Synthesis of polynorbornene‐poly(tert‐butyl acrylate) nanoparticles with original morphologies by tandem ROMP and ATRP in microemulsion

Composite latex particles based on homopolymers and graft‐copolymers composed of polynorbornene (PNB) and poly(tert‐butyl acrylate) (PtBA) were synthesized in microemulsion conditions by simultaneous combination of two distinct methods of polymerization: Ring‐opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Only one commercial compound (first generation Grubbs catalyst) was used to initiate the ROMP of norbornene (NB) and activate the ATRP of tert‐butyl acrylate (tBA). Well‐defined nanoparticles with hydrodynamic diameters smaller than 50 nm were prepared with original morphologies depending on the monomer compositions, the type of combination (polymer blend or graft‐copolymer), and the conditions of microemulsion polymerizations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Novel active ester‐bridged copolynorbornene materials containing terminal functional hydroxyl,amino, methacryloyl,or ammonium groups via ring‐opening metathesis polymerization

Several random and block copolynorbornenes with side chains containing terminal hydroxyl, amino, methacryloyl or ammonium groups were derived from the functional alkyl ester‐containing norbornenes by ring‐opening metathesis polymerization (ROMP). The main chain of ROMP‐type polynorbornene had a more important role for glass‐transition temperature in comparison with vinyl addition polymerization. There is little effect on glass‐transition temperature (about ?39 °C) of polynorbornenes with different length of alkyl side chain. The organosoluble copolynorbornenes with active crosslinkable methylacryloyl side chains derived from functional hydroxyl group were prepared to improve the thermal stability of poly(methyl methacrylate) [decomposition temperature (T_d)^10% = 325 °C in nitrogen] by forming networked AB crosslinked polymer (T = 367 °C in nitrogen). The sizes of nanometer‐scale polymeric micelles of block copolymers having hydrophobic alkyl ester and hydrophilic ammonium groups were measured in the range of 11–25 nm by scanning electron microscopy. These polymeric materials with various functional groups or amphiphilic architectures are accessible by ROMP, whose topology makes them particularly attractive for application potential such as biomedical and photoelectric materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4233–4247, 2005     

Bio‐Based Polyketones by Selective Ring‐Opening Radical Polymerization of α‐Pinene‐Derived Pinocarvone

The most abundant naturally occurring terpene, α‐pinene, which cannot be directly polymerized into high polymers by any polymerization method, was quantitatively converted under visible‐light irradiation into pinocarvone, which possesses a reactive exo methylene group. The bicyclic vinyl ketone was quantitatively polymerized in fluoroalcohols by selective (99 %) ring‐opening radical polymerization of the four‐membered ring, which results in unique polymers containing chiral six‐membered rings with conjugated ketone units in the main chain. These polymers display good thermal properties, optical activities, and contain reactive conjugated ketone units. Reversible addition fragmentation chain transfer (RAFT) polymerization was successfully accomplished by using appropriate trithiocarbonate RAFT agents, enabling the synthesis of thermoplastic elastomers based on controlled macromolecular architectures.     

Controllable ROMP Tacticity by Harnessing the Fluxionality of Stereogenic‐at‐Ruthenium Complexes

Readily accessible and easy‐to‐handle Ru complexes capable of generating all‐Z polynorbornene and polynorbornadiene by ring‐opening metathesis polymerization (ROMP) with controllable selectivity, ranging from ≈50 to ≥95 % syndiotactic, are introduced. It is demonstrated that the rate of non‐metathesis based polytopal isomerization and levels of syndiotacticity may be fine‐tuned by the adjustment of monomer concentration and catalyst's steric and electronic characteristics.     

Molecular Weight Control via Cross Metathesis in Photo‐Redox Mediated Ring‐Opening Metathesis Polymerization

Photo‐redox mediated ring‐opening metathesis polymerization (photo‐ROMP) is an emerging ROMP technique that uses an organic redox mediator and a vinyl ether initiator, in contrast to metal‐based initiators traditionally used in ROMP. The reversibility of the redox‐mediated initiation and propagation steps enable spatiotemporal control over the polymerization. Herein, we explore a simple, inexpensive means of controlling molecular weight, using alpha olefins as chain transfer agents. This method enables access to low molecular weight oligomers, and molecular weights between 1 and 30 kDa can be targeted simply by altering the stoichiometry of the reaction. This method of molecular weight control was then used to synthesize a functionalized norbornene copolymer in a range of molecular weights for specific materials applications.     

