Synthesis of Single-stranded Polynorbornene with Pendant Group Bearing Benzenedicarboxaldehyde and Long Alkyl Chain

An unprecedented single-stranded polynorbornene with the pendant group containing benzenedicarboxaldehyde and a long alkyl chain（12） was synthesized by ring-open metathesis polymerization（ROMP） of the corresponding monomer（11）,which was obtained via the esterification of two crucial intermediates,namely,2-hexadecyloxy-5-hydroxymethyl-1,3-benzenedicarboxaldehyde（7,obtained via 6 steps） and 4-（4-aza-tricyclo[5.2.1.0 2.6 ]-dec-8en-4-yl）benzoic acid（10）.The target compound and all the intermediates were characterized by infrared（IR）,1 H NMR and high resolution mass spectroscopy（HRMS） analysis.

Non-conjugated Polynorbornene Hosts with High Triplet Energy Levels for Solution-processed Narrowband Blue OLEDs

Three polymer hosts(namely PNB-tBuCz,PNB-Ac,PNB-TAc)containing non-conjugated polynorbornene(PNB)backbone and hole-transporting arylamine segments(carbazole,acridan and dendritic teracridan)in side chains are developed for solution-processed narrowband blue organic light-emitting diodes(OLEDs).It is found that the non-conjugated polynorbornenes can keep high triplet energy(ET)levels in range of 3.12-3.20 eV by interrupting the conjugation of repeating units,making them capable as host materials for blue emitters.Meanwhile,by increasing the electron-donating capability of side chain arylamine from carbazole to acridan and dendritic teracridan,the highest occupied molecular orbital(HOMO)levels for the polymer hosts are elevated from-5.50 eV to-5.11 eV,beneficial for reducing the hole injection barrier from anode to emissive layer.As a result,solution-processed OLEDs employing polynorbornenes with dendritic teracridan side chain(PNB-TAc)as host and boron,selenium,nitrogen-containing multiple resonance thermally activated delayed fluorescence emitter as dopant reveal efficient narrowband blue electroluminescence with emission peak at 474 nm,full-width at half maximum of 30 nm,together with maximum external quantum efficiency of 20.2%,representing the state-of-the-art device efficiency for solution-processed OLEDs with narrowband blue emission.

Ni(acac)_(2)Mediated Vinyl Polymerization of Norbornene in the Presence of Bulky Salicylaldiminate Ligands:An Effective Strategy to Access Soluble Polynorbornenes

Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives.Nevertheless,for such catalytic systems,insoluble polynorbornene(PNB)products are often produced which hampers their further detailed characterizations,such as molecular weights,polydispersities,stereoregularities,etc.In this work,we surprisingly found that for a traditional Ni(acac)_(2)/MAO system that was previously reported to give insoluble PNBs,incorporation of highly bulk salicylaldiminate ligands could significantly improve the solubility of the PNBs in common organic solvents,which allowed for subsequent thorough detailed analysis of the polymer products.Moreover,it was also observed that high-temperature polymerization was beneficial for further improving the PNB’s solubilities due to the decreased molecular weights and stereoregularities.Different ligand skeletons and ligand equivalents were also investigated to give a comprehensive view of their influences on the polymers’solubilities,and based on these results,a plausible mechanism that caused such a big difference was tentatively proposed.

Optically Active Nucleobase-Functionalized Polynorbornenes Mimicking Double-Helix DNA

The development of synthetic polymers that mimic the double-stranded helical structure of DNA is a fascinating topic in polymer science.In this study,we designed and synthesized two chiral norbornene monomers containing adenine and thymine,which were mixed to form a hydrogen-bonding complementary complex,by which a ring-opening metathesis polymerization(ROMP)was performed.High-resolution transmission electron microscopy(HRTEM)undoubtedly showed the self-assembly of the optically active complementary nucleobasefunctionalized polynorbornenes into a double helix.Computer simulations and a two-dimensional nuclear Overhauser effect spectroscopy(2DNOESY)experiment showed that the doublestranded helical polynorbornene was derived from a copolymer of alternating adenine and thymine units.

Polymerization of Norbornene via an Iron-Based Complex/MAO Catalytic System

Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.

Synthesis of Cobalt Containing Block Copolymers Via Ring Opening Metathesis Polymerizastion (ROMP)

In order to realize a metal containing nano-structure, a block-copolymer containing alkynyl groups in one block was designed and synthesized by living ring opening metathesis polymerization (ROMP) technique. The newly developed bis-3-bromopyridine complex of Grubbs catalyst was employed in the series of polymerization and it yielded the desired polymers with great molecular weight control and narrow polydispersities. The characteristics of the block copolymers were investigated by gel permeation chromatography, H- and 13H- NMR spectroscopy. Complexation of the alkynyl group containing block copolymers by treatment with dicobalt octacarbonyl occurred smoothly in 5 min at room temperature. GPC analysis before and after cobalt complexation indicated a significant increase of the hydrodynamic volume. AFM images of the films before and after the complexation also showed a noticeable change in its morphology where grain sizes become smaller and more regular upon complexation.

Synthesis of New Polymer Ionomers via Ring-Opening Metathesis Polymerization

The N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide (2a) and N-phenyl-exo-endo-nor-bornene-5,6-dicarboximide (2b) monomers were synthesized and polymerized via ring-opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine) benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II). Both catalysts were used to synthesize random and block high molecular weight copolymers which were further hydrogenated using a Wilkinson’s catalyst. Then, the saturated copolymers were modified by reacting with sodium 4-hydroxybenzene-sulfonate dihydrate to generate new ionomers with fluoro-sulfonic acid pendant groups.