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Takeshi Endo - One of the best experts on this subject based on the ideXlab platform.
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Synthesis and Cationic ring‐opening Polymerization of oxetane monomer containing five‐membered cyclic carbonate moiety via highly chemoselective addition of CO2
Journal of Polymer Science Part A: Polymer Chemistry, 2019Co-Authors: Naoto Aoyagi, Takeshi EndoAbstract:The bicyclic amidinium iodide effectively catalyzed the reaction of carbon dioxide and the epoxy‐containing oxetane under ordinary pressure and mild conditions with high chemoselectivity to give the corresponding oxetane monomer containing five‐membered cyclic carbonate quantitatively. The Cationic ring‐opening Polymerization of the obtained monomer by boron trifluoride diethyl ether proceeded to give linear polyoxetane bearing five‐membered cyclic carbonate pendant group in high yield. The molecular weight of the polyoxetane was higher than that of polyepoxide obtained by the Cationic ring‐opening Polymerization of epoxide monomer containing five‐membered cyclic carbonate. The cyclic carbonate functional crosslinked polyoxetanes were also synthesized by the Cationic ring‐opening coPolymerization of cyclic carbonate having oxetane and commercially available bisoxetane monomers. Analyses of the resulting polyoxetanes were performed by proton nuclear magnetic resonance, size exclusion chromatography, thermogravimetric analysis, and differential scanning calorimetry. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2606–2615
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Living Cationic ring‐opening Polymerization of five‐membered cyclic dithiocarbonate controlled by neighboring group participation of carbamate group
Journal of Polymer Science Part A: Polymer Chemistry, 2007Co-Authors: Suguru Motokucho, Atsushi Sudo, Takeshi EndoAbstract:A five-membered cyclic dithiocarbonate having phenylcarbamate moiety 1 underwent Cationic Ring-Opening Polymerization by using methyl trifluoromethanesulfonate as an initiator in nitrobenzene at 60 °C. Both of the corresponding first-order kinetic plot and conversion-molecular weight plot showed linearity to suggest the living fashion of the Polymerization, which was then supported by two-stage Polymerization experiment. The living fashion as well as the regioselective formation of the repeating unit suggested significant contribution of the neighboring group participation of the carbamate group to form a stabilized Cationic propagating end, of which structure was confirmed by performing an equimolar reaction of 1 and methyl trifluoromethanesulfonate with analyzing the resulting species by NMR spectroscopy.
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Synthesis and properties of the polythiourethanes obtained by the Cationic ring‐opening Polymerization of cyclic thiourethanes
Journal of Polymer Science Part A: Polymer Chemistry, 2006Co-Authors: Daisuke Nagai, Bungo Ochiai, Masato Sato, Takeshi EndoAbstract:The Cationic Ring-Opening Polymerization of a five-membered thiourethane [3-benzyl-1,3-oxazolidine-2-thione (BOT)] with boron trifluoride etherate afforded the corresponding polythiourethane with a narrow molecular weight distribution in an excellent yield. The molecular weight of the polymers could be controlled by the feed ratio of the monomer to the initiator. A kinetic study of the Polymerization revealed that the Polymerization rate of BOT (1.3 × 10−2 L mol−1 min−1) was two times larger than that of the six-membered thiourethane [3-benzyltetrahydro-1,3-oxazolidine-2-thione (BTOT); 6.8 × 10−3 L mol−1 min−1], and the monomer conversion obeyed the first-order kinetic equation. These observations, along with the successful results in the two-stage Polymerization, supported the idea that this Polymerization proceeded in a controlled manner. Block coPolymerizations of BOT with BTOT were also carried out to afford the corresponding di- and triblock copolymers with narrow molecular weight distributions. The order of the 5% weight loss temperatures was as follows: poly(3-benzyltetrahydro-1,3-oxazolidine-2-thione) [poly(BTOT)] > poly(BTOT54-b-BOT46) > poly(3-benzyl-1,3-oxazolidine-2-thione) [poly(BOT)]. This indicated that an increase in the BTOT unit content raised the decomposition temperature. The order of the refractive indices was poly(BOT) > poly(BTOT54-b-BOT46) > poly(BTOT54-b-BOT46-b-BTOT50) > poly(BTOT); this was in accord with the order of the sulfur content in the polymer chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4795–4803, 2006
