Direct synthesis of per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives

A convenient and direct per(poly)fluoroalkylmethyl-mtroducing cyclopropanation reaction was described. In the presence of CrCl3/Fe, per(poly)fluoroalkyl iodides reacted with diethyl allylmalonate and its analogs to give per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives in high yields. This reaction was considered to proceed by two steps: radical addition followed by cyclopropanation.     

Synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes——Utilizing potassium fluoride supported on alumina as a denydrohalogenating agent

Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.     

Keyword Index to Volume 15 (1997)

Ab initio molecular orbital theory,closo boron hydrides 102Ab initio crystal orbital,band structure,poly(P phenylene)289Absolute configuration, CD spectra, 8,8”一 biflavones,synthesis,optical resolution 464Ac voltammetry,square wave voltammetry,self. assembled monolayers,viologen 130a-Acetylaminoacrylate,chromic chloride/iron, per(poly)fluoroalkyl iodides 286Acidity,bromide,galactose,dual-frequency oscil- lations 25Activation model,hydrated transition metal ions, electronic factor,Landau.Z…     

THE COMPATIBILITY OF BLENDS OF POLY(VINYL CHLORIDE) OR CHLORINATED POLY(VINYL CHLORIDE) WITH POLY(METHYL METHACRYLATE)

IR spectral shifts of carbonyl vibrational absorption for ethyl acetate, which acts analogically as the structural unit of poly(methyl methacrylate), in cyclohexane, chloroform, chlorinated paraffins, poly(vinyl chloride) and chlorinated poly(vinyl chloride) were measured. The results suggest that there are specific interactions between the carbonyl groups and the chlorinated hydrocarbons which could be responsible for the apparent compatibility of poly(vinyl chloride)—poly(methyl methacrylate) and chlorinated poly(vinyl chloride)—poly(methyl methacrylate) blends. Additionally, the effects of the preparation mode of blend films on phase separation and observed compatibility are discussed.     

PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4''''-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4'-methylenebis(cinnamaldehyde)ethylenediimine] (PMBCen), poly[4,4'-methylenebis(cinnamaldehyde) 1,2-propylenediimine] (PMBCPn), poly[4,4'-methylenebis(cinnamaldehyde) 1,3-propylenediimine] (PMBCPR), poly[4,4'-methylenebis(cinnamaldehyde)l,2-phenylenediimine] (PMBCPh), poly[4,4'-methylene-bis(cinnamaldehyde)meso-stilbenediimine] (PMBCS), poly[4,4'-methylenebis(cinnamaldehyde)urea] (PMBCUR), poly[4,4'-methylenebis(cinnamaldehyde)semicarbazone] (PMBCSc), poly[4,4'-methylenebis(cinnamaldehyde)thiosemicarbazone] (PMBCTSc) and poly[4,4'-methylenebis(cinnamaldehyde)hydrazone] (PMBCH) were formed by polycondensation of 4,4'-methylenebis(cinnamaldehyde) with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and 'H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.     

Study on the reaction of triple helix poly(A:2I) with Cu~(2+)

The effect of Cu2+ on the triple-stranded helical structure of poly(A:2I) was studied by means of circular dichroism spectral method with the help of ultraviolet spectral and ethidium bromide fluorescence probe methods. It was found that Cu2+ destabilizes the structure of the triple helix poly(A:2I) and induces its structural transformations, meanwhile, the transformations can be partially reversed by a higher NaCl concentration. The structural transformations may be expressed by the following scheme: poly(A:2I) - poly(A:I) + poly(I)- poly(A) + 2poly(I)     

Urea-based polyacetylenes as an optical sensor for fluoride ions

Novel acetylenes carrying urea groups, 1-(4-ethynylphenyl)-3-(4-nitrophenyl) urea (1), 1-(4-propargyl)-3-(4-nitrophenyl) urea (2), were synthesized and polymerized with rhodium catalyst. Polymers [poly(1) and poly(2)] with moderate molecular weights were obtained in good yields. The anion sensing ability of poly(1) and poly(2) was estimated using the tetra-n-butylammonium (TBA) salts of a series of anions in DMF. Upon the addition of F-, the color of the DMF solution of poly(1) and poly(2) immediately turned to a different color, while the color of solution changed slightly upon addition of Cl-, HSO4-, Br-, and NO3-, indicating the F- sensing ability of poly(1) and poly(2). The 1H-NMR titrations of poly(1) revealed that the colorimetric response of poly(1) was triggered by the urea/F- interaction through the hydrogen bonding and/or deprotonation process. The absorption spectra titration and Hill plot analysis were carried out to measure the F- binding ability, and the Hill coefficient in the poly(1)/F- complexation was found to be 5.8. This result clearly indicated that this binding mode between poly(1) and F- was based on a positive homotropic allosterism.     

