Recent Studies on Single Site Metal Alkoxide Complexes as Catalysts for Ring Opening Polymerization of Cyclic Compounds

  • Asgar KayanEmail author


The selection of the catalyst is central to being able to control features and to better understand microstructures of polymers. New single-site metal alkoxide catalysts allow chemists to prepare regio/stereo regular polymers or copolymers that meet increasingly demanding performance requirements. These catalysts produce high molecular weights polymers with narrow polydispersity indexes or living properties and essentially regular polymers in structures. This review includes the synthesis, activity, and mechanistic aspects of especially single-site metal alkoxide catalysts with examples from my previous studies and recently published similar articles, beginning with an extensive survey on the aluminum, titanium, zirconium, and tin catalysts used to make polyethers, polyesters, and their derivatives. This review also compares the effects of ligands, substituents on ligands, and central metal atoms on ROP reactions. This review will provide the basis for the researchers who seek the new synthesis and application of catalysts in the future.

Graphic Abstract


Single site catalyst Metal alkoxide Ring-opening polymerization Mechanism Regio–stereo chemistry Cyclic compound 



This work was supported by the Kocaeli University (Project No. 2017/107)

Compliance with Ethical Standards

Conflict of interest

The author declares no competing financial interest.


  1. 1.
    Chisholm MH (2008) Catalytic formation of cyclic-esters and-depsipeptides and chemical amplification by complexation with sodium ions. J Organomet Chem 693:808–818CrossRefGoogle Scholar
  2. 2.
    Klein R, Wurm FR (2015) Aliphatic polyethers: classical polymers for the 21st century. Rapid Commun 36:1147–1165CrossRefGoogle Scholar
  3. 3.
    Poirier V, Roisnel T, Carpentier JF, Sarazin Y (2011) Zinc and magnesium complexes supported by bulky multidentate amino-ether phenolate ligands: potent pre-catalysts for the immortal ring-opening polymerisation of cyclic esters. Dalton Trans 40:523–534PubMedCrossRefPubMedCentralGoogle Scholar
  4. 4.
    Minyaev ME, Nifantev IE, Shlyakhtin AV, Ivchenko PV, Lyssenko KA (2018) Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization ofε-caprolactone with initiators of different natures. Acta Crystallogr C 74:548–557CrossRefGoogle Scholar
  5. 5.
    Garden JA, White AJ, Williams CK (2017) Heterodinuclear titanium/zinc catalysis: synthesis, characterization and activity for CO2/epoxide copolymerization and cyclic ester polymerization. Dalton Trans 46:2532–2541PubMedCrossRefPubMedCentralGoogle Scholar
  6. 6.
    Chisholm MH, Eilerts NW, Huffman JC, Iyer SS, Pacold M, Phomphrai K (2000) Molecular design of single-site metal alkoxide catalyst precursors for ring-opening polymerization reactions leading to polyoxygenates. 1. Polylactide formation by achiral and chiral magnesium and zinc alkoxides,(η3-L) MOR, where L= trispyrazolyl-and trisindazolylborate ligands. J Am Chem Soc 122:11845–11854CrossRefGoogle Scholar
  7. 7.
    Darensbourg DJ, Ganguly P, Billodeaux D (2005) Ring-opening polymerization of trimethylene carbonate using aluminum (III) and tin (IV) salen chloride catalysts. Macromolecules 38:5406–5410CrossRefGoogle Scholar
  8. 8.
    Darensbourg DJ, Poland RR, Escobedo C (2012) Kinetic studies of the alternating copolymerization of cyclic acid anhydrides and epoxides, and the terpolymerization of cyclic acid anhydrides, epoxides, and CO2 catalyzed by (salen) CrIIICl. Macromolecules 45:2242–2248CrossRefGoogle Scholar
  9. 9.
    Harrold ND, Li Y, Chisholm MH (2013) Studies of ring-opening reactions of styrene oxide by chromium tetraphenylporphyrin initiators Mechanistic and stereochemical considerations. Macromolecules 46:692–698CrossRefGoogle Scholar
  10. 10.
