Synthesis of a Macromer, MPEGAA, Used to Prepare an AMPS-modified Polyacrylic Acid Superplasticizer

A macromer, methoxypolyethylene glycol acrylate （MPEGAA）, was synthesized by direct esterification using methoxypolyethylene glycol （MPEG-1200） and acrylic acid （AA） as the main materials. MPEGAA was then used to prepare a polyacrylic acid superplasticizer modified with 2-acrylamido-2- methylpropane sulfonic acid （AMPS）. A single-factor test was performed to investigate the effects of the molar ratio of acid to alcohol （n（AA）/n（MPEG））, inhibitor amount, catalyst amount, temperature, and time of esterification on the synthesis of MPEGAA. The experimental results showed that the optimal esterification conditions were as follows： n（AA）/n（MPEG）, 3.5：1; amount of hydroquinone （as an inhibitor）, 1.2%; amount of para-toluenesulfonic acid （as a catalyst）, 5.5%; reaction temperature, 95 ~C; and reaction time, 6 h. The AMPS- modified polyacrylic acid superplasticizer prepared under the optimal esterification conditions enabled the achievement and maintenance of high cement dispersibility. At an admixture amount of 0.15%, the cement paste fluidity was initially as high as 300 mm, and then decreased to 315 mm after 1 h and to 290 mm after 2 h.

Synthesis and Properties of an AMPS-Modified Polyacrylic Acid Superplasticizer

A 2-acrylamide-2-methyl propylene sodium sulfonic （AMPS）-modified polyacrylic acid superplasticizer was synthesized using aqueous solution polymerization with the major monomers including the self-made active macromers polyethylene glycol mono-methyl ether acrylate acrylic （MPEGAA）, acrylic acid （AA）, AMPS, and sodium methyl allyl sulfonate （SMAS）. The ratios of the monomers were determined using an orthogonal experiment. This research focused on the effects of the dosages of different macromers, the polymerization conditions, and the length of MPEGAA side chains on the properties of the AMPS-modified polyacrylic acid super-plasticizer. The best polymerization conditions of the AMPS-modified polyacrylic acid superplasticizer are when （n（MPEGAA）：n（SMAS）：n（AMPS）：n（AA） equals 0.1：0.1：0.2：0.65, the molecular weight of monomethoxypolyethylene glycol is 1 200, the initiator ammonium persulfate accounts for 5% of the total mass of the polymerized monomers, the polymerization temperature is 80 ~C, and the reaction time is 4 h. The AMPS-modified polyacrylic acid superplasticizer synthesized in the best conditions exhibited excellent dispersivity and dispersion retainability. When the dosage ratio was 0.24%, the initial fluidity was 400 mm and the fluidity had nearly no loss after 1 h.

The Synthesis Technique of Polyacrylic Acid Superplasticizer

Using water separation technique,acrylic acid （AA） and polyethylene glycol （PEG） 1000,of which the ratio was 1.5,were esterified and the optimum esterification ratio of 90% could be reached under the condition of 110 ℃×3 h.Using polyoxyethylene acrylate macromonomer （PA） prepared in the esterification,AA and sodium methylacryl sulfonate （MAS） as monomers,a copolymer which could be used as superplasticizer was prepared by free radical coolymerization in n（PA）：n（AA）：n（MAS） of 1：7：3.When the synthesis condition was 80 ℃× 5 h,the optimal dosage of initiator was 3.0%-4.0%,the fluidity of cement paste with the samples could reach 270 mm.By analyzing the effect of the content of residual small molecule sulfonic monomer on the properties of sample,n（MAS）/n（PA） was controlled in a range of 2.5-3.8.

Effects of an AMPS-Modified Polyacrylic Acid Superplasticizer on the Performance of Cement-based Materials

A self-made AMPS-modified polyacrylic acid superplasticizer and two others of the same type but with different molecular structures, which are commercially available, are used in this study to investigate the effect of a 2-acrylamide-2-methyl propylene sulfonic （AMPS）-modified polyacrylic acid superplasticizer on the properties of cement-based materials. In the experiments, initial fluidity, 1 and 2 h fluidity over time after admixtion, bleeding rate of the net cement mortar, and adsorption capacity and rate of cement particles are determined by adding different dosages of the three superplasticizers into the cement paste to characterize the dispersivity and the dispersion retention capability of each superplasticizer. Water-reducing rates of three kinds of mortars are simultaneously determined to characterize the water-reducing capacity of each superplasticizer, as well as the 3 and 28 d compressive strengths to characterize the compression resistance. Results show that water-reducing effect and fluidity better maintain the capability of the AMPS-modified polyacrylic acid superplasticizer than the two commercially available polyacrylic acid superplasticizers, and the compressive strengths after 3 and 28 d show significant growth. In conclusion, the effects of water reduction and strengthening of the AMPS-modified polyacrylic acid superplasticizer are evidently better than those of the two commercially available polyacrylic acid superplasticizers.

