Properties of Absorbent Acrylic Foam Prepared Based on the Method of High Internal Phase Emulsion

Acrylate and methacrylate monomers absorbent acrylate foams were prepared based on the method of high internal phase emulsion (HIPE). The influence of reaction conditions on liquid absorption by acrylate foams was studied. The reaction conditions included monomer ratio, cross-linker amount, initiator amount, emulsifier amount, emulsion concentration, emulsification temperature, and the curing time. The reaction conditions were determined to achieve the best liquid absorption by acrylate foams. Acrylate foams were analyzed with Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results showed that when the monomer ratio was 9:1, cross-linking agent was 30% of monomer amount, initiator amount was 4% of the reactants amount, emulsifier amount was 8% of the reactants amount, the ratio of aqueous phase to oil phase was 32:1, emulsification temperature was 75°C, and curing time was 1.5 h, we could prepare the acrylate foam material with the best liquid absorption. Reaction of monomer and cross-linking agent was confirmed by FTIR analysis. The pore sizes of acrylate foam were between 1 μm and 8 μm according to SEM analysis. This material was very suitable to absorb aqueous fluids.     

pH-dependent color change of colloidal dispersions of gold nanoclusters: Effect of stabilizer

Gold nanoclusters protected by 3-mercaptopropionic acid (MPA-Au nanoclusters) were prepared by citrate-reduction of hydrogen tetrachloroaurate(III) in the presence of sodium 3-mercaptopropionate. Color of the dispersions of MPA-Au nanoclusters changed from red to purple by addition of hydrochloric acid and returned from purple to red by addition of an aqueous sodium hydroxide solution. This reversible response can be attributed to synchronized changes between dispersion and ordering of MPA-Au nanoclusters, determined by transmission electron microscopy. Gold nanoclusters protected by poly(acrylic acid) (PAA-Au nanoclusters) were prepared by UV irradiation of an aqueous solution of hydrogen tetrachloroaurate(III) in the presence of poly(sodium acrylate). The pH-dependent spectral change observed for MPA-Au was not observed for PAA-Au. UV-Vis absorption spectra of colloidal dispersions of PAA-Au nanoclusters after addition of hydrochloric acid and an aqueous sodium hydroxide solution were in good agreement with each other, suggesting the stability of PAA-Au nanoclusters to pH change. Received 18 October 2000 and Received in final form 10 April 2002     

紫外光引发合成阴离子聚丙烯酰胺及其表征

选择了三种单体：丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和丙烯酸(AA),在复合引发剂的作用下,紫外光照射共聚得到阴离子聚丙烯酰胺(APAM)。研究了单体配比、单体总质量分数以及引发剂浓度等因素对聚合反应的影响,以产物特性粘度为目标进行了制备条件的优化,并对聚合产物的紫外、红外、电镜等结构和热性能进行表征。结果表明,在单体配比为70∶10∶10、单体质量分数为40%、引发剂浓度0.20%、反应体系pH值为9.0以及光照60 min条件下,能够制得特性粘度为1.6×103 mL·g-1的阴离子聚丙烯酰胺。     

Intercalation of acrylic acid and sodium acrylate into kaolinite and their in situ polymerization

Novel nano-composites of poly (acrylic acid)-kaolinite were prepared, and intercalation and in situ polymerization were used in this process. The nano-composites were obtained by in situ polymerization of acrylic acid (AA) and sodium acrylate (AA_Na) intercalated into organo-kaolinite, which was obtained by refining and chemically modifying with solution intercalation step in order to increase the basal plane distance of the original clay. The modification was completed by using dimethyl-sulfoxide (DMSO)/methanol and potassium acetate (KAc)/water systems step by step. The materials were characterized with the help of XRD, FT-IR and TEM; the results confirmed that poly(acrylic acid) (PAA) and poly(sodium acrylate) (PAA_Na) were intercalated into the interlamellar spaces of kaolinite, the resulting copolymer composites (CC₀ : copolymer-crude kaolinite composite, CC₁ : copolymer-DMSO kaolinite composite, CC₂ : copolymer-KAc kaolinite composite) of CC₂ exhibited a lamellar nano-composite with a mixed nano-morphology, and partial exfoliation of the intercalating clay platelets should be the main morphology. Finally, the effect of neutralization degree on the intercalation behavior was also investigated.     

