Preparation of Nano-porous Materials(Ⅰ) by Polymerization of Amphiphile Self-assemblies

The polymerization of amphiphilic self assemblies is a promising method to synthesize nano structured materials with novel properties. These materials have many attractive features for their application in biomedical area and materials science, such as catalysis, separation, surface modification, and therapeutics areas. A general review on the polymerization of lipids and surfactant self assemblies to amphiphilic self assemblies is given in this paper with 49 references. The polymerization and the subsequently resulted structure of lipids in different morphologies are summarized. The polymerization of polymerizable surfactants(surfmers) in emulsion and liquid crystalline phases are also discussed. The potential application of new nano porous materials is briefly described.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Studies on the Self-condensing Vinyl Living Radical Polymerization of a Novel Acrylate Inimer

A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.

Synthesis of Highly Branched Poly(ε-caprolactone) by Self-condensing Atom Transfer Radical Polymerization of Macroinimers

Branched poly（ε-capmlactone） was synthesized by self-condensing atom transfer radical polymerization of macroinimer, α-acryloyoxy-ω-2-bromopropionyloxy poly（ε-caprolactone）, which was prepared by enzyme-catalyzed ring-opening polymerization of ε-caprolactone with 2-hydroxylethyl acrylate as initiator and esterification of the ω-hydroxyl group of the obtained poly（ε-caprolactone） by 2-bromopropionyl bromide.

Studies on the Self-condensing Vinyl Polymerization of a Novel Maleimide Inimer

The self-condensing vinyl polymerization(SCVP) of a novel maleimide inimer(initiator-monomer) 1, N-(4-α-bromobutyryloxy phenyl) maleimide with the complex of CuBr/Bipy(2, 2′-bipyridine) as the catalyst was studied. GPC was used to determine the molecular weight and the results show that the molecular weight increases exponentially with polymerization time during the first hour, and then the rate of increase molecular weight slows down. The molecular weight also increases with increasing dosage of the catalyst. The coincidence of the molecular weights determined by 1H NMR and GPC proves that the polymer obtained from the SCVP of inimer 1 has a linear structure, which is further verified by 13C NMR spectrum. A hyperbranched polymer was obtained by the copolymerization of inimer 1 and styrene.

Self-assembly of Gradient Copolymer Synthesized by Spontaneous Batch RAFT Emulsion Polymerization and Its Application on Encapsulating Ag Nanoparticles

The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy（TEM） analysis revealed that the P（TFEMA-grad-AA） can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P（TFEMA-grad-AA） micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles（NPs） were encapsulated by the P（TFEMA-grad-AA） micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P（TFEMA-grad-AA） had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.

Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries

Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.

聚合诱导-液晶驱动自组装制备含氟聚合物纳米纤维

含氟聚合物由于他们的低表面能、光电性能和生物相容性已经广泛用于各个领域。本文通过光引发在50℃下制备了聚甲基丙烯酸二甲氨乙酯-b-聚甲基丙烯酸2-(全氟辛基)乙酯(PDMAEMAm-b-PFMAn)纳米纤维。不同于一般的纳米纤维,得到的纳米纤维表面具有独特的凹凸起伏形似珍珠项链。通过动力学研究揭示了珍珠项链状纳米纤维的组装过程并且探究了反应温度、溶剂组成以及大分子链转移剂的聚合度对珍珠项链状纳米纤维的影响。结果表明,含氟液晶珍珠项链状纳米纤维的形成与液晶驱动力、核表面张力以及亲-疏溶剂的界面能三者的平衡关系相关。

Kinetic Study of Atom Transfer Radical Polymerization of 2-(N,N-Dimethylamino)ethyl Methacrylate

A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.

聚脲甲醛-生物油微胶囊的研制及性能探究

为研究微胶囊对沥青路面微裂纹的愈合效果,首先利用聚脲甲醛(作为微胶囊壁)和生物油(作为微胶囊心)采用原位聚合法制备微胶囊,采用扫描/透射电子显微镜和热重分析探究微胶囊的外观形貌和热稳定性;然后将微胶囊用于制备微胶囊/苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene, SBS)复合改性沥青,通过动态剪切流变仪和离析试验探究微胶囊的掺加对复合改性沥青路面性能的影响;最后通过延度愈合率试验验证微胶囊的愈合效果,并结合宏微观试验分析其愈合机理。结果表明:微胶囊呈现类球状,且表面较为粗糙,增大了与沥青的接触面积。微胶囊的热稳定性较好,其囊壁可承受沥青混合料生产过程中的高温环境。随着微胶囊的添加,复合改性沥青的低温塑性和耐热性均有所改善。此外,复合改性沥青的储能模量和损失模量也有所提升,即微胶囊的添加提升了SBS改性沥青的黏弹性能,这可能是由于添加的微胶囊与SBS和基质沥青具有很好的相容性,且微胶囊均匀分散在沥青内部并嵌入SBS呈现的网状结构中,这也在离析试验和荧光显微试验中得以证实。当微胶囊的掺量为0.4%时,复合改性沥青的愈合率达到最高。

Self-assembly synthesis of solid polymer electrolyte with carbonate terminated poly (ethylene glycol) matrix and its application for solid state lithium battery

A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.

