Block and random copolymerization of ε‐caprolactone,L‐, and rac‐lactide using titanium complex derived from aminodiol ligand

A series of di‐ and triblock copolymers [poly(L ‐lactide‐b‐ε‐caprolactone), poly(D,L ‐lactide‐b‐ε‐caprolactone), poly(ε‐caprolactone‐b‐L ‐lactide), and poly(ε‐caprolactone‐b‐L ‐lactide‐b‐ε‐caprolactone)] have been synthesized successfully by sequential ring‐opening polymerization of ε‐caprolactone (ε‐CL) and lactide (LA) either by initiating PCL block growth with living PLA chain end or vice versa using titanium complexes supported by aminodiol ligands as initiators. Poly(trimethylene carbonate‐b‐ε‐caprolactone) was also prepared. A series of random copolymers with different comonomer composition were also synthesized in solution and bulk of ε‐CL and D,L ‐lactide. The chemical composition and microstructure of the copolymers suggest a random distribution with short average sequence length of both the LA and ε‐CL. Transesterification reactions played a key role in the redistribution of monomer sequence and the chain microstructures. Differential scanning calorimetry analysis of the copolymer also evidenced the random structure of the copolymer with a unique T_g. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ring‐opening polymerization of 6‐hydroxynon‐8‐enoic acid lactone: Novel biodegradable copolymers containing allyl pendent groups

This article reports the synthesis and copolymerization of 6‐hydroxynon‐8‐enoic acid lactone. The ring‐opening polymerization of this lactone‐type monomer bearing a pendant allyl group led to new homopolymers and random copolymers with ε‐caprolactone and L ,L ‐lactide. The copolymerizations were carried out at 110 °C with Sn(Oct)₂ as a catalyst. The introduction of unsaturations into the aliphatic polyester permitted us to carry out different chemical transformations on this family of polymers. For example, this article reports the bromination, epoxidation, and hydrosylilation of the allyl group in the new polyester copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 870–875, 2000     

Living polymerization of D,L‐3‐methylglycolide initiated with bimetallic (Al/Zn) μ‐oxo alkoxide and copolymers thereof

D,L ‐3‐Methylglycolide (MG) was successfully polymerized with bimetallic (Al/Zn) μ‐oxo alkoxide as an initiator in toluene at 90 °C. The effect of the initiator concentration and monomer conversion on the molecular weight was studied. It is shown that the polymerization of MG follows a living process. A kinetic study indicated that the polymerization approximates the first order in the monomer, and no induction period was observed. ¹H NMR spectroscopy showed that the ring‐opening polymerization proceeds through a coordination–insertion mechanism with selective cleavage of the acyl–oxygen bond of the monomer. On the basis of ¹H NMR and ¹³C NMR analyses, the selective cleavage of the acyl–oxygen bond of the monomer mainly occurs at the least hindered carbonyl groups (P₁ = 0.84, P₂ = 0.16). Therefore, the main chain of poly(D,L ‐lactic acid‐co‐glycolic acid) (50/50 molar ratio) obtained from the homopolymerization of MG was primarily composed of alternating lactyl and glycolyl units. The diblock copolymers poly(ϵ‐caprolactone)‐b‐poly(D,L ‐lactic acid‐alt‐glycolic acid) and poly(L ‐lactide)‐b‐poly(D,L ‐lactic acid‐alt‐glycolic acid) were successfully synthesized by the sequential living polymerization of related lactones (ϵ‐caprolactone or L ‐lactide). ¹³C NMR spectra of diblock copolymers clearly show their pure diblock structures. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 357–367, 2001     

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     

Synthesis of three‐armed poly(trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L‐proline)‐block‐poly(ε‐caprolactone) copolymers

