A comprehensive experimental study of surfactant-free emulsion polymerization of styrene

Comprehensive experimental results are presented for surfactant-free emulsion polymerization of styrene with water-soluble, ionic initiators. Special emphasis is placed on the particle nucleation, the chemical structure of the nucleating species, the change of latex, particle and polymer properties as well as the development of particle morphology with polymerization time. Under special conditions the appearance in transmission electron microscopy pictures of less electron dense anomalous particles is observed. The formation of these structures is discussed and possible formation mechanisms presented. Dialysis of the latexes changed their properties drastically as they became unstable to coagulation. The original latexes did not change their properties over several months. Received: 25 November 1998 Accepted in revised form: 25 January 1999     

An overview on 12-polyurethane: Synthesis, structure and crystallization

The knowledge on linear aliphatic polyurethanes n-PUR has increased significantly due to a series of works made in these last years and published in recent literature. An overview of 12-polyurethane (12-PUR) embracing its synthesis, thermal properties, crystal structure and crystallization is given in this paper. The purpose is to provide a representative example able to reflect comprehensively the state of the art reached for the whole family. The synthesis of 12-PUR was accomplished in good yield and with acceptable molecular weight from 12-amino-1-dodecanol by applying a two-step method without isolation of the isocyanate alcohol precursor. 12-PUR is a semicrystalline polymer with an equilibrium melting temperature of 157 °C. It adopts a layered crystal structure similar to the α-form of nylons with chains in fully-extended conformation and arranged in hydrogen-bonded sheets in the antiparallel mode. This structure is thermally stable up to melting and is unable to undergo Brill transition. 12-PUR crystallized from dilute solution affording well-shaped lamellar crystals with a thickness of 8-9 nm and from the melt yielding either banded or fibrillar spherulitic textures displaying negative birefringence. Isothermal crystallization of 12-PUR from the melt took place with heterogeneous nucleation, while both crystallization rate and the finally attained crystallinity degree were highly depending on crystallization temperature.     

Synthesis and Analysis of Tm3+ Doped YF3 Upconversion Luminescent Nano-materials

<正>Upconversion(UC)phosphor Tm~(3+)doped YF_3 nano-crystals were prepared by hydrothermal method under different conditions and characterized by Field Transmission electron microscopy(TEM),Scanning electron microscopy(SEM)and X-ray diffraction(XRD).Their UC luminescence properties were studied by fluorescence spectrophotometer with 980 nm diode laser excitation,and impact of different grain sizes and morphology on the UC luminescence intensity was discussed.The fluorescence decay lifetime was calculated by Multi-exponential function fitting method.Results show that UC emission intensity was enhanced with the reduction of grain size,and the decay lifetime is 0.60 us.     

Synthesis and characteristics of poly(methyl methacrylate‐co‐methacrylic acid)/poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive semi‐hollow latex particles and their application to drug carriers

In this work, the poly(methyl methacrylate‐co‐methacrylic acid)/poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive composite semi‐hollow latex particles was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate‐co‐methacrylic acid) (poly (MMA‐MAA)) copolymer latex particles by the method of soapless emulsion polymerization. The second process was to polymerize methacrylic acid (MAA), N‐isopropylacrylamide (NIPAAm), and crosslinking agent, N,N′‐methylenebisacrylamide, in the presence of poly(MMA‐MAA) latex particles to form the linear poly(methyl methacrylate‐co‐methacrylic acid)/crosslinking poly(methacrylic acid‐co‐N‐isopropylacrylamide) (poly(MMA‐MAA)/poly(MAA‐NIPAAm)) core–shell latex particles with solid structure. In the third process, part of the linear poly(MMA‐MAA) core of core–shell latex particles was dissolved by ammonia to form the poly(MMA‐MAA)/poly(MAA‐NIPAAm) thermosensitive semi‐hollow latex particles. The morphologies of the semi‐hollow latex particles show that there is a hollow zone between the linear poly(MMA‐MAA) core and the crosslinked poly(MAA‐NIPAAm) shell. The crosslinking agent and shell composition significantly influenced the lower critical solution temperature of poly(MMA‐MAA)/poly(MAA‐NIPAAm) semi‐hollow latex particles. Besides, the poly(MMA‐MAA)/poly(MAA‐NIPAAm) thermosensitive semi‐hollow latex particles were used as carriers to load with the model drug, caffeine. The processes of caffeine loaded into the semi‐hollow latex particles appeared four situations, which was different from that of solid latex particles. In addition, the phenomenon of caffeine released from the semi‐hollow latex particles was obviously different from that of solid latex particles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3441–3451     

