Transcript Priplast polyester polyols

PRIPOL dimerised fatty acids
Large hydrocarbon part (C36)
• hydrophobic
• hydrolytic resistance of derivatives
• affinity for non-polar matrices and surfaces
O
=
C
H
O
Irregular non-crystalline structure
• flexibility
• low Tg
• flow, wetting
C
=
O
O
H
Di-functional constituent for:
• polyamides
• polyesters
• polyurethanes
Different forms of PRIPOL dimer
technology
PRIPOL dimer acid
H
O
O
C
C
O
O
H
H
O
O
H
PRIPOL dimer diol
PRIPLAST
polyesters
made with PRIPOL
dimer acid or
dimer diol
HO----
E-E
----- OH
A unique performance effect
PRIPOL and PRIPLAST technology provide
a unique combination of resistance against :
• Moisture
• Chemicals
• Heat
• Oxidation
• Radiation
Supportive data
Polyurethane samples were prepared from a range of Priplast
polyols and competitive technologies (hexane diol adipate,
polycaprolacton, hexane diol carbonate, PTMEG, PPG, and
polybutadiene diol)
All polyols used had molecular weight of 2000, except Priplast 3196,
which is 3000
All recipes were identical in molecular ratio: one part polyol, 2 parts of
butane diol, 3.1 parts of pure MDI
All polyurethanes were made via the prepolymer route: first a
prepolymer of polyol and MDI, followed by chain extension with
butane diol
Moisture uptake of PRIPLAST
dimerate and other polyurethanes
Moisture uptake at 23 C, %
2
1.8
Recipe :
1.6
1.4
1 Polyol
2 Butanediol
3.1 MDI
1.2
Conditions : 1 week in H2O dist.
1
0.8
0.6
0.4
0.2
PP
G
3
Po 8
ly
Pr
B
ip
D
la
st
H
DO
31
90
ca
rb
on
Pr
at
ip
e
la
st
31
Pr
92
ip
la
st
31
H
DO
95
Po
-a
di
ly
pa
ca
te
pr
ol
ac
B
to
DO
n
-a
di
pa
te
PT
M
EG
18
as
t
Pr
ip
l
Pr
ip
l
as
t
31
96
0
Hydrolysis of PU from PRIPLAST
dimerate and other polyols
Retention of tensile strength, %
Recipe :
1 Polyol
2 Butanediol
3.1 MDI
120
100
Conditions : 1 week in H2O
(dist.) at 90 C
80
60
40
20
te
ip
a
-a
d
DO
H
ca
as
t
pr
ol
a
ct
o
n
90
31
95
Pr
ip
l
as
t
31
38
Pr
ip
l
as
t
18
EG
Pr
ip
l
PT
M
31
as
t
Pr
ip
l
Po
ly
H
DO
ca
rb
o
na
te
92
0
Effect of UV-radiation on PU from
PRIPLAST dimerate and other polyols
Retention of tensile strength, %
Recipe :
120
100
1 Polyol
2 Butanediol
3.1 MDI
Conditions : 2 weeks exposure
to UV-B
80
60
40
20
PP
G
EG
PT
M
38
Pr
ip
l
as
t
18
95
Pr
ip
l
as
t
31
90
31
Pr
ip
l
as
t
31
as
t
Pr
ip
l
H
DO
-a
d
ip
a
te
92
0
Effect of oxidation on PU from
PRIPLAST dimerate and other polyols
Retention of tensile strength / elongation, %
120
Recipe :
100
1 Polyol
2 Butanediol
3.1 MDI
Conditions : Exposure
to 140 C
for 4 weeks
80
60
Strength
Elongation
40
20
D
B
ol
y
P
PG
P
P
TM
EG
38
18
as
t
P
rip
l
as
t
rip
l
P
B
D
O
-a
d
31
ip
a
te
95
0
PRIPLAST versus other diols :
stability of TPU
Retention of tensile strength, %
120
Recipe :
100
1 Polyol
2 Butanediol
3.1 MDI
Exposure for 2 weeks
80
60
EG-adipate
BDO-adipate
Priplast 3192
Priplast 1838
40
20
)
C
)
(2
3
C
0
M
et
ha
n
ol
(6
N
aO
H
5%
10
%
H
H
2S
ea
t
O
4
(2
(1
0
3
0
C
C
)
)
0
Weather resistance
Retention of tensile strength, %
110
100
90
80
70
PTMEG
HDO-adipate
Priplast 1838
