Investigation of pH sensitivity of poly(acrylic acid‐co‐acrylamide) hydrogel

It was found that the upper critical solution temperature (UCST) of poly(acrylic acid‐co‐acrylamide) hydrogel decreases with increase in pH. The UCST of samples equilibrated in a buffer at pH 2.5 was 33.7 °C, whereas it shifted to below 0 °C when swollen in buffers above pH 10. FT‐IR showed that COOH group of acrylic acid ionized gradually in alkaline media. The morphology change of the hydrogel swollen in different buffers was studied by environmental scanning electron microscopy (ESEM). ESEM images showed that the pore size of the sample increased with increase in pH, and in strongly basic media the three‐dimensional network was replaced by a ‘sausage‐like’ or ‘desert‐like’ structure. A study of the pH‐dependent release of cefazolin sodium was also carried out. Copyright © 2003 Society of Chemical Industry     

Absorbency and adsorption of poly(acrylic acid‐co‐acrylamide) hydrogel

Poly(acrylic acid‐co‐acrylamide) (PAAAM) hydrogels have been prepared from partly neutralized acrylic acid (AA) and acrylamide (AM) by solution polymerization, and their absorbency and adsorption in both CuCl₂ and FeCl₃ solutions have been investigated. PAAAM hydrogels and their complexes with Cu²⁺ or Fe³⁺ have been characterized by FTIR. The absorbency of PAAAM in both CuCl₂ and FeCl₃ solutions increases initially and then decreases as the absorbing time increases. The adsorption of PAAAM in both CuCl₂ and FeCl₃ solutions can be described by the pseudo‐second order chemisorption kinetics proposed by Ho and McKay, and the equilibrium uptake of Cu²⁺ on PAAAM can well be fit with the Langmuir adsorption isotherm. However, the equilibrium uptake of Fe³⁺ on PAAAM increases as the initial Fe³⁺ concentration increases for Fe³⁺ concentration smaller than 5.625 × 10^?3 mol/L, and then decreases with Fe³⁺ concentration. The largest uptakes for Cu²⁺ and Fe³⁺ are 247 and 173 mg/g, respectively. The results also show that the uptake of Cu²⁺ and Fe³⁺ on PAAAM increases remarkably when pH of the solution is changed from 2.3 to 4.2 and from 1.0 and 2.1, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of reaction parameters on water absorption of neutralized poly(acrylic acid‐co‐acrylamide) synthesized by inverse suspension polymerization

Highly water‐absorbing polymers of neutralized poly(acrylic acid‐co‐acrylamide) were synthesized in an effort to investigate the influences of reaction parameters on water absorption. In addition, the extent of water absorption and the absorption rate were studied to determine their relationship with the reaction parameters. This article explains the synthesis technique, characterization of the water‐absorbing copolymers, and their properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1349–1366, 1999     

Hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent polymers

A novel hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐Sodium Acrylate) (HECTS‐g‐(PAA‐co‐PSA)) superabsorbent polymer was prepared through graft copolymerization of acrylic acid and sodium acrylate onto the chain of hydroxyethyl chitosan. The structure of the polymer was characterized by FTIR. By studying the water absorption of the polymer synthesized under different conditions, the optimal conditions for synthesizing the polymer with the highest swelling ratio was defined. This superabsorbent polymer was further treated by the solvent precipitation method and by the freeze‐drying method. We found that the water absorption rate of the treated polymer was greatly increased and the microstructure of the treated polymer was changed from small pores to loose macro pores. The swelling processes of the polymers before and after modification fit first‐order dynamic processes. The amount of the residual acrylic acid was greatly decreased after treatments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and water absorbency of a novel poly(acrylate‐co‐acrylamide)/vermiculite superabsorbent composite

A novel poly(acrylate‐co‐acrylamide)/expanded vermiculite (EVMT) superabsorbent composite was synthesized by aqueous solution polymerization method. The water absorbency of the superabsorbent composite still reaches 850 g/g when 50 wt % EVMT is added, which is significant in decreasing the production cost of the superabsorbent composites. By controlling the molar ratio of acrylic acid monomer and acrylamide monomer, and neutralization degree of acrylic acid, the hydrophilic groups on the composite can be adjusted, and it is found that the collaborative absorbent effect of ? CONH₂, ? COOK, and ? COOH groups is superior to that of single ? CONH₂, ? COOK, or ? COOH group. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 735–739, 2007     

