In polymer chemistry, ringopening polymerization rop is a form of chaingrowth. Corresponding authors a department of chemistry, college of natural sciences, seoul national university, seoul 08826, korea email. The authors received no specific funding for this work. We have been interested in polymerization of cyclic olefins using transition metal catalysts. The ideas of catalyst matching for different monomers are discussed, and particular emphasis is given to the steric requirements of the catalysts. Ringopening polymerization of cyclosiloxanes request pdf. Significantly improved catalytic activity and monomer adaptability for the ring. Introduction rcm crossmetathesis romp the nobel prize in chemistry 2005. Polymers free fulltext ringopening polymerizationan. Handbook of ringopening polymerization request pdf. Switching from controlled ringopening polymerization. Abstractto obtain more insight in the ringopening polymerization of lactones, complex formation of the initiators tetraphenyltin, stannous octoate. Ring opening polymerization of lactide for the synthesis of poly lactic acid reported by keith a.
Background ringopening metathesis polymerization romp is one of the most used and studied chain growth polymerizations. Precise placement of single monomer units in living ring. Precursor routes to conducting polymers from the ringopening. Ringopening polymerization of lactones and lactides. Organocatalysts typically used for the ringopening polymerization rop of cyclic ester monomers are applied to a thiolactone.
Ring opening metathesis polymerization romp catalytic process. Synthesis of photocleavable polymethyl methacrylateblockdlactide via atomtransfer radical polymerization and ringopening polymerization hong li,1 sahas rathi,2 elizabeth s. Schmidt spontaneous alternating copolymerization of cyclic phosphorus compounds via phosphonium zwitterion intermediates takeo saegusa. Hydrogen bond mediated organocatalysts provide a robust and controllable synthetic route to well defined polyesters and polycarbonates. Stereoselective photoredox ringopening polymerization of. The increasing interest in the ring opening metathesis polymerization romp of norbornene derivatives containing functional groups has developed in recent years. However, the monomers of ring opening polymerization are not as readily available as the monomers of step polymerization. Sep 21, 2011 hamitou a, jerome r, hubert aj, teyssie p 1973 a new catalyst for the ringopening polymerization of lactones to polyesters. Ringopening polymerization can also proceed via free radical polymerization. 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. Sterner,2 hui zhao,3 shaw ling hsu,2 patrick theato,3 yongming zhang,1 e. 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. Molecular weight control via cross metathesis in photo.
The driving force of the reaction is relief of ring strain in cyclic olefins e. Switching from controlled ringopening polymerization crop. Online monitoring of ringopening metathesis polymerization of cyclooctadiene and a functionalized norbornene alina m. Synthesis of polypeptides by ringopening polymerization of a. Efficacy of process is dependent on catalyst polymer is also dependent on monomer structure potential monomers 1. 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. Bidentate phenoxides as ideal activating ligands for living. Ringopening metathesis polymerization romp is a type of olefin metathesis chaingrowth polymerization. Synthesis of functionalizable and degradable polymers by ringopening metathesis polymerization joshua m. The ringopening polymerization of oxepan2,7dione was initiated with 1 cationic initiators such as alcl3 and bf3. In the absence of an hbond donor, a nucleophilic polymerization mechanism is proposed. The use of tbup 2 instead of the tbup 4 superbase slows down the polymerization rate. Polymers with designed macromolecular architecture kajsa m. Bryan coughlin2 1school of chemistry and chemical engineering, shanghai jiaotong university, shanghai 200240, peoples republic of china.
