Poly(trimethylene carbonate) from Biometals‐Based Initiators/Catalysts: Highly Efficient Immortal Ring‐Opening Polymerization Processes

Hélou, Marion; Miserque, Olivier; Brusson, Jean-Michel; Carpentier, Jean‐François; Guillaume, Sophie M.

doi:10.1002/adsc.200800788

Cited by 54 publications

(20 citation statements)

References 96 publications

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“…Under the former solvent‐free conditions, high turnover frequencies (TOF) in the range 25–30 000 mol(TMC)⋅mol(Zn)⋅h −1 were achieved at 45–110 °C. These are about fivefold superior to those achieved, under strictly identical operating conditions, with other highly effective Zn systems such as [{BDI i Pr }Zn{N(SiMe 3 ) 2 }] ({BDI i Pr } − =CH(CMeNC 6 H 3 ‐2,6‐ i Pr 2 ) 2 ),8i,j while they are about an order of magnitude lower under the latter solution conditions. In both reaction media, the degree of control over the polymerization was satisfactory, as judged by the good match between calculated (determined from the monomer‐to‐benzyl alcohol ratio) and experimental (determined by SEC and NMR) molar mass values, and the relatively narrow molar mass distributions.…”

Section: Resultsmentioning

confidence: 61%

Discrete Cationic Zinc and Magnesium Complexes for Dual Organic/Organometallic‐Catalyzed Ring‐Opening Polymerization of Trimethylene Carbonate

Brignou

Guillaume

Roisnel

et al. 2012

Chemistry A European J

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We describe herein an original approach for the efficient immortal ring-opening polymerization (iROP) of trimethylene carbonate (TMC) under mild conditions using dual-catalyst systems combining a discrete cationic metal complex with a tertiary amine. A series of new zinc and magnesium cationic complexes of the type [{NNO}M](+) [anion](-) ({NNO}(-) = 2,4-di-tert-butyl-6-{[(2'-dimethylaminoethyl)methylamino]methyl}phenolate; M = Zn, [anion](-) = [B(C(6)F(5))(4)](-) (2), [H(2)N-{B(C(6)F(5))(3)}(2)](-) (3), and [EtB(C(6)F(5))(3)](-) (4); M = Mg, [anion](-) = [H(2)N{B(C(6)F(5))(3)}(2)](-) (7)) have been prepared from the corresponding neutral compounds [{NNO}ZnEt] (1) and [{NNO}-Mg(nBu)] (6). Compounds 2-4 and 7 exist as free ion pairs, as revealed by (1)H, (13)C, (19)F, and (11) B NMR spectroscopy in THF solution, and an X-ray crystallographic analysis of the bis(THF) adduct of compound 7, 7⋅(THF)(2). The neutral complexes 1 and 6, in combination with one equivalent or an excess of benzyl alcohol (BnOH), initiate the rapid iROP of TMC, in bulk or in toluene solution, at 45-60 °C (turnover frequency, TOF, up to 25-30,000 mol(TMC)⋅mol(Zn)⋅h(-1) for 1 and 220-240,000 mol(TMC)⋅mol(Mg)⋅h(-1) for 6), to afford H-PTMC-OBn with controlled macromolecular features. ROP reactions mediated by the cationic systems 2/BnOH and 7/BnOH proceeded much more slowly (TOF up to 500 and 3000 mol(TMC)⋅mol(Zn or Mg)⋅h(-1) at 110 °C) than those based on the parent neutral compounds 1/BnOH and 6/BnOH, respectively. Use of original dual organic/organometallic catalyst systems, obtained by adding 0.2-5 equiv of a tertiary amine such as NEt(3) to zinc cationic complexes [{NNO}Zn](+) [anion](-) (2-4), promoted high activities (TOF up to 18,300 mol(TMC)⋅mol(Zn)⋅h(-1) at 45 °C) giving H-PTMC-OBn with good control over the M(n) and M(w)/M(n) values. Variation of the nature of the anion in 2-4 did not significantly affect the performance of these catalyst systems. On the other hand, the dual magnesium-based catalyst system 7/NEt(3) proved to be poorly effective.

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Section: Resultsmentioning

confidence: 61%

Discrete Cationic Zinc and Magnesium Complexes for Dual Organic/Organometallic‐Catalyzed Ring‐Opening Polymerization of Trimethylene Carbonate

Brignou

Guillaume

Roisnel

et al. 2012

Chemistry A European J

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“…164,165 The successful (immortal) ROP of MLABe initiated by the zinc -diketiminate complex in presence of BnOH 82 then opened the route to its copolymerization with other cyclic monomers typically ring-opened polymerized by this same catalytic system 119,120 such as TMC. [166][167][168] Block copolymers P(MLABe-b-TMC) were synthesized by Guillaume and coworkers upon sequential ROP of MLABe and TMC, regardless of the order of monomer addition. However, these were more easily prepared upon polymerization of TMC prior to MLABe, the conversion of the -lactone being high-to-quantitative, whereas when MLABe was introduced first, the TMC conversion remained very sluggish.…”

Section: Copolymerization Of Mlabe With Other Monomersmentioning

confidence: 99%

Benzyl β-malolactonate polymers: a long story with recent advances

Jaffredo

Guillaume

2014

Polym. Chem.

