Water‐soluble copolymers. II. Inverse emulsion terpolymerization of acrylamide,sodium acrylate,and acryloyloxyethyl trimethylammonium chloride

Inverse emulsion terpolymerization of acrylamide, sodium acrylate, and acryloyloxyethyl trimethylammonium chloride was investigated. Aqueous monomer solutions were emulsified in diesel oil with a blend of two surfactants (SPAN80 and TWEEN80) using 2,2′‐azobis(2‐amidinopropen)‐dihydrochloride as the initiator. The effects of temperature, initiator concentration, monomer concentration and composition, and emulsifier content on the polymerization conversion and the polymer intrinsic viscosity were examined. Polymer intrinsic viscosity increased with a decreasing concentration of initiator and an increasing concentration of monomer. The sizes of the latex particles of the terpolymer emulsions were observed with a scanning electron microscope, and the structure of the terpolymer was identified by FTIR spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1381–1385, 2006     

Copolymers of acrylic acid with 2‐acryloyloxyethyl 2,4‐dichlorophenoxyacetate: Synthesis and herbicide release

Free‐radical copolymerization of acrylic acid with 2‐acryloyloxyethyl 2,4‐dichlorophenoxyacetate using 1.0 mol/L 1,4‐dioxane solution and 1.5 × 10^?2 mol/L of 2,2′ azobisisobutyronitrile as initiator has been carried out at 50°C. In addition to low conversion solution experiments performed to estimate the monomer reactivity ratios, three different copolymerizations over the whole range of conversions have been made. Theoretical values of cumulative copolymer composition, determined by the Mayo‐Lewis terminal model, have been correlated with those experimentally obtained. Finally, the herbicide release in three different aqueous pH buffer solutions has been evaluated in heterogeneous phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4238–4244, 2006     

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     

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

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

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     

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。     

Graft copolymerization of mixtures of acrylic acid and acrylamide onto polypropylene film

Liquid phase ultraviolet irradiation in the presence of benzophenone as a photosensitizer and barium hydroxide as a pH controller were used to graft the mixtures of acrylic acid and acrylamide to a polypropylene surface. The surface of the grafted polypropylene samples were characterized by Fourier transform infrared spectroscopy‐attenuated total reflectance, electron spectroscopy for chemical analysis, scanning electron microscopy, and a contact angle meter. The pH value of the reaction medium that produced the graft with equal molar ratio was found to be ∼ 3.77. The optimal reaction condition was found at a monomer feed of 25%, a reaction time of 30 min, and a benzophenone concentration of 1%. Surface tension of the samples increased to a value of 40 dyn cm⁻¹ due to the graft of the hydrophilic monomers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 251–256, 1999     

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     

Synthesis,characterization, and antitumor activity of poly(maleic anhydride‐co‐vinyl acetate‐co‐acrylic acid)

The ternary copolymerization of maleic anhydride (MA), vinyl acetate (VA), and acrylic acid (AA) [P(MA‐co‐VA‐co‐AA)], which is considered to be an acceptor–donor–acceptor system, was carried out in 1,4‐dioxane with benzoyl peroxide as an initiator at 70°C under a nitrogen atmosphere. Constants of complex formation for the monomer systems in the study were determined by UV–visible (hydrogen‐bonding complex) and ¹H‐NMR (charge transfer complex) methods, respectively. The results show that polymerization of the P(MA‐co‐VA‐co‐AA) system proceeds by an alternating terpolymerization mechanism. It is shown that the synthesized copolymers have typical polyelectrolyte behavior, ability for reversible hydrolysis–anhydrization reactions, and semicrystalline structures. In these cases, including radical polymerization, and formation of semicrystalline structures, the hydrogen‐bonding effect plays a significant role. The in vitro cytotoxicities of the synthesized terpolymer and alternating copolymer were evaluated using Raji cells (human Burkitt lymphoma cell line). The antitumor activities of prepared anion‐active copolymers were studied using methyl–thiazol–tetrazolium colorimetric assay and 50% of the cytotoxic dose of each copolymer and terpolymer were calculated. Hydrolyzed P(MA‐co‐VA‐co‐AA) and P(MA‐alt‐AA) copolymers have sufficiently high antitumor activity, which depends on the amount of hydrogen‐bonding carboxylic groups and their regular distribution in the side chain of functional macromolecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3425–3432, 2006     

