Synthesis and properties of renewable nonisocyanate polyurethanes (NIPUs) from dimethylcarbonate

Novel fully renewable AA‐BB type nonisocyanate polyurethanes (NIPUs) were synthesized using the transurethanization approach. Dicarbamate monomers were prepared by the reaction of a diamine with an excess of dimethylcarbonate (DMC), in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as catalyst. Then, the dicarbamate was reacted with a diol to afford the polymer, in presence of TBD or K₂CO₃ as catalyst. Several renewable diamines and diols were tested. The two steps were conducted under neat conditions. The obtained materials exhibited T_g values varying from ?38 to 42 ° C, T_m values varying from 42 to 204 °C , and thermal stabilities above 200 ° C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1351–1359     

Metal‐Free and Alkali‐Metal‐Catalyzed Synthesis of Isoureas from Alcohols and Carbodiimides

The first addition of alcohols to carbodiimides catalyzed by transition‐metal‐free compounds employs 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) and its alkali metal salts. Isoureas are obtained in short reaction times and high yields when TBDK is used as the catalyst. Control of the coordination sphere of potassium with exogenous chelating ligands, in combination with mechanistic DFT calculations, demonstrated the role and positive influence of the alkali‐metal cation on the kinetics.     

Magnetic nanoparticle γ‐Fe2O3‐immobilized 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene as a highly recyclable and efficient nanocatalyst for the synthesis of α′‐oxindole‐α‐hydroxyphosphonates

Magnetic nanoparticle γ‐Fe₂O₃‐immobilized 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene as a novel magnetic nanocatalyst was synthesized and characterized. The nanoparticle reagent catalyzed efficiently the synthesis of α′‐oxindole‐α‐hydroxyphosphonates from isatins and dimethyl phosphate under solvent‐free conditions at 60 °C. More importantly, the catalyst could be easily recovered by an external magnet and reused six times without significant loss of activity. Copyright © 2014 John Wiley & Sons, Ltd.     

The influence of organosuperbases on the structure and activity of dialkylgallium alkoxides in the polymerization of rac‐lactide: the road to stereo diblock PLA copolymers

Stereoselective polymerization of rac‐lactide is one of the most important issues as the properties of polylactide (PLA) depend strongly on its tacticity. There is, however, a paucity of catalysts that allow for easy switching between heteroselectivity and isoselectivity, which limits the synthesis of stereo copolymers of PLA and modification of polylactide properties. Dialkylgallium alkoxides activated by organosuperbases have been used as catalysts in the ring‐opening polymerization of racemic lactide (rac‐LA). The reaction of (S,S)‐[Me₂Ga(μ‐OCH(Me)CO₂Me)]₂ ( 1 ) with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) or 7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) resulted in the formation of isoselective gallium species, highly active in the polymerization of rac‐LA. DOSY (diffusion‐ordered spectroscopy) NMR was indicative for the presence of dimeric gallium species. However, the structure of model monomeric gallium alkoxide Me₂Ga(ON) (where ON is monoanionic bidentate ligand possessing organosuperbase functionality) shows that the presence of an organosuperbase may substantially weaken Ga?O_alkoxide?Ga bridges. The facile switch of stereoselectivity upon addition of organosuperbase to nonselective/heteroselective 1 allowed for the first time the synthesis of diblock polylactide comprised of isotactically and heterotactically enriched blocks. Copyright © 2013 John Wiley & Sons, Ltd.     

