Various kinds of transition metal complex are known to catalyze the ring opening metathesis polymerization. Romp is an emerging romp technique that uses an organic redox mediator and a vinyl ether initiator, in contrast to metal. The initiation and propagation mechanism is similar to that observed for thf and has been widely used to prepare block copolymers and chainendfunctionalized materials. Our strategy uses selective and quantitative single additions of cyclopropene cpe derivatives to precisely place functional moieties at desired locations along a polymer chain during the living ringopening metathesis polymerization romp of norbornenes nbes. Cationic ringopening polymerizations are also nucleophilic substitution reactions. Deming abstract this chapter summarizes methods for the synthesis of polypeptides by ring opening polymerization. However, the monomers of ring opening polymerization are not as readily available as the monomers of step polymerization. The ring opening polymerization of oxepan2,7dione was initiated with 1 cationic initiators such as alcl3 and bf3. The use of transition metals to control reactivity has been.
Lecture notes synthesis of polymers chemical engineering. In polymer chemistry, ringopening polymerization rop is a form of chaingrowth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer see figure. Ringopening polymerization can also proceed via free radical polymerization. The use of tbup 2 instead of the tbup 4 superbase slows down the polymerization rate.
Stereoselective photoredox ringopening polymerization of o. Polymers free fulltext ringopening polymerizationan. Two important polymerization fashions have been studied, ring opening metathesis polymerization and coordination insertion polymerization. Improved reactivity in the ringopening polymerization of. The overarching theme of my work pertains to the development of catalytic systems to affect the organocatalyzed ringopening polymerization of cyclic esters and carbonates. Dec 12, 2016 the ring strain the enthalpy of polymerization. Lithium hexamethyldisilazide initiated superfast ring. Background ringopening metathesis polymerization romp is one of the most used and studied chain growth polymerizations. Traditionally, the determination of kinetic parameters from dsc measurements is accomplished with isothermal data. Most largescale commercial processes rely on the former while some fine chemical syntheses rely on the. The driving force of the reaction is relief of ring strain in cyclic olefins e. Most of ringopening polymerizations are very rapid and involve cyclic compounds by ionic mechanisms in the presence of strong acids or bases when water and alcohols are excluded. Switching from controlled ringopening polymerization.
Ring opening polymerization can proceed via radical, anionic, or. The concepts discussed therein are again referred to throughout the following chapters. Recent developments in ringopening polymerization of. Recognition specificity of neoglycopolymers prepared by ring. Cc must be in a strained ring system romp no strain romp 100% conversion far from equilibrium cyclooctane cyclobutane romp 100% conversion cyclopentane not as. Photomediated ringopening metathesis polymerization. Significantly improved catalytic activity and monomer adaptability for the ring. In polymer chemistry, ringopening polymerization rop is a form of chaingrowth. The reaction produces living polymers with low polydispersities and predictable molecular weights. Introduction rcm crossmetathesis romp the nobel prize in chemistry 2005. Ring opening metathesis polymerization romp catalytic process. Fully degradable thioesterfunctional homo and alternating. Sterner,2 hui zhao,3 shaw ling hsu,2 patrick theato,3 yongming zhang,1 e. Synthesis of photocleavable polymethyl methacrylate.
Igarashi polymerization of aryl cyclic sulfonium zwitterions d. The method of ringopening metathesis polymerization romp is discussed in chapter 2. In 1976, the first commercial use of romp was used to synthesize. In situ generated rutheniumarene catalyst for photoactivated. H p may serve as a measure of the ring strain and the contribution of the polymerization entropy. Bidentate phenoxides as ideal activating ligands for. The increasing interest in the ring opening metathesis polymerization romp of norbornene derivatives containing functional groups has developed in recent years. From the previous study on ring opening insertion metathesis polymerization roimp, we found that norbornene was a good comonomer, allowing to efficient insertion or chain transfer with diacrylates to yield a,balternating copolymers scheme 1. Two experiments are frequently employed to follow the cationic polymerization of heterocyclic monomers. Sep 21, 2011 hamitou a, jerome r, hubert aj, teyssie p 1973 a new catalyst for the ringopening polymerization of lactones to polyesters.
Photomediated ringopening metathesis polymerization oleg davydovich literature seminar november 8, 2018 ringopening metathesis polymerization romp is a widelyused technqiue to produce bulk amounts of polymer. As expected, all initiators gave excellent control of pblg mws. T1 chain transfer in the ringopening metathesis polymerization of cyclooctadiene using discrete metal alkylidenes. Ringopening polymerization rop is, together w ith chain radical and ionic polymerization and condensation polymerization, one of the three paths to the polymers that are so important to life. A fast and living ringopening polymerization rop of. Catalytic ringopening copolymerization of epoxides and alicyclic anhydrides provides a new and attractive. Precise control of the location and sequence of monomers in a narrowdisperse polymer chain remains a significant challenge. Online monitoring of ringopening metathesis polymerization. The first is based on the polymerization of a low molar ratio of. Polarized functional group is represented by xy, where the atom x usually a carbon atom. Ringopening polymerization rop is an important technique for the preparation of high mw condensation polymers without the formation of volatile byproducts.
