Modification of amorphous and semicrystalline polyesters with bio-based monomers by melt copolymerization and solid state modification Overview of the Bio-based Performance Materials project #020 MoBioSol
Project goals Two main goals: 1. Bio-based copolyesters for (powder) coating applications. 2. Solid-state modification of PBT with bio-based building blocks for engineering plastics applications. Avantium, CRODA, DSM, TU/e and WUR-FBR project partners. / Department of Chemical Engineering and Chemistry PAGE 2
Role of partners in this project: Avantium (Ed de Jong): provided FDCA and its dimethylester Croda (Angela Smits): provided fattyacid dimer diol (FADD), C18 diol and assisted FBR with large-scale hydrogenation chemistry DSM Coating Resins Zwolle (Leendert Molhoek, Cindy Posthuma, Jan- Pieter Drijfhout, Gert Dijkstra, Paul Buijsen): powder coating evaluation and advising role DSM Ahead (Frank Bergman): advisor for FDCA-based coatings and analysis/evaluation of FADD-modified PBT FBR Wageningen (Daan van Es, Shanmugam Thiyagarajan, Linda Gootjes, Willem Vogelzang, Jacco van Haveren): synthesis of biobased building blocks to be polymerized at TU/e TU Eindhoven (Erik Gubbels, Bart Noordover, Lidia Jasinska, Han Goossens, Cor Koning*): polymer synthesis/characterization/evaluation *Also DSM Coating Resins Zwolle / Department of Chemical Engineering and Chemistry PAGE 3
Part 1: Poly(2,3-butylene-2,5-furandicarboxylate)- based coating resins Aim: Preparing novel bio-based polyester resins for (powder) coating applications. Target: Low MW, amorphous, hydroxyl end-capped (co)polyesters Main components * Comonomers: Melt copolymerization: 180-230 C, Titanium (IV) butoxide, 3-fold excess diol, 5-10 mol% comonomer, 28-30 hrs. * or its dimethylester A series of furan-based (co)polyesters was prepared and characterized. E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198. E. Gubbels, et al. Prog. Org. Coat. (Accepted).
Solvent (NMP)-based copolyester coating resins Resin Comonomer Content (mol%) M n (kg/mol) PDI T g ( C) OHV (mg KOH/gr) 8 - - 2.2 1.6 71 70.2 9 GLY 3 2.7 2.0 83 70.8 10 GLY 6 2.2 2.3 70 108 11 PER 4 2.2 3.5 83 68.8 12 PER 9 2.3 3.6 35 131 13 TMP 3 2.0 2.1 73 56.4 14 TMP 9 2.2 1.9 58 129 AV = 1-6 mg KOH/gr) Glycerol (GLY) Pentaerythritol (PER) Trimethylolpropane (TMP) E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198. / Department of Chemical Engineering and Chemistry PAGE 5
NMP-borne coatings cured with Desmodur N3600 Curing at 180 C, 20 min, N 2 atm. NMP, 1.1 eq Desmodur N3600 Coating thickness between the 40-50 μm. The colorless and transparent coatings showed good solvent resistance, hardness between 3H-4H and T g values in the order of 40-60 C. Desmodur N3600 E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198. / Department of Chemical Engineering and Chemistry PAGE 6 Coatings prepared from resins containing 6-9 mol% comonomer showed ductile behavior.
