聚丙烯酸甲酯接枝改性纳米纤维素

利用羰基二咪唑(CDI)的高活性活化纳米纤维素(NCC),使NCC表面带有高反应活性的碳碳双键。再以2-溴异丁酸乙酯为引发剂,铜丝为催化剂,制备出低分子量的聚丙烯酸甲酯(PMA)。然后采用活性自由基聚合将PMA接枝到活化的NCC表面,制备出PMA接枝改性的NCC。采用凝胶渗透色谱测定合成的PMA的分子量及分子量分布;通过傅立叶变换红外光谱及X射线衍射分析等测试方法对改性前后的NCC的结构和性能进行了分析。实验结果表明,通过单电子转移活性自由基聚合法合成的PMA分子量为2 000,分子量分布窄(分布指数为1.14),并且其成功接枝到NCC表面。     

Studies with gradient polymers of polystyrene and poly(methyl acrylate)

A series of [net-polystyrene]-ipn-[net-poly(methyl acrylate)] systems with gradients of poly(methyl acrylate) in a polystyrene matrix are prepared and tested mechanically. The results showed no distinct differences from that of corresponding interpenetrating polymer network (IPN) samples with similar compositions, in contrast to the substantially improved fracture strains obtained for [net-poly(methyl methacrylate)]-ipn-[-net poly(methyl acrylate)] gradient systems and their nongradient IPN's in our previous work. Hence, it is concluded that the toughening effect of gradient structure observed is not universally applicable for all gradient systems but it is unique for the acrylic system studied. Moduli-temperature responses and dynamic mechanical spectra of gradients and IPN's prepared in the current study are also presented. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1721–1725, 1999     

含规整 PMMA支链的 PBA合成及其力学性能

研究了聚甲基丙烯酸甲酯大单体与丙烯酸丁酯在苯中的共聚，该大单体由甲基丙烯酸甲酯在巯基乙酸链转移剂存在下聚合，用甲基烯酸缩不甘油酯封端，研究了共聚速率、大单体相对分子质量、大单体与小单体投料比、引发剂用量、单体浓度及共聚温度对接枝效率及共聚物相对分子质量的影响。用分级沉淀法精制共聚物。用凝胶渗透色谱法、红外光谱法及差示扫描量热法对共聚物进行表征，用蒸汽压式渗透压力计及膜渗透压测定了结构参数，结果表明，平均接枝数随转化率增加而降低，在一定的组成范围内，共聚物呈热塑性弹性体行为。     

Highly efficient and fast adsorption of Au(III) and Pd(II) by crosslinked polyethyleneimine-glutaraldehyde

An adsorbent (PEI-GA) is prepared by crosslinking polyethyleneimine with glutaraldehyde. PEI-GA shows outstanding adsorption performance towards Au(III) and Pd(II). PEI-GA presents large adsorption capacity towards Au(III) in a wide application pH range from 1 to 9. The adsorption capacities of PEI-GA for Au(III) and Pd(II) at 25°C reach 2575 and 497 mg/g, respectively. Au(III) and Pd(II) can be adsorbed completely within 10 min for 8.3 mg/L Au(III) and 20 min for 9.7 mg/L Pd(II). The adsorption equilibrium time required for 523.9 mg/L Au(III) and for 565.6 mg/L Pd(II) is 2 and 9 h, respectively. The Sips model is the most suitable to describe the adsorption isotherms which leads to more realistic adsorption capacities for both metals. PEI-GA also exhibits high selectivity and repeatability towards Au(III) and Pd(II). The adsorption mechanism involves redox, chelation coordination, and electrostatic interactions for Au(III), and coordination and electrostatic interactions for Pd(II).     

The adsorption of methyl nitrite on the Au(111) surface

The interaction of the methyl nitrite molecule (CH₃ONO) with the gold(111) surface has been studied by means of density functional calculations. The perfect Au(111) surface has been represented by a rather large cluster model, Au₂₂, that was in turn used to extract information about the preferred adsorption geometry of the CH₃ONO species. Vibrational frequencies and adsorption energy are also reported. The calculated adsorption energies are 31.2 kJ/mol with respect to gas phase cis-conformer and 35.1 kJ/mol with respect to trans-methyl nitrite, very close to the experimental adsorption energy of 33.5 kJ/mol. From the analysis of vibrational frequencies of gas phase and adsorbed species it is concluded that only the cis-conformer is present at the Au(111) surface.     