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Synthesis and Radical Polymerization of a Novel Macromonomer Obtained by Living Cationic Ring-Opening Polymerization of an Optically Active Cyclic Thiourethane by a New Initiator Carrying Styryl Group
Macromolecules, 2004Co-Authors: Atsushi Nagai, Bungo Ochiai, Takeshi EndoAbstract:A new Cationic initiator, 4-vinylbenzoic acid 2-methylsulfanyl-4,5-dihydrooxazolinium-4-ylmethyl ester trifluoromethanesulfonate (1), carrying both vinyl and triflate groups, was synthesized in quantitative yield by reaction of 1,3-oxazolidine-2-thione derivative with methyl trifluoromethanesulfonate. Living Cationic Ring-Opening Polymerization of an optically active cyclic thiourethane (SL) derived from l-serine was carried out by with 1 as an initiator in dichloromethane to give the corresponding macromonomers (MSL; Mn > 104, Mw/Mn < 1.18), and the molecular weight of MSL could be controlled by [SL]/[1]. MSL consists of the optically active thiourethane main chain and styryl group in the initiating end quantitatively. The radical homoPolymerization of MSL and the coPolymerization with styrene were carried out to obtain the corresponding polymers in higher yields. The obtained polymer from MSL showed higher specific rotation ([α]25D), melting point (Tm), and Cotton effect than MSL, supporting the stabili...
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Living Cationic Ring-Opening Polymerization by water-stable initiator: synthesis of a well-defined optically active polythiourethane
Chemical communications (Cambridge England), 2003Co-Authors: Atsushi Nagai, Bungo Ochiai, Takeshi EndoAbstract:Living Cationic Ring-Opening Polymerization under air and water was achieved using a well-defined water-resistant Cationic initiator in dichloromethane without purification at ambient temperature.
Richard Hoogenboom - One of the best experts on this subject based on the ideXlab platform.
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Cation−π Interactions Accelerate the Living Cationic Ring-Opening Polymerization of Unsaturated 2-Alkyl-2-oxazolines
Macromolecules, 2020Co-Authors: Elias Van Den Broeck, Bart Verbraeken, Karen Dedecker, Pieter Cnudde, Louis Vanduyfhuys, Toon Verstraelen, Kristof Van Hecke, Valentin Victor Jerca, Saron Catak, Richard HoogenboomAbstract:Cation–dipole interactions were previously shown to have a rate-enhancing effect on the Cationic Ring-Opening Polymerization (CROP) of 2-oxazolines bearing a side-chain ester functionality. In line...
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macropropagation rate coefficients and branching levels in Cationic ring opening Polymerization of 2 ethyl 2 oxazoline through prediction of size exclusion chromatography data
Macromolecules, 2019Co-Authors: Francisco J Arraez, Richard Hoogenboom, Valentin Victor Jerca, Xiaowen Xu, Paul H M Van Steenberge, Dagmar R DhoogeAbstract:A systematic kinetic study of the isothermal Cationic Ring-Opening Polymerization of 2-ethyl-2-oxazoline (EtOx) in acetonitrile initiated by methyl tosylate under microwave irradiation (353–413 K) for a target degree of Polymerization of 100 is reported as a basis for kinetic Monte Carlo simulations with parameters tuned based on monomer conversion and chain length data. It is highlighted that the size-exclusion chromatography (SEC) trace is needed to properly tune the less known macropropagation rate coefficient, which is related to the incorporation of enamine-terminated polymer chains resulting from chain transfer to monomer and which determines the contribution of linear and branched chains. A model-based design is applied to identify the reaction temperatures that lead to an optimum between the reaction time and control over molecular properties. A linear relationship is derived, which can be used to reliably assess the mass fraction of branched chains at sufficiently high monomer conversions based o...