A different polynorbornene backbone by combination of two polymer growth pathways: vinylic addition and ring opening via β-C elimination

A new polynorbornene skeleton has been found that contains bicyclic norbornane units and cyclohexenyl methyl linkages. The polymers have been synthesized using a nickel catalyst in the presence of a controlled amount of ligands with low or moderate coordination ability. The backbone structure is the result of a vinylic addition polymerization, via sequential insertions of norbornene into a Ni–C bond (bicyclic units) combined with an unusual ring opening of the norbornene structure by a β-C elimination (cyclohexenyl methyl units) to give a new Ni–C(alkyl) bond that continues the polymerization. The ring opening events are favored when the rate of propagation of the vinylic addition polymerization decreases, and this can be modulated by making the coordination of norbornene to the metal center less favorable using additional ligands.

A new polynorbornene skeleton that contains a mixture of bicyclic norbornane units and cyclohexenylmethyl moieties can be obtained using a nickel catalyst.     

Structural and free‐volume analysis for alkyl‐substituted palladium‐catalyzed poly(norbornene): A combined experimental and Monte Carlo investigation

Increasing the length of an alkyl side chain on a rigid polynorbornene (PNB) backbone is shown to decrease the glass‐transition temperature of the resultant polymer, decrease the density of the bulk polymer, decrease the number and average free‐volume element size present, and decrease the permeability of gases through the polymer. Methyl‐, butyl‐, and hexyl‐substituted PNBs were investigated. Experimental results were compared with predictions based on molecular modeling. By using models that provided good agreement between the experimental and simulated wide‐angle diffraction patterns, the distributions of free‐volume elements were predicted. These predictions clearly indicate that the number of large free‐volume elements decreases as the length of the side chain increases, suggesting that the flexible aliphatic side chains can be largely accommodated within the free volume between the rigid PNB backbones. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 215–233, 2006     

Ring‐Opening Metathesis Polymerization of Biomass‐Derived Levoglucosenol

The readily available cellulose‐derived bicyclic compound levoglucosenol was polymerized through ring‐opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass‐derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High‐molar‐mass polyacetals with apparent weight‐average molar masses of up to 100 kg mol^?1 and dispersities of approximately 2 were produced despite the non‐living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 °C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.     

Syntheses and characterization of functionalized polynorbornene dicarboximides for flexible substrates

In this study, we synthesized polynorbornene (PNB) dicarboximides substituted by monochlorophenyl group (PMCPhNDI) and dichlorophenyl group (PDCPhNDI) via ring‐opening polymerization using a ruthenium catalyst and investigated their thermal, mechanical, and optical properties. We also discussed the performance and application of the functionalized PNB dicarboximide films as flexible substrates for organic light‐emitting devices (OLEDs). The polymer films exhibited good optical transparency with an average transmittance of around 97% in the visible light region and good thermal stability with a 5% degradation temperature of >440°C. The polymers were applied for flexible displays, which were coated on indium tin oxide (ITO) thin films using a radio‐frequency planar magnetron sputtering system with changing the deposition substrate temperatures. A flexible OLED that was fabricated on the ITO‐grown polymer substrates exhibited a performance as comparable to the corresponding ITO‐grown glass substrates. Copyright © 2012 John Wiley & Sons, Ltd.     

Tuning the phase behavior of semicrystalline hydrogenated polynorbornene via epimerization

Hydrogenated polynorbornene (hPN) synthesized by ring‐opening metathesis polymerization (ROMP) exhibits a thermoreversible change in crystal polymorph at a temperature T _cc below its melting point, T _m. The polymorphic transition corresponds to a sharp increase in rotational disorder around the chain axis as the temperature is increased above T _cc. Saturation of ROMP polynorbornene (PN) to hPN can be achieved through both catalytic and noncatalytic approaches. Here, three different hydrogenation routes were employed on the same precursor polymer: catalytic routes over either supported Pd⁰ or a Ni/Al complex, and noncatalytic saturation with diimide. The different hydrogenation routes result in hPNs with varying degrees of epimerization of the cyclopentylene ring (from cis to trans); these epimerized units are included in the hPN crystals. The crystal structure of the rotationally ordered hPN polymorph, observed below T _cc, changes sharply at low levels of epimerization and then is weakly influenced by further increases in trans content. The stability of the rotationally ordered hPN polymorph decreases with increasing epimerization, as reflected in a reduction of T _cc from 134 °C to 92 °C at 22% epimerization. T _cc is less affected by epimerization than by the inclusion of a similar content of 5‐methylnorbornene units, reflecting the smaller size of the trans defect. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1188–1195     

