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Tailoring Chain Structures of L-Lactide and Ε-Caprolactone Copolyester

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Tailoring Chain Structures of L-Lactide and Ε-Caprolactone Copolyester RSC Advances View Article Online PAPER View Journal | View Issue Tailoring chain structures of L-lactide and 3- caprolactone copolyester macromonomers using Cite this: RSC Adv.,2017,7, 28661 rac-binaphthyl-diyl hydrogen phosphate-catalyzed ring-opening copolymerization with monomer addition strategy† Yanjiao Wang,a Ming Xia,b Xueqiang Kong,b Steven John Severtson*c and Wen-Jun Wang *a Copolymerizations involving polyester macromonomers (MMs) generated from biomass provide a new route for introducing high biomass content into existing polymeric products. Stannous 2-ethylhexanoate-catalyzed ring-opening copolymerization (ROcoP) is commonly utilized to synthesize MMs, but this approach generates polymer chains containing terminal metal residues and limits control of MM chain structures due to the 0 0 Creative Commons Attribution 3.0 Unported Licence. presence of transesterification side reactions (TSRs). Here, rac-1,1 -binaphthyl-2,2 -diyl-hydrogenphosphate (rac-BNPH) was used for the 2-hydroxylethyl methacrylate (HEMA) initiated ROcoP of L-lactide (L-LA) and 3-caprolactone (3-CL) to produce the well-defined MMs. The copolymerization kinetics and monomer feeding strategies, batch and semibatch, were studied, and the influence on MM chain structures was investigated using both 1Hand13C NMR analysis. The rac-BNPH was identified as an effective catalyst for the ROcoP of L-LA and 3-CL, producing narrowly dispersed MMs with a 96% retention of terminal vinyl groups associated with HEMA. The 3-CL was more reactive than L-LA, and the reactions exhibited Received 16th May 2017 characteristics of living polymerization. The TSRs could be significantly suppressed using batch operation Accepted 19th May 2017 or semibatch with fast 3-CL addition. It was found that slowing the 3-CL addition generated more This article is licensed under a DOI: 10.1039/c7ra05531e randomly and uniformly distributed comonomers along MM chains. In general, it is demonstrated here that rsc.li/rsc-advances the rac-BNPH catalyzed semibatch ROcoPs is an effective means for tailoring the chain structures of MMs. Open Access Article. Published on 30 May 2017. Downloaded 9/27/2021 1:20:34 PM. Introduction approach was introduced for increasing the biomass content in polymeric products by incorporating polyester gras into poly- – Polyesters have been used in a wide variety of products due to mers composed of acrylic backbones.5 8 This is achieved most their excellent mechanical properties, weather and corrosion commonly by growing polyester chains on initiators possessing resistance, and ease of processing. Polyesters generated from a reactive terminal vinyl group through catalyzed ring-opening biomass such as lactide are renewable and biodegradable polymerizations (ROPs) to generate macromonomers, MMs. making them well-suited for disposable packaging and The MMs are then polymerized with other monomers to garments.1,2 They are also nontoxic and biocompatible which produce the polymers possessing polyester side chains. This qualies them for biomedical applications.3,4 More recently, an approach opens a new route to convert a number of existing commodity products into more sustainable forms. Previous work on these hybrid materials demonstrates their aState Key Laboratory of Chemical Engineering, College of Chemical and Biological promise. Ishimoto et al.5 used 2-hydroxylethyl methacrylate, Engineering, Zhejiang University, Hangzhou, China 310027. E-mail: wenjunwang@ HEMA, as initiator to synthesize MMs with L-lactide, L-LA, con- zju.edu.cn; Fax: +86-571-8795-2772; Tel: +86-571-8795-2772 taining approximately six lactidyl units. The MMs were then bDepartment of Chemistry, Zhejiang University, Hangzhou 310027, China 310027 copolymerized with n-butyl methacrylate (BMA) using mini- cDepartment of Bioproducts and Biosystems Engineering, University of Minnesota, Saint Paul, Minnesota, USA 55108. E-mail: [email protected]; Fax: +1-612-624- emulsion polymerizations to generate PBMA-g-PLLA. Films cast 3005; Tel: +1-612-625-5265 from the formed latexes were reported to demonstrate good † Electronic supplementary information (ESI) available: Details about synthesis elastic properties. In their subsequent work, Ishimoto et al. 1 procedure of L-LA and 3-CL homo- and block macromonomers and their Hand utilized renewable itaconic anhydride (IAn) to generate PLLA 13 1 C NMR spectra and peak assignments, H NMR spectra for macromonomers gra copolymers using the MM approach as well as a copolymer of Runs B8, B5, SB1, and SB2, chemical shi assignments of carbonyl carbon approach in which PLLA chains are generated on a polymer sequences in macromonomers, and spin-lattice relaxation time (T1) for carbonyl carbons in 13C NMR spectrum of macromonomer. See DOI: 10.1039/c7ra05531e containing IAn repeat units. Both approaches resulted in This journal is © The Royal Society of Chemistry 2017 RSC Adv.,2017,7, 28661–28669 | 28661 View Article Online RSC Advances Paper materials that could be further optimized for plastic