Abrafati

So Paulo - 16, 17 e 18 de Setembro de 2013
13
o
Congresso Internacional de Tintas
USE OF POLYOL MIXTURES INCLUDING
POLYCARBONATE DIOL FOR IMPROVING
PERFORMANCE OF COATINGS OBTAINED FROM
WATERBORNE POLYURETHANE DISPERSIONS
Manuel Colera, Vctor Costa
UBE CHEMICAL EUROPE, S.A.
Vanesa Garca Pacios, Jos A. Jofre-Reche, Jos Miguel Martn-Martnez
Adhesion & Adhesives Laboratory
University of Alicante (Spain)
13
o
Introduction Experimental Results Conclusions
Outline
Introduction
Experimental
Results and discussion
Conclusions
2
13
o
Polyurethanes
Coatings & Inks
Adhesives
Automotive industry
Footwear
Biomaterials
APPLICATIONS
3
13
o
Polyurethanes
Soft segments Hard segments
Soft segments (SS): Polyol
Hard segments (HS): Isocyanate
+ chain extender
SEGMENTED STRUCTURE
4
13
o
Polyurethanes

O OH HO
n
Polyether

OH
O
O
O
OH
n
Polycarbonate
POLYOLS
5
13
o
Polyurethanes
Phase separation
Hard segments Soft segments
SEGMENTED STRUCTURE
6
13
o
Waterborne Polyurethane Dispersions (PUDs)

Polmero
-
-
-
-
-
-
-
- -
-
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
-
-
-
-
-
-
-
- -
-
Capa hidratada
(estabilizada por aniones)
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
---
--
--
--
--
--
--
-- --
--
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
-
-
-
-
-
-
-
- -
-
Capa hidratada
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
---
--
--
--
--
--
--
-- --
--
Polmero
---
--
--
--
--
--
--
-- --
--
Polmero
-
-
-
-
-
-
-
- -
-
Polmero
---
--
--
--
--
--
--
-- --
--
Capa hidratada
Hydrated layer
Anion
stabilization
PU
PU
PU
PU
STRUCTURE
7
13
o
SYNTHESIS
NCO
OCN
Polyaddition
(T = 80C; 450 rpm stirring)
+ ACETONE
+ TEA
SYNTHESIS OF PREPOLYMER
ACETONE SOLUTION OF PREPOLYMER
MIXING OF REACTIVES
Dissolution and neutralization
ACETONE/WATER SOLUTION OF PREPOLYMER
ACETONE/WATER SOLUTION OF PREPOLYMER
+ WATER
+ Hydrazine
Chain extension
WATERBORNE PUD
Distillation
- ACETONE
8
13
o
Solvent-borne Coatings
CURING PROCESS
9
13
o
Hard
segments
Soft segments
Ionic aggregates
STRUCTURE
10
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o
Solventborne Coatings
Environmentally
friendly coatings
Waterborne polyurethane
dispersions (PUDs)
Flexible coatings for
textiles & leather
finishing
Hard coatings for
flooring, wood and
metallic surfaces
11
13
o
Properties of POLYETHER DIOL in polyurethane coatings
High hydrolytic stability
Good elastomeric behavior
Excellent properties and flexibility at low
temperature
Resistance against microorganisms
12
13
o
Benefits of POLYCARBONATE DIOL (PCD) in polyurethane coatings
Excellent hydrolytic stability
High chemical resistance
Improved durability
High thermal stability
Stable properties from low temperature
High mechanical properties
13
13
o
State of the art
Da-Kong Lee, Hong-Bing Tsai, Ruey-Shi Tsai, Po Hung Chen. Preparation and
properties of transparent thermoplastic segmented polyurethanes derived
from different polyols. Polymer Engineering and Science 47,695-701 (2007).
PCDs
polyester polyols
polyether polyols
The polyurethanes
derived from
polycarbonate diols
exhibit higher
transparency
14
13
o
State of the art
Anna Kultys, Magdalena Rogulska, Halina Gluchowska. The effect of soft-
segment structure on the properties of novel thermoplastic polyurethane
elastomers based on an unconventional chain extender. Polymer
International 60, 652-659 (2011).
AFM phase images of TPUs obtained with polyether (PT-40) , polyester (PC-40) and polycarbonate diol (PH-40)
Polyether
Polyester
Polycarbonate
15
13
o
State of the art
Vanesa Garca-Pacios, Manuel Colera, Yoshiro Iwata, Jos Miguel Martn-Martnez.
Incidence of the polyol nature in waterborne polyurethane dispersions on their
performance as coatings on stainless steel. Progress in Organic Coatings DOI:
http://dx.doi.org/10.1016/j.porgcoat.2013.05.007
PUD
%

