PRIPLAST polyester polyols derived from dimerized fatty acids

Principles of Uniqema's oleochemical technology for polyurethanes

the basis: PRIPOL dimerized fatty acids

large hydrocarbon part (C36), chemically inert and water-repellant irregular structure, non-crystalline

O=C HO

C=O OH

difunctionality

flexible structure

Different forms of PRIPOL dimer technology

PRIPOL dimer acid

HOOC

COOH

PRIPOL dimer diol

HO

OH

PRIPLAST polyesters made with PRIPOL dimer acid or HO- ..... dimer diol

E.....E

.... - OH

Effects of PRIPOL and PRIPLAST technology

irregular structure

non-crystallinity

lasting elasticity low glass transition fluidity

Effects of PRIPOL and PRIPLAST technology

hydrocarbon nature

hydrophobicity absence of ether links

hydrolytic stability of esters stability against acid/base compatibility with organics

stability against heat, 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

recipe: conditions: 1 polyol (MW 2000), 2 butane diol, exposure to 90C water for 1 week 3 MDI

120 100 80 retention of tensile strength (%) 60 40 20 0

31 92 31 95 18 38 M EG 31 90 ol ac to n on a ip at e H D O -a d te

PT

po ly ca rb

po ly ca pr

Hydrolytic stability of TPU in boiling water

120

100

80 Retention of 60 strength (% ) 40 hexane diol adipate PTMEG Priplast 1838

20

0 0 5 10 Days 15 20

Priplast versus other diols: Stability of TPU (1)

Heat (100 C)
120 120

10% H2SO4 @ 23 C

% Retention 60 of strength 40
20 0

100 80

% Retention 60 of strength 40
20 0

100 80

EGadipate

BDadipate

Priplast 3192

Priplast 3196

EGadipate

BDadipate

Priplast 3192

Priplast 3196

5% NaOH @ 60 C
120 100 90 80 70 60 50 40 30 20 10 0

Methanol

% 80 Retention 60 of strength 40
20 0

% Retention of strength EGadipate BDadipate Priplast 3192 Priplast 3196

EGadipate

BDadipate

Priplast 3192

Priplast 3196

all results after 2 weeks of exposure

Emulsion stability of TPU at 50 C

120

100

80 Retention of 60 filmstrength (%) 40

BD-adipate HD-adipate Polycapro- lacton MPD- Terephthalate HD-carbonate PTMEG Priplast 1838

20

0 0 5 10 15 Days 20 25 30 35

Moisture uptake of dimerate and other polyurethanes

recipe: 1 polyol, 2 butane diol 3 MDI

conditions: 1 week in distilled water at 23C 2

1.8 1.6 1.4 1.2 1 moisture uptake at 0.8 23C, % 0.6 0.4 0.2 0
Pr ip la st 31 Pr 96 ip la po st 18 ly bu 38 te ne Pr di ol ip la st H D 31 O 90 ca rb on Pr at ip e la st 31 Pr 92 ip la st 31 H D 95 O ad po ip ly at ca e pr ol ac B to D n O -a di pa te PT M EG PP G

Effect of UV-radiation on PU from dimerate and other polyols

recipe: conditions: 1 polyol (MW 2000), 2 butane diol, exposure to UV-B for 2 weeks 3 MDI

100 90 80 70 60 retention of tensile 50 strength (%) 40 30 20 10 0 HDO-adipate Priplast 3192 Priplast 3195 Priplast 1838 PTMEG PPG

Effect of oxidation on PU from dimerate and other polyols

120 100 80 retention of tensile strength (% ) 60 40 20 0 retention of elongation (% )

100 90 80 70 60 50 40 30 20 10 0

95

38

PP G

PP G

te

EG

EG

95

38

te

PB -d io

PT M

-a d

-a d

as t

as t

as t

DO

Pr ip l

Pr ip l

Pr ip l

recipe: conditions: remarks:

1 polyol (MW 2000), 2 butane diol, 3 MDI exposure to 140 for 4 weeks polyethers are destroyed within days

Pr ip l

DO

as t

PT M

PB -d io

ip a

ip a

31

31

18

18

Weather resistance

120

100

80 Retention of strength 60 (%) 40 hexane diol adipate PTMEG Priplast 1838

20

0 0 200 400 600 800 1000 1200 Weather-o-meter, hours

PRIPOL and PRIPLAST technology gives polyurethanes with good mechanical properties

Moduli of PU made with PRIPLAST dimerate and other polyols

100% modulus 300% modulus
250

recipe:

200

1 part diol 2 parts butane diol 3.1 parts MDI

150 modulus, kg/cm2 100

50

0
-a di po pa ly te ca pr ol ac H D to O n -c ar bo na te PT M EG PP Pr G ip la st 31 Pr 95 ip la st 31 Pr 92 ip la st 31 Pr 90 ip la st 18 Pr 38 ip la st 31 po 96 ly B D di ol ip at e O -a d D B H D

