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1.
Abraham Chemtob Valrie Hroguez Yves Gnanou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(5):1154-1163
Latex particles based on 1,4‐polybutadiene were synthesized via dispersion ring‐opening metathesis copolymerization of 1,5‐cyclooctadiene with a α‐norbornenyl poly(ethylene oxide) macromonomer. Stable but polydisperse colloidal dispersions in the 50 nm to 10 μm size range were obtained. In this work, particular attention was paid to the effects of the kinetics of copolymerization on the structure of the graft copolymers formed and on the onset of turbidity. Strategies to prepare monodisperse polybutadiene particles were also designed through the growth of a polybutadiene shell from a well‐defined polynorbornene seed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1154–1163, 2004 相似文献
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Anne‐Claire Le Meur Cyril Aymonier Valérie Heroguez 《Journal of polymer science. Part A, Polymer chemistry》2012,50(9):1746-1754
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 相似文献
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Ruthenium‐based metathesis initiators: Development and use in ring‐opening metathesis polymerization
Ulrich Frenzel Oskar Nuyken 《Journal of polymer science. Part A, Polymer chemistry》2002,40(17):2895-2916
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 相似文献
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Liya Zhang Chunmei Song Jiahui Yu Dan Yang Meiran Xie 《Journal of polymer science. Part A, Polymer chemistry》2010,48(22):5231-5238
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 相似文献
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Alvaro Carrillo Ravi S. Kane 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3352-3359
This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl2Ru(CHPh)(PCy3)2] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004 相似文献
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Dafni Moatsou Amit Nagarkar Andreas F. M. Kilbinger Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2016,54(9):1236-1242
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 相似文献
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Zewang You Danyi Gao Ouyue Jin Xiaohua He Meiran Xie 《Journal of polymer science. Part A, Polymer chemistry》2013,51(6):1292-1301
Functional polynorbornenes (PNBEs) containing pyrrolidine moiety and bis(trifluoromethyl)biphenyl side group were synthesized via ring‐opening metathesis polymerization (ROMP), and the microstructure of polymer chain was characterized by NMR spectroscopy. Poly(N‐3,5‐bis(trifluoromethyl)biphenyl‐norbornene‐pyrrolidine) (PTNP) and poly(N‐phenyl‐norbornene‐pyrrolidine) (PPNP) are supposed to have practically trans double bonds and adopt isotactic syn conformation, whereas poly(N‐3,5‐bis(trifluoromethyl)biphenyl‐norbornene‐dicarboximide) (PTNDI) has both trans and cis double bonds and atactic microstructure. PTNP, PTNDI, and PPNP have much different dielectric constants of 20, 7, and 3, respectively, which is attributed to both the polar 3,5‐bis(trifluoromethyl)biphenyl group and the stereoregular chain structure. The existence of rigid pyrrolidine moiety has a positive contribution to form the tactic polymer chain during ROMP. Polymers are highly thermal stable up to ~300 °C. Having good dielectric properties and thermal stability, these functional PNBEs are expected as the potential dielectric material in thin film capacitors. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
9.
Alaa S. Abd‐El‐Aziz Rawda M. Okasha Leslie J. May Jeff Hurd 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):3053-3070
A number of classes of polynorbornenes containing cationic iron moieties within their side chains were prepared via ring‐opening metathesis polymerization with a ruthenium‐based catalyst. The iron‐containing polymers displayed excellent solubility in polar organic solvents. The weight‐average molecular weights of these polymeric materials were estimated to be in the range of 18,000–48,000. Thermogravimetric analysis of these polymers showed two distinct weight losses. The first weight loss was in the range of 204–260 °C and was due to the loss of the metallic moieties, whereas the second weight loss was observed at 368–512 °C and was due to the degradation of the polymer backbone. Cyclic voltammetry studies of the iron‐containing polymers showed that the 18 e? cationic iron centers underwent a reduction to give the neutral 19 e? complexes at half‐wave potential (E1/2) = ?1.105 V. Photolysis of the metallated polymers led to the isolation of the norbornene polymers in very good yields. Differential scanning calorimetry studies showed a sharp increase in the glass‐transition temperatures up to 91 °C when rigid aromatic side chains were incorporated into the norbornene polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3053–3070, 2006 相似文献