A series of novel types of three‐armed poly(trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline)‐block‐poly(ε‐caprolactone) (PHpr‐b‐PCL) copolymers were successfully synthesized via melt block copolymerization of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) and ε‐caprolactone (ε‐CL) with a trifunctional initiator trimethylolpropane (TMP) and stannous octoate (SnOct₂) as a catalyst. For the homopolycondensation of N‐CBz‐Hpr with TMP initiator and SnOct₂ catalyst, the number‐average molecular weight (M_n) of prepolymer increases from 530 to 3540 g mol^?1 with the molar ratio of monomer to initiator (3–30), and the molecular weight distribution (M_w/M_n) is between 1.25 to 1.32. These three‐armed prepolymer PHpr were subsequently block copolymerized with ε‐caprolactone (ε‐CL) in the presence of SnOct₂ as a catalyst. The M_n of the copolymer increased from 2240 to 18,840 g mol^?1 with the molar ratio (0–60) of ε‐CL to PHpr. These products were characterized by differential scanning calorimetry (DSC), ¹H NMR, and gel permeation chromatography. According to DSC, the glass‐transition temperature (T_g) of the three‐armed polymers depended on the molar ratio of monomer/initiator that were added. In vitro degradation of these copolymers was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1708–1717, 2005     

Polylactones, 56. ABA Triblock Copolymers Derived from ε‐Caprolactone or L‐Lactide and a Central Polysiloxane Block

A commercial oligosiloxane having two γ‐hydroxypropyl endgroups and a number‐average molecular weight (M̄_n) around 1 000 Da was condensed with Bu₂Sn(OMe)₂ yielding tin‐containing macrocycles but no polymers. These macrocycles reacted with γ‐thiobutyrolactone by insertion of one thiolactone per Sn—O bond. When ε‐caprolactone was added a ring‐expansion polymerization was initiated, so that the M̄_n could be controlled via the monomer/initiator (M/I) ratio. Triblock copolymers with free OH endgroups were obtained by removal of the Bu₂Sn group from the cyclic polymers with 1,2‐dimercaptoethane or methanol. Analogous cyclic and linear triblockcopolymers were prepared from L ‐lactide.     

Random copolymerization of l‐lactide and ε‐caprolactone by aluminum alkoxide complexes supported by N2O2 bis(phenolate)‐amine ligands

The bowl‐shaped aluminum alkoxide complexes bearing N₂O₂ bis(phenolate)‐amine ligands having different side arms as pyridine ( 1 ), dimethyl amine ( 2 ), and diethyl amine ( 3 ) were shown to be highly efficient and well behaved in the homopolymerization and copolymerization of l ‐lactide (LA) and ε‐caprolactone (ε‐CL) at 100 °C. The rates of copolymerization are similar for Complexes 1 – 3 where nearly full conversions were achieved in 60 h for [LA]:[CL]:[Al] ratio of 50:50:1. The minor adjustment of the side arms of the Catalysts 1 – 3 gave profound differences in the LA/ε‐CL copolymer sequences where tapered, gradient, and highly random structures were obtained in one system, respectively. The chelation of LA to Al metal after ring‐opening process and suitable steric hindrance of the side arms were believed to participate and saturate the aluminum metal centers giving different copolymer structures. The random LA/ε‐CL copolymer structure was confirmed by nuclear magnetic resonance and differential scanning calorimetry analysis. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1635–1644     

Effect of comonomer on thermal/mechanical and shape memory property of L‐lactide‐based shape‐memory copolymers

In this study, three kinds of L ‐lactide‐based copolymers, poly(lactide‐co‐glycolide) (PLGA), poly(lactide‐co‐p‐dioxanone) (PLDON) and poly(lactide‐co‐caprolactone) (PLC), were synthesized by the copolymerization of L ‐lactide (L) with glycolide (G), or p‐dioxanone (DON) or ε‐caprolactone (CL), respectively. The copolymers were easily soluble in common organic solvents. The compositions of the copolymers were determined by ¹H‐NMR. Thermal/mechanical and shape‐memory properties of the copolymers with different comonomers were compared. Moreover, the effect of the chain flexibility of the comonomers on thermal/mechanical and shape‐memory properties of the copolymers were investigated. The copolymers with appropriate lactyl content showed good shape‐memory properties where both the shape fixity rate (R_f)and the shape recovery rate (R_r) could exceed 95%. It was found that the comonomers with different flexible molecular chain have different effects on their thermal/mechanical and shape‐memory properties. Among them, PLGA has the highest mechanical strength and recovery rate while PLC copolymer has high recovery rate when the lactyl content exceeded 85% and the lowest transition temperature (T_trans). Copyright © 2007 John Wiley & Sons, Ltd.     

