Skip to main content
Disciplines
Automotive Business IT + Informatics Construction + Real Estate Electrical Engineering + Electronics Energy + Sustainability Insurance + Risk Finance + Banking Management + Leadership Marketing + Sales Mechanical Engineering + Materials
Events
DE
EN
Books
Journals
Topic Page
Marketing
Start single access now
Access for companies
EXTENDED SEARCH
Log in
Top
Polymer Bulletin
Published in: Polymer Bulletin 1/2024

16-02-2023 | ORIGINAL PAPER

Microwave-assisted solvent-free ring-opening polymerization of ε-caprolactone initiated by n-butyltin(IV) chlorides

Authors: Watcharee Funfuenha, Winita Punyodom, Puttinan Meepowpan, Wanich Limwanich

Published in: Polymer Bulletin | Issue 1/2024

Log in

Activate our intelligent search to find suitable subject content or patents.

search-config
loading …

Abstract

The microwave irradiation was successfully and firstly used to improve the solvent-free ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) with different n-butyltin(IV) chloride (nBumSnCln; m and n = 1–3) initiators such as tri-n-butyltin(IV) chloride (nBu3SnCl), di-n-butyltin(IV) dichloride (nBu2SnCl2), n-butyltin(IV) trichloride (nBuSnCl3). The performance of these n-butyltin(IV) chloride initiators in the synthesis of poly(ε-caprolactone) (PCL) was benchmarked and compared to the conventional initiating system of tin(II) 2-ethylhexanoate (Sn(Oct)2). The ROP of ε-CL with all initiating systems was completed in a short time of 30 min by using microwave power of 450 W. The chlorine (Cl) atom presented in the nBumSnCln initiators played an important role in the molecular weight of PCL. The higher amount of Cl in nBumSnCln and the lower PCL molecular weight were obtained. Under the condition used in this work, the performance of initiating systems in the synthesis of PCL via microwave irradiation was in the following order: nBu3SnCl > nBu2SnCl2 > nBuSnCl3 ≈ Sn(Oct)2. Surprisingly, the slowest nBu3SnCl initiator produced the highest weight average molecular weight (Mw = 6.31 × 104 g/mol) of PCL under microwave irradiation and solvent-free condition. The dispersity (Đ) of the synthesized PCL became narrower (Đ = 1.39–1.90) when the nBu3SnCl initiator was used instead of other initiating systems (Đ = 1.62–2.34). The synthesized PCLs were characterized by the Fourier transform infrared spectroscopy (FTIR), proton and carbon-nuclear magnetic resonance spectroscopy (1H- and 13C-NMR), and gel permeation chromatography (GPC) techniques. The mechanism of the ROP of ε-CL with all initiating systems was also explained. The microwave irradiation by a commercial microwave oven could be considered as an effective route in terms of the cost-effective and short synthesis time for biodegradable polymer production.

Graphical abstract

previous article Microwave-assisted fabrication for synthesis of magnetite chitosan-modified polymer composite hydrogel as rapid removal adsorbent for effective remediation of hazardous contaminants
next article Evaluation of antifouling/biofouling ability of a novel MIL101(Cr)/PES composite membrane for acetate wastewater treatment in MBR application

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

  • über 102.000 Bücher
  • über 537 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Finance + Banking
  • Management + Führung
  • Marketing + Vertrieb
  • Maschinenbau + Werkstoffe
  • Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

  • über 67.000 Bücher
  • über 390 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Maschinenbau + Werkstoffe




 

Jetzt Wissensvorsprung sichern!

