Polymerizability of Exo‐methylene‐lactide toward vinyl addition and ring opening

This work examines the stereochemical control and polymerizability of exo‐methylene‐lactide (MLA) or (6S)‐3‐methylene‐6‐methyl‐1,4‐dioxane‐2,5‐dione, a chiral monomer derived from l ‐lactide, toward vinyl‐addition and ring‐opening polymerization (ROP) pathways, respectively. Currently, no information on the stereochemistry of the vinyl‐addition polymerization of MLA is known, and the possible ROP pathway is unexplored. Accordingly, this work first investigated the stereochemical control and other characteristics of the radical polymerization of MLA and its copolymerization with an analogous exo‐methylene‐lactone, γ‐methyl‐α‐methylene‐γ‐butyrolactone (MMBL), and di‐methylene‐lactide (DMLA) or 3,6‐dimethylene‐1,4‐dioxane‐2,5‐dione. The MLA homopolymerization produced optically active, but atactic, vinyl‐type polymers having a specific rotation of [α]²³_D = ?42 ± 4°, a high T_g from 229 to 254 °C, and a medium (M_w = 76.3 kg/mol, ? = 1.16) to high (M_w = 358 kg/mol, ? = 2.83) molecular weight, depending on the solvent. The copolymerization of MLA with MMBL afforded copolymers exhibiting enhanced thermal stability, while its copolymerization with DMLA led to cross‐linked polymers. The results obtained from the model reactions designed to probe the possible ROP indicate that the nonpolymerizability of MLA by initiators or catalysts comprising acidic, protic, and/or nucleophilic reagents is due to the high sensitivity of MLA toward such common ROP reagents that trigger decomposition or other types of transformations of MLA forming nonpolymerizable derivatives. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1523–1532     

Kinetics of the ring‐opening metathesis polymerization of a 7‐oxanorbornene derivative by Grubbs' catalyst

The kinetics of the initiation and propagation of the ring‐opening metathesis polymerization of exo,exo‐5,6‐bis(methoxycarbonyl)‐7‐oxabicyclo[2.2.1]hept‐2‐ene catalyzed by Grubbs' catalyst (Cl₂(PCy₃)₂Ru?CHPh) were measured by ultraviolet–visible and ¹H NMR spectroscopy, respectively. Activation parameters for these processes were also determined. Although the ratio of the rate constant of initiation to the rate constant of propagation was determined to be less than 1 for this system, this polymerization showed many of the characteristics of a living system, including low polydispersities. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2125–2131, 2003     

Cationic addition polymerization of 1,4‐dioxene using gacl3 as lewis acid catalyst: Long‐lived species‐mediated polymerization

Effective cationic addition polymerization of 1,4‐dioxene, a six‐membered cyclic olefin with two oxygen atoms adjacent to the double bond, was performed using a simple metal halide catalyst system in dichloromethane. The polymerization was controlled when the reaction was conducted using GaCl₃ in conjunction with an isobutyl vinyl ether–HCl adduct as a cationogen at –78°C to give polymers with predetermined molecular weights and relatively narrow molecular weight distributions. The long‐lived properties of the propagating species were further confirmed by a monomer addition experiment and the analyses of the product polymers by ¹H NMR and MALDI–TOF–MS. Although highly clean propagation proceeded, the apparent rate constant changed during the controlled cationic polymerization of 1,4‐dioxene. The reason for the change was discussed based on polymerization results under various conditions. The obtained poly(1,4‐dioxene) exhibited a very high glass transition temperature (T_g) of 217°C and unique solubility. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Crosslinked polynorbornene particles synthesis by ring‐opening metathesis polymerization in dispersion

This article proposes the first report on the synthesis of nanometric crosslinked polynorbornene particles by ring‐opening metathesis polymerization in dispersion using ruthenium‐based complex (PCy₃)₂Cl₂Ru?CHPh as initiator. Stable but raspberry‐shaped particles were obtained. In this study, a particular attention was paid to the influence of the crosslinker nature and addition mode on reaction kinetics and morphology of the latex particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