60
50
40
30
20
10
0
0
125
250
375
500
625
750
Weather-O-Meter (hours)
875
1000
Hydrolytic stability of PU in boiling
water
Retention of tensile strength, %
110
100
90
80
70
PTMEG
HDO-adipate
Priplast 1838
60
50
40
30
20
10
0
0
2.5
5
7.5
10
Days
12.5
15
Mechanical properties of PU from
PRIPLAST dimerate and other polyols
crystalline adipate
Recipe: 1 polyol
2 BDO
3.1 MDI
PTMEG
Priplast 3192
HDO dimerate/adipate
Priplast 1838
HDO dimerate
Poly BD/rubber
Strain
ca
DO
DO
-a
d
-a
d
ip
a
ip
a
te
Pr
ip
l
Pr
ip
l
Pr
ip
l
Pr
ip
l
Pr
ip
l
Po
ly
B
D
350
96
38
90
92
95
400
31
18
31
31
31
450
as
t
as
t
as
t
as
t
as
t
PP
G
te
pr
ol
H
ac
DO
to
-c
n
ar
bo
na
te
PT
M
EG
Po
ly
H
B
modulus/strength (kg/cm2)
Effect of polyol on modulus and
tensile strength
500
100% modulus
300% modulus
break
300
250
200
150
Recipe
100
50
1 Polyol
2 BDO
3.1 MDI
0
Elongation of PU made with PRIPLAST
dimerate and other polyols
Elongation at break, %
800
Recipe :
700
1
Polyol
600
2 BDO
3.1 MDI
500
400
300
differences only for
different MW (3196
is mw 3000, all
others 2000) and
functuionality (polyBD)
200
100
D
B
Po
ly
96
as
t
31
38
Pr
ip
l
as
t
18
90
Pr
ip
l
as
t
31
92
Pr
ip
l
as
t
31
95
Pr
ip
l
as
t
31
EG
Pr
ip
l
PT
M
n
ct
o
te
pr
ol
a
ip
a
ca
-a
d
Po
ly
DO
H
B
DO
-a
d
ip
a
te
0
ca
DO
DO
-a
d
-a
d
ip
a
ip
a
te
Pr
ip
l
Pr
ip
l
Pr
ip
l
Pr
ip
l
Pr
ip
l
31
18
31
31
31
38
90
92
95
9
Po 6
ly
B
D
as
t
as
t
as
t
as
t
as
t
PP
G
te
pr
o
H
la
DO
ct
on
-c
ar
bo
na
te
PT
M
EG
Po
ly
H
B
Shore-A hardness of PU made with
PRIPLAST dimerate and other polyols
Shore A
100
Recipe :
1
80
70
60
Polyol
90
2 BDO
3.1 MDI
T(g) of PU made with PRIPLAST
dimerate and other polyols
Glasstransition temp., °C
Recipe :
1 Polyol
2 BDO
3.1 MDI
15
10
5
P1838 (*) =
0
1
-1-2.1
-5
-10
-15
-20
-25
-30
90
as
t
31
EG
Pr
ip
l
PT
M
(*
)
as
t
18
38
PP
G
Pr
ip
l
38
as
t
18
96
Pr
ip
l
as
t
31
92
Pr
ip
l
as
t
31
ct
on
Pr
ip
l
ap
ro
la
ly
c
po
H
DO
-a
d
ip
a
te
-35
PRIPLAST polyols for
elastomers
A unique combination of thermo-oxidative and hydrolysis resistance
Low-temperature flexibility and flex fatigue resistance
Low-modulus and soft-touch applications
Elastomers by one-shot
processing of PRIPLAST polyols
- Priplast polyols do not mix well with many other polyols (especially adipates), chain
extenders and isocyanates
- one-shot processing without precautions may cause difficulty: very brittle product,
or very sticky product
- good one-shot processing is possible by making a blend of PRIPLAST polyol and
chain extender (like butane diol), and convert this blend in a one-shot process
- if for some reason (cost, performance) it is considered to blend PRIPLAST polyol
with other polyester polyols, we recommend to NOT make a physical blend, but
instead work with one single PRIPLAST polyol made with a mixture of acids
Blending polyols
- very careful when mixing partially crystalline polyols
disturbance of crystallinity kills hydrolytic stability, green strength and
tensile strength. Acceptable combinations: 3192 with hexane diol adipate, 3195
