.e., it enters the metastable region at lower conversions) than a simultaneous polymerization starting from the same monomers. In every case, a semi-IPN is shown to be more compatible than an IPN owing to the fact that the average size of the bifunctional monomer increases less with conversion than the size of the trifunctional monomer. When a sequential polymerization begins from a swollen gel at equilibrium, any increase in the extent of reaction of the solvent monomer will lead to its segregation from the swollen gel. The critical Flory-Huggins interaction parameter provides a simple way to ascertain the possibility of phase separation during a simultaneous polymerization.     

Characterization of thermo-reversible gels by means of sedimentation equilibria

This paper describes the deformation of gels in a centrifugal field leading to a continuous equilibrium. A gel is considered to be a binary mixture of cross-linked polymer and solvent and is assumed to remain isotropic during the deformation. From the equation for the osmotically effective pressure, called swelling pressure, the thermodynamic properties of a gel can be calculated. For highly swollen gels the expression of Svedberg and Pedersen is obtained. It is shown that the complete concentration dependence of the swelling pressure in the concentration range of the maximally swollen gel up to that at the cell bottom can be measured in a single equilibrium experiment. The homogeneity of weakly cross-linked gels can be examined by means of the method described. Soluble parts which are not incorporated into the polymer network can also be detected if they are present. From the swelling pressure-concentration curves it is possible to derive the thermodynamic properties of the physically crosslinked gelatin/water gels that were investigated. These gels can be described by means of a slightly modified Flory-Huggins equation with an interaction parameter χw in the weight fraction scale, which depends linearly on concentration. The interaction parameters show a dependence on concentration which is explained by an increased branching and crosslinking of the polymer with increasing initial polymer concentration of the gels. At low initial polymer concentration, the primary chains have to aggregate to build up relatively long chains between the network junctions. The static shear modulus G which can be calculated from the network term has the same order of magnitude as the real part of the complex shear modulus which is measured at low frequency.     

Dual temperature‐ and pH‐sensitive hydrogels from interpenetrating networks and copolymerization of N‐isopropylacrylamide and sodium acrylate

Hydrogels responsive to both temperature and pH have been synthesized in the forms of sequential interpenetrating networks (IPNs) of N‐isopropylacrylamide (NIPAAm) and sodium acrylate (SA) and compared with the crosslinked random copolymers of N‐isopropylacrylamide and SA. Whereas the stimuli‐sensitive behaviors of copolymer hydrogels were strongly dependent on the ionic SA contents, the IPN hydrogels exhibited independent swelling and thermal behaviors of each network component. The sequences and media in the synthesis of IPNs influenced the swelling capacities of the IPNs, but not the temperature or pH ranges at which the swelling changes occurred. In IPNs, a more expanded primary gel network during the synthesis of the secondary network contributed to the better swelling of the final IPNs. Both the swelling and thermal behaviors of the IPNs suggest that poly(N‐isopropylacrylamide) and poly(sodium acrylate) are phase separated regardless of their synthesis conditions. The presence of the poly(sodium acrylate) network did not influence the temperature or the extent of phase transition of the poly(N‐isopropylacrylamide) network in the IPNs, but did improve the thermal stability of the IPNs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3293–3301, 2004     

Vibration damping materials based on interpenetrating polymer networks of carboxylated nitrile rubber and poly(methyl methacrylate)

Interpenetrating polymer networks (IPNs) based on carboxylated nitrile rubber (XNBR) and poly(methyl methacrylate)s were synthesized. Crosslinked XNBR was swollen in methyl methacrylate containing benzoyl peroxide as initiator and tetraethylene glycol dimethacrylate as crosslinking agent. The compositions of the IPNs were varied by changing the swelling time of the rubber in the methacrylate monomer. The dynamic mechanical properties of the IPNs were studied. The dynamic mechanical properties in the range 1–10⁵ Hz were obtained by the time‐temperature superposition of the data under multifrequency mode, which indicated high tan δ with good storage modulus in the entire frequency range. This indicates the suitability of these IPNs as vibration and acoustic dampers. Copyright © 2002 John Wiley & Sons, Ltd.     