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International audiencePoly (-benzyl malolactonate) (PMLABe) is an aliphatic renewable, biocompatible, biodegradable, hydrophobic polyester of the poly(hydroxyalkanoate) (PHA) family. Along with the hydrophilic parent poly(-malic acid) (PMLA), PMLABe and PMLA have been studied as materials for biomedical applications. Herein, advances on the synthesis of benzyl -malolactonate (MLABe) and the related alkyl -malolactonates (MLARs), PMLABe homopolymers and copolymers, are reviewed. Focus is placed on the ring-opening polymerization (ROP) of MLABe and on copolymers of MLABe, with relevant data on the performances of the initiating systems and on the PMLABes molecular characteristics, along with detailed mechanistic insights, being reported

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“…[1][2][3][4][5][6][7][8][9] A wide range of initiating systems based on main group as well as d and f transition-metal derivatives have been designed and successfully evaluated in the ringopening polymerization (ROP) of such heterocyclic monomers. [5][6][7][8][9][10][11][12][13] Although rather "basic" complexes such as zinc bis-alkoxide species prepared in situ from ZnEt 2 and ROH are efficient in living processes, [14][15][16] more sophisticated initiating systems involving metallocene and, more recently, post-metallocene ancillary ligands provide further control over the stereo-, regio-, and enantioselectivity, limiting sidereactions, and with high activity and productivity. [15][16][17][18][19] In rare-earth chemistry, alkoxide and aryl oxide initiating sysAbstract: Rare-earth-metal borohydrides are known to be efficient catalysts for the polymerization of apolar and polar monomers.…”

Section: Introductionmentioning

confidence: 98%

Bis(phosphinimino)methanide Borohydride Complexes of the Rare‐Earth Elements as Initiators for the Ring‐Opening Polymerization of ε‐Caprolactone: Combined Experimental and Computational Investigations

Jenter

Roesky

Ajellal

et al. 2010

Chemistry A European J

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Rare-earth-metal borohydrides are known to be efficient catalysts for the polymerization of apolar and polar monomers. The bis-borohydrides [{CH(PPh2 NSiMe3)2}La(BH4)2(THF)] and [{CH(PPh2NSiMe3)2}Ln(BH4)2] (Ln = Y, Lu) have been synthesized by two different synthetic routes. The lanthanum and the lutetium complexes were prepared from [Ln(BH4)3(THF)3] and K{CH(PPh2NSiMe3)2}, whereas the yttrium analogue was obtained from in situ prepared [{CH(PPh2NSiMe3)2}YCl2]2 and NaBH4. All new compounds were characterized by standard analytical/spectroscopic techniques, and the solid-state structures were established by single-crystal X-ray diffraction. The ring-opening polymerization (ROP) of ε-caprolactone initiated by [{CH(PPh2NSiMe3)2}La(BH4)2(THF)] and [{CH(PPh2NSiMe3)2}Ln(BH4)2] (Ln = Y, Lu) was studied. At 0 °C the molar mass distributions determined were the narrowest values (M(w)/M(n) = 1.06-1.11) ever obtained for the ROP of ε-caprolactone initiated by rare-earth-metal borohydride species. DFT investigations of the reaction mechanism indicate that this type of complex reacts in an unprecedented manner with the first B-H activation being achieved within two steps. This particularity has been attributed to the metallic fragment based on the natural bond order analysis.

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Poly(trimethylene carbonate) from Biometals‐Based Initiators/Catalysts: Highly Efficient Immortal Ring‐Opening Polymerization Processes

Abstract: International audienc

Cited by 54 publications

References 96 publications

Discrete Cationic Zinc and Magnesium Complexes for Dual Organic/Organometallic‐Catalyzed Ring‐Opening Polymerization of Trimethylene Carbonate

Discrete Cationic Zinc and Magnesium Complexes for Dual Organic/Organometallic‐Catalyzed Ring‐Opening Polymerization of Trimethylene Carbonate

Benzyl β-malolactonate polymers: a long story with recent advances

Bis(phosphinimino)methanide Borohydride Complexes of the Rare‐Earth Elements as Initiators for the Ring‐Opening Polymerization of ε‐Caprolactone: Combined Experimental and Computational Investigations

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