Photo-liberated amines for N-carboxyanhydride (PLANCA) ring-opening polymerization

2021 ◽  
Author(s):  
Sofia L. Goodrich ◽  
Megan R. Hill ◽  
Rebecca A. Olson ◽  
Brent S. Sumerlin
Keyword(s):  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Molecular Weights ◽  
Block Copolypeptides

Photo-liberated amines for N-carboxyanhydride (PLANCA) ring-opening polymerization affords narrow molecular weights, chain-end retention, and the formation of block copolypeptides.

Anionic Ring-Opening Polymerization Simulations for Hyperbranched Polyglycerols with Defined Molecular Weights

2013 ◽  
Vol 46 (21) ◽  
pp. 8458-8466 ◽  
Author(s):  
Florian Paulus ◽  
Maximilian E. R. Weiss ◽  
Dirk Steinhilber ◽  
Anatoly N. Nikitin ◽  
Christof Schütte ◽  
...  
Keyword(s):  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Molecular Weights ◽  
Anionic Ring

scholarly journals Synthesis and crossover reaction of TEMPO containing block copolymer via ROMP

2010 ◽  
Vol 6 ◽  
Author(s):  
Olubummo Adekunle ◽  
Susanne Tanner ◽  
Wolfgang H Binder
Keyword(s):  
Dicarboxylic Acid ◽  
Ring Opening ◽  
Laser Desorption ◽  
Ring Opening Polymerization ◽  
Ionization Mass ◽  
Laser Desorption Ionization ◽  
Block Copolymerization ◽  
Molecular Weights ◽  
Ionization Mass Spectroscopy ◽  
Rate Of Polymerization

We report on the block copolymerization of two structurally different norbornene monomers (±)-endo,exo-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid dimethylester (7), and (±)-endo,exo-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) ester (9) using ruthenium based Grubbs’ type initiators [(PCy3)2Cl2Ru(benzylidene)] G1 (PCy3 = tricyclohexylphosphine), [(H2IMes)(PCy3)Cl2Ru(benzylidene)] G2 (H2IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H2IMes)(py)2Cl2Ru(benzylidene)] G3 (py = pyridine or 3-bromopyridine) and Umicore type initiators [(PCy3)2Cl2Ru(3-phenylinden-1-ylidene)] U1 (PCy3 = tricyclohexylphosphine), [(H2IMes)(PCy3)Cl2Ru(3-phenylinden-1-ylidene)] U2 (H2IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H2IMes)(py)Cl2Ru(3-phenylinden-1-ylidene)] U3 (py = pyridine or 3-bromopyridine) via ring opening polymerization (ROMP). The crossover reaction and the polymerization kinetics were investigated using matrix assisted laser desorption ionization mass spectroscopy (MALDI-TOF) and nuclear magnetic resonance (NMR), respectively. MALDI showed that there was a complete crossover reaction after the addition of 25 equivalents of the second monomer. NMR investigation showed that U3 gave a faster rate of polymerization in comparison to U1. The synthesis of block copolymers with molecular weights up to M n = 31 000 g/mol with low polydispersities (M w/M n = 1.2) is reported.

Functionalized Polyesters via Stereoselective Electrochemical Ring-Opening Polymerization of O-Carboxyanhydrides

2020 ◽  
Author(s):  
Yongliang Zhong ◽  
quanyou feng ◽  
xiaoqian wang ◽  
jia chen ◽  
wenjun cai ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Catalytic System ◽  
Ring Opening ◽  
Electrical Current ◽  
Ring Opening Polymerization ◽  
Glass Transition Temperatures ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions

Ring-opening polymerization is used to prepare polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. Herein, we report a newly developed Co/Zn catalytic system that can be activated by an electrical current to mediate efficient ring-opening polymerization of enantiopure <i>O</i>-carboxyanhydrides, allowing for the synthesis of isotactic functionalized polyesters with high molecular weights (>140 kDa) and narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 1.1). We also demonstrate that these catalysts can be used for stereoselective ring-opening polymerization of racemic <i>O</i>-carboxyanhydrides to synthesize syndiotactic or stereoblock copolymers with different glass transition temperatures compared with their atactic counterparts.