聚丙烯酸/丙烯酰胺高吸水性树脂吸附性能

用反相悬浮聚合法合成了聚丙烯酸/丙烯酰胺高吸水性树脂(PAAAM),讨论了其吸附CuCl₂、NiCl₂、CoCl₂溶液中金属离子的性能,考察了溶液pH值和初始浓度对金属离子吸附的影响。结果表明,PAAAM在不同pH值及浓度区间,对金属离子的吸附能力有较大差异,可被用于Cu(II)、Ni(II)、Co(II)的分离。同时还探讨了PAAAM在混合金属离子溶液中的吸附性能及反复利用的可能性,发现在混合溶液中PAAAM表现出对Cu（II）有较好的选择性吸附能力;4次循环后对Cu(II)、Ni(II)、Co(II) 离子的吸附量为最大吸附量的80%以上,重复使用效果理想。     

Adsorption of cationic dyes on poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine‐O, Azure‐I and Pyronin‐Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure‐I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Factors influencing absorbent properties of saponified starch‐g‐(acrylic acid‐co‐acrylamide)

Mixtures of acrylamide (AM) and acrylic acid (AA) were grafted onto gelatinized maize starch by using ceric ammonium nitrate (CAN) as an initiator. These graft copolymers were hydrolyzed with alkali to yield hydrogels. The effects of different reaction variables, such as the concentration of the initiator and crosslinker, initial dilution of monomers, gelatinization conditions of starch, and the ratio of AM and AA in the monomer feed, on the water absorption capacities of these hydrogels have been examined. Absorption increases on gelatinizing starch at a higher temperature for a longer time as smaller granules gelatinize only under these conditions. The higher proportion of AA in the monomer feed enhances absorption due to formation of polyelectrolyte. The optimum conditions for obtaining maximum water absorbency established in the present study are granular maize starch = 2.0 g; gelatinization temperature = 95°C; gelatinization time = 60 min; AM = 1.0 g; AA = 4.0 g; CAN = 0.008 mol/L; N,N′‐methylene bisacrylamide = 1%. The product so formed was saponified with NaOH and then precipitated in excess of methanol. The dried and finely powdered product showed the maximum water absorbency of 510 g/g. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2480–2485, 2000     

Temperature‐responsive properties of poly(acrylic acid‐co‐acrylamide)‐graft‐oligo(ethylene glycol) hydrogels

A series of temperature‐ and pH‐responsive hydrogels were prepared from acrylic acid (AAc), acrylamide (AAm), oligo(ethylene glycol)monoacrylate (OEGMA), and oligo(ethylene glycol)diacrylate by varying the AAc:AAm molar ratio and the OEGMA content. Phase‐transition temperatures and swelling ratios of the obtained poly(AAc‐co‐AAm)‐graft‐OEG gels were measured as a function of temperature and pH. At pH < 5, the obvious transition temperatures ranging from 5 to 35°C were obtained as the AAc : AAm molar ratio was varied. The highest transition temperature was obtained at the AAc : AAm ratios of 5 : 5 and 6 : 4, and the sharp transition curves were observed at the AAc : AAm ratios from 5 : 5 to 8 : 2. The transition temperature further increased with increasing OEGMA content. It was suggested that OEG graft chains with a large mobility played an important role for the formation of hydrogen bonding in the hydrogels. The gels prepared here showed obvious reproducibility of the phase transition in response to temperature changes, which suggests the feasibility of their practical applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 798–805, 2001     

魔芋粉-丙烯酸-丙烯酰胺接枝共聚合成高吸水树脂

以魔芋粉,丙烯酸和丙烯酰胺等为原料,经接枝聚合合成了魔芋粉－丙烯酸－丙烯酰胺类超强吸水性树脂。讨论了引发剂,交联剂,丙烯酸,丙烯酰胺等用量以及反应时间和反应温度等因素对树脂吸水性能的影响。结果表明: 在魔芋粉与单体质量比为1:4,引发剂用量为0.35%（占单体的质量）,丙烯酸/丙烯酰胺（质量）为1:1,丙烯酸中和度为80% ,反应温度为55～65℃,交联剂用量为0.75%（占单体的质量）的条件下,制得的SAP吸去离子水可达720g/g,吸0.9%的NaCl溶液为110g/g。     