    Robert C, Ohkawara T, Nozaki K (2014) Manganese-corrole complexes as versatile catalysts for the ring-opening homo-and co-polymerization of epoxide. Chem Eur J 20:4789–4795PubMedCrossRefPubMedCentralGoogle Scholar
  11. 11.
    Mundil R, Hoštálek Z, Šeděnková I, Merna J (2015) Alternating ring-opening copolymerization of cyclohexene oxide with phthalic anhydride catalyzed by iron (III) salen complexes. Macromol Res 23:161–166CrossRefGoogle Scholar
  12. 12.
    Aida T, Sanuki K, Inoue S (1985) Well-controlled polymerization by metalloporphyrin. Synthesis of copolymer with alternating sequence and regulated molecular weight from cyclic acid anhydride and epoxide catalyzed by the system of aluminum porphyrin coupled with quaternary organic salt. Macromolecules 18:1049–1055CrossRefGoogle Scholar
  13. 13.
    Isnard F, Lamberti M, Pellecchia C, Mazzeo M (2017) Ring-opening copolymerization of epoxides with cyclic anhydrides promoted by bimetallic and monometallic phenoxy-imine aluminum complexes. ChemCatChem 9:2972–2979CrossRefGoogle Scholar
  14. 14.
    Garcés A, Sánchez-Barba LF, Fernández-Baeza J, Otero A, Fernández I, Lara-Sánchez A, Rodríguez AM (2018) Organo-aluminum and zinc acetamidinates: preparation, coordination ability, and ring-opening polymerization processes of cyclic esters. Inorg Chem 57:12132–12142PubMedCrossRefPubMedCentralGoogle Scholar
  15. 15.
    Sumrit P, Chuawong P, Nanok T, Duangthongyou T, Hormnirun P (2016) Aluminum complexes containing salicylbenzoxazole ligands and their application in the ring-opening polymerization of rac-lactide and ε-caprolactone. Dalton Trans 45:9250–9266PubMedCrossRefPubMedCentralGoogle Scholar
  16. 16.
    Yu CY, Chuang HJ, Ko BT (2016) Bimetallic bis (benzotriazole iminophenolate) cobalt, nickel and zinc complexes as versatile catalysts for coupling of carbon dioxide with epoxides and copolymerization of phthalic anhydride with cyclohexene oxide. Catal Sci Technol 6:1779–1791CrossRefGoogle Scholar
  17. 17.
    Chmura AJ, Davidson MG, Jones MD, Lunn MD, Mahon MF (2006) Group 4 complexes of amine bis (phenolate) s and their application for the ring opening polymerisation of cyclic esters. Dalton Trans 7:887–889CrossRefGoogle Scholar
  18. 18.
    Longo JM, Sanford MJ, Coates GW (2016) Ring-opening copolymerization of epoxides and cyclic anhydrides with discrete metal complexes: structure–property relationships. Chem Rev 116:15167–15197PubMedCrossRefPubMedCentralGoogle Scholar
  19. 19.
    Trott G, Saini PK, Williams CK (2016) Catalysts for CO2/epoxide ring-opening copolymerization. Philos Trans R Soc A 374:20150085CrossRefGoogle Scholar
  20. 20.
    Stanford MJ, Dove AP (2010) Stereocontrolled ring-opening polymerisation of lactide. Chem Soc Rev 39:486–494PubMedCrossRefPubMedCentralGoogle Scholar
  21. 21.
    Jianming R, Anguo X, Hongwei W, Hailin Y (2014) Review–recent development of ring-opening polymerization of cyclic esters using aluminum complexes. Des Monomers Polym 17:345–355CrossRefGoogle Scholar
  22. 22.
    Dijkstra PJ, Du H, Feijen J (2011) Single site catalysts for stereoselective ring-opening polymerization of lactides. Polym Chem 2:520–527CrossRefGoogle Scholar
  23. 23.
    Hoebbel D, Nacken M, Schmidt H (2001) On the influence of metal alkoxides on the epoxide ring-opening and condensation reactions of 3-glycidoxypropyltrimethoxysilane. J Sol-Gel Sci Technol 21:177–187CrossRefGoogle Scholar
  24. 24.
