Cyclic polylactides via simultaneous ring‐opening polymerization and polycondensation catalyzed by dibutyltin mercaptides

l ‐Lactide is polymerized in bulk at 160 °C either with dibutyltin bis(benzylmercaptide) (SnSBzl), dibutyltin bis(benzothiazole 2‐mercaptide) (SnMBT), or with dibutyltin bis(pentafluorothiophenolate) (SnSPF) as catalysts. SnSBzl yields linear polylactides having benzylthio‐ester end groups in addition to cyclic polylactides, whereas SnMBT and SnSPF mainly or exclusively yield cyclic polylactides. This finding, together with model reactions, indicates that the SnS catalysts promote a combined ring‐opening polymerization and polycondensation process including end‐to‐end cyclization. SnMBT caused slight racemization (3%–5%), when used at 160 °C. With SnSPF optically pure cyclic poly(l ‐lactide)s with high‐molecular weights can be prepared at 160 °C. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3767–3775     

About formation of cycles in Sn(II) octanoate‐catalyzed polymerizations of lactides

At first, formation of cycles in commercial poly(l ‐lactide)s is discussed and compared with benzyl alcohol‐initiated polymerizations performed in this work. This comparison was extended to polymerizations initiated with 4‐cyanophenol and pentafluorothiophenol which yielded cyclic polylactides via end‐biting. The initiator/catalyst ratio and the acidity of the initiator were found to be decisive for the extent of cyclization. Further polymerizations of l ‐lactide were performed with various diphenols as initiators/co‐catalysts. With most diphenols, cyclic polylactides were the main reaction products. Yet, only catechols yielded even‐numbered cycles as main reaction products, a result which proves that their combination with SnOct₂ catalyzed a ring‐expansion polymerization (REP). The influence of temperature, time, co‐catalyst, and catalyst concentrations was studied. Four different transesterification reactions yielding cycles were identified. For the cyclic poly(l ‐lactide)s weight average molecular weights (M_w's) up to 120,000 were obtained, but ¹H NMR end group analyses indicated that the extent of cyclization was slightly below 100%. The influence of various parameters like structure of initiator and catalyst and temperature on the formation of cyclic poly(l ‐lactide)s has been investigated. Depending on the chosen conditions, the course of the polymerization can be varied from a process yielding exclusively linear polylactides to mainly cyclic polylactides. Three different reaction pathways for cyclization reactions have been identified. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1915–1925     

Syntheses of trimethoxysilyl‐endcapped polylactones via 3‐mercaptopropyl trimethoxysilane

Monofunctional polylactones were prepared by Bu₂Sn(OMe)₂‐initiated ring‐opening polymerization of ε‐caprolactone (εCL) followed by acylation with bromoacetylbromide. Telechelic polylactones and polylactides were prepared via ring‐expansion polymerization with 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP) or 2,2‐dibutyl‐2‐stanna‐pentaoxacyclotridecane (Bu₂SnTEG) as cyclic initiator. In situ combination of the polymerization with condensation by means of bromoacetylbromide yielded polylactones having bromoacetate endgroups. These endgroups were subjected to nucleophilic substitution with 3‐mercaptopropyl trimethoxysilane (3‐MPTMS). Analogous experiments were conducted with dl‐lactide. The telechelic trimethoxysilyl‐endcapped polylactones were characterized by viscosity, ¹H and ¹³C NMR‐spectroscopy, and MALDI‐TOF mass spectrometry. The mass spectra revealed small amounts of cyclic oligolactones as byproducts in all samples. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3667–3674, 2005     

Polymerization of (L,L)‐lactide and copolymerization with ϵ‐caprolactone initiated by dibutyltin dimethoxide in supercritical carbon dioxide

Ring‐opening polymerization (ROP) of (L,L)‐lactide (LA) has been initiated by dibutyltin dimethoxide in supercritical carbon dioxide (sc CO₂). Polymerization is controlled and proceeds at quasi the same rate as in toluene, which indicates that the reactivity of the propagating species is not impaired by parasitic carbonation reaction. Random copolymerization of LA with ?‐caprolactone (CL) has also been studied in sc CO₂, and the reactivity ratios have been determined as 5.8 ± 0.5 for LA and 0.7 ± 0.25 for CL. These values have to be compared to 0.7 ± 0.25 for LA and 0.15 ± 0.05 for CL in toluene. Good control on ROP of CL and LA in sc CO₂ has been confirmed by the successful synthesis of diblock copolymers by sequential polymerization of CL and LA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2777‐2789, 2005     