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Fluorinated 2‑Alkyl-2-oxazolines of High Reactivity: Spacer-Length-Induced Acceleration for Cationic Ring-Opening Polymerization As a Basis for Triphilic Block Copolymer Synthesis
2017Co-Authors: Leonid I. Kaberov, Richard Hoogenboom, Bart Verbraeken, Anna Riabtseva, Jiri Brus, Yeshayahu Talmon, Petr Stepanek, Sergey K. FilippovAbstract:The synthesis of defined triphilic terpolymers with hydrophilic, lyophilic, and fluorophilic blocks is an important challenge as a basis for the development of multicompartment self-assembled structures with potential for, e.g., cascade catalysis and multidrug loading. The synthesis of fluorophilic poly(2-oxazoline)s generally suffers from a very low reactivity of fluorinated 2-oxazoline monomers in Cationic Ring-Opening Polymerization (CROP). We report a systematic study on overcoming the extremely low reactivity of 2-perfluoroalkyl-2-oxazolines in CROP by the insertion of methyl and ethyl hydrocarbon spacers between the 2-oxazoline ring and the trifluoromethyl group. The kinetic studies showed the gradual increase of the rate of Polymerization with increasing of the hydrocarbon spacer length. The monomer with an ethyl spacer was found to have similar reactivity as 2-alkyl-2-oxazolines and allowed the synthesis of defined triphilic triblock copolymers
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sulfolane as common rate accelerating solvent for the Cationic ring opening Polymerization of 2 oxazolines
ACS Macro Letters, 2015Co-Authors: Maarten Vergaelen, Bart Verbraeken, Bryn D Monnery, Richard HoogenboomAbstract:The search for alternative solvents for the Cationic Ring-Opening Polymerization (CROP) of 2-methyl-2-oxazoline (MeOx) is driven by the poor solubility of P(MeOx) in Polymerization solvents such as acetonitrile (CH3CN) and chlorobenzene as well as in MeOx itself. In this study, solvent screening has revealed that especially sulfolane is a good solvent for PMeOx. Unexpectedly, an increased propagation rate constant (kp) was found for the CROP of MeOx in sulfolane. Further extended kinetic studies at different temperatures (60–180 °C), revealed that the acceleration is due to an increase in frequency factor, while the activation energy (Ea) of the reaction is hardly affected. In order to explore the versatility of sulfolane as Polymerization solvent for the CROP of 2-oxazolines in general, also the Polymerization kinetics of other 2-oxazoline monomers, such as 2-ethyl-2-oxazoline (EtOx) and 2-phenyl-2-oxazoline (PhOx), have been studied, revealing a common acceleration of the CROP of 2-oxazoline monomers in...
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Systematic investigation of alkyl sulfonate initiators for the Cationic Ring-Opening Polymerization of 2-oxazolines revealing optimal combinations of monomers and initiators
European Polymer Journal, 2015Co-Authors: Mathias Glassner, Bryn D Monnery, Dagmar R. D'hooge, Jin Young Park, Paul H. M. Van Steenberge, Marie-françoise Reyniers, Richard HoogenboomAbstract:A systematic kinetic investigation of the living Cationic Ring-Opening Polymerization (CROP) involving 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, and 2-phenyl-2-oxazoline employing a series of alkyl sulfonate initiators with variation of the alkyl initiating fragment (methyl, ethyl, iso-propyl) and the leaving group/counterion (tosylate, nosylate, triflate) is reported. The study reveals that the initiation and propagation reactivity increases in the order tosylate < nosylate < triflate. Slow initiation is observed for EtOTs, while EtONs is a sufficiently fast initiator even for 2-phenyl-2-oxazoline. It is thus recommended to avoid the use of alkyl tosylates, except MeOTs, as initiators for the CROP of 2-alkyl-2-oxazolines. Although triflates are generally the best initiators, the use of the more stable and easier synthesizable nosylates provides a suitable alternative for the design of functional initiators for the CROP of 2-alkyl-2-oxazolines.
Ulrich S Schubert - One of the best experts on this subject based on the ideXlab platform.
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Cationic ring opening Polymerization of protected oxazolidine imines resulting in gradient copolymers of poly 2 oxazoline and poly urea
Polymer Chemistry, 2016Co-Authors: Meike N Leiske, Helmar Görls, Matthias Hartlieb, Fabian H Sobotta, Renzo M Paulus, Peter Bellstedt, Ulrich S SchubertAbstract:Poly(urea)s are a polymer class widely used in industry. Their utilization in biomedical applications is already described, however, the use of controlled Polymerization methods instead of polycondensation approaches would allow a better control over the degree of Polymerization and the dispersity of the resulting polymers, improving their suitability for this particular field of application. Cationic Ring-Opening Polymerization (CROP) as a chain growth Polymerization enables those requirements and, additionally, allows the coPolymerization with 2-oxazolines, which are generally known for their biocompatibility. In this report, a Boc protected oxazolidine imine monomer is synthesized and polymerized in a homoPolymerization, as well as in a coPolymerization with 2-ethyl-2-oxazoline (EtOx) via CROP. The synthesized polymers were analyzed regarding their chemical and physical properties, using NMR, GC, MALDI-MS, SEC, TGA and DSC. CoPolymerization kinetics revealed the formation of quasi-block copolymers, able to self-assemble in aqueous solution as indicated by DLS.
