pH–thermoreversible hydrogels. II. Synthesis and swelling behaviors of N-isopropylacrylamide-co-acrylic acid-co-sodium acrylate hydrogels

A series of pH–thermoreversible hydrogels are prepared from the three molar ratios of N-isopropylacrylamide (NIPAAm) and acrylic acid neutralized 50 mol % by sodium hydroxide (SA50) and N,N′-methylene bisacrylamide (NMBA). The influence of the environmental conditions, such as temperature and pH values, on the swelling behavior of these copolymeric gels is also investigated in this article. Results show that the hydrogels bearing negative charges exhibit different equilibrium swelling ratios under various pH media. The pH sensitivities of these gels also strongly depend on the molar ratio of SA50 in the copolymeric gels; thus, the more the SA50 content, the higher the gel pH sensitivity. These hydrogels exhibited thermosensitivity demonstrating a larger change of the equilibrium swelling ratio in aqueous media under temperature changes. An overshooting phenomenon is observed from the gel swelling kinetics under high-temperature conditions. The said hydrogels are also used to investigate the release of model drugs in this study. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1955–1967, 1999     

Thermoreversible hydrogel. V. Synthesis and swelling behavior of the N-isopropylacrylamide-co-trimethyl methacryloyloxyethyl ammonium iodide copolymeric hydrogels

A series of N-isopropylacrylamide/trimethyl methacryloyloxyethyl ammonium iodide (NIPAAm/TMMAI) copolymeric gels are prepared from the various molar ratios of NIPAAm, cationic monomer TMMAI, and N,N′-methylene bisacrylamide (NMBA) in this article. The influences of the amount of the cationic monomer in the copolymeric gels on the swelling behavior in water, various saline solutions, and various temperatures are investigated. Results show that the swelling ratios of copolymeric gels are significantly larger than those of pure homopolymer NIPAAm gel, and the more the TMMAI content, the higher the gel transition temperature. In the saline solution, results show that the swelling ratio of pure NIPAAm gel has not significantly changed with an increase of the salt concentration until the salt concentration is larger than 0.1M. The swelling ratios for the copolymeric gels NIPAAm/TMMAI decrease with increasing salt concentration. In various saline solutions, results show that the anionic effects are greater than cationic effects in the presence of common anion, different cations and common cation, and different anions for these hydrogels. Finally, we also tested the reversibility of the NIPAAm/TMMAI copolymeric gels. The deswelling and reswelling kinetics are dependent on the temperature, which is below or above the gel transition temperature. The gel with little TMMAI content has a good reversibility. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1793–1803, 1998     

pH/thermoreversible hydrogels III: Synthesis and swelling behaviors of (N-isopropylacrylamide-co-acrylic acid) copolymeric hydrogels

A series of pH-thermoreversible hydrogels exhibiting volume phase transition were synthesized by three degrees of neutralization (DN) of acrylic acid (AA) and N-isopropylacrylamide (NIPAAm). The influence of environmental conditions, such as temperature and pH, on the swelling behavior of these copolymeric gels is investigated in this article. Results show that the negatively charged hydrogels exhibit different equilibrium swelling ratios at different pH values depending on the ionic composition. The pH-sensitivities of these gels also strongly depend on the DN of AA in the copolymeric gels. The results show that the higher the DN, the higher the gel pH-sensitivity. These hydrogels based on a temperature-sensitive hydrogel demonstrate a larger change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a collapsed dehydrated network in response to a variation of temperature. On the other hand, a significant phenomenon that was found in the gel swelling kinetics was an overshooting under high temperature conditions. The presented hydrogels were used for release of model drugs that occur at the changes of surrounding conditions, such as temperature and pH, in this study. It was also found that the higher the DN of AA, the higher the gel transition temperature and the larger the release in a high temperature environment and, at the same time, the larger the swelling ratios.     