Phosphines: Nucleophilic organic catalysts for the controlled ring‐opening polymerization of lactides

A new metal‐free synthetic approach to the controlled ring‐opening polymerization (ROP) of lactide with nucleophilic phosphines as transesterification catalysts is described. P(Bu)₃, PhPMe₂, Ph₂PMe, PPh₃, and related phosphines are commercially available, inexpensive catalysts that generate narrowly dispersed polylactides with predictable molecular weights. These organic catalysts must be used in combination with an initiator, such as an alcohol, to generate an alcoholate ester α‐end group upon ROP. A likely polymerization pathway is through a monomer‐activated mechanism, with minimal active species, facilitating narrow molecular weight distributions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 844–851, 2002; DOI 10.1002/pola.10168     

Ring‐opening polymerization of cyclic esters promoted by phosphido‐diphosphine pincer group 3 complexes

Phosphido‐diphosphine Group 3 metal complexes 1–4 [(o‐C₆H₄PR₂)₂P‐M(CH₂SiMe₃)₂; R = Ph, 1 : M = Y, 2 : M = Sc; R = iPr, 3 : M = Y, 4 : M = Sc] are very efficient catalysts for the ring‐opening polymerization (ROP) of cyclic esters such as ε‐caprolactone (ε‐CL), L ‐lactide, and δ‐valerolactone under mild polymerization conditions. In the ROP of ε‐CL, complexes 1–4 promote quantitative conversion of high amount of monomer (up to 3000 equiv) with very high turnover frequencies (TOF) (～4 × 10⁴ mol_CL/mol_I h) showing a catalytic activity among the highest reported in the literature. The immortal and living ROP of ε‐CL and L ‐lactide is feasible by combining complexes 1–4 with 5 equiv of 2‐propanol. Polymers with controlled molecular parameters (M_n, end groups) and low polydispersities (M_w/M_n = 1.05–1.09) are formed as a result of fast alkoxide/alcohol exchange. In the ROP of δ‐valerolactone, complexes 1–4 showed the same activity observed for lactide (L ‐ and D ,L ‐lactide) producing high molecular weight polymers with narrow distribution of molar masses. Complexes 1–4 also promote the ROP of rac‐β butyrolactone affording atactic low molecular weight poly(hydroxybutyrate) bearing unsaturated end groups probably generated by elimination reactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Aluminum salen and salan complexes in the ring‐opening polymerization of cyclic esters: Controlled immortal and copolymerization of rac‐β‐butyrolactone and rac‐lactide

Aluminum‐based salen and salan complexes mediate the ring‐opening polymerization (ROP) of rac‐β‐butyrolactone (β‐BL), rac‐lactide, and ε‐caprolactone. Al‐salen and Al‐salan complexes exhibit excellent control over the ROP of rac‐β‐butyrolactone, yielding atactic poly(3‐hydroxybutyrate) (PHB) with narrow PDIs of <1.15 for Al‐salen and <1.05 for Al‐salan. Kinetic studies reveal pseudo‐first‐order polymerization kinetics and a linear relationship between molecular weight and percent conversion. These complexes also mediate the immortal ROP of rac‐β‐BL and rac‐lactide, through the addition of excess benzyl alcohol of up to 50 mol eq., with excellent control observed. A novel methyl/adamantyl‐substituted Al‐salen system further improves control over the ROP of rac‐lactide and rac‐β‐BL, yielding atactic PHB and highly isotactic poly(lactic acid) (P_m = 0.88). Control over the copolymerization of rac‐lactide and rac‐β‐BL was also achieved, yielding poly(lactic acid)‐co‐poly(3‐hydroxybutyrate) with narrow PDIs of <1.10. ¹H NMR spectra of the copolymers indicate a strong bias for the insertion of rac‐lactide over rac‐β‐BL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of cyclic poly(l‐lactide) catalyzed by Bismuth Salicylates—A combination of two drugs

l ‐lactide was polymerized in bulk at 160 or 180°C with mixtures of bismuth subsalicylate (BiSub) and salicylic (SA) as catalysts. The SA/Bi ratio and the monomer/Bi ratio were varied. The highest molecular weights (weight average, Mw) were achieved at a SA/Bi ratio of 1/1 (Mw up to 92 000 g mol^?1). l ‐Lactide was also polymerized with combinations of BiSub and silylated SA, and Mw values up to 120 000 g mol^?1 were achieved at 180°C. MALDI‐TOF mass spectrometry and Mark‐Houwink‐Sakurada measurements proved that under optimized reaction conditions the resulting polylactides consist of cycles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2056–2063     

