1

General presentation November – 2012

V. Costa, A.Nohales,

D. Gutiérrez, C.Gomez

www.ube.ind.br

2

Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

3

Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

4

Introduction UBE company

UBE Latin America

Serviços Ltda

UBE AROUND THE WORLD

UBE Industries, Ltd.

Billion € 5,835. turnover* (2011)

11.026 employees

UBE IN EUROPE

UBE Corporation Europe, S.A.

384 M€ turnover (2011)

370 employees (2011)

5

Introduction UBE company

UBE product line

- Specialty Chemicals & Products

Specialty Products (Polyimides, Battery materials, Separation membranes, Ceramics)

Fine Chemicals (DMC, Diols, PCD, diphenol derivatives)

Pharmaceuticals

- Chemicals & Plastics

Caprolactam

Polyamides

Synthetic Rubber

- Cement & Construction Materials

- Machinery and Metal Products

- Energy and Environment

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Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

7

Applications

8

Synthesis

Diisocyanate Macrodiol Chain extender

Soft segment Hard segment

Block copolymer

Synthesis

Hard segment of urethane groups

Soft segment Hard segment

9

9

Terminal – Backbone – Bridge – Backbone – Terminal

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

or by different molecular weight (n)

Durability properties:

Carbonate vs. ester & ether as bridge:

Higher hydrolysis

Higher chemical resistance

Excellent stain resistance

Better heat & weather resistance

Polycarbonate diol Polyester diol Polyether diol

Polyols structures

10

Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

11

Method

TPU – Elastomers: Cooperation with ICMUV (University of Valencia)

Synthesis:

Polyol: BuDL : MDI = 1 : 2 : 3 molar (Two-shot process)

T = 80ºC and P = atmospheric in Argon

Residence time = 3h to 5h

Solid content = 22%wt (Solvent DMA)

Hard segment content = 48 %

Films:

Thin Film applicator NEURTEK RK 0,2 mm thickness

Drying 80ºC for 24 h

12

Properties UH-100 PH-100 POLYESTER POLYETHER

Density (g/cm3) 1.20 1.22 1.25 1.11

Hardness (Shore A) 92 89 93 83

Modulus elongation 100% (Mpa)

34 34 20 13

Modulus elongation 200% (MPa)

60 66 40 23

Tensile strength(Mpa) 70 75 69 41

Elongation at break (%)

231 222 323 345

Tear strength (MPa) 168 154 123 92

Glass transitions 31 26 2 7

Mechanical properties

POLYESTER = 1,4-BUTANEDIOL ADIPATE POLYETHER = POLYPROPYLENE GLYCOL

13

TPU: Mechanical properties

0 50 100 150 200 250 300 350 400

0

10

20

30

40

50

60

70

80

Te

nsile

Str

ess (

MP

a)

Strain (%)

Ether

Ester

Carbonate (UH-PH)

14

PCD

Degradation Resistance of TPU

0

20

40

60

80

100

120

UH PH Polyether Polyester

% t

ensi

le s

tren

gth

ret

enti

on

hydrolisis temperature oil weather

15

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

Re

ten

tio

n o

f e

lon

gatio

n (

%)

Heating time (days)

TPU: Heating resistance at 120 ºC

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

Re

ten

tio

n o

f te

nsile

str

en

gth

(%

)

Heating time (days)

TPU-Polyether very poor: Heating resistance

Ether

Ester

Carbonate (UH-PH)

Ether

Ester

Carbonate (UH-PH)

TPU-PCD excellent:

Heating resistance

16

TPU: Hydrolysis resistance in water at 80 ºC

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

PH-PCD

Ether

Rete

ntion o

f te

nsile

str

ength

(%

)

Inmersion time (days)

Ester

UH-PCD

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

Rete

ntion o

f elo

ngation (

%)

Inmersion time (days)

TPU-Polyester very poor: water resistance

TPU-PCD excellent:

Hydrolytic resistance

Ester

Carbonate (UH-PH)

Ether

Ether

Ester

Carbonate (UH-PH)

17

0

20

40

60

80

100

PU-UH PU-PH PU-PBA PU-PPG

Retention of tensile strentgh (%)

0

20

40

60

80

100

PU-UH PU-PH PU-PBA PU-PPG

Retention of elongation (%)

TPU: Weather Resistance

TPU-PCD excellent:

weather resistance

Weather conditions:

λ= 340 nm borosilicate filters,

Radiation of 35 W m2 nm,

T= (653) ˚C.