Effect of Molecular Structure on the Performance of Polyacrylic Acid Superplasticizer

The effects of structure parameters, such as molecular structure, segment kinds, molecular weight, and organic functional groups, on the performance of polyacrylic acid superplasticizer were discussed. According to the differences of chain sections, functional groups, eic, polyacrylic acid superplasticizer could be divided into A, B, C three parts. Among them, A chain section included sulfonic acid groups, B chain section carboxyl groups, C chain section polyester. Polyacrylic acid superplasticizers with different matching of A, B, C chain sections, different length of C chain section and different molecular weights were synthesized by acrylic acid, polyethylene glycol, sodium methyl allylsulfonate; the relation between the molecular structure and perfolxnance was also studied. The expetimental results indicate that the water-reduction ratio increases obviously with the increment of the proportion of sodium methyl allylsulfonate chain section in the molecular; the slump retention increases greatly with the increment of the proportion of acrylic acid chain section; the dispersion of cement particles increases with the increment of the chain length of polyethylene glycol; when the molecular weight is in the range of 5000, the dispersion and slump retentibity increase with the increment of the average molecular weight of polymers.

A new approach for development of vaccine against visceral leishmaniasis: Lipophosphoglycan and polyacrylic acid conjugates

Objective: To determine the antileishmanial vaccine effectiveness of lipophosphoglycan(LPG) and polyacrylic acids(PAA) conjugates on in vivo mice models.Methods: LPG molecule was isolated and purified from large-scale Leishmania donovani parasite culture. Protection efficacies of LPG alone, in combination with Freund's adjuvant, in a physical mixture and in conjugate(consisting of various LPG concentrations) with PAA, were comparatively determined by various techniques, such as cultivation with the micro-culture method, assessment of in vitro infection rates of peritoneal macrophages, determination of parasite load in liver with Leishman-Donovan Units, and detection of cytokine responses.Results: Obtained results demonstrated that the highest vaccine-mediated immune protection was provided by LPG-PAA conjugate due to all parameters investigated. According to the Leishman-Donovan Units results, the sharpest decline in parasite load was seen with a ratio of 81.17% when 35 mg LPG containing conjugate was applied. This value was 44.93% for the control group immunized only with LPG. Moreover, decreases in parasite load were 53.37%, 55.2% and 65.8% for the groups immunized with 10 mg LPG containing LPG-PAA conjugate, a physical mixture of the LPG–PAA, and a mixture of LPG + Freund's adjuvant, respectively. Furthermore, cytokine results supported that Th1 mediated protection occurred when mice were immunized with LPG-PAA conjugate.Conclusions: It has been demonstrated in this study that conjugate of LPG and PAA has an antileishmanial vaccine effect against visceral leishmaniasis. In this respect, the present study may lead to new vaccine approaches based on high immunogenic LPG molecule and adjuvant polymers in fighting against Leishmania infection.

Radiation synthesis and characterization of polyacrylic acid hydrogels

The pH-sensitive polyacrylic acid (PAA) hydrogels were synthesized by gamma-ray irradiation at an am- bient temperature. The influences of dose, monomer concentration, cross-linking agent content, pH, and ionic strength on the swelling ratio (SR) of the PAA hydrogels were investigated in detail. The results show that the SR of the hy- drogel decreases with an increase in the dose, monomer concentration, and cross-linking agent content. In alkaline so- lution, the SR of the hydrogels is much higher than that in acid solution. Also, the ionic strength can influence the SR of the hydrogels. The more the concentration, the lower the

IN SITU INTERFEROMETRIC STUDY ON THE GELATION PROCESS OF POLYACRYLIC ACID GELS

In situ interferometry was used to investigate the gelation process of polyacrylic acid (PAA) gels. The basic principle of the in situ interferometry technique is illustrated. It can give sufficient information for non-destructive and successful investigation of the whole gelation process. The effect of initiator concentration on the gelation process was studied. The polymerization rate of AA increases with increasing initiator concentration. The error arising from the thermal effect in the gelation process can be neglected.