Novel synthesis of macroporous poly(N-isopropylacrylamide) hydrogels using oil-in-water emulsions

Porous N-isopropylacrylamide (NIPA) hydrogels having a unique structure, that is, spherelike cavities distributed randomly and a homogeneous network in the gel phase, were successfully synthesized by means of an emulsion templating method; this method involves the synthesis of NIPA gels in an oil-in-water (O/W) emulsion by free radical copolymerization with a cross-linker, followed by washing (removal) of the dispersed oil as a pore template (porogen). The synthesis conditions, O/W volume ratio, amount of added surfactant, and monomer concentration affect the internal pore structure, equilibrium swelling, and swelling/shrinking kinetics. A porous hydrogel swollen at 10 degrees C has a pore diameter distribution in the range of 1-40 microm, which was observed with a scanning electron microscope. Scanning electron micrographs and swelling degree reveal that the pore size and porosity can be adjusted by varying the O/W volume ratios and surfactant amounts. The porous hydrogels show very rapid swelling/shrinking in accordance with the temperature swing. The fast response is attributed to the convection flow of water through the macropores. In addition to a faster response gel, the emulsion templating method can yield potentially intelligent gels in which the pores function as spaces for reaction, separation, and storage.     

Hydrophobic interaction in poly(2-hydroxyethyl methacrylate) homogeneous hydrogel

Homogeneous poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel exhibits a narrow range of swelling at equilibrium in water (% H₂O, 41.09 ± 0.15 standard error of the mean of 24 samples), regardless of the dilution of the monomer solution and relatively low level of crosslinking. It is postulated that PHEMA hydrogel has, in addition to its covalently linked network structure, a secondary structure stabilized by hydrophobic bonding. The addition of microsolutes to the hydrogel seems to confirm this hypothesis. The hydrogel swells beyond its swelling equilibrium in water in presence of urea and its methyl derivatives. Swelling is also induced by organic solvents like alcohol and acetone, and by anions like iodide, acetate, trichloroacetate, and thiocyanate. Chlorides and sulfates produce a less swollen hydrogel than pure water, while bromides and cetylpyridinium chloride, in the concentrations tested, induce only a slight deswelling of the gel. When PHEMA gel prepared in organic solvent–water solutions is placed in water, the gel passes through an opaque state before becoming transparent again. This phenomenon is interpreted as being caused by the inability of water to solvate the hydrophilic ends of the unorganized polymer segments. Homogeneity returns to the gel after a rearrangement of the chains, directed by the interaction of the hydrophobic portions of the polymer segments, exposing to the solvent–water most of the hydrophilic sites in the network.     

Swelling behavior and network structure of hydrogels synthesized using controlled UV‐initiated free radical polymerization

N‐vinyl‐2‐pyrrolidone (VP) and 2‐hydroxyethyl methacrylate (HEMA) copolymeric gels have been synthesized using UV‐initiated photopolymerization to understand their characteristic behavior for development as a bioengineering material, specifically for tissue expansion. The properties of the gels have been investigated by systematic variation of the monomer feed composition and initiator and crosslinker concentrations as well as UV irradiation intensity, which was controlled by various photomasks. The swelling kinetics and network characteristics for the various hydrogels were investigated through the observation of gel swelling behavior in saline solutions and compression modulus determination of the fully swollen hydrogels. The equilibrium swelling ratio (q_e) of the gels increased as expected with increasing VP content and decreasing crosslinker concentration. However, it was found that as the amount of initiator or UV intensity increased, unexpectedly q_e also increased, which indicates a network structure with decreasing effective crosslink density (ν_e) (or increasing average molecular weight between crosslinks (M_c)). Based on this anomalous swelling behavior and thermal analysis of the gels, a molecular structure is proposed consisting of increasing number of dangling chain ends within the polymer network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1450–1462, 2008     

Swelling-shrinking behavior of a polyampholyte gel composed of positively charged networks with immobilized polyanions