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Sutthira Sutthasupa Kayo Terada Fumio Sanda Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2006,44(18):5337-5343
Amino acid‐derived novel norbornene derivatives, N,N′‐(endo‐bicyclo[2.2.1] hept‐5‐en‐2,3‐diyldicarbonyl) bis‐L ‐alanine methyl ester (NBA), N,N′‐(endo‐bicyclo[2.2.1]hept‐5‐en‐2,3‐diyldicarbonyl) bis‐L ‐leucine methyl ester (NBL), N,N′‐(endo‐bicyclo[2.2.1]hept‐5‐en‐2,3‐diyldicarbonyl) bis‐L ‐phenylalanine methyl ester (NBF) were synthesized and polymerized using the Grubbs 2nd generation ruthenium (Ru) catalyst. Although NBA, NBL, and NBF did not undergo homopolymerization, they underwent copolymerization with norbornene (NB) to give the copolymers with Mn ranging from 5200 to 38,100. The maximum incorporation ratio of the amino acid‐based unit was 9%, and the cis contents of the main chain were 54–66%. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5337–5343, 2006 相似文献
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Abraham Chemtob Valrie Hroguez Yves Gnanou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2705-2716
This study critically examines the similarities and differences between poly(ethylene oxide) (PEO) stabilized latices of polynorbornene and polybutadiene. Features such as the kinetics of copolymerization of norbornene and cyclooctadiene with a macromonomer of PEO, the particles' size and morphology, the type of copolymer formed, and the stability of these latices were investigated and the results obtained are considered. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2705–2716, 2004 相似文献
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Gregory S. Constable Alan J. Lesser E. Bryan Coughlin 《Journal of Polymer Science.Polymer Physics》2003,41(12):1323-1333
An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003 相似文献
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Jong Keun Lee Xing Liu Sung Ho Yoon Michael R. Kessler 《Journal of Polymer Science.Polymer Physics》2007,45(14):1771-1780
Dicyclopentadiene (DCPD) and 5‐ethylidene‐2‐norbornene (ENB) and their mixtures were analyzed after ring‐opening metathesis polymerization (ROMP) in the presence of Grubbs catalyst as potential candidate healing agents for self‐healing composite materials using two complementary methods, rotational dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Following isothermal DMA measurements at room temperature (RT = 25 °C) for 120 min, two consecutive dynamic temperature scan experiments were performed for each system. In the first dynamic temperature scans, there was an initial downward peak slightly above RT in the storage modulus versus temperature curve for samples with relatively slower reaction rates (i.e., DCPD and DCPD‐rich mixtures or low catalyst loadings) due to a combination of the glass transition followed by further residual reaction. However, no or negligible downward peaks were observed for the highly reactive ENB and ENB‐rich samples even at much lower catalyst loadings. Implications of the substantial decrease in storage modulus just above RT for the slowly reacting systems are discussed for healing of damage in composite materials at elevated temperatures. The maximum glass transition temperatures (Tg∞) from DMA of the fully cured samples were determined to be approximately 160 °C for DCPD and 120 °C for ENB, decreasing linearly with increased ENB in the blends. The glass transitions and further residual reactions above the glass transitions were confirmed by DSC. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1771–1780, 2007 相似文献
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Toshihiro Otsuki Kohei Goto Zen Komiya 《Journal of polymer science. Part A, Polymer chemistry》2000,38(Z1):4661-4668
New hydrogenated ring‐opening metathesis polymers with excellent thermal and optical properties were developed. These polymers were prepared by the ring‐opening metathesis polymerization of ester‐substituted tetracyclododecene monomers followed by the hydrogenation of the main‐chain double bond. The degree of hydrogenation was an important factor for the thermal stability of the polymers, and as complete hydrogenation as possible was necessary to obtain a thermally stable polymer. The completely hydrogenated ring‐opening polymer derived from 8‐methyl‐8‐methoxycarbonyl‐substituted monomer has a glass‐transition temperature of 171 °C and a 5% weight‐loss temperature of 446 °C. This polymer has excellent thermal and optical properties because of its bulky and unsymmetrical polycyclic structure in the main chain and is an alternative to glass or other transparent polymers such as poly(methyl methacrylate) and polycarbonate resin. This polymer has also been used in a wide variety of applications, such as optical lenses, optical disks, optical films, and optical fiber. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4661–4668, 2000 相似文献