applica- as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),37–40 N-methyl- tions. The synthesis of PLLA MMs having 2 to 20 repeat units TBD,41 and 1,8-diazabicyclo[5.4.0]-undec-7-ene32 were also with various hydroxyalkyl methacrylates (HAA) initiators effective in catalyzing ROP of LA, d-valerolactone, and 3-CL, and including HEMA, 2-hydroxyethyl acrylate (HEA), hydroxypropyl they demonstrated high activity in catalyzing LA polymerization methacrylate (HPMA), and 4-hydroxybutyl acrylate (HBA) were in nonpolar solvents. Among the organocatalysts, simple also reported.9 The MMs were further copolymerized with HAA in organic acids such as 1,10-binaphthyl-2,20-diyl- solution to produce PHAA-g-PLLA copolymers, which were hydrogenphosphate, BNPH, were found to possess high activi- applied as scaffolding materials for tissue engineering applica- ties in catalyzing the ROP of cyclic monoesters.19–21 It was re- tions. A more immediate application of these materials was ported that the chiral (R)-BNPH was used for ROcoP of 3-CL and demonstrated by Severtson et al.10,11 In order to tailor the thermal LA, but with very low LA incorporation in the copolymer.21 properties of the polyester MMs, 3-caprolactone, 3-CL, was Although various organocatalysts have been found to copolymerized with L-LA to manipulate glass transition temper- promote ROPs, most of them are ineffective when it comes to 42 atures (Tgs) of formed MMs with HEMA as initiator. The MMs catalyzing copolymerizations of ester monomers. Here, efforts having low Tg values were then used to replace the acrylic so to identify alternative catalyst for producing the HEMA initiated monomer in miniemulsion polymerizations to generate L-LA/3-CL copolymer MMs through catalyzed ROcoPs are pressure-sensitive adhesive (PSA) latexes containing 50 wt% reviewed. The focus is on nding an organocatalyst that is easier MMs, which provided equivalent and oen superior adhesive to produce, use, and remove once the reaction is complete. As properties to commercial latex products. It was also demon- will be discussed, rac-BNPH appears to be a promising candi- strated that the MM composition and chain length could be used date for the generation of MMs containing L-LA and 3-CL. To the to engineer adhesive properties. The use of the MMs approach best of our knowledge, this is the rst report of successful was further extended for the production of thermoplastic adhe- reactions for this system. The copolymerization kinetics sive materials. Much of the 2-ethylhexylacrylate (EHA) was including transesterication using different monomer feed ff Creative Commons Attribution 3.0 Unported Licence. replaced in a commercial acrylic hot-melt formulation with MMs strategies were studied. The e ect of feeding strategies on the synthesized from the hydroxyl ethylacrylamide initiated copoly- control of MM chain structures was also demonstrated. merization of L-LA and 3-CL. The hot-melt adhesives containing 50 wt% MM possessed excellent adhesive properties. In general, Experimental section the MM approach provides a path forward for synthesizing a broad array of polymer materials with high biomass contents. Materials The MMs discussed above were synthesized using stannous 2- The L-LA was purchased from Shenzhen Bright China Industrial ethylhexanoate, Sn(Oct)2, catalyzed ROP. Sn(Oct)2 is suitable for Co. Ltd. The 3-CL, HEMA, Sn(Oct)2, rac-BNPH, hexane, and – L-LA homopolymerizations and copolymerizations.12 15 Although hydroquinone were obtained from Sigma Aldrich (St. Louis, This article is licensed under a widely used in ROP to prepare polyesters, metal-based catalysts MO) and used as received. Deuterated chloroform (CDCl3) and possess complex structures and become bound to generated tetrahydrofuran (THF) were both purchased from J&K China polymers.16,17 This inhibits or prevents their removal from poly- Chemical, Ltd. Open Access Article. Published on 30 May 2017. Downloaded 9/27/2021 1:20:34 PM. mer products, limiting applications for the generated polymers. Furthermore, metal-catalyzed ring-opening copolymerizations, Synthesis of macromonomers ROcoPs, are typically accompanied by transesterication side Macromonomers were synthesized with a xed molar ratio of reactions, TSRs.18 In generating MMs, such reactions limit the HEMA/L-LA/3-CL ¼ 1/5/4 at a variety of temperatures and poly- control of chain structure and chain length.13 They also promote merization times. Prior to the bulk ROcoPs, reactants were heated the formation of cyclic units13 and MMs containing two vinyl and stirred continuously in a round-bottom ask, and the initiator heads, which act as a crosslinker during the subsequent contents were purged with nitrogen gas for approximately 10 min. copolymerization of MM with vinyl monomers. Thus, the prep- The ask was then sealed and lowered into a hot oil bath and the aration of well-dened MMs, with predictable chain structures contents were heated to the polymerization temperature prior to and chain lengths, requires that TSRs be minimized. the addition of 0.5 mol% catalyst using a syringe. Temperature Recently, there has been signicant interest in the use of was maintained during the copolymerization under constant metal-free organocatalysts for making polyesters.
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