Characterization of polyethylene with partially random chlorine substitution

A series of chlorine‐containing polymers were prepared by ring‐opening metathesis polymerization (ROMP) followed by hydrogenation. This synthesis route was chosen specifically so that chain microstructures would be obtained that resembled copolymers of ethylene and vinyl chloride. The chlorine content was varied by the copolymerization of 5‐chlorocyclooctene and cyclooctene. Differential scanning calorimetry, light microscopy, tapping‐mode atomic force microscopy, wide‐angle X‐ray diffraction (WAXD), and density were employed to characterize the polymers. The copolymers had certain restrictions on the length of the methylene sequence between substituted carbons, however, ROMP copolymerization introduced enough variation in the methylene sequence length that model copolymers with the equivalent of 14 mol % vinyl chloride or less closely resembled random copolymers of ethylene and vinyl chloride. These materials organized as spherulites and exhibited the orthorhombic crystal form. Constraints on the placement of chlorine atoms strongly affected the crystallization of polymers with more than the equivalent of 14 mol % vinyl chloride. More regular chlorine substitution along the polyethylene chain translated into better ordered crystal structures with sharp melting peaks. The granular morphology of these materials at ambient temperature was interpreted as fringed micellar crystals. The WAXD patterns provided definitive evidence that chains in the fringed micelle took the hexagonal crystal form. The lower density hexagonal form facilitated the crystallization of short ethylene sequences and accommodated chlorine atoms more easily than the orthorhombic form. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2062–2070, 2003     

Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal‐catalyzed polymerizations

A norbornene monomer bearing cyclic carbonate moiety ( NB‐CC ) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon dioxide under atmospheric pressure, which was efficiently catalyzed by lithium bromide. NB‐CC underwent the ring‐opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene), of which side chain inherited the cyclic carbonate moiety from the monomer without any deterioration. The same ROMP system was applicable to the copolymerization of NB‐CC and 5‐butyl‐2‐norbornene ( BNB ), which afforded the corresponding copolymer with a composition ratio same as a feed ratio. In addition, by using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, the copolymerization of NB‐CC and BNC proceeded successfully in a vinyl addition polymerization mode to give the corresponding poly(norbornene) having CC moiety in the side chain. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3896–3902, 2010     

SynthesisofNorbornene－EthyleneBlockCopolymerbythePolymerizationMechanismConversion￣＊

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Shape memory effects of polynorbornene modified by in-situ reactive thermoplastic polyurethane

Shape memory polymers (SMPs) based on polynorbornene (PNB) was prepared and modified by In-situ reactive thermoplastic polyurethane (TPU). Analysis shows that the TPU formed in PNB matrix slightly decreases T_g of PNB from 24.1 to ca. 23.4, which is beneficial to study the shape memory performance at room temperature. A small amount of TPU can be uniformly dispersed in PNB matrix to form interpenetrating network structure, which can significantly toughen and strengthen PNB. Simultaneously, the interpenetrating network can replace the physical entanglement of part of the PNB, increase the free volume among the molecular chains of PNB, make shape fixing easier, and reduce energy consumption in overcoming friction during the recovery process. Therefore, the PNB/TPU composites have higher shape fixing ratio and recovery ratio than PNB. When the content of TPU in PNB matrix is lower, the interpenetrating network of chain entanglements is formed with no phase separation; therefore, the improvement of shape memory performance is remarkable.     

Controlled vinyl‐type polymerization of norbornene with a Nickel(II) diphosphinoamine/methylaluminoxane catalytic system

A novel nickel‐based complex coordinated with an asymmetric diphosphinoamine ligand was synthesized and fully characterized. Single crystals of good quality were also obtained, and the solid‐state structure of the complex was studied via X‐rays diffraction. The catalytic activity of this Ni(II) complex in the vinyl‐type polymerization of norbornene was studied with methylaluminoxane (MAO) as the cocatalyst/activator. The influence of the reaction time, the equivalents of MAO used, and the concentration of the monomer on: (i) the activity of the catalytic system; (ii) the isolated yield of the polymer; and (iii) the molecular weight and molecular weight distribution of the polymer were investigated. The isolated polynorbornene (PNB) yields are significantly higher compared with those reported for other similar nickel‐based systems. The as‐obtained PNBs are characterized by high molecular weights and relatively narrow and monomodal molecular weight distributions (amongst the narrowest reported in the literature). The linear dependence of the molecular weight of the obtained PNB on the concentration of norbornene points toward a controlled polymerization reaction. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5241–5250, 2009     

