Achieve best-in class durability of your
Polyurethane-based Coatings and
Adhesives thanks to breakthrough
Polycarbonate Diols ETERNACOLL®
Dr. Manuel Colera
Business Development Manager
UBE Chemical Europe, S.A. Tuesday, October 21st 2014
1
Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
2
Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
3
Introduction of UBE
UBE Latin America Serviços Ltda
UBE WORLDWIDE: UBE Industries, Ltd. UBE IN EUROPE: UBE Corporation Europe, S.A.
6.377 M$ turnover (March 31st, 2014) 402 M€ turnover (July 29th, 2014)
11225 employees 391 employees
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UBE product line
Specialty Chemicals & Products Chemicals & Plastics
- Specialty Products - ɛ-Caprolactam
(Polyimides, Battery materials,
Separation membranes, Ceramics) - Polyamides
- Fine Chemicals - Synthetic Rubber
(Dimethyl carbonate, 1,5-pentane diol,
1,6-hexane diol, polycarbonate diol, Cement & Construction Materials
PCD, diphenol derivatives)
Machinery and Metal Products
- Pharmaceuticals
Energy and Environment
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Polycarbonate diol structure
Terminal – Backbone – Bridge – Backbone – Terminal
Polycarbonate diol Polyester diol Polyether diol
Polyurethane mechanical properties defined by using an optimum backbone (R)
or by different molecular weight (n)
Durability properties:
Carbonate vs. ester & ether as bridge:
Higher hydrolysis resistance
Higher chemical resistance
Excellent strain resistance
Flooring Artificial leather
Better heat & weather resistance
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Various possible applications
Oil & mining pipes coatings Wood coatings Inks
Pavements Flooring Automotive coatings
Automotive finishing Artifical leather Leather finishing
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Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
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Synthesis of PUs – Acetone method
Isocyanate Diol Emulsifiers
COOH
NCO + HO OH + HO OH + HO OH
OCN POLYOL de
Poliadipato DEG DMPA
IPDI 1,4 butanodiol
1. Prepolymer synthesis 1. SÍNTESIS DEL PREPOLÍMERO
T = 80ºC, Vagitación= 200 rpm
PREPOLÍMERO
SOLVENT-FREE PREPOLYMER
Neutralizer NCO
OCN
2. Acetone addition 2. DISOLUCIÓN DEL PREPOLÍMERO EN ACETONA,
T = 45-50ºC, Vagitación= 600 rpm
3. Neutralization 3. NEUTRALIZACIÓN CON TEA,
T= 45-50ºC, Vagitación= 600 rpm
4. Chain extension 4. EXTENSIÓN DE CADENA CON HIDRACINA,
Chain extender T ambiente, Vagitación= 600 rpm
5. ADICIÓN DE AGUA,
5. Water addition T ambiente, Vagitación= 800 rpm
POLYURETHANE
DISPERSIÓN POLYMER
DE POLIURETANO EN DISPERSED IN
AGUA/ACETONA
WATER/ACETONE
6. DESTILACIÓN DE LA ACETONA,
6. Acetone removal T = 50ºC, P= 300 mbar
DISPERSIÓN ACUOSA DE POLIURETANO
WATERBORNE POLYURETHANE DISPERSION
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Segmented structure of PUs
Soft segments Hard segments
Soft segments (SS): PCD moities
Hard segments (HS): Isocyanate + chain extender
Phase separation
Hard
segments Soft segments
Ionic aggregates
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Characterization of coatings
– Persoz hardness (ISO 1522:2007) – Yellowness index (ASTM D1925-70)
– Pencil hardness (ISO 15184:1998) – Chemical resistance (ISO 4211:1979)
– Gloss 60º (ISO 2813:1999)
Persoz pendulum 707 KP (ISO BYK Micro-TRI-Gloss Pencil hardness Colorimeter MINOLTA CR410
1522:2007) (ISO 2813:1999) (ISO 15184:1998) (ASTM D1925)
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Characterization of adhesives
– T-peel test (ISO 11339:2010)
– Single lap-shear test (ISO 4587:2003)
– Cross-cutter adhesion test (ISO 2409:2007)
Lap-Shear test
T-peel test BYK Cross cut tester
(ISO 4587:2003)
(ISO 11339:2010) (ISO 2409:2007)
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Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
13
Coatings – Persoz hardness
STARTING
PENDULUM FINAL ANGLE Time (s)
ANGLE
König 6º 3º oscillations x 1.4
Persoz 12º 4º oscillations x 1.0
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Coatings – Pencil hardness
Hard Soft
Pencil hardness measures the resistance of a coating to marking or the formation
of some other deffects, such as cracks.
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Coatings – Persoz & pencil hardness
Hardnesss Persoz
Pencil hardness
140
120 6B 6
100 5B 5
80 4B 4
60 3B 3
40 2B 2
20
0
B1
H0
Polycarbonate diol ETERNACOLL provides customizable coatings hardness and
improves the scratch resistance of coatings.
