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PRIPLAST polyester polyols derived from dimerized fatty acids
PRIPLAST polyester polyols derived from dimerized fatty acids
Principles of Uniqema's oleochemicaltechnology for polyurethanes
the basis: PRIPOL dimerized fatty acids
irregular structure,non-crystalline
large hydrocarbon part (C36), chemically inert and water-repellant
difunctionality flexible structure
C=OOH
O=CHO
Different forms of PRIPOL dimer technology
PRIPOL dimer acid
PRIPOL dimer diol
PRIPLAST polyesters made with PRIPOL dimer acid or dimer diol
HOOC COOH
HO OH
HO- ..... E.....E .... - OH
Effects of PRIPOL and PRIPLAST technology
irregular structure
non-crystallinity
lasting elasticitylow glass transition
fluidity
Effects of PRIPOL and PRIPLAST technology
hydrocarbon nature
hydrophobicity
absence of ether links hydrolytic stability of esters
stability against acid/basecompatibility with organics
stability againstheat, oxidation, UV
PRIPOL and PRIPLAST technology provide a unique combination of resistance against
moisture, chemicals, heat, oxidation, radiation
Hydrolysis of PU from dimerate and other polyols
0
20
40
60
80
100
120
polycarb
onate
PTMEG
P 3192
P 3195
P 1838
P 3190
polycap
rolacton
HDO-adipate
retention of tensile strength (%)
recipe: 1 polyol (MW 2000), 2 butane diol, 3 MDIconditions: exposure to 90C water for 1 week
Hydrolytic stability of TPU in boiling water
0
20
40
60
80
100
120
0 5 10 15 20Days
Retention of strength (% )
hexane diol adipatePTMEGPriplast 1838
Priplast versus other diols: Stability of TPU (1)
Heat (100 °C)
020406080
100120
EG-adipate
BD-adipate
Priplast3192
Priplast3196
% Retention
of strength
10% H2SO4 @ 23 °C
020406080
100120
EG-adipate
BD-adipate
Priplast3192
Priplast3196
% Retention
of strength
5% NaOH @ 60 °C
020406080
100120
EG-adipate
BD-adipate
Priplast3192
Priplast3196
% Retention
of strength
Methanol
0102030405060708090
EG-adipate
BD-adipate
Priplast3192
Priplast3196
% Retention
of strength
all results after 2 weeks of exposure
Emulsion stability of TPU at 50 °C
0
20
40
60
80
100
120
0 5 10 15 20 25 30 35Days
Retention of filmstrength (%)
BD-adipateHD-adipatePolycapro- lactonMPD- TerephthalateHD-carbonatePTMEGPriplast 1838
Moisture uptake of dimerate and otherpolyurethanes
00.20.40.60.8
11.21.41.6
1.82
Priplas
t 319
6Prip
last 1
838
polybuten
e diol
Priplas
t 319
0
HDO carb
onatePrip
last 3
192
Priplas
t 319
5HDO-ad
ipate
polycap
rolacton
BDO-adipate
PTMEG
PPG
moisture uptake at 23C, %
recipe: 1 polyol, 2 butane diol3 MDI
conditions: 1 week indistilled water at 23C
Effect of UV-radiation on PU fromdimerate and other polyols
0
10
20
30
40
50
60
70
80
90
100
HDO-adipate Priplast 3192 Priplast 3195 Priplast 1838 PTMEG PPG
retention of tensile strength (%)
recipe: 1 polyol (MW 2000), 2 butane diol, 3 MDIconditions: exposure to UV-B for 2 weeks
Effect of oxidation on PU from dimerateand other polyols
0
20
40
60
80
100
120
BDO-adipate
Priplas
t 319
5Prip
last 1
838
PTMEG
PPGPB-di
ol
retention of tensile
strength (%)
recipe: 1 polyol (MW 2000), 2 butane diol, 3 MDIconditions: exposure to 140 for 4 weeksremarks: polyethers are destroyed within days
0
10
20
30
40
50
60
70
80
90
100
BDO-adipate
Priplas
t 319
5Prip
last 1
838
PTMEG
PPGPB-di
ol
retention of elongation
(%)
Weather resistance
0
20
40
60
80
100
120
0 200 400 600 800 1000 1200Weather-o-meter, hours
Retention of strength (%)
hexane diol adipatePTMEGPriplast 1838
PRIPOL and PRIPLAST technology givespolyurethanes with good mechanical properties
Moduli of PU made with PRIPLASTdimerate and other polyols
0
50
100
150
200
250
BDO-adipate
HDO-adipate
polycap
rolacton
HDO-carb
onatePTMEG
PPGPrip
last 3
195
Priplas
t 319
2Prip
last 3
190
Priplas
t 183
8Prip
last 3
196
poly BD diol
modulus, kg/cm2
recipe: 1 part diol2 parts butane diol3.1 parts MDI
100% modulus300% modulus
Elongation of PU made with PRIPLASTdimerate and other polyols
0
100
200
300
400
500
600
700
800
BDO-adipate
HDO-adipate
polycap
rolacton
PTMEGPrip
last 3
195
Priplas
t 319
2Prip
last 3
190
Priplas
t 183
8Prip
last 3
196
poly BD diol
elongation, %
recipe: 1 part diol2 parts butane diol3.1 parts MDI
Tensile strength of PU made with PRIPLAST dimerate and other polyols
050
100150200250
300350400
450500
BDO-adipate
HDO-adipate
polycap
rolacton
PTMEG
PPGPrip
last 3
195
Priplas
t 319
2Prip
last 3
190
Priplas
t 183
8Prip
last 3
196
poly BD diol
tensile strength, kg/cm2
recipe: 1 part diol2 parts butane diol3.1 parts MDI
Effect of recipe on PU made with PRIPLAST dimerate and other polyols
0
100
200
300
400
500
600
700
Modulus 100% Modulus 300% Tensile Strength Hardness Elongation
tensile strength, modulus, kg/cm2
