硅粉表面改性及其分散效果评价

目的降低原状工业硅粉颗粒的团聚现象和聚集效应,提高其分散性,改善掺硅粉水泥基材料的力学及界面过渡区性能。方法采用表面化学修饰和机械分散两种改性方法,对硅粉进行表面改性。利用表面电位测试、紫外光谱分析、激光粒度分析、扫描电镜测试等试验手段,评价了改性前后硅粉颗粒的表面电位和减水剂分子吸附量、颗粒粒度分布,以及硅粉颗粒和硬化硅粉-水泥净浆的微观形貌。采用棱柱体试件,研究了改性硅粉对水泥-硅粉净浆抗折与抗压强度的影响。结果用氨丙基三乙氧基硅烷及磁力搅拌工艺对原状工业硅粉进行表面改性后,硅粉表面电位由-21 m V变为+3 m V,高性能聚羧酸减水剂吸附量提高了60%,硅粉中纳米级微细颗粒数量显著增加,大颗粒团聚现象明显降低,硅粉颗粒的分散性明显改善;改性硅粉使水泥-硅粉净浆的力学性能提高了11%~24%。结论采用氨基硅烷和磁力搅拌工艺对原状硅粉表面改性后,硅粉表面的电位由负值变为正值,减水剂吸附量显著增大,颗粒团聚性降低,纳米级颗粒数量增多,在水泥中分散性改善,水泥-硅粉水化产物的界面过渡区性能改善,掺硅粉水泥浆体的力学性能明显提高。     

丙烯腈共聚物的热性能与膜结构研究

以丙烯腈和衣康酸为共聚单体,偶氮二异丁腈为引发剂,使用自由基溶液聚合的方法在二甲基亚砜体系中制备聚丙烯腈树脂。采用氧化改性的方法将衣康酸氨化为衣康酸铵,与丙烯腈进行共聚反应。借助DSC、SEM等测试方法研究了氨化改性对共聚物的热性能及聚合物膜结构的影响。结果表明：共聚单体可以在较低温度下以离子机理引发氰基发生低聚反应,导致梯形环化结构的形成,有效降低放热起始温度。而衣康酸铵中的氨基可作为环化反应的催化剂,促进聚丙烯腈在预氧化过程中形成均匀的环化梯形结构。且铵盐具有亲水性,使纤维内部缺陷更容易弥合。     

Reaction of phenol‐ and thiophenol‐terminated compounds with bisoxazolines

Bulk reactions of phenolic compounds (bisphenol‐A and α,ω‐diphenol oligosulfone) or thiols (thiophenol and bis(4‐mercaptophenyl)sulfide) with bisoxazoline coupling agents, namely 2,2'‐(1,3‐phenylene)bis(2‐oxazoline) ( mbox ), 2,2'‐(1,4‐phenylene)bis(2‐oxazoline) ( pbox ), and 2,2'‐(2,6‐pyridylene)bis(2‐oxazoline) ( pybox ), were carried out in the bulk at 140–240°C. The reactions were followed by viscosimetry, size exclusion chromatography, and ¹H‐ and ¹³C‐NMR spectroscopy. The phenol/bisoxazoline bulk reactions at 240°C required the presence of sodium methoxide catalyst. Bisoxazoline pybox gave the best results in this case. Thiol and dithiol/bisoxazoline reactions were faster and did not require any catalyst. High‐molar‐mass polymers were obtained within 5 min at 200°C while using bis(4‐mercaptophenyl)sulfide (BMPS) and any of the bisoxazolines. The NMR spectra of model compounds and polymers were fully assigned, showing that the oxazoline/phenol and oxazoline/thiophenol (tph) polyaddition reactions proceed in the expected way, without any noticeable side reaction. All polymers were amorphous and displayed good thermal stability. Bisoxazolines were also used as coupling agents for the preparation of copolymers of BMPS and α,ω‐dicarboxy polyamide‐12 and for the preparation of polysulfone‐polyamide‐12 block copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of novel polyvinyl alcohol–lactic acid gels

