琥珀酸二异辛酯磺酸钠微乳体系中纳米银的制备及其连续相的影响

在琥珀酸二异辛酯磺酸钠(AOT)为表面活性剂、环己烷为连续相形成的微乳体系中, 利用水合肼还原AgNO₃制备了分散性良好的纳米银. 利用紫外-可见(UV-Vis)光谱和透射电镜(TEM)对所得产物进行了表征, TEM显微图像表明形成粒子为球形结构, 平均粒径为5.10 nm, 标准偏差为2.84 nm. 分别利用正己烷、正庚烷、正辛烷、环己烷和十二烷等作连续介质, 研究了微乳液中连续相对纳米银形成的影响. 随着正烷烃碳链长度的增加, 微乳液中胶束之间的交换速率增大, 形成粒子的平均粒径逐渐减小. 十二烷形成的微乳体系制备的纳米银溶胶具有最宽的共振吸收峰, 所得的纳米银粒子平均粒径最小. 环己烷形成的微乳液中反胶束具有特殊的界面强度, 导致纳米银晶核的形成速率过低, 纳米银晶粒的生长不完全.     

Synthesis of Poly(methyl methacrylate) Nanosize Particles by Differential Microemulsion Polymerization

Poly(methyl methacrylate) nanosize particles were synthesized by a differential microemulsion polymerization process. Sodium dodecylsulfate and ammonium persulfate were used as the surfactant and initiator, respectively. The effects of reaction conditions on the particle size have been investigated. A particle size of less than 20 nm in diameter has been achieved with surfactant/monomer and surfactant/water weight ratios of 1:18 and 1:120, i.e. much milder conditions than those previously reported in the literature.

TEM image of nanoparticles prepared via differential microemulsion polymerization.     

Multimonomer and cross-linked polymers formed by its copolymerization

Differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to examine the thermal behavior of the multimonomer poly[2-(10-undecenoyloxy)ethyl methacrylate] (PUDEM) within the temperature range from -80 to 400°C. DSC measurements indicated that the polymer side chains were able to crystallize in paraffinic phase. PUDEM, added to methyl methacrylate (MM), can effectively copolymerize with essentially no homopolymer produced as shown by DSC (single T _g). The value of T _g depends on the PUDEM content, degree of cross-linking and the presence of free MM in the cross-linked product. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spontaneous vesicle formation in aqueous solution of zwitterionic and anionic surfactant mixture

Vesicles form spontaneously in the aqueous mixtures of dodecyl sulfonate betaine (DSB) and sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT (AOT)) at certain mixing ratios, which has been demonstrated by microcalorimeter, negative-staining transmission electronic microscopy (TEM) and quasi-elastic light scattering (QELS) methods. The addition of NaCl will expand the range of vesicle formation, and monodispersed vesicles are obtained in the solution from the salinity of 0.03 to 0.09 M at the mixing molar ratio of 7/3 (DSB/AOT, mol/mol), with the polydispersity of the system lower than 0.1. To learn more about the structural change in the mixture, ultrasonic was employed finally. Meanwhile analysis was made from the viewpoint of molecular geometry structure.     

Synthesis of Poly(methyl methacrylate) Nanoparticles Initiated by 2,2′‐Azoisobutyronitrile via Differential Microemulsion Polymerization

The synthesis of nanosized poly(methyl methacrylate) initiated by 2,2′‐azoisobutyronitrile via differential microemulsion polymerization has been investigated. Poly(methyl methacrylate) with a molecular weight of around 1 × 10⁶ and a particle size of about 20 nm was achieved under mild reaction conditions. A typical condition was that the surfactant amount required could be as low as 1/130 of the monomer amount in weight, and the surfactant/water ratio could be as low as 1/600, which is much less than the corresponding amounts reported in the literature. “Molecular bricks”, i.e., nanoparticles in which there are only one or two polymer chains, can be achieved using mild conditions by differential microemulsion polymerization, which may have potential applications for making molecular devices.

