abrafati

So Paulo - 16, 17 e 18 de Setembro de 2013

13o Congresso Internacional de Tintas

USE OF POLYOL MIXTURES INCLUDING

POLYCARBONATE DIOL FOR IMPROVING

PERFORMANCE OF COATINGS OBTAINED FROM

WATERBORNE POLYURETHANE DISPERSIONS

Manuel Colera, Vctor CostaUBE CHEMICAL EUROPE, S.A.

Vanesa Garca Pacios, Jos A. Jofre-Reche, Jos Miguel Martn-Martnez Adhesion & Adhesives Laboratory

University of Alicante (Spain)



Introduction Experimental Results Conclusions

Outline

Introduction

Experimental

Results and discussion

Conclusions

2




Polyurethanes

Coatings & Inks

Adhesives

Automotive industry

Footwear

Biomaterials

APPLICATIONS

3




Polyurethanes

Soft segments Hard segments

Soft segments (SS): Polyol

Hard segments (HS): Isocyanate

+ chain extender

SEGMENTED STRUCTURE

4




Polyurethanes

O OHHO

n

Polyether

OHO

O

OOH

n

Polycarbonate

POLYOLS

5




Polyurethanes

Phase separation

Hard segments Soft segments

SEGMENTED STRUCTURE

6




Waterborne Polyurethane Dispersions (PUDs)

Polmero

-

-

-

-

-

-

-

--

-

Polmero

-

-

-

-

-

-

-

--

- Polmero

-

-

-

-

-

-

-

--

-

Polmero

-

-

-

-

-

-

-

--

-

Capa hidratada(estabilizada por aniones)

Polmero

-

-

-

-

-

-

-

--

-

Polmero

---

--

--

--

--

--

--

----

--

Polmero

-

-

-

-

-

-

-

--

- Polmero

-

-

-

-

-

-

-

--

-

Polmero

-

-

-

-

-

-

-

--

-


Polmero

-

-

-

-

-

-

-

--

-

Polmero

---

--

--

--

--

--

--

----

-- Polmero

---

--

--

--

--

--

--

----

--

Polmero

-

-

-

-

-

-

-

--

-

Polmero

---

--

--

--

--

--

--

----

--


Hydrated layer

Anion

stabilization

PU

PU

PUPU

STRUCTURE

7




SYNTHESIS


NCOOCN

Polyaddition

(T = 80C; 450 rpm stirring)

+ ACETONE

+ TEA

SYNTHESIS OF PREPOLYMER

ACETONE SOLUTION OF PREPOLYMER

MIXING OF REACTIVES

Dissolution and neutralization

(T = 40C; 450 rpm stirring)

ACETONE/WATER SOLUTION OF PREPOLYMER

ACETONE/WATER SOLUTION OF PREPOLYMER

(T = 40C; 900 rpm stirring)+ WATER

+ HydrazineChain extension

WATERBORNE PUD

Distillation - ACETONE

8




Solvent-borne Coatings

CURING PROCESS

9





Hard

segments Soft segments

Ionic aggregates

STRUCTURE

10




Solventborne CoatingsEnvironmentally

friendly coatings

Waterborne polyurethane

dispersions (PUDs)

Flexible coatings for

textiles & leather

finishing

Hard coatings for

flooring, wood and

metallic surfaces

11




Properties of POLYETHER DIOL in polyurethane coatings

High hydrolytic stability

Good elastomeric behavior

Excellent properties and flexibility at lowtemperature

Resistance against microorganisms

12




Benefits of POLYCARBONATE DIOL (PCD) in polyurethane coatings

Excellent hydrolytic stability

High chemical resistance

Improved durability

High thermal stability

Stable properties from low temperature

High mechanical properties13




State of the art

Da-Kong Lee, Hong-Bing Tsai, Ruey-Shi Tsai, Po Hung Chen. Preparation andproperties of transparent thermoplastic segmented polyurethanes derivedfrom different polyols. Polymer Engineering and Science 47,695-701 (2007).

PCDs

polyester polyols

polyether polyols

The polyurethanes

derived from

polycarbonate diols

exhibit higher

transparency

14




State of the art

Anna Kultys, Magdalena Rogulska, Halina Gluchowska. The effect of soft-segment structure on the properties of novel thermoplastic polyurethaneelastomers based on an unconventional chain extender. PolymerInternational 60, 652-659 (2011).

AFM phase images of TPUs obtained with polyether (PT-40) , polyester (PC-40) and polycarbonate diol (PH-40)

Polyether Polyester Polycarbonate

15




State of the art

Vanesa Garca-Pacios, Manuel Colera, Yoshiro Iwata, Jos Miguel Martn-Martnez.Incidence of the polyol nature in waterborne polyurethane dispersions on theirperformance as coatings on stainless steel. Progress in Organic Coatings DOI:http://dx.doi.org/10.1016/j.porgcoat.2013.05.007

PUD

%

R

e

t

e

n

t

i

o

n

o

f

c

h

e

m

i

c

a

l

r

e

s

i

s

t

a

n

c

e

16

Thermal degradation: 15 days @120 CWeathering: ISO 11507




Limitations of POLYCARBONATE DIOL (PCD) in polyurethane

coatings

Moderate flexibility and elastomeric properties

Improvable resistance to hydrolysis

Lower toughness and high stiffness

17




OBJECTIVE

Synthesis and structural characterization of PUDsobtained with mixtures of polyether and polycarbonatepolyols with similar molecular weight.

