Synthesis and characterization of new poly(butadiene-co-acrylic acid(g) acrylic acid) and poly(butadiene(g) acrylic acid)

Synthetic crosslinked polymers from oligomers of butadiene-co-acrylic acid (Mw 5000) or oligomers of butadiene (Mw 6000) and acrylic acids were obtained after grafting reactions using varying reactant ratios. Characterization of the new crosslinked polymers were carried out by use of FTIR, H-NMR, and ¹³C-NMR in the solid state and also with the swollen products in D₂O, DMF D7, or DMSO D6. Determinations of swelling in distilled water for the different synthesized hydrogels showed increase in the V/Vo ratios as the concentrations of anions (carboxylate) became higher. These values were sensitive to different pH values and changes in the concentrations of electrolytes. Different behavior was observed for the polymers obtained from mass and from synthesis in benzene. SEM analysis of the surfaces of the polymers obtained in mass showed a fibrous structure (with lower contents of carboxylic groups, and more swellable and with greater capacity to retain albumin). A porous surface was observed for products obtained in benzene (with higher content of carboxyl groups and capacity to retain cations such as copper and malachite green).     

Synthesis and characterization of a new poly(butadiene(g) acrylamide(g) acrylic acid)

Synthetic crosslinked polymers were obtained by reacting oligomers of polybutadiene (av. mol. wt. ∼6000) with acrylamide and acrylic acid. Characterization of these new block-crosslinked polymers was carried out by FTIR, ¹H-NMR, ¹³C-NMR, SEM analyses, DTA, and DTG. The polymers were washed with benzene, ethanol, water, and acetone and then dried at high vacuum. Determinations of the swelling ratio Vs/Vo for the poly (BuAAAm)H, acid form, and poly (BuAAAm)Na, sodium form, were carried out in distilled water, at different pH values and concentrations of electrolytes. Kinetic studies with diffusion of solvents were related to the network structures of the poly (BuAAAm) in acid and sodium forms.     

Cross-Linked Poly(acrylic acid) Microgels from Precipitation Polymerization

Cross-linked poly(acrylic acid) microgels were prepared via thermally initiated free-radical precipitation polymerization in a binary organic solvent. N,N′-Methylenebisacrylamide (MBA) and 2,2′-azobisisobutyronitrile were used as cross-linker and initiator, respectively. The effect of (MAB) concentration on different features of sample (i.e., spectral characteristics, glass transition temperature, equilibrium swelling, gel content and rheological properties) was investigated. The Flory-Rehner equation and rubber elasticity theory were used to discuss the network structure of polymer. Apparent and rotational viscosities were used to determine the optimal cross-linker concentration. The sample maximum with value of viscosity was obtained using 1.6 mmol/L of the cross-linker. In addition the m and n parameter of Ostwald equation were investigated as well.     

Poly(acrylic acid)-guided synthesis of helical polyaniline microwires

We present a facile method to prepare helical polyaniline (PANI) microwires or rods guided by poly(acrylic acid) (PAA). The average length and diameter of the helical strands were about 3.5 μm and 500 nm, respectively. The pitch distance was about 400 nm. The morphology of the helical PANI microwires was affected by the concentration of PAA. As the concentration was decreased to below 0.05 mg/ml, helical wire- or rod-like products were observed. The structure of the helical polyaniline microwires were characterized by means of TEM, SEM, XRD, FTIR and UV-vis spectroscopy.     

聚甲基丙烯酸/SBA-15复合物的制备

采用超声波分散技术,通过原位合成法将pH敏感的功能单体甲基丙烯酸(MAA)引入到介孔二氧化硅SBA-15的孔道内聚合,制备了pH敏感SBA-15/聚甲基丙烯酸(PMAA)纳米复合材料,对材料的结构和性能进行了测试。结果表明,介孔分子筛SBA-15/PMAA复合材料有较好的光学性能、热性能。聚合反应的发生并没有破坏SBA-15的有序介孔结构,显示出pH敏感性,有望在药物缓释领域得到应用。     

Poly(acrylic acid)-grafted magnetic nanoparticle for conjugation with folic acid

Poly(acrylic acid) (poly(AA))-grafted magnetite nanoparticles (MNPs) prepared via surface-initiated atom transfer radical polymerization (ATRP) of t-butyl acrylate, followed by acid-catalyzed deprotection of t-butyl groups, is herein presented. In addition to serve as both steric and electrostatic stabilizers, poly(AA) grafted on MNP surface also served as a platform for conjugating folic acid, a cancer cell targeting agent. Fourier transform infrared spectroscopy (FTIR) was used to monitor the reaction progress in each step of the syntheses. The particle size was 8 nm in diameter without significant aggregation during the preparation process. Photocorrelation spectroscopy (PCS) indicated that, as increasing pH of the dispersions, their hydrodynamic diameter was decreased and negatively charge surface was obtained. According to thermogravimetric analysis (TGA), up to 14 wt% of folic acid (about 400 molecules of folic acid per particle) was bound to the surface-modified MNPs. This novel nanocomplex is hypothetically viable to efficiently graft other affinity molecules on their surfaces and thus might be suitable for use as an efficient drug delivery vehicle particularly for cancer treatment.     