Unexpected efficiency of cyclic amidine catalysts in depolymerizing poly(ethylene terephthalate)

This article describes studies on the catalytic activity of several nitrogen‐based organic catalysts for the depolymerization of poly(ethylene terephthalate) (PET), in which a few cyclic amidines work more effectively than a potent, bifunctional guanidine‐based catalyst 1,5,7‐triazabicyclo‐[4,4,0]‐dec‐5‐ene (TBD) in the presence of short chain diols that play a role in activation of carbonyl groups through hydrogen bonding. Further studies prove that the catalytic efficiency at the above specific conditions depends only on the extent of activation of a hydroxyl group rather than simply the pK_a of the bases. For glycolysis with excess short‐chain alkanediols, 1,8‐diazabicyclo[5.4.0]undec‐7‐ene is the best catalyst. In contrast, TBD shows outstanding catalytic activity in depolymerizations of PET with mono‐alcohols and longer‐chain diols. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Organocatalytic synthesis of novel renewable non‐isocyanate polyhydroxyurethanes

Novel fully renewable AA‐BB type non‐isocyanate polyhydroxyurethanes were synthesized by the classical reaction between a diamine and a dicyclocarbonate. Sebacic acid was first reacted with an excess of glycerol carbonate, in presence of DCC and DMPA, leading to a renewable dicyclocarbonate monomer. Then, this monomer was reacted with several renewable diamines, in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), as organocatalyst, to afford linear and branched polymers. The obtained materials exhibited T_g values varied from ?27 to ?8 °C, T_m values varying from 100 to 165 °C, and thermal stabilities above 200 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 758–764     

Controlled ROP of β‐Butyrolactone Simply Mediated by Amidine,Guanidine, and Phosphazene Organocatalysts

Basic organocatalysts of the guanidine (1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene, TBD), amidine (1,8‐diazabicyclo[5.4.0]‐undec‐7‐ene, DBU), and phosphazene (2‐tert‐butylimino‐2‐diethylamino‐1,3‐dimethylperhydro‐1,3,2diazaphosphorine, BEMP) type do effectively polymerize β‐butyrolactone (BL). Poly(3‐hydroxybutyrate)s (PHBs) with controlled molecular features, that is, controlled molar masses, narrow molar mass distributions, and well‐defined functional end groups are thus formed at 60 °C from bulk monomer, with up to 21 500 g mol⁻¹. The formation of α,ω‐guanidine/amidine/phosphazene,crotonate functionalized PHBs, as demonstrated by NMR, SEC, and MALDI–ToF mass spectrometry analyses, mechanistically suggests the formation of N‐acyl‐α,β‐unsaturated propagating species that originate from 1:1 guanidine/amidine/phosphazene:BL adducts.     

Organocatalytic depolymerization of poly(ethylene terephthalate)

We describe the organocatalytic depolymerization of poly(ethylene terephthalate) (PET), using a commercially available guanidine catalyst, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). Postconsumer PET beverage bottles were used and processed with 1.0 mol % (0.7 wt %) of TBD and excess amount of ethylene glycol (EG) at 190 °C for 3.5 hours under atmospheric pressure to give bis(2‐hydroxyethyl) terephthalate (BHET) in 78% isolated yield. The catalyst efficiency was comparable to other metal acetate/alkoxide catalysts that are commonly used for depolymerization of PET. The BHET content in the glycolysis product was subject to the reagent loading. This catalyst influenced the rate of the depolymerization as well as the effective process temperature. We also demonstrated the recycling of the catalyst and the excess EG for more than 5 cycles. Computational and experimental studies showed that both TBD and EG activate PET through hydrogen bond formation/activation to facilitate this reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Experimental and computational studies of ring‐opening polymerization of ethylene brassylate macrolactone and copolymerization with ε‐caprolactone and TBD‐guanidine organic catalyst

The ring‐opening polymerization (ROP) of ethylene brassylate, catalyzed by the cyclic guanidine 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) is reported. Several experimental parameters were evaluated for bulk ROP process and polyesters, resulting in molecular weights between 3 and 15 kg mol^?1. End‐group analysis by ¹H nuclear magnetic resonnance (NMR) and matrix assisted laser desorption ionization time of flight computational studies supports the dual behavior of TBD, which can act as both a catalyst and initiator of the polymerization process. Under optimum conditions, semicrystalline poly(ethylene brassylate‐co‐ε‐caprolactone) random copolymers were synthesized. Depending on the comonomer content, our results showed a range of melting temperatures between 39 and 69 °C. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 552–561     