    Li P, Zerroukhi A, Chen J, Chalamet Y, Jeanmaire T, Xia Z (2009) Synthesis of poly (ɛ-caprolactone)-block-poly (n-butyl acrylate) by combining ring-opening polymerization and atom transfer radical polymerization with Ti [OCH2CCl3]4 as difunctional initiator: I. Kinetic study of Ti [OCH2CCl3]4 initiated ring-opening polymerization of ɛ-caprolactone. Polymer 50:1109–1117CrossRefGoogle Scholar
  25. 25.
    Schubert U (2003) Silica-based and transition metal-based inorganic-organic hybrid Materials—a comparison. J Sol-Gel Sci Technol 26:47–55CrossRefGoogle Scholar
  26. 26.
    Gökalp Y, Kayan A (2018) Synthesis and characterization of Ti-/Zr-diphenylpropanedione complexes and their application in the ring opening polymerization of Ɛ-caprolactone. J Turk Chem Soc Sec A 5:1095–1104CrossRefGoogle Scholar
  27. 27.
    Yalcin G, Yildiz U, Kayan A (2012) Preparation of Al, Ti, Zr-perfluoroheptanoate compounds and their use in ring opening polymerization. Appl Catal A 423:205–210CrossRefGoogle Scholar
  28. 28.
    Kayan A (2019) Inorganic-organic hybrid materials and their adsorbent properties. Adv Compos Hybrid Mater 2:34–45CrossRefGoogle Scholar
  29. 29.
    Caiut JMA, Rocha LA, Sigoli FA, Messaddeq Y, Dexpert-Ghys J, Ribeiro SJ (2008) Aluminoxane-epoxi-siloxane hybrids waveguides. J Non-Cryst Solids 354:4795–4799CrossRefGoogle Scholar
  30. 30.
    Caldara M, Colleoni C, Guido E, Re V, Rosace G (2016) Optical monitoring of sweat pH by a textile fabric wearable sensor based on covalently bonded litmus-3-glycidoxypropyltrimethoxysilane coating. Sens Actuators B 222:213–220CrossRefGoogle Scholar
  31. 31.
    Plutino MR, Guido E, Colleoni C, Rosace G (2017) Effect of GPTMS functionalization on the improvement of the pH-sensitive methyl red photostability. Sens Actuators B 238:281–291CrossRefGoogle Scholar
  32. 32.
    Van Leeuwen PWNM (2004) Homogeneous catalysis: understanding the art. Kluwer Academic Publishers, DordrechtCrossRefGoogle Scholar
  33. 33.
    Darensbourg DJ, Yarbrough JC (2002) Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst. J Am Chem Soc 124:6335–6342PubMedCrossRefPubMedCentralGoogle Scholar
  34. 34.
    Jacobsen EN (2000) Asymmetric catalysis of epoxide ring-opening reactions. Acc Chem Res 33:421–431PubMedCrossRefPubMedCentralGoogle Scholar
  35. 35.
    Chisholm MH, Zhou Z (2004) Concerning the mechanism of the ring opening of propylene oxide in the copolymerization of propylene oxide and carbon dioxide to give poly(propylene carbonate). J Am Chem Soc 126:11030–11039PubMedCrossRefPubMedCentralGoogle Scholar
  36. 36.
    Chisholm MH, Navarro-Llobet D (2002) NMR assignments of regioregular poly (propylene oxide) at the triad and tetrad level. Macromolecules 35:2389–2392CrossRefGoogle Scholar
  37. 37.
    Innocenzi P, Brusatin G, Guglielmi M, Signorini R, Bozio R, Maggini M (2000) 3-(Glycidoxypropyl)-trimethoxysilane-TiO2 hybrid organic–inorganic materials for optical limiting. J Non-Cryst Solids 265:68–74CrossRefGoogle Scholar
  38. 38.
    Wang J, Fan X, Tian W, Wang Y, Li J (2011) Ring-opening polymerization of γ-glycidoxypropyltrimethoxysilane catalyzed by multi-metal cyanide catalyst. J Polym Res 18:2133–2139CrossRefGoogle Scholar
  39. 39.
    Sang T, Li S, Ting HK, Stevens MM, Becer CR, Jones JR (2018) Hybrids of Silica/poly (caprolactone coglycidoxypropyl trimethoxysilane) as biomaterials. Chem Mater 30:3743–3751CrossRefGoogle Scholar
  40. 40.