Hot Melt Reactive Extrusion of Chitosan with Poly(acrylic acid)

The hot melt reactive extrusion of blends of chitosan and poly(acrylic acid) (PAA) was carried out without any process additives such as organic solvent or plasticizer. The maximum amount of chitosan in the blend during the extrusion process was kept at 40 wt%, since the melt viscosity of a system containing 50 wt% of chitosan exceeded the torque limitation of the equipment. The carboxylic groups of PAA interacted with the amine groups of chitosan during the melt process, and the system exhibited good melt flow. The interactions between these two polymers were explained by investigating the results obtained by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal transition behavior of PAA was altered with a decrease of more than 10°C in the peak melting point after extrusion. The infrared (IR) spectroscopic data confirmed the existence of a complex formation and possible hydrogen bonding between chitosan and PAA during the melt process. Scanning electron microscopy (SEM) micrographs indicated that chitosan was well-dispersed in the PAA blends up to 30 wt% chitosan, with no indication of loose particles or other disruptions on the upper and lower fractured faces. This smooth interface might have been caused by the interaction between amide bonds of chitosan and carboxylic groups of PAA.     

Forces Measured between Zirconia Surfaces in Poly(acrylic acid) Solutions

We have studied the forces between a sphere and a plane surface of yttria-partially-stabilized tetragonal-zirconia immersed in aqueous solutions of low-molecular-weight ( M _w= 10 000) poly(acrylic acid) (PAA) using atomic force microscopy. The measurements are performed at high pH where the adsorbed, highly charged anionic polyelectrolyte extends far into the solution, resulting in a combination of polymeric (steric) and electrostatic interactions. Analysis of the experimental data using scaling theory shows that the polymeric contribution dominates and that the electrostatic contribution is small at relatively high ionic strength (0.01 M NaCl). We find that the measured forces are highly dependent on time and interaction history of the absorbed PAA layer; consecutive compression-decompression cycles result in an increase of the surface coverage and the range of the repulsive polymeric interaction. This buildup of PAA at the interface is strongly related to attractive bridging interactions manifested as strong adhesion during decompression at less than full surface coverage. The force results are compared to rheological observations of zirconia suspensions stabilized by the same dispersant; the poor colloidal stability and high viscosity at low surface coverage of PAA are related to the attractive bridging interactions.     

壳聚糖/聚丙烯酸共聚物微球的制备及性能

以环己烷为油相,壳聚糖溶液为水相,运用反相乳液聚合法制得了具有pH敏感性的壳聚糖/聚丙烯酸共聚物微球。讨论了微球在pH=1～10缓冲溶液中的溶胀率变化,研究表明,微球在强酸性(pH≈1)和碱性(pH>7)条件下,溶胀率均在10倍以上;而在pH=2～6时溶胀较差,当pH=4时出现最低值,溶胀率低于1倍。光学显微镜所观察到的微球粒径均在40μm以内,且大小均匀。采用傅里叶红外光谱仪分析了不同配比样品特征峰的峰值和峰面积的变化。用722光栅分光光度计研究了共聚物微球包埋考马斯亮蓝的溶胀释放过程。     

Grafting acrylonitrile and acrylic acid monomers on cellulosic materials

Graft copolymers of acrylonitrile and of acrylic acid monomers on cellulosic materials were obtained by use of ceric ion initiator in aqueous medium at a 50% (w/w) cellulose-monomer ratio. The variations of poly(acrylonitrile) grafts and of the efficiency of grafting with ceric ion concentration, and of poly(acrylic acid) grafts with temperature are examined. The dependence of water retention capacity of the grafted fibers with the graft level is reported.     

Poly(acrylic acid)/poly(acrylamide) hydrogel adsorbent for removing methylene blue

Cationic dye can cause severe damage to the environment due to their refractory degradation, complex composition and strong stability. Hydrogels as adsorbents have been widely used to treatment the wastewater with dyestuff for their low prices, simple operations, and high efficiency. This work uses poly(acrylic acid) (PAA)/poly(acrylamide)(PAM)/calcium hydroxide nanoparticles (CHN) polymeric hydrogel absorbent to eliminate methylene blue (MB) dye. First, PAM/PAA/CHN hydrogel is produced through copolymerization of acrylic acid monomer and acrylamide monomer using inorganic CHN as cross-linker. And then, the adsorption performance of such PAM/PAA/CHN hydrogel adsorbent for adsorbing MB dye is explored at different conditions including pH, contacting time, adsorbent dosage, initial concentration of MB, and temperature. A maximum adsorption capability for adsorbing MB reaches 1,056 mg/g. Furthermore, the pseudo-first-order mode and Langmuir isotherm model can well describe adsorption behavior of MB dye onto such PAA/PAM/CHN hydrogel adsorbent. Thereby, as-prepared PAA/PAM/CHN hydrogel could be a potential adsorbent for eliminating organic dyes from wastewater.     