R
e
t
e
n
t
i
o
n

o
f

c
h
e
m
i
c
a
l

r
e
s
i
s
t
a
n
c
e
16
Thermal degradation: 15 days @120 C
Weathering: ISO 11507
13
o
Limitations of POLYCARBONATE DIOL (PCD) in polyurethane
coatings
Moderate flexibility and elastomeric properties
Improvable resistance to hydrolysis
Lower toughness and high stiffness
17
13
o
OBJECTIVE
Synthesis and structural characterization of PUDs
obtained with mixtures of polyether and polycarbonate
polyols with similar molecular weight.
Establish structure-properties relationships in PU
coatings.
Compare the performance of the PU coatings obtained
with mixtures of polyether and polycarbonate polyols before
and after thermal degradation and weathering.
18
13
o
Results Conclusions Experimental Introduction
MATERIALS
Polyols
Polyether (polytetramethylene glycol) (Mw: 1000 Da)
Polycarbonate of 1,6 hexane diol (Mw: 1011 Da) UBE
Chemical Europe (Spain)
Diisocyanate: IPDI
Internal emulsifier : DMPA
Neutralization agent : TEA
Chain extender : Hydrazine
Acetone
Deionized water.
Others
19
13
o
SYNTHESIS OF WATERBORNE POLYURETHANE DISPERSIONS
Stirrer
water
water
Desecator
Nitrogen
Acetone Method
20
13
o
PU COATINGS CHARACTERIZATION
Drying time
Thickness
Persoz hardness
Pencil hardness
Gloss
21
13
o
COATINGS CHARACTERIZATION
Yellowness index
Chemical resistance against ethanol
Cross-hatch adhesion adhesion to
substrate
Ageing tests
22
13
o
Experimental Conclusions Results Introduction
PCD (eq%)
M
w
= 1000 Da M
w
= 2000 Da
Drying time (h) Drying time (h)
0
50
75
90
100
>6
1
1
1
<2
>6
1.25
1.75
2
<2
DRYING TIME
23
13
o
0
10
20
30
40
50
60
70
80
0 20 40 60 80 100
T
h
i
c
k
n
e
s
s

(

m
)
Polycarbonate of 1,6 HD (eq%)
PU coating
Thermal degradation
Weathering
THICKNESS
M
w
= 1000 Da
24
13
o
0
10
20
30
40
50
60
70
80
0 20 40 60 80 100
T
h
i
c
k
n
e
s
s

(

m
)
PU coating
Thermal degradation
Weathering
THICKNESS
M
w
= 2000 Da
25
13
o
0
50
100
150
200
250
300
350
400
0 50 75 90 100
P
e
r
s
o
z

h
a
r
d
n
e
s
s

(
n
o
.

o
s
c
i
l
l
a
t
i
o
n
s
)
PU coating
Thermal degradation
Weathering
PERSOZ HARDNESS
M
w
= 1000 Da
30
13
o
PERSOZ HARDNESS
M
w
= 2000 Da
0
50
100
150
200
250
300
350
400
0 50 75 90 100
P
e
r
s
o
z

h
a
r
d
n
e
s
s

(
n
o
.

o
s
c
i
l
l
a
t
i
o
n
s
)
PU coating
Thermal degradation
Weathering
31
13
o
6B 5B 4B 3B 2B B HB F H 2H 3H 4H 5H 6H
PENCIL HARDNESS
PCD
(eq%)
Pencil hardness (M
w
= 1000 Da) Pencil hardness (M
w
= 2000 Da)
PU
coating
Thermal
degrad.
Wheathering
PU
coating
Thermal
degrad.
Wheathering
0 6B 2B - 6B 4B -
50 5B 6B 6B 6B 6B 6B
75 5B 6B F 6B 4B 3B - 4B
90 4B 4B F 6B 4B 5B
100 4B 3B 4B 6B 3B 4B
SOFT HARD
32
13
o
0
20
40
60
80
100
0 50 75 90 100
G
l
o
s
s

6
0

(
a
.
u
.
)
PU coating Thermal degradation Weathering
GLOSS 60
M
w
= 1000 Da
28
13
o
GLOSS 60
M
w
= 2000 Da
0
20
40
60
80
100
0 50 75 90 100
G
l
o
s
s

6
0

(
a
.
u
.
)
29
13
o
0
15
30
45
60
75
90
0 20 40 60 80 100
Y
e
l
l
o
w
n
e
s
s

i
n
d
e
x
PU coating
Thermal degradation
Weathering
YELLOWNESS
M
w
= 1000 Da
26
13
o
YELLOWNESS
M
w
= 2000 Da
0
15
30
45
60
75
90
0 20 40 60 80 100
Y
e
l
l
o
w
n
e
s
s

i
n
d
e
x
PU coating
Thermal degradation
Weathering
27
13
o
CHEMICAL RESISTANCE
M
w
= 1000 Da
3
3.5
4
4.5
5
0 50 75 90 100
C
h
e
m
i
c
a
l

r
e
s
i
s
t
a
n
c
e

(
a
.
u
.
)
33
13
o
CHEMICAL RESISTANCE
M
w
= 2000 Da
3
3.5
4
4.5
5
0 50 75 90 100
C
h
e
m
i
c
a
l

r
e
s
i
s
t
a
n
c
e

(
a
.
u
.
)
34
13
o
Experimental Results Conclusions Introduction
Polyether polyol-based coatings properties are improved by blending
polycarbonate polyol as copolyol:
Shorter drying time of the dispersions
Enhancement of scratch resistance
Higher coating hardness
Polyether polyol-based coatings durability is benefited by adding polycarbonate
polyol as copolyol:
Less initial properties modification after ageing
Lower yellowish of the coating due to degradation
35
13
o
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So Paulo - 16, 17 e 18 de Setembro de 2013

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