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     

正交试验优选机械活化玉米淀粉-丙烯酰胺-丙烯酸三元接枝共聚的工艺条件

以机械活化预处理后的玉米淀粉为主要原料,丙烯酰胺(AM)、丙烯酸(AA)为单体,采用反相乳液法合成了机械活化淀粉三元接枝共聚物;对机械括化玉米淀粉与AM/AA在反相乳液中接枝共聚反应的5个影响因素:单体配比、反应温度、中和度、引发剂浓度、油水体积比进行理论研究.以接枝率为考察对象,得到最佳反应条件为AM/AA质量比0.67、反应温度55℃、中和度85%、引发剂浓度7.30mmol/L、油水体积比1.2:1,在此实验条件下,单体转化率97.50%,接枝率58.95%,和接枝效率69.57%.对比坂淀粉在类似的条件下,单体转化率为90.70%,接枝率和接枝效率分别为53.55%和64.84%.机械活化显著的提高了玉米淀粉在反相乳液中的接枝共聚反应活性.     

Removal of basic dyes from aqueous solutions using starch‐graft‐acrylic acid copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The grafting percentages (GP%) of starch‐graft‐AA (St‐gr‐AA) copolymers were determined. When the AA molar concentrations were 0.3 and 0.5 mol/L, GP% of St‐gr‐AA copolymers were 10.5% (St‐gr‐AA‐1) and 14% (St‐gr‐AA‐2), respectively. St‐gr‐AA copolymers have been used for the adsorption of basic dye (Safranine T) from aqueous solutions. Effects of various parameters such as treatment time, initial pH of the solution (pH = 2–6), initial dye concentration (50– 500 mg/L), and GP% of starch graft copolymers were investigated.Basic dye removal capacities of the copolymers increase along with the augment of initial concentration of the adsorbate, GP% of the copolymers, and pH. The adsorption capacities for St‐gr‐AA‐1 and St‐gr‐AA‐2 reach 116.5 and 204 mg/g, respectively. Equilibrium adsorption data were obtained and fitted very well to Freundlich model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

魔芋接枝丙烯酸-丙烯酰胺共聚物/凹凸棒石复合材料的制备与表征

以水溶液聚合法制备了魔芋接枝丙烯酸-丙烯酰胺共聚物/凹凸棒石复合材料。考察了魔芋用量、凹凸棒石用量、中和度、丙烯酰胺用量等因素对复合材料吸液倍率的影响,并采用FTIR,SEM对复合材料进行表征。结果表明,凹凸棒石的适量加入可以提高复合材料的吸液倍率。当魔芋用量为丙烯酸单体质量的4%、凹凸棒石用量为6%、中和度为90%、丙烯酰胺用量为20%时,制备的复合材料的吸液倍率最高。红外光谱(FTIR)表明魔芋葡甘聚糖、丙烯酸、丙烯酰胺和凹凸棒石共同参与了接枝聚合反应;扫描电子显微镜(SEM)分析表明凹凸棒石与高分子复合效果良好。     

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     

Cellulose–poly(acrylamide or acrylic acid) interpenetrating polymer network membranes for the pervaporation of water–ethanol mixtures

A new type of interpenetrating polymer network (IPN) pervaporation membranes based on cellulose and synthetic polymers was developed. They were prepared by free-radical polymerization of acrylamide or acrylic acid in the presence (or absence) of the crosslinking agent (allyldextran or N,N′-methylenebisacrylamide) within cellophane films swollen in the reaction mixture. The swelling behavior of these membranes in water–ethanol solutions and their separation characteristics were investigated depending on the polyacrylamide (PAAm) or poly(acrylic acid) (PAA) content in the IPN (C_p) and for ionic cellulose–PAA membranes depending on the degree of neutralization of carboxylic groups and on the type of counterions. IPN membranes were selective over a wide range of ethanol concentration in the feed. The separation factor (α) and the permeation rate (P) significantly improved with increasing C_p in IPN membranes, especially for the cellulose–PAA(K⁺ form) membranes (for 86% EtOH feed at 50°C, and α and P values reached 1500 and 1.6 kg/m² h, respectively). The results for ionic and nonionic IPN membranes were compared. The separation characteristics of membranes were in good correlation with their swelling behavior. The α values of the membranes depended on the affinity of the IPN polymer chains functional groups for water. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 761–769, 1998     

