Processes for obtaining a polyol from palm oil, polyols obtained from the processes, products derived from such polyol and their method of preparation

Abstract

The present invention relates to the process for production of a polyol from palm oil and of rigid polyurethane foams prepared from said polyol derived from palm oil. On the one hand, this invention provides a method for obtaining monomeric polyols from palm oil that have hydroxyl number between 50 450 mgKOH/g sample. The polyols of the present application may be obtained by means of a procedure based on the following four mother routes: Route 1: maleinisation of the fatty acids of palm oil; Route 2: glycerolysis of palm oil; Route 3: trancesterification of palm oil; and Route 4: epoxidation of unsaturated carbon-carbon links of palm oil. Additionally, other modalities of the invention permit obtaining polyols from the combination of these mother routes. In other realizations of the invention polyurethanes are prepared from polyols obtained through any of the four routes or by combinations of the same.

Claims

1. A method for the production of polyol from palm oil, characterized by comprising the following steps: a. mixing a source of palm oil with formic acid in the presence of heat; b. adding hydrogen peroxide to the mixture of step a) and shake to obtain a reaction product of step b); c. washing the reaction product of step b) with water at a temperature between 55 C. and 65 C. to obtain a product of step c); d. washing the product obtained in the step c) with 5% sodium bicarbonate to obtain a product of reaction of step d); e. washing the product of reaction of step d) with water at a temperature between 55 C. and 65 C. to obtain a product of step e); f. washing the product obtained in step e) with 5% sodium chloride to obtain an aqueous phase and an organic phase; g. discarding the aqueous phase obtained in step f) to obtain an epoxidized oil; h. mixing the epoxidized oil obtained in step g) with glycerol and a catalyst, in the presence of heat and agitation, wherein the catalyst is sodium hydroxide; i. neutralizing the sodium hydroxide catalyst with drops of phosphoric acid to avoid the formation of soap; and j. obtaining the polyol resulting in a hydroxyl number between 400 and 440 mg KOH/g sample, wherein step h) has a reaction temperature that varies between 170 C. and 190 C. and has a time of reaction that varies between 40 and 50 minutes.

2. The method in accordance with claim 1, wherein the source of palm oil in step a) is the olein phase of crude palm oils.

3. The method in accordance with claim 1, wherein the source of palm oil in step a) is the olein phase of refined bleached and deodorized palm oil (RBD).

4. The method in accordance with claim 1, wherein step b) has a reaction temperature that varies between 45 C. and 55 C. and has a time of reaction that varies between 1 and 2 hours after the addition of hydrogen peroxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a flow chart exemplifying the production of a polyol from palm oil through Route 1.

(2) FIG. 2 shows a flow chart exemplifying the production of a polyol from palm oil through Route 2.

(3) FIG. 3 shows a flow chart exemplifying the production of a polyol from palm oil through Route 3.

(4) FIG. 4 shows a flow chart exemplifying the production of a polyol from palm oil through Route 4.

(5) FIG. 5 shows a flow chart exemplifying the production of a polyol from palm oil through the combination of Route 4 and Route 2.

DETAILED DESCRIPTION THE INVENTION

(6) The present invention relates to a process for the production of a polyol from palm oil and of rigid polyurethane foams with a polyol derived from palm oil mixed with a commercial polyol.

(7) The processes for the production of the polyols based on palm oil will be described by referring to FIGS. 1 to 5.

(8) FIG. 1 describes route 1 in a general manner. Specifically, this route includes two different methods, the first comprising the maleinization of palm oil through heating of the same and its mixture with maleic anhydride. The mixture is later reacted in the presence of reflux condenser and an inert atmosphere, and the reaction happens there during an established period, obtaining the polyol.

(9) The second method corresponds to the maleinization of fatty acids, beginning with a mixture of palm oil and sodium hydroxide and an ethanol-water solution. The mixture obtained is heated and stirred. Subsequently a small amount of concentrated sulfuric acid is added, showing the separation of the organic phase and the aqueous phase.