     

The relationship of conductivity to the morphology and crystallinity of polyaniline controlled by water content via reverse microemulsion

Conducting polyaniline (PANI) with the controllable morphology and crystallinity were successfully synthesized with different water content () in the reverse microemulsion stabilized with sodium bis(2-ethylhexyl)-sulfosuccinate (AOT). In the microemulsion, the systems containing the different amounts of water will show the different phase behaviors and structures. The influence of water content on morphology and crystallinity of conducting PANI was characterized by a number of techniques such as Fourier transform infrared spectra, UV–Visible, scanning electron microscopy, transmission electron microscopy, and X-ray powder diffraction and conductivity. In particular, we focus on the understanding of the relationship between the morphology and the crystallinity and the conductivity of PANI powder. With the increasing of the water content (W ₀ = 13.9, 27.8, 55.5, and 111.1) in the microemulsion system, the morphology and the crystallinity obviously changed and the values of relative conductivity are 0.05, 0.11, 2.7, and 1.8 S/cm, respectively.     

Synthesis of densely branched poly(methyl methacrylate)s via ATR copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Densely branched poly(methyl methacrylate)s have been synthesized by copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) using atom transfer free radical polymerization (ATRP). By employing the phenyl and benzyl esters of 2-bromo-2-methylpropionic acid as the initiators with 2,2-bipyridyl and Cu(I)Cl it has been possible to use high field ¹H nuclear magnetic resonance spectroscopy to evaluate in some detail the composition and structure of the branched PMMAs obtained. Parallel molar mass size exclusion chromatographic analysis using a multi-angle light scattering detector with a refractive index detector (MALS/SEC) has allowed the branched architecture of the products to be confirmed. Rather remarkably, high yields of branched PMMAs can be obtained without crosslinking using MMA/EGDMA molar feed ratios of up to 5/1 by appropriate adjustment of the molar feed of initiator. In particular by maintaining the EGDMA/initiator molar feed ratio ∼1/1 fully soluble products can be obtained that are densely branched since this feed ratio ensures that on average each living primary chain initiated contains on average only one branching EGDMA segment. As might be expected this controlled free radical process offers better control in the synthesis of branched polymer than the corresponding system we have reported using conventional free radical polymerization, and unlike the latter which requires the use of a chain transfer agent, the ATRP system requires no additional chain regulating component. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2375–2386, 2007     

Interface characterization in latex blend films by fluorescence energy transfer

Immiscible polymer blend films were formed by air drying aqueous dispersions containing mixtures of a high-T_g latex, poly(methyl methacrylate), and a film-forming low-T_g latex, poly(butyl methacrylate-co-butyl acrylate). Fluorescence energy transfer experiments were used to characterize the interfaces in these films, in which one component was labeled with a donor dye and the other with an acceptor. The quantum efficiency of energy transfer (Φ_ET) between the donors and acceptors is influenced by the interfacial contact area between the two polymer phases. As the amount of soft component in the blend is increased, Φ_ET approaches an asymptotic value, consistent with complete coverage of the hard polymer surface with soft polymer. This limiting extent of energy transfer is very sensitive to the total surface area in the film, with correspondingly more energy transfer at constant volume fraction for small hard particles. Some of the details of the energy transfer are revealed through a fluorescence lifetime distribution analysis. The presence of ionic surfactant (sodium dodecyl sulfate) in the dispersion from which the latex blend film is prepared reduces the cross-boundary energy transfer by 30%, which implies that in these films the surfactant decreases the interfacial contact. After annealing the surfactant-free blends above 100°C, we observe an increase in energy transfer, consistent with a broader interface between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1115–1128, 1998     

Synthesis of carbosilane block copolymers by means of a living anionic polymerization of 1,1-diethylsilacyclobutane