Microwave polymerization of poly(methyl acrylate): Conversion studies at variable power

Methyl acrylate (MA) was polymerized by microwave radiation at three different powers, namely, 200, 300, and 500 W. The percentage conversion of the reaction was followed by Fourier transform infrared (FTIR) spectroscopy. The specimen temperature during the polymerization process was measured to select a suitable temperature for comparison with the conventional method. The results indicate that a similar comparable temperature of about 52° was found for all the microwave power settings tested. The microwave polymerization process was compared with that of the thermal method at 52(±1)° under comparable reaction conditions. The reaction rate enhancement of the microwave polymerization compared to the thermal method was found to be as follows: 275% for the 500 W, 220% for the 300 W, and 138% for the 200 W, indicating a significant correlation between the reaction rate enhancement and the level of microwave power used.     

Polymerization in a magnetic field. 14. Possibilities to improve field effect during methyl acrylate polymerization

Magnetokinetic changes intervened in the radical polymerization of methyl acrylate in a continuous external magnetic field of 0.22 T was evidenced. The use of a matrix of polymerization, respectively, poly(ethylene glycol), was correlated with the obtained kinetic data. The occurring‐magnetokinetic changes were justified by the radical pair mechanism, Δg, which corresponds to the benzoyl peroxide decomposition into a magnetic field. The intervened magnetokinetic modifications during the reactions are correlated with the reaction conditions. The influence of the magnetic field is confirmed by the molecular weights of the obtained polymers, values interpreted from the viewpoint of the reaction conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1031–1036, 2004     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

Structure development in the phenolic resin/poly(methyl methacrylate-co-ethyl acrylate) copolymer blends

Single-phase mixtures of phenolic derivatives with three poly(methyl methacrylate-co-ethyl acrylate) copolymers [P(MMA-co-EA)s] were cured in the presence of hexamethylenetetramine and the reaction kinetics and phase-separation processes during cure were investigated by differential scanning calorimetry (DSC), light scattering, and optical microscopy (OM). DSC measurements revealed that the higher the fraction of multifunctional phenols in the total phenols the lower the conversion at gelation in the phenolic-rich phase. The time variation of the light-scattering profile during cure demonstrated the characteristic feature for spinodal decomposition. OM observation revealed that a cocontinuous two-phase structure appeared after a certain time lag and coarsened to a spherical domain structure consisting of phenolic resin particles dispersed in the P(MMA-co-EA)s matrix. The periodic distances, Λ_m, in the phase-separated structure changed with curing time: (1) The higher the component of MMA in P(MMA-co-EA)s and (2) the higher the fraction of multifunctional phenols in the total phenols, the smaller the Λ_m. These results may imply that the phase separation is suppressed by the faster gelation in the phenolic-rich phase so that the phase-separated structure can be fixed by the network formation in the phenolic-rich phase at the early stage of spinodal decomposition. This results in a two-phase structure with a shorter periodic distance. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1829–1837, 1998     

Modification of starch–poly(methyl acrylate) graft copolymers by steam jet cooking

Starch-g-poly(methyl acrylate) containing 12.3, 31.9, 51.7, and 58.3% PMA, by weight, were prepared by ceric ammonium nitrate-initiated polymerization of methyl acrylate onto granular cornstarch. The granular structures of these graft copolymers were not disrupted by steam jet cooking at 140°C. At most, only 13% of the polymer was dissolved, and this soluble fraction was comprised largely of starch. The probability of crosslinking within these graft copolymer granules was considered. Physical properties of extruded ribbons depended upon whether or not granular graft copolymers were jet cooked prior to extrusion. Although tensile strengths were not greatly affected by steam jet cooking, cooked samples showed significant increases in both percent elongation and tear resistance. The effects of jet cooking upon the properties of extruded ribbons can be explained by gelatinization of starch within the grafted starch granules. Although jet-cooked granules still remain intact, gelatinization of the starch moiety causes these granules to be less rigid, more deformable, and more easily plasticized by small amounts of water. Loss of starch crystallinity after steam jet cooking was proved by both differential scanning calorimetry and X-ray diffraction. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1021–1029, 1997     