Thermoreversible hydrogels. IV. Effect of some factors on the swelling behavior of N-tetrahydrofurfurylacrylamide

A thermoreversible hydrogel, poly(N-tetrahydrofurfurylacrylamide) [poly-(NTHFAAm) gel], was prepared from N-tetrahydrofurfurylacrylamide, which was synthesized from N-tetrahydrofurfurylamine and acryloyl chloride (through acylation), with N,N′-methylenebisacrylamide, a crosslinker, in various aqueous solutions. The influences of temperature, gel thickness, and polymerization media on the swelling behaviors in water were investigated. The effect of the gel thickness on the swelling ratio for NTHFAAm gel indicated that the equilibrium swelling time and diffusion coefficient for the thinner gel were faster than those for the thicker gels. The effects of different polymerization media on the gel swelling ratio showed that the larger the solvent molecular size and the poorer the miscibility of the monomer and solvent, the higher the swelling ratio and diffusion coefficient. The drug release profiles in the various gels were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1597–1603, 1998     

Thermoreversible hydrogels. XII. Effect of the polymerization conditions on the swelling behavior of the N‐isopropylacrylamide gel

The swelling behavior for the poly(N‐isopropylacrylamide) (NIPAAm) hydrogel prepared in various conditions such as various polymerization media, i.e., deionized water, acetone, and ethanol aqueous solution, and different polymerization temperatures were investigated in this work. The gels were also assessed for suitability in drug‐controlled release. The results indicated that the swelling behavior of the gel was dependent on the polymerization media and temperature, that is, the swelling ratios of gel were related to the pore size and the looser or denser structure of the gel. In addition, the pore size of the gel could be controlled by adjusting the surrounding temperature. Hence, the gel can be used to deliver drugs with different sizes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1604–1611, 2000     

Superabsorbent polymeric material. V. Synthesis and swelling behavior of sodium acrylate and sodium 2-acrylamido-2-methylpropanesulfonate copolymeric gels

A series of xerogels based on sodium acrylate (SA), sodium 2-acrylamido-2-methyl propanesulfonate (NaAMPS), and N,N-methylene-bis-acrylamide (NMBA) are prepared by inverse suspension polymerization. The water absorbency and swelling behavior for these high absorbent polymers in deionized water and transition salt solutions are investigated. Experimental results indicated that the absorbency in deionized water increases with an increase of the NaAMPS content in the copolymeric gels, which is related to the degree of charge density of the network and the strength of hydrophilic group. The extent of crosslinking agent also influenced the swelling capacity because of elastic chain force of the polymer chain. The absorbency in chloride salt solutions decreases with an increase in the ionic strength of salt. But the decrease of absorbency is different in monovalent and multivalent salt solution. This behavior can be accounted for in terms of counterion condensation or screening effect for monovalent cations, as well as complexation for multivalent cations. The swelling rates in various salt solutions for these xerogels are also investigated. At last, SA-NaAMPS copolymeric gels were used for ion adsorption. But the result showed that the adsorptive amount of transition metal ions for SA-NaAMPS copolymeric gels was lower than that for pure poly(SA) gel. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 229–237, 1998     

Thermoreversible hydrogels. VII. Synthesis and swelling behavior of poly(N‐isopropylacrylamide‐co‐3‐methyl‐1‐vinylimidazolium iodide) hydrogels

A series of N‐isopropylacrylamide/3‐methyl‐1‐vinylimidazolium iodide (NIPAAm/MVI) copolymer gels were prepared from the various molar ratios of NIPAAm, cationic monomer MVI, and N,N′‐methylene bisacrylamide (NMBA) in this study. The influence of the amount of MVI in the copolymer gels on the swelling behaviors was investigated in various aqueous saline solutions. Results showed that the swelling ratios (SRs) of copolymer gels were significantly greater than those of NIPAAm homopolymer gels, and the higher the MVI content, the higher the volume phase transition temperature. The SRs for the NIPAAm/MVI copolymer gels decreased with an increase of the salt concentration. In various saline solutions, results showed that the effect of divalent ions on the SR was greater than that of monovalent ions for these hydrogels. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3242–3253, 1999     

Thermoreversible swelling behaviour of hydrogels based on N-isopropylacrylamide with a hydrophobic comonomer

