Modification of amorphous and semicrystalline polyesters with bio-based monomers by melt copolymerization and solid state modification

“

Mo

dification of amorphous and

semi-crystalline polyesters with

bio

-based

monomers by melt copolymerization

and

sol

id state modification”

Overview of the Bio-based Performance

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.

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

Part 1:

Poly(2,3-butylene-2,5-furan-dicarboxylate)- based coating resins

Aim: “Preparing novel bio-based polyester resins for (powder) coating applications.”

Target: Low MW, amorphous, hydroxyl end-capped (co)polyesters

A series of furan-based (co)polyesters was prepared and characterized. Melt copolymerization:

180-230 °C,

Titanium (IV) butoxide, 3-fold excess diol, 5-10 mol% comonomer,

28-30 hrs.

Main components

Comonomers:

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

E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198.

Glycerol (GLY) Pentaerythritol (PER) Trimethylolpropane (TMP) AV = 1-6 mg KOH/gr)

NMP-borne coatings cured with

Desmodur N3600

/ Department of Chemical Engineering and Chemistry PAGE 6 E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198.

NMP,

1.1 eq Desmodur N3600

Curing at 180 °C, 20 min, N₂ atm.

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.

Coatings prepared from resins containing 6-9 mol% comonomer showed ductile behavior.

Poly(2,3-butylene-2,5-furandicarboxy-

late)-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

Powder coatings manufacturing

In close collaboration with the employees of DSM coating resins (Zwolle), powder coatings were prepared.

/ Department of Chemical Engineering and Chemistry PAGE 8 E. Gubbels, et al. Prog. Org. Coat. (Accepted).

These materials were cured using Vestagon B1530 (Desmodur N3600 too reactive for extrusion).

Other additives added:

Resiflow PV5 (flowing agent), Benzoin (degassing agent), TiO₂ (pigment).

Powder coatings performance

materials, with stiff network structure and high Tg after curing.

Coatings prepared from branched copolyesters showed reasonable

solvent resistance.

Coating Resin tcure

(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

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) .

/ Department of Chemical Engineering and Chemistry PAGE 10

Entry Final composition

(wt%) M_n (kg/mol) PDI OHV (mg KOH/gr) AV (mg KOH/gr) T_g (°C) 19 FADD:23BD [12:88] 3.5 2.6 25 10 92 20 FADD:23BD [24:76] 1.8 1.8 84 2.9 56 21 FADD:23BD [32:68] 3.0 3.2 21 8.9 65 22 FADD:23BD [45:55] 1.9 2.0 92 2.2 34 23 FADD:23BD [57:43] 1.7 1.8 112 2.2 14

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).

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)

Concept used for sub-projects 2a-c

Common solvent approach.

2a-c: Solid-state modification of PBT

with biobased monomers

/ Department of Chemical Engineering and Chemistry PAGE 14

Solid-state modification with FADD as toughening agent, turning PBT into a thermoplastic elastomer (TPE)

Various techniques have been used to evaluate the structure of the copolyesters on various length scales.

BTB

FTF

FTB / BTF FTB / BTF

Chemical microstructure as function

of wt% FADD and preparation method

Melt copolymerization (M-PC) or Solid-state modification (SSM)

For a randomness (R) value of 1, the chemical microstructure is random.

Materials prepared by SSM had a non-random structure (R <1)

Phase separation

/ Department of Chemical Engineering and Chemistry PAGE 16

Samples were annealed to study the phase separation (ps).

Transmission electron microscopy was used visualize the morphology.

PBT 10 wt% 24 wt% 41 wt%

0.2 μm

100 nm

SAXS: PS already below 20 wt% FADD

Does using SSM give benefits over melt copolymerization? (toughness of SSM and MP products very similar, higher than that of PBT)

Thermal properties

/ Department of Chemical Engineering and Chemistry PAGE 17

Clearly the thermal properties of the materials prepared by SSM are superior to those of the materials prepared by M-PC.

■ SSM ■ M-PC

Stable chemical microstructure

For entropic reasons a blocky copolyester tends to randomize in the melt.

Phase separation prevents randomization of the chemical microstructure and yielding a stable morphology.

/ Department of Chemical Engineering and Chemistry PAGE 18 Tm

Tc

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

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.

/ Department of Chemical Engineering and Chemistry PAGE 20

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

Randomization in the melt of

copolyester with ca. 20mol% comonomer

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)

Isohexides

Isohexides: rigid derivatives of carbohydrates (sugars)

Important achievement: improved route to diamines developed at FBR Scale-up developed together with CRODA

Glucose Sorbitol Isosorbide Diamines

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

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

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.

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

Overall conclusions

/ Department of Chemical Engineering and Chemistry 18-6-2014 PAGE 28

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.

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.,

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.)

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, 17-18th _{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 (125th _{edition), 31}th _{of July -}

8th _{of August, Ludwigshafen, Germany.}

• Gubbels, E. (2013). Oral Presentation at the Biobased Performance Materials symposium 2013, 26-27th _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, 16-22th _{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 245th _{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, 13-15th _{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

Acknowledgements

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).