Ring‐expansion polymerization of meso‐lactide catalyzed by dibutyltin derivatives

Meso‐Lactide was polymerized in bulk at 60, 80, and 100 °C by means of three different types of catalysts: dibutyltin sulfides (2,2‐dibutyl‐2‐stanna‐1,3‐dithiolane and 2,2′‐dibutyl‐2‐stanna‐1,3‐dithiane), dibutyltin derivatives of substituted catechols (BuCa, CyCa, and BzCa), and dibutyltin derivatives of 2,2′dihydroxybiphenyl (SnBi) and 2,2′‐dihydroxy‐1,1′‐binaphthyl (SnNa). Only the latter two catalysts were active at 60 °C. The architecture of the resulting polylactides depends very much on the structure of the catalyst and on the temperature. At the lowest temperature (60 °C), SnBi and SnNa mainly yielded even‐numbered linear chains, but SnNa also yielded even‐numbered cycles at 100 °C and short reaction times. In contrast, BuCa, CyCa, and BzCa mainly yielded odd‐numbered cycles, although the same catalysts yielded even‐numbered linear chains when benzylalcohol was added. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 749–759     

Synthesis and ring‐opening polymerization of new monoalkyl‐substituted lactides

New monoalkyl‐substituted lactides were synthesized by reaction of α‐hydroxy acids with 2‐bromopropionyl bromide, and polymerized with various catalysts in the presence of benzyl alcohol by ring‐opening polymerization (ROP). The classic tin(II) 2‐ethylhexanoate (Sn(Oct)₂) catalyst was leading to polymers with narrow distribution and predictable molecular weights, in polymerizations in bulk or toluene at 100 °C. The polymerization rate was corresponding to the steric hindrance of the alkyl substituents, such as butyl, hexyl, benzyl, isopropyl, and dimethyl groups. A yield of 83% was obtained with the hexyl‐substituted lactide after 1 h of polymerization. Excellent conversions (97%) could be achieved by using the alternative catalyst 4‐(dimethylamino)pyridine (DMAP). This latter organic catalyst was most efficient in polymerizing the more steric‐hindered lactides with good molecular weight and polydispersity control, in comparison to the tin(II) 2‐ethylhexanoate and tin(II) trifluoromethane sulfonate [Sn(OTf)₂] catalysts. The efficiency of the DMAP catalyst and the variability of the monomer synthesis route for new alkyl‐substituted lactides allow to prepare and to envision a wide range of new functionalized polylactides for the elaboration of tailored materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4379–4391, 2004     

Polylactones. LVIII. Star‐shaped polylactones with functional end groups via ring‐expansion polymerization with a spiroinitiator

Two more or less ethoxylated pentaerythritols were reacted with dibutyltin dimethoxide and yielded spirocyclic tin alkoxides that were soluble in hot toluene or in chlorobenzene, chloroform, and 1,1,2,2‐tetrachloroethane at room temperature. These solutions were used in situ as initiators for the ring‐expansion polymerization of ?‐caprolactone or β‐D,L ‐butyrolactone. The spirocyclic polylactones were reacted with various carboxylic acid chlorides and yielded four‐armed stars with the elimination of Bu₂SnCl₂. By variation of the acid chlorides, star arms with chloroacetate, 4‐bromobenzoate, 4‐nitrobenzoate, cinnamate, stearate, or methacrylate end groups were obtained. With 4‐chlorothiophenyl esters of N‐protected amino acids, N‐protected aminoacyl end groups were introduced. A complete functionalization of all star arms was not achieved in all cases, and structure–property relationships were examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1047–1057, 2002     

Neodymium‐based catalysts bearing phosphate ligands for ring‐opening polymerization of ɛ‐caprolactone

Neodymium‐based catalysts coordinated with phosphate ligands (NdCl₃·3L), where L = triethyl phosphate (TEP) or tris(2‐ethylhexyl) phosphate (TEHP), were synthesized. The ring‐opening polymerizations (ROP) of ɛ‐caprolactone (ɛ‐CL) with these catalysts in the presence of benzyl alcohol initiator were performed, yielding polymers with well‐defined molecular weights and relatively narrow polydispersity index (PDI = 1.22–1.65). In situ NMR analysis of the reaction between NdCl₃·3TEP and benzyl alcohol indicated that ROP proceeds through a coordination‐insertion mechanism. The end groups of the resultant polymers were determined using MALDI‐ToF mass spectrometry and NMR spectroscopy. The quasi‐living nature of this catalytic system was demonstrated by kinetic studies and the successful synthesis of the block copolymer poly(ɛ‐caprolactone)‐block‐poly(l ‐lactide) by sequential monomer addition. Kinetic studies revealed that the catalyst with the bulkier TEHP ligand increased the rate of ROP of ɛ‐CL as compared to the TEP ligand. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1289–1296     

