Two novel reactive poly(β‐cyanoethylsilsesquioxane) ( CN‐T ) and poly[(β‐cyanoethylsilsesquioxane)‐co‐(β‐methylsilsesquioxane)] ( CN‐Me‐T ) have been synthesized successfully for the first time via stepwise coupling polymerization (SCP). A variety of characterization methods including FTIR, 1H NMR, 29Si NMR, X‐ray diffraction (XRD), differential scanning calorimetry (DSC) and vapor pressure osmometry (VPO) were combined to demonstrate that the structures of the title polymers possess ordered ladder‐like structures. As expected, the ionic conductivity of these polymers mixed homogeneously with lithium perchlorate reached 10?6 S · cm?1 at room temperature and obviously increased with the raise of temperature.
Summary: The nature of the pH dependent collapse of poly(methacrylic acid) (PMAA) hydrogels is investigated using recent 1H solid‐state NMR methods. In aqueous solution, PMAA changes from an expanded conformation at high pHs to a compact contracted form at low pHs, where hydrogen bonds play a central role. In solid‐state 1H NMR spectra, recorded under fast magic angle spinning (MAS), dried PMAA samples previously collapsed at low pHs show characteristic signals in the spectral region of the carboxylic acid protons. With the aid of 2D 1H‐1H double‐quantum (DQ) MAS NMR spectra, three signals can be distinguished at 8, 10.5 and 12.5 ppm, which are attributed to free carboxylic groups and two different types of hydrogen bonded forms, respectively. The 12.5 ppm signal arises from the hydrogen bond with the shortest H? H distance, corresponding to the form that is most stable with respect to increasing temperature and pH. The weaker hydrogen‐bonded form (with a signal at 10.5 ppm) requires a slightly lower pH, while the free acid signal (at 8 ppm) emerges under the most acidic medium. Moreover, the stabilities of the hydrogen‐bonded carboxylic acid dimers can be inferred from the proton‐proton distances within the dimers, i.e. (275 ± 5) pm and (295 ± 15) pm for the protons at 12.5 and 10.5 ppm, respectively, which are determined by means of DQ MAS sideband patterns. Both the stability of the hydrogen bonds and the acidity of the protons may be related to the stereochemistry and the conformation of the PMAA chains.
An electroactive polymer with well‐defined oligoanilines in the main chain has been prepared by oxidative coupling polymerization. The detailed characteristics of the polymer were systematically studied by FT‐IR, 1H NMR, GPC and XRD. Its electrochemical behavior was explored with UV‐Vis spectra and cyclic voltammetry showing that its intrinsic electroactivity was maintained and exhibited three distinct reversible oxidative states. Its electrical conductivity is about 3.91 × 10?4 S · cm?1 in HCl‐doped form at room temperature. Furthermore, the polymer displays a dielectric constant of 48.4 and 13.6 at 10 and 1 MHz, respectively, mainly attributed to the improvement in delocalized charge density and electrical conductivity of the polymer by introduction of the conjugated oligoaniline segments.
Poly(3‐hexylthiophene)‐block‐poly(tetrahydrofuran) was synthesized by cationic ring‐opening polymerization of tetrahydrofuran (THF) using a poly(3‐hexylthiophene) macroinitiator. Poly(3‐hexylthiophene) macroinitiator used for the ring‐opening polymerization of THF was synthesized by reacting the hydroxypropyl end‐group with trifluoromethanesulfonic anhydride in the presence of 2,6‐di‐tert‐butylpyridine. 1H NMR spectroscopy and SEC data confirmed the formation of the di‐block copolymers. Field‐effect mobility of poly(3‐hexylthiophene)‐block‐poly(tetrahydrofuran) was measured in a thin‐film transistor configuration and was found to be 0.009 cm2 · V?1 · s?1.
