Search results for "Note"

Towards storage-stable high-content recycled tyre rubber modified bitumen

2018

The addition of crumb rubber particles as bitumen modifier can be currently considered as a well-established alternative to conventional polymers for bitumen modification. However, Recycle Tyre Rubber (RTR) modified binders still present drawbacks such as poor mix workability and hot storage stability. Within this study the authors try unlocking the full potential of devulcanised tyre rubber-heavy oils blend, named Liquid Rubber (LR), by exploring the possibility of tailoring recycled polymer modified bitumen with unconventional high-content of RTR and designed to overcome the above mentioned technological problems of RTR modified bitumen while keeping its advantages. Results show that LR-b…

Glass transition of polymer melts: Test of theoretical concepts by computer simulation.

2003

Abstract Polymers are good glass formers and allow for the study of melts near the glass transition in (meta-)stable equilibrium. Theories of the glass transition imply such an equilibrium and can, hence, be tested by the study of polymer melts. After a brief summary of the basic experimental facts about the glass transition in polymers, the main theoretical concepts are reviewed: mode coupling theory (MCT), entropy theory, free-volume theory, the idea of a growing length describing the size of cooperative regions, etc. Then, two basic coarse-grained models of polymers are described, which have been developed aiming at a test of these concepts. The first model is the bond-fluctuation model …

Combining Orthogonal Reactive Groups in Block Copolymers for Functional Nanoparticle Synthesis in a Single Step.

2017

We report on the synthesis of polysarcosine-block-poly(S-alkylsulfonyl)-l-cysteine block copolymers, which combine three orthogonal addressable groups enabling site-specific conversion of all reactive entities in a single step. The polymers are readily obtained by ring-opening polymerization (ROP) of corresponding α-amino acid N-carboxyanhydrides (NCAs) combining azide and amine chain ends, with a thiol-reactive S-alkylsulfonyl cysteine. Functional group interconversion of chain ends using strain-promoted azide–alkyne cycloaddition (SPAAC) and activated ester chemistry with NHS- and DBCO-containing fluorescent dyes could be readily performed without affecting the cross-linking reaction betw…

Orthogonally reactive amino acids and end groups in NCA polymerization

2017

Functional amino acids whose reactivity is compatible with the polymerization of α-amino acid-N-carboxyanhydrides (NCAs) have received a lot of attention in recent years. The appeal of these reactive monomers lies in the fact that the resulting polymers can be easily modified in one controlled post-polymerization step, leading to a variety of polypeptidic materials like helical non-natural polycations or glycopeptides. This review highlights recent developments in the field and focuses on the different reactive groups like alkynes, alkenes, azides, chlorides and S-alkylsulfonyls. Furthermore, the modifications after polymerization are discussed, pointing out advantages and challenges. Besid…

Crystalline CO2 -Based Aliphatic Polycarbonates with Long Alkyl Chains

2018

Carbon dioxide (CO2 ) is an easily available, renewable carbon source and can be utilized as a comonomer in the catalytic ring-opening polymerization of epoxides to generate aliphatic polycarbonates. Dodecyl glycidyl ether (DDGE) is copolymerized with CO2 and propylene oxide (PO) to obtain aliphatic poly(dodecyl glycidyl ether carbonate) and poly(propylene carbonate-co-dodecyl glycidyl ether carbonate) copolymers, respectively. The polymerization proceeds at 30 °C and high CO2 pressure utilizing the established binary catalytic system (R,R)-Co(salen)Cl/[PPN]Cl. The copolymers with varying DDGE:PO ratios are characterized via NMR, FT-IR spectroscopy, and SEC, exhibiting high molecular weight…

Microstructured Reactors for Polymer Synthesis: A Renaissance of Continuous Flow Processes for Tailor-Made Macromolecules?

2008

Organic synthesis in microfluidic devices has attracted increasing interest in recent years. However, little efforts had been undertaken to exploit this novel technology for polymer chemistry until several recent studies demonstrated the interesting potential of microreactors for the synthesis and modification of polymers. In fact, anionic polymerizations in continuous capillary flow-tube systems were established already in 1962 in pioneering work by Szwarc. Subsequent work focused on detailed kinetic analyses in such reactors. The present article explores different current strategies developed by several research groups to realize bulk and solution polymerizations using continuous flow mic…

New Perspectives of HPMA-based Copolymers Derived by Post-Polymerization Modification

2014

Poly[N-(2-hydroxypropyl) methacrylamide] (HPMA) was one of the first polymers applied as polymer drug conjugate in the clinics. Since then many attempts have been made to expand the functionality of HPMA-based copolymers from advanced synthetic pathways to multiple biomedical applications. This Feature Article highlights multifunctional HPMA based copolymers prepared by controlled radical polymerization and subsequent post-polymerization modification of activated ester precursor polymers via aminolysis. This approach combines precise control of the polymer's microstructure (molecular weight, dispersity, block copolymer formation, end group functionalization) with an easy introduction of var…

1996

The major new developments in electron crystallography and high resolution imaging of organic molecules are discussed. The aim is to show that the recent rapid advances in computer technology have made it possible to analyze molecules at a level or resolution which was impossible less than a decade ago, thus bringing the concept of molecular design to produce specific physical properties much nearer to realization

Poly(ethylene glycol) with Multiple Aldehyde Functionalities Opens up a Rich and Versatile Post-Polymerization Chemistry

2019

Two novel epoxide monomers 3,3-dimethoxy-propanyl glycidyl ether (DMPGE) and 3,3-dimethoxy-2,2-dimethylpropanyl glycidyl ether (DDPGE) were developed for the introduction of multiple aldehyde functionalities into the poly(ethylene glycol) (PEG) backbone. The acetal protecting group for the aldehyde functionality is stable against the harsh, basic conditions of the anionic ring-opening polymerization. Both monomers could be homopolymerized as well as copolymerized randomly with ethylene oxide (EO) in a controlled fashion. Copolymers with molecular weights (Mn) in the range of 4500–20100 g/mol and low dispersity (Mw/Mn) between 1.06 and 1.14 were obtained. The polymers were characterized by s…

“Clickable PEG” via anionic copolymerization of ethylene oxide and glycidyl propargyl ether

2017

A straight forward synthesis of poly(ethylene glycol) (PEG) with multiple alkyne groups distributed along the polymer chain is introduced. Direct access to clickable PEG is achieved by the monomer-activated anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) with glycidyl propargyl ether (GPgE). Notably for successful polymerization no protection of the alkyne unit is required owing to the mild reaction conditions. Defined PEG-co-PGPgE and PGPgE (co)polymers with PDIs of 1.18–1.60 and molecular weights of Mn = 3000–9500 g mol−1 were prepared. In situ1H NMR kinetic studies revealed remarkably disparate reactivity ratios of rEO = 14.8 and rGPgE = 0.076, representing a pronounc…