Polyampholyte gels were prepared by free radical polymerization of aqueous monomer solutions with the following composition: 69% N-isopropylacrylamide (thermosensitive neutral monomer), 1% N,N'-methylenebisacrylamide (cross-linker), 15% 1-vinylimidazole (cationic monomer), and either 15% acrylic acid (AAc, anionic monomer) or poly(acrylic acid) (PAAc, polyanion). We thus obtained two sorts of polyampholyte gels; that is, G1 with immobilized PAAc and G2 with randomly copolymerized AAc. The equilibrium swelling ratio (Qe) was studied as a function of the pH, NaCl concentration, and temperature. Also studied was the kinetics of swelling and shrinking in response to a sudden pH change. The significant results obtained were as follows: (i) A fully collapsed state was observed at pH 4.5-9.0 for G1 and at pH 4.5-7.0 for G2. (ii) Below and above these pH ranges, both gels were in a swollen state; therefore, an isoelectric point (pI) appeared in a wide pH range. (iii) At alkaline pH regions where a hysteresis was observed in the Qe versus pH curves of G1 and G2 as the pH was first increased then decreased, G1 exhibited very slow swelling-shrinking kinetics. (iv) An increase in the NaCl concentration allowed the gel to swell at pH approximately pI (antipolyelectrolyte behavior) but to shrink at pHs below and above the pI range (polyelectrolyte behavior). (v) The magnitude of the salt-induced shrinking of G1 is smaller than that of G2 at pH 10 and at NaCl concentrations > 0.01 M. (vi) At pH 10, an increase in the temperature from 35 to 50 degrees C led to a shrinking change of G1 but not of G2. These results were found to be explicable in terms of a different distribution of negative charges within the polyampholyte gel network.     

An analysis of the swelling equilibrium of an ionic polymer network in a binary liquid mixture

An equation which represents the swelling equilibrium of an ionic polymer network in a binary liquid mixture is introduced and evaluated numerically. Discontinuous volume changes are obtained with pertinent values of the parameters. From two types of dependence of the degree of ionic dissociation on the composition of a liquid mixture, two types of volume transitions of an ionic gel are illustrated. One is the transition typically seen in acrylamide gels, and the other is a re-entrant transition typical of isopropylacrylamide gels. The selective dissolution factor of two liquids into a swollen polymer network also becomes discontinuous in accordance with the discontinuous volume change. Transition points and the spinodal line are calculated from a generalized form of the free energy change of the swollen gel system. © 1994 John Wiley & Sons, Inc.     

Uniform nonspherical latex particles as model interpenetrating polymer networks

Polystyrene/polystyrene latex interpenetrating polymer networks (IPNs) were prepared by seeded emulsion polymerization of styrene–divinylbenzene mixtures in crosslinked monodisperse polystyrene particles. The resulting latexes comprised uniform nonspherical particles, e.g., ellipsodal and egg-like singlets, symmetry and asymmetric doublets, and ice cream cone-like and popcorn-like multiplets. The nonspherical particles, which were formed by separation of the second-stage monomer from the crosslinked seed network during swelling and polymerization, are excellent models for studying phase separation in IPN's. The degree of phase separation increased with increasing degree of crosslinking of the seed particles, monomer/polymer swelling ratio, polymerization temperature, and seed particle size, and with decreasing divinylbenzene concentration in the swelling monomer. The results were consistent with a thermodynamic analysis based on the elastic-retractile force of the polymer network, the monomer/polymer mixing force, and interfacial tension force.     

Swelling-contraction of sodium polyacrylate hydrogels in media with various pH values

The swelling kinetics of sodium polyacrylate gels has been studied in media with different pH values. The pH dependence of the degree of equilibrium swelling shows a maximum at pH 6. The degree of swelling decreases with an increase in the crosslink density, and this dependence follows an S-shaped pattern for all examined gels. When a gel swollen in media with pH 3–13 is dried in air, its contraction is reversible, while in the case of the gel swollen in acidic media at pH < 3, the process is irreversible owing to the replacement of sodium ions with protons.     