聚氨酯改性氟代聚丙烯酸酯的合成、表征与膜形态

在二月桂酸二丁基锡(T-12)作用下,将1,6-已二异氰酸酯(HDI)与聚乙二醇(PEG-200)在70℃反应合成—NCO封端的聚氨酯预聚体(PU),然后滴加甲基丙烯酸十二氟庚酯(RfAA)、丙烯酸羟丙酯(HPAA)和偶氮二异丁腈(AIBN)在甲基异丁基甲酮(MIBK)溶液中聚合反应4～6 h,再经丁酮肟(EtAO)封端,制得了一种新型聚氨酯改性氟代聚丙烯酸酯易去污整理剂(FPUA)。用红外光谱(IR)、核磁共振氢谱(1H-NMR)、核磁共振碳谱(13C-NMR)、原子力显微镜(AFM)和扫描电镜(SEM)等对FPUA的结构、成膜形态及应用性能进行了研究。结果表明:FPUA在亲水性纤维织物和单晶硅表面均能形成非单一结构的疏水膜。该膜附着在纤维表面,能使处理后织物表面水的静态接触角达到146.5°,色拉油的接触角达到132°,且易去污效果良好。     

Scanning and transmission electron microscopy studies on a model series of spherulitic segmented polyurethanes

Scanning (SEM) and transmission (TEM) electron microscopy studies were made on a model series of four segmented polyurethanes. The morphologies of both the homopolymers and of their mixtures were made by SEM while TEM was utilized to study only ultrathin films of the homopolymers. It was found that well-structured spherulitic morphologies could be induced in these systems and their mixtures, and that control over the textures could be maintained by solution casting conditions. The domains were observable via TEM, and the general orientation of this structure within the spherulites was noted. Deformation studies of the spherulitic textures were followed by both SEM and small-angle light scattering. It was concluded that, in general, the spherulites deform in a nonaffine manner–this is particularly true for the systems possessing a porous texture.     

Synthesis and Characterization of Novel Segmented Polyionenes Based on Polydimethylsiloxane Soft Segments

Novel polydimethylsiloxane (PDMS) based polyionenes were synthesized by a modified Menschutkin reaction involving reaction between bromo-terminated PDMS oligomers and various ditertiary amino compounds. In this study, the nature of the hard segment was varied by using various ditertiary amino compounds and in some cases by incorporating chain extenders, while the soft segment content was varied by changing the molecular weight of the PDMS oligomers. The mechanical properties of these materials were found to be dependent on both the nature and amount of the hard segments. These materials also showed distinct evidence of a microphase-separated morphology where under normal conditions, the hard segments formed in what are believed to be cylindrical ion-rich microdomains dispersed randomly in the soft PDMS matrix. When subjected to uniaxial deformation, the ionic cylinders were found to orient along their long axes in the stretch direction.     

Ethynylene‐containing donor–acceptor alternating conjugated polymers: Synthesis and photovoltaic properties

Four ethynylene‐containing donor‐acceptor alternating conjugated polymers P1 – P4 with 2,5‐bis(dodecyloxy) substituted phenylene or carbazole as the donor unit and benzothiadiazole (BTZ) as the acceptor unit were synthesized and used as donor polymers in bulk heterojunction polymer solar cells. The optical, electrochemical, and photovoltaic properties of these four polymers with the ethylene unit located at different positions of the polymer chains were systematically investigated. Our results demonstrated that absorption spectra and the HOMO and LUMO energy levels of polymers could be tuned by varying the position of the ethynylene unit in the polymer chains. Photovoltaic devices based on polymer/PC₇₁BM blend films spin coated from chloroform and dichlorobenzene solutions were investigated. For all four polymers, open circuit voltages (V_oc) higher than 0.8 V were obtained. P4 , with ethynylene unit between BTZ and thiophene, shows the best performance among these four polymers, with a V_oc of 0.94 V, a J_sc of 4.2 mA/cm², an FF of 0.40, and a PCE of 1.6%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Salt Responsive Morphologies of ssDNA‐Based Triblock Polyelectrolytes in Semi‐Dilute Regime: Effect of Volume Fractions and Polyelectrolyte Length

A comprehensive study is reported on the effect of salt concentration, polyelectrolyte block length, and polymer concentration on the morphology and structural properties of nanoaggregates self‐assembled from BAB single‐strand DNA (ssDNA) triblock polynucleotides in which A represents polyelectrolyte blocks and B represents hydrophobic neutral blocks. A morphological phase diagram above the gelation point is developed as a function of solvent ionic strength and polyelectrolyte block length utilizing an implicit solvent ionic strength method for dissipative particle dynamics simulations. As the solvent ionic strength increases, the self‐assembled DNA network structures shrinks considerably, leading to a morphological transition from a micellar network to worm‐like or hamburger‐shape aggregates. This study provides insight into the network morphology and its changes by calculating the aggregation number, number of hydrophobic cores, and percentage of bridge chains in the network. The simulation results are corroborated through cryogenic transmission electron microscopy on the example of the self‐assembly of ssDNA triblocks.     

复合微球的制备、性能及应用

本文综述了复合微球的制备、性能及其应用，并对其发展趋势作了展望．