Diphenyl phosphate/4‐dimethylaminopyridine as an efficient binary organocatalyst system for controlled/living ring‐opening polymerization of L‐lactide leading to diblock and end‐functionalized poly(L‐lactide)s

The ring‐opening polymerizations (ROPs) of ε‐caprolactone (ε‐CL) and L ‐lactide (LLA) have been studied using the organocatalysts of diphenyl phosphate (DPP) and 4‐dimethylaminopyridine (DMAP). The “dual activation” property of DPP and the “bifunctional activation” property of DPP/DMAP were confirmed by the NMR measurement for ε‐CL and its chain‐end model of poly(ε‐caprolactone) and for LLA and its chain‐end model of poly(L ‐lactide) (PLLA), respectively. The molar ratio of DPP/DMAP was optimized as 1/2 for the ROP of LLA leading to the well‐defined PLLA, such as the molecular weight determined from ¹H NMR measurement of 19,200 g mol^?1 and the narrow polydispersity of 1.10. Additionally, functional initiators were utilized for producing the end‐functionalized PLLAs. The DPP‐catalyzed ROPs of ε‐CL and its analogue cyclic monomers and then the DPP/DMAP‐catalyzed ROP of LLA produced block copolymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1047–1054     

Aluminum complex initiated copolymerization of lactones and DL‐lactide to form crystalline gradient block copolymers containing stereoblock lactyl chains

The homopolymerization reactions of several lactones, as well as the copolymerization reactions of DL‐lactide with these lactones were investigated using tridentate Schiff base aluminum complexes as the initiators. ε‐Caprolactone and δ‐valerolactone polymerized efficiently at room temperature to afford polyesters, whereas β‐butyrolactone only gave the corresponding oligomer. The copolymerization reactions of DL‐lactide with caprolactone and valerolactone yielded gradient block copolymers where the lactyl blocks formed crystalline stereoblocks as a consequence of the stereoselective polymerization of DL‐lactide in the presence of the aluminum complexes. These polymerization processes were highly controlled in nature, and block copolymerization where caprolactone copolymerized using poly(DL‐lactide)‐Al complex proceeded. The obtained gradient copolymer containing stereoblock lactyl blocks and caproyl blocks were analyzed using WAXD analysis to uncover existence of the crystalline stereoblock lactyl blocks in the copolymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2536–2544     

Efficient zinc initiators supported by NNO‐tridentate ketiminate ligands for cyclic esters polymerization

A series of zinc benzylalkoxide complexes, [LⁿZn(μ‐OBn)]₂ (L = L ¹ H – L ⁵ H ), supported by NNO‐tridentate ketiminate ligands with various electron withdrawing‐donating subsituents have been synthesized and characterized. X‐ray crystal structural studies revealed that complexes 2b and 4b are dinuclear bridging through the benzylalkoxy oxygen atoms with penta‐coordinated metal centers. All the metal complexes have acted as efficient initiators for the ring‐opening polymerization of L ‐lactide (within 12 min, 0 °C). Remarkably, a molecular weight of PLLA up to 580,000 can be achieved using [(L⁵Zn(μ‐OBn)]₂ ( 5b ) as an initiator. The kinetic studies for the polymerization of L ‐lactide with complex 3b at ?10 °C corresponded to first‐order reactions in the monomer. The ring‐opening polymerization (ROP) of ε‐caprolactone, ε‐decalactone, β‐butyrolactone and their copolymer with complex 3b was investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Polyester oligodiols by cationic AM copolymerization of L,L‐lactide and ε‐caprolactone initiated by diols

