The “solid-state” ring-opening cationic polymerization of 1,3,5-trioxane: frozen polymerization for suppression of oligomer formation and synthesis of ultrahigh molecular weight polymers

2021 ◽  
Author(s):  
Chihiro Suemitsu ◽  
Arihiro Kanazawa ◽  
Sadahito Aoshima
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Cationic Polymerization ◽  
Ring Opening ◽  
Molten State ◽  
Molecular Weights ◽  
Oligomer Formation ◽  
Ultrahigh Molecular Weight

Production of polyoxymethylene with higher molecular weights and lower oligomer ratios than those obtained by molten-state polymerization of 1,3,5-trioxane was demonstrated by conducting polymerization in a “solid state”.

scholarly journals Naturally-Derived Amphiphilic Polystyrenes Prepared by Aqueous Controlled/Living Cationic Polymerization and Copolymerization of Vinylguaiacol with R–OH/BF3·OEt2

Polymers ◽  
2018 ◽  
Vol 10 (12) ◽  
pp. 1404 ◽  
Author(s):  
Hisaaki Takeshima ◽  
Kotaro Satoh ◽  
Masami Kamigaito
Keyword(s):  
Molecular Weight ◽  
Ferulic Acid ◽  
Cationic Polymerization ◽  
Living Polymerization ◽  
Block Copolymerization ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Living Cationic Polymerization ◽  
Naturally Occurring ◽  
Weight Distributions

In this study, we investigated direct-controlled/living cationic polymerization and copolymerization of 4-vinylguaiacol (4VG), i.e., 4-hydroxy-3-methoxystyrene, which can be derived from naturally-occurring ferulic acid, to develop novel bio-based amphiphilic polystyrenes with phenol functions. The controlled/living cationic polymerization of 4VG was achieved using the R–OH/BF3·OEt2 initiating system, which is effective for the controlled/living polymerization of petroleum-derived 4-vinylphenol in the presence of a large amount of water via reversible activation of terminal C–OH bond catalyzed by BF3·OEt2, to result in the polymers with controlled molecular weights and narrow molecular weight distributions. The random or block copolymerization of 4VG was also examined using p-methoxystyrene (pMOS) as a comonomer with an aqueous initiating system to tune the amphiphilic nature of the 4VG-derived phenolic polymers. The obtained polymer can be expected not only to be used as a novel styrenic bio-based polymer but also as a material with amphiphilic nature for some applications.

scholarly journals Direct Synthesis and Characterization of Photo-Crosslinkable Biodegradable PLA-PEG-PLA Ttiblock Copolymer with Methacrylates Functions by Green Montmorillonite Clay Catalyst

2020 ◽  
Vol 14 (4) ◽  
pp. 474-480
Author(s):  
Mohamed Benachour ◽  
◽  
Aslya El-Kebir ◽  
Amine Harrane ◽  
Rachid Meghabar ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Cationic Polymerization ◽  
Direct Synthesis ◽  
Average Molecular Weight ◽  
Montmorillonite Clay ◽  
Synthesis And Characterization ◽  
Molecular Weights ◽  
One Step ◽  
Clay Catalyst

Di-methacrylated PLA-PEG-PLA triblock copolymers of polylactide and polyethylene glycol were synthesized in one-step process by bulk cationic polymerization of lactide in the presence of PEG with different average molecular weights, using Maghnite-H+, an acidic montmorillonite clay, as a solid non-toxic catalyst. The obtained di-methacrylated copolymer was analyzed by 1H NMR and DSC. The effect of Maghnite-H+ proportions and PEG average molecular weight on the copolymerization and methacrylation yields and on average molecular weight of the resulting copolymers was studied.

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.

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