pubs.acs.org

Perfectly Alternating Copolymer of Lactic Acid and Ethylene Oxide as a Plasticizing Agent for Polylactide
Kevin BechtoldMarc A. HillmyerWilliam B. Tolman

Abstract
The ring-opening polymerization of 3-methyl-1,4-dioxan-2-one (MDO) mediated by a catalytic system composed of Y[N(TMS)2]3 and benzyl alcohol (BnOH) led to a new polymer (PMDO) comprised of perfectly alternating lactic acid and ethylene oxide repeat units. Samples of PMDO were characterized by NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). In a series of MDO polymerizations ([MDO]0 = 3.0 M in toluene, between −30 and 60 °C), the equilibrium monomer concentrations were measured. The thermodynamic parameters for the polymerization reaction were determined:  ΔHp° = −12.1 ± 0.5 kJ mol-1 and ΔSp° = −42 ± 2 J mol-1 K-1. The glass transition temperature (Tg) of PMDO was determined to be ≈−24 °C by differential scanning calorimetry and found to vary little over the molecular weight range studied (3−21 kg/mol). Mixtures of low-molecular-weight PMDO and atactic polylactide (PLA) were prepared by solution casting and subsequent annealing significantly above the Tg's of the individual components. Miscibility of PLA and PMDO was evinced by single Tg's that were well-described by the Fox relationship for miscible blends. Because of its miscibility with PLA and low Tg, PMDO has potential as a macromolecular plasticizing agent for commercially relevant PLA.

Cited By

This article is cited by 67 publications.
Guanchun Wang, Ping Huang, Meiwei Qi, Chuanlong Li, Weirong Fan, Yongfeng Zhou, Rong Zhang, Wei Huang, Deyue Yan. Facile Synthesis of a H2O2-Responsive Alternating Copolymer Bearing Thioether Side Groups for Drug Delivery and Controlled Release. ACS Omega 2019, 4 (17) , 17600-17606. DOI: 10.1021/acsomega.9b02923.
Adrian G. Amador, Annabelle Watts, Angelika E. Neitzel, Marc A. Hillmyer. Entropically Driven Macrolide Polymerizations for the Synthesis of Aliphatic Polyester Copolymers Using Titanium Isopropoxide. Macromolecules 2019, 52 (6) , 2371-2383. DOI: 10.1021/acs.macromol.9b00065.
Hanying Luo, David Raciti, Chao Wang, and Margarita Herrera-Alonso . Macromolecular Brushes as Stabilizers of Hydrophobic Solute Nanoparticles. Molecular Pharmaceutics 2016, 13 (6) , 1855-1865. DOI: 10.1021/acs.molpharmaceut.6b00019.
Deborah K. Schneiderman and Marc A. Hillmyer . Aliphatic Polyester Block Polymer Design. Macromolecules 2016, 49 (7) , 2419-2428. DOI: 10.1021/acs.macromol.6b00211.
William M. Gramlich, Megan L. Robertson and Marc A. Hillmyer. Reactive Compatibilization of Poly(l-lactide) and Conjugated Soybean Oil. Macromolecules 2010, 43 (5) , 2313-2321. DOI: 10.1021/ma902449x.
Carolyn L. Wanamaker,, Leslie E. O'Leary,, Nathaniel A. Lynd,, Marc A. Hillmyer, and, William B. Tolman. Renewable-Resource Thermoplastic Elastomers Based on Polylactide and Polymenthide. Biomacromolecules 2007, 8 (11) , 3634-3640. DOI: 10.1021/bm700699g.
Z. Kulinski,, E. Piorkowska,, K. Gadzinowska, and, M. Stasiak. Plasticization of Poly(l-lactide) with Poly(propylene glycol). Biomacromolecules 2006, 7 (7) , 2128-2135. DOI: 10.1021/bm060089m.