Block polymerization of 1,1-diethylsilacyclobutane with styrene derivatives and methacrylate derivatives was investigated. Sequential addition of styrene to a living poly(1,1-diethylsilabutane), which was prepared from phenyllithium and 1,1-diethylsilacyclobutane in THF–hexane at −48°C, gave poly(1,1-diethylsilabutane)-b-polystyrene. Similarly, addition of 4-(tert-butyldimethylsiloxy)styrene to the living poly(1,1-diethylsilabutane) provided poly(1,1-diethylsilabutane)-b-poly(4-(tert-butyldimethylsiloxy)styrene). Poly(1,1-diethylsilabutane)-b-poly(methyl methacrylate) was obtained by treatment of living poly(1,1-diethylsilabutane) with 1,1-diphenylethylene followed by an addition of methyl methacrylate. Poly(1,1-diethylsilabutane)-b-poly(2-(tert-butyldimethylsiloxy)ethyl methacrylate) was also synthesized by adding 2-(tert-butyldimethylsiloxy)ethyl methacrylate to the living poly(1,1-diethylsilabutane) which was end-capped with 1,1-diphenylethylene in the presence of lithium chloride. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2699–2706, 1998     

New approach to block copolymerization of ethylene with polar monomers by the unique catalytic function of organolanthanide complexes

This paper describes the first examples of ABA‐ and AB‐type block copolymerizations of a nonpolar monomer, in this case ethylene, with polar monomers, such as methyl methacrylate (MMA), ϵ‐caprolactone (CL), and 2,2‐dimethyltrimethylene carbonate (DTC), initiated by the unique catalytic function of rare earth metal complexes [Sm(II) and Ln(III) (Ln = Y, Sm)] as initiators. The Sm(II) species conducts the ABA‐type triblock copolymerization, leading to poly(MMA‐co‐ethylene‐co‐MMA), poly(CL‐co‐ethylene‐co‐CL), or poly(DTC‐co‐ethylene‐co‐DTC) by the efficient catalysis of racemic Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBu)₂Sm(THF)₂ ( 1 ) or meso Me₂Si(Me₂SiOSiMe₂)(C₅H₂‐3‐tBu)Sm(THF) ( 2b ). The resulting block copolymers are completely insoluble in THF and CHCl₃, but the homopolymers of MMA, CL, and DTC are freely soluble in these solvents. TEM profiles provide direct evidence for the block copolymerizations, where the spheric morphology of homogeneously dispersed polar polymers was observed. Ln(III) species, such as racemic Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBuMe₂Si)YH ( 5 ) and Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBu)SmH ( 6 ), afford AB‐type block copolymers between ethylene and MMA or CL, whose TEM images reveal the homogeneous dispersion of poly(MMA) or poly(CL) units in the polyethylene region. The ABA‐ and AB‐type block copolymers demonstrate high break stress and high tensile modulus as compared with their corresponding blended polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4095–4109, 2000     

超临界二氧化碳微乳液增溶多元醇特性

用2.5%、5.0%和7.5% (w)的1,3-丙二醇(1,3-PDO)稀水溶液为模型物质, 以超临界二氧化碳为连续相, 以琥珀酸二酯磺酸钠(AOT)为表面活性剂, 乙醇为助剂, 在压力为6.9-10.3 MPa的范围内, 温度为30-50 °C时, 分别对三种AOT浓度下的四元体系AOT/CO₂/乙醇/水和五元体系AOT/CO₂/乙醇/1,3-PDO/水的热力学行为进行了实验研究. 实验结果证明: 通过合理调控系统的操作条件, 可以形成热力学稳定的超临界二氧化碳微乳液, 并能实现选择性增溶1,3-丙二醇. 该结果可为指导工业生产提供依据.     