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A Sugar Decorated Macromolecular Bottle Brush by Carbohydrate-Initiated Cationic Ring-Opening Polymerization
Macromolecules, 2011Co-Authors: Christine Weber, Richard Hoogenboom, Justyna A. Czaplewska, Anja Baumgaertel, Esra Altuntaş, Michael Gottschaldt, Ulrich S SchubertAbstract:The capability of a range of protected glucose- (Glc), galactose- (Gal), and fructose- (Fru) based tosylates and triflates to initiate the living Cationic Ring-Opening Polymerization of 2-ethyl-2-oxazoline (EtOx) was investigated by detailed kinetic studies utilizing 1H and 19F NMR spectroscopy and SEC as well as MALDI and ESI TOF mass spectrometry. The Glc and Gal tosylates and a sterically hindered Fru triflate revealed slow and incomplete initiation, whereas the Glc and Gal triflates resulted in living Polymerizations. Well-defined Glc as well as Gal α-end-functionalized PEtOx was obtained after deprotection. Functionalization of the living oxazolinium chain ends with methacrylate anions resulted in a macromonomer that was applied for RAFT Polymerization. Deprotection resulted in a comb polymer that is selectively functionalized with Glc at the ends of all side chains (DPbackbone = 13, DPside chains = 10, PDI = 1.11).
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efficient Cationic ring opening Polymerization of diverse cyclic imino ethers unexpected coPolymerization behavior
Macromolecules, 2011Co-Authors: Hanneke M L Lambermontthijs, Ulrich S Schubert, Martin W M Fijten, A J Van Der Linden, Bart M Van Lankvelt, Meta M Bloksma, Richard HoogenboomAbstract:The recently developed fast microwave-assisted Cationic Ring-Opening Polymerization procedure for 2-oxazolines seems to be ideally suited for slower polymerizing cyclic imino ether monomers. In this study we report the effect of the cyclic imino ether structure on the Polymerization rate under exactly the same microwave-assisted conditions revealing that indeed less reactive cyclic imino ethers, including 2-oxazines as well as 4- and 5-substituted 2-oxazolines, can be polymerized to at least 50% conversion for the slowest monomer, namely 5-methyl-2-butyl-2-oxazoline, within 10 h. In addition, the coPolymerization behavior of 4-ethyl-2-butyl-2-oxazoline with 2-methyl-2-oxazoline and 2-phenyl-2-oxazoline unexpectedly revealed faster incorporation of the less reactive 4-ethyl-2-butyl-2-oxazoline monomer compared to 2-phenyl-2-oxazoline due to the increased bulk of the latter monomer amplifying the sterical hindrance for Polymerization onto the 4-ethyl-2-butyl-2-oxazolinium propagating species.
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synthesis of poly 2 ethyl 2 oxazoline b poly styrene copolymers via a dual initiator route combining Cationic ring opening Polymerization and atom transfer radical Polymerization
Macromolecules, 2008Co-Authors: Remzi C Becer, Richard Hoogenboom, Renzo M Paulus, Charlesandre Fustin, Jeanfrancois Gohy, Stephanie Hoppener, Ulrich S SchubertAbstract:Block copolymers of 2-ethyl-2-oxazoline (EtOx) and styrene were synthesized by a combination of Cationic Ring-Opening Polymerization (CROP) and atom transfer radical Polymerization (ATRP). Initially, a detailed kinetic investigation for the alpha-bromoisobutyrylbromide (BrEBBr) initiated CROP of EtOx was performed in acetonitrile at different Polymerization temperatures ranging from 100 to 180 degrees C under microwave irradiation. Poly(2-ethyl-2-oxazoline) (PEtOx) homopolymers with controlled molecular weights and narrow polydispersity indices were synthesized in short reaction times. Polymers with relatively high molar masses and low polydispersity indices (M-n,M-SEC = 48 500 g/mol, PDI = 1.29) could also be obtained. Following the synthesis of a PEtOx macroinitiator (M-n,M-SEC = 3700 g/mol, PDI = 1.09), the ATRP of styrene was performed with CuBr and tris[2-(dimethylamino)ethyl]amine (Me(6)Tren) as catalytic system. The micellization behavior of the obtained amphiphilic block copolymers was further investigated by dynamic light scattering (DLS) and atomic force microscopy (AFM).
