Polycarbonate/polyethylene random block copolymers (RBCs) have been produced using olefin metathesis catalysis in a process termed segment interchange metathesis. An olefin metathesis catalyst tolerant of polar functionality was added to reagent polycarbonate and polyethylene polymers which contained internal unsaturated carbon–carbon bonds. Subsequent metathesis occurred, segmenting the reagent polymers, resulting in RBCs. The block copolymers self-assembled into microphase structures which persisted into the melt state as determined by small angle X-ray scattering (SAXS).
Summary: The success of metathesis chemistry techniques has sparked a tremendous interest in polymer and material chemistry. This contribution provides an overview of the state of the art in ring opening metathesis polymerisation (ROMP). It is intended to provide the reader with useful information on the interplay of initiators, monomers, and reaction conditions, thus aiding polymer chemists to utilise the ROMP toolbox. Prominent and illustrative examples from current research are given in the article.
Olefin isomerization side reactions that occur during ADMET polymerizations were studied by preparing polyesters via ADMET and subsequently degrading these polyesters via transesterification with methanol. The resulting diesters, representing the repeating units of the previously prepared polyesters, were then analyzed by GC‐MS. This strategy allowed quantification of the amount of olefin isomerization that took place during ADMET polymerization with second generation ruthenium metathesis catalysts. In a second step, it was shown that the addition of benzoquinone to the polymerization mixture prevented the olefin isomerization. Therefore, second generation ruthenium metathesis catalysts may now be used for the preparation of well‐defined polymers via ADMET with very little isomerization, which was not possible before.
Ring‐opening metathesis polymerization (ROMP) was used for the synthesis of monolithic capillary columns with inner diameters of 200 µm. The resulting polymeric monoliths were characterized by inverse size‐exclusion chromatography (ISEC). Surface functionalization was carried out in situ using 2‐(N,N‐dimethylaminoethyl)norborn‐5‐ene‐2‐ylcarboxylic amide ( 1 ). The resulting functionalized monoliths were successfully used in anion‐exchange chromatography of oligodeoxynucleotides.
An amphiphilic biodegradable polymer, poly(aspartic acid‐co‐lactic acid) (PAL), was synthesized by simply heating a mixture of aspartic acid (Asp) and L ‐lactide without additional catalysts or solvents. The unique branched architecture comprising succinimide units and lactic acid units was confirmed by IR and NMR spectroscopy. A copolymer of sodium aspartate and lactic acid (PALNa) was prepared by reacting PAL with an aqueous sodium hydroxide solution. The PAL was soluble in many organic solvents, while the PALNa was soluble in methanol and water. The hydrolytic degradation behavior of PAL varied with the copolymer composition. A higher Asp content resulted in a faster molecular weight decrease, and introducing glycolic acid units accelerated the degradation rate.
The stability of weak fluorine bonds in homogeneous catalyst is studied at the ab initio level for an arylpyridine post‐metallocene complex. The Ti···F···Hβ interaction scheme, involving the agostic bond with titanium and the H‐bond with an Hβ in the growing chain, is found to be the the most stable one. A possible optimal overlap involving the fluorine lone pairs is proposed. This three‐center interaction could play a role in the inhibition of Hβ transfer to the metal or to the monomer in the termination reactions.
Perfectly alternating copolymers can be synthesised by reacting diacrylates with terminal dienes using alternating diene metathesis polycondensation (ALTMET). This novel method is very versatile and allows preparation of diverse structures of polymers, including main‐chain liquid crystalline polymers.
Main‐chain liquid crystalline polymer obtained by ALTMET. 相似文献
Summary: An electrografting technique has been combined with ring‐opening metathesis polymerization (ROMP). Poly(allyl methacrylate) chains have been chemisorbed onto steel and carbon plates under an appropriate cathodic potential in N,N‐dimethylformamide. The allyl moieties have been converted into Ru catalysts active in ROMP of norbornene and its derivatives. Initiation of ROMP from the surface is an efficient strategy to prepare strongly adhering coatings of tunable thickness and hydrophilic/hydrophobic balance, depending on the norbornene derivative polymerized at the surface.