Novel block ionomers II. Synthesis and characterization of polyisobutylene‐based block cationomers

Various novel block cationomers consisting of polyisobutylene (PIB) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) segments were synthesized and characterized. The specific targets were various molecular weight diblocks (PIB‐b‐PDMAEMA⁺) and triblocks (PDMAEMA⁺‐b‐PIB‐b‐PDMAEMA⁺), with the PIB blocks in the DP_n = 50–200 range (number‐average molecular weight = 3,000–9000 g/mol) connected to blocks of PDMAEMA⁺ cations in the DP_n = 5–20 range (where DP is the number‐average degree of polymerization). The overall synthetic strategy for the preparation of these block cationomers had four steps: (1) synthesis by living cationic polymerization of mono‐ and diallyltelechelic polyisobutylenes, (2) end‐group transformation to obtain PIBs fitted with termini capable of mediating the atom transfer radical polymerization (ATRP) of DMAEMA, (3) ATRP of DMAEMA, and (4) quaternization of PDMAEMA to PDMAEMA ⁺I^? by CH₃I. Scheme 1 shows the microarchitecture and outlines the synthesis route. Kinetic and model experiments provided guidance for developing convenient synthesis methods. The microarchitecture of PIB–PDMAEMA di‐ and triblocks and the corresponding block cationomers were confirmed by ¹H NMR and FTIR spectroscopy and solubility studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3679–3691, 2002     

Synthesis of core/shell structure of glycidyl–functionalized poly(methyl methacrylate) latex nanoparticles via differential microemulsion polymerization

The differential microemulsion polymerization technique was used to synthesize the nanoparticles of glycidyl-functionalized poly(methyl methacrylate) or PMMA via a two-step process, by which the amount of sodium dodecyl sulfate (SDS) surfactant required was 1/217 of the monomer amount by weight and the surfactant/water ratio could be as low as 1/600. These surfactant levels are extremely low in comparison with those used in a conventional microemulsion polymerization system. The glycidyl-functionalized PMMA nanoparticles are composed of nanosized cores of high molecular weight PMMA and nano-thin shells of the random copolymer poly[(methyl methacrylate)-ran-(glycidyl methacrylate)]. The particle sizes were about 50 nm. The ratios of the glycidyl methacrylate in the glycidyl-functionalized PMMA were achieved at about 5–26 wt.%, depending on the reaction conditions. The molecular weight of glycidyl-functionalized PMMA was in the range of about 1 × 10⁶ to 3 × 10⁶ g mol⁻¹. The solid content of glycidyl-functionalized PMMA increased when the amount of added glycidyl methacrylate was increased. The glycidyl-functionalized polymer on the surface of nano-seed PMMA nanoparticles was a random copolymer which was confirmed by ¹H-NMR spectroscopy. The amounts of functionalization were investigated by the titration of the glycidyl functional group. The structure of the glycidyl-functionalized PMMA nanoparticles was investigated by means of TEM. The glycidyl-functionalized PMMA has two regions of T_g which are at around 90 °C and 125 °C, respectively, of which the first one was attributed to the poly[(methyl methacrylate)-ran-(glycidyl methacrylate)] and the second one was due to the PMMA. A core/shell structure of the glycidyl-functionalized PMMA latex nanoparticles was observed.     

水/AOT/正庚烷微乳体系中水结构的FT-IR研究

运用傅立叶变换红外光谱（ＦＴ－ＩＲ）对水／ＡＯＴ／正庚烷微乳体系中水的微结构进行了研究。结果表明，随着体系中加水量的增大，水分子Ｏ－Ｈ伸缩振动的红外光谱由３４９３ｃｍ＾－１向低频移动至３４１７ｃｍ＾－１，微乳体系中，水分子与ＡＯＴ分子的磺酸基作用的同时，与Ｎａ＾＋也有一定的作用，这两种离子对水分子Ｏ－Ｈ键的强度均有一定的影响，磺酸基的作用使水分子中Ｏ－Ｈ伸缩振动向高波数方向移动，而Ｎａ＾＋的作用与     

Macroporous poly(methyl methacrylate) produced by phase separation during polymerisation in solution

Polymethyl methacrylate (PMMA) sponges were obtained by polymerization in a solution with monomer/ethanol ratios up to 20:80. The material obtained after the elimination of the solvent present a homogeneous distribution of dispersed pores up to a monomer/ethanol ratio lower than 40:60. For higher ethanol contents in the reacting mixture, the morphology of the sponge corresponds to a network of PMMA microparticles, leaving large empty spaces leading to highly porous structure. The monomer/ethanol ratio during polymerization has a large influence on the porosity, thermal, and mechanical properties of the material and, for large solvent contents, on the size of the polymer microparticles.     

