rigid polyurethane foam from grape seed oilcongresse2kw.uclm.es/files/2013/12/gc-o3.pdf · rigid...

Título presentación

Institute of Chemical and Environmental Technology

Chemical Engineering Department

University of Castilla La Mancha

Ciudad Real, Spain

RIGID POLYURETHANE FOAM FROM

GRAPE SEED OIL

Antonio Díaz-Medino

Manuel Carmona

Ángel Pérez

J.F. Rodríguez

RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL


Ref: CTQ2008-06350

BES-2009-015202


http://www.mineco.gob.es/

Título presentación Título presentación

INTRODUCTION • Basic chemistry of polyurethane

• Renewable polyols

• Why using grape seed oil as a raw material?

SCOPE

• Epoxidation of Grape Seed Oil

• Epoxide ring opening and formation of the vegetable polyol

• Synthesis of polyurethane foam



1. Introduction

1.1. Basic chemistry of polyurethane

n HO-R-OH + n O=C=N-R´-N=C=O [ -CO-NH-R´-NH-CO-O-R-O- ]n

Polyol Isocianate Uretane


Biopoliol

?


1. Introduction

1.1. Basic chemistry of polyurethane

Formation of the initial alcoholate

Propagation



1.2. Renewable polyol

Biomass

Waste

Vegetable oils

Starch

Terpenes

...

Polimers

Cosmetics

Drugs

...

Biodegradation

Assimilation Extraction

Recycling

Processing Utilization



1. Introduction

1.2. Renewable polyol


Triglycerides

Vegetable

polyol


1. Introduction

1.3. Why using grape seed oil as a raw material?


Biopolyol production from grape seed oil

constitutes an economic

alternative for valuation of by-product

obtained from the wine

manufacture in the region of Castilla-La

Mancha (Spain)

Fatty acids Composition % weight

Lauric C12:0 0.0

Myristic C14:0 0.1

Palmitic C16:0 6.9

Palmitoleic C16:1 0.1

Estearic C18:0 4.0

Oleic C18:1 19.0

Linoleic C18:2 69.1

Linolenic C18:3 0.3

Arachidic C20:0 0.3

Gadoleic C20:1 0.0

Behenic C22:0 0.0

Erucic C22:1 0.0

Lignoceric C24:0 0.0

Nervonic C24:1 0.0


2. Epoxidation of grape seed oil

2.1. Mechanism reaction


Prileschajew’s Reaction Experimental conditions:

-Temperature: 60ºC

-Molar ratios: 0.5 and 2 between

acetic acid and hydrogen

peroxide respect to the

unsaturation content

-Catalyst: 2 % by weight of

sulphuric acid.



2.2. Experimental equipment and analytical techniques


Experimental Equipment

•UNE 53985-2 •UNE-EN 14111

•AOCS Official Method Cd 9-57

•AOCS Official Method Tx 1a-66

Determination of Hydroxyl

Index

Determination of Oxirane

Oxigen

Determination Acid Value

Determination of Iodine Index

Standards for the characterization of the products:

Analytical methods:

Gel permeation chromatography (GPC) Infrared Spectroscopy (FTIR)



2.3. Results

Temperature effect


T (ºC) Iodine Value

(g I2/100g) Conversion % Oxirane oxygen

Hydroxyl Value

(mg KOH/ g) ŋ

50 23.38 83.1 5.75 25.4 65.15

60 9.85 92.9 5.87 31.98 66.51

70 5.21 96.2 5.65 47.02 64.02

80 4.69 96.6 3.97 100.58 44.98

50 60 70 80

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

Mol of double bond trasformed

Mol of epoxidized double bond

Mol of hydroxylated double bond

Mol of dimerized double bond

Mol

/ 10

0g

T (ºC)



2.3. Results

Temperature effect


10 11 12 13 14 15 16 17

Retention Volume (ml)

50ºC

60ºC

70ºC

80ºC

T (ºC) Mw (g/mol)

50 1010

60 1152

70 1281

80 1599

10 11 12 13 14 15 16 17

Grape Seed Oil


Dimers

Trimers



2.3. Results

Purification Process


Purification by

successive

washes

•Acid Value: 10

mg KOH/g

Ion Exchange

Amberlite IRA 402

0.7 g de resin /g

product

•Acid Value 0.06 mg

KOH/g



2.3. Results

Kinetic model


4000 3500 3000 2500 2000 1500 1000 500

20

40

60

80

100

120

Grape Seed Oil

Tra

nsm

itta

nce

(%

)

