Phase transition in swollen gels 30. Temperature-induced phase transition in positively charged poly(N-isopropylacrylamide) hydrogels in water and aqueous NaCl solutions

Summary The swelling and mechanical behaviour of ionized networks of N-isopropylacrylamide with an ionic comonomer, (2-acrylamidoethyl)trimethylammonium chloride (mole fractions x _S= 0−0.1), in the presence of a crosslinker, N,N'-methylenebisacrylamide, was investigated in water as a function of temperature and in aqueous NaCl solutions (c _NaCl= 10⁻⁵− 1 M) at 23 °C. On heating, a continuous decrease in the swelling degree in water, Q _w, was observed; increasing x _S shifts the volume transition temperature, T _tr, (from the swollen to collapsed state) to higher temperatures. The expected decrease in the swelling degree, Q, with increasing NaCl concentration in aqueous NaCl solutions was observed and two shrinking regions in ionic gels were found. The decrease in Q _w with increasing temperature and the decrease in Q with increasing c _NaCl are accompanied by an increase in equilibrium shear modulus of gels, so that the mechanical behaviour of gels is predominantly determined by the swelling degree. The experimental swelling behaviour could be, in the first approximation, described by the theory of polyelectrolyte networks in which repulsion of charges on the chain and finite chain extensibility were considered. Received: 7 June 2001 / Accepted: 21 September 2001     

Swelling of acrylamide gels made at various onset temperatures: an optical transmission study

Optical transmission experiments were performed using a UV–visible spectrometer during the swelling of polyacrylamide (PAAm) gels. These gels were prepared from acrylamide with N,N′‐methylenebisacrylamide at various onset temperatures (T_on) by free radical crosslinking copolymerization in water and dried before use for swelling experiments. Transmitted light intensity (I_tr) from the gels increased during early stages when PAAm gels were immersed in water at room temperature and then decreased continuously as swelling time was increased. Decrease in I_tr was attributed to the increase in the scattered light intensity which may originate from the contrast between ‘frozen blob clusters’ and holes in the swelling gel. Decrease in I_tr was modelled using the Li–Tanaka equation from which time constants (τ₁) and collective diffusion coefficients (D₀) were determined for the PAAm gels prepared at different onset temperatures. τ₁ and D₀ were found to be dependent on T_on. The correlation between T_on and τ₁ and D₀ was explained in terms of the size of microgels formed during gelation. © 2003 Society of Chemical Industry     

Observations by DSC on bound water structure in some physically crosslinked hydrogels

Linear, compositionally homogeneous copolymers containing 23–62 wt% N-vinyl-2-pyrrolidone (VP) were prepared by a semi-continuous copolymerisation with methyl methacrylate (MMA) in the absence of chemical crosslinker. Films cast from solution in chloroform were swollen in water at various temperatures (T) within the range 283–343 K. The total water content (11–80 wt%) of the resultant hydrogels at swelling equilibrium, as well as its subdivision into freezing and non-freezing water components, were measured and found to be dependent on copolymer composition and T. The network structure of these hydrogels is considered to arise from a combination of normal VP–water interactions with physical crosslinking due to hydrophobic MMA sequences, and the novel, albeit only semi-quantitative, findings are discussed on this basis.     

Swelling and mechanical behavior of ionized poly(acrylamide-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="Italic">N,N</Emphasis>’-diethylacrylamide) gels in water/acetone mixtures and in water at various temperatures

Summary Ionized networks of random copolymers of acrylamide (AAm) and N,N’-diethylacrylamide (DEAAm) (mole ratios of x_AAm/x_DEAAm=1/0,0.75/0.25,0.5/0.5,0.30/70,0.15/0.85,0/1) with various amounts of ionic comonomer-sodium methacrylate (MNa) (mole ratios to all monomers x_MNa=0.0,0.025,0.05) and crosslinker – N,N’-methylenbisacrylamide (MBAAm) were prepared at high dilution in water. Their swelling and mechanical behavior was investigated in water at various temperatures (from 10 to 90 °C) and in water/acetone (w/a) mixtures at room temperature. For some copolymers the transition region from expanded to collapsed state was observed at critical concentration of acetone, a_c, in w/a mixtures or at critical temperature, T_c, in water. It was found that with increasing content of DEAAm component in copolymers the a_c values increase; the similar increase was observed with increasing x_MNa. Neat PDEAAm and copolymers with the highest DEAAm content exhibit temperature transition; both increasing amount of AAm and charges bound on the chains (x_MNa) in copolymers shifts the T_c temperatures to higher values very efficiently (for more than 20 °C).     