    Yalcin G, Kayan A (2012) Synthesis and characterization of Zr, Ti, Al-phthalate and pyridine-2-carboxylate compounds and their use in ring opening polymerization. Appl Catal A 433:223–228CrossRefGoogle Scholar
  41. 41.
    Schütz C, Dwars T, Schnorpfeil C, Radnik J, Menzel M, Kragl U (2007) Selective polymerization of propylene oxide by a tin phosphate coordination polymer. J Polym Sci Part A 45:3032–3041CrossRefGoogle Scholar
  42. 42.
    Huang BH, Tsai CY, Chen CT, Ko BT (2016) Metal complexes containing nitrogen-heterocycle based aryloxide or arylamido derivatives as discrete catalysts for ring-opening polymerization of cyclic esters. Dalton Trans 45:17557–17580PubMedCrossRefPubMedCentralGoogle Scholar
  43. 43.
    Lalrempuia R, Breivik F, Törnroos KW, Le Roux E (2017) Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2. Dalton Trans 46:8065–8076PubMedCrossRefPubMedCentralGoogle Scholar
  44. 44.
    Romain C, Thevenon A, Saini PK, Williams CK (2016) In: Carbon dioxide and organometallics, vol 53. Springer, Switzerland, pp 101–142Google Scholar
  45. 45.
    Kayan A (2012) Polymerization of 3-glycidyloxypropyltrimethoxysilane with different catalysts. J Appl Polym Sci 123:3527–3534CrossRefGoogle Scholar
  46. 46.
    Yalçın G, Kayan A (2012) Ring-opening polymerization of isopropylglycidyl ether (IPGE) with new catalysts of Ti, Sn, Al-alkoxides and comparison of its reactivity. Des Monomers Polym 15:405–416CrossRefGoogle Scholar
  47. 47.
    Misaka H, Sakai R, Satoh T, Kakuchi T (2011) Synthesis of high molecular weight and end-functionalized poly (styrene oxide) by living ring-opening polymerization of styrene oxide using the alcohol/phosphazene base initiating system. Macromolecules 44:9099–9107CrossRefGoogle Scholar
  48. 48.
    Kayan A (2015) Synthesis of poly (styrene oxide) with different molecular weights using tin catalysts. Des Monomers Polym 18:545–549CrossRefGoogle Scholar
  49. 49.
    Grobelny Z, Matlengiewicz M, Jurek-Suliga J, Golba S, Skrzeczyna K, Kwapulińska D (2017) Ring opening polymerization of styrene oxide initiated with potassium alkoxides and hydroxyalkoxides activated by 18-crown-6: determination of mechanism and preparation of new polyether-polyols. Polym Bull 74:4763–4780CrossRefGoogle Scholar
  50. 50.
    Mert O, Kayan A (2014) Synthesis and characterization of substituted salicylate zirconium compounds and their catalytic activity over ε-caprolactone. J Incl Phen Macrocycl Chem 80:409–416CrossRefGoogle Scholar
  51. 51.
    Thurston JH, Kumar A, Hofmann C, Whitmire KH (2004) Heterobimetallic Bi (III)-Ti(IV) coordination complexes: synthesis and solid-state structures of BiTi4 (sal)6(μ-OiPr)3 (OiPr)4, and the cyclic isomers Bi4Ti4(sal)10 (μ-OiPr)4(OiPr)4 and Bi8Ti8 (sal)20(μ-OiPr)8 (OiPr)8. Inorg Chem 43:8427–8436PubMedCrossRefPubMedCentralGoogle Scholar
  52. 52.
    Stavila V, Thurston JH, Whitmire KH (2009) Selective arylation reactions of bismuth-transition metal salicylate complexes. Inorg Chem 48:6945–6951PubMedCrossRefPubMedCentralGoogle Scholar
  53. 53.
    Espinoza SM, Patil HI, San Martin Martinez E, Casañas Pimentel R, Ige PP (2018) Poly-ε-caprolactone (PCL), a promising polymer for pharmaceutical and biomedical applications: focus on nanomedicine in cancer. Int J Polym Mater Po 1–42Google Scholar
  54. 54.