(10) Then, saturated sodium chloride solution is added. After of the complete separation of the phases, the aqueous phase is eliminated. By means of warming and agitation of the organic phase the fatty acids may be obtained, which are mixed with previously blocked glycerol through an MEK (Methyl ethyl ketone) reaction, carried out with sulfonic toluene acid as a catalyst and toluene as a solvent. The fatty acids then react with the glycerol blocked in the presence of a catalyst, sulfonic toluene acid, and heat. The product of this reaction is evaporated to obtain blocked monoglyceride, which subsequently reacts in a nitrogen and maleic anhydride atmosphere. Sulfuric acid is added to the product of this reaction. The organic phase obtained is washed and submitted to evaporation to finally obtain the polyol.

(11) Now thus, FIG. 2 summarizes route 2 which corresponds to the production of polyol from palm oil through glycerolysis. This route comprises the reaction between the palm oil and glycerol, terbutanol as a solvent and sodium hydroxide as a catalyst in the presence of heat. The product of this reaction is neutralized with hydrochloric acid and submitted to evaporation for elimination of the solvent. The phase obtained is separate through the addition of n-hexane, allowing the residual glycerin to be discarded from the polyol finely obtained.

(12) FIG. 3 summarizes route 3, related to the production of polyol from palm oil modified through transesterification with pentaerythritol. This route comprises the reaction between palm oil, pentaerythritol and lead oxide in the presence of heat with continuous agitation and in an inert nitrogen atmosphere. The product of the reaction is treated with n-hexane, allowing formation of two phases: the precipitate that contains glycerol is then discarded and the other phase is submitted to evaporation to obtain the polyol.

(13) On the other hand, route 4 is summarized in FIG. 4 and comprises a process of epoxidation of the fatty acid methyl esters of (FAME), which are previously obtained through methanolysis of palm oil. This methanolysis comprises the reaction between the palm oil and methanol in presence of sodium hydroxide. Subsequently the glycerin phase is discarded and the phase of interest is washed with phosphoric acid, discarding the solids formed and neutralizing. The product (FAME) is submitted to evaporation to remove the excess methanol.

(14) In this way, the FAME are made to react with formic acid in the presence of hydrogen peroxide. The reaction is evidenced by the color change from orange to clear yellow. Subsequently, the product is washed with water, sodium bicarbonate and sodium chloride, neutralizing the solution, which then undergoes evaporation to remove the moisture and allow obtaining the polyol.

(15) FIG. 5 describes other modalities of the invention, which correspond to the combination of routes 2 and 4 and are established in more detail below.

(16) One of these modalities allows obtaining polyol from of the olein phase of crude palm oil, using lead oxide as a catalyst. The method is then carried out through the epoxidation of the olein phase of crude palm oil with formic acid, in the presence of heat. Subsequently hydrogen peroxide is added and stirred. The reaction is evidenced by the change of color from orange to clear yellow. The product of the reaction is washed with water, sodium bicarbonate and sodium chloride, discarding the aqueous phase and subjecting the organic phase to glycerolysis (reaction with glycerin) using lead oxide as catalyst to thus obtained the polyol.

(17) Another mode of the invention corresponds to obtaining the polyol from the olein phase of crude palm oil using NaOH as a catalyst. This mode comprises the same steps mentioned for the previous mode, with the difference that the glycerolysis of the organic phase is done in the presence of sodium hydroxide, with a posterior neutralization of the excess catalyst with phosphoric acid.

(18) Yet another mode of the invention allows obtaining polyol from the olein phase of refined, bleached and deodorized palm oil (RBD). For this purpose the same steps are used as for the previous embodiments, using the raw material mentioned and sodium hydroxide as a catalyst in the glycerolysis.

(19) The last mode corresponds to obtaining polyol from of the olein phase of refined, bleached and deodorized palm oil (RBD), but employing lead oxide as catalyst. In the same way, the steps already mentioned above are used, with the exception that the olein phase of RBD is used as raw material and lead oxide as catalyst in the glycerolysis.

(20) The routes and modalities described thus allow obtaining the polyurethane foams through the reaction of the polyols produced with methylene diphenyl diisocyanate (MDI).