Poly(2,3-butylene-2,5-furandicarboxylate)-based powder coatings (Co)polyesters were synthesized on a larger scale (50 g). Resin Comonomer Content (mol%) M n (kg/mol) PDI T g ( C) OHV (mg KOH/gr) 15 - - 3.1 2.1 92 36.6 16 GLY 3 2.7 1.9 83 70.8 17 TMP 4 2.3 2.1 68 82.8 18 PER 5 2.3 2.9 70 79.9 / Department of Chemical Engineering and Chemistry PAGE 7
Powder coatings manufacturing In close collaboration with the employees of DSM coating resins (Zwolle), powder coatings were prepared. These materials were cured using Vestagon B1530 (Desmodur N3600 too reactive for extrusion). Other additives added: Resiflow PV5 (flowing agent), Benzoin (degassing agent), TiO 2 (pigment). E. Gubbels, et al. Prog. Org. Coat. (Accepted). / Department of Chemical Engineering and Chemistry PAGE 8
Powder coatings performance All coatings were hard and brittle materials, with stiff network structure and high Tg after curing. Coatings prepared from branched copolyesters showed reasonable solvent resistance. Coating Resin t cure (min) Acetone Double Rubs T g, coating ( C) Impact resistance (60/10 IP) Pencil Hardness C5 15 30 47 114 -/- 2H C6 16 25 100/4 118 -/- H C7 17 25 100/3 116 -/- H C8 18 25 100/3 118 -/- F E. Gubbels, et al. Prog. Org. Coat. (Accepted). / Department of Chemical Engineering and Chemistry PAGE 9
Flexibilized furan-based coatings More ductile coatings were desired and to this end Croda s fatty acid dimer diol was added to the initial reaction mixture. Linear copolyesters were prepared (no GLY or PER added). Entry Final composition (wt%) M n (kg/mol) PDI OHV (mg KOH/gr) AV (mg KOH/gr) T g ( C) 19 20 21 22 23 FADD:23BD [12:88] FADD:23BD [24:76] FADD:23BD [32:68] FADD:23BD [45:55] FADD:23BD [57:43] 3.5 2.6 25 10 92 1.8 1.8 84 2.9 56 3.0 3.2 21 8.9 65 1.9 2.0 92 2.2 34 1.7 1.8 112 2.2 14 / Department of Chemical Engineering and Chemistry PAGE 10
Performance flexibilized coatings Coating Resin Acetone Double Rubs Impact test (60 10 IP) Pencil hardness C9 19 70 - +/- 3H C10 20 70 +/- +/- 3H C11 21 70 +/- +/- 3H C12 22 100/5 +/- +/- 3H C13 23 100/4 +/- +/- 2H Solvent-cast, Vestagon-cured coatings still hard materials, but enhanced flexibility. Point of attention: solvent resistance, because of the use of linear resins (relatively low functionality). / Department of Chemical Engineering and Chemistry PAGE 11
Part 2: Solid-state modification of PBT with (partially) renewable building blocks Multiple sub-projects were carried out using solid-state modification (SSM) as tool for the modification of PBT. Sub-project 2a: Modification of PBT with Croda s fatty acid dimer diol (FADD) Sub-project 2b: Incorporation into PBT of sugar-based residues (made at UPC, Barcelona) Sub-project 2c: PBT-based poly(ester amide)s modified with pentamers (made at FBR) / Department of Chemical Engineering and Chemistry PAGE 12
Concept used for sub-projects 2a-c O H F 3 C C F 3 H O O O O O H n Comonomer Random copolyester Common solvent approach. Blocky copolyester with random amorphous phase Blocky copolyester with non-random amorphous phase / Department of Chemical Engineering and Chemistry PAGE 13
2a-c: Solid-state modification of PBT with biobased monomers Solid-state modification with FADD as toughening agent, turning PBT into a thermoplastic elastomer (TPE) / Department of Chemical Engineering and Chemistry PAGE 14
Chemical microstructure as function of wt% FADD and preparation method Various techniques have been used to evaluate the structure of the copolyesters on various length scales. BTB Melt copolymerization (M-PC) or Solid-state modification (SSM) FTF FTB / BTF FTB / BTF For a randomness (R) value of 1, the chemical microstructure is random. Materials prepared by SSM had a nonrandom structure (R <1) / Department of Chemical Engineering and Chemistry PAGE 15
Phase separation Samples were annealed to study the phase separation (ps). Transmission electron microscopy was used visualize the morphology. 0.2 μm PBT 10 wt% 24 wt% 41 wt% 100 nm / Department of Chemical Engineering and Chemistry PAGE 16 SAXS: PS already below 20 wt% FADD
Thermal properties Does using SSM give benefits over melt copolymerization? (toughness of SSM and MP products very similar, higher than that of PBT) SSM M-PC Clearly the thermal properties of the materials prepared by SSM are superior to those of the materials prepared by M-PC. / Department of Chemical Engineering and Chemistry PAGE 17