with butane diol adipate
- only recommended for the propolymers, for reasons of limited compatibility
PRIPLAST polyols for coatings
- for exceptional weatherability and protection (anticorrosive applications)
- for exceptional flexibility, flex fatigue resistance
- for adhesion to low-energy substrates like plastics
- for 2K, moisture cure and aqueous dispersion type
PRIPLAST technology for
polyurethane coatings: benefits
hydrocarbon character,
strength (preservation of hydrogen bonds)
hydrophobicity
durability (hydrolytic resistance)
substrate protection (moisture barrier)
adhesion to low energy substrates
non-crystallinity,
strength (flow, substrate wetting)
low glass transition
long open time
durability (low-temperature flexibility,
stress absorption)
PRIPLAST technology for PU
coatings: conditions
No NMP or other cosolvents
solids content at least 35%
particle size max. 500 nm
aliphatic diisocyanates for colour stability reasons
PRIPLAST technology in aqueous
polyurethane dispersions
recipe:
44g Priplast 3195, 6.0g DMPA at 130C/10 mbar for 30 minutes
break vacuum with N2, cool to 110C, add 38.9g IPDI in 10 minutes, react for 1 hour
cool to 60C and add 35g acetone, stir until a clear solution is obtained
cool to 50C, add 6g BDO** and 25g acetone slowly, then another 10g of acetone
react to NCO-number 1.8 (20 hours without catalyst, about 8 hours with catalyst)
add 140g acetone
add mix of 3.1g IPDA+0.3g NH4OH (25%)+20g water, react for 5 hours
add 1.8g NH4OH (25%), stir for half an hour
add 100g water while intensively stirring, until phase inversion (CRITICAL step)
add 50g of water, then remove acetone at 50C under gradually increased vacuum
(down to 450 mbar, to prevent foaming)
** to increase crosslinking: use 5.5g BDO with 0.5g TMP
Formulations
Priplast 3195 (2000 MW)
Priplast 3195, with TMP crosslinker
hexane diol/neopentylglycol (1/1 molar basis) adipate, 1700 MW
(Fomrez ER 191)
hexane diol/neopentylglycol (1/1 molar basis) adipate/dimerate (1/1 weight
basis), 1700 MW
Reference: Commercially available benchmark (aliphatic polyester polyol,
4% NMP, 40% solids, sold at about Euro 7/kg dispersion)
PRIPLAST technology in aqueous
polyurethane dispersions
- resulting white dispersions have 40% solids and 100-200 nm particles,
and give clear transparent film
- film blocking of Priplast-based materials exceeds that of commercial
PU dispersions
- freeze thaw stability: >1 month at -5/+40C
Properties of coatings
based on PRIPLAST and other polyols
Polyol
% water uptake
adhesion cross cut
24h/23°
24h/50°
alufoil
steel
acryl
PVC
ABS
PRIPLAST 3195
2
0
0
0
0
0
PRIPLAST 3195/TMP
3
8
slight haze
7
slight haze
0
0
0
0
0
HDO/NPG adipate
9
0
0
5
0
0
HDO/NPG
adipate/dimerate
3
14
white
8
slight haze
0
0
5
0
0
Commercial PUD
8
15
white
4
0
0
1
1
Chemical resistance of coatings
based on PRIPLAST and other polyols
Polyol
ethanol butter
(50%)
1h
24h
desin- coffee
fectant
10 min 24h
water
16 h
ethyl
aceton
acetate
10 sec 10 sec
PRIPLAST 3195
1
PRIPLAST 3195/TMP 3
