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. 2023 Sep 13;11(38):14216-14225.
doi: 10.1021/acssuschemeng.3c04178. eCollection 2023 Sep 25.

Itaconic Acid as a Comonomer in Betulin-Based Thermosets via Sequential and Bulk Preparation

Alexandra M Lehman-Chong  1   2 , Casey L Cox  1   2 , Emre Kinaci  2 , Sarah E Burkert  3 , Megan L Dodge  3 , Devin M Rosmarin  3 , James A Newell  1   2 , Lindsay Soh  3 , Melissa B Gordon  3 , Joseph F Stanzione 3rd  1   2
Affiliations

Itaconic Acid as a Comonomer in Betulin-Based Thermosets via Sequential and Bulk Preparation

Alexandra M Lehman-Chong et al. ACS Sustain Chem Eng. .

Abstract

The inherent chemical functionalities of biobased monomers enable the production of renewably sourced polymers that further advance sustainable manufacturing. Itaconic acid (IA) is a nontoxic, commercially produced biobased monomer that can undergo both UV and thermal curing. Betulin is a biocompatible, structurally complex diol derived from birch tree bark that has been recently studied for materials with diverse applications. Here, betulin, IA, and biobased linear diacids, 1,12-dodecanedioic acid (C12) and 1,18-octadecanedioic acid (C18), were used to prepare thermosets using sequential and bulk curing methods. Thermoplastic polyester precursors were synthesized and formulated into polyester-methacrylate (PM) resins to produce sequential UV-curable thermosets. Bulk-cured polyester thermosets were prepared using a one-pot, solventless melt polycondensation using glycerol as a cross-linker. The structure-property relationships of the thermoplastic polyester precursors, sequentially prepared PM thermosets, and bulk-cured polyester thermosets were evaluated with varying IA content. Both types of thermosets exhibited higher storage moduli, Tgs, and thermal stabilities with greater IA comonomer content. These results demonstrate the viability of using IA as a comonomer to produce betulin-based thermosets each with tunable properties, expanding the scope of their applications and use in polymeric materials.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. General Reaction Schemes for the Sequentially Prepared and Bulk-Cured Thermosets
Figure 1
Figure 1
Representative (a) APC and (b) DSC traces from the 2nd heating ramp of thermoplastic polyesters synthesized with 25/75 (C12/IA75-TP), 50/50 (C12/IA-TP), 75/25 (C12/IA25-TP), and 100/0 (C12/IA-TP) mol diacid/IA. Traces are normalized and stacked for clarity.
Figure 2
Figure 2
Representative FTIR spectra of (1) betulin, (2) IA, (3) MenMA monomer, (4) PMenMA, (5) 10 wt % C12/IA-meth uncured, (6) 10 wt % C12/IA-meth cured, (7) 25 wt % C12/IA-meth uncured, (8) 25 wt % C12/IA-meth cured, and (9) 25 wt % C12-meth cured.
Figure 3
Figure 3
DMA comparing (a,b) representative E′, E″, and tan δ curves for PM thermosets with IA and (c,d) representative E′, E″, and tan δ curves for PM polymers with and without IA.
Figure 4
Figure 4
DMA comparing representative (a) E′, E″, and (b) tan δ curves for the bulk-cured polyester thermosets.
Figure 5
Figure 5
Representative TGA thermograms of the bulk-cured polyester thermosets in N2.
See this image and copyright information in PMC

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