Substituent effect on cationic ring-opening polymerization behavior of seven-membered cyclic carbonates

Matsuo, Jyuhou; Sanda, Fumio; Endo, Takeshi

doi:10.1002/(sici)1521-3935(20000301)201:5<585::aid-macp585>3.0.co;2-n

Cited by 12 publications

(23 citation statements)

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“…In a previous study on the cationic ROP of R-Me7CC promoted by TfOH or TfOMe, Endo et al reported that the carbonyl region of the 22.5 MHz spectra of poly(R-Me7CC) in CDCl 3 contains three resonances at δ 155-156 ppm, which are diagnostic of the diad sequences (Scheme 5). 4 The central, most intense resonance was assigned to indistinguishable diads A and D that arise from regioregular enchainment of the monomer units, that is, regioregular cleavage of either of the O-C(O)O bonds in R-Me7CC. In addition, they observed two other resonances, at higher and lower field apart from the aforementioned central resonance respectively (Δδ = ca.…”

Section: Resultsmentioning

confidence: 70%

“…The zinc β-diiminate complex [(BDI iPr )Zn(N(SiMe 3 ) 2 )] successfully used in the iROP of the six-membered ring monomer TMC 10a-e was similarly active toward the (i)ROP of R-and β-Me7CC under very mild conditions (20-60°C), either in toluene solution or in bulk (Table 1, entries 4-16; Table 2, entries [4][5][6][7][8][9][10][11][12][13][14][15][16][17]. In the presence of 1 equiv of BnOH, the ROP of R-Me7CC (100-500 equiv) in toluene or in bulk proceeded quantitatively within 5-180 min (Table 1, entries 4-9, 13-14).…”

Section: Resultsmentioning

confidence: 99%

“…In the presence of 1 equiv of BnOH, the ROP of R-Me7CC (100-500 equiv) in toluene or in bulk proceeded quantitatively within 5-180 min (Table 1, entries 4-9, 13-14). Likewise, the ROP of β-Me7CC, in solution as well as in bulk, gave almost quantitative conversions within similar reaction times (5 to 50 min; Table 2, entries [4][5][6][7][8][9][10][13][14][15]. Performing the ROP reactions in bulk required shorter reaction times to reach full conversion, as compared [11][12][16][17], the zinc catalytic system remained similarly active.…”

Section: Resultsmentioning

confidence: 99%

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Polycarbonates Derived from Green Acids: Ring-Opening Polymerization of Seven-Membered Cyclic Carbonates

et al. 2010

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Methyl substituted seven-membered ring carbonates (7CCs), namely, 4-methyl-and 5-methyl-1,3-dioxepan-2-one (R-Me7CC and β-Me7CC), have been synthesized in high yields (up to 70%) upon cyclization of the corresponding R,ω-diols issued from green renewable acids. ("Immortal") ring-opening polymerization of these monomers has been carried out using various catalysts combined with an alcohol acting as a co-initiator and a chain transfer agent. The Lewis acid Al(OTf) 3 , the organometallic complexes [(BDI iPr )Zn(N(SiMe 3 ) 2 )] ((BDI iPr ) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)-imino)-2-pentene] and [(ONOO tBu )Y(N(SiHMe 2 ) 2 )(THF)] (ONOO tBu = amino-alkoxy-bis(phenolate)) or the organic 4-N,N-dimethylaminopyridine (DMAP), 1.5.7-triazabicyclo-[4.4.0]dec-5-ene (TBD) or 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) successfully afforded the corresponding poly(R-and β-Me7CC)s with quite good control and activities. The dissymmetry of the monomers raises the question of catalyst selectivity in the ring-opening of the 7CCs. Detailed microstructural analyses of the poly(7CC)s using 1 H and 13 C NMR and MALDI-ToF-MS techniques revealed (1) the higher regioselectivity -with preferential ring-opening at the most hindered oxygen-acyl O-C(O)O bond, that is, closest to the R-Me substituentof the zinc-based system followed by the yttrium, as compared to the lack of selectivity of the aluminum one, in the ring-opening polymerization (ROP) of R-Me7CC; (2) the absence of regioselectivity in the ROP of β-Me7CC, whichever the catalyst system used, most likely as a result of the OC(O)O further remote substitution site; (3) the expected R-hydroxy,ω-alkoxyester chain ends. Differential scanning calorimetry (DSC) analyses of these polymers underlined the influence of the position of the methyl substituent on the glass transition temperature. Noteworthy, this study represents the first synthesis of the β-Me7CC monomer and of the resulting polycarbonates.