inform now
Literature
1.
Stridsberg KM, Ryner M, Albertsson AC (2002) Controlled ring-opening polymerization: polymers with designed macromolecular architecture. Adv Polym Sci 157:41–65CrossRef
2.
Albertsson AC, Varma IK (2003) Recent developments in ring opening polymerization of lactones for biomedical applications. Biomacromol 4:1466–1486CrossRef
3.
Cabaret OD, Vaca BM, Bourissou D (2004) Controlled ring-opening polymerization of lactide and glycolide. Chem Rev 104:6147–6176CrossRef
4.
Phetsuk S, Molloy R, Nalampang K, Meepowpan P, Topham PD, Tighe BJ, Punyodom W (2020) Physical and thermal properties of l-lactide/ε-caprolactone copolymers: the role of microstructural design. Polym Int 69(3):248–256CrossRef
5.
Gupta AP, Kumar V (2007) New emerging trends in synthetic biodegradable polymers–polylactide: a critique. Eur Polym J 43(10):4053–4074CrossRef
6.
Kowalski A, Libiszowski J, Duda A, Penczek S (2000) Polymerization of L, L-dilactide initiated by tin(II) butoxide. Macromolecules 33:1964–1971CrossRef
7.
Boontharika T, Limwanich W, Meepowpan P, Punyodom W (2021) Tin(II) n-hexoxide as new initiator for the ring-opening polymerization of ε-caprolactone: isoconversional kinetics analysis by non-isothermal DSC. Chiang Mai J Sci 48(2):276–291
8.
Sriyai M, Chaiwon T, Molloy R, Meepowpan P, Punyodom W (2020) Efficiency of liquid tin(ii) n-alkoxide initiators in the ring-opening polymerization of l-lactide: kinetic studies by non-isothermal differential scanning calorimetry. RSC ADV 10:43566–43578CrossRefPubMedPubMedCentral
9.
Kricheldorf HR, Weidner SM (2021) ROP of l-lactide and caprolactone catalyzed by tin(II) and tin(IV) acetates-switching from COOH terminated linear chains to cycles. J Polym Sci 59:439–450CrossRef
10.
11.
Weidner SM, Kricheldorf HR (2022) SnOct2-catalyzed ROPs of l-lactide initiated by acidic OH- compounds: switching from ROP to polycondensation and cyclization. J Polym Sci 60(5):785–793CrossRef
12.
Punyodom W, Limwanich W, Meepowpan P (2017) Tin(II) n-butyl L-lactate as novel initiator for the ring-opening polymerization of ε-caprolactone: kinetics and aggregation equilibrium analysis by non-isothermal DSC. Thermochim Acta 655:337–343CrossRef
13.
Mekpothi T, Meepowpan P, Sriyai M, Molloy R, Punyodom W (2021) Novel poly(methylenelactide-g- l-lactide) graft copolymers synthesized by a combination of vinyl addition and ring-opening polymerizations. Polymers 13(19):3374CrossRefPubMedPubMedCentral
14.
Wang L, Bochmann M, Cannon RD, Carpentier JF, Roisnel T, Sarazin Y (2013) Kinetic analysis of the living ring-opening polymerisation of l-lactide with tin(II) initiators. Eur J Inorg Chem 2013(34):5896–5905CrossRef
15.
Kricheldorf HR, Sumbel MV, Saunders IK (1991) Polylactones. 20. polymerization of ε-caprolactone with tributyltin derivatives: a mechanistic study. Macromolecules 24:1944–1949CrossRef
16.
Limwanich W, Meepowpan P, Nalampang K, Kungwan N, Molloy R, Punyodom W (2015) Kinetics and thermodynamics analysis for ring-opening polymerization of ε-caprolactone initiated by tributyltin n-butoxide using differential scanning calorimetry. J Therm Anal Calorim 119:567–579CrossRef
17.
Punyodom W, Meepowpan P, Thapsukhon B, Dumklang M, Limwanich W (2022) Investigation of the initiating and catalytic behavior of tri-n-butyltin(IV) n-butoxide in ring-opening polymerization of ε-caprolactone and transesterification of poly(L-lactic acid). Chiang Mai J Sci 49(1):27–38CrossRef
18.
Kricheldorf HR, Weidner SM (2021) Polymerization of l-lactide with SnCl2: a low toxic and eco-friendly catalyst. J Polym Environ 29:2504–2516CrossRef
19.
Punyodom W, Meepowpan P, Limwanich W (2022) Determination of the activation parameters for the ring-opening polymerization of ε-caprolactone initiated by Sn(II) and Zn(II) chlorides using the fast technique of DSC. Thermochim Acta 710:179160CrossRef
20.
Limwanich W, Meepowpan P, Kungwan N, Punyodom W (2020) Influence of butyl group of tin chloride initiators on the non-isothermal DSC ring-opening polymerization of ε-caprolactone: the studies of kinetics, mechanism and polymer synthesis. Thermochim Acta 683:178458CrossRef
21.