Cationic copolymerization of L,L ‐lactide (LA) and ε‐caprolactone (CL) initiated by low molecular weight diols in the presence of acid catalyst gives corresponding copolyesters terminated at both ends with hydroxyl groups in practically quantitative yield. Copolymerization proceeds by Activated Monomer mechanism. LA is consumed preferentially and at the later stages of copolymerization the reaction mixture is enriched with CL. In spite of that, random distribution of both units is observed and end‐groups are mainly ? LA‐OH groups and not ? CL‐OH groups. This is explained by the fact that to reach high conversion of both comonomers the relatively long reaction times are required and at those conditions transesterification reaction becomes significant. Thus the microstructure of copolymers and the nature of the end‐groups is governed by transesterification rather then by the kinetics of comonomers incorporation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3090–3097, 2007     

Controllable ring‐opening copolymerization of L‐lactide and (3S)‐benzyloxymethyl‐(6S)‐methyl‐morpholine‐2,5‐dione initiated by a biogenic compound creatinine acetate

Ring‐opening copolymerization (ROCP) of L ‐lactide (L ‐LA) and (3S)‐benzyloxymethyl‐(6S)‐methyl‐morpholine‐2,5‐dione [(3S, 6S)‐BMMD] initiated by creatinine acetate, a biogenic organic compound, was performed in the bulk at 130 °C. The copolymerization was well controlled as evidenced by that both the measured values of number‐average molecular weight (M_n,NMR(OH) and M_n,NMR(COOH)) and serine molar fraction (F_Bz.ser) of synthesized copolymers were close to the corresponding theoretical values; and that the higher isotacticity of synthesized copolymers (85–86%) and lower racemization degree of the ROCP. After removing O‐benzyls of the copolymers with Et₃SiH/Et₃N/CH₂Cl₂ under catalysis of PdCl₂, functional biodegradable copolymers of L ‐lactic acid (L ‐Lac) and L ‐Ser with designed molar fraction of serine (F_ser 1.35%, 3.57%, 5.41%), narrow molecular weight distribution (polydispersity index 1.10–1.36), and improved hydrophilicity (θ_stat 82.3–89.6°) were finally obtained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of multiblock copolymers composed of poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one) outer blocks and poly(L‐lactide) inner blocks

Ethylene glycol (EG) initiated, hydroxyl‐telechelic poly(L ‐lactide) (PLLA) was employed as a macroinitiator in the presence of a stannous octoate catalyst in the ring‐opening polymerization of 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) with the goal of creating A–B–A‐type block copolymers having polycarbonate outer blocks and a polyester center block. Because of transesterification reactions involving the PLLA block, multiblock copolymers of the A–(B–A)_n–B–A type were actually obtained, where A is poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one), B is PLLA, and n is greater than 0. ¹H and ¹³C NMR spectroscopy of the product copolymers yielded evidence of the multiblock structure and provided the lactide sequence length. For a PLLA macroinitiator with a number‐average molecular weight of 2500 g/mol, the product block copolymer had an n value of 0.8 and an average lactide sequence length (consecutive C₆H₈O₄ units uninterrupted by either an EG or MBC unit) of 6.1. For a PLLA macroinitiator with a number‐average molecular weight of 14,400 g/mol, n was 18, and the average lactide sequence length was 5.0. Additional evidence of the block copolymer architecture was revealed through the retention of PLLA crystallinity as measured by differential scanning calorimetry and wide‐angle X‐ray diffraction. Multiblock copolymers with PLLA crystallinity could be achieved only with isolated PLLA macroinitiators; sequential addition of MBC to high‐conversion L ‐lactide polymerizations resulted in excessive randomization, presumably because of residual L ‐lactide monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6817–6835, 2006     