Osmotic deswelling of weakly charged poly(acrylic acid) solutions and gels

The osmotic pressure of weakly charged aqueous poly(acrylic acid) (PAA) solutions and the swelling pressure PAA gels were studied by osmotic deswelling at different degrees of ionization (α). In solution, the osmotic pressure was found to scale linearly with concentration, whereas the scaling power of the swelling pressure of gels was higher (1.66). The effect of the ionization degree on the osmotic coefficient in PAA solutions was in agreement with the theory of Borue and Erukhimovich [Macromolecules, 21 , 3240 (1988)]. Ionization increases the swelling capacity of the PAA gels until a plateau is reached at about 35% neutralization. The concentration at equilibrium swelling scales as C_e ～ α^?0.6. The contribution of the network to the gel swelling pressure is evaluated by subtracting the osmotic pressure of the polymer solution at the same concentration and degree of ionization. In swollen gels the extended network opposes swelling. As the gel is osmotically deswelled, a state of zero network pressure exists at a certain concentration, below which the network elasticity favors swelling. The crossover concentration shifts to lower values as the degrees of ionization increases. © 1995 John Wiley & Sons, Inc.     

Taguchi optimized synthesis of collagen-g-poly(acrylic acid)/kaolin composite superabsorbent hydrogel

A novel biopolymer-based hydrogel composite was synthesized through chemical crosslinking by graft copolymerization of partially neutralized acrylic acid onto the hydrolyzed collagen. The Taguchi method, a robust experimental design, was employed for the optimization of the synthesis based on the swelling capacity of the hydrogels. This method was applied for the experiments and standard L16 orthogonal array with five factors and four levels. In the synthesis of the composite superabsorbent, N,N′-methylene bisacrylamide (MBA) as crosslinker, ammonium persulfate (APS) as initiator, acrylic acid (AA) as monomer, neutralization percent (NU), and collagen/kaolin weight ratio were used as important factors. From the analysis of variance of the test results, the most effective factor controlling equilibrium swelling capacity was obtained and maximum water absorbency of the optimized final product was found to be 674 g/g. The surface morphology of the gel was examined using scanning electron microscopy. Furthermore in this research, swollen gel strength of composite SAPs already swollen under realistic conditions (saline solution absorbency under load) was determined.     

STUDY ON THE SWELLING BEHAVIOUR OF COPOLYMER HYDROGEL

The states of water in poly (N-vinylpyrrolidone-methylmethacrylate) and poly (N-vinylpyrroli-done-2-hydroxyethyl methacrylate) hydrogels have been studied by means of DSC. The effect ofpolmer structure on equilibrium swelling extent of water has been examined. It was found that thestate of water and the water content in different hydrogels were dependent on the kind of monomer used,the component of copolymer, the sequence distribution of the monomer unit and the degree of cross-linking (including chemical and physical) to a great extent. The equilibrium water content of thehydrogel may be regarded as the sum of the different state of swollen water contents of the hydrogel.Based on these, a semiempirical formula used to estimate the equilibrium water content of the copolymerhydrogels was presented.     

共聚水凝胶溶胀特性的研究

本文用差示扫描量热法研究了聚[N-乙烯基吡咯烷酮-甲基丙烯酸甲酯] 和聚[N-乙烯基吡咯烷酮-甲基丙烯酸β羟乙酯]两种共聚水凝胶中水存在的状态,考察了聚合物结构对平衡溶胀度的影响。结果表明,共聚单体的种类、共聚物组成、序列分布、化学交联度等结构因素对水存在的状态及各种状态水的含量都有很大影响,平衡吸水率可看作各种状态溶胀的水量的加和,以此为基础,提出了估算共聚水凝胶平衡吸水率的半经验公式。     

Effect of filler networking on the response of thermosensitive composite hydrogels

Several composite hydrogels of poly(N-isopropylacrylamide) (pNIPAAm) with sodium montmorillonite (NaMM) have been synthesized using a fixed polymer/NaMM ratio (4:1 wt./wt.), but various monomer concentrations, in order to obtain hydrogels with different degrees of swelling, and thus different clay contents in the swollen state. For comparison, unfilled pNIPAAm gels have been also prepared at the same concentrations. The equilibrium swelling behaviour of the gels has been studied both in the swollen and in the shrunk state. In the swollen state, the polymer volume fraction increases with the initial monomer concentration C₀. In the shrunk state, the polymer fraction in pNIPAAm hydrogels is dependent on the specimen size and on C₀, whereas in the composite gels a constant polymer content is observed. When subjected to stepwise heating from 25 to 45 °C, unfilled gels undergo only poor deswelling. By contrast, complete deswelling takes place in composite gels. The latter show half-shrinking times varying over two orders of magnitude, depending on the monomer concentration and on the procedure followed to disperse NaMM, which determine the overall dispersion state of the filler, as evidenced by transmission electron microscopy (TEM). In particular, TEM observations show clay networking above a percolation threshold near 2.5 wt.% of NaMM. The effect of the incorporation of clay on the response to thermal stimuli is discussed in terms of the ability of NaMM to hinder the hydrophobic association of pNIPAAm segments and in terms of its dispersion state. It is suggested that, above the percolation threshold, NaMM forms a hydrophilic, physical network, through which water can flow also above the volume transition temperature, where pNIPAAm acquires a hydrophobic character.     

