The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines

Geert Noordzij, Yara van den Boomen, Catherine Gilbert, Daan van Elk, Manta Roy, Karel Wilsens, Sanjay Rastogi

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

This study reports, for the first time, semi-crystalline polymers based on bis-pyrrolidone dicarboxylic acids (BPDA) derived from renewable itaconic acid and various diamines. Rigid BPDA monomers could be obtained in high purity and yield from dimethyl itaconate, instead of the normally used itaconic acid as the starting material. The reduction in the melting point of dimethyl-BPDA monomers, compared to that of normal BPDA monomers, enables melt-polycondensation thus avoiding the need for a solvent in the oligomerization step. Under standard polycondensation conditions, the dimethyl-BPDA monomer with a rigid trans-cyclohexanediamine (t-CH-BPDA) could readily be polymerized with linear aliphatic diols (C6 to C12) to yield high molecular weight polyesters. These polyesters are the first in their class to be reported semi-crystalline, having a Tg between 65 and 33 °C and a Tm between 213 and 184 °C, with an increasing aliphatic chain length. Furthermore, even in the presence of hydrophilic pyrrolidone groups, semi-crystalline polyesters based on t-CH-BPDA showed high stability in water with no significant water uptake. Preliminary studies show that t-CH-BPDA monomers can also be polymerized into semi-crystalline polyamides, although insolubility and an unstable melt prevented the accurate characterization of the synthesized polyamides. Though trans-cyclohexanediamine is currently not available from biomass, the potential biomass content in the described semi-crystalline polyesters ranges from 71% for the C6 diol up to 81% for the C12 diol
Original languageEnglish
Pages (from-to)4049-4058
Number of pages10
JournalPolymer Chemistry
Volume10
Issue number29
DOIs
Publication statusPublished - 20 Jun 2019

Keywords

  • BIOPOLYAMIDES
  • MONOMERS
  • PERFORMANCE
  • PLASTICS
  • POLYAMIDES
  • POLYESTERS
  • POST-POLYMERIZATION MODIFICATION
  • RESINS
  • SURFACTANTS
  • VERSATILE BUILDING-BLOCK

Cite this

Noordzij, Geert ; van den Boomen, Yara ; Gilbert, Catherine ; van Elk, Daan ; Roy, Manta ; Wilsens, Karel ; Rastogi, Sanjay. / The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines. In: Polymer Chemistry. 2019 ; Vol. 10, No. 29. pp. 4049-4058.
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title = "The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines",
abstract = "This study reports, for the first time, semi-crystalline polymers based on bis-pyrrolidone dicarboxylic acids (BPDA) derived from renewable itaconic acid and various diamines. Rigid BPDA monomers could be obtained in high purity and yield from dimethyl itaconate, instead of the normally used itaconic acid as the starting material. The reduction in the melting point of dimethyl-BPDA monomers, compared to that of normal BPDA monomers, enables melt-polycondensation thus avoiding the need for a solvent in the oligomerization step. Under standard polycondensation conditions, the dimethyl-BPDA monomer with a rigid trans-cyclohexanediamine (t-CH-BPDA) could readily be polymerized with linear aliphatic diols (C6 to C12) to yield high molecular weight polyesters. These polyesters are the first in their class to be reported semi-crystalline, having a Tg between 65 and 33 °C and a Tm between 213 and 184 °C, with an increasing aliphatic chain length. Furthermore, even in the presence of hydrophilic pyrrolidone groups, semi-crystalline polyesters based on t-CH-BPDA showed high stability in water with no significant water uptake. Preliminary studies show that t-CH-BPDA monomers can also be polymerized into semi-crystalline polyamides, although insolubility and an unstable melt prevented the accurate characterization of the synthesized polyamides. Though trans-cyclohexanediamine is currently not available from biomass, the potential biomass content in the described semi-crystalline polyesters ranges from 71{\%} for the C6 diol up to 81{\%} for the C12 diol",
keywords = "BIOPOLYAMIDES, MONOMERS, PERFORMANCE, PLASTICS, POLYAMIDES, POLYESTERS, POST-POLYMERIZATION MODIFICATION, RESINS, SURFACTANTS, VERSATILE BUILDING-BLOCK",
author = "Geert Noordzij and {van den Boomen}, Yara and Catherine Gilbert and {van Elk}, Daan and Manta Roy and Karel Wilsens and Sanjay Rastogi",
year = "2019",
month = "6",
day = "20",
doi = "10.1039/c9py00463g",
language = "English",
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pages = "4049--4058",
journal = "Polymer Chemistry",
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The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines. / Noordzij, Geert; van den Boomen, Yara ; Gilbert, Catherine; van Elk, Daan; Roy, Manta; Wilsens, Karel; Rastogi, Sanjay.