Tridentate anilido‐aldimine magnesium and zinc complexes as efficient catalysts for ring‐opening polymerization of ε‐caprolactone and L‐lactide

A novel tridentate anilido‐aldimine ligand, [o‐C₆H₄(NHAr)? HC?NCH₂CH₂NMe₂] (Ar = 2,6‐ⁱPr₂C₆H₃, L ‐H, 1 ), has been prepared by the condensation of N, N‐dimethylethylenediamine with one molar equivalent of 2‐fluoro‐benzaldehyde in hexane, followed by the addition of the lithium salt of diisopropylaniline in THF. Magnesium (Mg) and zinc (Zn) complexes supported by the tridentate anilido‐aldimine ligand have been synthesized and structurally characterized. Reaction of L ‐H ( 1 ) with an equivalent amount of MgⁿBu₂ or ZnEt₂ produces the monomeric complex [ L MgⁿBu] ( 2 ) or [ L ZnEt] ( 3 ), respectively. Experimental results show that complexes 2 and 3 are efficient catalysts for ring‐opening polymerization of ε‐caprolactone (CL) and L ‐lactide (LA) in the presence of benzyl alcohol and catalyze the polymerization of ε‐CL and L ‐LA in a controlled fashion yielding polymers with a narrow polydispersity index. In both polymerizations, the activity of Mg complex 2 is higher than that of Zn complex 3 , which is probably due to the higher Lewis acidity and better oxophilic nature of Mg²⁺ metal. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4927–4936, 2009     

Microwave syntheses of poly(ε‐caprolactam‐co‐ε‐caprolactone)

Microwave irradiation was applied to synthesize poly(ε‐caprolactam‐co‐ε‐caprolactone) directly from the anionic catalyzed ring opening of two cyclic monomers, ε‐caprolactam and ε‐caprolactone using a variable frequency microwave furnace, programmed to a set temperature and controlled by a pulsed power on–off system. Dielectric properties of ε‐caprolactam, ε‐caprolactone, and their mixture were measured in the microwave range from 0.4 to 3 GHz, showing that both ε‐caprolactam and ε‐caprolactone exhibited effective absorption of microwave energy to induce a fast chemical reaction. The microwave induced anionic copolymerization of ε‐caprolactam and ε‐caprolactone generated copoly(amide‐ester)s in yields as high as 70%. Conventional thermal and microwave copolymerization studies were also conducted for comparison with the microwave results. These studies demonstrated that an effective and efficient microwave method to copolymerize ε‐caprolactam with ε‐caprolactone in higher yield, higher amide content, and higher T_g 's, relative to the thermal process, has been developed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1379–1390, 2000     

Phosphido‐diphosphine pincer aluminum complexes as catalysts for ring opening polymerization of cyclic esters

New aluminum alkyl complexes, supported by o‐phenylene‐derived phosphido diphosphine pro‐ligands [Ph‐PPP]‐H and [ⁱPr‐PPP]‐H ([Ph‐PPP]‐H = bis(2‐diphenylphosphinophenyl)phosphine; [ⁱPr‐PPP]‐H = bis(2‐diisopropylphosphinophenyl)phosphine) are reported. Compounds [Ph‐PPP]AlMe₂ ( 1 ), [ⁱPr‐PPP]AlMe₂ ( 2 ), and [Ph‐PPP]AlⁱBu₂ ( 3 ) have been synthesized by reaction of the pro‐ligand with the appropriate trialkyl aluminum precursor and have been characterized by ¹H, ¹³C and ³¹P NMR spectroscopy. The solution NMR data and theoretical calculations suggest for all complexes trigonal bipyramidal structures with C_2v symmetry in which the phosphido diphosphine ligand acts as a κ³ coordinated ligand. All complexes promote the ring‐opening polymerization of ε‐caprolactone, L‐ and rac‐lactide. Polyesters with controlled molecular parameters (M_n, end groups) and low polydispersities are obtained. Upon addition of isopropanol, efficient binary catalytic systems for the immortal ring‐opening polymerization of the cyclic esters are produced. Preliminary investigations show the ability of these complexes to promote copolymerization of l ‐lactide and ?‐caprolactone to achieve copolymers whose microstructures are depending on the structure of the catalyst. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 49–60     