This article describes a process for esterifying polyvinyl alcohol (PVA) with L‐lactide (LLA) and D,L‐lactic acid (LA), using ethyl acetate and N,N′‐dimethyl formamide at temperatures varying from 120 to 150°C. The grafting process was carried out under nitrogen to avoid possible oxidation or other degradation of the process ingredients and product. Lower T_g values were obtained for the PVA/LLA graft copolymers of higher LLA content suggesting some compatibility in the amorphous phase. Higher T_g values were observed for PVA/LA graft copolymers that yielded tough polymer films. The structure of the copolymers was studied by solid‐state ¹³C‐NMR, infrared spectroscopy, and differential scanning calorimetry (DSC). The PVA/LA films exhibited melt processability and good mechanical properties such as yield strength, tensile energy at break, modulus, and elongation at break. The polymer films produced through compression molding at 100°C showed good swelling properties. The transport coefficient (n) values determined from the plot of log(M_t/M_∞) vs. log t indicate Fickian behavior, and they are consistent with the reported literature values for other PVA systems. The nature of water in gels [bound water (W_b), freezing (W_f), and freezing bound (W_fb), and water content (W_t)] was evaluated from DSC data. The results demonstrate that PVA/LA hydrogels with good combination of thermal, physicomechanical, and swelling properties can be prepared via the lactic acid esterification of PVA polymer process described. Besides being melt processable, the PVA/LA gels exhibit a melting point, which indicates possibly use of higher temperatures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Separation and preconcentration of some heavy‐metal ions using new chelating polymeric hydrogels

Two new chelating polymeric hydrogels, crosslinked polyacrylamide/triethylenetetraamine/CS₂Na (hydrogel I) and crosslinked polyacrylamide/diethylenetriamine/CS₂Na (hydrogel II), were prepared by the transamidation and dithiocarbamylation of crosslinked polyacrylamide. The products were characterized with elemental analysis and IR spectroscopy. In both polymeric hydrogels, the optimum pH for the removal of Cd(II), Pb(II), and Zn(II) ions ranged from 7 to 8, from 6 to 7, and from 7 to 8, respectively. The sorption isotherms of the investigated metal ions on the prepared hydrogels were developed, and the equilibrium data fitted the Langmuir and Freundlich isotherm models well. At the optimum pH for each metal ion, the maximum sorption capacities of hydrogel I toward Cd(II), Pb(II), and Zn(II) ions, estimated from the Langmuir model, were 5.3, 0.63, and 1.27 mmol/g, respectively, and those of hydrogel II were 4.1, 0.59, and 0.89 mmol/g, respectively. The experimental sorption capacities of hydrogel I toward Cd(II), Pb(II), and Zn(II) ions were 4.5, 0.6, and 1.2 mmol/g, respectively. In the case of hydrogel II, the capacities were 3.7, 0.52, and 0.88 mmol/g in the same prescribed order. The thermodynamic parameters (the free energy of sorption, enthalpy change, and entropy change) for cadmium, lead, and zinc sorption on the prepared polymers were also determined from the temperature dependence. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pervaporation membranes from natural rubber latex grafted with poly(2‐hydroxyethyl methacrylate) (NR‐g‐PHEMA) for the separation of water–acetone mixtures

NR‐graft‐PHEMA latexes were synthesized by the use of graft emulsion polymerization. By increasing the HEMA monomer concentration, we found that the grafting percentage (GP) also increased. In addition, GP increased significantly at low initiator concentrations before it leveled off at moderate concentrations, and a slight decrease was observed at high initiator concentrations. NR‐g‐PHEMA latexes were prepared as pervaporation membranes for the separation of water–acetone mixtures. From the equilibrium swelling, the nonideal behavior of membrane swelling in water–acetone mixtures was found such that there appeared the maximum swelling degree at a certain concentration of liquid mixtures. Moreover, the water concentration at maximum swelling shifted to high water concentration with increasing amount of graft‐PHEMA. The sorption study suggested the preferential sorption of water on the membranes. Also, the sorption isotherms implied that there was a coupling between water and acetone molecules. Pervaporation separation of water–acetone mixtures was studied with NR‐g‐PHEMA membranes. As the feed water concentration increased, the partial water fluxes increased in contrast to the partial fluxes of acetone. From the permeation ratio, θ_w, the strong coupling of acetone on the water transport was observed, particularly for the membrane with high graft‐PHEMA under acetone‐rich conditions. As the feed temperature increased, the total permeation across the membranes was enhanced. The partial fluxes of water and acetone as a function of temperature followed the Arrhenius relationship by which the activation energies for permeation were estimated as 3.53 kJ/mol for water and 21.95 kJ/mol for acetone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) (PVPVAc‐g‐PCL) was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone (VP)/vinyl acetate (VAc) comonomer and PCL macromonomer containing a reactive 2‐hydroxyethyl methacrylate terminal. The graft copolymer was designed in order to improve the interfacial adhesiveness of an immiscible blend system composed of cellulose acetate/poly(ε‐caprolactone) (CA/PCL). Adequate selections of preparation conditions led to successful acquisition of a series of graft copolymer samples with different values of molecular weight ( ), number of grafts (n), and segmental molecular weight of PVPVAc between adjacent grafts (M_n (between grafts)). Differential scanning calorimetry measurements gave a still immiscible indication for all of the ternary blends of CA/PCL/PVPVAc‐g‐PCL (72 : 18 : 10 in weight) that were prepared by using any of the copolymer samples as a compatibilizer. However, the incorporation enabled the CA/PCL (4 : 1) blend to be easily melt‐molded to give a visually homogeneous film sheet. This compatibilizing effect was found to be drastically enhanced when PVPVAc‐g‐PCLs of higher and M_n (between grafts) and lower n were employed. Scanning electron microscopy revealed that a uniform dispersion of the respective ingredients in the ternary blends was attainable with an assurance of the mixing scale of several hundreds of nanometers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of poly(vinyl amine)‐grafted crosslinked poly(vinyl alcohol) microspheres