An efficient avenue to poly(styrene)‐block‐poly(ε‐caprolactone) polymers via switching from RAFT to hydroxyl functionality: Synthesis and characterization

The recently introduced procedure of quantitatively switching thiocarbonyl thio capped (RAFT) polymers into hydroxyl terminated species was employed to generate narrow polydispersity (PDI ≈ 1.2) sulfur‐free poly(styrene)‐block‐poly(ε‐caprolactone) polymers (26,000 ≤ M_n/g·mol^?1 < 45,000). The ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) was conducted under organocatalysis employing 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). The obtained block copolymers were thoroughly analyzed via size exclusion chromatography (SEC), NMR, as well as liquid adsorption chromatography under critical conditions coupled to SEC (LACCC‐SEC) to evidence the block copolymer structure and the efficiency of the synthetic process. The current contribution demonstrates that the RAFT process can serve as a methodology for the generation of sulfur‐free block copolymers via an efficient end group switch. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Activation of SO2 by N/Si+ and N/B Frustrated Lewis Pairs: Experimental and Theoretical Comparison with CO2 Activation

The guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and the substituted derivatives [TBD–SiR₂]⁺ and TBD–BR₂ reacted with SO₂ to give different FLP–SO₂ adducts. Molecular structures, elucidated by X-ray diffraction, showed some structural similarities with the analogous CO₂ adducts. Thermodynamic stabilities were both experimentally evidenced and computed through DFT calculations. The underlying parameters governing the relative stabilities of the different SO₂ and CO₂ adducts were discussed from a theoretical standpoint, with a focus on the influence of the Lewis acidic moiety.     

Theoretical study of TBD-catalyzed carboxylation of propylene glycol with CO2

The mechanisms for the reaction of propylene glycol (PG) with CO₂ catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were theoretically investigated by density functional theory (DFT) method at the B3LYP/6-311++G(d,p) level. Through analyzing the optimized structures and energy profiles along the reaction paths, the PG-activated route was identified as the most probable reaction path, in which the rate-determining step was the nucleophilic attack of one of the O atoms in CO₂ on the hydroxyl linked C atom in PG with energy barrier 56.96 kcal/mol. The catalytic role of TBD could be considered as a proton bridge activated by the synergistic action of its N atoms.     

1,5,7-Triazabicyclo[4.4.0]dec-5-en als Reaktionsmedium: Präparativ ergiebige einstufige Herstellung von Etioporphyrin aus Protoporphyrin

1,5,7-Triazabicyclo[4.4.0]dec-5-ene as Reaction Medium: An Efficient One-Step Formation of Etioporphyrine from Protoporphyrine Heating the commercially available protoporphyrine ( 4 ) in molten 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) at 200° for 4 h under exclusion of O₂ produces etioporphyrine ( 6 ) in 60–70% yield by bisdecarboxylation and concomitant reduction of the two vinyl groups. Mesoporphyrine ( 5 ) is bisdecarboxylated to 6 in over 80% yield under these conditions in TBD as well as in DBU as the reaction medium.     

Stereoregular polycarbonate synthesis: Alternating copolymerization of CO2 with aliphatic terminal epoxides catalyzed by multichiral cobalt(III) complexes

Completely stereoregular polycarbonate synthesis was achieved with the use of unsymmetric multichiral cobalt‐based complexes bearing a derived chiral BINOL and an appended 1,5,7‐triabicyclo[4.4.0] dec‐5‐ene as catalyst for the copolymerization of CO₂ and aliphatic terminal epoxides at mild conditions. The (S,S,S)‐Co(III) complex 1c with sterically hindered substituent group is more stereoregular catalyst for the copolymerization of CO₂ and racemic propylene oxide to afford a perfectly regioregular poly(propylene carbonate) (PPC), with >99% head‐to‐tail linkages, >99% carbonate linkages, and a K_rel of 24.4 for the enchainment of (R)‐epoxide over (S)‐epoxide. The isotactic PPC exhibits an enhanced glass transition temperature of 47 °C, which is 10–12 °C higher than that of the corresponding irregular polycarbonate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Acid-base cooperativity of heterogeneous catalyst containing acidic framework and sterically hindered base for aldol condensation