(21) For said purpose, the polyol obtained is mixed with a short chain polyol (diethylene 1,6 butanediol), a catalyst (dibutyltin dilaurate, tin octoate, tertiary amine catalysts, water, a surfactant (Silicone or organosiloxane-based), and methylene diphenyl diisocyanate (MDI). The reaction leads to the formation of foam of rigid polyurethane.

(22) Depending on the hydroxyl number obtained for the polyol, flexible, semi-rigid and rigid polyurethane foams may be obtained, as indicated below:

(23) TABLE-US-00001 Hydroxyl No. 50 100 150 200 250 300 350 400 Foam Type Flexible Semi-rigid Rigid

(24) Within of the applications that these types of foam have, the following may be noted:

(25) TABLE-US-00002 Polyurethane Application Rigid Molded parts, soles for footwear Semi-rigid Thermal insulation, soundproofing insulation, waterproofing, floral foam, chairs adapted to the user (mainly for disabled people) Flexible Foam for bras, mattresses

EXAMPLES

(26) The following examples is presented with the purpose of illustrating the invention and are in no way a limitation, inasmuch as the person moderately skilled in the matter can recognize the possible variations.

Example 1Obtaining Polyol Using the First Method of Route 1

(27) 300 grams of palm oil were laced in the 250 ml reaction flask. Separately, 65.7 grams of maleic anhydride were weighed and were added to the reaction flask. The same was heated to 180 C. Subsequently the reflux condenser was adapted and the reaction flask placed on a heating iron with magnetic agitation to 1300 allowing the reaction to take place during 3 hours in a low nitrogen atmosphere. The product of this reaction is the maleinised oil that was cooled to the 100 C. and to which an amount of 30.85 g of glycerol was added. The reaction was allowed to continue and the acidity index tracked every 30 minutes up to a value of 90 mg KOH/g sample, thus obtaining the polyol.

Example 2Obtaining Polyol Using the Second Method of Route 2

(28) 150 grams of palm oil were placed in a 1000 ml precipitation glass. Subsequently 33.5 g of NaOH and 100 ml of a 1:1 ethanol-water solution were added. The reaction was carried out at a temperature of 80 C. during 30 minutes. The solution was stirred slightly in manual form. Then, drops of concentrated sulfuric acid were added. The separation of the organic phase and the aqueous phase was then observed. To complete the solution, 100 ml of saturated sodium chloride solution were added. The solution was left at rest while the phases separated. Subsequently the aqueous phase was discarded and is the rest transferred to a separation funnel, washing with hot water. The pH of discarded wash water was measured to verify it was neutral. Separately, the organic phase was transferred to an lateral release Erlenmeyer, the temperature was increased to 80 C., and the phase was stirred continuously; This procedure was carried out in a vacuum. The fatty acids were obtained as a product.

(29) 70.83 grams of glycerol were separately weighed and placed in a 500 ml reaction flask. Then 62.90 grams of MEK (methyl ethyl ketone) were added together with 1.8 grams of sulfonic toluene acid and 70 ml of toluene. The reaction was carried out at 90 C. during 2 hours. In this way the blocked glycerol was obtained.

(30) To 40 grams of the fatty acids obtained above, 19.5 grams of blocked glycerol were added in a 500 ml reactor. Subsequently 1.8 grams of sulfonic toluene acid were added and the remaining solution underwent heating at 90 C. with magnetic agitation of 1200 rpm, leaving the reaction to develop for three and a half hours. Then the product of the reaction was moved to a separation funnel, also washing with hot water and measuring the pH of outgoing wash water until it was neutral. The product of this washing is consecutively put under rotoevaporation during 3 hours at a temperature of 90 C. and in vacuum conditions. By these means the blocked monoglyceride was obtained. Afterwards 25 grams of the blocked monoglyceride are taken and placed in a 500 ml reaction flask. Subsequently 9.2 grams of maleic anhydride are added and the reaction is carried out at 200 C. with magnetic agitation during 3 hours in a low nitrogen atmosphere. The product is left to cool to 100 C. without stopping the agitation. Four drops of concentrated sulphuric acid are immediately added slowly, dissolved in 3 ml of distilled water, and the reaction is allowed for another hour. A hot water wash is then carried out and the result left decanting throughout the night.