Hydrogels were prepared by free radical polymerisation in aqueous solution of N-isopropylacrylamide (NIPA) and of NIPA with di-n-propylacrylamide (DPAM), di-n-octylacrylamide (DOAM) or di-dodecylacrylamide (DDAM) as hydrophobic comonomer. N,N-methylene bisacrylamide (BIS) and glyoxal bis(diallyacetal) (GLY) were used as crosslinkers. A series of copolymers with three different comonomer contents was synthesised and for some polymers three different crosslinker concentrations were employed. The swelling equilibrium of these hydrogels was studied as a function of temperature, hydrophobic comonomer species and content in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS). In pure water the gels showed a discontinuous volume phase transition at 33 and 30 °C for PNIPA and hydrophobically modified PNIPA copolymeric hydrogels, respectively. The swelling ratio r and the transition temperature (LCST) increased at low temperatures with the addition of SDS, this is ascribed to the conversion of non-ionic PNIPA gels into polyelectrolyte gels through the binding of SDS. At SDS concentration below 0.5 wt%, gels exhibited a single discontinuous volume transition at 36-38 °C. However, for SDS concentration above 0.5 wt%, two discontinuous volume transitions at 36-40 and 70 °C were observed. Additionally, the replacement of BIS by the novel octafunctional crosslinker glyoxal bis(diallylacetal) (GLY) yielded an increase in the swelling ratio.     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999     

Poly[2-(hydroxyethyl methacrylate)-co-(sulfobetaine)]s hydrogels: 1. Synthesis and swelling behaviors of the 2-(hydroxyethyl methacrylate)-co-2-(vinyl-1-pyridinium propane sulfonate) hydrogels

A series of the 2-hydroxyethyl methacrylate/2-vinyl-l-pyridinium propane sulfonate (HEMA/VPPS) copolymeric gels have been prepared from HEMA and zwitterionic monomer VPPS of various molar ratios. The influence of the amount of VPPS in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures was investigated. Results indicate that the PHEMA hydrogels exhibit an overshooting phenomenon in their dynamic swelling behavior. The maximum overshooting value decreases with increasing temperature. The same results are also shown for the lower VPPS content HEMA/VPPS copolymeric gels. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55 °C. Then, the minimum swelling ratio disappears gradually with increasing VPPS content in HEMA/VPPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/VPPS copolymeric gels increase rapidly with increasing salt concentration, for salts with a smaller ratio of charge/radius.     

Thermoreversible hydrogels X: Synthesis and swelling behavior of the (N‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm) and sodium‐2‐acrylamido‐2‐methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH‐reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1760–1768, 2000     

Poly(2-hydroxyethyl methacrylate-co-sulfobetaine) hydrogels. II. Synthesis and swelling behaviors of the [2-hydroxyethyl methacrylate-co-3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate] hydrogels

A series of the 2-hydroxyethyl methacrylate/3-dimethyl-(methacryloyloxyethyl)ammonium propane sulfonate (HEMA/DMAPS) copolymeric gels was prepared from various molar ratios of HEMA and the zwitterionic monomer DMAPS. The influence of the amount of the zwitterionic monomer in the copolymeric gels on the swelling behaviors in water, various saline solutions, and temperature was investigated. The results indicate that the PHEMA hydrogel (D0) and lower DMAPS content of the HEMA/DMAPS copolymeric gel (D1) exhibit overshooting phenomena in the dynamic swelling behavior. The maximum overshooting value decreases with increase in temperature. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55°C. Then, the minimum swelling ratio diminishes gradually with increasing of the DMAPS content in the HEMA/DMAPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/DMAPS copolymeric gels increase rapidly with increasing of concentration of the salt with a smaller ratio of the charge/radius. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2021–2034, 1998     

High-rate polymerization of acrylonitrile and butyl acrylate based on a concentrated emulsion

A mixture of acrylonitrile and butyl acrylate was polymerized starting from a concentrated emulsion in water. The polymerization was initiated at room temperature by a redox system, consisting of reductants dissolved in the water phase and an oxidant dissolved in the dispersed phase. The initial polymerization was carried out adiabatically with self-heating until a temperature of about 70 °C was reached; this was followed by additional heating in a water bath at a higher temperature, up to a total polymerization time of 30 min. The conversion thus achieved was higher than that obtained via the adiabatic process alone. An optimum temperature during the additional heating was observed. Because of the gel effect, the molecular weight of the product increased with time and the reaction rate became affected by diffusion. The additional heating enhanced the mobility of the species in the system, thus ensuring a final product with a composition near that of the feed.     