One‐pot synthesis of polymeric nanoparticle by ring‐opening metathesis polymerization

Shell‐functionalized polymeric nanoparticle was prepared through the method of polymerization‐induced self‐assembly of block copolymers [poly(2,3‐bis(2‐bromoisobutyryloxymethyl)‐5‐norbornene)‐block‐poly(7‐oxanorborn‐5‐ene‐exo‐exo‐2,3‐dicarboxylic acid dimethyl ester), PBNBE‐b‐PONBDM] via one‐pot ring‐opening metathesis polymerization of 2,3‐bis(2‐bromoisobutyryloxymethyl)‐5‐norbornene (BNBE) and 7‐oxanorborn‐5‐ene‐exo‐exo‐2,3‐dicarboxylic acid dimethyl ester (ONBDM) in a selective solvent. The compositions and the molecular weights of the copolymers were estimated by ¹H‐NMR and gel permeation chromatography. The micelles were characterized by dynamic light scattering, transmission electron micrograph, and atomic force microscopy. The results indicated that the spherical micelles constructed with bromine‐bearing PBNBE shell and PONBDM core were stable and reproducible in toluene. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

In an attempt to introduce monomer sequence control in a growing polynorbornene via ring‐opening metathesis polymerization, we employ dioxepins to efficiently determine the location of the monomers on the macromolecule backbone. Owing to the acid‐labile acetal group, dioxepins allow scission of the polymer at the point of the dioxepin insertion and thus provide an indirect way to determine the monomer location. Additionally, dioxepins are used as spacers in the synthesis of multiblock polynorbornenes that are readily cleavable to afford the individual polynorbornene blocks. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1236–1242     

Novel doubly polymerizable functional norbornene: Its synthesis,reactivity, and macromolecular architectures from a dual cure via ring‐opening metathesis polymerization and radical photopolymerization

A novel doubly polymerizable functional norbornene, 5‐(methacryloyloxyethylamino carboxylmethyl)bicyclo[2.2.1]hept‐2‐ene (NBMOACM), was prepared. The ring‐opening metathesis polymerization (ROMP) of NBMOACM was carried out to prepare polymers with crosslinkable side chains with the Grubbs catalyst. No gel formation occurred during the ROMP of NBMOACM. The ¹H NMR spectrum of poly(NBMOACM) showed broad signals between 5.10 and 5.40 ppm, corresponding to the vinyl protons of the cis and trans double bonds of the ring‐opened polymer. Increasing the ratio of the monomer concentration to the catalyst concentration resulted in the formation of higher molecular weight polymers. Poly(NBMOACM) was incorporated into poly(methyl methacrylate) [poly(MMA)] to produce AB crosslinked materials. These crosslinked materials [1 wt % poly(NBMOACM), 10% weight loss temperature = 300 °C in air] had higher thermal stability than pure poly(MMA) (10% weight loss temperature = 276 °C in air). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6287–6298, 2006     

Frontal polymerization synthesis of starch-grafted hydrogels: Effect of temperature and tube size on propagating front and properties of hydrogels

The frontal polymerization process was used to produce superabsorbent hydrogels based on acrylic acid monomers grafted onto starch. Using a simple test tube which was nonadiabatic and permitted contact with air, the effects of initial temperature and tube size on the propagating front of grafting copolymerization and the properties of hydrogels were explored. The unrestricted access of the reaction mixture to oxygen delayed the formation of self-propagating polymerization front. The ignition time was markedly lengthened with the increasing of tube size attributed to the formation of large amounts of peroxy radicals. The front velocity dependence on initial temperature could be fit to an Arrhenius function with the average apparent activation energy of 24 kJ mol(-1), and on tube size to a function of higher order. The increase of the initial temperature increased the front temperature, which lead to more soluble oligomers and higher degree of crosslinking. The interplay of two opposite effects of oligomer and crosslinking determined the sol and gel content. An increase in tube size had two effects on the propagating front. One was to reduce heat loss. The other effect was to increase the number of escaping gas bubbles. The combined action of the two effects resulted in a maximum value of front temperature, an increase in sol content and a reduction in gel content with tube size. The highest swelling capacity of hydrogels was obtained when the initial temperature or tube size favored a formation of porous microstructure of hydrogels.     