Crosslinked poly(vinyl alcohol) (CPVA) microspheres were first prepared via the suspension polymerization of vinyl acetate and the alcoholysis of poly(vinyl acetate). Afterwards, a two‐step method involving graft polymerization and Hofmann degradation was used to prepare functional poly(vinyl amine)‐grafted crosslinked poly(vinyl alcohol) (PVAm–CPVA) microspheres, onto which poly(vinyl amine) (PVAm) macromolecules were grafted. The graft polymerization of acrylamide (AM) on CPVA microspheres was performed with cerium salt as the initiator in an acidic aqueous medium, resulting in polyacrylamide (PAM)‐grafted CPVA microspheres. Subsequently, the grafted PAM was transformed into PVAm via the Hofmann degradation reaction, and PVAm–CPVA microspheres were prepared. The effects of the main factors on the graft polymerization and Hofmann degradation were examined, and the reaction mechanisms were researched in depth. The experimental results showed that for the graft polymerization of AM on CPVA microspheres initiated by cerium salt, the acid concentration and the amount of cerium salt affected the grafting degree of PAM greatly. For the Hofmann degradation reaction of the grafted PAM, the amination degree of PVAm–CPVA microspheres was obviously affected by the amount of sodium hypochlorite in the presence of sodium hydroxide. The preliminary adsorption tests showed that PVAm–CPVA microspheres were multifunctional and had strong adsorption ability for Fe(III) ions by chelation action and for chromate ions (CrO) by strong electrostatic interactions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Immobilized metal ions cellophane–PGMA‐grafted membranes for affinity separation of β‐galactosidase enzyme. I. Preparation and characterization

Immobilized Cu²⁺ ions affinity cellophane–poly(glycidyl methacrylate) (PGMA)‐grafted membranes have been prepared through three steps. The first step was introducing of epoxy groups to its chemical structure through grafting process with PGMA. Factors affecting the grafting process have been studied and grafting percentage (GP) up to 233% has been obtained. The second step was converting the introduced epoxy groups to sulfonic ones. It was found that maximum amount of sulfonic groups (2.7 mmol/g) was obtained with minimum GP (46.08%). The third and last step was the immobilization of Cu²⁺ ions into sulfonated grafted membranes obtained from the previous step. Maximum amount of immobilized Cu²⁺ ions was found to be 60.9 ppm per gram of polymer. The verification of the grafting and sulfonation steps has been performed through characterization of the obtained membranes using FTIR, TGA, and EDAX analysis. Finally, Cu²⁺‐immobilized membranes have been evaluated in separation of β‐galactosidase (β‐Gal) enzyme from its mixture with bovine serum albumin (BSA) in different pH medium. Maximum protein adsorption, for both proteins, has been obtained at pH range 4–4.5; as 90 and 45% for β‐Gal and BSA, respectively. The results showed high affinity toward β‐Gal separation although BSA concentration (0.5%) is 20‐folds of β‐Gal (0.025%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The synthesis of PHA‐g‐(PTHF‐b‐PMMA) multiblock/graft copolymers by combination of cationic and radical polymerization

A new and promising method for the diversification of microbial polyesters based on chemical modifications is introduced. Poly(3‐hydroxy alkanoate)‐g‐(poly(tetrahydrofuran)‐b‐poly(methyl methacrylate)) (PHA‐g‐(PTHF‐b‐PMMA)) multigraft copolymers were synthesized by the combination of cationic and free radical polymerization. PHA‐g‐PTHF graft copolymer was obtained by the cationic polymerization of THF initiated by the carbonium cations generated from the chlorinated PHAs, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHx) in the presence of AgSbF₆. Therefore, PHA‐g‐PTHF graft copolymers with hydroxyl ends were produced. In the presence of Ce⁺⁴ salt, these hydroxyl ends of the graft copolymer can initiate the redox polymerization of MMA to obtain PHA‐g‐(PTHF‐b‐PMMA) multigraft copolymer. Polymers obtained were purified by fractional precipitation. In this manner, their γ‐values (volume ratio of nonsolvent to the solvent) were also determined. Their molecular weights were determined by GPC technique. The structures were elucidated using ¹H‐NMR and FTIR spectroscopy. Thermal analyses of the products were carried out using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009