Achieve best-in class durability of your

Polyurethane-based Coatings and

Adhesives thanks to breakthrough
Polycarbonate Diols ETERNACOLL

Dr. Manuel Colera

Business Development Manager
UBE Chemical Europe, S.A.

Tuesday, October 21st 2014

Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
2

Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
3

Introduction of UBE

UBE Latin America Servios Ltda

UBE WORLDWIDE: UBE Industries, Ltd.

UBE IN EUROPE: UBE Corporation Europe, S.A.

6.377 M$ turnover (March 31st, 2014)

402 M turnover (July 29th, 2014)

11225 employees

391 employees
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UBE product line

Specialty Chemicals & Products

-

Specialty Products

- -Caprolactam

(Polyimides, Battery materials,

Separation membranes, Ceramics)

- Polyamides

Fine Chemicals

- Synthetic Rubber

(Dimethyl carbonate, 1,5-pentane diol,

1,6-hexane diol, polycarbonate diol,
PCD, diphenol derivatives)

Chemicals & Plastics

Pharmaceuticals

Cement & Construction Materials

Machinery and Metal Products

Energy and Environment

Polycarbonate diol structure

Terminal Backbone Bridge Backbone Terminal

Polycarbonate diol

Polyester diol

Polyether diol

Polyurethane mechanical properties defined by using an optimum backbone (R)

or by different molecular weight (n)
Durability properties:
Carbonate vs. ester & ether as bridge:
Higher hydrolysis resistance
Higher chemical resistance
Flooring

Excellent strain resistance

Artificial leather

Better heat & weather resistance

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Various possible applications

Oil & mining pipes coatings

Wood coatings

Inks

Pavements

Flooring

Automotive coatings

Automotive finishing

Artifical leather

Leather finishing

Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
8

Synthesis of PUs Acetone method

Isocyanate

Diol

NCO

Emulsifiers

HO

OH

Poliadipato
POLYOL de
1,4 butanodiol

OCN
IPDI

HO

OH

COOH

HO

DEG

OH

DMPA

1. SNTESIS DEL PREPOLMERO

1. Prepolymer synthesis

T = 80C, Vagitacin= 200 rpm

PREPOLMERO
SOLVENT-FREE
PREPOLYMER

Neutralizer

NCO
OCN

Chain extender

2. Acetone addition

2. DISOLUCIN DEL PREPOLMERO EN ACETONA,

T = 45-50C, Vagitacin= 600 rpm

3. Neutralization

3. NEUTRALIZACIN CON TEA,

T= 45-50C, Vagitacin= 600 rpm

4. Chain extension

4. EXTENSIN DE CADENA CON HIDRACINA,

T ambiente, Vagitacin= 600 rpm

5. Water addition

5. ADICIN DE AGUA,
T ambiente, Vagitacin= 800 rpm

POLYURETHANE
POLYMER
IN
DISPERSIN
DE POLIURETANO
EN DISPERSED
AGUA/ACETONA
WATER/ACETONE

6. DESTILACIN DE LA ACETONA,
T = 50C, P= 300 mbar

6. Acetone removal

DISPERSIN ACUOSA DE POLIURETANO

WATERBORNE POLYURETHANE DISPERSION

Segmented structure of PUs

Soft segments

Hard segments

Soft segments (SS): PCD moities

Hard segments (HS): Isocyanate + chain extender

Phase separation

Hard
segments
Soft segments
Ionic aggregates
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Characterization of coatings
Persoz hardness (ISO 1522:2007)

Yellowness index (ASTM D1925-70)

Pencil hardness (ISO 15184:1998)

Chemical resistance (ISO 4211:1979)

Gloss 60 (ISO 2813:1999)

Persoz pendulum 707 KP (ISO

1522:2007)

BYK Micro-TRI-Gloss
(ISO 2813:1999)

Pencil hardness
(ISO 15184:1998)

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Colorimeter MINOLTA CR410

(ASTM D1925)

Characterization of adhesives
T-peel test (ISO 11339:2010)
Single lap-shear test (ISO 4587:2003)
Cross-cutter adhesion test (ISO 2409:2007)

Lap-Shear test
(ISO 4587:2003)

T-peel test
(ISO 11339:2010)

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BYK Cross cut tester

(ISO 2409:2007)

Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
13

Coatings Persoz hardness

PENDULUM

STARTING
ANGLE

FINAL ANGLE

Time (s)

Knig

oscillations x 1.4

Persoz

12

oscillations x 1.0

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Coatings Pencil hardness

Soft

Hard

Pencil hardness measures the resistance of a coating to marking or the formation

of some other deffects, such as cracks.

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Coatings Persoz & pencil hardness

Hardnesss Persoz

Pencil hardness

140
120
100
80
60
40
20
0

6B 6
5B 5
4B 4
3B 3
2B 2
B1
H0

Polycarbonate diol ETERNACOLL provides customizable coatings hardness and

improves the scratch resistance of coatings.