    Woodruff MA, Hutmacher DW (2010) The return of a forgotten polymer-Polycaprolactone in the 21st century. Prog Polym Sci 35:1217–1256CrossRefGoogle Scholar
  55. 55.
    Reyes-López SY, Richa AM (2013) The ring-opening polymerization of ε-caprolactone catalyzed by molybdenum trioxide: a kinetic approach study using NMR and DSC data. Macromol Symp 325:21–37CrossRefGoogle Scholar
  56. 56.
    He X, Tu G, Zhang F, Huang S, Cheng C, Zhu C, Chen D (2018) Bis-(salicylaldehyde-benzhydrylimino) nickel complexes with different electron groups: crystal structure and their catalytic properties toward (co) polymerization of norbornene and 1-hexene. RSC Adv 8:36298–36312CrossRefGoogle Scholar
  57. 57.
    Kricheldorf HR, Berl M, Scharnagl N (1988) Poly (lactones). 9. Polymerization mechanism of metal alkoxide initiated polymerizations of lactide and various lactones. Macromolecules 21:286–293CrossRefGoogle Scholar
  58. 58.
    Dubois P, Jacobs C, Jérôme R, Teyssie P (1991) Macromolecular engineering of polylactones and polylactides. 4. Mechanism and kinetics of lactide homopolymerization by aluminum isopropoxide. Macromolecules 24:2266–2270CrossRefGoogle Scholar
  59. 59.
    Mun SD, Hong YJ, Kim YJ (2007) Synthesis, X-ray structure, and l-lactide/ε-caprolactone polymerization behavior of monomeric aryloxytitanatrane. Bull Korean Chem Soc 28:698–700CrossRefGoogle Scholar
  60. 60.
    Silawanich A, Muangpil S, Kungwan N, Meepowpan P, Punyodom W, Lawan N (2016) Theoretical study of efficiency comparison of Ti (IV) alkoxides as initiators for ring-opening polymerization of ε-caprolactone. Comp Theor Chem 1090:17–22CrossRefGoogle Scholar
  61. 61.
    Kricheldorf HR, Langanke D (2002) Polylactones 54: ring-opening and ring-expansionpolymerizations of ϵ-caprolactone initiated by germanium alkoxides. Polymer 43:1973–1977CrossRefGoogle Scholar
  62. 62.
    Pappuru S, Chakraborty D, Sundar JV, Roymuhury SK, Ramkumar V, Subramanian V, Chand DK (2016) Group 4 complexes of salicylbenzoxazole ligands as effective catalysts for the ring-opening polymerization of lactides, epoxides and copolymerization of ε-caprolactone with L-lactide. Polymer 102:231–247CrossRefGoogle Scholar
  63. 63.
    Appavoo D, Omondi B, Guzei IA, Van Wyk JL, Zinyemba O, Darkwa J (2014) Bis (3,5-dimethylpyrazole) copper (II) and zinc (II) complexes as efficient initiators for the ring opening polymerization of ε-caprolactone and d, l-lactide. Polyhedron 69:55–60CrossRefGoogle Scholar
  64. 64.
    Medina DA, Contreras JM, López-Carrasquero FJ, Cardozo EJ, Contreras RR (2018) Use of samarium (III)–amino acid complexes as initiators of ring-opening polymerization of cyclic esters. Polym Bull 75:1253–1263CrossRefGoogle Scholar
  65. 65.
    Saito T, Aizawa Y, Yamamoto T, Tajima K, Isono T, Satoh T (2018) Alkali metal carboxylate as an efficient and simple catalyst for ring-opening polymerization of cyclic esters. Macromolecules 51:689–696CrossRefGoogle Scholar
  66. 66.
    Chen P, Chisholm MH, Gallucci JC, Zhang X, Zhou Z (2005) Binding of propylene oxide to porphyrin-and salen-M (III) cations, where M= Al, Ga, Cr, and Co. Inorg Chem 44:2588–2595PubMedCrossRefPubMedCentralGoogle Scholar
  67. 67.
    Bernard A, Chatterjee C, Chisholm MH (2013) The influence of the metal (Al, Cr and Co) and the substituents of the porphyrin in controlling the reactions involved in the copolymerization of propylene oxide and cyclic anhydrides by porphyrin metal (III) complexes. Polymer 54:2639–2646CrossRefGoogle Scholar
  68. 68.