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Acetyl Halide Initiator Screening for the Cationic Ring‐Opening Polymerization of 2‐Ethyl‐2‐Oxazoline
Macromolecular Chemistry and Physics, 2008Co-Authors: Renzo M Paulus, Richard Hoogenboom, C. Remzi Becer, Ulrich S SchubertAbstract:Kinetic investigations on the Cationic Ring-Opening Polymerization of 2-ethyl-2-oxazoline were conducted using acetyl chloride, acetyl bromide, and acetyl iodide as initiators. Various Polymerization temperatures ranging from 80 to 220 °C were applied under microwave irradiation. The resulting Polymerization mixtures were characterized with GC and GPC for the determination of monomer conversion and molecular weight distribution, respectively. Well defined polymers with narrow molecular weight distributions ( = 6 000 Dalton, PDI ≈ 1.10) were obtained with all three initiators.
Cai-yuan Pan - One of the best experts on this subject based on the ideXlab platform.
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Synthesis of a Multi Alternating‐Arm‐Containing Dendritic Star Copolymer by RAFT and Cationic Ring‐Opening Polymerization
Macromolecular Rapid Communications, 2008Co-Authors: Ling Zhong, Yongfeng Zhou, Deyue Yan, Cai-yuan PanAbstract:A new dendritic heteroarm star copolymer that contains multi-alternating arms of poly(ethylene oxide-tetrahydrofuran) (P(EO-THF)) and poly(methyl methacrylate) (PMMA) on a dendritic polyester core has been synthesized by a 'core-first' approach by combination of sequential Cationic Ring-Opening Polymerization (CROP) and reversible addition-fragmentation transfer (RAFT) Polymerization initiated by a dendritic macroinitiator (3) capped with multi-alternating terminal carboxylic acid groups (used directly to initiate the ROP of THF in the presence of EO as a Polymerization promoter to attain P(EO-THF) arms) and dithio-benzoate groups (used to initiate RAFT Polymerization of MMA to attain PMMA arms). The structures of the products were confirmed by NMR spectroscopy, GPC-MALLS, and DSC measurements.
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Synthesis of comb-shaped copolymers by combination of reversible addition–fragmentation chain transfer Polymerization and Cationic Ring-Opening Polymerization
Polymer, 2005Co-Authors: Wenping Wang, Ye-zi You, Chun-yan Hong, Cai-yuan PanAbstract:Abstract Comb-shaped graft copolymers with poly(methyl acrylate) as a handle were synthesized by reversible addition–fragmentation chain transfer (RAFT) Polymerization and Ring-Opening Polymerization (ROP) techniques in three steps. First, copolymers of poly(styrene-co-chloromethyl styrene), poly(St-co-CMS), were prepared by RAFT coPolymerization of St and CMS using 1-(ethoxycarbonyl)prop-1-yl dithiobenzoate (EPDTB) as RAFT agent. Second, the Polymerization of MA using poly(St-co-CMS)-SC(S)Ph as macromolecular chain transfer agent produced block copolymer poly(St-co-CMS)-b-PMA. Third, Cationic Ring-Opening Polymerization of THF was performed using poly(St-co-CMS)-b-PMA/AgClO4 as initiating system to produce comb-shaped copolymers. The structures of the poly(St-co-CMS), poly(St-co-CMS)-b-PMA and final comb-shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC).
