Uso de policarbonato diol para poliuretano de alto rendimiento Dr. Manuel Colera Departamento de I+D+i y Nuevos Negocios

Outline of the presentation

1. UBE Corporation Europe S.A. 2. Polycarbonate diol for PUD 3. High-performance of PUD polycarbonate diol: coatings

due

to

4. High-performance of PUD polycarbonate diol: adhesives

due

to

5. Conclusions 2

UBE Industries Ltd.

Nombre corporativo: Sede: Año de fundación: Empleados (2009): Volumen de ventas (2009):

UBE Industries Ltd. Ube / Tokio (Japón) 1.897 11.264 4.150 MM Eur.

Química básica y plásticos Especialidades químicas Cementos y materiales de construcción Maquinaria y metalurgia Energía y medio ambiente

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UBE en el mundo

4

UBE en Europa

Poliamidas y Copoliamidas Caprolactama y Fertilizantes Química Fina

1967

2001

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Química Fina Productos Farmacéuticos Especialidades Químicas Polibutadieno Maquinaria

1960

UBE en España –

Castellón es la sede central europea de UBE desde 2001.

–

Actividad en I+D: • Inversión en I+D: 1,5% de las ventas locales. • Actividades principales de I+D: – Química fina (creado en 1999, 10 personas): i. Desarrollo de nuevos productos de química fina (PCD, HDL, PDL) ii. Nuevo proceso de producción de laurilactama iii. Reactor fotocatalítico para tratamiento de aguas – Plásticos de ingeniería (creado en 2005, 10 personas): i. Terpolímeros (Terpalex) ii. Film de poliamida con altas propiedades retráctiles iii. Tubos para combustibles y biodiesel con altas propiedades de barrera •

Convenios de colaboración: Universidades españolas (UV, UPV, UJI, UAM, UCM), CSIC e institutos Tecnológicos (AIMPLAS, AINIA)

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Outline of the presentation

1. UBE Corporation Europe S.A. 2. Polycarbonate diol for PUD 3. High-performance of PUD polycarbonate diol: coatings

due

to

4. High-performance of PUD polycarbonate diol: adhesives

due

to

5. Conclusions 7

Terminal – Backbone – Bridge – Backbone – Terminal O R

R HO

O

O

OH

n Polycarbonate diol lower reactivity

Polyester diol poor hydrolysis resistance

Polyether diol low radical oxidation stability

Desired mechanical properties can be achieved using an optimum backbone (R) R

Durability properties: Carbonate vs. ester & ether as bridge − Higher hydrolysis & chemical resistance − Excellent stain resistance − Better heat & weather resistance

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Polycarbonate diol grades tested in this study (Mw = 1000) Homopolymer: − UH100: backbone: 1,6-hexanediol

Copolymer: − PH100: backbone: 1,5-pentanediol 1,6-hexanediol

− BH100: backbone: 1,4-butanediol, 1,6-hexanediol

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Acetone method

Waterborne polyurethane dispersions were prepared by way of acetone method: 1.Polyol+(80ºC)+stirring (220rpm) 2. DMPA 3. IPDI 4. Acetone (45-55ºC) 5. TriEthylAmine (acetone solution) 6. Hydrazyne (aqueous solution) 7. Distillate water + stirring (440rpm) 8. Removal of acetone (50ºC)

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Outline of the presentation

1. UBE Corporation Europe S.A. 2. Polycarbonate diol for PUD 3. High-performance of PUD polycarbonate diol: coatings

due

to

4. High-performance of PUD polycarbonate diol: adhesives

due

to

5. Conclusions 11

Coatings – Properties1 Properties Chemical resistance Hardness Persoz Pencil hardness Gloss 60o Yellowness index Cross-cut test

Method ISO 4211:1979 ISO 1522:2007 ISO 15184:1998 ISO 2813:1999 ASTM D1925-70 ISO 2409:2007

Unit

%

BH-100 4 72 3B 96 7.4 0

1 Stainless

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

Coatings based on polycarbonate diol show: − Better chemical resistance: double than PPG or PBA-based coatings − Improved scratch resistance: harder coatings acc. to pencil test − Higher gloss − Lower yellowish − Better adhesion to substrate

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PH-100 4 62 3B 99 7.7 0

UH-100 4 121 4B 78 8.9 0

PPG2 2 33 5B 79 10.8 1

PBA3 2 109 6B 38 9.8 2

ISO 4211:1979

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

Chemical resistance

Chemical resistance

diols.

