bio-based solutions for high-performance polyurethane...
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Bio-based Solutions for High-Performance Polyurethane Adhesives Angela Smits Bio-based Adhesives Conference 2013
Bio-based building blocks sustainable solutions
CRODA: Naturally derived speciality chemicals and sustainable products Global trend towards bio-based raw materials • Automotive: renewability targets, light weight design • Electronics: ‘green’ mobile phones, computers, gadgets • Sportswear: positive health and environment image • Packaging: improve carbon footprint
• Bio-based monomers: special dimer fatty acid, dimer diol, dimer diamine • Bio-based polyester polyols – up to 100% bio-based • Durability: impact modifiers for structural epoxies
Different forms of dimer fatty acids technology derived from natural oils
Dimer acid PRIPOL Dimer diol PRIPOL Dimer diamine PRIAMINE Polyesters polyols made with dimer acid (or dimer diol) PRIPLAST
HO---- ----- OH E--E
n
H2N NH2
OH OH
COOH COOH
Dimerised fatty acids technology Properties
Large hydrocarbon part (C36) • hydrophobic, water-repellent • hydrolytic resistance of derivatives • thermal resistance • affinity for low polarity matrices and surfaces • low Tg
Irregular non-crystalline structure • flexibility • good flow and wetting • low modulus, no strain hardening • no shrinkage
Di-functional constituent for • polyamides • polyesters • polyimides • polyurethanes, etc.
C=O
OH
O=C
HO
The PU adhesives in this study
• Polyurethanes from 1 single polyol; Priplast or conventional polyol • Reactive PU adhesives: prepared with excess solid MDI, moisture cured • PUD adhesives: prepared with IPDI, OH functional PU, tested without cross-linking
• Incorporating dimethyl propionic acid DMPA for water dispersion
Polyester polyol PUD particle size (nm)
Hexane diol adipate 18
Priplast 3192, semi-crystalline 45
Priplast 3293, semi-crystalline 100% bio-based 82
Priplast 3238, amorphous 100% bio-based 125
Flexibility of reactive polyurethanes flexible and no strain hardening
0
40
80
120
160
200
0 200 400 600 800Strain (%)
Priplast 3192semicrystallinePriplast 1838amorphousHDO-adipate
Mw of the polyols is 2000 NCO:OH = 2 Mechanical properties were measured after full cure
Modulus (kg/cm2)
-30
-20
-10
0
10
HDO-adipa
te
PTMEG
Priplas
t 319
2
Priplas
t 319
6
Priplas
t 183
8PPG
Priplas
t 183
8 (*)
Polyca
prolac
ton
Priplas
t 319
0
Recipe : 1 Polyol 2 Butanediol 3.1 MDI P1838 (*) = 1-1-2.1
Low Tg of polyurethanes flexibility also at low temperatures
Gla
ss tr
ansi
tion
tem
p. [o C
]
Adhesion to a variety of substrates PUD lap shear adhesion: good from smooth to fibrous substrates
0
0.5
1
1.5
2
Adh
esio
n (M
Pa)
HDO-adipate Priplast 3192 Priplast 3293 Priplast 3238
PUD was applied to both sides of the film, dried and re-activated at 70oC. A steel weight was used to join the two parts. Test on an Instron tensile tester.
