Synthesis of Novel Cyclic Poly(ε-caprolactone-co-γ-triethylsilyloxy-ε-caprolactone)

doi:10.3724/SP.J.1095.2014.30657

Chinese Journal of Applied Chemistry

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Synthesis of Novel Cyclic Poly(ε-caprolactone-co-γ-triethylsilyloxy-ε-caprolactone)

LIU Chao, YANG Changzhen, LI Weixue, ZHANG Yonglin, YAO Junshan, LEI Liangcai, LI Haiying^*

(College of Chemistry and Materials Science,Liaoning SHIHUA University,Fushun 113001,China)

Received:2013-12-23 Revised:2014-02-14 Published:2014-09-04 Online:2014-09-04
Contact: Li

Abstract

Abstract: Design and synthesis of well-defined polymers are of the utmost importance for the reliable establishment of macromolecular structure-properties relationships. This work reports a novel strategy to synthesize cyclic random copolyesters with triethylsilyloxy groups. The ring-opening polymerization of a mixture of εCL and functional monomer γ-triethylsilyloxy-ε-caprolactone (γ-Et3SiOεCL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane(DSDOP) to obtain a precursor, i.e., a living cyclic copolyester(LCP(εCLcoγEt3SiOεCL)). When the comonomers were converted completely, a fresh feed of α-(1-acryloyloxyethyl)-ε-caprolactone(αAEεCL) was added to the polymerization medium to achieve a living cyclic block copolyester, poly((εCLcoγEt3SiOεCL)-b-(αAEεCL)). Finally, stable functional cyclic copolyester free of tin dialkoxides, i.e., cP(εCLcoγEt3SiOεCL)(Mn,NMR=28500), was synthesized by intramolecular photo cross-linking of acrylic unsaturations in the proximity of the living cyclic chain under the irradiation of ultraviolet light. The structure and properties of the copolymers were characterized by size-exclusion chromatography(SEC), proton nuclear magnetic resonance spectroscopy(1H NMR), and differential scanning calorimetry(DSC) technologies. The strategy herein disclosed has been successfully tested for the synthesis of functional cyclic copolyesters with high relative molecular mass in high efficiency.

Key words: living ring opening polymerization, cyclic random copolyester, cyclic poly(&, gamma, -triethylsiloxy-&, epsilon, -caprolactone), intramolecular cross-linking reaction, macrocyclic poly(&, epsilon, -caprolactone)

CLC Number:

O633.1

LIU Chao, YANG Changzhen, LI Weixue, ZHANG Yonglin, YAO Junshan, LEI Liangcai, LI Haiying*. Synthesis of Novel Cyclic Poly(ε-caprolactone-co-γ-triethylsilyloxy-ε-caprolactone)[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30657.

References

[1] Kramers H A. The Behavior of Macromolecules in Inhomogeneous Flow[J]. Chem Phys,1946,14: 415-424.

[2] Wollman E L,Jacon F,Hayes W. Conjugation and Genetic Recombination in Escherichia Coli K-12[C]//.Cold Spring Harbor Symposia on Quantitative Biology,1956,21:141-162.

[3] Fiers W,Sinsheimer R L. The Structure of the DNA of Bacteriophage IX174[J]. Mol Biol,1962,5:408-419.

[4] Gorbunov A A,Skvortsov A M. Patterns of the Behaviour of Ring Macromolecules in Pores[J]. Polym Sci USSR,1984,26:2305-2314.

[5] Hadjichristidis N,Iatrou H,Pitsikalis M,et al. Macromolecular Architectures by Living and Controlled/Living Polymerizations[J]. Polym Sci,2006,31:1068-1132.

[6] Roovers J. Cyclic Polymers[M]. 2nd Ed. Semlyen J A,Ed. Kluwer,Dordrecht,The Netherlands,2000,347-383.

[7] Boyd L A,Grayson S M. Synthetic Approaches for the Preparation of Cyclic Polymers[J]. Chem Soc Rev,2009,38:2202-2213.

[8] Hadziioannou G,Cotts P M,Brinke G,et al. Thermodynamic and Hydrodynamic Properties of Dilute Solution of Cyclic and Linear Polystyrenes[J]. Macromolecules,1987,20(3):493-497.

[9] Endo K. Synthesis and Properties of Cylic Polymers[J]. Adv Polym Sci,2008,217:121-183.

[10] Geiser D,Hcker H. Preparation of Macrocyclic Polystyrene[J]. Polym Bull,1980,2:591-597.

[11] Adachi K,Takasugi H,Tezuka Y. Telechelics Having Unstrained Cyclicammonium Salt Groups for Electrostatic Polymer Self-Assembly and Ring-Emitting Covalent Fixation[J]. Macromolecules,2006,39:5585-5588.