A wide variety of materials can be prepared in this manner, including polyamides, aliphatic polyesters, silicones, polyalkylenes via ringopening metathesis polymerization, and epoxide. An external file that holds a picture, illustration, etc. The most recent modification on the polymer matrix is based on using ring opening polymerization of the silorane molecules. Despite the decreased ability of thioesters and thiols versus esters and alcohols to hbond, hbonding organocatalystsa thiourea in combination with. Ring opening polymerization of lactide for the synthesis. Fully degradable thioesterfunctional homo and alternating. Most largescale commercial processes rely on the former while some fine chemical syntheses rely on the. The general mechanism for anionic ringopening polymerization. The concepts discussed therein are again referred to throughout the following chapters. Photomediated ringopening metathesis polymerization. The molecular weight of ring opening polymerization depends on conversion and the monomer. Improved reactivity in the ringopening polymerization of.
Synthesis of polypeptides by ring opening polymerization of aamino acid ncarboxyanhydrides jianjun cheng and timothy j. Online monitoring of ringopening metathesis polymerization. Request pdf handbook of ringopening polymerization this comprehensive, truly onestop reference discusses monomers, methods, stereochemistry. Pla is produced from renewable resources such as corn and. Differential scanning calorimetry dsc and in situ ftir have been used to investigate. The use of transition metals to control reactivity has been. The first is based on the polymerization of a low molar ratio of. Pdf thermodynamics of cationic ringopening polymerization. Recent developments in ringopening polymerization of. Ring opening polymerization an overview sciencedirect.
A naphthoxazine containing a latent catalyst based on. 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. Synthesis of photocleavable polymethyl methacrylateblockdlactide viaatomtransfer radical polymerization and ringopening polymerization hong li,1 sahas rathi,2 elizabeth s. Ringopening polymerization the ringopening polymerization consists of both chain and step polymerization as far as kinetics and mechanisms are concerned. Ring opening polymerization of lactide for the synthesis of. S p are strongly affected by solvents of different polarity figure figure3 3. Polarized functional group is represented by xy, where the atom x usually a carbon atom. The first highmolecular weight polymers m n up to 10 5 with a repeating unit were prepared by rop as early as in 1976. Examples of polymers prepared by ringopening polymerization 1.
Synthesis of polydisulfides with narrow molecular weight. B rush polymers have received considerable attention in recent years due to their unique, dense and extended wormlike macromolecular architecture, in comparison with traditional. The reactive center can be radical, anionic or cationic. 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. Two experiments are frequently employed to follow the cationic polymerization of heterocyclic monomers.
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. Ring opening metathesis polymerization romp is a type of olefin metathesis chaingrowth polymerization. Catalytic ringopening polymerization of epoxides, anhydrides. 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. Kinetic and mechanistic study of heterogeneous double. Kiessling a valuable approach for creating synthetic polymers is the ringopening metathesis polymerization romp. Ring opening polymerization the ring opening polymerization consists of both chain and step polymerization as far as kinetics and mechanisms are concerned. The reactivity of ti3oclonep9 in the ringopening polymerization rop of. The method of ringopening metathesis polymerization romp is discussed in chapter 2. Dec 12, 2016 the ring strain the enthalpy of polymerization. A polythioester by organocatalytic ringopening polymerization. Smart polymeric materials by ringopening metathesis polymerization. New polymers by ring opening polymerization of norbornene derivatives with polar substituents s.
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. The ring opening polymerization of oxepan2,7dione was initiated with 1 cationic initiators such as alcl3 and bf3. The method of ring opening metathesis polymerization romp is discussed in chapter 2. Precise control of the location and sequence of monomers in a narrowdisperse polymer chain remains a significant challenge. Catalytic ring opening copolymerization of epoxides and alicyclic anhydrides provides a new and attractive. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. Ringopening metathesis polymerization romp is a powerful and broadly applicable method to synthesize polymeric materials with unique architectures and useful functions. Various kinds of transition metal complex are known to catalyze the ring opening metathesis polymerization. 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. The cationic ring opening polymerization of 2oxazolines has also been shown to have living characteristics if initiated with triflate derivatives.