Homogeneous complex solution formed through interactions of poly(acrylamide‐co‐acrylic acid)/poly(acrylamide‐co‐dimethyldiallylammonium chloride) complex with M n+ hydration metal ions in aqueous media

A homogeneous complex solution, formed through inter‐polyelectrolyte complexation of poly(acrylamide‐co‐acrylic acid) (P(AM‐AA)) with poly(acrylamide‐co‐dimethyldiallylammonium chloride) (P(AM‐DMDAAC)) and interaction of the P(AM‐AA)/P(AM‐DMDAAC) complex with M ⁿ⁺ hydrated metal ion, was prepared and the structure and properties of the P(AM‐AA)/P(AM‐DMDAAC)/M ⁿ⁺ homogeneous complex solution were studied by UV spectrometry, dynamic light scattering and viscometry. The experimental results show that the homogeneous complex solution can be obtained by controlling the composition of the P(AM‐AA)/P(AM‐DMDAAC) complex and the M ⁿ⁺ metal ion content. Compared to the constituents, ie the P(AM‐AA) solution, the P(AM‐DMDAAC) solution and the P(AM‐AA)/P(AM‐DMDAAC) complex solution, the P(AM‐AA)/P(AM‐DMDAAC)/M ⁿ⁺ complex solution has a new peak at 270 nm in its UV spectrum, a larger hydrodynamic radius, and hence a higher solution viscosity, all of which indicate that there exist specific interactions between polymers and M ⁿ⁺ metal ions. These interactions lead to the formation of a network structure and hence an obvious increase not only in solution viscosity but also in resistance of the polymer solution to simple salts, to temperature changes and to shearing. © 2001 Society of Chemical Industry     

新型改性高吸水树脂P(AA-AM)的合成及性能评价

以N,N’-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,丙烯酸、丙烯酰胺为原料,合成出原位自交联高吸水树脂P(AA-AM)。通过正交实验得出最佳合成工艺为:n(丙烯酸)∶n(丙烯酰胺)=4.5∶1,单体浓度5%,中和度70%,交联剂0.12%,引发剂0.30%(以上均相对AM、AA总量而言);产物的最大吸液性能为:吸蒸馏水最大倍率QW=2 152.4 g/g,吸10%盐水最大倍率Q盐水=28.5 g/g;由于引入适量的AM,产物吸水率和吸盐率得到大幅度的提高,产物形态由最初的粘接颗粒变成分散颗粒。     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

Study of the interaction of poly(acrylic acid) and poly(acrylic acid‐poly acrylamide) complex with bone powders and hydroxyapatite by using TGA and DSC

The thermo gravimetric analysis (TGA) and differential scanning calorimetric analysis (DSC) were used to study the thermal degradation of poly(acrylic acid) PAA and poly(acrylamide) PAAm as well as the compound obtained from their interactions. The examination of the thermal curves revealed that the characteristics of the curves of the compound resulting from the cooperative interactions are different from those of the constituent polymers. The differences in the characteristics of the thermal curves were attributed to the formation of an interpolymer complex resulting from the interaction of PAA with PAAm at low pH value. These two thermal techniques were also used to investigate the thermal behavior of the compounds obtained from the interaction of PAA and (PAA‐PAAm) mixture with bone powders (BP) and hydroxyapatite (HA). It was found that the TGA, DTG, and DSC curves do not show the peak of formation and degradation of PAA anhydride which provided strong evidence for the consumption of PAA in the reaction between the polymer and BP. The interaction between PAA and the thermally treated BPs and HA was investigated. Moreover the interaction between the mixture of PAA and PAAm at different pH values and the BPs and HA was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Siloxane-modified poly(acrylic acid) synthesized in supercritical CO2

Copolymerization of acrylic acid and 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (TMSPMA) in supercritical carbon dioxide was successfully carried out. The products were obtained in the form of dry white powder with diameter about 0.2 μm. Viscosities of 2% aqueous solution of the copolymers dramatically increased as the content of TMSPMA in the copolymer increased and it was much higher than that of poly(acrylic acid). In addition, the viscosity of the copolymers showed a strong dependence on pH with a maximum at pH 5.0, which is due to the cooperation of intermolecular association and electrostatic repulsion.     