In: Polymer Chemistry, Vol. 10, No. 29, 20.06.2019, p. 4049-4058.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines

AU - Noordzij, Geert

AU - van den Boomen, Yara

AU - Gilbert, Catherine

AU - van Elk, Daan

AU - Roy, Manta

AU - Wilsens, Karel

AU - Rastogi, Sanjay

PY - 2019/6/20

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N2 - This study reports, for the first time, semi-crystalline polymers based on bis-pyrrolidone dicarboxylic acids (BPDA) derived from renewable itaconic acid and various diamines. Rigid BPDA monomers could be obtained in high purity and yield from dimethyl itaconate, instead of the normally used itaconic acid as the starting material. The reduction in the melting point of dimethyl-BPDA monomers, compared to that of normal BPDA monomers, enables melt-polycondensation thus avoiding the need for a solvent in the oligomerization step. Under standard polycondensation conditions, the dimethyl-BPDA monomer with a rigid trans-cyclohexanediamine (t-CH-BPDA) could readily be polymerized with linear aliphatic diols (C6 to C12) to yield high molecular weight polyesters. These polyesters are the first in their class to be reported semi-crystalline, having a Tg between 65 and 33 °C and a Tm between 213 and 184 °C, with an increasing aliphatic chain length. Furthermore, even in the presence of hydrophilic pyrrolidone groups, semi-crystalline polyesters based on t-CH-BPDA showed high stability in water with no significant water uptake. Preliminary studies show that t-CH-BPDA monomers can also be polymerized into semi-crystalline polyamides, although insolubility and an unstable melt prevented the accurate characterization of the synthesized polyamides. Though trans-cyclohexanediamine is currently not available from biomass, the potential biomass content in the described semi-crystalline polyesters ranges from 71% for the C6 diol up to 81% for the C12 diol

AB - This study reports, for the first time, semi-crystalline polymers based on bis-pyrrolidone dicarboxylic acids (BPDA) derived from renewable itaconic acid and various diamines. Rigid BPDA monomers could be obtained in high purity and yield from dimethyl itaconate, instead of the normally used itaconic acid as the starting material. The reduction in the melting point of dimethyl-BPDA monomers, compared to that of normal BPDA monomers, enables melt-polycondensation thus avoiding the need for a solvent in the oligomerization step. Under standard polycondensation conditions, the dimethyl-BPDA monomer with a rigid trans-cyclohexanediamine (t-CH-BPDA) could readily be polymerized with linear aliphatic diols (C6 to C12) to yield high molecular weight polyesters. These polyesters are the first in their class to be reported semi-crystalline, having a Tg between 65 and 33 °C and a Tm between 213 and 184 °C, with an increasing aliphatic chain length. Furthermore, even in the presence of hydrophilic pyrrolidone groups, semi-crystalline polyesters based on t-CH-BPDA showed high stability in water with no significant water uptake. Preliminary studies show that t-CH-BPDA monomers can also be polymerized into semi-crystalline polyamides, although insolubility and an unstable melt prevented the accurate characterization of the synthesized polyamides. Though trans-cyclohexanediamine is currently not available from biomass, the potential biomass content in the described semi-crystalline polyesters ranges from 71% for the C6 diol up to 81% for the C12 diol

KW - BIOPOLYAMIDES

KW - MONOMERS

KW - PERFORMANCE

KW - PLASTICS

KW - POLYAMIDES

KW - POLYESTERS

KW - POST-POLYMERIZATION MODIFICATION

KW - RESINS

KW - SURFACTANTS

KW - VERSATILE BUILDING-BLOCK

U2 - 10.1039/c9py00463g

DO - 10.1039/c9py00463g

M3 - Article

VL - 10

SP - 4049

EP - 4058

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 29

ER -