甲基丙烯酸甲酯—丙烯酸丁酯共聚物微观结构研究

用＾１３Ｃ ＮＭＲ研究了由基团转移共聚得的的甲基丙烯酸甲酯－丙烯酸酯共聚物的微观结构，共聚物中单体链节的三元组含量从季碳和羰基碳的共振信号测得，实验测得的三元组分数与通过竞聚率和单体组成比按末端基效应模式的计算值相符，丙烯酸丁酯由于具有大得多的竞聚率值而呈现较强的均聚倾向。     

Rheological Properties of Template Polymerization Polyacrylamide Aqueous Solutions

In this work, the aqueous solution rheology properties of both partially hydrolyzed polyacrylamide (HPAM) and the template copolymer (TPAM) synthesized from acrylic acid (AA) and acrylamide (AM) were investigated using an advanced rheometer and viscometer. The results were correlated with the corresponding molecular structures of HPAM and TPAM, which were characterized by high-resolution nuclear magnetic resonance. It was found that the thickening ability of TPAM is much stronger than that of HPAM due to its unique microblocky structure, while the viscosity of TPAM was more sensitive to shear rate. Furthermore, the effect of polymer concentration was also tested in an oscillation shear mode. It showed that the characteristic relaxation time of TPAM was much higher than that of HPAM at the high concentrations. The research on salt-resistance properties showed that the viscosity retention of TPAM was similar to HPAM at the same NaCl concentration. But, unexpectedly, at the same CaCl₂ concentration the viscosity retention of TPAM was much lower than that of HPAM, indicating a poor divalent salt-resistance property.     

Preparation of BA/ST/AM nano particles by ultrasonic emulsifier-free emulsion polymerization

A kind of nano particle of butyl acrylate (BA)/styrene (ST)/acrylamide (AM) was prepared through a new method that was ultrasonic emulsifier-free emulsion polymerization, which was a kind of environmental protection and economical method. And no any volatile organic solvent (VOC), emulsifier and initiator were used in this method. Only water was used as solvent. The effects of sonic intensity, sonic time, inorganic salt content, N2 flow velocity, etc. on monomer conversion were studied. TEM photographs showed that its particles size was about 80 nm, which was less than particles size (about 140 nm) through conventional emulsifier-free emulsion polymerization method. The FTIR spectrum showed that after extracted by water for 48 h, CHCl3 for 48 h and THF for 48 hr, respectively, the sample obtained by this way was a ternary copolymer of BA, ST and AM, but not a blend of poly(butyl acrylate), polystyrene and polyacrylamide.     

Synthesis and Characterization of Methylacrylic Acid and Butyl Acrylate Grafted onto Ethylene-Propylene-Diene Terpolymer

A multi-component polymer of methacrylic acid (MAA) and butyl acrylate (BA) grafted onto ethylene-propylene-diene (EPDM) terpolymer was synthesized in toluene using benzoyl peroxide (BPO) as initiator. The effect of EPDM/MAA-BA ratio and MAA/BA ratio on the grafting ratio of polymerization was investigated. The products were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), surface energy, inherent viscosity, and atomic force microscopy (AFM). The results showed that the MAA and BA monomers were successfully grafted onto EPDM. Furthermore, after being grafted, the polarity of the surface of the EPDM-g-MAA-BA increased with increasing grafting ratio, and the morphology of its surface became more smooth.     

Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate

Nano-sized calcium carbonate (CaCO₃) particles were modified by heptadecafluorodecyl trimethoxysilane under acidic water condition. An ordinary polyacrylate prepared via radical copolymerization of methyl methacrylate, butyl acrylate, acrylic acid and β-hydroxyethyl methacrylate was used as the binder to form hydrophobic coatings with the modified CaCO₃. Super hydrophobic coating with water contact angle of 155° was obtained from modified CaCO₃ and the polyacrylate at their weight ratio of 8/2 by a simple procedure. Based on surface analysis by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), the super hydrophobicity can be attributed to both the surface microstructure and surface enrichment of fluoroalkyl chains. Due to a low water sliding angle, carbon black powder on super hydrophobic surface was easily removed by rolling water droplet. Furthermore, the anti-frosting performance of different surfaces was investigated, which indicated that the frost formed on superhydrophobic surface was greatly retarded compared with that on bare copper surface. The surface kept super hydrophobicity even after freezing-thawing treatment for 10 times.     

Preparation of Polymethylacrylic Acid Standard Samples for GPC Applications via a Precipitation Fractionation-Separated Step Hydrolysis Method

A series of polymethylacrylic acid (PMAA) standard samples were prepared from fractionated PMMA samples followed by a two-step hydrolysis. The six PMMA standard samples with narrow molecular weight distributions were produced by free radical polymerization and fractionated with toluene-petroleum ether. Their average molecular weights ranged from 3.1 × 10³ to 4.3 × 10⁴, dispersion coefficients were less than 1.5, and their gel permeation chromatography (GPC) peak shapes were symmetrical. The PMMA standard samples were dissolved in dioxane, and then hydrolyzed in a saturated NaOH-methanol solution for 24 h, the methanol then evaporated, and after that the PMMA samples were hydrolyzed in a 2 mol ·L ^?1 NaOH aqueous solution for 24 h. The ¹H-NMR results showed that the two-step hydrolysis degree was higher than 98.70%. The PMAA standard samples were obtained after acidifying the hydrolysates, namely polymethacrylic acid sodium salt, and their molecular weights were constant during the separation process. The acid–base titration results showed the purities of the PMAA samples were greater than 98.6%, and their molecular weight distributions were symmetrical and narrow. The molecular weights of the PMAA were determined by the stoichiometric relationship of the hydrolysis reaction. Compared with viscosimetry, the results of both methods were basically the same, and their errors were less than 10%.     

Improving the hydrophilicity of poly(vinylidene fluoride) porous membranes by electron beam initiated surface grafting of AA/SSS binary monomers

Poly(vinylidene fluoride) (PVDF) membranes were pre-irradiated by electron beam in vacuum, and then the hydrophilic sulfonate groups were introduced by the single step grafting method with binary monomer solution of acrylic acid (AA) and sodium 4-styrenesulfonate (SSS). The effect of binary monomer ratio and pH of reaction solution on the degree of grafting was investigated. The surface chemical change was characterized by Fourier transform infrared attenuated total reflection spectroscopy (FT-IR-ATR) and X-ray photoelectron spectroscopy (XPS). Morphological changes on the membrane surface were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface hydrophilicity of the modified membrane was characterized through water contact angle measurement. It was found that the water contact angle of the membrane surface decreased significantly when compared with the original one, indicating the improvement of the surface hydrophilicity.     

具有核壳结构的纳米凝胶的相变

通过可逆加成-断裂链转移聚合合成了一系列不同分子量的聚丙烯酸大分子链转移剂,用¹H NMR和水相GPC对其进行了表征．以三硫代碳酸盐的聚丙烯酸钾作为稳定剂,在水相中进行N-异丙基丙烯酰胺(NIPAM)的分散聚合合成了一种具有多重响应的核壳结构的纳米凝胶．结合动态光散射的表征研究了聚丙烯酸稳定PNIPAM表面的能力,发现稳定表面的能力与其分子量及用量密切有关．利用动态光散射以及zeta电位分析仪研究了在溶液中纳米凝胶相转变和zeta电位对温度以及pH值的依赖性．     

Hydrogen bonding and liquid crystallinity of low molar mass and polymeric mesogens containing benzoic acids: a variable temperature Fourier transform infrared spectroscopic study

The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.     