Phase transition in swollen gels

Summary The swelling and mechanical behaviour of networks of copolymers of acrylamide, methylenebisacrylamide and sodium 2-(2-carboxybenzoyloxy)ethylmethacrylate (mole fraction of salt x _s =0–0.2) in water-acetone mixtures was investigated. In the range x _s 0.01 phase transition (collapse) was observed, with both the extent of the collapse and the critical acetone concentration in the mixture at collapse, a _c , increasing with increasing concentration of the salt. A comparison between these results and those obtained for networks with a quaternary ammonium salt led to a conclusion that an exchange of the positive charge of the ammonium salt (NCl) for the negative charge of the sodium salt (COONa) in the side chain decreases the critical content of salt necessary for the collapse, X _s ^c , from 0.03 to 0.01, and the collapse takes place at lower concentrations of acetone. The collapse may also take place in a mixed solvent waterethanol; the dependence of network swelling on the concentration of ethanol is roughly the same as that on the concentration of acetone.     

Copolymerization and thermal behavior of methyl methacrylate with N‐(phenyl/p‐tolyl) itaconimides

This study describes the synthesis, characterization, and thermal behavior of copolymers of methyl methacrylate (MMA) and N‐p‐tolyl itaconimide (PTI)/N‐phenyl itaconimide (I). Homopolymerization and copolymerization of N‐(phenyl/p‐tolyl) itaconimide with MMA was carried out by use of various mole fractions of N‐aryl itaconimide in the initial feed from 0.1 to 0.5, using azobisisobutyronitrile as an initiator and tetrahydrofuran as the solvent. The copolymer composition was determined by ¹H‐NMR spectroscopy using the proton resonance signals attributed to –OCH₃ of MMA (δ = 3.5–3.8 ppm) and the aromatic protons (δ = 7.0–7.5 ppm) of N‐aryl itaconimide. The reactivity ratios of the monomers were found to be r₁ (PTI) = 1.33 ± 0.05/r₂ (MMA) = 0.24 ± 0.03 and r₁ (I) = 1.465 ± 0.035/r₂ (MMA) = 0.385 ± 0.005. The molecular weight of the copolymers decreased with increasing mole fraction of N‐aryl itaconimide in the copolymers. Glass‐transition temperature (T_g) and thermal stability of PMMA increased with increasing amounts of itaconimides in the polymer backbone. A significant increase in the percentage char yield at 700°C was observed on incorporation of a low mole fraction of N‐aryl itaconimides. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1195–1202, 2003     

Two-stage swelling of acrylamide gels: A photon transmission study

Acrylamide gels were prepared from acrylamide (AAm) with various N,N′-methylenebis(acrylamide) (Bis) contents by free-radical crosslinking copolymerization (FCC) in water and dried before used for swelling experiments. Photon transmission measurements were performed using a UV-visible (UVV) spectrometer during the swelling of polyacrylamide gels. Transmitted light intensity I_tr increased linearly at very early times when acrylamide gels were immersed in water, then decreased continuously as swelling time increased. The behavior of I_tr was modeled assuming two-stage swelling mechanisms for the swelling acrylamide gels. The increase in I_tr at early times was quantified using a linear diffusion model and a linear relaxation constant k₀ was measured. The decrease in I_tr was modeled using the Li–Tanaka equation, from which time constants τ₁ and cooperative diffusion coefficients D₀ were determined for acrylamide gels with varying Bis content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 894–906, 2001     

Synthesis and properties of novel polyvinyl alcohol–lactic acid gels

This article describes a process for esterifying polyvinyl alcohol (PVA) with L‐lactide (LLA) and D,L‐lactic acid (LA), using ethyl acetate and N,N′‐dimethyl formamide at temperatures varying from 120 to 150°C. The grafting process was carried out under nitrogen to avoid possible oxidation or other degradation of the process ingredients and product. Lower T_g values were obtained for the PVA/LLA graft copolymers of higher LLA content suggesting some compatibility in the amorphous phase. Higher T_g values were observed for PVA/LA graft copolymers that yielded tough polymer films. The structure of the copolymers was studied by solid‐state ¹³C‐NMR, infrared spectroscopy, and differential scanning calorimetry (DSC). The PVA/LA films exhibited melt processability and good mechanical properties such as yield strength, tensile energy at break, modulus, and elongation at break. The polymer films produced through compression molding at 100°C showed good swelling properties. The transport coefficient (n) values determined from the plot of log(M_t/M_∞) vs. log t indicate Fickian behavior, and they are consistent with the reported literature values for other PVA systems. The nature of water in gels [bound water (W_b), freezing (W_f), and freezing bound (W_fb), and water content (W_t)] was evaluated from DSC data. The results demonstrate that PVA/LA hydrogels with good combination of thermal, physicomechanical, and swelling properties can be prepared via the lactic acid esterification of PVA polymer process described. Besides being melt processable, the PVA/LA gels exhibit a melting point, which indicates possibly use of higher temperatures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Photon transmission technique for monitoring formation and swelling of polyacrylamide gels