Phillip Hanefeld,, Ullrich Westedt,, Ralf Wombacher,, Thomas Kissel,, Andreas Schaper,, Joachim H. Wendorff, and, Andreas Greiner. Coating of Poly(p-xylylene) by PLA-PEO-PLA Triblock Copolymers with Excellent Polymer−Polymer Adhesion for Stent Applications. Biomacromolecules 2006, 7 (7) , 2086-2090. DOI: 10.1021/bm050642k.
Eyal Barnea,, Dorit Moradove,, Jean-Claude Berthet,, Michel Ephritikhine, and, Moris S. Eisen. Surprising Activity of Organoactinide Complexes in the Polymerization of Cyclic Mono- and Diesters. Organometallics 2006, 25 (2) , 320-322. DOI: 10.1021/om050966p.
Afia S. Karikari,, Wesleigh F. Edwards,, Jeffrey B. Mecham, and, Timothy E. Long. Influence of Peripheral Hydrogen Bonding on the Mechanical Properties of Photo-Cross-Linked Star-Shaped Poly(d,l-lactide) Networks. Biomacromolecules 2005, 6 (5) , 2866-2874. DOI: 10.1021/bm050375i.
Xiang-hua Yu,, Jun Feng, and, Ren-xi Zhuo. Preparation of Hyperbranched Aliphatic Polyester Derived from Functionalized 1,4-Dioxan-2-one. Macromolecules 2005, 38 (15) , 6244-6247. DOI: 10.1021/ma048839c.
Odile Dechy-Cabaret,, Blanca Martin-Vaca, and, Didier Bourissou. Controlled Ring-Opening Polymerization of Lactide and Glycolide. Chemical Reviews 2004, 104 (12) , 6147-6176. DOI: 10.1021/cr040002s.
Donghui Zhang,, Jianyan Xu,, Luis Alcazar-Roman,, Loren Greenman,, Christopher J. Cramer,, Marc A. Hillmyer, and, William B. Tolman. Isotactic Polymers with Alternating Lactic Acid and Oxetane Subunits from the Endoentropic Polymerization of a 14-Membered Ring. Macromolecules 2004, 37 (14) , 5274-5281. DOI: 10.1021/ma049571s.
Yiwang Chen,, Zhihong Jia,, Andreas Schaper,, Magnus Kristiansen,, Paul Smith,, Ralf Wombacher,, Joachim H. Wendorff, and, Andreas Greiner. Hydrolytic and Enzymatic Degradation of Liquid-Crystalline Aromatic/Aliphatic Copolyesters. Biomacromolecules 2004, 5 (1) , 11-16. DOI: 10.1021/bm034388c.
Charlotte K. Williams,, Laurie E. Breyfogle,, Sun Kyung Choi,, Wonwoo Nam,, Victor G. Young, Jr.,, Marc A. Hillmyer, and, William B. Tolman. A Highly Active Zinc Catalyst for the Controlled Polymerization of Lactide. Journal of the American Chemical Society 2003, 125 (37) , 11350-11359. DOI: 10.1021/ja0359512.
Yiwang Chen,, Ralf Wombacher,, Joachim H. Wendorff,, Jeroen Visjager,, Paul Smith, and, Andreas Greiner. Design, Synthesis, and Properties of New Biodegradable Aromatic/Aliphatic Liquid Crystalline Copolyesters. Biomacromolecules 2003, 4 (4) , 974-980. DOI: 10.1021/bm0340164.
Esther M. Frick,, Andrew S. Zalusky, and, Marc A. Hillmyer. Characterization of Polylactide-b-polyisoprene-b-polylactide Thermoplastic Elastomers. Biomacromolecules 2003, 4 (2) , 216-223. DOI: 10.1021/bm025628b.
Yasser Assem, Heba A. Mohamed, Rana Said, Ahmed El-Masry. Preparation of amphiphilic block copolymers (polyethylene adipate-block-polyethylene glycol) and its application in rotogravure ink formulations. Pigment & Resin Technology 2018, 186 DOI: 10.1108/PRT-02-2017-0020.