    Chatterjee C, Chisholm MH (2013) Ring-opening polymerization reactions of propylene oxide catalyzed by porphyrin metal (3+) complexes of aluminum, chromium and cobalt. Chem Rec 13:549–560PubMedCrossRefPubMedCentralGoogle Scholar
  69. 69.
    Xia W, Salmeia KA, Vagin SI, Rieger B (2015) Concerning the deactivation of cobalt (III)-based porphyrin and salen catalysts in epoxide/CO2 copolymerization. Chem Eur J 21:4384–4390PubMedCrossRefPubMedCentralGoogle Scholar
  70. 70.
    Praban S, Piromjitpong P, Balasanthiran V, Jayaraj S, Chisholm MH, Tantirungrotechai J, Phomphrai K (2019) Highly efficient metal (iii) porphyrin and salen complexes for the polymerization of rac-lactide under ambient conditions. Dalton Trans 48:3223–3230PubMedCrossRefPubMedCentralGoogle Scholar
  71. 71.
    Yaman H, Kayan A (2017) Synthesis of novel single site tin porphyrin complexes and the catalytic activity of tin tetrakis (4-fluorophenyl) porphyrin over ε-caprolactone. J Porphyrins Phthalocyanine 21:231–237CrossRefGoogle Scholar
  72. 72.
    Wang X, Thevenon A, Brosmer JL, Yu I, Khan SI, Mehrkhodavandi P, Diaconescu PL (2014) Redox control of group 4 metal ring-opening polymerization activity toward l-lactide and ε-caprolactone. J Am Chem Soc 136:11264–11267PubMedCrossRefPubMedCentralGoogle Scholar
  73. 73.
    Yildiz BC, Kayan A (2017) Preparation of single-site tin (IV) compounds and their use in the polymerization of ε-caprolactone. Des Monomers Polym 20:89–96PubMedCrossRefPubMedCentralGoogle Scholar
  74. 74.
    Mert O, Kayan A (2013) Synthesis of silyliminophenolate zirconium compounds and their catalytic activity over lactide/epoxide. Appl Catal A 464:322–331CrossRefGoogle Scholar
  75. 75.
    Odian G (2004) Principles of polymerization. Wiley, HobokenCrossRefGoogle Scholar
  76. 76.
    Kayan A, Mert O (2014) Preparation of l-Lactide/3-glycidyloxypropyltrimethoxysilane copolymeric materials with various catalysts. J Inorg Organomet Polym Mater 24:1055–1062CrossRefGoogle Scholar
  77. 77.
    Penczek S, Pretula J, Lewiński P (2017) Dormant polymers and their role in living and controlled polymerizations; influence on polymer chemistry, particularly on the ring opening polymerization. Polymers 9:646PubMedCentralCrossRefGoogle Scholar
  78. 78.
    Mandal M, Monkowius U, Chakraborty D (2016) Cadmium acetate as a ring opening polymerization catalyst for the polymerization of rac-lactide, ε-caprolactone and as a precatalyst for the polymerization of ethylene. J Polym Res 23:220CrossRefGoogle Scholar
  79. 79.
    Sauer A, Kapelski A, Fliedel C, Dagorne S, Kol M, Okuda J (2013) Structurally well-defined group 4 metal complexes as initiators for the ring-opening polymerization of lactide monomers. Dalton Trans 42:9007–9023PubMedCrossRefPubMedCentralGoogle Scholar
  80. 80.
    Della Monica F, Luciano E, Roviello G, Grassi A, Milione S, Capacchione C (2014) Group 4 metal complexes bearing thioetherphenolate ligands. Coordination chemistry and ring-opening polymerization catalysis. Macromolecules 47:2830–2841CrossRefGoogle Scholar
  81. 81.
    Liu DC, Li CY, Lin PH, Chen JD, Tsai CY, Lin CH, Ko BT (2018) Titanium complexes bearing benzotriazole iminophenolate ligands as efficient catalysts for ring-opening polymerization of cyclic esters. Inorg Chem Commun 90:1–7CrossRefGoogle Scholar
  82. 82.