Chemical synthesis of novel biodegradable polyesters

1995 ◽  
Vol 41 (13) ◽  
pp. 282-288 ◽  
Author(s):  
Y. Hori ◽  
Y. Takahashi ◽  
A. Yamaguchi ◽  
T. Hagiwara
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Lactone Ring ◽  
Ring Opening Polymerization ◽  
Optically Active ◽  
Bond Breaking ◽  
Carbonyl Carbon ◽  
Biodegradable Polyesters ◽  
Molecular Weights ◽  
High Molecular Weight Poly

Distannoxane complexes catalyze the ring-opening polymerization of optically active β-butyrolactone (β-BL) to afford a high molecular weight poly(3-hydroxybutyrate). When 1-ethoxy-3-chlorotetrabutyldistannoxane was used as a catalyst (catalyst/(R)-β-BL = 1/8000 at 100 °C for 4 h), poly((R)-3-hydroxybutyrate) was obtained from (R)-β-BL in a yield of 99%. The copolymerizations of (R)-β-BL with racemic β-BL in several ratios gave corresponding stereocopolymers. The copolymerizations of (R)-β-BL with ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, and L-lactide afforded novel optically active and biodegradable polyesters of high molecular weights, comprising (R)-3-hydroxybutyrate (3HB). The polymerization of (R)-β-BL catalyzed by the distannoxane complexes proceeded by bond breaking between the carbonyl carbon and oxygen atom of the lactone ring (acyl cleavage) with retention of the configuration and little or no racemization. Polymers that have over 80 mol% of the (R)-3HB unit were found to have almost the same degree of biodegradability as the copolyester of 3-hydroxybutyrate and 11% 3-hydroxyvalerate produced by the microbial method.Key words: distannoxane, ring-opening polymerization, poly(3-hydroxybutyrate), poly(3-hydroxyalkanoates), biodegradable polymer.

scholarly journals Functionalized Polyesters via Stereoselective Electrochemical Ring-Opening Polymerization of O-Carboxyanhydrides

2020 ◽  
Author(s):  
Yongliang Zhong ◽  
quanyou feng ◽  
xiaoqian wang ◽  
jia chen ◽  
wenjun cai ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Glass Transition ◽  
Catalytic System ◽  
Ring Opening ◽  
Electrical Current ◽  
Ring Opening Polymerization ◽  
Glass Transition Temperatures ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions

Ring-opening polymerization is used to prepare polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. Herein, we report a newly developed Co/Zn catalytic system that can be activated by an electrical current to mediate efficient ring-opening polymerization of enantiopure <i>O</i>-carboxyanhydrides, allowing for the synthesis of isotactic functionalized polyesters with high molecular weights (>140 kDa) and narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 1.1). We also demonstrate that these catalysts can be used for stereoselective ring-opening polymerization of racemic <i>O</i>-carboxyanhydrides to synthesize syndiotactic or stereoblock copolymers with different glass transition temperatures compared with their atactic counterparts.

scholarly journals Photocatalyst-Independent Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides: Stereocontrol and Mechanism

2021 ◽  
Author(s):  
Yongliang Zhong ◽  
quanyou feng ◽  
xiaoqian wang ◽  
Lei Yang ◽  
Rong Tong
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Precious Metal ◽  
Ring Opening Polymerization ◽  
Oxidative Status ◽  
Mechanistic Studies ◽  
Glass Transition Temperatures ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Weight Distributions

Photoredox ring-opening polymerization of <i>O</i>-carboxyanhydrides allows for the synthesis of polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. While powerful, obviating the use of precious metal-based photocatalysts would be attractive from the perspective of simplifying the protocol and enabling unexpected reactivity. Herein, we report the Co and Zn catalysts that are activated by external light to mediate efficient ring-opening polymerization of <i>O</i>-carboxyanhydrides, without the use of exogenous precious metal-based photocatalysts. Our methods allow for the synthesis of isotactic polyesters with high molecular weights (>200 kDa) and narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 1.1). Mechanistic studies indicate that light activates the oxidative status of Co<sup>III</sup> intermediate that is generated from the regioselective ring-opening of the <i>O</i>-carboxyanhydride. We also demonstrate that the use of Zn or Hf complexes together with Co can allow for stereoselective photoredox ring-opening polymerizations of multiple racemic <i>O</i>-carboxyanhydrides to synthesize syndiotactic and stereoblock copolymers, which vary widely in their glass transition temperatures.

scholarly journals One-Pot Synthesis of Star Copolymers by the Combination of Metal-Free ATRP and ROP Processes

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1577 ◽  
Author(s):  
Gorkem Yilmaz
Keyword(s):  
Visible Light Irradiation ◽  
Ring Opening ◽  
Reaction Medium ◽  
Ring Opening Polymerization ◽  
One Pot ◽  
Metal Free ◽  
Molecular Weights ◽  
Star Copolymers ◽  
Living Polymerizations ◽  
Chromatographic Evidence