Preparation and characterization of poly(N‐tert‐butylacrylamide‐co‐acrylamide) ferrogel

Magnetic‐field‐sensitive gel, called ferrogel, was prepared by a two‐step procedure in which first step requires synthesis of the poly(N‐tert‐butylacrylamide‐co‐acrylamide) [P(NTBA‐co‐AAm)] hydrogel and during second step magnetite (Fe₃O₄) particles were formed in the hydrogel via coprecipitation of Fe(II) and Fe(III) ions in alkaline medium at 70°C. The obtained ferrogel was characterized by attenuated total reflectance Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy dispersive spectroscopy, and electron spin resonance measurements. The magnetic responsive of the ferrogel was also investigated by applying magnetic field to the ferrogel. The extent of a bending degree of the ferrogel depends on the applied magnetic field strength. In addition, the magnetic responsive studies also indicated that formed magnetite content in the hydrogel is high enough to achieve considerable magnetic response to external magnetic field. As a result, the P(NTBA‐co‐AAm) ferrogel may be useful for potential applications in magnetically controlled drug release systems, magnetic‐sensitive sensors, and pseudomuscular actuators. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of poly(acrylic acid‐co‐acrylamide)/kaolin and release kinetics of urea from it

A series of poly(acrylic acid‐co‐acrylamide)/kaolin [poly(AA‐co‐Am)/kaolin] composites were prepared by aqueous solution copolymerization of partially neutralized acrylic acid and acrylamide in the presence of kaolin nanopowder, which was synthesized to act as a release carrier of urea fertilizer. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the effect of urea concentration on the swelling was investigated. Furthermore, the effects of the contents of crosslinker, kaolin, and acrylamide, the neutralization degree of acrylic acid, and temperature, pH, and ionic strength of release medium on water absorbency and diffusion coefficient of urea release from poly(AA‐co‐Am)/kaolin were studied systematically. It was found that urea loading percentage could be adjusted by urea concentration of swelling medium, and urea diffusion coefficient could be regulated through the contents of crosslinker, kaolin, and acrylamide, and the neutralization degree of acrylic acid. Additionally, temperature and ionic strength of release medium may also affect the urea release process. The conclusions obtained could provide theoretical basis for urea diffusion behavior in superabsorbent used in agriculture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Immobilization of chymotrypsin with interpolymer complexes of P(TM‐co‐AAm)/PAA

Chymotrypsin was immobilized with interpolymer complexes formed by the cationic polymer poly(allyltrimethyl ammonium chloride‐co‐acrylamide) [P(TM‐co‐AAm)] and poly(acrylic acid) (PAA). The introduction of a small amount of cationic groups led to a much stronger polymer–polymer interaction between P(TM‐co‐AAm) and PAA. The characteristic pH sensitivity of this kind of complex provided the possibilities of controlling the activity of the immobilized enzyme and separating the immobilized enzyme from the batch by changing the pH of the medium. Compared with the free enzyme, the immobilized chymotrypsin had higher thermal stability, acid–base stability, and stability in use. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2013–2018, 2001     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

Poly(lactide‐co‐glycolide) solution behavior in supercritical CO2, CHF3, and CHClF2

Cloud point and solution density data between 20 and 100°C and pressures to 3000 bar are presented for poly(lactide) (PLA) and poly(lactide‐co‐glycolide) (PLGA_x, where the molar concentration of glycolide in the backbone x ranges from 0 to 50 mol %) in supercritical CO₂, CHClF₂, and CHF₃. PLA dissolves in CO₂ at pressures near 1400 bar, in CHF₃ at pressures of 500 to 750 bar, and in CHClF₂ at pressures of 20–100 bar. As glycolide (GA) is added to the backbone of PLGA, the cloud point pressure increases by 50 bar/(mol GA) in CO₂, 25 bar/(mol GA) in CHF₃, and by only 2.5 bar/(mol GA) in CHClF₂. PLGA₅₀ does not dissolve in CO₂ to pressures of 3000 bar whereas it is readily soluble in CHClF₂ at pressures as low as 100 bar at 50°C. In comparison, the increases in cloud point pressure with increasing weight average molecular weight (M_w) are only approximately 2.3 bar/(1000 M_w) for PLGA copolymers in CO₂. The solution densities with all three SCF solvents range from 1.1 to 1.5 g/cm³ and they vary only by a small amount over the 80°C range used to obtain cloud point data. More than likely, the ability of the acidic hydrogen in CHF₃ and CHClF₂ to complex with the ester linkage in PLGA makes these better solvents than CO₂ especially since any change in favorable energetic interactions is magnified due to the liquid‐like densities exhibited by these SCF solvents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1155–1161, 2001