The in situ, real-time photon transmission technique was used to monitor the free radical crosslinking copolymerization of acrylamide and N,N′-methylenebisacrylamide (Bis). Gelation experiments were performed with various Bis contents at various wavelengths. It was observed that the transmitted photon intensity, I _tr, decreased dramatically at a certain reaction time, which is attributed to the increase in scattered light intensity, I _sc, during the formation of microgels in the system. The increase in I _scwas modeled using Rayleigh's equation where the reaction time was found to be proportional to the volume of the microgels. The disc-shaped polyacrylamide (PAAm) gels were dried before use during swelling experiments. Transmitted light intensity, I _tr, from the gel increased at initial stages when PAAm gels were immersed in water and then decreased exponentially as the swelling time increased. Decrease in I _trwas attributed to the lattice heterogeneities, which might have originated between microgels and holes in the swelling gel. Decrease in I _trwas modeled using the Li–Tanaka equation from which cooperative diffusion coefficients, D _c, were determined for gels of various Bis contents. It is observed that the D _cvalues increased with the Bis content.     

Effect of LCST on the swelling of PAAm-NIPA copolymers: a fluorescence study

Temperature sensitive copolymers were prepared by free radical crosslinking copolymerization in aqueous solution with different molar percentage of N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as a crosslinker and an initiator, respectively. The steady-state fluorescence (SSF) technique was used to determine the low critical phase transition temperature (LCST) for PAAm-NIPA copolymers. Swelling experiments were performed in water at various temperatures by real time monitoring of pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. The Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of pyranine intensity during the swelling of PAAm-NIPA copolymers. The Li–Tanaka equation was used to determine the swelling time constants, τ ₁ and the cooperative diffusion coefficients, D ₀ from fluorescence intensity, weight and volume variations of the copolymers at various temperatures. It was observed that τ ₁ first increased up to LCST, and then decreased; naturally D ₀ decreased up to LCST and then increased upon increasing temperature. It was understood that (LCST) increases as PAAm contents increase in the PAAm-NIPA copolymers.     

Preparation and properties of novel soluble aromatic polyetherimides from 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride and aromatic diamines

New aromatic polyetherimides containing the 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride unit were prepared by a conventional two-step method from 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride and several diamines. This procedure yielded high molecular weight polyetherimides with inherent viscosities of 0.22–1.29 dL/g. Most of the corresponding polyetherimides were soluble in organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,N-dimethylacetamide, and methylene chloride under ambient temperature. The glass transition temperatures (T_g) of these polymers were in the range of 207–264°C and the temperatures of 10% weight loss were over 520°C at a heating rate 20°C/min in nitrogen. © 1996 John Wiley & Sons, Inc.     

Methyl methacrylate–N-chlorophenyl maleimide copolymers: Effect of structure on properties

The article describes the preparation of cast acrylic sheets by copolymerizing methyl methacrylate (MMA) with varying mole fractions of N-o-chlorophenyl maleimide (OC), N-m-chlorophenyl maleimide (MC), and N-p-chlorophenyl maleimide (PC) using benzoyl peroxide as an initiator. The effect of incorporation of varying mole fraction of N-chlorophenyl maleimides in poly(methyl methacrylate) backbone on the optical, physicomechanical, and thermal properties of cast acrylic sheets were evaluated. Vicat softening temperature, glass transition temperature (T_g) and thermal stability of the copolymers increased with an increase in the maleimide content. The solar transmittance and percentage of transmittance of the copolymer sheets having low mole fractions of N-chlorophenyl maleimides (i.e., 0.025–0.085) were found to be comparable with that of PMMA. Further increase in the comonomer content resulted in a decrease in the percentage of transmittance. Copolymer sheets having low mole fractions of N-chlorophenyl maleimides (0.025–0.108) have tensile strength comparable to that of PMMA, whereas the percentage of elongation decreased. Tensile modulus increased with increasing mole fraction of N-chlorophenyl maleimides. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 527–534, 1998     

Real‐time temperature and photon transmission measurements for monitoring phase separation during the formation of poly(N‐isopropylacrylamide) gels

Phase separation during the formation of poly(N‐isopropylacrylamide) (PNIPA) hydrogels was investigated using real‐time photon transmission and temperature measurements. The hydrogels were prepared by free‐radical crosslinking polymerization of N‐isopropylacrylamide (NIPA) in the presence of N,N′‐methylenebisacrylamide (BAAm) as a crosslinker in an aqueous solution. The onset reaction temperature T₀ was varied between 20 and 28°C. Following an induction period, all the gelation experiments resulted in exothermic reaction profiles. A temperature increase of 6.5 ± 0.6°C was observed in the experiments. It was shown that the temperature increase during the formation and growth process of PNIPA gels is accompanied by a simultaneous decrease in the transmitted light intensities I_tr. The decrease in I_tr at temperatures below the lower critical solution temperature of PNIPA was explained by the concentration fluctuations due to the inhomogeneity in the gel network. At higher temperatures, it was shown that the gel system undergoes a phase transition via a spinodal decomposition process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3589–3595, 2002     