1 Priplast 1838 2 MDI, 1 BDO 1 Priplast 1838 3 MDI, 2 BDO 1 Priplast 1838 4 MDI, 3 BDOColumn 4 Column 5 Column 6
Hardness of PU made with PRIPLASTdimerate and other polyols
010
20304050
607080
90100
BDO-adipate
HDO-adipate
polycap
rolacton
HDO-carb
onatePTMEG
PPGPrip
last 3
195
Priplas
t 319
2Prip
last 3
190
Priplas
t 183
8Prip
last 3
196
poly BD diol
Shore A hardness
recipe: 1 part diol2 parts butane diol3.1 parts MDI
PRIPOL and PRIPLAST products can be easily converted to polyurethane
Polyurethane elastomers from PRIPLAST polyols
- weigh polyol plus isocyanate in the desired quantities (depending onrecipe), mix and heat to 60C
- reaction causes temperature increase to about 75C- keep the mix at 80C for one hour, then cool back to 60C- add the chain extender in the required ratio, keep mixing as long as
possible- at about 70C, the mixture looses transparency, then quickly pour out- keep at 100C overnite to complete reaction
The prepolymer route is crucial, because of the polarity difference between hydrophobic dimerate ester and the polar chain extender
PU-dispersions with PRIPLAST dimeratepolyols
. 1 mole of polyol (Priplast 3190, 3192, 3195) + 2 moles ofdimethylolpropionic acid (DMPA)
. dissolve in the same weight of MEK, add 0.05% tertiairy butyl tinlaurate, and homogenize at 60C
. add IPDA, achieving an NCO/OH ratio of 0.95, during half an hour
. allow reaction to complete at 65C overnight
. neutralize the acidity of DMPA with an equimolar amount ofdimethylethanol amine (DMEA), stir for one hour
. add water, and see the system go from solution though emulsionto dispersion
. distill off MEK through a thin film evaporator at 40C and fullvacuum
The resulting product has about 35% solids, and can be used for coatings and adhesives
Moisture curable adhesives from PRIPLAST dimerate polyols
- weigh 1 mole of polyol and 2 to 3 moles MDI
- allow to react for 2 hours at 80C
- apply to substrate
- allow for extensive moisture curing (slow because of the water repellancy of dimer acid)
the adhesive can be used for many applications, with particular benefits in the areas of adhesion to low-energy surfaces, and in applications that require both resistance against hydrolytic attack (moisture, alkali, acid, methanol) and radical attack (heat, oxygen, UV, chlorine)
Example of moisture curing adhesive based on PRIPLAST polyols
. PTMEG, hexane diol adipate, Priplast 3192 (all MW 2000) andPriplast 3196 (MW 3000) are reacted with 2.5 mol/(mol polyol) of MDI
. applied between two layers of untreated HDPE, thickness 0.3-0.4mm, surface 25x25 mm
. curing 9 days at ambient, then 5 days at 50C/90% RH
. lap shear test according to ASTM D1002-99 at tensile speed 25mm/min, preconditioning 48 hours at 23C/50% RH
Adhesion to low-energy substrates with various moisture-cured PU
0
2
4
6
8
10
12
14
16
18
PTMEG HDO-AD P 3192 P 3196
Load/width at
maximum load
(N/mm)
1 mole polyol with 2.5 mole MDIlap shear adhesion to untreated polyethylene according to ASTM D 1002/99all failures are of adhesive type
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
PTMEG HDO-AD P 3192 P 3196
stress at maximum load (MPa)
PRIPOL and PRIPLAST Products
Dimer diol: Pripol 2033
specifications:
acid value max. 0.20 mg KOH/gsaponification value max. 2.0 mg KOH/ghydroxyl value 200-215 mg KOH/gcolor APHA max. 50moisture max. 0.10 %monomer alcohol max. 2.0 %dimer alcohol min. 94.5 %trimer alcohol max. 1.5 %viscosity typically 2500 mPa.s
molecular weight is about 570
PRIPLAST polyester polyols
features usesPriplast 3190 liquid, MW 2000, OH-value 52-60
very low glass transition temp. (-55C)hydrolytic/thermal /oxidative stability
elastomers with low- temperature impaneeds, elastic coatings, primers, seala
Priplast 3191 liquid, MW 1700, hydrolytic stability water-repellant foam
Priplast 3192 solid, mp 50C, MW 2000hydrolytic/thermal /oxidative stability
PU coatings and adhesives (textile, woleather), leather finishing
Priplast 3195* solid, MW 2000, OH-value 52-60hydrolytic/thermal /oxidative stability
PU coatings and adhesives (textile, wood, leather), leather finishing
Priplast 1838* liquid, MW 2000, OH value 52-60extreme hydrolytic stability, thermal/oxidative stability, low polarity, hydrocarbon compatibility
elastomers, sealants, bitumen modification
Priplast 3196* liquid, MW 3000, OH-value 34-40extreme hydrolytic stability, low polarity, hydrocarbon compatibility,
elastomers, sealants, bitumen modification
Priplast 3197* liquid, MW 2000, OH-value 52-60extreme hydrolytic stability, low polarity, hydrocarbon compatibility
elastomers, sealants, soft products
Priplast 3198 liquid, MW 1300extreme hydrolytic stability, low polarity
adhesives, bitumen modification
