An efficient synthetic procedure for the phosphonation of aromatic polymers was developed and is here exemplified for polyphenylsulfone. This procedure involved the bromination of the polymer and the subsequent bromine‐phosphorus exchange by means of a Pd(0)‐catalyzed P? C coupling reaction. In the resulting product, the phosphonate ester pendant groups were attached to aromatic rings of the polymer chain without alkylene spacer units. A substitution degree of almost one phosphonate moiety per repeating unit of the polymer was achieved in the presence of Pd2(dba)3 · CHCl3 as catalyst at 120 °C. Polymers with free phosphonic acid groups were prepared by ester hydrolysis.
The behavior of the ring‐expansion homopolymerization of 2 (phenoxymethyl)thiirane (PMT) and propylene sulfide (PS), respectively, with thiazolidine‐2,4‐dione (TZD) as a cyclic initiator is investigated. The polymerizations show steadily growing molar masses with increasing monomer conversions. In addition, reversible merging reactions between rings are observed, with up to six merged macrocycles formed. The degree of merging is strongly dependent on the initial monomer concentration, whereas temperature has only a small impact. Under optimized conditions, ring‐poly(PMT) polymer with values of Mn up to 50 250 g mol?1 and dispersities down to 1.11 can be synthesized. DSC and ESI‐MS measurements of the novel ring‐poly(PS) prove the formation of ring polymer having topological purity above 95%.
The control of the radical polymerization of styrene by 2,2,15,15‐tetramethyl‐1‐aza‐4,7,10,13‐tetraoxacyclopentadecan‐1‐oxyl is reported here in bulk at 90 °C, 120 °C and in miniemulsion. Similarly, the control by its sodium complex is reported in bulk at 90 °C.
Summary: Equimolar mixtures of O‐permethylated and O‐perdeuteromethylated cyclodextrins were submitted to cationic ring‐opening polymerisation (CROP) with Et3OPF6 or BF3 · Et2O as initiator in dichloromethane. Reaction started after an incubation time and yielded a polymeric product, which was partially degraded again during competing chain transfer reaction. Average block length was determined by ESI‐MS after partial methanolysis and was found to be close to the theoretical value of 14 for β‐cyclodextrin in the early stage of the reaction, but decreased to 2–5 during further chain transfer reactions accompanied by an equilibration of α‐ and β‐configurated glucosidic linkages to a ratio of 64:36. Molecular weight was estimated from end group analysis and GPC to reach about 29 000 as a maximum. From 31P NMR spectra of the initiator it was obvious that PF is partly hydrolysed to PO2F under participation of the glass surface.
Summary: Copolymerizations of ethylene and disubstituted diallylsilanes (CH2CH CH2 )2R2Si (R = CH3, C6H5) have been investigated with various zirconocene catalysts using methylaluminoxane as a cocatalyst. The bridged stereospecific catalysts showed a higher reactivity for disubstituted diallylsilanes than the non‐bridged aspecific catalysts. Disubstituted diallylsilanes were incorporated into the polymer chain via cyclization insertion preferentially, and formed 3,5‐disubstituted silacyclohexane units in the polyethylene main chain. A zirconocene catalyst, dimethylsilylenebis(indenyl)zirconium dichloride, produced a copolymer containing pendant allyl groups derived from the 1,2‐insertion of diallyldiphenylsilane without cyclization.
Amorphous, hydrophobic telechelic hydrocarbon diols were synthesized using acyclic diene metathesis (ADMET) polymerization. These diols can be used in hydrolysis and UV resistant polyurethanes. The hydrocarbon backbone is based on a mimic of an ethylene/isobutylene polymer, made by the ADMET polymerization of a gem‐dimethyl substituted α,ω‐diene followed by hydrogenation of the polymer's repeat unit unsaturation. Chain termination reactants (CTR's) having one, three, and nine methylene “spacers,” respectively, between their olefin and alcohol precursor group were used to cap the polymer chain ends to yield 2.0 functional telechelics. Use of the medium length CTR in a polymerization–depolymerization scheme, resulted in amorphous (Tg = ?56 °C) telechelic diols with good molecular weight control.
