RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL

Transcription

1 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

2 Ref: CTQ BES

3 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

4 1. Introduction 1.1. Basic chemistry of polyurethane Biopoliol? n HO-R-OH + n O=C=N-R -N=C=O [ -CO-NH-R -NH-CO-O-R-O- ] n Polyol Isocianate Uretane

5 1. Introduction 1.1. Basic chemistry of polyurethane Formation of the initial alcoholate Propagation

6 1.2. Renewable polyol Biodegradation Assimilation Biomass Extraction Waste Utilization Recycling Polimers Cosmetics Drugs... Processing Vegetable oils Starch Terpenes...

7 1. Introduction 1.2. Renewable polyol Triglycerides Vegetable polyol

8 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: Linoleic C18: 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

9 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.

10 2. Epoxidation of grape seed oil 2.2. Experimental equipment and analytical techniques Standards for the characterization of the products: AOCS Official Method Tx 1a-66 AOCS Official Method Cd 9-57 Determination of Hydroxyl Index Determination of Oxirane Oxigen Determination of Iodine Index Determination Acid Value UNE-EN UNE Experimental Equipment Analytical methods: Gel permeation chromatography (GPC) Infrared Spectroscopy (FTIR)

11 Mol / 100g 2. Epoxidation of grape seed oil 2.3. Results Temperature effect T (ºC) Iodine Value (g I 2 /100g) Conversion % Oxirane oxygen Hydroxyl Value (mg KOH/ g) ŋ ,8 0,7 0,6 Mol of double bond trasformed Mol of epoxidized double bond Mol of hydroxylated double bond Mol of dimerized double bond 0,5 0,4 0,3 0,2 0,1 0, T (ºC)

12 2. Epoxidation of grape seed oil 2.3. Results Temperature effect Grape Seed Oil T (ºC) Mw (g/mol) Retention Volume (ml) Trimers Dimers 50ºC 60ºC 70ºC 80ºC Retention Volume (ml)

13 2. Epoxidation of grape seed oil 2.3. Results Purification Process Purification by successive washes Acid Value: 10 mg KOH/g Ion Exchange Amberlite IRA g de resin /g product Acid Value 0.06 mg KOH/g

14 Transmittance (%) Transmittance (%) Transmittance (%) Transmittance (%) Transmittance (%) Transmittance (%) 2. Epoxidation of grape seed oil 2.3. Results Kinetic model Grape Seed Oil min Double Bond Double Bond min min Wave Number (cm -1 ) min min 50 0 Hydroxyl Epoxide Wave number (cm -1 )

15 2. Epoxidation of grape seed oil 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

16 [ ] (mol/l) 2. Epoxidation of grape seed oil 2.3. Results Kinetic model [Epoxide] exp [Double Bond] exp [Hydroxyl] exp [Dimer] exp [Epoxide] mod Kinetic Constants l mol-1 min [Double Bond] mod [Hydroxyl] mod [Dimer] mod K E K E K E K E K E K E-12 Time (min)

17 3. Epoxide ring opening and formation of the vegetable polyol 3.1. Experimental equipment and analytical techniques GPC FT-IR Standards for the characterization of the products: Experimental Equipment AOCS Official Method Cd 9-57 AOCS Official Method Tx 1a- 66

18 3. Epoxide ring opening and formation of the vegetable polyol 3.2. Mechanism reaction Epoxidized oil Epoxidized oil + Glycerol = Vegetable Polyol + = Glycerol Vegetable Polyol 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

19 Transmittance (%) Transmittance (%) Transmittance (%) 3. Epoxide ring opening and formation of the vegetable polyol 3.3. Results % Oxirane Oxygen Hydroxyl Value (mg KOH/ g) Mw (g/mol) 100 Grape Seed Oil Epoxidised oil Vegetable Polyol % Oxirane Oxygen Hydroxyl Value (mg KOH/ g) Mw (g/mol) Epoxidized Oil 50 Epoxidized Oil Vegetable Polyol 0 Vegetable Polyol Hydroxyl Retention Volume (ml) Wave Number (cm -1 )

20 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 Rigid polyurethane foam from grape seed oil. Scanning Electron Microscopy (SEM)

21 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.

22 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