A “Mitsubishi emblem” tetrauclear aluminum complex containing two unsymmetric N2O2‐ligands and a symmetric NO3‐ligand as initiator for polymerization of rac‐lactide

A novel hydroxy‐, methoxy‐, and phenoxy‐bridge “Mitsubishi emblem” tetranuclear aluminum complex ( 1 ) is synthesized from an unsymmetric amine‐pyridine‐bis(phenol) N₂O₂‐ligand (H₂L¹) and a symmetric amine‐tris(phenol) NO₃‐ligand (H₂L²). Two same configuration chiral nitrogen atoms are formed in the tetranuclear Al complex upon coordination of the unsymmetric tertiary amine ligand to central Al. Complex 1 initiates controlled ring‐opening polymerization (ROP) of rac‐lactide and afford polylactide (PLA) with narrow molecular weight distributions (M_w/M_n = 1.05–1.19). The analysis of ¹H NMR spectra of the oligomer indicates that the methoxy group is the initiating group and the ring‐opening polymerization of lactide follows a coordination‐insertion mechanism. The Homonuclear decoupled ¹H NMR spectroscopy suggests the isotactic‐rich chains is preferentially formed in PLA. The study on kinetics of the ROP of lactide reveals the homopropagation rate is higher than the cross‐propagation rate, which is in agreement with the observed isotactic selectivity in the ROP of rac‐lactide. The stereochemistry of the polymerization was also supported by activation parameters. The introduction of unsymmetric ligand H₂L¹ has an effect on stereoslectivity of polymerization. This result may be of interest for the design of multinuclear metal complex catalysts containing functionalized ligands. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2084–2091     

End‐functionalized polylactides using a calcium‐based precatalyst: Synthesis and insights by mass spectrometry

A simple and convenient method for the synthesis of end functionalized polylactides (PLAs) under mild conditions by ring opening polymerization (ROP) in the absence of potentially toxic catalysts is described. Various alcohols were used as initiators in combination with Ca[N(SiMe₃)₂]₂(THF)₂ as the precatalyst in THF at room temperature. Tailored end functionalities were obtained in a controlled fashion. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐ToF‐MS) and electrospray ionization quadrupole time of flight mass spectrometry (ESI‐Q‐ToF‐MS) analysis were performed to investigate the end groups. The results confirmed that the end group fidelity was maintained in the isolated PLAs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 437–448     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010     

Polymerizability of Exo‐methylene‐lactide toward vinyl addition and ring opening

This work examines the stereochemical control and polymerizability of exo‐methylene‐lactide (MLA) or (6S)‐3‐methylene‐6‐methyl‐1,4‐dioxane‐2,5‐dione, a chiral monomer derived from l ‐lactide, toward vinyl‐addition and ring‐opening polymerization (ROP) pathways, respectively. Currently, no information on the stereochemistry of the vinyl‐addition polymerization of MLA is known, and the possible ROP pathway is unexplored. Accordingly, this work first investigated the stereochemical control and other characteristics of the radical polymerization of MLA and its copolymerization with an analogous exo‐methylene‐lactone, γ‐methyl‐α‐methylene‐γ‐butyrolactone (MMBL), and di‐methylene‐lactide (DMLA) or 3,6‐dimethylene‐1,4‐dioxane‐2,5‐dione. The MLA homopolymerization produced optically active, but atactic, vinyl‐type polymers having a specific rotation of [α]²³_D = ?42 ± 4°, a high T_g from 229 to 254 °C, and a medium (M_w = 76.3 kg/mol, ? = 1.16) to high (M_w = 358 kg/mol, ? = 2.83) molecular weight, depending on the solvent. The copolymerization of MLA with MMBL afforded copolymers exhibiting enhanced thermal stability, while its copolymerization with DMLA led to cross‐linked polymers. The results obtained from the model reactions designed to probe the possible ROP indicate that the nonpolymerizability of MLA by initiators or catalysts comprising acidic, protic, and/or nucleophilic reagents is due to the high sensitivity of MLA toward such common ROP reagents that trigger decomposition or other types of transformations of MLA forming nonpolymerizable derivatives. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1523–1532     