0
0
1
1
0
0
0
0
5
4
5
5
HDO/NPG adipate
HDO/NPG/AA/C36
0-1
0-1
0
0
1
1
0
0
0
0
5
5
5
5
Commercial PUD
5
1
5
2
5
4
4
Properties of coatings
based on PRIPLAST and other polyols
Polyol
Elongation
Hardness
Impact Gloss
(%)
König
pencil
(cm.kg)
(20°)
(60°)
(85°)
PRIPLAST 3195
PRIPLAST 3195
with 3% TMP
290
108
4B
> 200
135
137
113
300
114
B
> 200
166
141
118
HDO/NPG adipate
HDO/NPG
adipate/ dimerate
170
101
HB
> 200
152
125
113
180
101
F
> 200
149
135
111
Commercial PUD
273
120
B
> 200
158
138
114
Gloss measured in gloss units
Stability of PU dispersions
based on PRIPLAST polyols
Retention of filmstrength (%)
110
kept at 50C
100
90
BD-adipate
HD-adipate
Polycapro- lacton
MPD- Terephthalate
HD-carbonate
PTMEG
Priplast 1838
80
70
60
50
40
30
20
10
0
5
10
15
Days
20
25
30
35
Benefits of PRIPLAST technology
for PU dispersion coatings
outstanding dispersion stability
outstanding weatherability and low moisture absorption
outstanding chemicals resistance
good flexibility, hardness and gloss
readily manufacturable
PRIPLAST polyols for adhesives
For hot melts, reactive hot melts, polyurethane dispersions
for thermo-oxidative and hydrolytic resistance
for flexibility, also at low temperatures
for adhesion to low-energy substrates
for universal adhesion on a variety of substrates
Polyol effect of adhesion to steel
final strength of moisture cured adhesive
adhesive strength (N/mm2)
8
6
4
2
0
PPG
PTMEG
HDO
adipate
3198
1838
3195
PRIPLAST products
3190
Polyol effect on adhesion to plastic
final strength of moisture cured adhesive
0.6
adhesive strength (N/mm2)
Untreated polyethylene
2.5 MDI/1 polyol
0.4
0.2
0
PPG
PTMEG
HDO
adipate
3198
1838
3195
PRIPLAST products
3190
Advice on PRIPLAST polyols for
adhesives
Specially recommended for applications with long open time.
Green strength is typically low because of non-crystalline character,
but specialist advice is available to overcome this
moisture curing is slower because of hydrophobicity
PRIPLAST 3191 in water repellent,
flexible PU sealant foam
• Low water absorption, hence good water sealing
properties
• Good hydrolytic resistance and compression set
over conventional polyester foams, hence improved
life cycle
• Low fogging
• Low air permeability, hence improved sealing
properties
Compression set of PU foam from
PRIPLAST dimerate vs. other polyols
Compression set after hydrolysis, %
100
80
60
40
20
at
e
di
p
A
P
rip
l
as
t
po
31
ly
o
91
r
et
he
ol
y
P
l
0
Water seal test
Acrylic plates
PU foam sealant
100 mm
(dyecut, 50% compressed)
Water
Water seal properties
Leaking of water after :
- PU from Priplast 3191 : > 24 hrs
- Conventional PU : < 10 min
Water absorption test
Acrylic plates, clamped
PU foam sealant
(dyecut, 50% compressed)
Water
Water absorption properties
- PU from Priplast 3191 : < 1% V/V
- Conventional PU : 20 % V/V
24 hrs. immersion in water
Physical properties
Characteristic
Priplast 3191
polyester
foam
Density, kg/m3
50
Water absorption (ASTM D 994)
< 1%
> 20%
Water seal properties
> 24 hrs
< 10 min.