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Section: Resultsmentioning

confidence: 70%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Polycarbonates Derived from Green Acids: Ring-Opening Polymerization of Seven-Membered Cyclic Carbonates

et al. 2010

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“…(1) Kazuhisa Terao et al synthesize PTMC with two terminal hydroxyl groups by ring-opening polymerization of trimethylene cyclocarbonate (TMC), using DBU (1, 8diazodicyclic undecano-7-ene) as the catalyst and polyethylene glycol as the initiator [68]. Abdou Khadri Diallo et al synthesize the random copolymer P (CHC-co-TMC) of cyclohexene carbonate CHC and TMC by using organic catalyst TBD [55].…”

Section: Cationic Ring-opening Polymerization Of Cyclic Carbonatementioning

confidence: 99%

Research Progress of Biodegradable Polyester Polyols Based on Ring-Opening Polymerization of Cyclohexene Carbonate

Wang¹,

Gui²,

Qi³

et al. 2020

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The polycarbonate polyols(PCD) obtained by ring-opening polymerization of a general cyclic monomer is mostly a linear flexible structure, which is used as a raw material to synthesize polyurethanes, and it is difficult to simultaneously ensure good thermal-mechanical properties and weather resistance due to insufficient rigidity of the main chain. However, PCD based on ring-opening polymerization of cyclohexene carbonate (CHC), endowing with polyurethanes good mechanical properties, weather ability and biological stability because of the rigid structure of six-membered aliphatic rings in the main chain. Therefore, in this paper, the method and principle of preparing new polycarbonate polyols based on ring-opening polymerization of cyclohexene carbonate (CHC) are introduced. And the problems and countermeasures in its development and its application in polyurethane materials are discussed.

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“…[5][6][7][8][9][10] Homopolymerization of sixand seven-membered cyclic carbonates (6CC and 7CC) have been reported before. [1,3,[11][12][13][14][15][16][17][18][19][20] A typical property of cyclic carbonates is their volume expansion during polymerization in contrast to the usual contracting monomers such as vinyl monomers; [21,22] therefore, the cyclic carbonates are regarded as versatile monomers from the viewpoint of precise molding. In the field of material science, the copolymerization of the cyclic carbonates with other monomers as a means of controlling volume shrinkage is an important application.…”

Section: Introductionmentioning

confidence: 99%

Cationic Copolymerization Behavior of Glycidyl Phenyl Ether with Seven‐Membered Cyclic Carbonate

Morikawa

Sudo

Nishida

et al. 2005

Macro Chemistry & Physics

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Summary: To clarify the cationic copolymerization behavior of epoxide and cyclic carbonate, the copolymerization behavior of glycidyl phenyl ether (GPE) with seven‐membered cyclic carbonate (7CC) was carried out using methyl trifluoromethanesulfonate (MeOTf) as a cationic initiator. The addition of 7CC accelerated the consumption rate of GPE, and the resulting copolymers were richer in 7CC‐derived unit compared to the feed ratio of 7CC. During the copolymerization, a large amount of five‐membered cyclic carbonate having a phenoxymethyl group (PM‐5CC) was produced as a by‐product, which suggests the corresponding spiroorthocarbonate was formed as an intermediate and that residual oxytetramethylene (OTM) unit was incorporated into the copolymer sequence. From 1H NMR analysis, it was found that the copolymers had a statistically random sequence consisting of GPE, 7CC, and OTM units. magnified image

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Substituent effect on cationic ring-opening polymerization behavior of seven-membered cyclic carbonates

Cited by 12 publications

References 3 publications

Polycarbonates Derived from Green Acids: Ring-Opening Polymerization of Seven-Membered Cyclic Carbonates

Polycarbonates Derived from Green Acids: Ring-Opening Polymerization of Seven-Membered Cyclic Carbonates

Research Progress of Biodegradable Polyester Polyols Based on Ring-Opening Polymerization of Cyclohexene Carbonate

Cationic Copolymerization Behavior of Glycidyl Phenyl Ether with Seven‐Membered Cyclic Carbonate

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