Microwave‐assisted synthesis and characterization of biodegradable block copolyesters based on poly(3‐hydroxyalkanoate)s and poly(D,L‐lactide)

Microwave (MW)‐assisted ring‐opening polymerization (ROP) provides a rapid and straightforward method for engineering a wide array of well‐defined poly(3‐hydroxyalkanoate)‐b‐poly(D,L ‐lactide) (PHA‐b‐PLA) diblock copolymers. On MW irradiation, the bulk ROP of D,L ‐lactide (LA) could be efficiently triggered by a series of monohydroxylated PHA‐based macroinitiators previously produced via acid‐catalyzed methanolysis of corresponding native PHAs, thus affording diblock copolyesters with tunable compositions. The dependence of LA polymerization on temperature, macroinitiator structure, irradiation time, and [LA]₀/[PHA]₀ molar ratio was carefully investigated. It turned out that initiator efficiency values close to 1 associated with conversions ranging from 50 to 85% were obtained only after 5 min at 115 °C. A kinetic investigation of the MW‐assisted ROP of LA gave evidence of its “living”/controlled character under the experimental conditions selected. Structural analyses and thermal properties of biodegradable diblock copolyesters were also performed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Block copolymers via macromercaptan initiated ring opening polymerization

Poly(styrene) macromercaptanes (M_n = 1900, 3600, and 6100 g mol^?1, PDI ≈ 1.2) derived from thiocarbonyl thio capped polymers prepared via reversible addition fragmentation chain transfer polymerization were employed to initiate the ring opening polymerization (ROP) of D ,L ‐lactide under conditions of organo‐catalyis employing 4,4‐dimethylaminopyridine. Poly(styrene)‐block‐poly(lactide) polymers of number average molecular weights up to 25,000 g mol^?1 (PDI ≈ 1.2 to 1.6) were obtained and characterized via multiple detection size exclusion chromatography (SEC) using refractive index as well as UV detection. In addition, diffusion ordered nuclear magnetic resonance and liquid chromatography at critical conditions (of both polystyrene as well as poly(lactide) were employed to assess the copolymers' structure. Furthermore, it was demonstrated that polyethylenes capped with a thiol moiety can also be readily chain extended in a ROP employing D ,L ‐lactide, evidenced via NMR and high temperature SEC. This study indicates that the direct use of macromercaptantes is indeed a methodology to switch from a radical to a ROP process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of end‐functionalized polymers and copolymers of cyclopentadiene with vinyl ethers by cationic polymerization

A series of cyclopentadiene (CPD)‐based polymers and copolymers were synthesized by a controlled cationic polymerization of CPD. End‐functionalized poly(CPD) was synthesized with the HCl adducts [initiator = CH₃CH(OCH₂CH₂X)Cl; X = Cl ( 2a ), acetate ( 2b ), or methacrylate] of vinyl ethers carrying pendant functional substituents X in conjunction with SnCl₄ (Lewis acid as a catalyst) and n‐Bu₄NCl (as an additive) in dichloromethane at −78 °C. The system led to the controlled cationic polymerizations of CPD to give controlled α‐end‐functionalized poly(CPD)s with almost quantitative attachment of the functional groups (F_n ∼ 1). With the 2a or 2b /SnCl₄/n‐Bu₄NCl initiating systems, diblock copolymers of 2‐chloroethyl vinyl ether (CEVE) and 2‐acetoxyethyl vinyl ether with CPD were also synthesized by the sequential polymerization of CPD and these vinyl ethers. An ABA‐type triblock copolymer of CPD (A) and CEVE (B) was also prepared with a bifunctional initiator. The copolymerization of CPD and CEVE with 2a /SnCl₄/n‐Bu₄NCl afforded random copolymers with controlled molecular weights and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight = 1.3–1.4). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 398–407, 2001     

Alkaline Earth Metal‐Mediated Highly Iso‐selective Ring‐Opening Polymerization of rac‐Lactide

Alkaline earth (Ae) metal complexes of the aminophosphine borane ligand are highly active and iso‐selective catalysts for the ring‐opening polymerization (ROP) of rac‐lactide (LA). The polymerization reactions are well controlled and produce polylactides with molecular weights that are precise and narrowly distributed. Kinetic studies reveal that the ROP of rac‐LA catalyzed by all Ae metal complexes had a first‐order dependency on LA concentration as well as catalyst concentration. A plausible reaction mechanism for Ae metal complex‐mediated ROP of rac‐LA is discussed, based on controlled kinetic experiments and molecular chain mobility.