Effect of a set of acids and polymerization conditions on the architecture of polycarbonates obtained via ring opening polymerization

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Abstract

Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69% TMP-PTMC and 31% of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.

LanguageEnglish
Pages1502-1511
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume55
Issue number9
DOIs
StatePublished - 1 May 2017

Fingerprint

polycarbonate
Ring opening polymerization
Polycarbonates
Polymers
Polymerization
Propane
Acids
Monomers
Trifluoroacetic acid
Cationic polymerization
Toluene
Drug products
Carbonates

Keywords

  • catalysis
  • cationic ring opening polymerization
  • fumaric acid
  • MALDI
  • methanesulfonic acid
  • polycarbonates
  • trifluoroacetic acid

Cite this

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title = "Effect of a set of acids and polymerization conditions on the architecture of polycarbonates obtained via ring opening polymerization",
abstract = "Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69{\%} TMP-PTMC and 31{\%} of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.",
keywords = "catalysis, cationic ring opening polymerization, fumaric acid, MALDI, methanesulfonic acid, polycarbonates, trifluoroacetic acid",
author = "I. Jim{\'e}nez-Pardo and {van der Ven}, L.G.J. and {van Benthem}, R.A.T.M. and A.C.C. Esteves and {de With}, G.",
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TY - JOUR

T1 - Effect of a set of acids and polymerization conditions on the architecture of polycarbonates obtained via ring opening polymerization

AU - Jiménez-Pardo,I.

AU - van der Ven,L.G.J.

AU - van Benthem,R.A.T.M.

AU - Esteves,A.C.C.

AU - de With,G.

PY - 2017/5/1

Y1 - 2017/5/1

N2 - Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69% TMP-PTMC and 31% of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.

AB - Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69% TMP-PTMC and 31% of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.

KW - catalysis

KW - cationic ring opening polymerization

KW - fumaric acid

KW - MALDI

KW - methanesulfonic acid

KW - polycarbonates

KW - trifluoroacetic acid

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U2 - 10.1002/pola.28492

DO - 10.1002/pola.28492

M3 - Article

VL - 55

SP - 1502

EP - 1511

JO - Journal of Polymer Science, Part A: Polymer Chemistry

T2 - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

SN - 0887-624X

IS - 9

ER -