The hydrophobicity of the polymer coating may be controlled by hydrolysis of the polynorbornene derivative. 相似文献
Poly(para‐phenylene vinylene) (PPV) and its derivatives are important semiconducting polymers for organic electronics. Herein, an alkene metathesis approach to obtain PPVs is reported. Tri(iso propyl)silyl‐substituted norbornadienes are employed as solubilizing agents. As PPV precursors divinylbenzene is used for acyclic diene metathesis and paracyclophane diene for a ring‐opening metathesis polymerization‐type approach. The resulting polymers are analyzed by gel permeation chromatography (GPC), UV‐vis, fluorescence, and nuclear magnetic resonance (NMR) spectroscopy. All of the polymers show good solubility in common solvents.
A nickel α‐diimine catalyst was used for Grignard metathesis (GRIM) polymerization of 2,5‐dibromo 3‐hexylthiophene and 2‐bromo‐5‐iodo‐3‐hexylthiophene monomers. GRIM polymerization of 2‐bromo‐5‐iodo‐3‐hexylthiophene generated regioregular polymers with molecular weights ranging from 3 000 to 12 000 g · mol−1. The nickel α‐diimine catalyst was also successfully used for the GRIM polymerization of a bulky benzodithiophene monomer.
High–throughput‐screening (HTS) tools and methods are used more and more, especially in industry, in the search for new, selective organometallic catalysts. In most cases, the approach is, in essence, empirical, and the strategy is to increase the number of experiments that can be run at a given place in a given time. Highly miniaturized, parallel reaction setups have been implemented for the rapid assessment of whether novel catalysts resulting from the structural amplification of a basic framework are “good” or “bad” with respect to the properties of interest, and, depending on the response, worthy of a subsequent, more‐careful evaluation. In this article, we demonstrate that it is possible to utilize these state‐of‐the‐art HTS platforms with a different strategy: the rapid generation of reliable kinetic data for mechanistic studies in view of a thorough understanding and rational catalyst design. Ziegler–Natta‐type catalytic olefin polymerization will be used throughout as an example.
Self‐doped sulfonated polyaniline (PSA) has been synthesized on the surface of micellar nanoparticles made from positively charged surfactants by biocatalysis. The conformation forced by the electrostatic charge interactions between the positively charged micelle and the negatively charged PSA increases the conductivity of the PSA by three orders of magnitude. The pure PSA recovered from ion exchange, however, shows quite similar electrical properties compared with sulfonated polyanilines reported earlier. The increased conductivity of PSA complexes is as a result of the increased charge carrier concentration caused by a certain conformational locking.
Polycondensation of 1‐(2‐pyrimidinyl)pyrrole with 2,7‐dibromo‐9,9‐dioctylfluorene via Ru‐catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2‐pyrimidinyl substituent, into the pyrrole monomer induces ortho‐metalation and provides the site‐selective direct arylation polycondensation at the α‐position of pyrrole unit without the protection of β‐position. The removal of 2‐pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer.
Summary: A chiral, regioregular poly[3‐(4‐alkoxyphenyl)thiophene] has been prepared and studied. Films prepared by fast evaporation of the solvent, consist of random‐coils, while films prepared by slow evaporation are composed of chirally aggregated, coplanar strands. Heat treatment transforms the random‐coils into aggregated films via an intermediate state, which was characterized as chiral, coplanar, unaggregated polymer strands.
Overview of the possible aggregation processes. 相似文献
Summary: A model study with four norbornene derivatives with different groups connecting a functional unit to the norbornene reveals that the “anchor groups” influence the polymerisation rate constants of ring opening metathesis (ROM) polymerisations. Consequently, polydispersities and molecular weights are affected. The observed effects are explained by different tendencies of the anchor groups to coordinate to the ruthenium centre during the resting state of the propagation.
A functionalised monomer where F is the functional unit, S is a spacer, A is an anchor group and P is the polymerisable group. 相似文献