Thermoreversible hydrogels. II. Effect of some factors on the swelling behavior of N,N-dimethylacrylamide and n-butoxymethyl acrylamide copolymeric gels

A series of thermoreversible hydrogels are prepared from the various molar ratios of N,N-dimethylacrylamide (DMA), n-butoxymethyl acrylamide (nBMA), and N,N′-methylenebisacrylamide (NMBA). The influences of the amount of DMA in the copolymeric gels, temperature, and polymerization media on the swelling behaviors in water are investigated. Results indicate that the higher the DMA content in the hydrogel systems the higher the swelling ratio and the gel transition temperature. The effects of the gel thickness on the swelling ratio for DMA/nBMA copolymeric gels indicate that the equilibrium swelling time and diffusion coefficient for the thinner gel (1.5 mm) from the dried state to the completely swollen state are obviously faster than are those for the thicker gels (2.0 and 3.5 mm). The effects of the different polymerization media on the swelling ratio for DMA/nBMA copolymeric gels also show that the larger the solvent molecular size and the poor miscibility of the monomer and solvent the higher the swelling ratio and the diffusion coefficient. The drug release in these copolymeric gel systems are also investigated. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:909–916, 1997     

Rapid swelling and deswelling of thermoreversible hydrophobically modified poly(N-isopropylacrylamide) hydrogels prepared by freezing polymerisation

Rapid response thermally sensitive hydrophobically modified poly(N-isopropylacrylamide) hydrogels have been synthesised successfully using a two-step polymerisation method, the initial polymerisation being carried out at 20 °C, followed by polymerisation at −28 °C for 24 h. The results show that the swelling/deswelling rates of poly[N-isopropylacrylamide-co-(di-n-propylacrylamide)] P(NIPA-co-DPAM) hydrogels prepared by two-step polymerisation are much faster than for the same type of hydrogels prepared via conventional methods (30 °C for 24 h), i.e. the time for the former xerogel to absorb 70 and 90 wt% is just 30 and 240 min, respectively, compared to the latter xerogel which takes 1600 and 2500 min to absorb the same amounts of water. During deswelling (shrinking), the hydrogel loses 95 wt% water in 1 min, compared to a timescale for the corresponding cross-linked copolymers prepared by conventional methods of about 5 h for 50 wt% water loss. Scanning electron microscopy, and flotation experiments together with swelling ratio studies reveal that the polymeric network of the former hydrogel is characterised by an open structure with more pores and higher swelling ratio but lower mechanical strength compared to the latter hydrogels. Such rapid response hydrogels have potential applications in separation and drug release technologies for example.     

Thermoreversible hydrogels XIII: Synthesis and swelling behaviors of [N-isopropylacrylamide-co-sodium 2-acrylamido-2-methylpropyl sulfonate-co-N,N-dimethyl(acrylamido propyl) ammonium propane sulfonate] copolymeric hydrogels

A series of copolymeric hydrogels were prepared from various molar ratios of N-isopropylacrylamide (NIPAAm), sodium-2-acrylamido-2-methylpropyl sulfonate (NaAMPS) and N,N′-dimethyl(acrylamido propyl) ammonium propane sulfonate (DMAAPS). The swelling behaviors of these copolymeric hydrogels were investigated in various saline solutions. The result showed that the phase transition temperatures of these gels changed insignificantly, and the thermosensitivity, in contrast, diminished. In addition, the copolymer gels exhibited polyelectrolytic behavior under lower salt concentration (10⁻⁵∼10⁻¹ M), exhibited a nonionic gel (like NIPAAm) behavior at the salt concentration from 0.1 to 0.4 M, and showed an antipolyelectrolytic behavior (polyzwitterionic effect) at a salt concentration over 0.4 M. Finally, the presented coplymeric gels are investigated for use in drug release application.     

