pripol dimerised fatty acids large hydrocarbon part (c36) hydrophobic hydrolytic resistance of...
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PRIPOL dimerised fatty acids
C=OOH
O=C HO
Large hydrocarbon part (C36) • hydrophobic• hydrolytic resistance of derivatives• affinity for non-polar matrices and surfaces
Irregular non-crystalline structure• flexibility• low Tg• flow, wetting
Di-functional constituent for:• polyamides• polyesters• polyurethanes
Different forms of PRIPOL dimer technology
HOOC COOH
HO OH
HO---- ----- OHE-E
PRIPOL dimer acid
PRIPOL dimer diol
PRIPLASTpolyestersmade with PRIPOLdimer acid ordimer diol
A unique performance effect
PRIPOL and PRIPLAST technology providea 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
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
Pripla
st 3
196
Pripla
st 1
838
Poly
BD
Pripla
st 3
190
HDO c
arbona
te
Pripla
st 3
192
Pripla
st 3
195
HDO-a
dipat
e
Polyc
apro
lact
on
BDO-a
dipat
e
PTMEG
PPG
Moisture uptake at 23 C, %
Recipe : 1 Polyol2 Butanediol3.1 MDI
Conditions : 1 week in H2O dist.
Hydrolysis of PU from PRIPLAST dimerate and other polyols
0
20
40
60
80
100
120
HDO c
arbona
te
Pripla
st 3
192
PTMEG
Pripla
st 1
838
Pripla
st 3
195
Pripla
st 3
190
Polyc
apro
lact
on
HDO-a
dipat
e
Retention of tensile strength, % Recipe : 1 Polyol2 Butanediol3.1 MDI
Conditions : 1 week in H2O (dist.) at 90 C
Effect of UV-radiation on PU from PRIPLAST dimerate and other polyols
0
20
40
60
80
100
120
HDO-a
dipat
e
Pripla
st 3
192
Pripla
st 3
190
Pripla
st 3
195
Pripla
st 1
838
PTMEG
PPG
Retention of tensile strength, % Recipe : 1 Polyol2 Butanediol3.1 MDI
Conditions : 2 weeks exposure to UV-B
Effect of oxidation on PU from PRIPLAST dimerate and other polyols
0
20
40
60
80
100
120
Strength
Elongation
Retention of tensile strength / elongation, %
Recipe : 1 Polyol2 Butanediol3.1 MDI
Conditions : Exposure to 140 C for 4 weeks
PRIPLAST versus other diols : stability of TPU
0
20
40
60
80
100
120
EG-adipate
BDO-adipate
Priplast 3192
Priplast 1838
Retention of tensile strength, %
Recipe : 1 Polyol2 Butanediol3.1 MDI
Exposure for 2 weeks
Weather resistance
0
10
20
30
40
50
60
70
80
90
100
110
0 125 250 375 500 625 750 875 1000
Weather-O-Meter (hours)
PTMEG
HDO-adipate
Priplast 1838
Retention of tensile strength, %
Hydrolytic stability of PU in boiling water
0
10
20
30
40
50
60
70
80
90
100
110
0 2.5 5 7.5 10 12.5 15
Days
PTMEG
HDO-adipate
Priplast 1838
Retention of tensile strength, %
Mechanical properties of PU from PRIPLAST dimerate and other polyols
Strain
Str
ess
PTMEG
Poly BD/rubber
Priplast 1838HDO dimerate
Priplast 3192HDO dimerate/adipate
crystalline adipate
no strain hardening
strain
hard
ening
Recipe: 1 polyol2 BDO3.1 MDI
Effect of polyol on modulus and tensile strength
0
50
100
150
200
250
300
350
400
450
500
mo
du
lus
/str
en
gth
(k
g/c
m2
) 100% modulus
300% modulus
break
Recipe
1 Polyol2 BDO3.1 MDI
Elongation of PU made with PRIPLAST dimerate and other polyols
0
100
200
300
400
500
600
700
800
BDO-a
dipat
e
HDO-a
dipat
e
Polyc
apro
lact
on
PTMEG
Pripla
st 3
195
Pripla
st 3
192
Pripla
st 3
190
Pripla
st 1
838
Pripla
st 3
196
Poly
BD
Elongation at break, %
differences only for different MW (3196 is mw 3000, all others 2000) and functuionality (poly-BD)
Recipe :1 Polyol2 BDO3.1 MDI
Shore-A hardness of PU made with PRIPLAST dimerate and other polyols
60
70
80
90
100
BDO-a
dipat
e
HDO-a
dipat
e
Polyc
apro
lact
on
HDO-c
arbon
ate
PTMEG
PPG
Pripla
st 3
195
Pripla
st 3
192
Pripla
st 3
190
Pripla