The synthesis and characterization of polyimide homopolymers based on 5(6)‐amino‐1‐(4‐aminophenyl)‐1,3,3‐trimethylindane

The isomeric diamine monomer 5(6)‐amino‐1‐(4‐aminophenyl)‐1,3,3‐trimethylindane (DAPI) was successfully synthesized via the dimerization of α‐methylstyrene followed by nitration and reduction. High molecular weight, soluble polyimides were synthesized via ester–acid solution imidization techniques and had glass‐transition temperature values ranging from 247 to 369 °C. The polymers were soluble in common organic solvents because of the asymmetric and nonplanar nature of DAPI and displayed good short‐term thermal stability by thermogravimetric analysis, as shown by their 5% weight‐loss values above 500 °C in air. The DAPI/(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) polyimide also showed 2‐h thermal stability at 400 °C under nitrogen, despite the partial aliphatic character. Refractive index values as low as 1.571 were observed for DAPI/6FDA, which allows an estimated dielectric constant of 2.47 to be derived. The permeation of O₂ and N₂ was conducted on thin dense films. The bulky, bent, and isomeric nature of DAPI imparted film‐forming membranes that permitted high O₂ permeability. In combination with 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), DAPI had a good combination of O₂ permeability and O₂/N₂ selectivity values of 2.8 Ba and 7.3, respectively. The polymerization method utilized to facilitate the cyclization of DAPI/BTDA to the polyimide affected the final thermal properties of the resulting polymer. The chemical imidization of DAPI/BTDA generated a polyimide with a glass‐transition temperature value of 311 °C and a 5% weight‐loss value in air of 457 °C. However, thermal and ester–acid imidization routes yielded an increase in the thermal properties. The ester–acid solution imidization of DAPI/BTDA produced a polymer glass‐transition temperature value of 333 °C and a 5% weight‐loss value of 525 °C in air. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2840–2854, 2000     

Ruthenium‐based metathesis initiators: Development and use in ring‐opening metathesis polymerization

For many years, olefin metathesis has been a central topic of industrial and academic research because of its great synthetic utility. The employed initiators cover a wide range of compounds, from simple transition‐metal salts to highly sophisticated and well‐defined alkylidene complexes. Currently, ruthenium‐based catalysts are at the center of attention because of their remarkable tolerance toward oxygen, moisture, and numerous functionalities. This article focuses on recent developments in the field of ring‐opening metathesis polymerization using ruthenium‐based catalysts. ruthenium‐based initiators and their applications to the preparation of advanced polymeric materials are briefly reviewed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2895–2916, 2002     

Fast and effective copper(0)‐mediated simultaneous chain‐ and step‐growth radical polymerization at ambient temperature

Vinyl‐conjugated monomer (methyl acrylate, MA) and allyl 2‐bromopropanoate (ABP)‐possessing unconjugated C?C and active C? Br bonds were polymerized via the Cu(0)‐mediated simultaneous chain‐ and step‐growth radical polymerization at ambient temperature using Cu(0) as catalyst, N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand and dimethyl sulfoxide as solvent. The conversion was reached higher than 98% within 20 h. The obtained polymers showed block structure consisting of polyester and vinyl polymer moieties. The Cu(0)‐catalyzed simultaneous chain‐ and step‐growth radical polymerization mechanism was demonstrated by NMR, matrix‐assisted laser desorption ionization time‐of‐flight, and GPC analyses. Furthermore, the obtained copolymers of MA and ABP were further modified with poly(N‐isopropylamide) through radical thiol‐ene “click” chemistry from the terminal double bond. The thermoresponsive behavior of this block copolymer was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3907–3916     