Synthesis and characterization of polystyrene‐supported glucosamine resin and its adsorption behavior for Au(III)

A novel chelating resin, crosslinking polystyrene‐supported glucosamine (PS‐GA), was prepared and its structure was confirmed by FTIR, elemental analysis, and X‐ray photoelectron spectroscopy. The adsorption properties of PS‐GA for Au(III) were investigated. PS‐GA resin possessed excellent enriching property to Au(III) ions and adsorption proportion E% could reach to about 90 shortly after 3 h. The adsorption dynamics of Au(III) showed that the adsorption was controlled by liquid film diffusion and the apparent activation energy E_a was 12.91 kJ mol^?1. Both Langmuir model and Freundlich model could describe the isothermal process of Au(III), and ΔG, ΔH, ΔS values were calculated. The mechanism of adsorption for Au(III) was confirmed by FTIR, SEM, and XPS. The results showed that redox reaction occurred and both coordination and ion‐exchange existed simultaneously in the adsorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4581–4586, 2006     

Adsorption of heavy‐metal ions on poly(ethylene imine)‐immobilized poly(methyl methacrylate) microspheres

Poly(methyl methacrylate) (PMMA) microspheres carrying poly(ethylene imine) (PEI) were prepared for the removal of heavy‐metal ions (copper, cadmium, and lead) from aqueous solutions with different amounts of these ions (50–600 mg/L) and different pH values (3.0–7.0). Ester groups in the PMMA structures were converted to imine groups in a reaction with PEI as a metal‐chelating ligand in the presence of NaH. The adsorption of heavy‐metal ions on the unmodified PMMA microspheres was very low [3.6 μmol/g for Cu(II), 4.6 μmol/g for Cd(II), and 4.2 μmol/g for Pb(II)]. PEI immobilization significantly increased the heavy‐metal adsorption [0.224 mmol/g for Cu(II), 0.276 mmol/g for Cd(II), and 0.126 mmol/g for Pb(II)]. The affinity order of adsorption (in moles) was Cd(II) > Cu(II) > Pb(II). The adsorption of heavy‐metal ions increased with increasing pH and reached a plateau value around pH 5.5. Their adsorption behavior was approximately described with the Langmuir equation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 197–205, 2001     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

Imparting antifouling properties of silicone hydrogels by grafting poly(ethylene glycol) methyl ether acrylate initiated by UV light

Both hydrophilic and antifouling surfaces were prepared on silicone hydrogels with poly(ethylene glycol) methyl ether acrylate (PEGMA) grafted by UV-induced radical polymerization. The PEGMA-grafted silicone hydrogels were characterized by graft yield and static water contact angle measurements. According to the results, the graft yield reached a maximum at 8 min of UV exposure time and 20 wt% PEGMA concentration. The modified silicone hydrogels possessed hydrophilic surfaces with the lowest water contact angle of 36°. The oxygen permeability and transparency of the PEGMA-grafted silicone hydrogels were as high as the unmodified silicone hydrogel. The mechanical property of silicone hydrogels was maintained at about 95% of the tensile strength and elastic modulus after the PEGMA grafting. The in vitro single protein adsorption on the PEGMA-grafted silicone hydrogels decreased by 70–80% compared to the unmodified silicone hydrogel. The PEGMA-grafted silicone hydrogel is expected to be a novel biomaterial, which possesses excellent surface hydrophilicity, antifouling property, oxygen permeability, and mechanical property. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatoargentate(III)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) using potassium diperiodatoargentate(III) [Ag(III)]–PVA redox system as initiator was studied in an alkaline medium. Some structural features and properties of the graft copolymer were confirmed by Fourier‐transfer infrared spectroscopy, scanning electron microscope, X‐ray diffraction and thermogravimetric analysis. The grafting parameters were determined as a function of concentrations of monomer, initiator, macromolecular backbone (X?_n = 1750, M? = 80 000 g mol^?1), reaction temperature and reaction time. A mechanism based on two single‐electron transfer steps is proposed to explain the formation of radicals and the initiation profile. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate and n‐butyl acrylate, were also used to produce graft copolymerizations. It has been confirmed that grafting occurred to some degree. Thermogravimetric analysis was performed in a study of the moisture resistance of the graft copolymer. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of amphiphilic graft copolymer poly(ethylene oxide)-graft-poly(methyl acrylate)