Haichao Huang, Lijie Chen, Guolin Song, Guoyi Tang. An efficient plasticization method for poly(lactic acid) using combination of liquid-state and solid-state plasticizers. Journal of Applied Polymer Science 2018, 35, 46669. DOI: 10.1002/app.46669.
Ting Wu, Yue He, Jin-Ping Qu. Effect of continuous elongational flow on structure and properties of poly(L-lactic acid)/poly(ethylene glycol) blend and its organo-modified montmorillonite nanocomposites. Polymer Composites 2018, 33 DOI: 10.1002/pc.24918.
Hande Celebi, Elif Gunes. Combined effect of a plasticizer and carvacrol and thymol on the mechanical, thermal, morphological properties of poly(lactic acid). Journal of Applied Polymer Science 2018, 135 (8) , 45895. DOI: 10.1002/app.45895.
Xueyan He, Zhaobin Qiu. Effect of poly(ethylene adipate) with different molecular weights on the crystallization behavior and mechanical properties of biodegradable poly(L-lactide). Thermochimica Acta 2018, 659, 89-95. DOI: 10.1016/j.tca.2017.11.010.
Ting Wu, Ding Yuan, Jin-Ping Qu. Preparation of poly(L-lactide)/poly(ethylene glycol)/organo-modified montmorillonite nanocomposites via melt intercalation under continuous elongation flow. Journal of Polymer Engineering , Article ASAP.
Rajendra Kumar Singla, Mohammad Tahir Zafar, Saurindra N. Maiti, Anup K. Ghosh. Physical blends of PLA with high vinyl acetate containing EVA and their rheological, thermo-mechanical and morphological responses. Polymer Testing 2017, 63, 398-406. DOI: 10.1016/j.polymertesting.2017.08.042.
GEORGE WYPYCH. EFFECT OF PLASTICIZERS ON PROPERTIES OF PLASTICIZED MATERIALS. 2017,,, 209-332. DOI: 10.1016/B978-1-895198-97-3.50012-3.
Gareth Ross, Sukunya Ross, Brian J. Tighe. Bioplastics. 2017,,, 631-652. DOI: 10.1016/B978-0-323-35824-8.00023-2.
Chuanlong Li, Chuanshuang Chen, Shanlong Li, Tahir Rasheed, Ping Huang, Tong Huang, Yinglin Zhang, Wei Huang, Yongfeng Zhou. Self-assembly and functionalization of alternating copolymer vesicles. Polymer Chemistry 2017, 8 (32) , 4688-4695. DOI: 10.1039/C7PY00908A.
Aswini Kumar Mohapatra, Smita Mohanty, Sanjay K Nayak. Properties and characterization of biodegradable poly(lactic acid) (PLA)/poly(ethylene glycol) (PEG) and PLA/PEG/organoclay. Journal of Thermoplastic Composite Materials 2016, 29 (4) , 443-463. DOI: 10.1177/0892705713518812.
Cheng Xing, Laurent M. Matuana. Epoxidized soybean oil-plasticized poly(lactic acid) films performance as impacted by storage. Journal of Applied Polymer Science 2016, 133 (10.1002/app.v133.12) , n/a-n/a. DOI: 10.1002/app.43201.
Yu-heng Ma, Shu-wang Ge, Wei Wang, Qiang Zheng, Yun-wei Zuo, Chang-jiang Zhong, Bai-wang Sun. Novel perchlorate and phosphate salts of vinpocetine: Characterization, relative solid-state stability evaluation and Hirshfeld surface analysis. Journal of Molecular Structure 2016, 1105, 1-10. DOI: 10.1016/j.molstruc.2015.10.029.
Collins Obuah, Yemanlall Lochee, Orpah Zinyemba, Johan H.L. Jordaan, Daniel P. Otto, James Darkwa. (Ferrocenylpyrazolyl)zinc(II) acetate complexes as initiators and catalysts for the ring opening polymerization of ϵ-caprolacton.. Journal of Molecular Catalysis A: Chemical 2015, 406, 185-193. DOI: 10.1016/j.molcata.2015.05.021.