Summary: Poly[ethylene‐co‐(butyl acrylate)‐co‐(carbon monoxide)] (polyEBC) samples, prepared from 13C‐labeled carbon monoxide, were characterized using two dimensional (2D) pulsed field gradient (PFG) 750 MHz NMR spectroscopy. To elucidate the complex mixture of structures present in this terpolymer, 2D 1H/13C‐heteronuclear multiple bond correlation (HMBC) experiments were conducted by selectively exciting the enhanced peaks resulting from 13C‐labeling. High resolution 2D NMR combined with 13C‐labeling of the polymer greatly simplifies the 2D NMR spectra, selectively enhances the weak peaks from low occurrence C‐centered triad structures and aids in their resonance assignments.
1,2,4‐triazole‐functional PGMA polymers have been synthesized and their anhydrous proton‐conducting properties were investigated after doping with phosphoric acid and triflic acid. PGMA was prepared by solution polymerization and then modified with 1H‐1,2,4‐triazole (Tri) and 3‐amino‐1,2,4‐triazole (ATri). FT‐IR, 13C NMR and elemental analysis verify the high immobilization of the triazoles in the polymer chain. Phosphoric‐acid‐doped polymers showed lower Tg and higher proton conductivities. PGMA‐Tri 4 H3PO4 showed a maximum water‐free proton conductivity of approximately 10?2 S · cm?1 while that of PGMA‐ATri 2 H3PO4 was 10?3 S · cm?1. The structure and dynamics of the polymers were explored by 1H MAS and 13C CP‐MAS solid‐state NMR.
3,5‐Bis(bromomethyl)pyridine hydrobromide and 3,5‐bis(bromobutyl)pyridine hydrobromide were synthesized from commercially available 3,5‐lutidine. The poly(N‐alkylation) of these monomers readily yielded new hyperbranched polyelectrolytes. The progress of reaction was followed by 1H NMR. A second‐order kinetic scheme fits the experimental data. Rate constants and activation parameters were determined, showing the higher reactivity of 3,5‐bis(bromomethyl)pyridine hydrobromide. This was explained by the electron‐attractive effect of pyridinium groups on the ? CH2Br end groups. The structures of the hyperbranched poly[3,5‐bis(alkylene)pyridinium]s were investigated by 1H and 13C NMR spectroscopy and a preliminary study of their properties is reported.
We present the synthesis and characterization of the compounds formed in a mixture of vinylphosphonic acid (VPA) and acetic anhydride used for the radical‐initiated VPA polymerization. High‐molecular‐weight PVPA with up to 109 000 g · mol−1 was obtained from the polymerization of a mixture containing VPA, VPAAnh, VPADiAnh and their acetylated derivatives. Relative reactivities of these compounds were estimated. The resulting polymers were characterized by viscosimetry, light scattering and NMR measurements. The complexity of the polymer structure increases with increasing anhydride content in the reaction feed as can be concluded from the 1H, 13C and 31P NMR spectra. This finding is in accordance with a cyclopolymerization mechanism resulting in five‐ and six‐membered anhydride rings within the polymer chain.
Summary: A dipolar filter pulse sequence combined with cross‐polarization‐MAS is applied to characterize the phase distribution, morphology, and spin diffusion within a high‐density polyethylene sample. A new method to obtain quantitative 13C NMR by combining cross‐polarization‐MAS and spin diffusion NMR is presented. The derived crystallinity is consistent with the corresponding crystallinity obtained by 1H NMR.
Illustration of the pulse sequence(s) applied in the present work. 相似文献
A novel stereo‐regular organo‐bridged ladder‐like polymethylsiloxane ( LPMS ) was synthesized by a stepwise coupling polymerization on the basis of an amido H‐bonding‐assisted self‐assembling template. The monomer N,N′‐bis{4‐[3‐(diethoxymethylsilyl)propoxy]‐phenyl}terephthalamide ( M ), prepared by hydrosilylation reaction at high temperature, was hydrolyzed in a dilute solution at a low temperature to form a ladder‐like supramolecular intermediate through amido H‐bonding interactions, which was further condensed to form the polymer LPMS . A combination of techniques including 1H NMR, 29Si NMR, and FT‐IR spectroscopies X‐ray diffraction (XRD), and differential scanning calorimetry (DSC) were used to characterize the titled polymer LPMS , and the results indicate that the polymer possesses an ordered ladder‐like structure.