含规整 PMMA支链的 PBA合成及其力学性能

研究了聚甲基丙烯酸甲酯大单体与丙烯酸丁酯在苯中的共聚,该大单体由甲基丙烯酸甲酯在巯基乙酸链转移剂存在下聚合,用甲基烯酸缩不甘油酯封端,研究了共聚速率、大单体相对分子质量、大单体与小单体投料比、引发剂用量、单体浓度及共聚温度对接枝效率及共聚物相对分子质量的影响。用分级沉淀法精制共聚物。用凝胶渗透色谱法、红外光谱法及差示扫描量热法对共聚物进行表征,用蒸汽压式渗透压力计及膜渗透压测定了结构参数,结果表明,平均接枝数随转化率增加而降低,在一定的组成范围内,共聚物呈热塑性弹性体行为。     

Network structure and compositional effects on tensile mechanical properties of hydrophobic association hydrogels with high mechanical strength

Hydrophobic association hydrogels (HA-gels) were successfully prepared through micellar copolymerization of acrylamide (AM) and a small amount of octylphenol polyoxyethylene acrylate (OP-4-AC) in an aqueous solution containing sodium dodecyl sulfate (SDS). HA-gels exhibited excellent mechanical properties and transparency. Especially, HA-gels possessed the capability of re-forming, such as self-healing and molding. From Fourier transform infrared, swelling behavior and re-forming capability of HA-gels, the network structure was established. On the basis of the micellar copolymerization theory, the statistical molecular theory of rubber elastic, and using uniaxial stretching data, the length of the hydrophobic microblocks, the effective network chain density and the molecular weight of the chain length between cross-linking points were evaluated for all HA-gels; furthermore, they were also evaluated for the region of medium deformation by the Mooney-Rivlin theory. For HA-gels, we investigated in detail the effects of the content of compositions in the initial solution, OP-4-AC, SDS and AM, on their tensile mechanical properties on the basis of the proposed network structure. The results clearly indicate their tensile strength, fracture energy, elastic modulus, and elongation strongly depended on their composition content.     

Mechanism of the polymerization of n-butyl acrylate initiated by N,N-diethyldithiocarbamate derivatives. Part 1. Photolysis of butyl-2-(N,N-diethyldithiocarbamyl)propionate and oligomerization of butyl acrylate

The photolysis of n-butyl-(N,N-diethyl dithiocarbamyl)propionate (RTC), an initiator for ‘living’ free radical polymerizations, has been investigated in order to elucidate the mechanism of these polymerizations. The photolysis yields tetraethylthiuram disulphide (TED), and its degradation products, butyl acrylate, butyl propionate and head-to-head dimer of butyl acrylate. These compounds result from reactions following the homolytic bond breaking of the carbon–sulphur bond of RTC, and correspond to termination reactions in the case of a polymerization. However, a functionalized head-to-tail dimer of butyl acrylate is also formed. Photolysis of RTC in the presence of a small amount of butyl acrylate, which mimics a polymerization process, leads mainly to the formation of functionalized oligomers of butyl acrylate. The change of the concentrations of these compounds with reaction time is an argument in favour of a possible reactivation of the functionalized oligomers. © 1998 SCI.     

丙烯酸(酯)改性聚醋酸乙烯酯乳液的研制

采用半连续种子乳液聚合法,使用丙烯酸(AA)功能性单体和丙烯酸丁酯(BA)软单体对醋酸乙烯酯(VAc)进行了共聚改性,制备出高固含量(50.2%)的聚醋酸乙烯酯(PVAc)改性乳液。该乳液适合用于喷雾干燥法制备可再分散聚合物粉末,并且其耐水性和耐碱性等都得到了明显地改善。对影响共聚物的诸多因素进行了较为全面地考察,得出最佳的工艺条件为:AA用量为主单体质量的3%～4%,BA用量为主单体质量的5%～10%,保护胶体用量为混合单体质量的7.5%～15%,引发剂用量为混合单体质量的0.4%～0.5%,阴/非离子型复合乳化剂的质量比为1∶2～1∶3、用量为混合单体质量的2%～3%,分散剂、消泡剂和酸碱缓冲剂等助剂均为适量,加料时间为3～4h,反应温度为70～75℃。