Dynamic Behavior and Mass Transport in Polyacrylic Acid Gel by Dynamic Light Scattering

Dynamic behaviors on polyacrylic acid (PAA) gels and mass (small molecules) transports in the gels have been studied mainly by dynamic light scattering (DLS). The cross-linking degree (fc), monomer concentration (Cm) and temperature of the gels have significant influences on its dynamic behavior and mass transport in the gels. The increase of fc leads to decrease of the mesh sizes of the gels, thus the obstacle of the gels for mass transport is increased. As a result, small molecular diffusion Dk in the gels is decreased. So even if for small molecules, the Dk also is influenced.

Effects of an AMPS-modified Polyacrylic Acid Superplasticizer on the Performance of Concrete Materials

A self-made 2-acrylamide-2-methyl propylene sulfonic （AMPS）-modified polyacrylic acid superplasticizer and two other commercially available superplasticizers with different molecular structures are used in this study to investigate the effect of an AMPS-modified polyacrylic acid superplasticizer on the properties of concrete materials. In the experiments, initial and 1.5 h slumps over time after admixtion are determined by adding different dosages of three superplasticizers into the premixed concrete to characterize the slump loss resistance of the premixed concrete. The water-reducing rates of three different types of concrete are determined to characterize the water-reducing capacity of the concrete with each superplasticizer. The 3, 7 and 28 d compressive strength is determined to characterize the mechanical properties of the concrete with each superplasticizer. In the meanwhile, 1, 1.5 and 2.0 h slump loss rates over time after admixtion are determined by adding different dosages of the three superplasticizers into the high-performance concrete （HPC） to characterize the slump loss resistance of HPC. The 7, 28, 60 and 90 d compressive strength is determined to characterize the compressive properties of HPC with each superplasticizer. The dry shrinkage rates of three different types of HPC are determined with each superplasticizer. Electric flux after standard curing for 56 d and chloride ion diffusion coefficient after curing for 28 d of I-IPC are determined to characterize the impermeability of HPC with each superplasticizer. The cross-section was examined using a scanning electron microscopy （SEM） system. Results demonstrate that the AMPS-modified polyacrylic acid superplasticizer has better water-reducing effect and slump than the two commercially available polyacrylie acid superplasticizers. The AMPS-modified polyacrylic acid superplasticizer also shows significant improvement of the compressive strength, especially in comprehensive performance of HPC. In conclusion, the AMPS-modified polyacrylic acid superplastieizer is particularly suitable for the preparation of HPC.

Preparation and Properties of pH-Responsive Intelligent Medical Dressing Based on Bacterial Cellulose/Polyacrylic Acid

Bacterial cellulose/polyacrylic acid (BC/PAA) pH-responsive hydrogels were prepared by free-radical polymerization (in situ) using BC as the raw material and AA as the monomer. The hydrogels were loaded with curcumin (Cur) to prepare pH-responsive intelligent medical dressings. The preparation process of the hydrogels was optimized by a single factor and response surface experiment using their swelling degree as an index. The structures of BC/PAA pH-responsive hydrogels were characterized by scanning electron microscope (SEM), Fourier Transform Infrared spectrometer (FTIR), X-ray diffraction (XRD), and tensile tester, and the swelling properties, mechanical properties, bacteriostatic properties, and drug release behavior were investigated. The results showed that the BC/PAA pH-responsive hydrogel has a three-dimensional network structure with the swelling rate up to 1600 g/g, compressive strength of up to 8 KPa, and good mechanical properties, and the drug release behavior was in line with the logistic dynamics model, and it has good inhibitory effects on common pathogens of wound infection: E. coli, S. aureus, and P. aeruginosa.

Oxygen self-doping pyrolyzed polyacrylic acid as sulfur host with physical/chemical adsorption dual function for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with high theoretical capacity and energy density need to solve problems such as the high decomposition energy barrier of Li2S and large volume change of sulfur in the charging process caused by the shuttle effect before practical application.Herein,a green synthesis method is used to prepare polyacrylic acid(PAA)superabsorbent material,and then the pyrolyzed PAA(P/PAA)material is obtained as the positive electrode of Li-S battery.Density functional calculation reveals that the oxygen self-doping pyrolyzed polyacrylic acid(P/PAA)delivered stronger binding energy toward Li2S species in carbonyl C=O than that of graphite powder(GP)which are-1.58 eV and-1.02 eV,respectively.Coupled with the distribution of relaxation time analysis and the in-situ electrochemical impedance approach,it is further demonstrated that the designed P/PAA as sulfur host plays a physical/chemical adsorption dual function in maintaining the stability and rate performance of batteries.With an initial discharge capacity of 1258 mAh/g at 0.1 C and a minimal capacity decline of 0.05%per cycle even after 800 cycles at 0.5 C,the produced cathode demonstrated outstanding electrochemical performance.The average Coulombic efficiency is nearly 100%.The P/PAA electrodes may typically retain 96%of their capacity while declining on average only 0.033%per cycle after 130 cycles at 3 C.This effort provides a new method for the future development of heteroatomic self-doping superabsorbent with promising adsorption properties for polysulfides as cathode materials of Li-S batteries.