5 4 3 2 Stainless steel

1

5 4 3 2 1

ABS 0

Polyester-based PUD

UBE ETERNACOLL® based PUD

Coatings – Chemical resistance

Stainless steel ABS

0

Substrate

Substrate

Oak wood

UH50

Oak wood UH100

UH200 UH300

Hard segments

PCD grade

− Chemical resistance of PUD coatings just slightly depends on substrate and can be adjusted by polycarbonate diols molecular weight & hard segments content. − For every substrate, there is an suitable grade of polycarbonate diol for providing an excellent chemical resistance to PUD coatings.

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Durability assays Heat resistance: - On stainless steel plates - Retention of hardness Persoz, gloss 60º and thickness: Px

P

- Increment of yellowness index:

Px − P ⋅ 100 P

Artificial weathering: - On stainless steel plates - Retention of hardness Persoz, thickness, cross-cut Countertypes: - PPG: Polypropylene glycol, Mw ~ 1000 - PBA: Poly(1,4-butylene adipate), Mw ~ 1000

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⋅ 100

Coatings – Heat resistance

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

UBE ETERNACOLL®

Retention of gloss 60o

Retention of hardness Persoz Retention (%)

Retention (%)

200

100

175 80

150 125

60

100 40

75 50

20

25 0

0 Polycarbonate diol grade

Polycarbonate diol grade

Increment of yellow index on oak wood (%) Increment of yellowness index

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Increment (%)

1500

30

1250

25

1000

20

750

15 500

10 250

5 0 Polycarbonate diol grade

0 0

15

5

10

15

20

Coatings – Artificial ageing

ISO 11507:2007

UBE ETERNACOLL®

Retention of hardness Persoz

Retention of thickness

Retention (%)

Retention (%)

100

100

80

80

60

60

40

40

20

20

0

0 Polycarbonate diol grade

Polycarbonate diol grade

Worst cross cut adhesion, even after ageing

Loss of thickness

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Outline of the presentation

1. UBE Corporation Europe S.A. 2. Polycarbonate diol for PUD 3. High-performance of PUD polycarbonate diol: coatings

due

to

4. High-performance of PUD polycarbonate diol: adhesives

due

to

5. Conclusions 17

Adhesives – Properties1 Properties Drying time4 Cross-cut test T-peel test Lap-shear strength

Method ASTM D5895-03 ISO 2409:2007 ISO 11339:2010 ISO 4587:2003

Unit h kN/m kPa

BH-100 90%

24 ± 1 h

48 ± 1 h

Increment of T-peel test

HR > 90%

Increment (%)

200,0

150,0

100,0

50,0

time (days)

0,0 Polycarbonate diol grade

Cycle D11 Water immersion, cold and dry heat

T (ºC)

72 ± 1 h

24 ± 1 h

72 ± 1 h HR < 15%

Increment of T-peel test Increment (%)

20,0

15,0

10,0

5,0

time (hours)

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0,0 Polycarbonate diol grade

Outline of the presentation

1. UBE Corporation Europe S.A. 2. Polycarbonate diol for PUD 3. High-performance of PUD polycarbonate diol: coatings

due

to

4. High-performance of PUD polycarbonate diol: adhesives

due

to

5. Conclusions 20

Using polycarbonate diol, we can conclude that… Coatings based on polycarbonate diol show: − Better chemical resistance − Improved scratch resistance − Higher gloss − Lower yellowish

Coatings

− Better adhesion to substrate

Chemical resistance of coatings: − Can be adjusted by polycarbonate diols molecular weight & hard segments content. − Depending on substrate, there is an suitable grade of polycarbonate diol.

Adhesives based on polycarbonate diol show: − Shorter complete drying time

Adhesives

− Stronger adhesion to substrates − Improved peel resistance − Enhanced lap-shear strength

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Flooring

Artificial leather

Wood coating & paints

Leather finishing

Using polycarbonate diol, we can enhance coatings for applications such as…

Automotive

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Automotive finishing

Thanks for your attention !!