111024 CYTED-IBERQUIMIA_pptx

Uso de policarbonato diol para
poliuretano de alto rendimiento
Dr. Manuel Colera
Departamento de I+D+i y Nuevos Negocios
Outline of the presentation
1. UBE Corporation Europe S.A.
2. Polycarbonate diol for PUD
3. High-performance
of
PUD
polycarbonate diol: coatings
due
to
4. High-performance
of
PUD
polycarbonate diol: adhesives
due
to
5. Conclusions
2
UBE Industries Ltd.
Nombre corporativo:
Sede:
Año de fundación:
Empleados (2009):
Volumen de ventas (2009):
UBE Industries Ltd.
Ube / Tokio (Japón)
1.897
11.264
4.150 MM Eur.
Química básica y plásticos
Especialidades químicas
Cementos y materiales de construcción
Maquinaria y metalurgia
Energía y medio ambiente
3
UBE en el mundo
4
UBE en Europa
Poliamidas y Copoliamidas
Caprolactama y Fertilizantes
Química Fina
1967
2001
5
Química Fina
Productos Farmacéuticos
Especialidades Químicas
Polibutadieno
Maquinaria
1960
UBE en España
–
Castellón es la sede central europea de UBE desde 2001.
–
Actividad en I+D:
•
Inversión en I+D: 1,5% de las ventas locales.
•
Actividades principales de I+D:
– Química fina (creado en 1999, 10 personas):
i.
Desarrollo de nuevos productos de química fina (PCD, HDL, PDL)
ii.
Nuevo proceso de producción de laurilactama
iii. Reactor fotocatalítico para tratamiento de aguas
– Plásticos de ingeniería (creado en 2005, 10 personas):
i.
Terpolímeros (Terpalex)
ii.
Film de poliamida con altas propiedades retráctiles
iii. Tubos para combustibles y biodiesel con altas propiedades de barrera
•
Convenios de colaboración: Universidades españolas (UV, UPV, UJI, UAM, UCM), CSIC e
institutos Tecnológicos (AIMPLAS, AINIA)
6
Outline of the presentation
1. UBE Corporation Europe S.A.
2. Polycarbonate diol for PUD
3. High-performance
of
PUD
polycarbonate diol: coatings
due
to
4. High-performance
of
PUD
polycarbonate diol: adhesives
due
to
5. Conclusions
7
Terminal – Backbone – Bridge – Backbone – Terminal
O
R
R
HO
O
O
OH
n
Polycarbonate diol
lower reactivity
Polyester diol
poor hydrolysis resistance
Polyether diol
low radical oxidation stability
Desired mechanical properties can be achieved using an optimum backbone (R)
R
Durability properties: Carbonate vs. ester & ether as bridge
− Higher hydrolysis & chemical resistance
− Excellent stain resistance
− Better heat & weather resistance
8
Polycarbonate diol grades tested in this study (Mw = 1000)
Homopolymer:
− UH100:
backbone: 1,6-hexanediol
Copolymer:
− PH100:
backbone: 1,5-pentanediol 1,6-hexanediol
− BH100:
backbone: 1,4-butanediol, 1,6-hexanediol
9
Acetone method
Waterborne polyurethane dispersions were prepared by
way of acetone method:
1.Polyol+(80ºC)+stirring (220rpm)
2. DMPA
3. IPDI
4. Acetone (45-55ºC)
5. TriEthylAmine (acetone solution)
6. Hydrazyne (aqueous solution)
7. Distillate water + stirring (440rpm)
8. Removal of acetone (50ºC)
10
Outline of the presentation
1. UBE Corporation Europe S.A.
2. Polycarbonate diol for PUD
3. High-performance
of
PUD
polycarbonate diol: coatings
due
to
4. High-performance
of
PUD
polycarbonate diol: adhesives
due
to
5. Conclusions
11
Coatings – Properties1
Properties
Chemical resistance
Hardness Persoz
Pencil hardness
Gloss 60o
Yellowness index
Cross-cut test
Method
ISO 4211:1979
ISO 1522:2007
ISO 15184:1998
ISO 2813:1999
ASTM D1925-70
ISO 2409:2007
Unit
%
BH-100
4
72
3B
96
7.4
0
1 Stainless
steel plates (ISO 1514:2004), after 7 days at 23 ºC and 50%
Polypropylene glycol, Mw ∼ 1000
3 PBA: Poly(1,4-butylene adipate), Mw ∼ 1000
2 PPG:
Coatings based on polycarbonate diol show:
− Better chemical resistance:
double than PPG or PBA-based coatings
− Improved scratch resistance:
harder coatings acc. to pencil test
− Higher gloss
− Lower yellowish
− Better adhesion to substrate
12
PH-100
4
62
3B
99
7.7
0
UH-100
4
121
4B
78
8.9
0
PPG2
2
33
5B
79
10.8
1
PBA3
2
109
6B
38
9.8
2
ISO 4211:1979
In a same PUD formulation, impressively noticeable
results only replacing traditional polyols with polycarbonate
Chemical resistance
Chemical resistance
diols.