Thermal behavior and tensile properties of poly(ethylene terephthalate‐co‐ethylene isophthalate)

Poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI) homopolymers were synthesized by the two‐step melt polycondensation process of ethylene glycol (EG) with dimethyl terephthalate (DMT) and/or dimethyl isophthalate (DMI), respectively. Nine copolymers of the above three monomers were also synthesized by varying the mole percent of DMI with respect to DMT in the initial monomer feed. The thermal behavior was investigated over the entire range of copolymer composition by differential scanning calorimetry (DSC). The glass transition (T_g), cold crystallization (T_cc), melting (T_m), and crystallization (T_c) temperatures have been determined. Also, the gradually increasing proportion of ethyleno‐isophthalate units in the virgin PET drastically differentiated the tensile mechanical properties, which were determined, and the results are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 200–207, 2000     

Swelling properties of copolymeric hydrogels prepared by gamma irradiation

Crosslinked xerogels in the form of rods have been prepared to > 99.9% conversion by the γ-ray initiated copolymerization in vacuo ob n-butyl acrylate (BA) with N-vinyl-2-pyrrolidone (VP) in the presence and absence of a crosslinking agent. Thin (about 0.5 mm) disks were swollen in water at 21°C, the final equilibrium swelling being the true water content only for copolymers of high BA content. At low-medium BA content, swelling was accompanied by the release of a small water-soluble fraction, leading to a slightly reduced apparent value for the water content. True water contents could be obtained more rapidly by prior Soxhlet extraction with boiling water. For xerogels containing > about 75% VP by weight, the resultant hydrogels had water contents > about 80%. The influences of dose, dose rate copolymer composition, and concentration of crosslinker on the water content, sol fraction, and extension ratio were investigated. A high level of reproducibility in properties of the hydrogels was obtained by numerous replicate experiments. The feasibility of scaling up the preparation to produce long (60 cm) xerogel rods of uniform properties has been demonstrated. For these copolymers, swelling in several common organic solvents generally exceeds that in water.     

Phase transition in swollen gels

Summary The swelling and mechanical behaviour of networks of copolymers of acrylamide, methylenebisacrylamide and of the quaternary salt-N,N,N-trimethyl-N-methacrylamido-2-ethylammonium chloride (mole fraction of salt x _s =0-0.17) in water-acetone mixtures was investigated. In the range x _s >0.01 the phase transition was observed; with increasing concentration x _s both the extent of transition and the critical concentration of acetone in the mixture, at which the collapse takes place, increase. It was found that, compared with the ester group, the attachment of the positive charge to the main chain through the amide bond increases the extent of transition and decreases the critical acetone concentration. The jumpwise change in the gel volume accompanying the collapse is accompanied by a similar change in the shear modulus of the gel.Dedicated to Dr. Karel Duek on the occasion of his 60th birthday for his important contribution to polymer science     

Radiation synthesis of poly(N‐vinylpyrrolidone‐co‐methacrylic acid) hydrogels and their usability in uranyl ion adsorption

In this study, N‐vinylpyrrolidone(VP)/methacrylic acid (MAA) mixtures have been prepared at three different mole percents which the methacrylic acid composition around 5, 10, and 15%. Poly(N‐vinylpyrrolidone‐co‐methacrylicacid) P(VP/MAA) hydrogels irradiated at 3.4 kGy have been used for swelling and diffusion studies in water and uranyl ion solutions. The influence of dose, pH, relative amounts of monomers in MAA/VP monomer mixtures on the swelling properties have been investigated. P(VP/MAA) hydrogels were swollen in distilled water at pH 7.0. P(VP/MAA)1 hydrogel containing 36% (mole percent) methacrylic acid showed the maximum percent swelling in water. Adsorption isotherms were constructed for uranyl ions and P(VP/MAA) hydrogel systems. It has been found that P(VP/MAA) hydrogels have very high uptake of the uranyl ions succesfully in water containing uranyl ions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006     

Swelling behavior of pH‐ and temperature‐sensitive copolymers containing 2‐hydroxy‐ethyl methacrylate and N‐vinyl‐2‐pyrrolidone crosslinked with new crosslinkers

Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (VP) and homopolymers of HEMA and VP were crosslinked in the presence of different mol% of melamine trimethacrylamide (MMAm) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked HEMA and VP copolymers, VP and HEMA series were evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MMAm concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. This behavior is explained on the basis that amide groups of VP or crosslinkers could be hydrolyzed to form negatively charged carboxylate ion groups in the produced networks in response to an external pH variation. Copyright © 2004 Society of Chemical Industry