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Coatings Persoz & pencil hardness

Thickness (m)

Polytetramethylene glycol
Polyadipate of 1,6-hexane diol
ETERNACOLL PH100

Persoz hardness (no.

oscillations)

Pencil hardness x 10

Polycarbonate diol ETERNACOLL provides balanced hardness properties.

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Coatings Gloss 60

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Coatings Yellowness index

Yellowish

Colourless

CIE 1931 color space chromaticity diagram

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Coatings Gloss 60 and Yellowness index

Gloss 60o

Yellowness index

100
90
80
70
60
50
40
30

12
10
8
6
4
2
0

Polycarbonate diol ETERNACOLL maximizes coating gloss, and reduces

yellowish of colourless coatings.

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Coatings Gloss 60 and Yellowness index

20 m

Polytetramethylene glycol-based PU

25 m

Polyadipate of 1,6-hexane diol-based PU

Phases separation

+
Cristallinity

=
Gloss 60o
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20 m

ETERNACOLL PH100-based PU

Coatings Chemical resistance

PUD (fresh: 200 m)

Stainless steel 304

10 min
Ethanol

Stainless steel 304

22

Code

Damaged Surface

Intact coating

Slight change in gloss or

color

Light mark

Strong mark

Coating removal

Coatings Chemical resistance

Chemical resistance
5
4
3
2
1
0

Polycarbonate diol ETERNACOLL based coatings do not suffer any damage after
chemical attack.

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Coatings Durability tests

Heat resistance:
- ISO 3248:1998 (15 days @ 120 C)
- On stainless steel plates

Artificial weathering:
- Cycle H: ISO 11507:4892-3 (total duration: 200 h):
Stage

Function

1
2
3

UV
Condensacin

Irradiance
(W/m2)
0.71
n/a

Temperature (C)

Time (h: min)

60
50

4:00
4:00

Go to Stage 1

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Coatings Durability tests

Variation of hardness Persoz (%)

100
80
60
40
20
0

Variation of thickness (%)

100
80
60
Heat resistance 40
20
Weatherability
0

Polycarbonate diol ETERNACOLL

based coatings do not change initial
hardness and coating thickness after
exposure to extreme harsh conditions.

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Heat resistance
Weatherability

Coatings Durability tests

Variation of gloss 60o (%)

100
80
60
40
20
0

Increment of yellowness (%)

Heat resistance
Weatherability

Polycarbonate diol ETERNACOLL

minimizes gloss and color changes of
coatings after exposure to extreme harsh
conditions.

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300
250
200
150
100
50
0

Heat resistance
Weatherability

Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
27

Adhesives T-peel test

PVC
PUD
PVC

28

Adhesives Single lap-shear test

Aluminium

Aluminium

29

PUD

Adhesives Cross-cutter adhesion test

PUD (fresh: 200 m)

Stainless steel 304

Stainless steel 304

30

Code

Description

Damaged surface

No modification

Light loosening of
coating (< 5 %)

Light loosening of
the borders of the
coating
(5 to 10 %)

Partial loosening of
the coating
(15 to 35 %)

Strong loosening of
the coating
(35 to 65 %)

Very strong
loosening of the
coating
(> 65 %)

Adhesives Adhesion properties

T-peel (kN/m) & Lap shear (kPA)

Cross-cutter adhesion
5

3
2

Lap shear

T-peel

Polycarbonate diol ETERNACOLL

provides
balanced
adhesion
properties, meeting those of premium
polyols.

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2
1
0

Adhesives Cyclic ageing

T (C)

48 1 h

48 1 h

HR < 15%

HR > 90%

24 1 h

T (C)

48 1 h

72 1 h

24 1 h

72 1 h
HR < 15%

HR > 90%

time
(days)

time
(hours)

ISO 9142:2003 - Cycle D5

ISO 9142:2003 - Cycle D11

Dry heat, wet heat and cold

Water immersion, cold and dry heat

Internal standard

32

Adhesives Cyclic ageing

Variation of T-peel (%)

400
350
300

Total loss of adhesion due to softening

250
200

Internal standard

150
100

Cycle D5

50

Cycle D11

0
ETERNACOLL
PH100

Polytetramethylene Polyadipate of 1,6glycol

hexane diol

Polycarbonate diol ETERNACOLL minimizes adhesion decrease of adhesives after

exposure to extreme harsh conditions.

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Outline
INTRODUCTION
EXPERIMENTAL: SYNTHESIS, ANALYSIS AND CHARACTERIZATION
COATINGS PROPERTIES
ADHESIVES PROPERTIES

CONCLUSIONS
34

Conclusion
Polyurethane coatings based on PCD present higher
durability against heating, hydrolysis, weather & chemicals
than benchmark polyether and polyester polyol countertypes.
Those adhesives based on PCD show same adhesion
properties, improving adhesion to substrates and retaining
initial designed properties in harsh environments.

The use of PCDs is the key to synthesize a family of high

performance PU coatings and adhesives, due to their excellent
properties.

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Thank you for your

attention!

Dr. Manuel Colera

Business Development Manager
UBE Chemical Europe, S.A.

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