Stable chemical microstructure For entropic reasons a blocky copolyester tends to randomize in the melt. Tm Tc Tg Phase separation prevents randomization of the chemical microstructure and yielding a stable morphology. / Department of Chemical Engineering and Chemistry PAGE 18
Project 2b: SSM of PBT with sugar-derivatives FADD-based systems: retained crystallization but decreased T g values. Aim: The incorporation of rigid sugar-based residues to obtain PBT-based copolyesters with increased T g values, while retaining the crystalline features of PBT. Work carried out in close collaboration with the group of Sebastian Muñoz-Guerra (UPC, Barcelona). Cristina Lavilla Aguilar spent three months within SPM for this collaboration. / Department of Chemical Engineering and Chemistry PAGE 19
Thermal properties Reaction conditions were modified (T = 160-175 C, lower gas flow w.r.t. FADD work) to minimize the volatilization of the comonomer. E. Gubbels, L. Lavilla, et al. J. Polym. Sci. Part A:Polym. Chem. 2014, 52, 164-177 / Department of Chemical Engineering and Chemistry PAGE 20
Randomization in the melt of copolyester with ca. 20mol% comonomer Randomization starts within 10 min! Lack of phase separation. Clear difference with the phase-separating FADD-based copolyesters. - FADD copolyesters: stable in melt up to at least 30-40 min - Sugar derivatives-based copolyesters: randomization after 10 min - Croda s C18 diol-based polyesters: randomization after 30 min in melt / Department of Chemical Engineering and Chemistry PAGE 21
Project 2c: (Partially) biobased pentamers for incorporation into PBT Target: development of rigid biobased ester-amide blocks for incorporation into PBT via SSM and acting as organic nucleating agents Pentamers: 2* 1,4-BDO + 2* aromatic diacid (Ar) + 1* diamine (R) Diacids: FDCA and TA (reference) Diamines: diaminoisosorbide, diaminoisoidide and 1,4-BDA (reference) 22
Isohexides Isohexides: rigid derivatives of carbohydrates (sugars) Glucose Sorbitol Isosorbide Diamines Important achievement: improved route to diamines developed at FBR Scale-up developed together with CRODA * Thiyagarajan; Gootjes; Vogelzang; van Haveren; van Es, ChemSusChem 2011, 4, 1823-1829 23
TA-based pentamers Method development via reference compounds 1,4-BDO, TA, diamines In case of 1,4-BDA (putrescine, biobased), synthesis successful, resin grade material produced Diaminohexides much more challenging, purification or pentamer is difficult 24
FDCA-based Pentamers Target pentamers: 1,4- BDO/FDCA/diamine (XX) Diamines: 1,4-BDA, isohexide diamines FDCA trimers already challenging moderate yields elaborate purification TA procedures ineffective due to differences in reactivity and solubility High purity 1,4-BDA based pentamer prepared on small scale
Project 2c: SSM of PBT with pentamers Aim: Preparing PBT-based copolymers with enhanced crystallization from the melt. Proof of principle with rigid pentamer building block based on putrescine, which shows a strong tendency to organize in the melt by H-bonding. / Department of Chemical Engineering and Chemistry PAGE 26
Non-isothermal crystallization Crystallization experiments were preformed at various cooling rates. PBT modified with 2.5-5 mol% pentamer crystallizes much more readily compared to pure PBT ( ). Explanation: Pre-orientation of the PBT chains when the pentamer is incorporated. / Department of Chemical Engineering and Chemistry PAGE 27
Overall conclusions Furan-based (co)polyesters are interesting for (powder) coating applications. Optimization is required. Toughness can be adjusted by incorporation of FADD monomer. Solid-state modification of semi-crystalline polyesters with bio-based building blocks is a powerful tool for the preparation of novel, partially renewable materials and shows clear advantages w.r.t. melt modification. Generated block copolymer structure is preserved in the melt for phase-separated, FADD-based copolyesters. The incorporation by SSM of partially biobased nucleating agents could be interesting for improved crystallization properties of PBT. Successful BPM project with excellent collaboration between partners! / Department of Chemical Engineering and Chemistry 18-6-2014 PAGE 28