Dry cycle of 102 min continuous by 1 min of spray water (raining simulation).

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MDI Butanediol

PH

(PCD)

Raw materials

UHC

(polyester &PCD)

PTMG

(polyether)

PCL

(polyester)

UT

(polyether & PCD)

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Method TPU elastomers

System Molar ratio macrodiol:MDI:BDL

Hard segment content (wt%)

PUPH100-48 1:3:2 48

PUPH200-32 1:3:2 32

PUUHC100-48 1:3:2 48

PUUHC200-32 1:3:2 32

PUUT200-32 1:3:2 32

PUPTMG100-48 1:3:2 48

PUPTMG200-32 1:3:2 32

PUPCL100-48 1:3:2 48

PUPCL200-32 1:3:2 32

Synthesis:

Two-shot process in 100% solid content .

T = 70 ºC and atmospheric pressure in

Argon.

Residence time = 1 hour.

30 seconds at 2000 rpm after add BD

Curing for 12 hours at 50 bars & 100°C

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Properties PUPH100-48 PUUHC100-48 PUPCL100-48 PUPTMG100-48

Hardness (Shore A) 92 81 -- 81

Modulus elongation 100% (Mpa)

251 202 151 141

Modulus elongation 200% (MPa)

352 333 261 221

Tensile strength(Mpa)

363 444 472 423

Elongation at break (%)

23514 25617 3617 38222

Mechanical properties

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Mechanical properties

Polyol Molecular weight1000g/mol

0 50 100 150 200 250 300 350 400 450

0

10

20

30

40

50

60

Te

nsile

Str

ess (

MP

a)

Strain (%)

Ether

Ester UHC

PH

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Properties PUPH200 -32

PUUHC200-32

PUPCL200 -32

PUUT200 -32

PUPTMG200-32

Hardness (Shore A) 86 76 -- -- 75

Modulus elongation

100% (Mpa)

121 81 61 81 71

Modulus elongation

200% (MPa)

241 141 101 111 111

Modulus elongation

300% (Mpa)

391 233 161 161 161

Tensile strength(Mpa)

502 406 465 321 374

Elongation at break (%)

3581 45818 56016 55710 61023

Mechanical properties

23

Mechanical properties

Polyol Molecular weight 2000g/mol

PH Esther

0 50 100 150 200 250 300 350 400 450 500 550 600 650

0

10

20

30

40

50

60T

en

sile

Str

ess (

MP

a)

Strain (%)

UHC Ether

UT

Ester PH

24

Heating resistance

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

PUPH100-48

PUUHC100-48

PUPTMG100-48

Rete

nti

on

of

ten

sile

str

en

gh

t (%

)

Heating time (days)

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

PUPH100-48

PUUHC100-48

PUPTMG100-48

Rete

nti

on

of

elo

ng

ati

on

(%

)

Heating time (days)

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140 PUPH200-32

PUUHC200-32

PUPTMG200-32

Rete

nti

on

of

ten

sile

str

en

gh

t (%

)

Heating time (days)

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140

PUPH200-32

PUUHC200-32

PUPTMG200-32

Rete

nti

on

of

elo

ng

ati

on

(%

)

Heatin time (days)

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DMA results

Figure Storage modulus and Tan δ as a function of temperature

for the different segmented polyurethanes synthesized.

-100 -50 0 50 100 150 200

0,1

1

10

100

1000

10000

PUPH200-32

PUUHC200-32

PUPTMG200-32

PUUT200-32

Temperature (°C)

Sto

rag

e m

od

ulu

s (

MP

a)

Polyols Molecular Weight 2000 g/mol

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4ta

n

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Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

27

27

Coatings based on ETERNACOLL© show:

Better chemical resistance

Improved scratch resistance

Higher gloss

Lower yellowish

Better adhesion to substrate

Coatings – Properties1

PUD WATERBORNE COATINGS

Properties Method Unit PH-100 UH-100 PPG2 PBA3

Chemical resistance ISO 4211:1979 4 4 2 2

Hardness Persoz ISO 1522:2007 62 121 33 109

Pencil hardness ISO 15184:1998 3B 4B 5B 6B

Gloss 60o ISO 2813:1999 % 99 78 79 38

Yellowness index ASTM D1925-70 7.7 8.9 10.8 9.8

Cross-cut test ISO 2409:2007 0 0 1 2 1 Stainless steel plates (ISO 1514:2004), after 7 days at 23 ºC and 50% 2 PPG: Polypropylene glycol, Mw 1000 3 PBA: Poly(1,4-butylene adipate), Mw 1000

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Chemical resistance of PUD coatings just slightly depends on substrate and can be adjusted by UBE ETERNACOLL®

polycarbonate diols molecular weight & hard segments content.