Polyglycidols of tunable degree of branching db have been synthesized via ringopening multibranching polymerization rombp of glycidol in the absence of any initiators using heterogeneous double metal cyanide dmc catalysts. The ringopening metathesis polymerization romp of cyclic olefins was discovered in. Abstractto obtain more insight in the ringopening polymerization of lactones, complex formation of the initiators tetraphenyltin, stannous octoate. Handbook of ringopening polymerization request pdf. Herein, the thionolactone dibenzoc,eoxepane5thione dot was subjected to azobisisobutyronitrile aibninitiated freeradical homopolymerization, which produced a thioesterfunctional homopolymer with a. Alcoholpromoted ringopening alkyne metathesis polymeri zation daniel w. Ringopening polymerization of cyclosiloxanes request pdf.
Pdf cyclic oligomers in the cationic ring opening polymerization. Opening polymerization introductionanionic ringopening polymerizationcationic ringopening. A wide variety of materials can be prepared in this manner, including polyamides, aliphatic polyesters, silicones, polyalkylenes via ring opening metathesis polymerization, and epoxide. A variety of heterogeneous and homogeneous catalysts have been developed. Polymerization sulfonated allylic lactone radical polymerization to form a polyester allows for introduction of functional groups into backbone sulfur, as opposed to n or o, allows for less chain transfer due to h abstraction along the chain phelan, et al. Ring opening polymerization rop is, together w ith chain radical and ionic polymerization and condensation polymerization, one of the three paths to the polymers that are so important to life.
The reactivity of ti3oclonep9 in the ringopening polymerization rop of. We activate the wellknown alkyne metathesis precatalyst, ntbuar 3 mo cch 2 ch 3, with phenolic ligands that have. Examples of polymers prepared by ringopening polymerization 1. Synthesis of polypeptides by ringopening polymerization. Ring opening polymerization rop is an important technique for the preparation of high mw condensation polymers without the formation of volatile byproducts. Mechanisms and thermodynamics of ring opening polymerization were established in the 1950s. Ringopening polymerization the ringopening polymerization consists of both chain and step polymerization as far as kinetics and mechanisms are concerned. B rush polymers have received considerable attention in recent years due to their unique, dense and extended wormlike macromolecular architecture, in comparison with traditional. Bidentate phenoxides as ideal activating ligands for living. S p are strongly affected by solvents of different polarity figure figure3 3. An external file that holds a picture, illustration, etc. Pla is produced from renewable resources such as corn and. The molecular weight of ring opening polymerization depends on conversion and the monomer. The ring opening polymerization has the advantage over step polymerization for high molecular weight polymer.
Synthesis of polydisulfides with narrow molecular weight. Request pdf handbook of ringopening polymerization this comprehensive, truly onestop reference discusses monomers, methods, stereochemistry. Andrew marvell centre for medieval and early modern studies archaeology and landscapes studies research centre wetland archaeology and environments research centre blaydes maritime centre centre for applied research and evaluation centre for british politics centre for city and regional studies centre for criminology and criminal justice centre for end of life studies centre for european. A polythioester by organocatalytic ringopening polymerization. New polymers by ring opening polymerization of norbornene derivatives with polar substituents s. Kinetic and mechanistic study of heterogeneous double. Most of ring opening polymerizations are very rapid and involve cyclic compounds by ionic mechanisms in the presence of strong acids or bases when water and alcohols are excluded. Synthesis of photocleavable polymethyl methacrylateblockdlactide via atomtransfer radical polymerization and ringopening polymerization hong li,1 sahas rathi,2 elizabeth s. Ring opening polymerization the ring opening polymerization consists of both chain and step polymerization as far as kinetics and mechanisms are concerned. The rop of pdl proceeds to high conversion not only at 80 c in bulk but also at room temperature and in dilute solution.
Synthesis of polypeptides by ring opening polymerization of aamino acid ncarboxyanhydrides jianjun cheng and timothy j. The reactive center can be radical, anionic or cationic. The general mechanism for anionic ringopening polymerization. In the absence of an hbond donor, a nucleophilic polymerization mechanism is proposed.
A naphthoxazine containing a latent catalyst based on. Stereoselective photoredox ringopening polymerization of. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. We have been interested in polymerization of cyclic olefins using transition metal catalysts. The chemical structure of this naphthoxazine monomer has been confirmed by 1h nmr, c nmr, and ftir and its purity by elemental analysis. Catalytic ring opening polymerization of epoxides, anhydrides and co. University of birmingham organocatalytic ringopening. These monomers open their molecular structures with local volumetric expansion and this may partly or totally compensate for volumetric shrinkage from cc or similar polymerization. Pdf thermodynamics of cationic ringopening polymerization.