An ionic conjugated polymer with aromatic functional groups, poly{2‐ethynyl‐N‐[4‐(methylthio)benzylpyridinium bromide]}, was synthesized via the activated polymerization of 2‐ethynylpyridine by using 4‐(methylthio)benzyl bromide without any additional initiator or catalyst. The polymerization proceeded well in polar solvents such as DMF, DMSO, NMP and pyridine, and produced high yields. NMR, IR, and UV‐vis spectroscopy confirmed a conjugated polymer backbone system containing N‐(4‐(methylthio)benzylpyridinium bromide as substituents. The photoluminescence maximum peak of the polymer was located at 508 nm, which corresponds to the photon energy level of 2.44 eV. The cyclovoltammograms of the polymer exhibited an electrochemically stable window in the ?1.32 to 1.92 V region.
The amphiphilic triblock copolymer PLA‐b‐PLL‐b‐MPEG is prepared in three steps through acylation coupling between the terminal amino groups of PLA‐b‐PZLL‐NH2 and carboxyl‐terminal MPEG, followed by the deprotection of amines. The block copolymers are characterized via FT‐IR, 1H NMR, DSC, GPC, and TEM. TEM analysis shows that the triblock polymers can form polymeric micelles in aqueous solution with a homogeneous spherical morphology. The cytotoxicity assay indicates that the final triblock polymer micelles after deprotection show low cytotoxicity against Bel7402 human hepatoma cells. MPEG and PLL were introduced into the main chain of PLA affording a kind of ideal bioabsorbable polymer materials, which is expected to be useful in drug and gene delivery.
A series of poly(2‐alkyl‐6‐phenylphenylene ether)s were prepared by the oxidative polymerization of 2‐alkyl‐6‐phenylphenols. Their dielectric constants were approximately 2.5, whereas it was found that the phenyl group at the 6‐position clearly increased the Q factor of the polymer compared with poly(2,6‐dimethylphenylene ether), PPE. These values were qualitatively predicted from the polarizability and the molar volume calculated by the theoretical analysis of the unit structure at the HF/6‐31G* level.
Monodisperse hyper‐crosslinked polystyrene nanospheres with ultrahigh specific surface area were successfully prepared by emulsifier‐free miniemulsion polymerization and post‐crosslinking. The specific surface area and the total pore volume of hyper‐crosslinked nanospheres were increased with increasing the concentration of vinybenzyl chloride in monomer mixture. The hyper‐crosslinked nanospheres exhibited excellent swelling capacity in thermodynamically good and poor solvent. Furthermore, the nanospheres with specific surface area of 1 223 m2 · g?1 adsorbed 2.13 wt.‐% hydrogen at 163 K/1.5 MPa. Overall, the present study provided a simple method to prepare monodisperse microporous hyper‐crosslinked polymer nanospheres.
The present paper reports the synthesis of π‐conjugated organometallic polymer networks based on poly[2,5‐dioctyloxy‐1,4‐diethynyl‐phenylene‐alt‐2,5,‐bis(2′‐ethylhexyloxy)‐1,4‐phenylene] (EHO‐OPPE), a soluble poly(p‐phenylene ethynylene) (PPE) derivative. The ethynylene moieties of the polymer coordinate to Pt0 centers, which act as conjugated cross‐links. These materials are readily accessible through ligand‐exchange reactions between the linear PPE and Pt(styrene)3. The in‐situ NMR investigation of model reactions of Pt(styrene)3 with diphenylacetylene (DPA) has shown that the ethynylene moieties comprised in the PPE readily coordinate to Pt0 centers under release of the relatively weakly‐bound styrene ligands. Spin‐coating has resulted in cross‐linked films of good optical quality. We also have been able to produce PPE‐Pt‐gels with high solvent content (> 95 wt.‐%). As expected, the coordination of Pt markedly influences the photophysical characteristics of the PPE. The photoluminescence is efficiently quenched, and the absorption maximum in the visible regime experiences a hypsochromic shift.