铁离子配位聚丙烯酸基芬顿催化纤维的制备及其性能

为改善聚丙烯酸(PAA)纤维的性能,在湿法纺丝过程中基于铁离子配位反应成功制备了可拉伸PAA初生纤维,利用后拉伸以及热定型工艺优化纤维性能,并探究其作为Fenton催化剂在染料废水处理领域的应用。结果表明:相较硫酸铁盐,氯化铁盐配位的PAA纤维具有更为优异的力学性能和尺寸稳定性;后拉伸和热定型工艺可显著提高PAA纤维的力学性能和催化活性,并抑制铁离子的流失,拉伸20倍且在130℃定型的纤维断裂强度为1.42 cN/dtex,与未拉伸纤维相比提高了914.3%,且可在3 min内脱色90%以上的亚甲基蓝(MB),循环使用40次未出现脱色率衰减现象。

氧化石墨烯/聚丙烯酸基导电黏附凝胶的制备与性能

现有导电凝胶材料在实际使用时存在诸多缺陷,因此设计出一种兼具高强度、高黏附性和高导电性的凝胶材料具有重要的应用意义。本文以丙烯酸(AAc)和丙烯酸-N-羟基琥珀酰亚胺酯(AAc-NHS ester)为基体,聚乙二醇二丙烯酸酯(PEGDA)为交联剂,引入氧化石墨烯(GO)作为增效成分,通过光引发一步聚合法制备了复合凝胶材料(PAA-NHS/GO)。GO的引入提高了体系的交联度,增强了凝胶的稳定性并赋予了凝胶高导电特性。PAA-NHS/GO的拉伸强度、断裂伸长率、电导率分别可达0.336MPa、302.6%和0.93S/m。复合凝胶的功能基团能与组织表面产生强黏附效果,黏附强度超过40kPa,同时还具备高生物安全性和优异的生物相容性。在外力作用下,复合凝胶表现出稳定的应变传感特性。而在用于心电信号监测时,复合凝胶的灵敏度高,并可实现稳定清晰的信号传输。PAA-NHS/GO作为新型导电黏附凝胶,有望用于柔性可穿戴、生物传感、电子皮肤等领域。

魔芋葡甘聚糖接枝聚丙烯酸敷料对糖尿病皮损治疗作用的研究

目的探究魔芋葡甘聚糖(KGM)接枝聚丙烯酸(AA)敷料对糖尿病皮肤损伤的修复作用。方法采用自由基聚合方法制备(KGM-AA)敷料,进行吸水性实验检测KGM-AA敷料的吸水性能与黏性;通过扫描电子显微镜观察材料冻干后结构及形态。将KGM-AA水凝胶与小鼠成纤维细胞L929体外共培养24 h后,进行细胞活死染色及CCK-8检测,探究细胞的活性及生长状况。将血管内皮细胞接种到KGM、KGM-AA和空白对照上,于接种后第2、4、6、8小时时间点观察血管形成情况。通过小鼠腹腔注射STZ造糖尿病模型,当随机血糖连续2次大于11.1 mmol/L即造模成功。将所获得的高血糖糖尿病小鼠于颈后处制造直径为1 cm圆形伤口并随机分为3组,一组为不做处理空白对照组,另2组分别用KGM及KGM-AA敷料对小鼠创面进行治疗,观察伤口的愈合情况。于创伤后第7、14天时取伤口处皮肤进行苏木精-伊红(HE)染色,观察伤口愈合及炎症、增生等情况。结果KGM-AA敷料具有良好的吸水能力,吸水后的KGM-AA呈现均匀的多孔结构,孔径均大于10μm。与小鼠L929共培养后发现,细胞成功进入吸水形成的凝胶内部,细胞存活率大于95%,可以为细胞附着提供良好的环境且对细胞生长及活性无显著影响。成管实验结果显示,与KGM相比,接种6 h左右KGM-AA组血管数量明显多于KGM组,差异有显著性统计学意义(P<0.01),该差异一直维持到接种后的第10小时。体内实验表明,与对照组相比,创口用KGM-AA敷料处理过的高血糖小鼠在治疗7 d时创面皮肤比未接受治疗组更加完整。结论KGM-AA敷料吸水性及生物相容性良好,吸水后形成均匀多孔结构,形成保护膜的同时为细胞附着提供了良好生长条件,同时表现出良好的促进血管生成特性和潜在的调节皮肤损伤能力,是理想的伤口敷料和细胞递送材料。

