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