Jian Zhang, Jianyong Jin, Ralph Cooney, Qiang Fu, Greg G. Qiao, Sylvie Thomas, Tim C. Merkel. Synthesis of perfectly alternating copolymers for polymers of intrinsic microporosity. Polymer Chemistry 2015, 6 (28) , 5003-5008. DOI: 10.1039/C5PY00570A.
Nowsheen Goonoo, Archana Bhaw-Luximon, Isaac A. Rodriguez, Gary L. Bowlin, Dhanjay Jhurry. Poly(ester-ether)s: I. Investigation of the Properties of Blend Films of Polydioxanone and Poly(methyl dioxanone). International Journal of Polymeric Materials 2014, 63 (10) , 527-537. DOI: 10.1080/00914037.2013.854224.
Tong Huang, Motohiro Miura, Shogo Nobukawa, Masayuki Yamaguchi. Crystallization Behavior and Dynamic Mechanical Properties of Poly(l-Lactic Acid) with Poly(Ethylene Glycol) Terminated by Benzoate. Journal of Polymers and the Environment 2014, 22 (2) , 183-189. DOI: 10.1007/s10924-014-0638-y.
Zhaobin Qiu, Pin Zhou. Effect of biodegradable poly(ethylene adipate) with low molecular weight as an efficient plasticizer on the significantly enhanced crystallization rate and mechanical properties of poly( l -lactide). RSC Adv. 2014, 4, 51411-51417. DOI: 10.1039/C4RA08827A.
George Z. Papageorgiou, Vasilios Tsanaktsis, Dimitrios N. Bikiaris. Crystallization of poly(butylene-2,6-naphthalate-co-butylene adipate) copolymers: regulating crystal modification of the polymorphic parent homopolymers and biodegradation. CrystEngComm 2014, 16 (34) , 7963-7978. DOI: 10.1039/C4CE00651H.
Aswini Kumar Mohapatra, S. Mohanty, S.K. Nayak. Effect of PEG on PLA/PEG blend and its nanocomposites: A study of thermo-mechanical and morphological characterization. Polymer Composites 2013, , n/a-n/a. DOI: 10.1002/pc.22660.
Lidong Feng, Xinchao Bian, Zhiming Chen, Gao Li, Xuesi Chen. Mechanical, aging, optical and rheological properties of toughening polylactide by melt blending with poly(ethylene glycol) based copolymers. Polymer Degradation and Stability 2013, 98 (9) , 1591-1600. DOI: 10.1016/j.polymdegradstab.2013.06.025.
Mohammed Arifur Rahman, Diego De Santis, Gloria Spagnoli, Giorgio Ramorino, Maurizio Penco, Vu Thanh Phuong, Andrea Lazzeri. Biocomposites based on lignin and plasticized poly( L -lactic acid). Journal of Applied Polymer Science 2013, 129 (1) , 202-214. DOI: 10.1002/app.38705.
P. Ma, A.B. Spoelstra, P. Schmit, P.J. Lemstra. Toughening of poly (lactic acid) by poly (β-hydroxybutyrate-co-β-hydroxyvalerate) with high β-hydroxyvalerate content. European Polymer Journal 2013, 49, 1523-1531. DOI: 10.1016/j.eurpolymj.2013.01.016.
Zhizhong Su, Kui Huang, Mingsui Lin. Thermal and Mechanical Properties of Poly(lactic acid)/Modified Carbon Black Composite. Journal of Macromolecular Science, Part B 2012, 51 (8) , 1475-1484. DOI: 10.1080/00222348.2011.632741.
Yangshuo Liu, Wenbao Chen, Hyung-Il Kim. Synthesis, Characterization, and Hydrolytic Degradation of Polylactide/Poly(ethylene glycol)/Nano-silica Composite Films. Journal of Macromolecular Science, Part A 2012, 49 (4) , 348-354. DOI: 10.1080/10601325.2012.662077.