聚二烯丙基二甲基氯化铵-丙烯酰胺-丙烯酸的制备与表征

以丙烯酸(AA)、丙烯酰胺(AM)用量和体系pH等作为考察因素,以聚合物配合质量分数为2%铬粉应用于皮革鞣制工艺的应用效果为指标,对聚二烯丙基二甲基氯化铵-丙烯酰胺-丙烯酸(PDM-AM-AA)的制备条件进行了优化.结果表明:当n(DM):n(AM):n(AA)=1:2:3,体系pH=5.5时,聚合物产率达94.53%,配合质量分数为2%铬粉应用于皮革鞣制工艺效果较好.对所制备产物的结构采用红外光谱、X射线衍射和差示扫描量热进行了表征,表征结果表明三种单体成功发生了聚合.     

Improvement in the water‐absorbing properties of superabsorbent polymers (acrylic acid‐co‐acrylamide) in supercritical CO2

Superabsorbent resins prepared by ultraviolet radiation‐inducing polymerization techniques with acrylic acid/acrylamide were treated with supercritical carbon dioxide (SC‐CO₂). The water‐absorbing properties of the treated resins were greatly improved. The water‐absorbing properties of resins treated with SC‐CO₂ in the pressure range of 10–35 MPa and the temperature range of 40–60°C were studied. The effects of the treatment time and depressurizing speed of CO₂ after treatment were also examined. Obviously, different results were found for particles of different sizes. Smaller particles were more efficient under the same treatment conditions. Samples were tested with differential scanning calorimetry. The results showed that the plasticizing effect of CO₂ reduced the glass‐transition temperature of the polymer, and it was proposed that the plasticization effect might have led to polymer chain redistribution and better flexibility. Minor changes in the surface morphology of the particles were observed with scanning electron microscopy. The extraction of the unpolymerized monomers by SC‐CO₂ was also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2272–2278, 2002     

Sonochemical polymerization of acrylic acid and acrylamide in the presence of a new redox system— A comparative study

Acrylic acid and acrylamide were polymerized by a peroxydisulfate–suberic acid redox system under a nitrogen atmosphere both in the presence and in the absence of ultrasound (at constant frequency). The rate of polymerization was determined for different concentrations of monomer, initiator, and activator and for different percentages of ultrasonic intensity. The polymers were characterized by X‐ray diffraction and ¹H‐NMR spectroscopy. A probable mechanism is proposed to explain the experimental results obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3685–3692, 2003     

Swelling of crosslinked poly(methylmethacrylate‐acrylic acid) copolymers in serum and saline solutions

In recent articles, our research group explored the use of crosslinked Poly(methylmethacrylate‐acrylic acid) and composites based on this copolymer for bone implant applications such as suture anchors. The swelling response of this system was studied first in vitro, using a 0.85 g/100‐mL saline solution (chosen because it simulates well the in vivo environment), and later in vivo by using samples implanted for various time periods in the lateral femoral condyles of New Zealand white rabbits. It was found that the swelling response of the crosslinked copolymer in vivo was much greater than that in the saline solution. The present investigation was conducted to determine the mechanism of excessive swelling in the in vivo tests. The approach used was to establish the changes occurring in the chemical structure of the copolymer due to immersion in serum. A number of hypotheses that can potentially explain the observed excessive swelling in serum were investigated and are discussed in this article. The results of this study indicate that the mechanism of excessive swelling in serum was the neutralization of  COOH groups in the copolymer to produce salts of acrylic acid, which are known to result in greater swell due to their higher degree of dissociation compared to free acid. It was also found that, for compositions containing the acrylic salts (produced by preswelling in high pH solutions and drying), the swelling behavior in serum was similar to that in saline solution, and more importantly, equilibrium swelling was reached in a relatively shorter time period, which has several practical advantages for bioimplant applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1653–1664, 2001