高机械性能的聚(丙烯酸-co-甲基丙烯酸十八酯)疏水缔合凝胶的溶胀行为研究

以丙烯酸(AA)、甲基丙烯酸十八酯(OMA)、十二烷基硫酸钠(SDS)为原料,采用胶束共聚的方法合成了疏水缔合(HA)凝胶.在HA凝胶内部,表面活性剂SDS与疏水单体OMA组成的增溶胶束起到物理交联作用,将亲水的聚合物链交联起来.通过单向拉伸试验证实了该凝胶具有较高的机械性能.此外,也测试了HA凝胶在不同pH值溶液中的溶胀行为.结果显示,HA凝胶具有特殊的溶胀行为,其溶胀过程可以分为凝胶溶蚀、溶胀平衡和凝胶瓦解3个阶段.在强酸性条件下,凝胶的溶胀被抑制,没有出现凝胶瓦解阶段.在强碱性条件下,凝胶的溶胀被促进,溶胀平衡阶段被越过.盐的存在也会抑制HA凝胶的溶胀,但在SDS溶液中,溶液中的SDS会促使凝胶中的疏水改性聚合物溶解到溶液中去,组成新的缔合结构,而使溶液增稠。     

Swelling Behaviour of Isotropic Poly(n-butyl acrylate) Networks in Isotropic and Anisotropic Solvents

Summary: The swelling properties of photochemically crosslinked poly(n-butyl acrylate) (PABu) networks in isotropic and anisotropic solvents were investigated experimentally. The purpose of this study was to examine the swelling kinetics of PABu networks in isotropic solvents and to compare the results obtained which those observed in the case of the low molecular weight liquid crystal 4-cyano-4′-n-pentyl-biphenyl known as 5CB. The phase diagrams were established in terms of composition and temperature for isotropic solvents, as toluene, acetone, cyclohexane, and methanol, and 5CB, using the plateau values corresponding to equilibrium states of swelling. The polymer networks were prepared via free radical polymerization/crosslinking processes by ultraviolet (UV) radiation of initial mixtures made up from a monomer, a crosslinker, and a photoinitiator. PABu networks with several crosslinking densities were formed using different quantities of difunctional monomer hexanedioldiacrylate (HDDA). Immersion of these networks in excess solvent allows measuring the solvent uptake by determination of the weight in isotropic solvents and diameter in an anisotropic solvent (5CB). Swelling data were rationalized by calculating weight and diameter ratios considering swollen to dry network states of the samples.     

IPAAm凝胶在丙酮水溶液中溶胀行为的关联与预报

基于Maurer和Prausnitz的凝胶相平衡条件，建立了凝胶的溶胀模型.模型假设凝胶是以凝胶组分及凝胶吸收的溶液为核心，以弹性半渗透膜为壳的复合体.并采用UNIQUAC方程计算凝胶相及与之共存液相的Gibbs过剩自由能，采用“phantomnetwork”理论计算凝胶的弹性自由能，采用“自由体积”计算分子的尺度效应.同时以N-异丙基丙烯酰胺（IPAAm）为单体合成了IPAAm凝胶.研究了25 ℃时IPAAm凝胶在丙酮水溶液中的溶胀行为，并测定了丙酮在胶体相和与之共存液相中的分配，以检验模型的关联与预报能力.结果表明,模型预报的单体总量和交联剂浓度对凝胶溶胀的影响与实验符合得很好.而且凝胶溶胀时，能很好地预测丙酮在两相中的分配,表明模型具有很好的关联和预报能力.