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Upendar Reddy Gandra Santhosh Kumar Podiyanachari Antsar R. Hlil Ihor Kulai Saeed Al‐Meer Mohammed Al‐Hashimi Hassan S. Bazzi 《Journal of polymer science. Part A, Polymer chemistry》2019,57(16):1741-1747
Ring‐opening metathesis polymerization (ROMP) of thioether‐derived oxanorbornene imide ( M1 ) and its copolymerization with various cycloolefin comonomers such as cyclopentene ( M2 ), cyclopent‐3‐en‐1‐ol ( M3 ), cycloheptene ( M4 ), and cyclooctene ( M5 ) using Hoveyda–Grubbs second generation catalyst has been investigated. Polymerizations were performed at two different temperatures (0 and 25 °C) and the obtained functional poly(olefin)s were characterized by nuclear magnetic resonance 1H and 13C (NMR), and infrared spectroscopy as well as size exclusion chromatography, differential scanning calorimetry, and thermogravimetric analysis analyses. Additionally, the dependence of the polymer composition on the reaction temperature and monomer feed was studied with time‐dependent 1H NMR experiments. Copolymerization of M1 with a five‐membered cycloolefin monomer M2 showed relatively low ROMP reactivity irrespective of the reaction conditions in comparison to M3 , M4 , and M5 monomers. In general, the degree of monomer incorporation into poly(olefin)s were determined in the order of M5 > M3 > M4 > M2 , and that sheds light on the effect of cycloolefin ring strain energies in the ruthenium‐alkylidene initiated ROMP. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1741–1747 相似文献
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The radical ring‐opening polymerization (RROP) behavior of the following monomers is reviewed, and the possibility for application to functional materials is described: cyclic disulfide, bicyclobutane, vinylcyclopropane, vinylcyclobutane, vinyloxirane, vinylthiirane, 4‐methylene‐1,3‐dioxolane, cyclic ketene acetal, cyclic arylsulfide, cyclic α‐oxyacrylate, benzocyclobutene, o‐xylylene dimer, exo‐methylene‐substituted spiro orthocarbonate, exo‐methylene‐substituted spiro orthoester, and vinylcyclopropanone cyclic acetal. RROP is a promising candidate for producing a wide variety of environmentally friendly functional polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 265–276, 2001 相似文献
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Joseph A. Paquette Sabastine Ezugwu Vishal Yadav Giovanni Fanchini Joe B. Gilroy 《Journal of polymer science. Part A, Polymer chemistry》2016,54(12):1803-1813
Redox‐active 6‐oxoverdazyl polymers were synthesized via ring‐opening metathesis polymerization (ROMP) and their solution, bulk, and thin‐film properties investigated. Detailed studies of the ROMP method employed confirmed that stable radical polymers with controlled molecular weights and narrow molecular weight distributions (Ð < 1.2) were produced. Thermal gravimetric analysis of a representative example of the title polymers demonstrated stability up to 190 °C, while differential scanning calorimetry studies revealed a glass transition temperature of 152 °C. Comparison of the spectra of 6‐oxoverdazyl monomer 12 and polymer 13 , including FT‐IR, UV‐vis absorption, and electron paramagnetic resonance spectroscopy, was used to confirm the tolerance of the ROMP mechanism for the 6‐oxoverdazyl radical both qualitatively and quantitatively. Cyclic voltammetry studies demonstrated the ambipolar redox properties of polymer 13 (E1/2,ox = 0.25 and E1/2,red = ?1.35 V relative to ferrocene/ferrocenium), which were consistent with those of monomer 12 . The charge transport properties of thin films of polymer 13 were studied before and after a potential of 5 V was applied, revealing a drastic drop in the resistivity from 106?1010 Ω m or more to 1.7 × 104 Ω m and suggesting the potential usefulness of polymer 13 in bistable electronics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1803–1813 相似文献
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Hatice Mutlu Michael A. R. Meier 《Journal of polymer science. Part A, Polymer chemistry》2010,48(24):5899-5906
The ring‐opening metathesis polymerization (ROMP) of fatty acid functionalized norbornenes was explored in the presence of dichloro[1,3‐bis(2,4,6‐trimethylphenyl)‐2‐imidazolidinylidene](benzylidene)bis(3‐bromopyridine)ruthenium(II) ( C3 ) at room temperature. The investigated monomers were derived from fatty acids with different chain lengths (C6, C8, C10, C12, C14, C16, and C18) and can therefore contribute to the development of more sustainable, bio‐based polymeric materials. The polymerizations initiated by C3 proceeded in a living fashion with good initiation efficiency, and thus the synthesis of well‐defined polymers with narrow polydispersities was accomplished. All prepared polymers were fully characterized (GPC, DSC, TGA, NMR) and the results of these investigations are discussed within this contribution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献