Ligand‐exchange reaction between EHO‐OPPE and [Pt(PhCH?CH2)3] leading to the target EHO‐OPPE‐Pt0 networks. 相似文献
The polymerization of metal salts of N‐chloroacetyl‐β‐alanine and N‐chloroacetyl‐4‐aminobutyric acid was investigated. The former gives a mixture of polymer and a seven‐membered cyclic compound constituted of glycolic and β‐alanine units, and its reaction proceeds in the solid state. However, liquefaction is observed in the second case giving rise to a polymer with a moderate molecular weight. Condensation kinetics of both sodium and silver salts of N‐chloroacetyl‐β‐alanine have been studied by differential scanning calorimetry. Copolymers of glycolic acid and β‐alanine with a molar ratio of glycolic acid/β‐alanine varying from 0.5 to 1.0 have been synthesized by thermal reaction of co‐precipitated crystals of the sodium salts of chloroacetic acid and N‐chloroacetyl‐β‐alanine. NMR spectroscopy indicates that copolymers tend to have a random distribution. The resulting new poly(ester amide)s have been characterized by spectroscopy and thermal analysis.
DSC heating runs corresponding to different mixtures of the sodium salts of chloroacetic acid and chloroacetyl‐β‐alanine. 相似文献
Summary: The 2,4,6‐tri‐O‐acetyl‐3‐deoxy‐D ‐erythro‐hex‐2‐enono‐1,5‐lactone, briefly Ac‐Gluc‐enlactone (GEL) ( 1 ), is easily synthesized in an one‐step reaction from glucono‐δ‐lactone with good yields. Free radical polymerizations of GEL with vinyl esters with side chain of different length including fatty acids esters were carried out in substance or in solution under various conditions. The structures and chemical compositions of the polymers were established by elemental analysis, FT‐IR‐, 1H‐, and 13C NMR spectroscopy. Copolymerization kinetics were investigated. Characteristic properties of polymers, e.g. molecular weight, optical rotation, and thermal properties are reported. The products are of interest as components in commodities with binding and adhesive properties.
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.
A new two‐dimensional‐conjugated polymer (PBDTT3‐TPA) containing benzodithiophene (BDT) and a side chain isolation comonomer is designed and synthesized. Interestingly, PBDTT3‐TPA is compatible with higher lowest unoccupied molecular level (LUMO) acceptors of indene‐C60 bisadduct (ICBA), and polymer solar cells based on PBDTT3‐TPA/ ICBA show an open‐circuit voltage (VOC) of ca. 0.80 V and a power conversion efficiency of 2.48% under AM1.5G illumination of at 100 mW cm?2. Furthermore, the energy loss in the corresponding fullerene acceptor devices is discussed, and the increase in the observed VOC is explained quantitatively by the up‐shifted LUMO energy of ICBA (0.17 eV) and the reduced saturation current (JSO) in the blends.
Summary: Solid‐state 2H NMR spectroscopy was used to examine the chain dynamics of perdeuterated poly(oxyethylene) (d‐POE) inside α‐cyclodextrin (α‐CD) nanotubes. The nanotubes were prepared by aqueous self‐assembly of α‐CD onto either low‐molecular‐weight (1.5 kg/mol) or high‐molecular‐weight (25.8 kg/mol) monodisperse d‐POE. At a given temperature, POE chain segments exhibit faster dynamics when included inside the CD nanotubes as compared to the bulk. Even at 150 K, when no large‐angle dynamics are detected in bulk POE, evidence for chain motions in the nanotube‐confined POE is observed. The 2H line shapes representing this motion were modeled by a discrete 3‐site jump using a ln‐Gaussian distribution of correlation times. An activation energy of 15 ± 1 kJ/mol was determined and the motion envisioned as gauche defects propagating along the primarily trans chains included within CD nanotubes. As the nanotube length decreased, the jump angle became much less defined and more isotropic motions were observed for POE segments at elevated temperatures (>270 K).