Establish structure-properties relationships in PUcoatings.

Compare the performance of the PU coatings obtainedwith mixtures of polyether and polycarbonate polyols beforeand after thermal degradation and weathering.

18



Results ConclusionsExperimentalIntroduction

MATERIALS

Polyols

Polyether (polytetramethylene glycol) (Mw: 1000 Da) Polycarbonate of 1,6 hexane diol (Mw: 1011 Da) UBE

Chemical Europe (Spain)

Diisocyanate: IPDI Internal emulsifier : DMPA Neutralization agent : TEA Chain extender : Hydrazine Acetone Deionized water.

Others

19




SYNTHESIS OF WATERBORNE POLYURETHANE DISPERSIONS

Stirrer

water

water

Desecator

Nitrogen

Acetone Method

20




PU COATINGS CHARACTERIZATION

Drying time

Thickness

Persoz hardness

Pencil hardness

Gloss

21




COATINGS CHARACTERIZATION

Yellowness index

Chemical resistance against ethanol

Cross-hatch adhesion adhesion tosubstrate

Ageing tests

22



Experimental ConclusionsResultsIntroduction

PCD (eq%)

Mw = 1000 Da Mw = 2000 Da

Drying time (h) Drying time (h)

0

50

75

90

100

>6

1

1

1

6

1.25

1.75

2




0

10

20

30

40

50

60

70

80

0 20 40 60 80 100

T

h

i

c

k

n

e

s

s

(

m

)

Polycarbonate of 1,6 HD (eq%)

PU coating

Thermal degradation

Weathering

THICKNESSMw = 1000 Da

24




0

10

20

30

40

50

60

70

80

0 20 40 60 80 100

T

h

i

c

k

n

e

s

s

(

m

)


PU coating

Thermal degradation

Weathering

THICKNESSMw = 2000 Da

25




0

50

100

150

200

250

300

350

400

0 50 75 90 100

P

e

r

s

o

z

h

a

r

d

n

e

s

s

(

n

o

.

o

s

c

i

l

l

a

t

i

o

n

s

)


PU coating

Thermal degradation

Weathering

PERSOZ HARDNESSMw = 1000 Da

30




PERSOZ HARDNESSMw = 2000 Da

0

50

100

150

200

250

300

350

400

0 50 75 90 100

P

e

r

s

o

z

h

a

r

d

n

e

s

s

(

n

o

.

o

s

c

i

l

l

a

t

i

o

n

s

)


PU coating

Thermal degradation

Weathering

31



6B 5B 4B 3B 2B B HB F H 2H 3H 4H 5H 6H


PENCIL HARDNESS

PCD (eq%)

Pencil hardness (Mw = 1000 Da) Pencil hardness (Mw = 2000 Da)

PU coating

Thermal degrad. Wheathering

PU coating

Thermal degrad. Wheathering

0 6B 2B - 6B 4B -

50 5B 6B 6B 6B 6B 6B

75 5B 6B F 6B 4B 3B - 4B

90 4B 4B F 6B 4B 5B

100 4B 3B 4B 6B 3B 4B

SOFT HARD

32




0

20

40

60

80

100

0 50 75 90 100

G

l

o

s

s

6

0

(

a

.

u

.

)


PU coating Thermal degradation Weathering

GLOSS 60Mw = 1000 Da

28




GLOSS 60Mw = 2000 Da

0

20

40

60

80

100

0 50 75 90 100

G

l

o

s

s

6

0

(

a

.

u

.

)



29




0

15

30

45

60

75

90

0 20 40 60 80 100

Y

e

l

l

o

w

n

e

s

s

i

n

d

e

x


PU coating

Thermal degradation

Weathering

YELLOWNESSMw = 1000 Da

26




YELLOWNESSMw = 2000 Da

0

15

30

45

60

75

90

0 20 40 60 80 100

Y

e

l

l

o

w

n

e

s

s

i

n

d

e

x


PU coating

Thermal degradation

Weathering

27




CHEMICAL RESISTANCEMw = 1000 Da

3

3.5

4

4.5

5

0 50 75 90 100

C

h

e

m

i

c

a

l

r

e

s

i

s

t

a

n

c

e

(

a

.

u

.

)



33




CHEMICAL RESISTANCEMw = 2000 Da

3

3.5

4

4.5

5

0 50 75 90 100

C

h

e

m

i

c

a

l

r

e

s

i

s

t

a

n

c

e

(

a

.

u

.

)



34



Experimental Results ConclusionsIntroduction

Polyether polyol-based coatings properties are improved by blendingpolycarbonate polyol as copolyol:

Shorter drying time of the dispersions

Enhancement of scratch resistance

Higher coating hardness

Polyether polyol-based coatings durability is benefited by adding polycarbonatepolyol as copolyol:

Less initial properties modification after ageing

Lower yellowish of the coating due to degradation

35



THANK YOU FOR YOUR

ATTENTION

Documents

abrafati