Ring‐opening polymerization and block copolymerization of L‐lactide with divalent samarocene complex

Divalent samarocene complex [(C₅H₉C₅H₄)₂Sm(tetrahydrofuran)₂] was prepared and characterized and used to catalyze the ring‐opening polymerization of L ‐lactide (L‐LA) and copolymerization of L‐LA with caprolactone (CL). Several factors affecting monomer conversion and molecular weight of polymer, such as polymerization time, temperature, monomer/catalyst ratio, and solvent, were examined. The results indicated that polymerization was rapid, with monomer conversions reaching 100% within 1 h, and the conformation of L‐LA was retained. The structure of the block copolymer of CL/L‐LA was characterized by NMR and differential scanning calorimetry. The morphological changes during crystallization of poly(caprolactone) (PCL)‐b‐P(L‐LA) copolymer were monitored with real‐time hot‐stage atomic force microscopy (AFM). The effect of temperature on the morphological change and crystallization behavior of PCL‐b‐P(L‐LA) copolymer was demonstrated through AFM observation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2667–2675, 2003     

Strontium‐based initiator system for ring‐opening polymerization of cyclic esters

An amino isopropoxyl strontium (Sr‐PO) initiator, which was prepared by the reaction of propylene oxide with liquid strontium ammoniate solution, was used to carry out the ring‐opening polymerization (ROP) of cyclic esters to obtain aliphatic polyesters, such as poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). The Sr‐PO initiator demonstrated an effective initiating activity for the ROP of ε‐caprolactone (ε‐CL) and L‐lactide (LLA) under mild conditions and adjusted the molecular weight by the ratio of monomer to Sr‐PO initiator. Block copolymer PCL‐b‐PLLA was prepared by sequential polymerization of ε‐CL and LLA, which was demonstrated by ¹H NMR, ¹³C NMR, and gel permeation chromatography. The chemical structure of Sr‐PO initiator was confirmed by elemental analysis of Sr and N, ¹H NMR analysis of the end groups in ε‐CL oligomer, and Fourier transform infrared (FTIR) spectroscopy. The end groups of PCL were hydroxyl and isopropoxycarbonyl, and FTIR spectroscopy showed the coordination between Sr‐PO initiator and model monomer γ‐butyrolactone. These experimental facts indicated that the ROP of cyclic esters followed a coordination‐insertion mechanism, and cyclic esters exclusively inserted into the Sr–O bond. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1934–1941, 2003     

Synthesis and characterization of poly(3,3 bis(azidomethyl)oxetane‐co‐ε‐caprolactone)s

The quasi‐living cationic copolymerization of 3,3‐bis(chloromethyl)oxetane (BCMO) and ε‐caprolactone (ε‐CL), using boron trifluoride etherate as catalyst and 1,4‐butanediol as coinitiator, was investigated in methylene chloride at 0°C. The resulting hydroxyl‐ended copolymers exhibit a narrow molecular weight polydispersity and a functionality of about 2. The reactivity ratios of BCMO (0.26) and ε‐CL (0.47), and the T_g of the copolymers, indicate their statistical character. The synthesis of poly(3,3‐bis(azidomethyl)oxetane‐co‐ε‐caprolactone) from poly(BCMO‐co‐ε‐CL) via the substitution of the chlorine atoms by azide groups, using sodium azide in DMSO at 110°C, occurs without any degradation, but the copolymers decompose at about 240°C. All polymers were characterized by vapor pressure osmometry or steric exclusion chromatography, ¹H‐NMR and FTIR spectroscopies, and DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1027–1039, 1999