. EFFECT OF PLASTICIZERS ON PROPERTIES OF PLASTICIZED MATERIALS. 2012,,, 209-306. DOI: 10.1016/B978-1-895198-50-8.50012-6.
Marcin Kowalczyk, Miroslaw Pluta, Ewa Piorkowska, Nelli Krasnikova. Plasticization of polylactide with block copolymers of ethylene glycol and propylene glycol. Journal of Applied Polymer Science 2012, , n/a-n/a. DOI: 10.1002/app.36563.
Hongzhi Liu, Jinwen Zhang. Research progress in toughening modification of poly(lactic acid). Journal of Polymer Science Part B: Polymer Physics 2011, 49 (15) , 1051-1083. DOI: 10.1002/polb.22283.
Yemanlall Lochee, Dhanjay Jhurry, Archana Bhaw-Luximon, Afksendiyos Kalangos. Biodegradable poly(ester-ether)s: ring-opening polymerization of D,L-3-methyl-1,4-dioxan-2-one using various initiator systems. Polymer International 2010, 59 (9) , 1310-1318. DOI: 10.1002/pi.2871.
Rahul M. Rasal, Amol V. Janorkar, Douglas E. Hirt. Poly(lactic acid) modifications. Progress in Polymer Science 2010, 35 (3) , 338-356. DOI: 10.1016/j.progpolymsci.2009.12.003.
Licheng Tan, Yiwang Chen, Yang Wang, Weihua Zhou, Xiaohui He. . Journal of Thermal Analysis and Calorimetry 2010,,, 269. DOI: 10.1007%2Fs10973-009-0101-9.
Elena Rabinovich, Sinai Aharonovich, Mark Botoshansky, Moris S. Eisen. Thorium 2-pyridylamidinates: synthesis, structure and catalytic activity towards the cyclo-oligomerization of ε-caprolactone. Dalton Transactions 2010, 39 (29) , 6667. DOI: 10.1039/c000661k.
Ruyin Wang, Chaoying Wan, Shifeng Wang, Yong Zhang. Morphology, mechanical properties, and durability of poly(lactic acid) plasticized with Di(isononyl) cyclohexane-1,2-dicarboxylate. Polymer Engineering & Science 2009, 49 (12) , 2414-2420. DOI: 10.1002/pen.21490.
Zhiyuan Jia, Juanjuan Tan, Changyu Han, Yuming Yang, Lisong Dong. Poly(ethylene glycol- co -propylene glycol) as a macromolecular plasticizing agent for polylactide: Thermomechanical properties and aging. Journal of Applied Polymer Science 2009, 114 (2) , 1105-1117. DOI: 10.1002/app.30638.
Y. Chen, L. Tan, W. Zhou, J. Su, Y. Yang, Y. Hu. Synthesis and structure of biodegradable hexylene terephthalate-co-lactide copolyesters. Journal of Thermal Analysis and Calorimetry 2009, 96 (1) , 307-313. DOI: 10.1007/s10973-008-9031-1.
F. Byrne, P. G. Ward, J. Kennedy, N. Imaz, D. Hughes, D. P. Dowling. The Effect of Masterbatch Addition on the Mechanical, Thermal, Optical and Surface Properties of Poly(lactic acid). Journal of Polymers and the Environment 2009, 17 (1) , 28-33. DOI: 10.1007/s10924-009-0119-x.
Xiuli Hu, Xuesi Chen, Haibo Cheng, Xiabin Jing. Cinnamate-functionalized poly(ester-carbonate): Synthesis and its UV irradiation-induced photo-crosslinking. Journal of Polymer Science Part A: Polymer Chemistry 2009, 47 (1) , 161-169. DOI: 10.1002/pola.23134.