Nano Fibrous Cerium（IV） Hydrogen Phosphate Membrane Self Supported Indole Polymerization Agent

Nanosized fibrous cerium（IV） hydrogen phosphate membrane, Ce（HPO4）2·2.9H20 （nCePf）, was prepared and characterized by chemical, XRD （X-ray diffraction）, TGA （thermogravimetric analysis）, SEM （scanning electron microscopy） and TEM （transmission electron microscopy）. Novel supported nanofibrous Ce（IV） phosphate/polyiondole nanocomposite membranes were prepared via in-situ chemical oxidation of the monomer that was promoted by the reduction of Ce（IV） ions present in the inorganic matrix. The presence of Ce（IV） ions allows redox reactions necessary to oxidative polymerization to occur. The resultant material was characterized by TGA, elemental （C, H, N） analysis and FT-IR （Fourier transform spectroscopy）. SEM images of the resulting nanocomposite reveals a uniform distribution of the polymer on the inorganic matrix. Amount of polyindole polymer present in the composite is found to be - 7.0%.

聚(乙二醇)-b-聚(N-己基甘氨酸)两嵌段共聚物的合成及其在乙腈/氯仿混合溶剂里的自组装

分子自组装是一种普遍存在于生命体系中的现象,其形成的复杂结构在生物学功能中起着至关重要的作用。聚类肽是一类很有前途的拟肽聚合物,其优良的结构可设计性和可调控的自组装行为可为基础研究和生物技术应用提供独特的性能。通过开环聚合设计合成了具有结晶性能的聚(乙二醇)-b-聚(N-己基甘氨酸)(PEG-b-PNHG)两嵌段共聚物。表征并分析了PEG-b-PNHG的结构和结晶性。在PNHG段结晶驱动的作用下,该聚合物在乙腈/氯仿混合溶剂中自组装得到盘状的胶束聚集体。结合聚类肽良好的生物相容性和结构多样性,所制备的嵌段自组装纳米材料在药物传递、生物工程等领域具有较好的应用价值。

RADICAL POLYMERIZATION OF N, N-DI(2-2'-METHYL-ACRYLOYLOXY-PROPYL)-PARA-TOLUIDINE FUNCTIONAL MONOMER

Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of (MP)_2PT in toluene took place. The kinetics of (MP)_2PT polymerization and the ESR spectra of LPO-(MP)2PT-MNP systems were determined respectively.

VINYL POLYMERIZATION OF NORBORNENE CATALYZED BY [2-(2-BENZIMIDAZOLYL)-6-((1-ARYLIMINOETHYL)PYRIDYL)]NICKEL CHLORIDE/MAO SYSTEM

The catalytic system of[2-(2-benzimidazolyl)-6-((1-aryliminoethyl)pyridyl)]nickel chloride/MAO(methylalu- minoxane)was found to be good active for vinyl polymerization of norbornene and provided polymers with relative narrow molecular distributions.Various reaction parameters,such as the ratios of nickel precursor to MAO or monomer norbornene, and the nature of the ligands in complexes were carefully investigated to realize their effects on the catalytic activities, polymer molecular weight and molecular we...

KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

α,α-dimethoxy-α-Phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator. Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyi benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and k_p/k_1^(1/2) value were found to be 0.5 and 0.066 mol(-1/2)l^(1/2)s^(-1/2), respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.

基于N-正己基甘氨酸的新型三嵌段聚类肽纳米胶束

通过开环聚合(ROP)合成了侧链含亲水基团氨基修饰的聚(乙二醇)-b-聚(N-正己基甘氨酸)-b-聚(N-烯丙基甘氨酸)(PEG-b-PNHG-b-P(NAG-g-NH_(2)))嵌段共聚类肽。该聚合物在水中在亲疏水和结晶的作用下可自发组装形成高度均一有序的蠕虫状胶束,长度约为120 nm,而调节溶液为酸性条件下则组装形成直径约为20 nm的球形胶束。这种结晶驱动自组装行为为制备超分子纳米结构提供了一种简便方法,同时由于聚类肽优异的生物相容性,使得该纳米胶束在纳米材料及生物医学应用等领域显示出极大的潜力。

基于聚(乙二醇)-b-聚(N-正十二烷基)甘氨酸嵌段共聚物的合成与组装

通过开环聚合(ROP)合成了一种具有结晶驱动自组装的嵌段共聚物聚(乙二醇)-b-聚(N-(正十二烷基)甘氨酸(PEG-b-PNDG)。利用DSC表征了嵌段聚合物的结晶行为。该聚合物在不同比例的二氧六环和氯仿的混合有机溶剂中可以组装形成直径分别为40 nm左右的球形胶束和220 nm左右的球形聚集体。合成的聚合物具有良好的生物相容性。