Effect of flexibility of grafted polymer on the morphology and property of nanosilica/PVC composites

In this study, poly(methyl methacrylate)-grafted-nanosilica (PMMA-g-silica) and a copolymer of styrene (St), n-butyl acrylate (BA) and acrylic acid (AA)-grafted-nanosilica (PSBA-g-silica) hybrid nanoparticles were prepared by using a heterophase polymerization technique in an aqueous system. The grafted polymers made up approximately 50 wt.% of the resulted hybrid nanoparticles which showed a spherical and well-dispersed morphology. The silica hybrid nanoparticles were subsequently used as fillers in a poly(vinyl chloride) (PVC) matrix to fabricate PVC nanocomposite. Morphology study of PVC nanocomposites revealed that both PMMA- and PSBA-grafted-silica had an adhesive interface between the silica and PVC. The tensile strength and elongation to break were found to be improved significantly in comparison with that of untreated nanosilica/PVC composites. Finally our results clearly demonstrated that the properties (e.g. chain flexibility, composition) of the grafted polymer in the hybrid nanoparticles could significantly affect the dispersion behavior of hybrid nanoparticles in PVC matrix, dynamic mechanical thermal properties and mechanical properties of the resulted PVC composites.     

掺杂丙烯酸酯单体合成及泡沫制备技术

 通过丙烯酸、2-甲基丙烯酸、巴豆酸与五氯苯酚的酯化反应实现了3种丙烯酸酯单体的掺杂改性合成,采用核磁共振和质谱测试技术对掺杂丙烯酸酯单体进行了表征。利用掺杂改性后的丙烯酸单体与季戊四醇四丙烯酸酯之间的共聚反应,结合超临界萃取技术,制备出理论密度为50 mg·cm^-3、掺杂氯元素质量百分数平均值最高约为15%的掺杂丙烯酸酯聚合物泡沫。通过测定聚合物凝胶速率,初步探讨了掺杂丙烯酸酯单体与多元丙烯酸酯单体的共聚合反应机理。     

Applications of a polymeric microgel template/ultrasonic degradation method: preparation of poly(sodium acrylate)/La(OH)3 nano-composites

A polymeric microgel template/ultrasonic degradation method for the preparation of organic-inorganic nano-composites is proposed and successfully used in the preparation of poly(sodium acrylate) (PAANa) and lanthanium hydroxide nano-composites (PAANa/La(OH)(3)). The nano-composites were prepared via three steps. La(NO(3))(3) was trapped within the PAANa microgels first, and then the metal ions within the microgels were hydrolyzed by slow introduction of ammonia. Finally, the composites of the micro-particles were degraded by ultrasonic treatment. The product was characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The average diameter of the composites prepared in this way is about 50 nm and the size distribution of them is narrow. TGA analysis shows that the content of La(OH)(3) in the composites is about 20%.     

Preparation and Characterization of P(MAA-g-EG) Nanospheres for Protein Delivery Applications

Novel complexation hydrogel nanospheres of poly(methacrylic acid-grafted-poly(ethylene glycol)) (P(MAA-g-EG)) were prepared by dispersion polymerization to be used for protein delivery applications. Polymerization was conducted in solvents such as deionized water, ethanol/water, sodium hydroxide, hydrochloric acid, and acetic acid solutions. When polymerizing in deionized water we produced nanospheres without agglomeration. Photon correlation spectroscopy studies revealed that the nanospheres possessed a narrow particle size distribution and the size was inversely proportional to the concentration of poly(ethylene glycol) incorporated in the monomer mixture. These nanospheres exhibited pH-sensitivity comparable to that encountered in hydrogel films with the same composition. The composition of the nanospheres was investigated by transmission Fourier transform infrared spectroscopy. The comparison between hydrogel films and nanospheres with the same monomer composition revealed that nanospheres possessed similar spectral characteristics than hydrogel films prepared by the same techniques. These nanospheres could be used for calcitonin release under physiological conditions.     