    Su CK, Chuang HJ, Li CY, Yu CY, Ko BT, Chen JD, Chen MJ (2014) Oxo-bridged bimetallic group 4 complexes bearing amine-bis (benzotriazole phenolate) derivatives as bifunctional catalysts for ring-opening polymerization of lactide and copolymerization of carbon dioxide with cyclohexene oxide. Organometallics 33:7091–7100CrossRefGoogle Scholar
  83. 83.
    Su YC, Liu WL, Li CY, Ko BT (2019) Air-stable di-nuclear yttrium complexes as versatile catalysts for lactide polymerization and copolymerization of epoxides with carbon dioxide or phthalic anhydride. Polymer 167:21–30CrossRefGoogle Scholar
  84. 84.
    Carpentier JF (2015) Rare-earth complexes supported by tripodal tetradentate bis (phenolate) ligands: a privileged class of catalysts for ring-opening polymerization of cyclic esters. Organometallics 34:4175–4189CrossRefGoogle Scholar
  85. 85.
    Ligny R, Hänninen MM, Guillaume SM, Carpentier JF (2018) Steric vs. electronic stereocontrol in syndio-or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes. Chem Commun 54:8024–8031CrossRefGoogle Scholar
  86. 86.
    Jiang MT, Kosuru SR, Lee YH, Lu WY, Vandavasi JK, Lai YC, Chen HY (2018) Factors influencing catalytic behavior of titanium complexes bearing bisphenolate ligands toward ring-opening polymerization of L-lactide and ε-caprolactone. Exp Polym Lett 12:126–135CrossRefGoogle Scholar
  87. 87.
    Xie H, Wu C, Cui D, Wang Y (2018) Ligand-free scandium alkyl and alkoxide complexes for immortal ring-opening polymerization of lactide. J Organomet Chem 875:5–10CrossRefGoogle Scholar
  88. 88.
    Jones MD, Wu X, Chaudhuri J, Davidson MG, Ellis MJ (2017) Zirconium amine tris (phenolate): a more effective initiator for biomedical lactide. Mater Sci Eng C 80:69–74CrossRefGoogle Scholar
  89. 89.
    Li X, Yang B, Zheng H, Wu P, Zeng G (2018) Synthesis and characterization of salen-Ti (IV) complex and application in the controllable polymerization of D L-lactide. PLoS ONE 13:e0201054PubMedPubMedCentralCrossRefGoogle Scholar
  90. 90.
    Marin P, Tschan MJL, Haquette P, Roisnel T, del Rosal I, Maron L, Thomas CM (2019) Single-site cobalt and zinc catalysts for the ring-opening polymerization of lactide. Eur Polym J 120:109208CrossRefGoogle Scholar
  91. 91.
    Sarazin Y, Carpentier JF (2015) Discrete cationic complexes for ring-opening polymerization catalysis of cyclic esters and epoxides. Chem Rev 115:3564–3614PubMedCrossRefPubMedCentralGoogle Scholar
  92. 92.
    Osorio Meléndez D, Castro-Osma JA, Lara-Sánchez A, Rojas RS, Otero A (2017) Ring-opening polymerization and copolymerization of cyclic esters catalyzed by amidinatealuminum complexes. J Polym Sci Part A 55:2397–2407CrossRefGoogle Scholar
  93. 93.
    Gao J, Zhu D, Zhang W, Solan GA, Ma Y, Sun WH (2019) Recent progress in the application of group 1, 2 & 13 metal complexes as catalysts for the ring opening polymerization of cyclic esters. Inorg Chem Front 6:2619–2652CrossRefGoogle Scholar
  94. 94.
    Redshaw C (2017) Use of metal catalysts bearing Schiff base macrocycles for the ring opening polymerization (ROP) of cyclic esters. Catalysts 7:165CrossRefGoogle Scholar
  95. 95.
    Tian J, Zhang W (2019) Synthesis, self-assembly and applications of functional polymers based on porphyrins. Prog Polym Sci 95:65–117CrossRefGoogle Scholar
  96. 96.
    Dagorne S, Normand M, Kirillov E, Carpentier JF (2013) Gallium and indium complexes for ring-opening polymerization of cyclic ethers, esters and carbonates. Coord Chem Rev 257:1869–1886CrossRefGoogle Scholar
  97. 97.