Thio‐bromo “Click,” post‐polymerization strategy for functionalizing ring opening metathesis polymerization (ROMP)‐derived materials

The use of a thio‐bromo click strategy as an efficient postpolymerization tool is described. Norbornene derivatives bearing an α‐bromo ester could be polymerized using Grubbs 2^nd generation initiator to provide α‐bromo ester‐containing homo‐and block copolymers that could be efficiently functionalized through reactions with various thiols. A one‐pot strategy was also used, in which up to four different thiols were reacted simultaneously. This chemistry could also be used as an efficient cross‐linking strategy to form ROMP‐based gels as well as a tool for terminal functionalization of polypropylene‐based oligomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 179–185     

Homo‐ and copolymerization of norbornene and 5‐norbornene‐2‐yl acetate with bis‐(β‐ketonaphthylamino)palladium(II)/B(C6F5)3 catalytic system

The polymerization of norbornene with bis(β‐ketonaphthylamino) palladium(II), Pd{CH₃C(O)CHC[N(naphthyl)]CH₃}₂, in combination with tris(pentafluorophenyl)borane (B(C₆F₅)₃), was investigated by varying the B:Pd(II) molar ratio, monomer concentration, reaction temperature, and time. The catalytic activity was found to reach 2.8 × 10⁴ gPolymer/(molPd^?h) and the obtained polynorbornene (PNBE) was confirmed to be vinyl addition polymer and showed good thermo‐stability (T_dec > 350°C), but exhibited poor solubility in organic solvents due to the relative higher stereo regularity. Pd{CH₃C(O)CHC[N(naphthyl)]CH₃}₂/B(C₆F₅)₃ system is also an active catalyst for copolymerization of norbornene and 5‐norbornene‐2‐yl acetate (NBE‐OCOCH₃) in toluene with moderate yields (in 9.2–36.5% yields) and produces the addition‐type copolymer with relatively high molecular weights (0.96 × 10⁴–2.13 × 10⁴ g/mol). The incorporation of functional group in the copolymer can be controlled up to 0.9–23.5 mol% by varying the NBE‐OCOCH₃ monomer feed ratios from 10 to 90%. The copolymers are proved to be noncrystalline and show good solubility in common organic solvents and excellent thermal stability up to 350°C. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of novel hyperbranched polymer through cationic ring‐opening multibranching polymerization of 2‐hydroxymethyloxetane

The cationic ring‐opening multibranching polymerization of 2‐hydroxymethyloxetane ( 1 ) as a novel latent AB₂‐type monomer was carried out using trifluoromethane sulfonic acid or trifluoroboron diethyl etherate by a slow‐monomer‐addition (SMA) method. The polymer yield of poly‐1 ranged from ca. 58–88%, which increase with the increasing monomer addition time on the SMA method. The absolute molecular weights (M_w,MALLS) and the polydispersities of poly‐1 were in the range of 8,000–43,500 and 1.45–4.53, respectively, which also increased with the increasing monomer addition time. The Mark‐Houwink‐Sakurada exponents α in 0.2 M NaNO₃ aq. were determined to be 0.02–0.25 for poly‐1 , indicating that poly‐1 has compact forms in the solution because of the highly branched structure. The degree of the branching value of poly‐1 , which was calculated by Frey's equation, ranged from ca. 0.50 to 0.58, which increased with the increasing monomer addition time. The steady shear flow of poly‐1 in aqueous solution exhibited a Newtonian behavior with steady shear viscosities independent of the shear rate. The results of the MALLS, NMR, and viscosity measurements indicated that poly‐1 is composed of a highly branched structure, i.e., the hyperbranched poly (2‐hydroxymethyloxetane). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011