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Coatings – Persoz & pencil hardness
Thickness (µm)
Polytetramethylene glycol
Polyadipate of 1,6-hexane diol
ETERNACOLL® PH100
Persoz hardness (no.
Pencil hardness x 10
oscillations)
Polycarbonate diol ETERNACOLL provides balanced hardness properties.
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Coatings – Gloss 60º
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Coatings – Yellowness index
Yellowish
Colourless
CIE 1931 color space chromaticity diagram
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Coatings – Gloss 60º and Yellowness index
Gloss 60o Yellowness index
100 12
90
10
80
70 8
60 6
50 4
40 2
30 0
Polycarbonate diol ETERNACOLL maximizes coating gloss, and reduces
yellowish of colourless coatings.
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Coatings – Gloss 60º and Yellowness index
20 µm 25 µm 20 µm
Polytetramethylene glycol-based PU Polyadipate of 1,6-hexane diol-based PU ETERNACOLL® PH100-based PU
Phases separation
+
Cristallinity
=
Gloss 60o
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Coatings – Chemical resistance
PUD (fresh: 200 µm)
Code Damaged Surface
Stainless steel 304 5 Intact coating
Slight change in gloss or
4
color
10 min 3 Light mark
Ethanol 2 Strong mark
1 Coating removal
Stainless steel 304
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Coatings – Chemical resistance
Chemical resistance
5
4
3
2
1
0
Polycarbonate diol ETERNACOLL based coatings do not suffer any damage after
chemical attack.
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Coatings – Durability tests
Heat resistance:
- ISO 3248:1998 (15 days @ 120 ºC)
- On stainless steel plates
Artificial weathering:
- Cycle H: ISO 11507:4892-3 (total duration: 200 h):
Irradiance
Stage Function Temperature (ºC) Time (h: min)
(W/m2)
1 UV 0.71 60 4:00
2 Condensación n/a 50 4:00
3 Go to ‘Stage 1’
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Coatings – Durability tests
Variation of hardness Persoz (%) Variation of thickness (%)
100 100
80 80
60 60
40 Heat resistance 40 Heat resistance
20 20
Weatherability Weatherability
0 0
Polycarbonate diol ETERNACOLL
based coatings do not change initial
hardness and coating thickness after
exposure to extreme harsh conditions.
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Coatings – Durability tests
Variation of gloss 60o (%) Increment of yellowness (%)
100 300
80 250
60 200
150
40 Heat resistance 100 Heat resistance
20 50
Weatherability Weatherability
0 0
Polycarbonate diol ETERNACOLL
minimizes gloss and color changes of
coatings after exposure to extreme harsh
conditions.
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Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
27
Adhesives – T-peel test
PVC
PUD
PVC
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Adhesives – Single lap-shear test
Aluminium
PUD
Aluminium
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Adhesives – Cross-cutter adhesion test
Code Description Damaged surface
PUD (fresh: 200 µm)
0 No modification -
Light loosening of
1
Stainless steel 304 coating (< 5 %)
Light loosening of
the borders of the
2
coating
(5 to 10 %)
Partial loosening of
3 the coating
(15 to 35 %)
Strong loosening of
4 the coating
(35 to 65 %)
Very strong
loosening of the
5 -
coating
(> 65 %)
Stainless steel 304
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Adhesives – Adhesion properties
T-peel (kN/m) & Lap shear (kPA) Cross-cutter adhesion
5
5 4
4
3
3
2
2 Lap shear
1
1
T-peel 0
0
Polycarbonate diol ETERNACOLL
provides balanced adhesion
properties, meeting those of premium
polyols.
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Adhesives – Cyclic ageing
T (ºC) T (ºC) 72 1 h 24 1 h 72 1 h
48 1 h 48 1 h 24 1 h 48 1 h
HR < 15%
HR < 15% HR > 90% HR > 90%
time
(days) time
(hours)
ISO 9142:2003 - Cycle D5 ISO 9142:2003 - Cycle D11
Dry heat, wet heat and cold
Water immersion, cold and dry heat
Internal standard
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Adhesives – Cyclic ageing
Variation of T-peel (%)
400
350
300
Total loss of adhesion due to softening
250
200
Internal standard
150
100 Cycle D5
50
Cycle D11
0
ETERNACOLL ® Polytetramethylene Polyadipate of 1,6-
PH100 glycol hexane diol
Polycarbonate diol ETERNACOLL minimizes adhesion decrease of adhesives after
exposure to extreme harsh conditions.
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Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES
CONCLUSIONS
34
Conclusion
Polyurethane coatings based on PCD present higher
durability against heating, hydrolysis, weather & chemicals
than benchmark polyether and polyester polyol countertypes.
Those adhesives based on PCD show same adhesion
properties, improving adhesion to substrates and retaining
initial designed properties in harsh environments.
The use of PCDs is the key to synthesize a family of high
performance PU coatings and adhesives, due to their excellent
properties.
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Thank you for your
attention!
Dr. Manuel Colera
Business Development Manager
UBE Chemical Europe, S.A.
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