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     

碱溶性聚(丙烯酸丁酯/丙烯酸)的合成及性能

合成了碱溶性聚(丙烯酸丁酯/丙烯酸)〔P(BA/AA)〕,探讨了丙烯酸用量及不同引发体系对其表面张力、离心稳定性和乳化性的影响,对其结构进行了表征。傅里叶红外光谱(FTIR)分析表明,P(BA/AA)中无C C存在,聚合完全;差示扫描量热(DSC)分析表明,共聚物的玻璃化转变温度(Tg)为21.3℃;透射电镜(TEM)测定了P(BA/AA)的平均粒径小于100 nm,粒径分布均匀。以该共聚物为表面活性剂与丙烯酸酯类进行乳液聚合制备了皮革涂饰剂,应用于皮革涂饰后,革样的物理机械性能较采用常规乳化剂制备的丙烯酸树脂涂饰革样抗水性提高了28.08%,透气性提高了18.5%,耐湿擦性提高了半级,耐折牢度无明显变化。     

Dendrigraft with citric acid on acrylonitrile/acrylic acid copolymer electrospun fibres

Acrylonitrile/acrylic acid copolymers were synthesized with different mole fractions (1, 2, 5 and 10 mol%) of acrylic acid (AA) in the feed by aqueous suspension polymerization, and bead‐free fibres (295–375 nm in diameter) were made from the copolymers in dimethylformamide solutions by electrospinning. In a heterogeneous system containing electrospun fibre mats, dendritic molecules were grown by reaction between carboxylic acid of AA and –OH groups of citric acid activated by dicyclohexylcarbodiimide. The products were analysed using ¹H NMR, ¹³C NMR and Fourier transform infrared spectroscopies, density determination, scanning electron microscopy, optical microscopy, differential scanning calorimetry and pH response properties. With decreasing AA content, the isotacticity of the copolymers decreases with a more random distribution of the co‐monomers which leads to higher percentage conversions of dendrigraft due to reduced steric hindrance. On the formation of dendrigraft, the percentage conversion of the reactions decreases with an increase of generation number and AA content. A reduction of density for the first generation and then an increase with increasing generation are observed. During oxidation stabilization of fibres with a decrease of AA content and an increase in generation number, the amount of liberated heat increases. Fibres containing more carboxylic groups show significantly greater amounts of swelling/de‐swelling in basic and acidic media, respectively. To be used as nanocarbon fibre precursors, or as active particles for loading with guest molecules, or as pH actuators, the first generation of dendrigrafted fibres are expected to have the greatest potential among the various samples examined. © 2013 Society of Chemical Industry     

Synthesis and Characterization of Poly(acrylic acid)/Poly(vinyl alcohol)-xanthan Gum Interpenetrating Network (IPN) Superabsorbent Polymeric Composites

Initially interpenetrating network (IPN) hydrogel was prepared by dispersing xanthan gum (XG) into poly(vinyl alcohol) (PVA) backbone in an aqueous medium. Polyacrylic acid (PAA)/Poly (vinyl alcohol)-Xanthan gum IPN superabsorbent composite were fabricated well by dispersing the prepared IPN hydrogel in acrylic acid and polymerized in a complete aqueous environment through chemical cross-linking method. These superabsorbent polymeric composites were analytically evaluated by scanning electron microscopy (SEM), Fourier Transform Infrared Spectra (FTIR), Thermal analysis (DSC) and X-ray diffraction (XRD) analysis. Simultaneously water absorbency, swelling kinetics and water retention abilities of this prepared superabsorbent polymeric composites were also investigated systematically.     