Polyethylene-supported poly(methyl methacrylate<Emphasis Type="Italic">-co-</Emphasis>butyl acrylate)-based novel gel polymer electrolyte for lithium ion battery

A new copolymer, poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)), was synthesized by emulsion polymerization with different mass ratio of methyl methacrylate (MMA) and butyl acrylate (BA). The membranes were prepared by phase inversion and corresponding gel polymer electrolytes (GPEs) were obtained by immersing the membrane into a liquid electrolyte. In this design, the hard monomer MMA provided the copolymer with good electrolyte uptake, while the soft monomer BA provided the GPE with strong adhesion between the anode and cathode of lithium ion battery. The properties of the resulting product were investigated by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectra, scanning electron spectroscopy, linear sweep voltammetry, thermogravimetric analysis, cyclic voltammetry, electrochemical impedance spectroscopy and charge/discharge test. The results show that the obtained GPE based on P(MMA-co-BA) with the mass ratios of MMA and BA = 6:1 exhibits good conductivity (as high as 1.2 × 10^?3 S cm^?1) at room temperature and high electrochemical stability (up to 4.9 V vs. Li/Li⁺). With the application of the polyethylene (PE)-supported GPE in Li/Li(Li_0.13Ni_0.30Mn_0.57)O₂ battery, the battery presents good cyclic stability (maintaining 95.4 % of its initial discharge capacity after 50 cycles) at room temperature.     

Synthesis and Aqueous Solution Properties of a Novel NonIonic,Amphiphilic Comb-Type Polyacrylamide

Nowadays comb-type polyacrylamides are deemed to be the most promising oil-displacing agent in the field of enhanced oil recovery (EOR). We describe the synthesis of a nonionic, amphiphilic macromer (OPAE) with acrylic acid (AA) and t-octylphenoxypolyoxyehylene (OP) by an esterification reaction. The macromer was then copolymerized with acrylamide (AM) under a free radical initiator system and a comb-type modified polyacrylamide (MPAM) was obtained. The structures of OPAE and the MPAM were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR) and dynamic laser light scattering. In order to compare with partially hydrolyzed polyacrylamide (HPAM), the aqueous solution of the MPAM had a higher apparent viscosity, especially in brine. We suggest that the reason was that the branched chains enhanced the rigidity of the MPAM, and made the molecules have a larger hydrodynamic radius, especially in brine, endowing the copolymer with excellent salt tolerance.     

Synthesis and Characterization of Multi-layered Core/Shell Particles by Sequential Emulsion Polymerization

A series of core/shell particles were prepared by sequential emulsion polymerization. The core/shell particles consisting of poly(methyl methacrylate) core grafted with using rubbery layer [poly(butyl acrylate)co-(styrene)] and then glassy layer [poly(methyl methacrylate)-co-(ethyl acrylate)] were prepared. The conditions which led to controlled particle size and morphology were discussed. A highly cross-linked structure was formed in both the cores and the shells by using a cross-linking agent, which could prevent the migration of hydrophobic shells to the inside of the particles. The core/shell particles were characterized by Fourier-transform infrared spectroscopy, solid state ¹³C-NMR. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were used to determine the thermal stability and glass transition temperature of the core/shell particles, respectively. Results of the particle size analysis indicate that particle sizes were decreased when there is a rubbery layer as outer layer (0.44 μm) whereas it increases when there is a glassy layer as outer layer (324 μm). Scanning electron microscopy (SEM) also confirms the multi-layers formation in the polymer.