傅立叶变换红外光谱对琥珀酸-2-乙基己基磺酸钠非极性溶液中 反胶束结构的研究

利用衰减全反射傅立叶变换红外光谱(ATR-FTIR), 对琥珀酸-2-乙基己基磺酸钠(AOT)的反胶束结构进行了研究. 通过对红外光谱进行二维相关分析, 可以分辨出AOT分子在CCl4溶液中具有旁式和反式两种结构, 随着温度的升高, 旁式结构向反式结构转变, 反胶束体系能量降低, 38 ℃时, 反式结构所占比例达到最大值, 此时反胶束具有最大尺寸, 并处于最稳定的能量状态. 随着温度的进一步升高, 反式结构开始向旁式结构转变, 反胶束尺寸变小, 直至最后反胶束被破坏.     

Conformation and Aggregation Behavior of Polyelectrolyte with Primary Amino Pendant Groups in Water or THF/Water Binary Solvent Mixture and Their Effect on the Morphology of AOT Vesicles in Aqueous Media

Cationic polyelectrolyte with primary amine pendant groups, poly (4-vinyl benzyl amine hydrochloride salt) (poly (4-VBAHS)), was characterized by static light scattering. Using light scattering measurement, the conformation transition of poly (4-VBAHS) chains in pure water, and THF/H₂O (v/v: 1/3) binary solvent mixture was discussed. Concentration-dependent multiple morphologies including interpenetrating networks, tubular micelles, branched micelles, hexagonal phases, vesicles, and needle crystals were observed by TEM. In addition, effect of poly (4-VBAHS) on the morphology, stability, and critical vesicle/micelle concentration of anionic surfactant sodium bis (2-ethylhexyl) sulfosucciante vesicles were detected using dynamic light scattering, zeta potential, surface tension, and transmission measurements.     

Structure and properties of poly(methyl methacrylate) particles prepared by a modified microemulsion polymerization

Nanoscale poly(methyl methacrylate) (PMMA) particles were prepared by modified microemulsion polymerization. Different from particles made by traditional microemulsion polymerization, the particles prepared by modified microemulsion polymerization were multichain systems. PMMA samples, whether prepared by the traditional procedure or the modified procedure, had glass-transition temperatures (T_g's) greater than 120 °C and were rich in syndiotactic content (55–61% rr). After the samples were dissolved in CHCl₃, there were decreases in the T_g values for the polymers prepared by the traditional procedure and those prepared by the modified process. However, a more evident T_g decrease was observed in the former than in the latter; still, for both, T_g was greater than 120 °C. Polarizing optical microscopy and wide-angle X-ray diffraction indicated that some ordered regions formed in the particles prepared by modified microemulsion polymerization. The addition of a chain-transfer agent resulted in a decrease in both the syndiotacticity and T_g through decreasing polymer molecular weight. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 733–741, 2004     

Effect of crosslinking on porous poly(methyl methacrylate) produced by phase separation

Porous polymethyl methacrylate scaffolds were produced by phase separation during polymerisation in solution, using ethanol as solvent, with monomer/ethanol weight ratios from 80/20 up to 20/80 and different ethylenglycol dimethacrylate contents (1, 5 and 10 wt%) as crosslinker agent. For ethanol weight ratios equal to or lower than 50 wt%, the material presents a homogeneous distribution of dispersed pores. For higher ethanol contents, a highly interconnected porous structure is obtained. The transition from one type of morphology to the other can be also controlled with the amount of crosslinker added in the reactive mixture. Bulk polymethyl methacrylate samples (non-porous) with the same crosslinking densities were also synthesised as reference. The effect of crosslinker is studied by porosity measurements, scanning electron microscopy, dynamic-mechanical spectroscopy and differential scanning calorimetry.