Novel routes to polyelectrolytes and reactive polymers via ROMP

Schitter, R; Jocham, Daniel; Stelzer, Franz; Moszner, Nobert; Völkel, Th.

doi:10.1002/1097-4628(20001003)78:1<47::aid-app80>3.3.co;2-c

Cited by 10 publications

(13 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The intermediate alcohol and the desired acrylate were fully characterized and their structures confirmed by 1 H NMR, 13 C NMR and FTIR spectroscopies and high-resolution mass spectrometry (HRMS, in the case of the final acrylate) (see experimental and supporting information). The synthesis and (co)polymerization of (meth) acrylic (oxa)norbornene derivatives has been reported previously 58 although have not, to the best of our knowledge, been employed in a synthetic approach as described herein. It is important to note that while C contains two C]C bonds (the acrylic species and the non-activated C]C bond in the bicyclic ring structure) it is only the former that is susceptible to thiol-Michael addition while the internal, ROMP active, ring C]C bond remains intact under such reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

et al. 2012

View full text Add to dashboard Cite

The nucleophile initiated thiol-Michael reaction of a wide range of mono and multifunctional thiols with a novel acrylic exo-7-oxanorbornene is described. We highlight how this process affords ready access to a large library of thioether-based substrates in a quick and convenient fashion. New substrates containing, for example, ester, fluoro, and siloxy functionality polymerized in a controlled fashion with Grubbs' first generation (G1) catalyst, RuCl 2 (PCy 3 ) 2 CHPh, yielding homopolymers with controlled, predetermined molecular weights and polydispersity indices in the range 1.10-1.31. Other examples containing -OH (alcohol, diols, sugars) and certain heterocyclic functionality could only be polymerized to high conversion in a controlled manner with the Grubbs' third generation catalyst, RuCl 2 (3-BrPy) 2 (ImMesH 2 )CHPh. Examples of copolymers with statistical and block architectures were also prepared yielding well-defined materials with controlled molecular weights and narrow, unimodal molecular weight distributions. Efficient, sequential post-polymerization modification of an AB diblock copolymer bearing protected alkyne and protected sugar functionality afforded access to additional new block copolymers including amphiphilic species as well as a common material susceptible to Cu(I)-catalyzed alkyne-azide coupling. Finally, we show that the common, and key, acrylic functional exo-7-oxanorbornene substrate can, if desired, be directly (co)polymerized with the Grubbs' G1 catalyst yielding (co)polymers containing electron-deficient ene functional groups that can be modified post-polymerization.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Indeed, the ROMP of methacrylate containing monomers has been previously reported. 58 While not investigated in detail, the direct homo-and copolymerization of C was demonstrated. (Co)Polymerizations were performed with the G1 catalyst for a target molecular weight of 10,000.…”

Section: Resultsmentioning

confidence: 99%

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

et al. 2012

View full text Add to dashboard Cite

show abstract

“…[136][137][138][139][140][141][142] However, some functional groups such as hydroxyl and carboxylic group will do harm to the reactivity of ROMP catalyst. 143 As a result, PNB with these groups should be obtained via alternative ways. For example, it is well known that Schrock or Grubbs's catalysts have high tolerance of various functional groups such as ethers, esters, amides, amines, and sulfides.…”

Section: Effect Of Specific Interactions On Rheological Propertiesmentioning

confidence: 99%

“…It is reported that carboxylic acid group will reduce the reactivity of ROMP catalyst. 143 As a result, PNB with carboxylic acid group cannot be obtained directly from ROMP of 5-norbornene-2-carboxylic acid. A suitable protection group was needed to protect the carboxylic acid group.…”

Section: Synthesis Of Hydrogenated Polynorbornene With Carboxylic Acimentioning

confidence: 99%

Rheology of Miscible Polymer Blends with Hydrogen Bonding

Yang

2008

Macromolecules

View full text Add to dashboard Cite

Poly(4-vinylphenol) (PVPh) was blended with four different polymers: poly(vinyl methyl ether) (PVME), poly(vinyl acetate) (PVAc), poly(2-vinylpyridine) (P2VP), and poly(4-vinylpyridine) (P4VP) by solvent casting. The miscibility of these four PVPhbased blend systems was investigated using differential scanning calorimetry (DSC) and the composition-dependent glass transition temperature (T g) was predicted by a thermodynamic theory. The hydrogen bonds between phenolic group in PVPh and ether group, carbonyl group or pyridine group was confirmed by Fourier transform infrared (FTIR) spectroscopy. The fraction of hydrogen bonds was calculated by the Coleman-Graf-Painter association model. Linear dynamic viscoelasticity of four PVPh-based miscible polymer blends with hydrogen bonding was investigated. Emphasis was placed on investigating how the linear dynamic viscoelasticity of miscible polymer blends with specific interaction might be different from that of miscible polymer blends without specific interaction. We have found that an application of time-temperature superposition (TTS) to the PVPh-based miscible blends with intermolecular hydrogen bonding is warranted even when the difference in the component glass transition temperatures is as large as about 200 °C, while TTS fails for miscible polymer blends without specific interactions. On the basis of such an observation, we have concluded that hydrogen bonding suppressed concentration fluctuations in PVPh-based miscible blends. It has been found that both the intra-association (self-association

show abstract

“…Early attempts by Harrison and Feast19 to polymerize the norbornene dicarboxylic acid monomer (using ROMP with transition metal salts in aqueous media) led to broad polydispersities and yielded only low molecular weights. Later, other groups used the popular ruthenium‐based catalysis developed by Grubbs to obtain the desired poly( exo,exo ‐5‐norbornene‐2,3‐dicarboxylic acid) or one of its stereoisomers with reasonably narrow polydispersities and good molecular weight control 11, 20, 21. However, they were using protection–deprotection chemistry, which added further steps and thus cost to the polymer synthesis.…”

Section: Introductionmentioning

confidence: 99%

Water‐soluble polymers from acid‐functionalized norbornenes

Lienkamp

Kins

Alfred

et al. 2009

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

Unprotected exo,exo-5-norbornene-2,3-dicarboxylic acid and exo,exo-7-oxa-5-norbornene-2,3-dicarboxylic acid were polymerized via ring-opening metathesis polymerization. This reaction yielded polymers with molecular weights (M n from GPC) ranging from 31 to 242 kg/mol and polydispersity indices between 1.05 and 1.12, using Grubbs' third generation catalyst. The water solubility as a function of pH value of the polymers was investigated by dynamic light scattering (DLS). DLS and acid-base titration revealed that the oxanorbornene polymer was water soluble over a wider pH range than its norbornene analog.

show abstract

Novel routes to polyelectrolytes and reactive polymers via ROMP

Cited by 10 publications

References 0 publications

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

Rheology of Miscible Polymer Blends with Hydrogen Bonding

Water‐soluble polymers from acid‐functionalized norbornenes

Contact Info

Product

Resources

About