st 1
838
Pripla
st 3
196
Poly
BD
Shore A
Recipe :1 Polyol2 BDO3.1 MDI
T(g) of PU made with PRIPLAST dimerate and other polyols
-35
-30
-25
-20
-15
-10
-5
0
5
10
15
HDO-a
dipat
e
polyca
prol
acto
n
Pripla
st 3
192
Pripla
st 3
196
Pripla
st 1
838
PPG
Pripla
st 1
838
(*)
PTMEG
Pripla
st 3
190
Glasstransition temp., °C Recipe :1 Polyol2 BDO3.1 MDI
P1838 (*) =1-1-2.1
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 dispersionsrecipe:
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 coatingsbased on PRIPLAST and other polyols
Polyol % water uptake adhesion cross cut 24h/23° 24h/50° alufoil steel acryl PVC ABS
PRIPLAST 3195 2 8 0 0 0 0 0slight haze
PRIPLAST 3195/TMP 3 7 0 0 0 0 0slight haze
HDO/NPG adipate 9 14 0 0 5 0 0white
HDO/NPG 3 8 0 0 5 0 0 adipate/dimerate slight haze
Commercial PUD 8 15 4 0 0 1 1white
Chemical resistance of coatingsbased on PRIPLAST and other polyols
Polyol ethanol butter desin- coffee water ethyl aceton(50%) fectant acetate1 h 24h 10 min 24h 16 h 10 sec 10 sec
PRIPLAST 3195 1 0 1 0 0 5 5PRIPLAST 3195/TMP 3 0 1 0 0 4 5
HDO/NPG adipate 0-1 0 1 0 0 5 5HDO/NPG/AA/C36 0-1 0 1 0 0 5 5 Commercial PUD 5 1 5 2 5 4 4
Properties of coatingsbased on PRIPLAST and other polyols
Polyol Elongation Hardness Impact Gloss (%) König pencil (cm.kg) (20°) (60°) (85°)
PRIPLAST 3195 290 108 4B > 200 135 137 113PRIPLAST 3195 with 3% TMP 300 114 B > 200 166 141 118
HDO/NPG adipate 170 101 HB > 200 152 125 113HDO/NPG adipate/ dimerate 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
10
20
30
40
50
60
70
80
90
100
110
0 5 10 15 20 25 30 35
Days
Ret
entio
n of
film
stre
ngth
(%
)
BD-adipate
HD-adipate
Polycapro- lacton
MPD- Terephthalate
HD-carbonate
PTMEG
Priplast 1838
kept at 50C
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
0
2
4
6
8
PPG PTMEG HDOadipate
3198 1838 3195 3190
adh
esiv
e st
ren
gth
(N/m
m2)
PRIPLAST products
Polyol effect on adhesion to plastic
final strength of moisture cured adhesive
0
0.2
0.4
0.6
PPG PTMEG HDOadipate
3198 1838 3195 3190
adh
esiv
e st
ren
gth
(N/m
m2)
Untreated polyethylene
2.5 MDI/1 polyol
PRIPLAST products
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
0
20
40
60
80
100Compression set after hydrolysis, %
Water seal test
Acrylic plates
PU foam sealant(dyecut, 50% compressed)
Water
100
mm
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 Conventionalpolyester polyester foamfoam (low fogging grade)
Density, kg/m3 50 50
Water absorption (ASTM D 994) < 1% > 20%
Water seal properties > 24 hrs < 10 min.
Air permeability, litre / min < 15 50
Non fogging properties : - Reflectrometric method 96.6 % 85.1 % (3 hrs / 100 °C) - Gravimetric method 0.70 mg 0.95 mg (16 hrs / 100 °C)
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 max. 0.20 mg KOH/g• saponification value max. 2.0 mg KOH/g• hydroxyl value 202 - 212 mg KOH/g• colour APHA max. 50 Hazen• moisture max. 0.10 %• monomer alcohol max. 2.0 %• dimer alcohol min. 96.5 %• trimer alcohol max. 1.5 %• viscosity typically 2500 mPa.s at 25 °C
MW = approx. 540
PRIPLAST polyester polyols:portfolio3192 semi-crystalline best hydrolytic stability (like polycarbonate diol),
MW 2000 best tensile strength (similar to PTMEG), best green strength. for coatings, elastomers, adhesives
3195 semi-crystalline, cheaper alternative to 3192 (slightly less for
MW 2000 hydrolytic stability, green strength, tensile strength)
3190 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:specificationsPRIPLAST 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