slides - Biobased Performance Materials

“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, JanPieter 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
Mn
(kg/mol)
PDI
Tg
(°C)
OHV
(mg
KOH/gr)
Resin
Comonomer
Content
(mol%)
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)
E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198.
/ Department of Chemical Engineering and Chemistry
PAGE 5
Glycerol (GLY)
Pentaerythritol
(PER)
Trimethylolpropane
(TMP)
NMP-borne coatings cured with
Desmodur N3600
Curing at 180 °C, 20 min, N2 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 Tg
values in the order of 40-60 °C.
Desmodur N3600
Coatings prepared from resins containing 6-9 mol%
comonomer showed ductile behavior.
E. Gubbels, et al. Eur. Pol. J. 2013, 49, 3189-3198.
/ Department of Chemical Engineering and Chemistry
PAGE 6
Poly(2,3-butylene-2,5-furandicarboxylate)-based powder coatings
(Co)polyesters were synthesized on a larger scale (50 g).
Resin
Comonomer
Content
(mol%)
Mn
(kg/mol)
PDI
Tg
(°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),
TiO2 (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
tcure
(min)
Acetone
Tg,
Double
coating
Rubs
(°C)
Impact resistance
Pencil
(60/10 IP)
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%)
Mn
(kg/mol)
PDI
OHV
(mg KOH/gr)
AV
(mg KOH/gr)
Tg
(°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
/ Department of Chemical Engineering and Chemistry
PAGE 10
Performance flexibilized coatings
Acetone
Impact test
Pencil
Double Rubs
(60|10 IP)
hardness
Coating
Resin
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
OH
F3C
O
O
O
H
CF3
Comonomer
Random
copolyester
HO
O
n
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%
100 nm
/ Department of Chemical Engineering and Chemistry
PAGE 16
SAXS: PS already
below 20 wt% FADD
41 wt%
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 Tg values.
Aim: “The incorporation of rigid sugar-based residues to obtain PBT-based
copolyesters with increased Tg 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: 1,4BDO/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., MunozGuerra, S. (2013). Macromolecules, 46(11), 4335-4345.
• Gubbels, E., Jasinska-Walc, L., Noordover, B.A.J., Koning, C.E. (2013). Eur. Pol. J., 49, 31883198.
• 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., MunozGuerra, 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
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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), 31th 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, 6-11th 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
/ 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
This work has been performed as part of the Bio-Based
Bart Noordover
Performance Materials (BPM) Programme (BPM-020).
Lidia Jasinska
PAGE 32
Han Goossens

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