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Priplast polyester polyols

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					PRIPOL dimerised fatty acids


Large hydrocarbon part (C36)
• hydrophobic
• hydrolytic resistance of derivatives
• affinity for non-polar matrices and surfaces



                    =
                    C
                    O
                                             =
                                             O
                                             C
                    O
                    H
                                             H
                                             O




Irregular non-crystalline structure        Di-functional constituent for:
• flexibility                              • polyamides
• low Tg                                   • polyesters
• flow, wetting                            • polyurethanes
  Different forms of PRIPOL dimer
  technology


PRIPOL dimer acid      O H
                       C O
                       O O
                       H C




PRIPOL dimer diol            O
                             HH
                              O


PRIPLAST
polyesters
made with PRIPOL    HO----   E-E    ----- OH
dimer acid or
dimer diol
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 Polyol
       1.6                2 Butanediol
                          3.1 MDI
       1.4
       1.2
               Conditions : 1 week in H2O dist.
           1
       0.8
       0.6
       0.4
       0.2
           0
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Hydrolysis of PU from PRIPLAST
dimerate and other polyols
      Retention of tensile strength, %                                                     Recipe :         1 Polyol
                                                                                                            2 Butanediol
      120                                                                                                   3.1 MDI

      100
                                                                                           Conditions : 1 week in H2O
                                                                                                        (dist.) at 90 C
        80

        60

        40

        20

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Effect of UV-radiation on PU from
PRIPLAST dimerate and other polyols
         Retention of tensile strength, %                                            Recipe :    1 Polyol
                                                                                                 2 Butanediol
    120                                                                                          3.1 MDI

    100
                                                                                     Conditions : 2 weeks exposure
                                                                                                  to UV-B
        80


        60


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Effect of oxidation on PU from
PRIPLAST dimerate and other polyols
            Retention of tensile strength / elongation, %

 120                                                                      Recipe :   1 Polyol
                                                                                     2 Butanediol
 100                                                                                 3.1 MDI

                                                                          Conditions : Exposure
     80                                                                                to 140 C
                                                                                       for 4 weeks
     60
                                                                                Strength
     40                                                                         Elongation


     20


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PRIPLAST versus other diols :
stability of TPU
      Retention of tensile strength, %

 120
                                                                         Recipe :   1 Polyol
                                                                                    2 Butanediol
 100                                                                                3.1 MDI

  80                                                                     Exposure for 2 weeks

  60
                                                                              EG-adipate
  40                                                                          BDO-adipate
                                                                              Priplast 3192
  20                                                                          Priplast 1838


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Weather resistance

      Retention of tensile strength, %
110

100

 90

 80

 70

 60                                                          PTMEG
                                                             HDO-adipate
 50
                                                             Priplast 1838
 40

 30

 20

 10

  0
      0   125   250    375   500   625   750    875   1000
                      Weather-O-Meter (hours)
Hydrolytic stability of PU in boiling
water
      Retention of tensile strength, %
110

100

 90

 80

 70

 60                                                      PTMEG
                                                         HDO-adipate
 50
                                                         Priplast 1838
 40

 30

 20

 10

  0
      0     2.5     5      7.5          10   12.5   15
                                 Days
Mechanical properties of PU from
PRIPLAST dimerate and other polyols

                                crystalline adipate
    Recipe: 1 polyol
            2 BDO
                                PTMEG
            3.1 MDI
                                Priplast 3192
                                HDO dimerate/adipate




                                Priplast 1838
                                HDO dimerate

                                Poly BD/rubber




                       Strain
                                          modulus/strength (kg/cm2)
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                                              100
                                                             150
                                                                   200
                                                                         250
                                                                               300
                                                                                     350
                                                                                           400
                                                                                                 450
                                                                                                       500




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                                                                                                             Effect of polyol on modulus and




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                                                                                       300% modulus
                                                                                       100% modulus




                                   2 BDO
                                                    Recipe



                                   3.1 MDI
                                   1 Polyol
Elongation of PU made with PRIPLAST
dimerate and other polyols

        Elongation at break, %
      800
                                                                                                                        Recipe :
      700
                                                                                                                        1    Polyol
      600
                                                                                                                        2 BDO
      500                                                                                                               3.1 MDI

      400

      300

      200                                                                                                              differences only for
                                                                                                                       different MW (3196
                                                                                                                       is mw 3000, all
      100                                                                                                              others 2000) and
                                                                                                                       functuionality (poly-
        0                                                                                                              BD)
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                                                                                              Shore-A hardness of PU made with
                                                                                              PRIPLAST dimerate and other polyols



                                                               1


                                                3.1 MDI
                                                                        Recipe :



                                                2 BDO
                                                               Polyol
T(g) of PU made with PRIPLAST
dimerate and other polyols

        Glasstransition temp., °C                                                                          Recipe :
       15                                                                                                  1 Polyol
                                                                                                           2 BDO
       10
                                                                                                           3.1 MDI
         5
                                                                                                           P1838 (*) =
         0
                                                                                                                         1
        -5                                                                                                 -1-2.1
       -10

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    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         8             0         0       0       0     0
                               slight haze
PRIPLAST 3195/TMP    3         7             0         0       0       0     0
                               slight haze

HDO/NPG adipate      9         14            0         0       5       0     0
                               white
HDO/NPG              3         8             0         0       5       0     0
  adipate/dimerate             slight haze

Commercial PUD       8         15            4         0       0       1     1
                               white
Chemical resistance of coatings
based on PRIPLAST and other polyols


Polyol            ethanol butter   desin- coffee   water   ethyl   aceton
                  (50%)            fectant                 acetate
                  1h      24h      10 min 24h      16 h    10 sec 10 sec

PRIPLAST 3195     1       0        1      0        0       5       5
PRIPLAST 3195/TMP 3       0        1      0        0       4       5

HDO/NPG adipate   0-1     0        1      0        0       5       5
HDO/NPG/AA/C36    0-1     0        1      0        0       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         290          108     4B       > 200     135     137     113
PRIPLAST 3195
 with 3% TMP          300          114     B        > 200     166     141     118

HDO/NPG adipate       170          101     HB       > 200     152     125     113
HDO/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
                                 110
                                                                                kept at 50C
                                 100
 Retention of filmstrength (%)




                                 90

                                 80                                                BD-adipate
                                                                                   HD-adipate
                                 70
                                                                                   Polycapro- lacton
                                 60                                                MPD- Terephthalate
                                 50                                                HD-carbonate
                                                                                   PTMEG
                                 40
                                                                                   Priplast 1838
                                 30

                                 20

                                 10
                                       0   5   10   15      20   25   30   35

                                                     Days
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
                             8
 adhesive strength (N/mm2)




                             6


                             4


                             2


                             0
                                 PPG   PTMEG    HDO      3198   1838   3195   3190
                                               adipate   PRIPLAST products
Polyol effect on adhesion to plastic
final strength of moisture cured adhesive

                              0.6
                                    Untreated polyethylene
                                    2.5 MDI/1 polyol
  adhesive strength (N/mm2)




                              0.4




                              0.2




                               0
                                    PPG   PTMEG    HDO       3198   1838   3195   3190
                                                  adipate    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
        Compression set after hydrolysis, %
  100


   80


   60


   40


   20


    0



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                                              A
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   Conventional
                                polyester       polyester foam
                                foam            (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:
portfolio
3192   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:
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

				
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