Publications (9 published/accepted) Thiyagarajan, S.; Gootjes, L.; Vogelzang, W.; Van Haveren, J.; Van Es, D. ChemSusChem 2011, 4, 1823-1829 Gubbels, E., Jasinska-Walc, L., Koning, C.E. (2013). J. Polym. Sci. A: Polym. Chem., 51(4), 890-898. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Goossens, J.G.P., Koning, C.E. (2013). Macromolecules, 46(10), 3975-3984. Lavilla, C., Gubbels, E., Martínez de Ilarduya, A., Noordover, B.A.J., Koning, C.E., Munoz- Guerra, S. (2013). Macromolecules, 46(11), 4335-4345. Gubbels, E., Jasinska-Walc, L., Noordover, B.A.J., Koning, C.E. (2013). Eur. Pol. J., 49, 3188-3198. Gubbels, E., Jasinska-Walc, L., Noordover, B.A.J., Koning, C.E. (2014). Prog Org. Coat., 77, 277-284. Gubbels, E., Lavilla, C., Martínez de Ilarduya, A., Noordover, B.A.J., Koning, C.E., Munoz- Guerra, S. (2014). J. Polym. Sci. Part A: Polym. Chem., 52, 164-177. Lavilla-Aguilar, C., Gubbels, E., Martínez de Ilarduya, A., Noordover, B.A.J., Koning, C.E., Munoz-Guerra, S. (2014). Green chemistry, 16, 1789-1798. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Spoelstra, A.B., Noordover, B.A.J., Goossens, J.G.P., Koning, C.E. (2014). Polymer (Accepted in May 2014). / Department of Chemical Engineering and Chemistry PAGE 29
Publications (4 in preparation) Gubbels, E., Noordover, B.A.J., Goossens, J.G.P., Koning, C.E. Macromol. Chem. Phys. (In preparation). Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Spoelstra, A.B., Noordover, B.A.J., Goossens, J.G.P., Koning, C.E. Macromol. Chem. Phys. (In preparation). Gubbels, E., Noordover, B.A.J., Goossens, J.G.P., Koning, C.E. (2013). J. Vis. Exp. (In preparation). Gubbels, E., Noordover, B.A.J., Koning, C.E., Review of solid state modification of polycondensates (In preparation. Probably to be submitted to Prog. Polym. Sci.) / Department of Chemical Engineering and Chemistry PAGE 30
Presentations (9) Gubbels, E., Jasinska-Walc, L., Noordover, B.A.J., Hermida Merino, D., Spoelstra, A.B., Goossens, J.G.P. & Koning, C.E. (2013), Partially bio-based engineering plastics prepared by solid-state modification. Oral Presentation at the Dutch Polymer Days 2014, 17-18 th of March 2014, Lunteren, The Netherlands. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Noordover, B.A.J., Spoelstra, A.B., Goossens, J.G.P. & Koning, C.E. (2013). Poster presentation at the BASF summer course 2013 (125 th edition), 31 th of July - 8 th of August, Ludwigshafen, Germany. Gubbels, E. (2013). Oral Presentation at the Biobased Performance Materials symposium 2013, 26-27 th of June 2013, Wageningen, The Netherlands. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Noordover, B.A.J., Spoelstra, A.B., Goossens, J.G.P. & Koning, C.E. (2013). Oral Presentation at the European Polymer Federation meeting, 16-22 th of June 2013, Pisa, Italy. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Noordover, B.A.J., Spoelstra, A.B., Goossens, J.G.P. & Koning, C.E. (2013). Oral Presentation at the 245 th ACS meeting 2013, 6-11 th of April 2013, New Orleans, United States of America. Gubbels, E., Jasinska-Walc, L., Hermida Merino, D., Noordover, B.A.J., Spoelstra, A.B., Goossens, J.G.P. & Koning, C.E. (2013). Poster presentation at the Dutch Polymer Days 2013, 13-15 th of March 2013, Lunteren, The Netherlands. Gubbels, E., Jasinska-Walc, L. & Koning, C.E. (2012). Poster presentation at the Dutch Polymer Days 2012, 12-13 March 2012, Lunteren, The Netherlands. Gubbels, E., Jasinska-Walc, L. & Koning, C.E. (2011). Poster presentation at the Dutch Polymer Days 2011, 14-15 March 2011, Velthoven, The Netherlands. Koning, C.E., Solid state modification of PBT with renewable building blocks, Oral presentation at Polycondensation 2014, September 2014, Tokyo, Japan / Department of Chemical Engineering and Chemistry PAGE 31
Acknowledgements Angela Smits Ed de Jong Leendert Molhoek Frank Bergman Cindy Posthuma Jan-Pieter Drijfhout Paul Buijsen Gert Dijkstra Daan van Es Shanmugam Thiyagarajan Linda Gootjes Willem Vogelzang Jacco van Haveren Erik Gubbels Cristina Lavilla Aguilar Bart Noordover Lidia Jasinska Han Goossens PAGE 32 This work has been performed as part of the Bio-Based Performance Materials (BPM) Programme (BPM-020).