General presentation November 2012 V. Costa, A.Nohales, D

1

General presentation November ï 2012

V. Costa, A.Nohales,

D. Gutiérrez, C.Gomez

www.ube.ind.br

http://www.ube.ind.br/

2

Index

Introduction UBE company

Polyurethanes

TPU elastomers

Waterborne PUD: coatings and adhesives

Conclusions

3

Index


Polyurethanes

TPU elastomers


Conclusions

4


UBE Latin America

Serviços Ltda

UBE AROUND THE WORLD

UBE Industries, Ltd.

Billion ú 5,835. turnover* (2011)

11.026 employees

UBE IN EUROPE

UBE Corporation Europe, S.A.

384 Mú turnover (2011)

370 employees (2011)

5


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

6

Index


Polyurethanes

TPU elastomers


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 ï Backbone ï Bridge ï Backbone ï 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


Polyurethanes

TPU elastomers


Conclusions

11

Method

TPU ï 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 Ą 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

% te

nsi

le s

tre

ngth

rete

ntio

n

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

Re

ten

tio

n o

f te

nsile

str

en

gth

(%

)

Inmersion time (days)

Ester

UH-PCD

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 (

%)

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:

ɚ= 340 nm borosilicate filters,

Radiation of 35 W m2 nm,

T= (65°3) ęC.

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:

VTwo-shot process in 100% solid content .

VT = 70 ºC and atmospheric pressure in

Argon.

VResidence time = 1 hour.

V30 seconds at 2000 rpm after add BD

VCuring for 12 hours at 50 bars & 100ÁC

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

Hardness (Shore A) 92 81 -- 81

Modulus elongation 100% (Mpa)

25°1 20°2 15°1 14°1

Modulus elongation 200% (MPa)

35°2 33°3 26°1 22°1

Tensile strength(Mpa)

36°3 44°4 47°2 42°3


235°14 256°17 361°7 382°22


21


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

22

Properties PUPH200 -32

PUUHC200-32

PUPCL200 -32

PUUT200 -32

PUPTMG200-32

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

Modulus elongation

100% (Mpa)

12°1 8°1 6°1 8°1 7°1

Modulus elongation

200% (MPa)

24°1 14°1 10°1 11°1 11°1

Modulus elongation

300% (Mpa)

39°1 23°3 16°1 16°1 16°1

Tensile strength(Mpa)

50°2 40°6 46°5 32°1 37°4


358°1 458°18 560°16 557°10 610°23


23


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

Re

ten

tio

n o

f te

nsile

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

Re

ten

tio

n o

f e

lon

ga

tio

n (

%)

Heating time (days)

0 10 20 30 40 50 60

0

20

40

60

80

100

120

140 PUPH200-32

PUUHC200-32

PUPTMG200-32

Re

ten

tio

n o

f te

nsile

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

Re

ten

tio

n o

f e

lon

ga

tio

n (

%)

Heatin time (days)

25

DMA results

Figure Storage modulus and Tan ŭ 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 d

26

Index


Polyurethanes

TPU elastomers


Conclusions

27

27

Coatings based on ETERNACOLL© show:

- Better chemical resistance

- Improved scratch resistance

- Higher gloss

- Lower yellowish

- Better adhesion to substrate

Coatings ï Properties 1

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

28

28

- 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 ï Chemical resistance ISO 4211:1979

Po

lye

ste

r-b

ase

d P

UD

UB

E E

TE

RN

AC

OL

L®

-b

ased

P

UD

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

polyols with UBE ETERNACOLL® polycarbonate diols.


29

29

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


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 ï Artificial ageing ISO 11507:2007


0

20

40

60

80

100

Retention (%)


Retention of hardness Persoz

0

20

40

60

80

100

Retention (%)


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 ï Properties 1

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 ï Heat & weather resistance

PUD WATERBORNE ADHESIVES

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

UBE ETERNACOLL®

33

Index


Polyurethanes

TPU elastomers


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

35

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

ish

ing

UBE ETERNACOLL®

36

Further information in: www.ube.ind.br

[email protected] / [email protected]

Muito Obrigado !!

Thanks for your attention !!

Documents

General presentation November 2012 V. Costa, A.Nohales, D