[12] Yamamoto T,Tezuka Y. Topological Chemistry:A Cyclic Approach Toward Novel Properties and Functions[J]. Polym Chem,2011,2:1930-1941.

[13] Oike H,Kobayashi S,Mouri T,et al. Kyklo-Telechelics:Tailored Synthesis of Cyclic Poly(tetrahydrofuran)s Having Two Functional Groups at Opposite Positions[J]. Macromolecules,2001,34:2742-2744.

[14] Schapppacher M,Deffieux A. Synthesis of Macrocyclic Poly(2-chloroethyl vinyl ether)s[J]. Makromol Chem Rapid Commun,1991,12:447-453.

[15] Laurent B A,Grayson S M. An Efficient Route to Well-Defined Macrocyclic Polymers via “Click” Cyclization[J]. J Am Chem Soc,2006,128:4238-4239.

[16] Hoskins J N,Grayson S M. Cyclic polyesters:Synthetic Approaches and Potential Applications[J]. Polym Chem,2011,2:289-299.

[17] Xu J,Ye J,Liu S Y. Synthesis of Well-Defined Cyclic Poly(N-isopropylacrylamide) via Click Chemistry and Its Unique Thermal Phase Transition Behavior[J]. Macromolecules,2007,40(25):9103-9110.

[18] Dong Y Q,Tong Y Y,Li Z Ch,et al. Preparation of Tadpole-Shaped Amphiphilic Cyclic PS-b-Linear PEO via ATRP and Click Chemistry[J]. Macromolecules,2009,42(8):2940-2948.

[19] Zhu X,Zhou N,Zhang Zh,et al. Cyclic Polymers with Pendent Carbazole Units: Enhanced Fluorescence and Redox Behavior[J]. Angew Chem Int Ed,2011,50(29):6615-6618.

[20] CHEN Leiyan,XU Bolin,LI Haiying,et al. Synthesis of Cyclic Poly(ε-caprolactone) by High Efficient Ring-Closing Metathesis Reaction[J]. Acta Polym Sin,2012,7:743-748(in Chinese).

陈磊燕,徐博林,李海英,等. 由高效双键易位闭环反应合成环状聚ε-己内酯[J]. 高分子学报,2012,7：743-748.

[21] Christopher W,Bielawski,Grubbs,et al. An “Endless” Route to Cyclic Polymers[J]. Science,2002,297:2041-2044.

[22] He T,Zheng G H,Pan C Y. Synthesis of Cyclic Polymers and Block Copolymers by Monomer Insertion into Cyclic Initiator by a Radical Mechanism[J]. Macromolecules,2003,36(16):5960-5966.

[23] Li H,Debuigne A,Jerome R,et al. Synthesis of Macrocyclic Poly(ε-caprolactone) by Intramolecular Cross-Linking of Unsaturated End Groups of Chains Precyclic by the Initiation[J]. Angew Chem Int Ed,2006,45:2264-2267.

[24] Li H Y,Riva R,Jerome R,et al. Combination of Ring-Opening Polymerization and “Click” Chemistry for the Synthesis of an Amphiphilic Tadpole-Shaped Poly(ε-Caprolactone) Grafted by PEO[J]. Macromolecules,2007,40(4):824-831

[25] Ge Z S,Zhou Y M,Liu S Y,et al. High-Efficiency Preparation of Macrocyclic Diblock Copolymers via Selective Click Reaction in Micellar Media[J]. J Am Chem Soc,2009,131(5):1628-1629.

[26] Kricheldorf H R,Lee S R,Schittenhelm N. Macrocyclic Polymerization of (thio)Lactones-Stepwise Ring Expansion Contraction[J]. Macromol Chem Phys,1998,199:273-282.

[27] LI Erli,BA Wenjun,LI Haiying,et al. Synthesis of Cyclic Poly(ε-caprolactone)-g-poly(L-lactide) from Living Macrocyclic Precursor[J]. Chinese J Synth Chem,2013,21(1):6-10(in Chinese).

李二丽，巴文军，李海英,等. 由活性大分子环状前体合成环状聚ε-己内酯接枝聚L-乳酸[J]. 合成化学，2013，21(1):6-10.

[28] Crescenzi V,Manzini G,Calzolari G,et al. Thermodynamics of Fusion of Poly-β-propiolactone and Poly-γ-caprolactone. Comparative Analysis of the Melting of Aliphatic Polylactone and Polyester Chains[J]. Eur Polym J,1972,8:449-463.

Synthesis of Novel Cyclic Poly(ε-caprolactone-co-γ-triethylsilyloxy-ε-caprolactone)

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