For every substrate, there is an suitable grade of UBE ETERNACOLL® polycarbonate diol for providing an excellent

chemical resistance to PUD coatings.

Coatings – Chemical resistance ISO 4211:1979

Po

lye

ste

r-b

ase

d P

UD

UB

E E

TE

RN

AC

OLL

® -

ba

se

d

PU

D

In a same PUD formulation, impressively noticeable results only replacing traditional

polyols with UBE ETERNACOLL® polycarbonate diols.

PUD WATERBORNE COATINGS

29

29

Coatings – Heat resistance ISO 3248:1998 – Measurements after 15 days at 120 ºC

PUD WATERBORNE COATINGS

0

250

500

750

1000

1250

1500

Increment (%)

Polycarbonate diol grade

Increment of yellowness index

0

5

10

15

20

25

30

35

0 5 10 15 20

Increment of yellow index on oak wood (%)

UH100

UH200

Polyether

Polyester

UBE ETERNACOLL®

30

30

Coatings – Artificial ageing ISO 11507:2007

PUD WATERBORNE COATINGS

0

20

40

60

80

100

Retention (%)

Polycarbonate diol grade

Retention of hardness Persoz

0

20

40

60

80

100

Retention (%)

Polycarbonate diol grade

Retention of thickness

UBE ETERNACOLL®

Loss of thickness

Worst cross cut adhesion

31

31

Adhesives based on ETERNACOLL© show:

Shorter complete drying time

Stronger adhesion to substrates

Improved peel resistance

Enhanced lap-shear strength

Adhesives – Properties1

PUD WATERBORNE ADHESIVES

1 Acetone method: % solids w/w = 38, NCO/OH in prepolymer = 1.5

Without additives 2 PPG: Polypropylene glycol, Mw 1000 3 PBA: Poly(1,4-butylene adipate), Mw 1000 4 Dry-through time

Properties Method Unit PH-100 UH-100 PPG2 PBA3

Drying time4 ASTM D5895-03 h <2 <2 >6 >6

Cross-cut test ISO 2409:2007 0 0 1 2

T-peel test ISO 11339:2010 kN/m 1.9 2.9 0.3 1.6

Lap-shear strength ISO 4587:2003 kPa 4.8 3.4 3.1 3.3

PH-100-based coating PPG-based coating

32

32

Adhesives – Heat & weather resistance

PUD WATERBORNE ADHESIVES

Heat resistance ISO 3248:1998 Measurements after 15 days at 120 ºC

UBE ETERNACOLL®

33

Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

34

Conclusions

-PCD CAN BE USED TO FORMULATE COATINGS, ADHESIVES

AND ELASTOMERS (CASE)

-THE CARBONATE GROUP INTERACTS MORE THAN ESTER

AND ETHER GROUP WITH HARD SEGMENT

-CARBONATE GROUP PROVIDE THE STRONGEST LINKING

GROUP FOR POLYOL USED IN HIGH PERFORMANCE

POLYURETANES

- PCD ACHIEVES THE HIGHEST DURABILITY MATERIALS

AGAINST HEATING, HYDROLYSIS, CHEMICALS, WEATHERING

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35

Applications

UBE ETERNACOLL® polycarbonate diols are recommended for PUD coatings of surfaces with chemicals and/or high

heat exposure: no yellowish, excellent retention of original mechanical & adhesion properties, and gloss.

Au

tom

otive

Art

ific

ial le

ath

er

Le

ath

er

fin

ish

ing

Flo

orin

g

Wo

od

co

atin

g &

pa

ints

Au

tom

otive

fin

ishin

g

UBE ETERNACOLL®

36

Further information in: www.ube.ind.br

v.costa@ube.es / d.hernandes@ube.ind.br

Muito Obrigado !!

Thanks for your attention !!