Imidodiphosphoric acid as a bifunctional catalyst for the controlled ring-opening polymerization of δ-valerolactone and ε-caprolactone

Kan, Suli; Yu, Jie‐Hui; He, Xiaojiang; Jia, Chen; Wu, Hao; Ouyang, Pingkai; Guo, Kai; Li, Zhenjiang

doi:10.1039/c3py00667k

Cited by 52 publications

(37 citation statements)

References 44 publications

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“…Such features of the organophosphates coupled with the easy handling of the bulk polymerization are highly favorable for the industrial scale production of aliphatic polyesters. min to give a narrowly dispersed PVL with the M n,NMR value of 2,400 that was in good agreement with the M n,th value (2,500), as listed in 17 2,500 -7,900 and 1.07 -1.09, respectively (runs 18 -20 in Table 2). The 1 H NMR spectra of all the obtained polymers showed signals corresponding to a 3-phenyl-1-propoxy group at the α-chain end, suggesting that PPA was incorporated as the initiator in all cases ( Figures S5, S7, and S9).…”

Section: Ring-opening Polymerization Of Cyclic Esters Catalyzed By Orsupporting

confidence: 61%

“…7 Considerable effort has been directed toward the evaluation of various types of both organic acids/bases for the ROP of cyclic esters, 7-37 cyclic carbonates, [38][39][40][41][42][43] epoxides, [44][45][46][47] lactams, 48 cyclic (carbo)siloxanes, 49 cyclic phosphates, [50][51][52][53][54] etc. Regarding the ROP of cyclic esters, organic Brønsted acids, e.g., methane sulfonic acid (MSA) and triflimide, were found to be suited for the polymerization of lactones, [8][9][10][11][12][13][14][15][16][17][18][19] whereas organic bases, e.g., 1,8-diazadicyclo [5.4.0]undec-7-ene (DBU) and 4-dimethylaminopyridine (DMAP), were effective for the ROP of the lactide (LA). 7,[20][21][22][23][24]26 In addition, the bifunctional catalytic system possessing two activation sites for the monomer and propagating chain end also turned out to be effective for the ROP of ε-caprolactone (ε-CL) and LA.…”

Section: Introductionmentioning

confidence: 99%

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Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

et al. 2015

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Abstract. The ring-opening polymerizations (ROPs) of ε-caprolactone (ε-CL), -varelolactone, 1,5-dioxepan-2-one, trimethylene carbonate, and L-lactide were performed in the bulk using an organophosphate, such as diphenyl phosphate, bis(4-nitrophenyl)phosphate, and di(2,6-xylyl)phosphate, as the catalyst. The ROPs proceeded in a well-controlled manner even in the bulk condition to afford well-defined aliphatic polyesters, polyester-ether, and polycarbonate with relatively low dispersities. Notably, the amount of the loaded catalyst was successfully reduced when compared to the conventional organophosphate-catalyzed ROP in solution. A kinetic study revealed the controlled/living nature of the present bulk ROP system, which allowed us to produce the block copolymers composed of polyesters, polyester-ether, and polycarbonate in one-pot. Syntheses of the end-functionalized poly(ε-caprolactone)s (PCLs) and poly(trimethylene carbonate) were successfully demonstrated using alcohol initiators possessing highly reactive functional groups. Furthermore, the α,ω-dihydroxy telechelic PCL-diol as well as the three-and four-armed star-shaped PCL-polyols were also easily obtained by using the polyols as an initiator. Finally, the one-pot synthesis of polyurethane via the ROP of ε-CL and subsequent urethane forming reaction was demonstrated by taking advantage of the dual catalytic abilities of the organophosphate for both the ROP and polyurethane synthesis.

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Section: Ring-opening Polymerization Of Cyclic Esters Catalyzed By Orsupporting

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

et al. 2015

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“…However, at higher monomer:catalyst ratios, a plateauing of the polymer molecular weight was observed ( 37 Organocatalysts have also demonstrated good activity with moderate control. 38 Our current catalyst is the first indium complex capable of δ-valerolactone polymerization that achieves faster activity and greater control than many current catalysts. It should be noted that while the polymerizations of other monomers proceed under greater control, it is not necessarily a detriment to have slightly broad molecular weight distributions.…”

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confidence: 99%

High activity of an indium alkoxide complex toward ring opening polymerization of cyclic esters

Quan

Diaconescu

2015

Chem. Commun.