SYNTHESIS, CHARACTERIZATION AND THERMAL DEGRADATION KINETICS OF POLY(IMINO ISOPHTHALOYL IMINO (2,4,8,10-TETRAOKSOASPIRO [5,5] UNDEKAN-3,9-DIPROPYLENE))

A new polymer,poly(imino isophthaloyl imino(2,4,8,10-tetraoksoaspiro[5,5]undekan-3,9-dipropylene)) [poly(IPIT)]was synthesized by an interfacial polycondensation reaction.The characterization of poly(IPIT)was conducted by using FT-IR,~(13)C-NMR,TG and DTA techniques.The kinetics of the thermal degradation of poly(IPIT)was investigated by thermogravimetric analysis at different heating rates.TG curves showed that the thermal decomposition of poly(IPIT) occurred in three stages.The apparent activation ener...     

COMPATIBILITY STUDIES ON POLYMER/WAX AND POLYMER/RESIN-ASPHALTENE BY VISCOMETRY AND PHOTOMICROGRAPHY

The compatibility of mixtures of polymeric pour point depressants, i.e. poly(ethylene-co-vinylacetate) (EVA), poly (EVA-graft-octadecylacrylate) (EVA-g-POA ), poly (ethylene-co-octadecylacrylate) (EOA) and poly(ethylene oxide-co-propylene oxide) (EO-co-PO) withwax or resin-asphaltene from crude oil have been studied by means of dilute-solution vis-cometry. It was found that each mixture pair is incompatible, but the degrees of incompati-bility are quite different, which are in good agreement with the results from photomicrog-raphy.     

THE EFFECT OF MODIFICATION OF COORDINATING GROUPS ON THE CATALYTIC BEHAVIORS OF POLYMER CATALYSTS

Several polymer-supported palladium complex catalysts containing two different coordinatinggroups were prepared and the cooperative effect of the coordinating groups on the catalytic behaviorsof polymer catalysts was studied. It was found that poly(acrylic acid-co-acrylonitrile)-Pd complex(PAA-AN-Pd) is a more active and stable catalyst for hydrogenation than both poly(acrylic acid)-Pd and poly(acrylonitrile)-Pd complexes. A marked change of catalytic behaviors of poly(N-substituted maleamic acid-co-styrene)-Pd complexes was observed in comparison with poly(maleicacid-co-styrene)-Pd complex. Acetophenone was reduced to 1-phenyl ethanol by poly(N-phenylmaleamic acid-Co-styrene)-Pd complex (N-1-Pd), but ethylbenzene was obtained using poly(maleicacid-co-styrene)-Pd complex as a catalyst. The influence of solvents, additives and N/Pd gramatomic ratio on the catalytic behaviors of the polymer complexes was investigated.     

Synthesis and properties of conjugated fluoroalkyl ether-substituted polythiophenes prepared in organic solvent and supercritical carbon dioxide

A number of new fluoroalkyl ether-containing polythiophenes are synthesized via oxidative polymerization in supercritical CO₂ (scCO₂) and chloroform. In both cases, high-molecular-mass polymers with high yields are prepared. The properties of the polymers synthesized in scCO₂, such as molecular mass, polydispersity, conjugation, and UV absorption, are similar to the properties of the polymers obtained in chloroform. All poly(fluoroalkyl ether thiophenes) show solubility in DMF, toluene, THF, chloroform, and acetone. The glass-transition temperatures of the polymers are in the range 58–82°C, and the temperatures corresponding to 10% loss in their weight are in the ranges 248–294 and 260–303°C for poly(fluoroalkyl ether thiophenes) synthesized in scCO₂ and chloroform, respectively. All polymers fluoresce in the blue region with emission maxima at 506 to 526 nm. Because of the unique combination of fluoroalkyl and carbonyl groups, poly(fluoroalkyl ether thiophenes) feature good solubility in scCO₂, which is a promising alternative solvent for the oxidative polymerization of fluoroalkyl ether thiophenes.     

Humidity-dependent wetting properties of high hysteresis surfaces

The advancing contact angle (thetaadv) of water on thin films ( approximately 1 microm) of poly(ethylene glycol) (PEG) with fluoroalkyl endgroups (6 kg/mol PEG with 10-carbon fluoroalkyl, denoted 6KC10) changes strongly with relative humidity (RH). Films of 6KC10 on silicon wafers pretreated with a fluorinated alkylsilane (TFOS) display thetaadv increasing from 75 degrees at 12% RH to 95 degrees at 94% RH. The surprising transition to nonwetting character at high humidity is attributed to fluoroalkyl groups ordering at the air-hydrogel interface when they are liberated by dissolution of PEG crystallites above 85% RH. When water is withdrawn from a drop on 6KC10, the contact line does not recede. This extreme hysteresis is attributed to restructuring of the gel to bury the fluoroalkyl groups when in contact with water.     

SYNTHESIS OF 3-PER(POLY)FLUOROALKYLPYRAZOLES

ＳＹＮＴＨＥＳＩＳＯＦ３－ＰＥＲ（ＰＯＬＹ）ＦＬＵＯＲＯＡＬＫＹＬＰＹＲＡＺＯＬＥＳＳＹＮＴＨＥＳＩＳＯＦ３－ＰＥＲ（ＰＯＬＹ）ＦＬＵＯＲＯＡＬＫＹＬＰＹＲＡＺＯＬＥＳ￥ＸｉａｏＱｉｎｇＴＡＮＧａｎｄＣｈａｎｇＭｉｎｇＨＵ（ＳｈａｎｇｈａｉＩｎｓｔｉ...     