Licheng Tan, Yiwang Chen, Yang Wang, Weihua Zhou, Xiangjun Zhu, Xiaohui He, Jiying Su, Suping Cui. In Vivo Evaluation of Butylene Terephthalate-ethylene Oxide-DL, Lactide Polymer as Porous Scaffolds for Tissue Engineering. Journal of Bioactive and Compatible Polymers 2009, 24 (1) , 43-55. DOI: 10.1177/0883911508099368.
Yiwang Chen, Xiangjun Zhu, Licheng Tan, Jiying Su. Melting bulk reaction between poly(butylene terephthalate) and poly(ethylene glycol)/DL-oligo(lactic acid). Journal of Applied Polymer Science 2008, 108 (4) , 2171-2179. DOI: 10.1002/app.27876.
Xiang Jun Zhu, Yiwang Chen, Jiying Suxiaohui He, Licheng Tan, Yang Wang. Synthesis of Aliphatic-Aromatic Copolyesters by a Melting Bulk Reaction Between Poly(butylene terephthalate) and DL-Oligo(lactic acid). High Performance Polymers 2008, 20 (2) , 166-184. DOI: 10.1177/0954008307080267.
Shigeki Matsunaga. Tris[1,1,1-trimethyl- N -(trimethylsilyl)silanaminato]-yttrium. 2008,, DOI: 10.1002/047084289X.rn00787.
Congming Xiao, Yueying He. Tailor-made unsaturated poly(ester- amide) network that contains monomeric lactate sequences. Polymer International 2007, 56 (6) , 816-819. DOI: 10.1002/pi.2220.
Y CHEN, Y YANG, J SU, L TAN, Y WANG. Preparation and characterization of aliphatic/aromatic copolyesters based on bisphenol-A terephthalate, hexylene terephthalate and lactide mioties. Reactive and Functional Polymers 2007, 67 (5) , 396-407. DOI: 10.1016/j.reactfunctpolym.2007.02.011.
Cuiqing Teng, Hong Xu, Kai Yang, Muhuo Yu. The Preparation and Biodegradable Properties of Poly( L ‐lactic acid)‐Poly(ϵ‐caprolactone) Multiblock Copolymers. Journal of Macromolecular Science, Part A 2006, 43 (11) , 1877-1886. DOI: 10.1080/10601320600941276.
E. Piorkowska, Z. Kulinski, A. Galeski, R. Masirek. Plasticization of semicrystalline poly(l-lactide) with poly(propylene glycol). Polymer 2006, 47 (20) , 7178-7188. DOI: 10.1016/j.polymer.2006.03.115.
G MONTAUDO, F SAMPERI, M MONTAUDO. Characterization of synthetic polymers by MALDI-MS. Progress in Polymer Science 2006, 31 (3) , 277-357. DOI: 10.1016/j.progpolymsci.2005.12.001.
Z. Kulinski, E. Piorkowska. Crystallization, structure and properties of plasticized poly(l-lactide). Polymer 2005, 46 (23) , 10290-10300. DOI: 10.1016/j.polymer.2005.07.101.
John Meurig Thomas, Robert Raja. DESIGNING CATALYSTS FOR CLEAN TECHNOLOGY, GREEN CHEMISTRY, AND SUSTAINABLE DEVELOPMENT. Annual Review of Materials Research 2005, 35 (1) , 315-350. DOI: 10.1146/annurev.matsci.35.102003.140852.
Massimo Baiardo, Giovanna Frisoni, Mariastella Scandola, Michel Rimelen, David Lips, Kurt Ruffieux, Erich Wintermantel. Thermal and mechanical properties of plasticized poly(L-lactic acid). Journal of Applied Polymer Science 2003, 90 (7) , 1731-1738. DOI: 10.1002/app.12549.
Y. Hu, M. Rogunova, V. Topolkaraev, A. Hiltner, E. Baer. Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity. Polymer 2003, 44, 5701-5710. DOI: 10.1016/S0032-3861(03)00614-1.

https://pubs.acs.org/doi/abs/10.1021/ma0114887