Scale Inhibitor and Dispersant Based on Poly(Acrylic Acid) Obtained by Redox‐Initiated Polymerization

Low molar mass poly(acrylic acid) (PAA) is generally obtained by free radical polymerization of acrylic acid (AA) in aqueous solution, using thermal initiators and some chain transfer agent. However, under such conditions it is rather difficult to efficiently produce molar masses as low as those required for obtaining an effective dispersant. In this work, the semibatch polymerization of AA at 45 °C is considered, using potassium persulfate (KPS) and sodium metabisulfite (KPS/NaMBS), or alternatively KPS and sodium hypophosphite (KPS/NaHP) as redox initiators to produce PAA of controlled low molar masses. These initiation systems allow the production of PAA with M_n as low as 2.0 kDa, relatively narrow molar mass distribution (1.5 < M_w/M_n < 3.0), and low branching degree. Most of the investigated polymerizations reach almost complete conversions (>95%); and it is verified that both reductants, NaMBS and NaHP, also behave as chain transfer agents. Finally, the investigated process with redox couples allowed the production of PAA with acceptable dispersant and antiscaling properties.     

聚丙烯酸/聚丙烯酰胺水溶液复合特性的研究

通过酸度、电导率、粘度、接触角的测定,研究了聚丙烯酸 (PAA) /聚丙烯酰胺 (PAM) 水溶液复合物及复合物膜的结构和性能。结果表明,酸度、温度、浓度和复合比影响PAA/PAM的复合水溶液中大分子链的构象和流体力学体积,适度的氢键作用可以形成均相的复合溶液。经过热处理和未经热处理的聚合物膜表现出了不同的亲水性能。     

聚丙烯酸环境响应行为的研究

采用介观动力学分子模拟(Mesodyn)和耗散颗粒动力学(DPD)分子模拟与流变等实验技术相结合的方法, 研究了pH/无机盐敏感聚合物聚丙烯酸PAA在水溶液中的环境响应行为, 考察了聚合物浓度、溶液离子强度、聚合物表面电荷对PAA相行为的影响. 实验结论与模拟结果符合得很好, 对照分析给出了聚丙烯酸的环境响应机制, 为设计和应用环境敏感的智能体系提供指导和理论依据.     

Paclitaxel‐Loaded β‐Cyclodextrin‐Modified Poly(Acrylic Acid) Nanoparticles through Multivalent Inclusion for Anticancer Therapy

A nanoassembled drug delivery system for anticancer treatment, formed by the host–guest interactions between paclitaxel (PTX) and β‐cyclodextrin (β‐CD) modified poly(acrylic acid) (PCDAA), is successfully prepared. After such design, the aqueous solubility of PTX is greatly increased from 0.34 to 36.02 μg mL^?1, and the obtained PCDAA‐PTX nanoparticles (PCDAA‐PTX NPs) exhibit a sustained PTX release behavior in vitro. In vitro cytotoxicity finds that PCDAA‐PTX NPs can accumulate significantly in tumor cells and remain the pharmacological activity of PTX. The in vivo real‐time biodistribution of PCDAA‐PTX NPs is investigated using near‐infrared fluorescence imaging, indicating that the PCDAA‐PTX NPs can effectively target to the tumor site by the enhanced permeability and retention effect in H22 tumor‐bearing mice. Through in vivo antitumor examination, PCDAA‐PTX NPs exhibit superior efficacy in impeding the tumor growth compared to the commercially available Taxol®.

     

Low‐Temperature,Rapid Copolymerization of Acrylic Acid and Sodium Acrylate in Water

Regulating the aqueous polymerization of acrylic acid (AA) is a major opportunity for future materials design, requiring the development of scalable, industry‐oriented procedures that afford modest molar mass and dispersity control without long reaction times and environmentally demanding conditions. To address these challenges, this report presents the rapid copolymerization of aqueous mixtures of AA and sodium acrylate using an inexpensive and scalable protocol based on alkyl iodides/sodium iodide as mediators in water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1414–1419     

Molar Mass Distribution and Chain Conformation of Polysaccharides from Fortunella margarita （Lour.） Swingle