不同条件制备聚丙烯酸水凝胶的结构与性能

采用乳液聚合方法将引发剂过硫酸铵(APS)和乳化剂十二烷基硫酸钠(SDS)制备出聚丙烯酸树脂乳液,再加入不同条件交联剂固化成聚丙烯酸(PAA)水凝胶,并探究使用紫外固化和热固化2种不同固化方式及不同固化时间对PAA水凝胶性能的影响。通过氮气等温吸脱附曲线测试(Brunauer-Emmet-Teller,BET)、扫描电子显微镜(scanning electron microscope,SEM)、热失重分析(thermogravimetric analysis,TGA)、溶胀度、力学测试等方法,对水凝胶的性能进行表征分析。结果表明,形成的PAA水凝胶主要为片状颗粒材料,在紫外固化20 min条件下,其孔径主要分布在2~4 nm;且在热固化条件下,当交联剂质量浓度为0.06、0.07 g/mL时PAA水凝胶溶胀度可达到667%,在交联剂质量浓度为0.09 g/mL时拉伸强度可达到60 k Pa。综上所述,对比紫外固化和热固化2种方法以及不同条件交联剂下制备的PAA水凝胶的差异,对理解和优化PAA水凝胶的制备具有一定的指导意义。

海藻酸钠包埋污泥颗粒的耐磨性能研究

为了探究海藻酸钠(SA)包埋颗粒耐磨性的影响因素,以SA包埋活性污泥颗粒为研究对象,探究了SA添加量以及不同包埋强化剂对颗粒耐磨性能的影响。结果表明:增加SA添加量制备颗粒污泥的耐磨性能也随之增强,但是当添加量高于2.0%(质量分数)时,耐磨性能增强效果不明显;颗粒耐磨性能增强对于水样的电导以及COD没有明显的影响;单独添加羧甲基纤维素(CMC)、卡拉胶等包埋强化剂不能增加颗粒的耐磨性,聚丙烯酸高吸水树脂(PA)、聚乙烯吡咯烷酮-K30/-K90会降低颗粒的耐磨性;CMC/PA、卡拉胶/PA的复合添加对颗粒耐磨性能有显著的增强作用,卡拉胶/PA的组合增强效果略优于CMC/PA,且增加卡拉胶的添加量对颗粒的耐磨性有增强作用。

聚N-异丙基丙烯酰胺/聚丙烯酸水凝胶的制备及性能研究

当外界环境发生变化时,环境敏感型水凝胶的物理性质或化学性质会随之发生改变,大部分水凝胶对环境的响应比较单一。以丙烯酸(AA)和N-异丙基丙烯酰胺(NIPAm)为原料制备的聚N-异丙基丙烯酰胺/聚丙烯酸水凝胶既可以对温度变化也可以对pH值变化做出响应。实验采用一锅法制备了聚N-异丙基丙烯酰胺/聚丙烯酸水凝胶,通过调节丙烯酸的中和度、丙烯酸(AA)和N-异丙基丙烯酰胺(NIPAm)两种单体的配比、交联剂N,N′-亚甲基双丙烯酰(BIS)和引发剂过硫酸钾(KPS)的用量,研究其对水凝胶的吸水性能、拉伸性能的影响,并考察了所制备的聚N-异丙基丙烯酰胺/聚丙烯酸水凝胶对温度及pH响应性能。实验结果表明:当丙烯酸的中和度为125%、n(NIPAm)∶n(AA)=0.3∶1、BIS的质量分数为0.5%、KPS的质量分数为1%时,制备的水凝胶溶胀率最大且有一定的弹性,室温下吸水率达179.73 g/g。该水凝胶在酸性缓冲溶液(pH值=3)中收缩,当缓冲溶液的pH值大于3,水凝胶发生溶胀,具有灵敏可逆的pH响应性能,同时该水凝胶兼具热缩温敏性能。