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. Ringopening polymerization rop is an important technique for the preparation of high mw condensation polymers without the formation of volatile byproducts. 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. Traditionally, the determination of kinetic parameters from dsc measurements is accomplished with isothermal data. Mechanisms and thermodynamics of ring opening polymerization were established in the 1950s. Precursor routes to conducting polymers from the ring. Stereoselective photoredox ringopening polymerization of o. The ring opening polymerization has the advantage over step polymerization for high molecular weight polymer. T1 chain transfer in the ringopening metathesis polymerization of cyclooctadiene using discrete metal alkylidenes. Nov 23, 2017 by combining this tandem nhc photogenerator system with metathesis inactive rucl 2 p. Lithium hexamethyldisilazide initiated superfast ring.
Ring opening polymerization rop is an important technique for the preparation of high mw condensation polymers without the formation of volatile byproducts. Alcoholpromoted ringopening alkyne metathesis polymeri. Catalytic ring opening polymerization of epoxides, anhydrides and co. 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. 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. Lecture notes synthesis of polymers chemical engineering. Ring opening polymerization can proceed via radical, anionic, or. 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.
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. 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. 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. The reaction produces living polymers with low polydispersities and predictable molecular weights. Ringopening metathesis polymerization with ultrafast. Synthesis of photocleavable polymethyl methacrylate. Igarashi polymerization of aryl cyclic sulfonium zwitterions d. The radical ring opening polymerization rrop of thionolactones provides access to thioester backbonefunctional copolymers but has, to date, only been demonstrated on acrylic copolymers. We activate the wellknown alkyne metathesis precatalyst, ntbuar 3 mo cch 2 ch 3, with phenolic ligands that have.
The ideas of catalyst matching for different monomers are discussed, and particular emphasis is. The polynieri7ntion has been carried out either in bulk without solvent or in. As expected, all initiators gave excellent control of pblg mws. A fast and living ringopening polymerization rop of. Herein, the thionolactone dibenzoc,eoxepane5thione dot was subjected to azobisisobutyronitrile aibninitiated freeradical homopolymerization, which produced a thioesterfunctional homopolymer with a. Cationic ringopening polymerizations are also nucleophilic substitution reactions. Recognition specificity of neoglycopolymers prepared by ring.
N2 the ringopening metathesis polymerization of cyclooctadiene cod in the presence of a difunctional chain transfer agent cta was investigated. Deming abstract this chapter summarizes methods for the synthesis of polypeptides by ring opening polymerization. In 1976, the first commercial use of romp was used to synthesize. University of birmingham organocatalytic ringopening.
The rop of pdl proceeds to high conversion not only at 80 c in bulk but also at room temperature and in dilute solution. In situ generated rutheniumarene catalyst for photoactivated. The ringopening metathesis polymerization romp of cyclic olefins was discovered in. Fast and selective organocatalytic ringopening polymerization by. The overarching theme of my work pertains to the development of catalytic systems to affect the organocatalyzed ringopening polymerization of cyclic esters and carbonates. 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. Oh as part of its monomer structure has been synthesized through a simple onepot reaction at room temperature. Ring opening polymerization an overview sciencedirect topics. Synthesis of polypeptides by ringopening polymerization. Pdf cyclic oligomers in the cationic ring opening polymerization. H p may serve as a measure of the ring strain and the contribution of the polymerization entropy.
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. However, organocatalysts tend to be either highly selective or highly active. Two important polymerization fashions have been studied, ring opening metathesis polymerization and coordination insertion polymerization. Photomediated ring opening metathesis polymerization oleg davydovich literature seminar november 8, 2018 ring opening metathesis polymerization romp is a widelyused technqiue to produce bulk amounts of polymer.
Rutheniuminitated ring opening metathesis polymerization of. Bidentate phenoxides as ideal activating ligands for. Opening polymerization introductionanionic ringopening polymerizationcationic ringopening. The chemical structure of this naphthoxazine monomer has been confirmed by 1h nmr, c nmr, and ftir and its purity by elemental analysis. Organocatalytic ringopening polymerization of llactide in bulk. Alcoholpromoted ringopening alkyne metathesis polymeri zation daniel w.