A completely metal-free strategy is demonstrated for the preparation of star copolymers by combining atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) for the syntheses of block copolymers. These two different metal-free controlled/living polymerizations are simultaneously realized in one reaction medium in an orthogonal manner. For this purpose, a specific core with functional groups capable of initiating both polymerization types is synthesized. Next, vinyl and lactone monomers are simultaneously polymerized under visible light irradiation using specific catalysts. Spectral and chromatographic evidence demonstrates the success of the strategy as star copolymers are synthesized with controlled molecular weights and narrow distributions.

scholarly journals Polymers of ε-Caprolactone Using New Copper(II) and Zinc(II) Complexes as Initiators: Synthesis, Characterization and X-Ray Crystal Structures

Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1239 ◽  
Author(s):  
Andrés Posada ◽  
Mario Macías ◽  
Santiago Movilla ◽  
Gian Miscione ◽  
León Pérez ◽  
...  
Keyword(s):  
Single Crystal ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Nmr Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Molecular Weights ◽  
Full Characterization ◽  
Solvent Free Conditions

Five of six new Zn(II) and Cu(II) complexes were active in the ring-opening polymerization (ROP) of ε-caprolactone (CL) under solvent-free conditions, producing polycaprolactones (PCLs) of high crystallinity with molecular weights between 22,900 and 38,700 g mol−1 and decomposition temperatures above 260 °C. 1H NMR analysis demonstrated that the PCLs obtained were mainly linear, having hydroxymethylene groups at the chain ends. The results obtained indicated a significant improvement in terms of the ratio of monomer:initiator compared to related Cu(II) and Zn(II) complexes. In addition, the structures of the complexes 1 and 4 were determined by single-crystal X-ray diffraction. The synthesis and full characterization of all complexes are described in this paper.

Synthesis and characterization of novel β-cyclodextrin cored poly(α-caprolactone)s by anionic ring opening polymerization

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Yingzhi Guo ◽  
Changjiang Yu ◽  
Zhongwei Gu
Keyword(s):  
Molecular Weight ◽  
Physical Properties ◽  
Ring Opening ◽  
Monomer Conversion ◽  
Ring Opening Polymerization ◽  
Molar Ratio ◽  
Molecular Weights ◽  
Molar Ratios ◽  
Anionic Ring ◽  
Feed Molar Ratio

Abstract By anionic ring opening polymerization initiated by cyclodextrin oxyanions generated from NaH and β-cyclodextrin(β-CD), novel biodegradable β- CD cored star-shaped poly(ε-caprolactone)s (s-PCLs) were synthesized and then characterized by means of FTIR, GPC, 1H-NMR. The effects of different feed molar ratios of NaH and β-CD on arm number and on the molecular weight of s-PCLs, and the relationship between the polymerization time and monomer conversion were investigated. Moreover, the physical properties of linear PCL (l-PCL) and s- PCLs with similar molecular weights but different arm number were studied and compared by DSC, SEM and intrinsic viscosity measurement, respectively. It was found that the feed molar ratio of NaH and β-CD is an important factor which influences both the molecular weight and arm number. The melting points and intrinsic viscosities of s-PCLs with similar molecular weights were lower than that of l-PCL, and were found to decrease with increasing arm number. Both SEM and AFM showed that the surface morphology of s-PCL films was different from that of l-PCL. These results indicated that s-PCL with different arms and physical properties could be synthesized using just a β-CD core by adjusting the feed molar ratio of NaH and β-CD

Synthesis and Characterization of Hydroxy-telechelic Four-arm Star-shaped Oligo(tetrahydrofuran), Their Crosslinking, and Thermomechanical Investigation of the Poymer Network

2012 ◽  
Vol 1403 ◽  
Author(s):  
Ke-Ke Yang ◽  
J. Zotzmann ◽  
A. Lendlein ◽  
M. Behl
Keyword(s):  
Shape Memory ◽  
Ring Opening ◽  
Polymer Network ◽  
Ring Opening Polymerization ◽  
Synthesis And Characterization ◽  
Shape Memory Material ◽  
Molecular Weights ◽  
Initiation System ◽  
Cationic Ring Opening Polymerization

ABSTRACTHere the synthesis of hydroxy-telechelic four-arm star-shaped oligotetrahydrofuran (4PTHF) with controllable molecular weight was explored, which was perfomed as living cationic ring-opening polymerization of THF using pentaerythritol and trifluoromethanesulfonicanhydride as initiation system. The molecular weights of the 4PTHF were a function of the reaction time. A polymer network was prepared from the hydroxy-telechelic 4PTHF precursor by crosslinking with diisocyanate and the shape-memory properties were determined. High values for Rf and Rr > 98% were obtained even at high programmed elongations, which suggest the 4PTHF-network as a promising shape-memory material. These materials might have a great potential, as the upscaling of synthesis could be successfully demonstrated.

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