5
4
3
2
Stainless steel
1
5
4
3
2
1
ABS
0
Polyester-based PUD
UBE ETERNACOLL® based PUD
Coatings – Chemical resistance
Stainless steel
ABS
0
Substrate
Substrate
Oak wood
UH50
Oak wood
UH100
UH200
UH300
Hard segments
PCD grade
− Chemical resistance of PUD coatings just slightly depends on substrate and can be adjusted by polycarbonate diols
molecular weight & hard segments content.
− For every substrate, there is an suitable grade of polycarbonate diol for providing an excellent chemical resistance to
PUD coatings.
13
Durability assays
Heat resistance:
- On stainless steel plates
- Retention of hardness Persoz, gloss 60º and thickness: Px
P
- Increment of yellowness index:
Px − P
⋅ 100
P
Artificial weathering:
- On stainless steel plates
- Retention of hardness Persoz, thickness, cross-cut
Countertypes:
- PPG: Polypropylene glycol, Mw ~ 1000
- PBA: Poly(1,4-butylene adipate), Mw ~ 1000
14
⋅ 100
Coatings – Heat resistance
ISO 3248:1998 – Measurements after 15 days at 120 ºC
UBE ETERNACOLL®
Retention of gloss 60o
Retention of hardness Persoz
Retention (%)
Retention (%)
200
100
175
80
150
125
60
100
40
75
50
20
25
0
0
Polycarbonate diol grade
Polycarbonate diol grade
Increment of yellow index on oak wood (%)
Increment of yellowness index
35
Increment (%)
1500
30
1250
25
1000
20
750
15
500
10
250
5
0
Polycarbonate diol grade
0
0
15
5
10
15
20
Coatings – Artificial ageing
ISO 11507:2007
UBE ETERNACOLL®
Retention of hardness Persoz
Retention of thickness
Retention (%)
Retention (%)
100
100
80
80
60
60
40
40
20
20
0
0
Polycarbonate diol grade
Polycarbonate diol grade
Worst cross cut
adhesion, even
after ageing
Loss of thickness
16
Outline of the presentation
1. UBE Corporation Europe S.A.
2. Polycarbonate diol for PUD
3. High-performance
of
PUD
polycarbonate diol: coatings
due
to
4. High-performance
of
PUD
polycarbonate diol: adhesives
due
to
5. Conclusions
17
Adhesives – Properties1
Properties
Drying time4
Cross-cut test
T-peel test
Lap-shear strength
Method
ASTM D5895-03
ISO 2409:2007
ISO 11339:2010
ISO 4587:2003
Unit
h
kN/m
kPa
BH-100
<2
0
0.2
4.9
PH-100
<2
0
1.9
4.8
UH-100
<2
0
2.9
3.4
PPG2
>6
1
0.3
3.1
PBA3
>6
2
1.6
3.3
1 Acetone
method: % solids w/w = 38, NCO/OH in prepolymer = 1.5
Without additives
2 PPG: Polypropylene glycol, Mw ∼ 1000
3 PBA: Poly(1,4-butylene adipate), Mw ∼ 1000
4 Dry-through time
Adhesives based on polycarbonate diol show:
− Shorter complete drying time
− Stronger adhesion to substrates
− Improved peel resistance
− Enhanced lap-shear strength
BH-100-based coating
18
PPG-based coating
Adhesives – Cyclic ageing
ISO 9142:2003
UBE ETERNACOLL®
Cycle D5
T (ºC)
Dry heat, wet heat and cold
48 ± 1 h
48 ± 1 h
HR < 15%
HR > 90%
24 ± 1 h
48 ± 1 h
Increment of T-peel test
HR > 90%
Increment (%)
200,0
150,0
100,0
50,0
time
(days)
0,0
Polycarbonate diol grade
Cycle D11
Water immersion, cold
and dry heat
T (ºC)
72 ± 1 h
24 ± 1 h
72 ± 1 h
HR < 15%
Increment of T-peel test
Increment (%)
20,0
15,0
10,0
5,0
time
(hours)
19
0,0
Polycarbonate diol grade
Outline of the presentation
1. UBE Corporation Europe S.A.
2. Polycarbonate diol for PUD
3. High-performance
of
PUD
polycarbonate diol: coatings
due
to
4. High-performance
of
PUD
polycarbonate diol: adhesives
due
to
5. Conclusions
20
Using polycarbonate diol, we can conclude that…
Coatings based on polycarbonate diol show:
− Better chemical resistance
− Improved scratch resistance
− Higher gloss
− Lower yellowish
Coatings
− Better adhesion to substrate
Chemical resistance of coatings:
− Can be adjusted by polycarbonate diols molecular weight & hard segments content.
− Depending on substrate, there is an suitable grade of polycarbonate diol.
Adhesives based on polycarbonate diol show:
− Shorter complete drying time
Adhesives
− Stronger adhesion to substrates
− Improved peel resistance
− Enhanced lap-shear strength
21
Flooring
Artificial leather
Wood coating & paints
Leather finishing
Using polycarbonate diol, we can enhance coatings for applications
such as…
Automotive
22
Automotive finishing
Thanks for your attention !!