Deshayes G, Mercier FAG, Degee P, Verbruggen I, Biesemans M, Willem R, Dubois P (2003) Mechanistic study of Bu2SnCl2-mediated ring-opening polymerization of ε-caprolactone by multinuclear NMR spectroscopy. Chem Eur J 9:4346–4352CrossRefPubMed
22.
Sobczak M (2012) Ring-opening polymerization of cyclic esters in the presence of choline/SnOct2 catalytic system. Polym Bull 68:2219–2228CrossRef
23.
Weidner SM, Meyer A, Falkenhagen J, Kricheldorf HR (2021) SnOct2-catalyzed and alcohol-initiated ROPs of l-lactide –about the influence of initiators on chemical reactions in the melt and the solid state. Eur Polym J 153:110508CrossRef
24.
Pretula J, Slomkowski S, Penczek S (2016) Polylactides—methods of synthesis and characterization. Adv Drug Deliv Rev 107:3–16CrossRefPubMed
25.
Liao LQ, Liu LJ, Zhang C, He F, Zhou RX, Wan K (2002) Microwave-assisted ring-opening polymerization of ε-caprolactone. J Polym Sci A Polym Chem 40:1749–1755CrossRef
26.
Tan Y, Cai S, Liao L, Wang Q, Liu L (2009) Microwave-assisted ring-opening polymerization of ε-caprolactone in presence of hydrogen phosphonates. Polym J 41(10):849–854CrossRef
27.
Xu Q, Zhang C, Cai S, Zhu P, Liu L (2010) Large-scale microwave-assisted ring-opening polymerization of ε-caprolactone. J Ind Eng Chem 16:872–875CrossRef
28.
Yang G, Ma E, Zhang S, Liu Z, Pei D, Jin H, Liu J, Du W (2022) Microwave-assisted in situ ring-opening polymerization of ε-caprolactone in the presence of modified halloysite nanotubes loaded with stannous chloride. RSC Adv 12:1628–1637CrossRefPubMedPubMedCentral
29.
Weidner SM, Kricheldorf HR (2017) Transesterifcation in the solid state of cyclic and linear poly(l-lactide)s. Macromol Chem Phys 218:1700114CrossRef
30.
31.
Bener S, Yilmaz G, Yagci Y (2021) Directly and indirectly acting photoinitiating systems for ring-opening polymerization of ε-caprolactone. Chem Photo Chem 5(12):1089–1093
32.
Bero M, Czapla B, Dobrzyński P, Janeczek H, Kasperczyk J (1999) Copolymerization of glycolide and ε-caprolactone, 2. Random copolymerization in the presence of tin octoate. Macro Mol Chem Phys 200(4):911–916CrossRef
33.
Liau CP, Ahmad MB, Shameli K, Yunus WMZW, Ibrahim NA, Zainuddin N, Then YY (2014) Preparation and characterization of polyhydroxybutyrate/polycaprolactone nanocomposites. Sci World J 2014:572726CrossRef
34.
Elzein T, Eddine MN, Delaite C, Bistac S, Dumas P (2004) FTIR study of polycaprolactone chain organization at interfaces. J Coll Interface Sci 273(2):381–387CrossRef
35.
Kricheldorf HR, Sumbel MV (1988) Polylactones 15. Reactions of δ-valerolactone and ε-caprolactone with acidic metal bromides. Makromol Chem 189(2):317–331CrossRef
36.
Güney A, Gardiner C, McCormack A, Malda J, Grijpma DW (2018) Thermoplastic PCL-b-PEG-b-PCL and HDI polyurethanes for extrusion-based 3D-printing of tough hydrogels. Bioengineering 5:99CrossRefPubMedPubMedCentral
Metadata
Title
Microwave-assisted solvent-free ring-opening polymerization of ε-caprolactone initiated by n-butyltin(IV) chlorides
Authors
Watcharee Funfuenha
Winita Punyodom
Puttinan Meepowpan
Wanich Limwanich
Publication date
16-02-2023
Publisher
Springer Berlin Heidelberg
Published in
Polymer Bulletin / Issue 1/2024
Print ISSN: 0170-0839
Electronic ISSN: 1436-2449
DOI
https://doi.org/10.1007/s00289-023-04720-w

Other articles of this Issue 1/2024

Polymer Bulletin 1/2024 Go to the issue

ORIGINAL PAPER

Adsorption of lead and tetracycline in aqueous solution by magnetic biomimetic bone composite

ORIGINAL PAPER

Active bio composites films based on PLA/olive wood flour (Olea europaea L.)/cinnamon essential oil

ORIGINAL PAPER

Synergistic effect of fiber surface treatment and nanoclays on the damping behaviors of polyester composites reinforced with palmyra fruit fibers

ORIGINAL PAPER

Hybrid cross-linked nanocomposite hydrogels based on Elaeagnus angustifolia gum: effect of clay content on water uptake and gel characteristics

ORIGINAL PAPER

Designing of anti-corrosive poly (γ-glycidoxypropyltriethoxysilane)-coated aluminum alloy via electro-polymerization: effect of cerium nitrate concentration

ORIGINAL PAPER

Microstructure–properties relationship in ethylene-propylene diene monomer (EPDM)/nitrile butadiene rubber (NBR)/halloysite nanotubes (HNTs) nanocomposites

Premium Partners

    Image Credits