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STUDY ON Cationic Ring-Opening Polymerization MECHANISM OF 3-ETHYL-3-HYDROXYMETHYL OXETANE
Journal of Macromolecular Science Part A, 2002Co-Authors: Ying-fang Zou, Cai-yuan PanAbstract:ABSTRACT Cationic Ring-Opening Polymerization of 3-ethyl-3-hydroxylmethyl oxetane was carried out using BF3·O(C2H5)2 as initiator, and a branched polyether was formed. Typical SEC curves show that the polymer consists of two fractions: one has higher molecular weight (11.7×104∼ 9.2×104) and the other has lower molecular weight (3.8×103∼4.0×103). This probably resulted from the chain-tran sfer reaction of two propagating polymer chains. The structure of the polyEHMO formed was characterized by 1H and 13C NMR spectra. The degree of branching is mainly affected by the propagation mechanism. As the molar ratio of [I]0/[EHMO]0 in feed increased, the degree of branching also increased.
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Investigation on Cationic Ring-Opening Polymerization of 1,5,7,11-tetraoxaspiro [5,5] undecane in the presence of low molecular weight tetraols
Polymer, 2001Co-Authors: Yan-ming Guo, Ying-fang Zou, Cai-yuan PanAbstract:Abstract A new four-armed tetraol, poly(1,5,7,11-tetraoxaspiro [5,5] undecane) tetraol (poly(TOSU)), was prepared by the Cationic Ring-Opening Polymerization of TOSU using BF 3 ·OEt 2 as initiator. Its structure was characterized by 1 H, 13 C NMR and FTIR spectra. GPC curves showed that the polymer obtained had two fractions with higher and lower molecular weights; however, each had a relatively narrow molecular weight distribution. The molecular weights of the polycarbonate tetraols were controlled by the molar ratio of TOSU consumed to initial BHDU. The mechanism of the Polymerization was discussed.
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Study on Cationic ring‐opening Polymerization of 1,3‐dioxepane with oxocarbenium salt as initiator
Journal of Polymer Science Part A: Polymer Chemistry, 1999Co-Authors: Cai-yuan PanAbstract:Poly (1,3-dioxepane) [PDOP] triol was prepared by Cationic Ring-Opening Polymerization with [C 2 H 5 C(CH 2 OCH 2 CH 2 CO + ClO - 4 ) 3 ], trioxocarbenium perchlorate, as an initiator. The structures of the PDOP triols obtained were verified by 1 H-NMR, FTIR, and GPC results. Initiation, propagation, and termination mechanisms were discussed based on the structural analysis of the polyacetal polyols. The results of GPC, NMR, and IR measurements showed that the PDOP triols obtained had similar branch chain lengths. Number-average molecular weights were determined by vapor pressure osmometry (VPO), end group titration and 1 H-NMR.
Valentin Victor Jerca - One of the best experts on this subject based on the ideXlab platform.
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Cation−π Interactions Accelerate the Living Cationic Ring-Opening Polymerization of Unsaturated 2-Alkyl-2-oxazolines
Macromolecules, 2020Co-Authors: Elias Van Den Broeck, Bart Verbraeken, Karen Dedecker, Pieter Cnudde, Louis Vanduyfhuys, Toon Verstraelen, Kristof Van Hecke, Valentin Victor Jerca, Saron Catak, Richard HoogenboomAbstract:Cation–dipole interactions were previously shown to have a rate-enhancing effect on the Cationic Ring-Opening Polymerization (CROP) of 2-oxazolines bearing a side-chain ester functionality. In line...
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macropropagation rate coefficients and branching levels in Cationic ring opening Polymerization of 2 ethyl 2 oxazoline through prediction of size exclusion chromatography data
Macromolecules, 2019Co-Authors: Francisco J Arraez, Richard Hoogenboom, Valentin Victor Jerca, Xiaowen Xu, Paul H M Van Steenberge, Dagmar R DhoogeAbstract:A systematic kinetic study of the isothermal Cationic Ring-Opening Polymerization of 2-ethyl-2-oxazoline (EtOx) in acetonitrile initiated by methyl tosylate under microwave irradiation (353–413 K) for a target degree of Polymerization of 100 is reported as a basis for kinetic Monte Carlo simulations with parameters tuned based on monomer conversion and chain length data. It is highlighted that the size-exclusion chromatography (SEC) trace is needed to properly tune the less known macropropagation rate coefficient, which is related to the incorporation of enamine-terminated polymer chains resulting from chain transfer to monomer and which determines the contribution of linear and branched chains. A model-based design is applied to identify the reaction temperatures that lead to an optimum between the reaction time and control over molecular properties. A linear relationship is derived, which can be used to reliably assess the mass fraction of branched chains at sufficiently high monomer conversions based o...