A wide variety of materials can be prepared in this manner, including polyamides, aliphatic polyesters, silicones, polyalkylenes via ringopening metathesis polymerization, and epoxide. Porter date 2 march 2006 introduction poly lactic acid pla shows promise as a valuable alternative to petroleumbased polymers for uses as plastics, fibers, and coatings. Kiessling a valuable approach for creating synthetic polymers is the ringopening metathesis polymerization romp. Hydrogen bond mediated organocatalysts provide a robust and controllable synthetic route to well defined polyesters and polycarbonates. The authors received no specific funding for this work. Request pdf ringopening polymerization of cyclosiloxanes for over 50 years this reaction has been extensively used in industry and in chemical laboratories as the basic method of the. Steigerwald, and colin nuckolls in contrast to the widespread adoption of olefin ringopening metathesis polymerization, there are few reported examples of ringopening alkyne metathesis polymerization.
Switching from controlled ringopening polymerization crop. Ring opening polymerization of lactide for the synthesis. The ideas of catalyst matching for different monomers are discussed, and particular emphasis is. Ringopening polymerization of lactones and lactides. Precursor routes to conducting polymers from the ringopening. Ringopening metathesis polymerization with ultrafast. Stridsberg abstract this thesis summarizes the development of new catalyst systems for ringopening polymerization and their use in the production of macromolecules with advanced architecture. Molecular weight control via cross metathesis in photo. The first highmolecular weight polymers m n up to 10 5 with a repeating unit were prepared by rop as early as in 1976.
Corresponding authors a department of chemistry, college of natural sciences, seoul national university, seoul 08826, korea email. Ring opening polymerization of lactide for the synthesis of. Ringopening metathesis polymerization romp is a powerful and broadly applicable method to synthesize polymeric materials with unique architectures and useful functions. N2 the ringopening metathesis polymerization of cyclooctadiene cod in the presence of a difunctional chain transfer agent cta was investigated. Schmidt spontaneous alternating copolymerization of cyclic phosphorus compounds via phosphonium zwitterion intermediates takeo saegusa. Jun 14, 2017 investigation of the parameters of the ball.
Precise placement of single monomer units in living ring. Catalytic ringopening polymerization of epoxides, anhydrides. Precursor routes to conducting polymers from the ring. The cationic ring opening polymerization of 2oxazolines has also been shown to have living characteristics if initiated with triflate derivatives. The ideas of catalyst matching for different monomers are discussed, and particular emphasis is given to the steric requirements of the catalysts. Ring opening polymerization an overview sciencedirect topics. Alcoholpromoted ringopening alkyne metathesis polymeri. Synthesis of photocleavable polymethyl methacrylateblockdlactide viaatomtransfer radical polymerization and ringopening polymerization hong li,1 sahas rathi,2 elizabeth s. Rutheniuminitated ring opening metathesis polymerization of. Bryan coughlin2 1school of chemistry and chemical engineering, shanghai jiaotong university, shanghai 200240, peoples republic of china. Rcm ring closing metathesis rom ring opening metathesis romp ring opening metathesis polymerization admet acyclic diene metathesis. New polymers by ringopening polymerization of norbornene derivatives with polar substituents s. Synthesis of polypeptides by ringopening polymerization of a.
Ring opening metathesis polymerization romp is a type of olefin metathesis chaingrowth polymerization. Differential scanning calorimetry dsc and in situ ftir have been used to investigate. Synthesis of functionalizable and degradable polymers by ringopening metathesis polymerization joshua m. Despite the decreased ability of thioesters and thiols versus esters and alcohols to hbond, hbonding organocatalystsa thiourea in combination with. Online monitoring of ringopening metathesis polymerization of cyclooctadiene and a functionalized norbornene alina m. An industrial application is the production of nylon6. Organocatalytic ringopening polymerization of llactide in bulk. The most recent modification on the polymer matrix is based on using ring opening polymerization of the silorane molecules. Smart polymeric materials by ringopening metathesis polymerization.
Ring opening polymerization of lactide for the synthesis of poly lactic acid reported by keith a. Catalytic ring opening copolymerization of epoxides and alicyclic anhydrides provides a new and attractive. The radical ring opening polymerization rrop of thionolactones provides access to thioester backbonefunctional copolymers but has, to date, only been demonstrated on acrylic copolymers. Steigerwald, and colin nuckolls in contrast to the widespread adoption of olefin ring opening metathesis polymerization, there are few reported examples of ring opening alkyne metathesis polymerization. Efficacy of process is dependent on catalyst polymer is also dependent on monomer structure potential monomers 1. The ringopening polymerization of oxepan2,7dione was initiated with 1 cationic initiators such as alcl3 and bf3. Polymers with designed macromolecular architecture kajsa m. Organocatalysts typically used for the ringopening polymerization rop of cyclic ester monomers are applied to a thiolactone. Oh as part of its monomer structure has been synthesized through a simple onepot reaction at room temperature. The polynieri7ntion has been carried out either in bulk without solvent or in. Ringopening metathesis polymerization romp is a type of olefin metathesis chaingrowth polymerization.