A novel well-defined amphiphilic graft copolymer of poly(ethylene oxide) as main chain and poly(methyl acrylate) as graft chains is successfully prepared by combination of anionic copolymerization with atom transfer radical polymerization (ATRP). The glycidol is protected by ethyl vinyl ether first, then obtained 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) is copolymerized with EO by initiation of mixture of diphenylmethyl potassium and triethylene glycol to give the well-defined poly(EO-co-EPEE), the latter is deprotected in the acidic conditions, then the recovered copolymer [(poly(EO-co-Gly)] with multi-pending hydroxyls is esterified with 2-bromoisobutyryl bromide to produce the ATRP macroinitiator with multi-pending activated bromides [poly(EO-co-Gly)_(ATRP)] to initiate the polymerization of methyl acrylate (MA). The object products and intermediates are characterized by NMR, MALDI-TOF-MS, FT-IR, and SEC in detail. In solution polymerization, the molecular weight distribution of the graft copolymers is rather narrow (M_w/M_n < 1.2), and the linear dependence of Ln [M₀]/[M] on time demonstrates that the MA polymerization is well controlled.     

Synthesis and characterization of poly(hydroxamic acid) chelating resin from poly(methyl acrylate)‐grafted sago starch

A new chelating ion‐exchange resin containing the hydroxamic acid functional group was synthesized from poly(methyl acrylate) (PMA)‐grafted sago starch. The PMA grafted copolymer was obtained by a free‐radical initiating process in which ceric ammonium nitrate was used as an initiator. Conversion of the ester groups of the PMA‐grafted copolymer into hydroxamic acid was carried out by treatment of an ester with hydroxylamine in an alkaline solution. The characterization of the poly(hydroxamic acid) chelating resin was performed by FTIR spectroscopy, TG, and DSC analyses. The hydroxamic acid functional group was identified by infrared spectroscopy. The chelating behavior of the prepared resin toward some metal ions was investigated using a batch technique. The binding capacities of copper, iron, chromium, and nickel were excellent and the copper capacity was maximum (3.46 mmol g⁻¹) at pH 6. The rate of exchange of the copper ion was very fast that is, t_1/2 < 5 min. It was also observed that the metal ion‐sorption capacities of the resin were pH‐dependent and its selectivity toward the metal ions used is in the following order: Cu²⁺ > Fe³⁺ > Cr³⁺ > Ni²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > As³⁺ > Pb²⁺. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1256–1264, 2001     

An inelastic electron tunnelling spectroscopy (IETS) study of poly(vinylacetate) poly(methyl methacrylate) and poly(vinylalcohol) adsorbed on aluminium oxide

IETS is used to investigate the adsorption of poly(vinylacetate) (PVA), poly(methylmethacrylate) (PMMA), and poly(vinylalcohol) (PVOH) on aluminium oxide. These polymers are of interest in the field of adhesion science, and until now synthetic macromolecules have not been studied in this way. Both commercially available polymers and those synthesized in our laboratory have been used. On the basis of IET spectra presented here, and existing i.r. spectra it is believed that PMMA and PVA undergo ester cleavage at the oxide surface leading to their subsequent adsorption. For PMMA this is thought to be via carboxylate anions generated on the polymer side groups, while PVA is expected to be adsorbed as PVOH. Bonding of PVOH to the oxide is not fully understood, but may occur by the formation of an AlOC bridge. Another possibility for the above polymers, that of intermolecular hydrogen bonding between polar polymer side groups, and adsorbed hydroxyl species present on the oxide surface, cannot be ruled out.     

Mechanical properties of a poly(methyl acrylate) nanocomposite containing regularly-arranged silica particles

Summary In an earlier investigation, poly(methyl acrylate) nanocomposites containing silica particles were found to have novel optical properties when the particles were regularly spaced rather than randomly located. The availability of these materials was used to determine whether there was any difference in the particles' reinforcing ability between ordered and random arrangements. The two types of composites were compared using near-equilibrium mechanical property measurements in uniaxial or equi-biaxial deformation, and dynamic mechanical properties measurements. It was found that having the filler particles regularly arranged had little effect on these properties, and that there was no anisotropy in their mechanical behavior. Related experiments could possibly be used to clarify the long-standing question of the importance of particle aggregation in elastomer reinforcement.