改性聚天冬氨酸/聚丙烯酸/羧甲基纤维素复合高吸水性树脂的制备及其性能

以聚琥珀酰亚胺(KPSI)、丙烯酸(AA)和羧甲基纤维素(CMC)为原料,采用水溶液聚合法合成改性聚天冬氨酸/聚丙烯酸/羧甲基纤维素复合高吸水性树脂(KPAsp/PAA/CMC)。通过红外光谱(FTIR)、热重分析(TGA)和扫描电镜(SEM)对产物的结构、热稳定性和表面形态进行表征。探讨了CMC和AA用量对复合吸水性树脂吸液性能的影响,结果表明,当m(CMC)∶m(AA)∶m(KPSI)=0.15∶3∶1时,树脂的吸液性能最佳,在去离子水和质量分数0.9%的NaCl水溶液(生理盐水)中的吸液倍率分别达到843 g/g和130 g/g。研究了不同组成KPAsp/PAA/CMC吸水性树脂的盐敏感性、温度敏感性和pH敏感性,以及树脂在人工血、人工尿和不同体积分数乙醇水溶液的吸液性能,结果表明,复合树脂盐敏感性提高,在盐溶液中的吸液大小顺序为NaClFeCl_3CaCl_2;低临界溶解温度(LCST)比KPAsp提高了15℃;在溶液pH=5和pH=9出现了两吸液高峰;在人工血和人工尿中的最大吸液倍率为211 g/g和142 g/g,在体积分数为50%的乙醇水溶液中的最大吸液倍率为295 g/g。     

Effect of Magnesium Ions on the Adsorption of Poly(acrylic acid) onto Alumina

The adsorption isotherms of poly(acrylic acid) (PAA) onto alumina powder have been determined as a function of pH, ionic strength, and magnesium-ion concentration. The adsorption of PAA is strongly enhanced by magnesium ions in alkaline media but less affected under acidic conditions. The adsorption isotherms display a maximum when PAA is fully complexed with magnesium ions in the solution, corresponding to a ratio of 0.25 ± 0.05 [Mg²⁺]/[acrylic acid monomer]. The decrease in adsorbed amount with an increase in PAA concentration at constant magnesium-ion concentration is related to a decrease in the complexation ratio.     

表面紫外光接枝聚丙烯酸的聚电解质刷型纳米纤维素晶须

为了研究快速地制备改性纳米纤维素的方法,将低相对分子质量(简称分子量,下同)聚丙烯酸(PAA)以紫外光引发聚合的方法接枝到纳米纤维素晶须上,制备出聚电解质刷型纳米纤维素晶须。采用红外光谱、固体核磁、透射电镜、X射线衍射、热重分析等对刷型纳米纤维素晶须进行了表征测试。考察了单体浓度、光引发剂用量、紫外光照射时间等对接枝聚合反应的影响。结果表明,PAA与纳米纤维素晶须的质量比大于1∶1,光引发剂用量为纳米纤维素晶须质量的0.8%~1.0%,反应时间为90 s时,所得接枝产物中羧基含量最高,达到0.012 75 mol/g。紫外光接枝减少了制备改性纳米纤维素的步骤和时间,将扩展纳米纤维素的表面改性方法和用途。     

聚丙烯酸钠在中空纤维超滤膜表面的吸附研究

以KCl溶液为背景电解质液,测得聚砜中空纤维超滤膜等电点的pH值为2.9±0.1.当聚丙烯酸钠溶液pH值在等电点附近时,溶质在膜表面吸附量显著增大,导致膜通量迅速下降.研究了不同温度下膜表面吸附量随时间的变化,结果表明:吸附反应可用拟二级速率方程来描述,温度为293～308 K时,速率常数在0.359～0.604 m2·g-1·min-1内递增.考察不同pH值和离子强度对吸附过程的影响可得:当pH值为2.6～9时,平衡吸附量由0.218下降至0.012 g·m-2;当离子强度为0.0～0.1 mol·L-1时,平衡吸附量由0.218降低至0.154 g·m-2.进一步研究了平衡浓度对吸附量的影响,结果表明当聚丙烯酸钠浓度为0.05～5.0 g·L-1及pH≤4时,Langmuir吸附等温线对实验数据能较好地拟合,方程参数qm和b值的大小随膜表面吸附量的增大而增大.     

Copolymer of acrylonitrile/acrylic acid solid surface film dendrigrafted with citric acid

BACKGROUND: The aim of the present work was to improve the properties of acrylic polymer, which is a major fibre‐forming polymer. Acrylonitrile/acrylic acid copolymer, P(AN/AA), was chosen for this purpose and it was intended to study the condition for the formation of hydroxyl groups through the formation of hyperbranched polymers. RESULTS: The synthesis of a dendritic polymer of citric acid (CA) in the solid phase on a P(AN/AA) core is described. The product was analysed using the elemental analysis technique and ¹H NMR. Dendritic molecules were grown by a reaction between the carboxylic acid of acrylic acid and hydroxyl group of CA activated by dicyclohexylcarbodiimide. Products were analysed using Fourier transform infrared and NMR spectroscopy. CONCLUSION: The formation of CA dendrigraft on P(AN/AA) films in a heterogeneous system is possible. The percentage conversion of the copolymer reaction with CA was calculated based on the NMR results. The percentage conversion showed a gradual reduction with an increase in step numbers. The contact angle of water on the films was affected by the percentage conversion of the reactions. A calculation scheme is presented to show that the low degree of conversion leads to an increase in hydrophobic groups. Copyright © 2008 Society of Chemical Industry