Air permeability, litre / min
< 15
Non fogging properties :
- Reflectrometric method
(3 hrs / 100 °C)
- Gravimetric method
(16 hrs / 100 °C)
Conventional
polyester foam
(low fogging grade)
50
50
96.6 %
85.1 %
0.70 mg
0.95 mg
Application of PRIPLAST 3191
based foams
• Automotive industry, sealants for :
–
–
–
–
–
–
Airconditioning systems
Windows
Head and tail lamps
Mirrors
Door locks
Sun roofs
• General industry, sealants for :
– Airconditioning and ventilation
– Roof windows
– Refrigerators
Starting formulation
Component
Parts by weight
Priplast 3191
100
Silicone stabiliser (a)
1.0
SCS 6524 (b)
2.0
DMCHA
0.20
DMEA
0.20
Niax A1 (c)
0.20
Stannous octoate or DBTDL
0.05 – 0.10
Water
3.5
TDI, T65 (index 100)
44.7
(a) : Tegostab B-8002, ex. Th. Goldschmidt
(b) : Dispersant ex. Uniqema
(c) : Tertiary amine catalyst ex. Osi Specialities
Choosing the PRIPLAST polyol
that is required
2 categories:
partially crystalline products: 3192, 3195
amorphous products: 3190, 3196, 3197, 3198, 1838, 1839
partially crystalline:
crystallinity gives additional tensile strength (esp. 3192)
crystallinity gives green strength in adhesives
crystallinity is good for hydrolytic stability
crystallinity comes with lower ingredient cost (because of adipic)
amorphous:
for adhesion to non-polar substrates and compatibilizing with non-polar matrices
for low glass transition temperatures (pressure sensitive adhesives, very flexible coatings)
PRIPOL 2033 , dimerdiol
Specifications :
•
•
•
•
•
•
•
•
•
acid value
saponification value
hydroxyl value
colour APHA
moisture
monomer alcohol
dimer alcohol
trimer alcohol
viscosity
MW = approx. 540
max. 0.20
mg KOH/g
max. 2.0
mg KOH/g
202 - 212
mg KOH/g
max. 50
Hazen
max. 0.10
%
max. 2.0
%
min.
96.5
%
max. 1.5
%
typically 2500 mPa.s at 25 °C
PRIPLAST polyester polyols:
portfolio
3192
3195
3190
semi-crystalline
best hydrolytic stability (like polycarbonate diol),
MW 2000
best tensile strength (similar to PTMEG), best green
strength. for coatings, elastomers, adhesives
semi-crystalline,
cheaper alternative to 3192 (slightly less for
MW 2000
hydrolytic stability, green strength, tensile strength)
amorphous, MW 2000
adhesives and coatings for low-energy substrates
applications that require a very low Tg (-20C and lower)
users that require a low-viscosity liquid
3196
amorphous, MW 3000
compatibilizing, pressure sensitive adhesives
3197
amorphous
compatibilizing
3198
amorphous, MW 1300
coloured, for adhesives, primer coatings
1838
amorphous, MW 2000
pressure sensitive adhesives, compatibilizing
1839
amorphous, MW 2000
coloured cost-effective alternative to 1838
3191
amorphous, MW 1700
water-repellant foam
PRIPLAST polyester polyols:
specifications
PRIPLAST
acid value
OH-value
Colour
Moisture
mg KOH/g
mg KOH/g
Gardner
%
3192
max. 0.5
52-60
max. 2
max. 0.1
3195
max. 1.0
52-60
max. 2
max. 0.10
3190
max. 1.0
52-60
max. 2
max. 0.08
3196
max. 0.5
34-40
max. 2
max. 0.1
3197
max. 0.5
52-60
max. 2
max. 0.08
3198
max. 1
78-88
max. 6
max. 0.01
1838
max. 1.0
52-60
max. 2
max. 0.08
1839
max. 1.0
52-60
max. 6
max. 0.08
3191
0.7-1.5
68-73
-
max. 0.07