Wave Number (cm-1)

4000 3500 3000 2500 2000 1500 1000 500

0

50

100

0

50

100

0

50

100

0

50

100

0

50

100

Tra

nsm

ittan

ce (

%)

Wave number (cm-1)

240 min

Tra

nsm

ittan

ce (

%) 180min

Tra

nsm

ittan

ce (

%) 120min

Tra

nsm

ittan

ce (

%) 60min

Tra

nsm

ittan

ce (

%) 30min

Double

Bond

Double

Bond

Hydroxyl

Epoxide



2.3. Results

Kinetic model


1) A+B↔C+D

2) C+E→F+A

3) F+D→G

4) F+G→H

5) F+H→I

A: Acetic acid

B:Hydrogen

Peroxide

C: Peracetic Acid

D: Water

E: Double Bond

F: Epoxide

G:Hydroxyl

H: Dimers

I: Trimers



2.3. Results

Kinetic model


0 50 100 150 200 250

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

[ ]

(m

ol/

l)

Time (min)

[Epoxide]exp

[Double Bond]exp

[Hydroxyl]exp

[Dimer]exp

[Epoxide]mod

[Double Bond]mod

[Hydroxyl]mod

[Dimer]mod

Kinetic Constants l·mol-1·min-1

K0 7.30E-03

K0´ 2.58E-02

K1 1.18E-01

K2 7.17E-05

K3 7.49E-01

K4 1.00E-12


3. Epoxide ring opening and formation of the vegetable polyol

3.1. Experimental equipment and analytical techniques


Experimental Equipment

GPC

FT-IR

AOCS Official Method Cd 9-57 AOCS Official Method Tx 1a-

66

Standards for the characterization of the products:



3.2. Mechanism reaction


Experimental conditions:

-Temperature: 80ºC

-Pressure: 50 Bar

-Molar ratios: 1.1 between Glycerol

and the Oxirane concentration.

-Catalyst: 10 mg of DMC Catalyst

(Cobalt-Zinc Double Metal Cyanide

Complex).

-Time: 2h

Epoxidized

oil + Glycerol = Vegetable

Polyol

Epoxidized

oil

Glycerol Vegetable

Polyol

+ =



3.3. Results


10 11 12 13 14 15 16 17


Epoxidized Oil

Vegetable Polyol

4000 3500 3000 2500 2000 1500 1000 500

0

50

100

0

50

100

0

50

100

Tra

nsm

itta

nce

(%

)

Wave Number (cm-1)

Vegetable Polyol

Tra

nsm

itta

nce

(%

) Epoxidized Oil

Tra

nsm

itta

nce

(%

) Grape Seed Oil% Oxirane

Oxygen

Hydroxyl Value

(mg KOH/ g) Mw (g/mol)

Epoxidised oil 5.87 31.98 1151.75

% Oxirane

Oxygen

Hydroxyl Value

(mg KOH/ g)

Mw

(g/mol)

Vegetable

Polyol 1.06 80.84 1800.94

Hydroxyl


4. Sinthesis of Polyurethane Foam

4.1. Results


Polyol 100

Water 2,5

Tegostab 1,5

Tegoamin BDE 2,5

MDI (Methylene Diphenyl

Diisocyanate ) 100

Scanning Electron

Microscopy (SEM)

Rigid polyurethane foam

from grape seed oil.

Título presentación RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL

5. Conclusions

1. Epoxidation and subsequent ring opening allowed the functionalization of

vegetable oils for the production of polyols having different molecular weight and

functionality.

2. The epoxidation reaction of vegetable oil exhibited the highest selectivity towards

epoxide functional groups. Nevertheless, this selectivity was dependent on

temperature.

3. The ion exchange technology by using Amberlite IRA-402 allowed to get the total

removal of residual sulphuric acid and acetic acid from the epoxidized oil.

4. A polyol having a maximum acid value of 0.07 mg KOH/, a hydroxyl number 81 mg

KOH/g and a molecular weight of 1800 g/mol, proper to produce RPU foams was

synthesized.

5. A rigid polyurethane foam exhibiting good mechanical and physical properties

was synthesized from the natural grape seed oil.


Institute of Chemical and Environmental Technology

Chemical Engineering Department

University of Castilla La Mancha

Ciudad Real, Spain

Thank you for your attention

Antonio Díaz-Medino

Manuel Carmona

Ángel Pérez

J.F. Rodríguez


rigid polyurethane foam from grape seed oilcongresse2kw.uclm.es/files/2013/12/gc-o3.pdf · rigid...

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