Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography
The use of renewable sources for optical 3D printing instead of petroleum-based materials is increasingly growing. Combinations of photo- and thermal polymerization in dual curing processes can enhance the thermal and mechanical properties of the synthesized thermosets. Consequently, thiol-ene/thiol...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-03-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/6/872 |
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| author | Sigita Grauzeliene Aukse Navaruckiene Edvinas Skliutas Mangirdas Malinauskas Angels Serra Jolita Ostrauskaite |
| author_facet | Sigita Grauzeliene Aukse Navaruckiene Edvinas Skliutas Mangirdas Malinauskas Angels Serra Jolita Ostrauskaite |
| author_sort | Sigita Grauzeliene |
| collection | DOAJ |
| description | The use of renewable sources for optical 3D printing instead of petroleum-based materials is increasingly growing. Combinations of photo- and thermal polymerization in dual curing processes can enhance the thermal and mechanical properties of the synthesized thermosets. Consequently, thiol-ene/thiol-epoxy polymers were obtained by combining UV and thermal curing of acrylated epoxidized soybean oil and epoxidized linseed oil with thiols, benzene-1,3-dithiol and pentaerythritol tetra(3-mercaptopropionate). Thiol-epoxy reaction was studied by calorimetry. The changes of rheological properties were examined during UV, thermal and dual curing to select the most suitable formulations for laser direct writing (LDW). The obtained polymers were characterized by dynamic-mechanical thermal analysis, thermogravimetry, and mechanical testing. The selected dual curable mixture was tested in LDW 3D lithography for validating its potential in optical micro- and nano-additive manufacturing. The obtained results demonstrated the suitability of epoxidized linseed oil as a biobased alternative to bisphenol A diglycidyl ether in thiol-epoxy thermal curing reactions. Dual cured thermosets showed higher rigidity, tensile strength, and Young’s modulus values compared with UV-cured thiol-ene polymers and the highest thermal stability from all prepared polymers. LDW results proved their suitability for high resolution 3D printing—individual features reaching an unprecedented 100 nm for plant-based materials. Finally, the biobased resin was tested for thermal post-treatment and 50% feature downscaling was achieved. |
| first_indexed | 2024-03-10T13:18:28Z |
| format | Article |
| id | doaj.art-860769d817774635901f9ab19c001b6f |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T13:18:28Z |
| publishDate | 2021-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-860769d817774635901f9ab19c001b6f2023-11-21T10:12:22ZengMDPI AGPolymers2073-43602021-03-0113687210.3390/polym13060872Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-LithographySigita Grauzeliene0Aukse Navaruckiene1Edvinas Skliutas2Mangirdas Malinauskas3Angels Serra4Jolita Ostrauskaite5Department of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu Rd. 19, LT-50254 Kaunas, LithuaniaDepartment of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu Rd. 19, LT-50254 Kaunas, LithuaniaLaser Research Center, Faculty of Physics, Vilnius University, Sauletekis Ave. 10, LT-10223 Vilnius, LithuaniaLaser Research Center, Faculty of Physics, Vilnius University, Sauletekis Ave. 10, LT-10223 Vilnius, LithuaniaDepartment of Analytical and Organic Chemistry, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, Edifici N4, 43007 Tarragona, SpainDepartment of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu Rd. 19, LT-50254 Kaunas, LithuaniaThe use of renewable sources for optical 3D printing instead of petroleum-based materials is increasingly growing. Combinations of photo- and thermal polymerization in dual curing processes can enhance the thermal and mechanical properties of the synthesized thermosets. Consequently, thiol-ene/thiol-epoxy polymers were obtained by combining UV and thermal curing of acrylated epoxidized soybean oil and epoxidized linseed oil with thiols, benzene-1,3-dithiol and pentaerythritol tetra(3-mercaptopropionate). Thiol-epoxy reaction was studied by calorimetry. The changes of rheological properties were examined during UV, thermal and dual curing to select the most suitable formulations for laser direct writing (LDW). The obtained polymers were characterized by dynamic-mechanical thermal analysis, thermogravimetry, and mechanical testing. The selected dual curable mixture was tested in LDW 3D lithography for validating its potential in optical micro- and nano-additive manufacturing. The obtained results demonstrated the suitability of epoxidized linseed oil as a biobased alternative to bisphenol A diglycidyl ether in thiol-epoxy thermal curing reactions. Dual cured thermosets showed higher rigidity, tensile strength, and Young’s modulus values compared with UV-cured thiol-ene polymers and the highest thermal stability from all prepared polymers. LDW results proved their suitability for high resolution 3D printing—individual features reaching an unprecedented 100 nm for plant-based materials. Finally, the biobased resin was tested for thermal post-treatment and 50% feature downscaling was achieved.https://www.mdpi.com/2073-4360/13/6/872dual curingoptical 3D printinglaser direct writingclick reactionsthiol-enethiol-epoxy |
| spellingShingle | Sigita Grauzeliene Aukse Navaruckiene Edvinas Skliutas Mangirdas Malinauskas Angels Serra Jolita Ostrauskaite Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography Polymers dual curing optical 3D printing laser direct writing click reactions thiol-ene thiol-epoxy |
| title | Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography |
| title_full | Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography |
| title_fullStr | Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography |
| title_full_unstemmed | Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography |
| title_short | Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography |
| title_sort | vegetable oil based thiol ene thiol epoxy resins for laser direct writing 3d micro nano lithography |
| topic | dual curing optical 3D printing laser direct writing click reactions thiol-ene thiol-epoxy |
| url | https://www.mdpi.com/2073-4360/13/6/872 |
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