A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites,which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes,was synthesized by postgrafting of 1,5,7- triazabicyclo[4.4.0]dec-5-ene(TBD,a sterically hindered organic base) onto Al-MCM-41 molecular sieve.     

Acceleration effects of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene with 2‐methylimidazole‐intercalated α‐zirconium phosphate as a latent thermal initiator in the reaction of glycidyl phenyl ether and hexahydro‐4‐methylphthalic anhydride

The catalytic effects of 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene (TBD) with 2‐methylimidazole‐intercalated α‐zirconium phosphate (α‐ZrP?2MIm) in the reaction of glycidyl phenyl ether (GPE) and hexahydro‐4‐methylphthalic anhydride (MHHPA) were investigated. The reaction did not proceed within 1 h at 60 °C. On increasing the temperature to 100 °C, the conversion reached 93% for 1 h. Without the addition of TBD, the conversion was 67% at 100 °C for 1 h. Under storage conditions at 25 °C for 7 days, the conversion of GPE was only 18%. The curing behavior of 2,2‐bis(4‐glycidyloxyphenyl)propane (DGEBA) and MHHPA in the presence of TBD with α‐ZrP?2MIm was evaluated by differential scanning calorimetry. The addition of TBD with α‐ZrP?2MIm as a latent thermal initiator, the storage stability was maintained and the reaction proceeded rapidly under heating conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2557–2561     

Functional aliphatic polyesters and nanoparticles prepared by organocatalysis and orthogonal grafting chemistry

We describe the use of organic catalysis for the ring‐opening polymerization of functionalized lactones and conversion of the resulting aliphatic polyesters into crosslinked nanoparticles that carry additional functional groups amenable to further modification. Specifically, highly functional aliphatic polyester homopolymers, as well as random and block copolymers, were prepared by 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene catalysis, giving polyesters with pendent alkene and alkyne groups. Azide‐alkyne click and thiol‐ene chemistries were used for postpolymerization modification of diblock copolymers possessing alkene groups on one block and alkyne groups on the other block. The polyesters were crosslinked using azide/alkyne cycloaddition, by reaction of α,ω‐diazides with the pendent alkynes on the polyester backbone. This gave polyester nanoparticles possessing alkene functionality, which were subjected to further modification using thiol‐ene reactions to introduce additional functionality. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Carbene‐9‐BBN Ring Expansions as a Route to Intramolecular Frustrated Lewis Pairs for CO2 Reduction

Reactions of phosphine‐derived carbenes with 9‐borabicyclo[3.3.1]nonane (9‐BBN) result in ring‐expansion reactions to generate novel intramolecular frustrated Lewis pairs (FLPs). These FLPs effect the catalytic reduction of CO₂ in the presence of boranes to give BOB and methoxy‐borate species.     

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) an efficient homogeneous catalyst for aldol condensation reactions. Study of the catalyst recovery and reusability using CO2

In this work it was shown that TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), a cheap and commercially available guanidine base, efficiently catalyzes aldol condensation reactions yielding interesting products for pharmacological and fragrance industries. This methodology works under solvent-less conditions and affords with very good conversions the corresponding products. Moreover, a simple and effective separation protocol using the CO₂ fixation was employed. The catalyst could be recovered and re-used for three consecutive runs without significant loss of activity.     

Solvent‐free ring‐opening polymerization of lactones with hydrogen‐bonding bisurea catalyst

Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100