In order to study the effects of different extraction methods on the molar mass distribution and chain conformation of Fortunella margarita(Lour.) Swingle polysaccharides(FP), we used extraction by hot water(WFP), ultrasonic-assisted treatment(UFP), microwave-assisted treatment(MFP) and ultrasonic/microwave-assisted treatment(UMFP), and then Fourier transform infrared(FT-IR) spectroscopy as well as 1H and 13 C nuclear magnetic resonance(NMR) spectroscopy to characterize the structural properties of FP extracted. The molar weight(Mw), polydispersity index(Mw/Mn), root-mean-square(RMS) turning radius(Rg), molar mass distribution and chain conformation of FP were studied systematically using size-exclusion chromatography(SEC), multi-angle laser light-scattering(MALLS) and refractive index(RI). WFP, UFP, MFP and UMFP are all typical carbohydrates according to 1H NMR, 13 C NMR and FT-IR measurements. The type of glycosidic linkage is mainly a β-glycosidic bond with a small amount of α-glycosidic bond. The results obtained by the SEC-MALLS-RI system showed the molar masses of WFP and UMFP were distributed mainly in the range of 5.0×106~1.0×107 g·mol–1 and they accounted for 57.80% and 56.84% of total FP, respectively. The molar masses of UFP and MFP were distributed mainly in the 1.0×106~5.0×106 g·mol–1 range, which accounted for 38.24% and 52.39% of FP, respectively. WFP and UMFP in water were uniform spherical polymers; UFP and MFP were typical highly branched polymers and the degree of branching for MFP was higher compared to UFP. These results indicated the ultrasonic- and microwave-assisted extraction methods caused a significant decrease of the molar mass of FP but the ultrasonic/microwave synergistic extraction method had no effect.     

聚天冬氨酸的合成研究

以L-天冬氨酸为原料,磷酸为催化剂,在不同溶剂中进行缩聚反应,合成中间体聚丁二酰亚胺(PSI),当混合溶剂为m三甲苯／m环丁砜=7／3时,可得到较高分子量的PSI。当催化剂与单体的质量比为0．14时,分子量达到最大值。将PSI碱解得到聚天冬氨酸。     

Polymer-Based Superhydrophobic Coating Fabricated from Polyelectrolyte Multilayers of Poly(allylamine hydrochloride) and Poly(acrylic acid)

Superhydrophobic films mainly based on poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) polyelectrolyte multilayer have been deposited onto cleaned glass substrate by a layer-by-layer dip coating method. 3 bilayers of the PAH and PAA was directly coated onto the substrate as an underlying layer for subsequent coating. Desired surface roughness on the polyelectrolyte bilayers was created by etching the bilayers in hydrochloric acid solution so as to create the open pore having suitable size at the surface. Then, nanoparticles such as SiO₂ and TiO₂ of various sizes were deposited onto the etched polyelectrolyte bilayers. Finally, the surfaces were further modified with semifluorinated silane followed by cross-linking at 180 °C for 2 h to obtain desirable surface morphological features. The effect of etching time and addition of nanoparticles on surface morphology was investigated using an atomic force microscope (AFM). Wetting ability of the prepared film was determined by measuring water droplet contact angle using a goniometer. Adhesion between the superhydrophobic films and the substrate was evaluated by using a standard tape test method (D3359). The adhesion was improved by reducing the organic content in the films.     

Molar Mass and Structural Characteristics of Poly[(lactide-co-(aspartic acid)] Block Copolymers

Summary: We report on various synthetic procedures for the preparation of biodegradable and biocompatible poly(lactide-co-aspartic acid) block copolymers based on natural monomeric units – lactic acid and aspartic acid. Multiblock poly(lactide-co-aspartic acid) copolymers of different comonomer composition were synthesized by heating a mixture of L-aspartic acid and L,L-lactide in melt without the addition of any catalyst or solvent and with further alkaline hydrolysis of the cyclic succinimide rings to aspartic acid units. Diblock poly(lactide-co-aspartic acid) copolymers with different block lengths were prepared by copolymerization of amino terminated poly(β-benzyl-L-aspartate) homopolymer and L,L-lactide with subsequent deprotection of the benzyl protected carboxyl group by hydrogenolysis. The differences in the structure, composition, molar mass characteristics, and water-solubility of the synthesized multiblock and diblock poly(lactide-co-aspartic acid) copolymers are discussed.     

瓜胶/聚丙烯酸互穿聚合物网络水凝胶对模型药物的负载与控制释放

考察了以牛乳清蛋白(BSA)为模型药物,通过相平衡分配法制备载药瓜胶(GG)/聚丙烯酸(PAA)互穿聚合物网络(IPN)水凝胶的工艺条件.借助紫外可见光谱仪研究了载药水凝胶在结肠酶存在下的控制释放行为.结果表明:载药容量(CM)随瓜胶、丙烯酸用量的增加而下降,半IPN水凝胶的Cm较全IPN的略大;结肠酶能明显提高半IPN与全IPN中的BSA释放速率,且提高幅度随GG含量的增加而加快,GG/PAA IPN水凝胶具有结肠定位降解的特性,有望成为靶向结肠给药的理想载体材料.     