Elongation of PU made with PRIPLAST dimerate and other polyols

recipe: 1 part diol 2 parts butane diol 3.1 parts MDI

800 700 600 500 elongation, % 400 300 200 100 0

31 95 31 90 ol ac to n M EG 31 92 18 38 31 96 po ly ip ip di ol B D e at at e

-a d

-a d

PT

Pr ip la st

Pr ip la st

po ly ca pr

Pr ip la st

Pr ip la st

Pr ip la st

Tensile strength of PU made with PRIPLAST dimerate and other polyols

recipe: 1 part diol 2 parts butane diol 3.1 parts MDI

500 450 400 350 300 tensile strength, kg/cm2 250 200 150 100 50 0
ip po at ly e ca pr ol ac to n 31 95 Pr ip la st 31 92 Pr ip la st 31 90 Pr ip la st 18 38 Pr ip la st 31 96 po ly B D di ol M EG ip at e PP G

-a d

-a d

PT

Pr ip la st

Effect of recipe on PU made with PRIPLAST dimerate and other polyols

700 600 500 400 300 200 100 0 Modulus 100% Modulus 300% Tensile Strength Hardness Elongation

tensile strength, modulus, kg/cm2

1 Priplast 1838 2 MDI, 1 BDO Column 4

1 Priplast 1838 3 MDI, 2 BDO Column 5

1 Priplast 1838 4 MDI, 3 BDO Column 6

Hardness of PU made with PRIPLAST dimerate and other polyols

recipe: 1 part diol 2 parts butane diol 3.1 parts MDI

100 90 80 70 60 Shore A hardness 50 40 30 20 10 0

-a di po pa ly te ca pr ol ac H D to O n -c ar bo na te PT M EG PP Pr G ip la st 31 Pr 95 ip la st 31 Pr 92 ip la st 31 Pr 90 ip la st 18 Pr 38 ip la st 31 po 96 ly B D di ol ip at e O D B H -a d D

PRIPOL and PRIPLAST products can be easily converted to polyurethane

Polyurethane elastomers from PRIPLAST polyols

weigh polyol plus isocyanate in the desired quantities (depending on recipe), 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 dimerate polyols

. . . . . . . 1 mole of polyol (Priplast 3190, 3192, 3195) + 2 moles of dimethylolpropionic acid (DMPA) dissolve in the same weight of MEK, add 0.05% tertiairy butyl tin laurate, 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 of dimethylethanol amine (DMEA), stir for one hour add water, and see the system go from solution though emulsion to dispersion distill off MEK through a thin film evaporator at 40C and full vacuum

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) and Priplast 3196 (MW 3000) are reacted with 2.5 mol/(mol polyol) of MDI applied between two layers of untreated HDPE, thickness 0.3-0.4 mm, 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 25 mm/min, preconditioning 48 hours at 23C/50% RH

. .

Adhesion to low-energy substrates with various moisture-cured PU

1 mole polyol with 2.5 mole MDI lap shear adhesion to untreated polyethylene according to ASTM D 1002/99 all failures are of adhesive type

0.7 0.6 0.5 stress at 0.4 maximum load (MPa) 0.3 0.2 0.1 0 PTMEG HDO-AD P 3192 P 3196

18 16 14 12 Load/width at 10 maximum 8 load (N/mm) 6 4 2 0 PTMEG HDO-AD P 3192 P 3196

PRIPOL and PRIPLAST Products

Dimer diol: Pripol 2033

specifications: acid value saponification value hydroxyl value color APHA moisture monomer alcohol dimer alcohol trimer alcohol viscosity max. 0.20 mg KOH/g max. 2.0 mg KOH/g 200-215 mg KOH/g max. 50 max. 0.10 % max. 2.0 % min. 94.5 % max. 1.5 % typically 2500 mPa.s

molecular weight is about 570

PRIPLAST polyester polyols

features Priplast 3190 liquid, MW 2000, OH-value 52-60 very low glass transition temp. (-55C) hydrolytic/thermal /oxidative stability liquid, MW 1700, hydrolytic stability solid, mp 50C, MW 2000 hydrolytic/thermal /oxidative stability uses

elastomers with low- temperature impa needs, elastic coatings, primers, seala water-repellant foam

Priplast 3191 Priplast 3192 Priplast 3195* Priplast 1838*

PU coatings and adhesives (textile, wo leather), leather finishing

solid, MW 2000, OH-value 52-60 PU coatings and adhesives (textile, hydrolytic/thermal /oxidative stability wood, leather), leather finishing liquid, MW 2000, OH value 52-60 elastomers, sealants, bitumen extreme hydrolytic stability, thermal/oxidative stability,modification low polarity, hydrocarbon compatibility liquid, MW 3000, OH-value 34-40 elastomers, sealants, bitumen extreme hydrolytic stability, low polarity, hydrocarbon modification compatibility, elastomers, sealants, soft products liquid, MW 2000, OH-value 52-60 extreme hydrolytic stability, low polarity, hydrocarbon compatibility
liquid, MW 1300 extreme hydrolytic stability, low polarity

Priplast 3196*

Priplast 3197*

Priplast 3198

adhesives, bitumen modification