Conjugated polyelectrolytes and their neutral precursors: aminoalkyl‐substituted polyfluorenes (PFNs) with different 4,7‐bis(N‐methylpyrrol‐2‐yl)‐2,1,3‐benzothiadiazole (PBT) contents were synthesized by Suzuki coupling reaction. Their quaternized ammonium polyelectrolyte derivatives were obtained through a post‐polycondensation treatment on the terminal amino groups. The resulting copolymers PFNBr–PBT are soluble in polar solvents such as methanol, DMF, and DMSO. Using the conjugated polyelectrolytes PFNBr–PBT5 as gate dielectric material, poly(3‐hexylthiophene) (P3HT) ‐based field‐effect transistors (FETs) show a high drain current of almost 4.5 mA within a gate voltage of only ?3 V. The calculated hole mobility of P3HT is about 0.58 cm2 · V?1 · s?1.
Summary: Polymeric systems containing side‐chain photoactive chromophores were prepared by free‐radical copolymerization of N‐vinylcarbazole with 4‐methacryloyloxyazobenzene and 4‐methacryloyloxy‐4′‐cyanoazobenzene. The resulting materials were characterized by size exclusion chromatography, TGA and DSC thermal analysis, FT‐IR, 1H NMR, UV‐vis, and fluorescence spectroscopy and photoisomerization experiments. In all cases, the copolymer composition was almost independent of the feed composition, in agreement with the strong tendency of the investigated monomers to alternating copolymerization. Spectroscopic and thermal data clearly highlighted the occurrence of charge‐transfer electronic interactions between electron‐rich carbazole rings and electron‐poor azobenzene chromophores. These interactions facilitate the trans‐cis photoisomerization of azobenzene side‐chains.
Aromatic proton NMR spectra of different poly(MCA‐co‐NVK) samples. 相似文献
Quantitative ESR and 1H NMR spectroscopies have been used to study the homolysis and decomposition, respectively, of alkoxyamines derived from TEMPO and PROXYL nitroxides. It is shown that alkoxyamines substituted in the β position with a tert‐butoxy group have different activation parameters than those bearing a 1‐phenethyl fragment, however, there is compensation between transition state enthalpy and entropy, resulting in most cases in similar transition state free energies and homolysis kinetics. On the other hand, β‐substituted alkoxyamines show a much lower tendency to undergo decomposition, while species derived from TEMPO are more prone to decomposition than those from the substituted PROXYL derivative investigated. These findings are used to explain the observed differences in polymerisation behaviour of the various alkoxyamines.
Two new donor/acceptor copolymers PBDTPhBT1 and PBDTPhBT2 with alternating benzodithiophene ( BDT ) and bisthiophene‐phthalimide ( PhBT ) units were synthesized by Stille coupling reaction. The copolymers showed identical optical bandgaps of 1.98 eV. The HOMO energy levels are ?5.35 and ?5.32 eV for PBDTPhBT1 and PBDTPhBT2 , respectively. The bulk heterojunction solar cell devices based on these copolymers as donors and PC71BM as acceptor displayed high open‐circuit voltages of 0.90–0.93 V and achieved power conversion efficiency of 1.54% under the illumination of AM 1.5, 100 mW · cm?2.
ArF laser irradiation of gaseous mixtures of carbon disulfide and silane allows efficient deposition of Si? S bond‐containing poly(thiacarbosilanes) incorporating SiS bodies. These SiS/poly(thiacarbosilane) composites are the first example of silicon sulfide/polymer composites. Composite formation is analyzed by GC/MS analysis of volatile products and the structure of the composite as determined by electron microscopy and FT‐IR spectra. The composites undergo reaction with air moisture and methanol vapor, evolve H2S and evolve to nano‐sized poly(thiacarbosiloxane)s and poly(methoxythiacarbosiloxane)s.
Summary: Degradation studies of cis‐1,4‐polyisoprene were carried out using first and second generation Grubbs catalysts to achieve end‐functionalized acetoxy oligomers in both an organic solvent and a latex phase at room temperature. Well‐defined acetoxy telechelic polyisoprene structures were obtained in a selective manner with a range of from 10 000 to 30 000, with a polydispersity index of around 2.5.
Structure produced by the metathetic depolymerization of hydroxy telechelic cis‐1,4‐polyisoprene. 相似文献
A novel graft copolymer is synthesized from commercially available poly(vinyl alcohol) using ring‐opening polymerization. For the polymerization reaction of novel brush‐like poly(vinyl alcohol)‐graft‐poly(?‐caprolactone‐co‐(3‐/7‐(prop‐2‐ynyl)oxepan‐2‐one) 5 Sn(Oct)2 is used as a catalyst. The formation of the graft copolymer is confirmed by 1H NMR, 13C NMR, and Fourier transform infrared (FTIR) spectroscopy. Furthermore, the modification of the novel synthesized graft copolymer via a “click” reaction to implement adamantane groups is described. The success of the “click” reaction is proven by 1H NMR spectroscopy and visualized by decomplexation of cyclodextrin with included phenolphthalein.