全氟或多氟烷基氯代烷在保险粉引发下与芳香烃 的反应

全氟或多氟烷基氯代烷在保险粉引发下在DMSO溶剂中可以与富电子芳香烃反应,方便地得到氟烷基化的产物。氟烷基化产物的结构和产率主要取决于取代基的供电子能力和位置。     

Synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes—Utilizing potassium fluoride supported on alumina as a dehydrohalogenating agent

Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.     

Latices of poly(fluoroalkyl mathacrylate)‐b‐poly(butyl methacrylate) copolymers prepared via reversible addition–fragmentation chain transfer polymerization

Poly(fluoroalkyl mathacrylate)‐block‐poly(butyl methacrylate) diblock copolymer latices were synthesized by a two‐step process. In the first step, a homopolymer end‐capped with a dithiobenzoyl group [poly(fluoroalkyl mathacrylate) (PFAMA) or poly(butyl methacrylate) (PBMA)] was prepared in bulk via reversible addition–fragmentation chain transfer (RAFT) polymerization with 2‐cyanoprop‐2‐yl dithiobenzoate as a RAFT agent. In the second step, the homopolymer chain‐transfer agent (macro‐CTA) was dissolved in the second monomer, mixed with a water phase containing a surfactant, and then ultrasonicated to form a miniemulsion. Subsequently, the RAFT‐mediated miniemulsion polymerization of the second monomer (butyl methacrylate or fluoroalkyl mathacrylate) was carried out in the presence of the first block macro‐CTA. The influence of the polymerization sequence of the two kinds of monomers on the colloidal stability and molecular weight distribution was investigated. Gel permeation chromatography analyses and particle size results indicated that using the PFAMA macro‐CTA as the first block was better than using the PBMA RAFT agent with respect to the colloidal stability and the narrow molecular weight distribution of the F‐copolymer latices. The F‐copolymers were characterized with ¹H NMR, ¹⁹F NMR, and Fourier transform infrared spectroscopy. Comparing the contact angle of a water droplet on a thin film formed by the fluorinated copolymer with that of PBMA, we found that for the diblock copolymers containing a fluorinated block, the surface energy decreased greatly, and the hydrophobicity increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 471–484, 2007     

PDMS network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)‐fluoroalkyl side chains for fouling‐release coatings. I. Chemistry and stability of the film surface

Amphiphilic copolymers of a methacrylic monomer (SiMA) carrying a polysiloxane side chain and an acrylic monomer (ZA) with a mixed poly(ethylene glycol) (PEG)‐fluoroalkyl side chain (10–85 mol % ZA) were incorporated as the surface‐active components into poly(dimethylsiloxane) (PDMS) network blends at different loadings (1 and 4 wt % with respect to PDMS). Wettability of the coating surfaces was investigated by contact angle measurements, and their surface chemical composition was determined by angle‐resolved X‐ray photoelectron spectroscopy. It was found that the surface segregation of the fluoroalkyl segments of the amphiphilic copolymers was responsible for the high enrichment in fluorine concentration within 10 nm of the coating surface. The PEG segments were also concentrated at the polymer?air interface. The chemical composition of the films was proven to be relatively little affected by immersion in water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Preparation and applications of novel fluoroalkyl end-capped oligomers/calcium carbonate nanocomposites

Calcium chloride reacted with sodium carbonate in the presence of a variety of self-assembled molecular aggregates formed by fluoroalkyl end-capped acrylic acid, 2-methacryloyloxyethane sulfonic acid, dimethylacrylamide, and acryloylmorpholine oligomers in aqueous solutions to afford the corresponding fluorinated oligomers/calcium carbonate composites in excellent to moderate isolated yields. These fluorinated calcium carbonate composites thus obtained were shown to have a good dispersibility not only in water but also in traditional organic media including fluorinated solvents. Dynamic light scattering measurements (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that these fluorinated composites are nanometer-size-controlled particles and well dispersed in these media. Cross-linked fluoroalkyl end-capped acrylic acid co-oligomer containing poly(oxyethylene) units was also applied to the preparation of new cross-linked fluorinated calcium carbonate nanocomposites under similar conditions. The obtained cross-linked fluorinated calcium carbonate nanocomposites were found to have an extremely higher dispersibility in aqueous and organic media including fluorinated solvents, compared to that of the corresponding fluoroalkyl end-capped oligomer nanocomposites. In particular, it was verified that these fluorinated calcium carbonate nanocomposites are applicable to the dispersion above poly(methyl methacrylate) (PMMA) film surface. Interestingly, field-emission SEM (FE-SEM) images of the cross-section of the modified PMMA films showed that calcium carbonate particles dispersed into these PMMA films could be arranged regularly above the modified film surface. More interestingly, cross-linked fluorinated oligomeric aggregates were able to provide suitable host moieties for the crystallization of calcium carbonate.