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Abstract. An indium complex supported by a ferrocene-derived Schiff base ligand has an unprecedented high activity toward ε-caprolactone, δ-valerolactone, and β-butyrolactone. L-lactide, D,L-lactide, and trimethylene carbonate polymerizations also showed moderate to high activity.Over the past two decades, the ring-opening polymerization of cyclic esters has been increasingly studied because of the promise to produce biodegradable polymers from biomass. In our recent studies, a cerium complex supported by a Schiff base ligand with a ferrocene backbone polymerized L-lactide in a controlled fashion. 24 Phosphinimine analogues with yttrium and indium also demonstrated good activity in lactide and trimethylene carbonate polymerizations. 22 Therefore, we decided to combine indium's activity with the Schiff base, ferrocene-derived ligand in order to study the activity of the resulting complexes toward a broad range of cyclic ester polymerizations. Additional motivation was found from recent studies that point to the biocompatibility, robustness, and high activity of indium catalysts in the ring opening polymerization of cyclic esters. 10,25 Herein, we report a ferrocene-derived Schiff base indium complex that possesses a remarkable range of activity toward cyclic esters and exceptionally fast polymerization rates with lactones. Compound (salfen)In(O t Bu) (salfen = 1,1'-di(2,4-di-tert-butyl-6-iminephenoxy)ferrocene) represents the first indium precatalyst capable of δ-valerolactone polymerization and the most active indium catalyst to date in the polymerization of β-butyrolactone and ε-caprolactone. The polymerization rates of ε-caprolactone are even competitive with those of current industrial catalysts.Compound (salfen)In(O t Bu) was synthesized from the reaction of (salfen)InCl and freshly sublimed KO t Bu. In turn, (salfen)InCl was synthesized by combining InCl3 with K2(salfen), which was generated from H2(salfen) and two equivalents of KH (Eq 1). Needle crystals of (salfen)InCl were isolated from a diethyl ether solution. The solid state molecular structure (Figure 1) shows a distorted octahedral indium center and a THF molecule coordinated trans to the chloride ligand. Similarly to the phosphinimine indium chloride analogue previously reported by us, 22 a long In-Fe distance (3.98 Å) and a staggered configuration of the Cp rings were apparent. Elongation of the In-heteroatom distances compared to other compounds, such as (salen)InCl (salen = N,N ' -bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (rac-or (R,R)-H2(ONNO))) 9 and (phosfen)In(OPh) (phosfen = 1,1'-di(2-tert-butyl-6-diphenylphosphiniminophenoxy)ferrocene), 22 by about 0.25 Å possibly compensates for the distortion caused by the staggered Cp rings.

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“…Their application was first demonstrated by Yount et al in the form of tetralithium adenylyl imidodiphosphate (AMP‐PNP) as a nonhydrolyzable analog of adenosine triphosphate (ATP), a competitive inhibitor in the kinetic studies of ATP‐dependent enzymes. In chemistry, imidodiphosphate esters have been used as bifunctional catalysts for asymmetric spiroacetalization and controlled ring‐opening polymerization of δ‐valerolactone and ε‐caprolactone . Other reactions that can be catalyzed by imidodiphosphates include polymerization and Mannich‐type reactions …”

Section: Introductionmentioning

confidence: 99%

Ethyl ester and silyl ester of imidodiphosphate: An alternative route to access phosphorus‐nitrogen‐phosphorus bonds via Staudinger reaction

Low

Levalois-Grützmacher

2018

Heteroatom Chemistry

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We present herein an alternative synthesis route to obtain tetraethyl imidodiphosphate (EtO) 2 P(O)NH(O)P(OEt) 2 (3) and its silylester derivative tetrakis(trimethylsilyl) imidodiphosphate (Me 3 SiO) 2 P(O)NH(O)P(OSiMe 3 ) 2 (4) involving a phosphorazidate intermediate (1) and the Staudinger reaction. Compared to previous methods, this synthesis route is simpler, more atom efficient, and energetically inexpensive.Moreover, the final compounds are obtained with larger yield and higher purity.

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Imidodiphosphoric acid as a bifunctional catalyst for the controlled ring-opening polymerization of δ-valerolactone and ε-caprolactone

Cited by 52 publications

References 44 publications

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

Organophosphate-catalyzed bulk ring-opening polymerization as an environmentally benign route leading to block copolyesters, end-functionalized polyesters, and polyester-based polyurethane

High activity of an indium alkoxide complex toward ring opening polymerization of cyclic esters

Ethyl ester and silyl ester of imidodiphosphate: An alternative route to access phosphorus‐nitrogen‐phosphorus bonds via Staudinger reaction

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