0
2
4
6
Adhe
sion
(MPa
)
Priplast 3238 Priplast 3293
rigid PVC birch wood
Adhesion to a variety of substrates Reactive PU lap shear: High strength to hard, smooth plastics
Mw of the polyols is 2000 NCO:OH = 2
polyamide-6 polycarbonate
polystyrene PET film
NB = no break, slipped from the clamps SF = substrate failure
0
0.5
1
1.5
2
2.5
3
Adhe
sion
(M
Pa)
Priplast1838
Priplast3192
HDO-Adipate
PTMEG
0
0.5
1
1.5
2
2.5
3
Adhe
sion
(M
Pa)
Priplast1838
Priplast3192
HDO-Adipate
PTMEG
0
0.2
0.4
0.6
0.8
1
Adhe
sion
(M
Pa)
Priplast1838
Priplast3192
HDO-Adipate
PTMEG0
0.5
1
1.5
2
Adhe
sion
(M
Pa)
Priplast1838
Priplast3192
HDO-Adipate
PTMEG
SF SF SF SF
NB NB
Adhesion to hard, smooth substrates Reactive PU on polycarbonate – 100% bio-based Priplast
0
0.5
1
1.5
2
2.5
Adhe
sion
(MPa
)
HDO-Adipate
PPG PTMEG Priplast1838
Priplast3192
Priplast3238
Priplast3293
Priplast3286
Mw of the polyols is 2000 NCO:OH = 2 NB = no break, slipped from the clamps
NB
adhesives based on conventional polyols
NB NB
0
0.2
0.4
0.6
PEG PTMEG HDO-Adipate
Priplast3192
Priplast1838
Priplast3293
Priplast3286
Adhe
sion
(M
Pa)
Adhesion to low-energy substrates – untreated PE
adhesives based on conventional polyols
Mw of the polyols is 2000 NCO:OH = 2
Low moisture absorption of PU Priplast brings water resistance versus other polyols
0
0.4
0.8
1.2
1.6
2
Priplas
t 319
6
Priplas
t 183
8
Poly B
D
Priplas
t 319
0
HDO carbo
nate
Priplas
t 319
2
HDO-adipa
te
Polyca
prolac
tone
BDO-adipa
te
PTMEG
PPG
Moisture uptake at 23oC (%)
Recipe : 1 Polyol 2 Butane diol 3.1 MDI Conditions : 1 week in H2O dist.
Water resistance of PUD
• PUD without cross-linker • Priplast as good as cross-linked HDO-adipate (rating 3-4) • Adding 5% NCO cross-linker makes Priplast-based films nearly water resistant
• Spot test: water 16h – Rating 0 = very good, no mark; 5 = poor, damaged
Polyester polyol Water resistance
Hexane diol adipate 5
Priplast 3192 3
Priplast 3293 2
Priplast 3238 3
Durability: Thermo-oxidative stability of reactive PU based on Priplast
0%
20%
40%
60%
80%
100%
Rete
ntio
n of
pro
pert
ies
HDO-Adipate Priplast 3192 PPG PolyBD
Tensile strengthElongation
Cured polyurethane hot melt films Aged 4 weeks at 140oC Retention of mechanical properties
unsaturated diol; no ether / ester
Durability: Hydrolysis resistance PU aged in hot water – 100% bio-based Priplast
0
20
40
60
80
100
Priplast 3286 Priplast 3238 Priplast 3293 PTMEG HDO-adipate
Recipe : 1 Polyol 2 Butanediol 3.1 MDI Conditions : 1 week in H2O (dist.) at 90oC
Retention of tensile strength [%]
Summary of bio-based technology
Priplast dimer-based polyols: • Unique combination of hydrolytic and thermo-oxidative stability • Good mechanical properties: flexible, no strain hardening, low Tg
• Exceptional adhesion to a multitude of substrates • Excellent water resistance • High renewable content, up to 100%
• To protect substrates from moisture • To improve adhesion to low polarity substrates (plastics) • To adhere dissimilar materials • To obtain flexible adhesives
Thank you !
PU-dispersion basic recipe used, OH-terminated
• 100 g Priplast 3192, 13 g DMPA at 130°C / 25 mbar for 40 minutes • Break vacuum with N2, cool to 110°C, add 31g IPDI in 10 minutes, add acetone 35 g • Cool to 60°C and add 35 g acetone, stir until a clear solution is obtained • Cool to 50°C, react to NCO-number < 1 (theoretical OH-value 3.6) • Add 11 g TEA, stir for half an hour • Add 220 g water while intensively stirring, until phase inversion (CRITICAL step) • Then remove acetone at 50°C under gradually increased vacuum (to prevent
foaming), down to 100 mbar
• DMPA = dimethylol propionic acid; two OH-groups to build into the polyurethane, remaining carboxylic acid group to disperse into water
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