Summary: In this article we describe the synthesis of various monomers modified with triphenyl‐1,3,5‐triazine side groups as electron transport moieties. By nitroxide‐mediated polymerization with a TEMPO unimer it was possible to obtain polymers with a narrow polydispersity. Furthermore, by living radical polymerization block copolymers were obtained from these monomers. Therefore, microphase separated structures are accessible which possess hole conducting moieties in one phase and electron conducting moieties in the other phase.
General build‐up of the copolymers consisting of hole and electron conductor. 相似文献
Polymers with narrow molecular weight distributions and controlled architectures were generated by living ring‐opening metathesis polymerization of exo‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboximide. The dicarboximide units have been previously shown to exhibit biological activity, can selectively bind to the nucleic acid base adenine by hydrogen‐bonding, and are readily functionalizable. Block copolymers containing these moieties were generated, and underwent self‐assembly into nanoscale spherical aggregates, with surface localized molecular recognition motifs.
Crystalline‐branched supramolecular structures (CBSSs) with surface area (Brunauer‐Emmett‐Teller model) up to 350 m2 · g?1 were synthesized by in situ self‐assembly of the zigzag polyimide macromolecules under solvent‐thermal condition. The pore formation mechanism in these polyimides was supposed to be different from any microporous polymers ever reported. Although this family of porous polyimide does not belong to covalent organic frameworks (COFs), their high degree of crystallinity shows the possibilities that the dynamic covalent chemistry for synthesizing COFs could be extended from easily hydrolyzable B? O bond to a more stable imido bond. Therefore, we believe that these CBSSs could be useful in many applications, e.g., catalyst carriers and low‐K materials.
Chain contraction and collapsing kinetics of pyrene‐labeled poly(N‐isopropylacrylamide) (PNIPAM) single chains ( = 3.64 × 105 g · mol?1, = 1.17) were investigated by employing the stopped‐flow technique coupled with fluorescence and light scattering detections, which can achieve millisecond jumping of solvent quality from good to above and below the θ‐solvent condition at small quench depths. It was found that the coil‐to‐crumpled globule transition proceeds via an isotropic one stage process and the obtained characteristic relaxation times exhibit a monotonic decrease with increasing quench depths. The obtained experimental results were in qualitative agreement with previous theoretical considerations.
New polyurethanes containing Y‐shaped chromophores, symmetrical derivatives of 4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(dimethylamino)styryl]‐4H‐pyran, have been prepared. The polymers show high glass transition temperatures (Tg) and a good thermal stability. SHG measurements on poled polymer films of the synthesized polymers have been carried out and a maximum d33 of 15 pm · V?1 has been found at 1 368 nm fundamental wavelength. Time stability measurements on the most active polymer have shown that after the initial fast relaxation, the d33 value remains constant at 80 °C for 60 d.
Two terthiophenes bearing core fluorinated thienyl units have been synthesised as potential semiconductor materials for organic field‐effect transistors. Polymerisation of these compounds has been achieved using conventional iron(III) chloride oxidative coupling methods and by electrochemical oxidation. Characterisation of the fluorinated materials has been achieved by absorption spectroscopy and cyclic voltammetry. A soluble hexyl‐functionalised polymer (poly 8b ) was used in an OFET device; hole mobilities were measured up to 3 × 10?3 cm2 · V?1 · s?1, and the device had an on/off ratio of 105 and a turn‐on voltage of +4 V.
Summary: The RAFT‐CLD‐T methodology is demonstrated to be not only applicable to 1‐substituted monomers such as styrene and acrylates, but also to 1,1‐disubstituted monomers such as MMA. The chain length of the terminating macromolecules is controlled by CPDB in MMA bulk free radical polymerization at 80 °C. The evolution of the chain length dependent termination rate coefficient, k, was constructed in a step‐wise fashion, since the MMA/CPDB system displays hybrid behavior (between conventional and living free radical polymerization) resulting in initial high molecular weight polymers formed at low RAFT agent concentrations. The obtained CLD of kt in MMA polymerizations is compatible with the composite model for chain length dependent termination. For the initial chain‐length regime, up to a degree of polymerization of 100, kt decreases with α (in the expression k = k · i−α) being close to 0.65 at 80 °C. At chain lengths exceeding 100, the decrease is less pronounced (affording an α of 0.15 at 80 °C). However, the data are best represented by a continuously decreasing non‐linear functionality implying a chain length dependent α.