    Osten KM, Mehrkhodavandi P (2017) Indium catalysts for ring opening polymerization: exploring the importance of catalyst aggregation. Acc Chem Res 50:2861–2869PubMedCrossRefPubMedCentralGoogle Scholar
  98. 98.
    Kremer AB, Mehrkhodavandi P (2019) Dinuclear catalysts for the ring opening polymerization of lactide. Coord Chem Rev 380:35–57CrossRefGoogle Scholar
  99. 99.
    Thevenon A, Cyriac A, Myers D, White AJ, Durr CB, Williams CK (2018) Indium catalysts for low-pressure CO2/epoxide ring-opening copolymerization: evidence for a mononuclear mechanism. J Am Chem Soc 140:6893–6903PubMedCrossRefPubMedCentralGoogle Scholar
  100. 100.
    Ghosh S, Gowda RR, Jagan R, Chakraborty D (2015) Gallium and indium complexes containing the bis (imino) phenoxide ligand: synthesis, structural characterization and polymerization studies. Dalton Trans 44:10410–10422PubMedCrossRefPubMedCentralGoogle Scholar
  101. 101.
    Lyubov DM, Tolpygin AO, Trifonov AA (2019) Rare-earth metal complexes as catalysts for ring-opening polymerization of cyclic esters. Coord Chem Rev 392:83–145CrossRefGoogle Scholar
  102. 102.
    Yu C, Zhang L, Shen Z (2003) Ring-opening polymerization of ε-caprolactone using rare earth tris (4-tert-butylphenolate)s as a single component initiator. Eur Polym J 39:2035–2039CrossRefGoogle Scholar
  103. 103.
    Zhang L, Yu C, Shen Z (2003) Characteristics, kinetics and Mechanism of ε-Caprolactone polymerization by lanthanide tris (2.6-dimethylphenolate)s. Polym Bull 51:47–53CrossRefGoogle Scholar
  104. 104.
    Zhang L, Niu Y, Wang Y, Wang SL (2008) Ring-opening polymerization of ɛ- caprolactone by lanthanide tris (2, 4, 6-tri-tert-butylphenolate) s: characteristics, kinetics and mechanism. J Mol Catal A 287:1–4CrossRefGoogle Scholar
  105. 105.
    Guillaume SM, Kirillov E, Sarazin Y, Carpentier JF (2015) Beyond stereoselectivity, switchable catalysis: some of the last frontier challenges in ring-opening polymerization of cyclic esters. Chem Eur J 21:7988–8003PubMedCrossRefPubMedCentralGoogle Scholar
  106. 106.
    Paul S, Zhu Y, Romain C, Brooks R, Saini PK, Williams CK (2015) Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates. Chem Commun 51:6459–6479CrossRefGoogle Scholar
  107. 107.
    Taherimehr M, Sertã JPCC, Kleij AW, Whiteoak CJ, Pescarmona PP (2015) New iron pyridylamino-bis (phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates. ChemSusChem 8:1034–1042PubMedCrossRefPubMedCentralGoogle Scholar
  108. 108.
    Devaine-Pressing K, Kozak CM (2017) Mechanistic studies of cyclohexene oxide/CO2 copolymerization by a chromium (III) pyridylamine-bis (phenolate) complex. ChemSusChem 10:1266–1273PubMedCrossRefPubMedCentralGoogle Scholar
  109. 109.
    Ni K, Kozak CM (2018) Kinetic studies of copolymerization of cyclohexene oxide with CO2 by a diamino-bis (phenolate) chromium (III) complex. Inorg Chem 57:3097–3106PubMedCrossRefPubMedCentralGoogle Scholar
  110. 110.
    Brocas AL, Mantzaridis C, Tunc D, Carlotti S (2013) Polyether synthesis: from activated or metal-free anionic ring-opening polymerization of epoxides to functionalization. Prog Polym Sci 38:845–873CrossRefGoogle Scholar
  111. 111.
    Kayan A (2019) Copolymerization reactions of butadiene monoxide with 3-glycidyloxypropyltrimethoxysilane and styrene oxide and their glycol derivatives. J Appl Polym Sci 136:47074Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Arts and SciencesKocaeli UniversityKocaeliTurkey

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