Ring‐opening metathesis polymerization as a route to controlled copolymers of ethylene and polar monomers: Synthesis of ethylene–vinyl chloride‐like copolymers

A series of ethylene–vinyl chloride‐like copolymers were prepared by ring‐opening metathesis polymerization (ROMP). The route to these materials included the bulk polymerization of 5‐chlorocyclooctene and 5,6‐dichlorocyclooctene with the first‐generation Grubbs' catalyst, followed by diimide hydrogenation of the resulting unsaturated polymers. In addition, the amount of chlorine in these materials was varied by the copolymerization of 5‐chlorocyclooctene with cyclooctene. These materials were fully characterized by NMR (¹H and ¹³C), gel permeation chromatography, and Fourier transform infrared spectroscopy. Finally, hydroboration was carried out on the ROMP product of 5‐chlorocyclooctene to yield a polymer, which was effectively a vinyl alcohol–vinyl chloride–ethylene terpolymer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2107–2116, 2003     

Living ring opening metathesis polymerization of mesogenic norbornene derivatives

A new class of SCLCPs was prepared by polymerizing mesogenic norbornene derivatives using Mo(CHCMe₂R)(N-2,6-C₆H₃-i-Pr₂)(O-t-Bu)₂ (R = CH₃ or Ph). Monomers based on norbornene ring systems were chosen because the rings are highly strained and therefore yield irreversible polymerizations. The Mo-alkylidene initiators were chosen because they initiate norbornene derivatives relatively fast and quantitatively, and provide stable chain ends which have low reactivity to both the internal double bonds of the polymer backbone and the functional groups present in the monomers. The apparent absence of termination and transfer reactions in ROMP results in polymerizations which appear to be living, and the fast initiation and irreversible chain growth leads to polymers with narrow molecular weight distributions in which the degree of polymerization is controlled by the ratio of monomer to initiator used. The resulting well-defined polymers were used to determine the most basic structure-property relationships of this new class of SCLCPs. The thermotropic behavior of both terminally attached and laterally attached SCLCPs based on polynorbornene backbones becomes independent of molecular weight at approximately 25 repeat units. In addition, polydispersity was found to have no effect on the breadth of nematic phase transitions in the terminally attached polymers, with the transition temperature determined simply by the number average degree of polymerization.     

Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions

Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single‐turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring‐opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components.     

Ring Opening Metathesis Polymerization of Bicyclic α,β‐Unsaturated Anhydrides for Ready‐to‐be‐grafted Polymers Having Tailored pH‐Responsive Degradability

Polymers having α,β‐unsaturated anhydrides as repeating units were synthesized by ring opening metathesis polymerization (ROMP). The anhydride moieties were ready‐to‐be‐grafted with amines to form acid‐labile cis‐α,β‐unsaturated acid amide linkages. The pH‐responsive reversible de‐grafting can be controlled by changing the intramolecular accessibility between acid and amide groups. The alendronate‐grafted ROMP polymers showed distinct pH‐dependent cytotoxicity according to the anhydride structures.     

Application of carbon arc‐generated Mo‐ and W‐based catalyst systems to the ROMP of norbornene

This study focuses on the application of the carbon arc‐generated molybdenum‐ and tungsten‐based catalyst systems, MoCl₅? C and WCl₆? C, to effect ring‐opening metathesis polymerization (ROMP) of bicyclo[2.2.1]hept‐2‐ene (norbornene). The results are compared with those previously obtained by the electrochemically generated MoCl₅? ē? Al? CH₂Cl₂ and WCl₆? ē? Al? CH₂Cl₂ systems. The polymer products are characterized using ¹H and ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermo gravimetric analysis. According to NMR spectra analyses, the molybdenum‐based catalyst system produced polynorbornene with ca 48% cis structure whereas tungsten system produced ca 56% cis structure polynorbornene and in both cases the polynorbornene had a blocky distribution. Copyright © 2009 John Wiley & Sons, Ltd.