窄分子量分布的聚丙烯酸的合成及其阻垢性能

以水为溶剂,采用可逆加成-断裂链转移自由基聚合(RAFT)方法,合成了分子量2400～9000的聚丙烯酸。GPC分析表明,所合成的聚丙烯酸具有很窄的分子量分布(多分散系数PDI约为1.2)。阻垢性能测定结果表明,用RAFT方法合成的聚丙烯酸比采用普通自由基聚合得到的商品聚丙烯酸阻垢剂具有更好的阻垢性能。如当分子量约为2400的聚丙烯酸的质量浓度分别为2和10mg/L时,其阻碳酸钙垢的阻垢率分别为83.8%和97.5%,而在相同质量浓度下商品聚丙烯酸阻垢剂的阻碳酸钙垢的阻垢率则仅分别为21.3%和42.9%。阻垢作用随温度升高(50～90℃)而降低的幅度也明显小于商品聚丙烯酸阻垢剂,80℃时二者的阻垢作用差别最大,而这正是一般冷却水达到的最高温度。在所研究的分子量范围内,所合成的聚丙烯酸分子量愈小则其阻垢性能愈好。     

Preparation and Characterization of pH-sensitive Hydrogel Film of Chitosan/Poly(acrylic acid) Copolymer

A hydrogel film of chitosan/poly(acrylic acid) (CS/PAAc) copolymer with the property of pH sensitivity, was prepared by irradiating the chitosan film, which was then swelled by aqueous AAc solutions of different concentrations. The effects of the feed ratio of chitosan and AAc on the properties of the hydrogels, such as swelling ratio and pH-sensitivity, were determined. Fourier transform infrared (FT-IR) spectroscopy was applied in the attenuated total reflectance (ATR) mode for analyzing the structure change of the hydrogels after the treatment in buffer solutions of different pHs.     

聚乙二醇-聚乳酸共聚物药物载体

本文综述了聚乙二醇与聚乳酸共聚亲水改性的最新进展, 包括嵌段和星型结构聚乙二醇-聚乳酸共聚物(PEG-PLA)及其端基化衍生物的合成。同时概述了该共聚物以胶束、微粒、水凝胶和囊泡形式担载亲水、疏水及蛋白质类药物的应用,特别介绍了静电纺丝制备的PEG-PLA超细纤维载体及其释药特性。     

非离子聚(N-乙烯基-2-吡咯烷酮)凝胶在线型聚(丙烯酸)溶液中的溶胀特性

研究了在线型聚 (丙烯酸 ) (PAA)溶液中链长、pH、离子强度和水 /二甲亚砜混合溶剂组成对非离子聚 (N-乙烯基 - 2 -吡咯烷酮 ) (PVP)水凝胶溶胀特性的影响 .发现聚酸浓度的变化引起凝胶显著的体积相变 ,这是因为凝胶和聚合物通过氢键形成了大分子间凝胶 -聚合物复合物 .凝胶的溶胀特性取决于聚酸的链长而不是离子强度 .随着pH值和水 /二甲亚砜混合溶剂组成的变化 ,凝胶的溶胀率 (SR)发生变化     

Production of Poly(acrylic acid) Particles Dispersed in Organic Media

Summary: A process for preparation of poly(acrylic acid) particles dispersed in oil is presented. The process comprises two steps: the first step involves the preparation of a poly(acrylic acid) solution, while the second step consists in the preparation of the polymer particles by dispersing the polymer solution in an organic phase. During the second step, modification of the polymer chain structure can be performed through chemical reactions. One of the advantages of the proposed process is the possibility to produce particles loaded with drugs or other chemical compounds. Besides that, if the continuous phase is vegetable oil, purification of the reaction medium may not be necessary.     

聚丙烯酸功能化多壁碳纳米管

Covalent functionalization of multiwalled carbon nanotubes （MWNT） with poly（acrylic acid） has been successfully achieved via grafting of poly（acryloyl chloride） on nanotube surface by esterification reaction of acyl chloride-bound polymer with hydroxyl functional groups present on acid-oxidized MWNT and hydrolysis of polymer attached to nanotubes. Polymer-functionalized MWNT could possess remarkably high solubility in water, and their aqueous solution was very stable without any observable black deposit for a long time. Characterizations of such functionalized MWNT samples using Fourier transform infrared spectrometer, transmission electron microscopy and nuclear magnetic resonance techniques indicated that poly（acrylic acid） was covalently attached to the surface of MWNT.     

超临界CO2溶胀聚合法制备聚丙烯酸/尼龙1313及聚苯乙烯/尼龙1313共混物

超临界CO2溶胀聚合法制备聚丙烯酸/尼龙1313及聚苯乙烯/尼龙1313共混物;超临界CO2;聚丙烯酸;聚苯乙烯;尼龙1313;共混