(31) The following day is the aqueous phase was discarded and the organic phase was rotoevaporated at 80 C. during an hour and a half, thus obtaining the polyol.

Example 3Obtaining Polyol Using Route 2

(32) In a 500 ml reaction flask, coupled with a reflux condenser, a heating surface and a magnetic agitator, 64.5 grams of palm oil were added, along with 40 grams of glycerol, 20 ml of terbutanol and 4.5 grams of sodium hydroxide. The conditions of operation were, temperature: 90 C., time: 2 hours and agitation: 1300 rpm.

(33) Once the time of reaction had elapsed the mixture was cooled to temperature and the catalyst neutralized with an HCl solution at 10%, verifying the pH with a paper indicator. The glycerin and the residual solvent were then removed and the product of interest was rotoevaporated to ensure the complete elimination of solvent in the solution. The rotoevaporation temperature was 90 C. and was carried out during 3 hours.

(34) Finally the phases were separated in a separation funnel, where 60 ml of n-hexane were added with vigorous stirring and constant releasing of pressure. The result was left in repose and the bottom phase discarded, which contained residual glycerin. A polyol was obtained with a hydroxyl number value of 523.23 mg KOH/g sample.

Example 4Obtaining Polyol Using Route 3

(35) In a 500 ml reaction flask 40.0 grams of palm oil were weighed, along with 4.32 grams of pentaerythritol and 0.02 grams of lead oxide. Subsequently, the flask was placed on a heating surface where the mixture remained in reaction at a temperature of 200 C., with continuous agitation, an inert atmosphere of nitrogen and water reflux condenser during 2 hours. It was then left to cool and 40 ml of n-hexane were added in a separation funnel, stirring and releasing pressure. The phases were allowed to separate to further discard the precipitate and the glycerol. The other phase was submitted to rotoevaporation at 70 C. with constant agitation for 3 hours, thus obtaining the polyol, with a hydroxyl number value of 11.86 mg KOH/g sample.

Example 5Obtaining Polyol Using Route 4

(36) Initially the methanolysis of palm oil was carried out, in a 500 ml reaction flask, taking 500 grams of palm oil, together with 160.8 g of methanol and 9 grams of sodium hydroxide. The mixture was carried out at a temperature of 70 C. with agitation of 1000 rpm during 1 and a half hours.

(37) After the reaction time, the product was taken to a separation funnel to discard the glycerin phase that was in the bottom. The phase of interest was then washed with 100 ml of 0,015N phosphoric acid at 60 C., the solids formed were discarded, and repeated the wash was repeated with water at 60 C. until the pH was neutralized. The phase of interest was then submitted to rotoevaporation during 3 hours at a temperature of 80 C., for removal of excess methanol. The product obtained corresponds to the fatty acid methyl esters (FAME).

(38) Separately, in a 1000 ml reaction flask, 190 grams of FAME were added along with 7.71 grams of formic acid. The mixture was heated at 40 C. and agitated at 800 rpm.

(39) 20.85 grams of hydrogen peroxide were then added drop by drop during 1 hour. After the addition of hydrogen peroxide, the reaction continued during 11 hours with constant temperature and agitation. The evidence of the reaction was seen in the change of color from orange to clear yellow. Hot water washes were immediately conducted with until the pH increased to 5. Then a washing with 100 ml of bicarbonate sodium solution at 5% and sodium chloride at 5% was performed. The process ended with hot water washes until completely neutralized.

(40) The resulting mixture was rotoevaporated during 4 hours at 90 C. to remove moisture. The polyol was obtained.

Example 6Obtaining Polyol Using Routes 2 and 4 (Epoxidation and Glycerolysis) from the Olein Phase of Crude Palm Oil and Using Lead Oxide as Catalyst

(41) 200 grams of the olein phase of crude palm oil and 9.97 grams of formic acid were placed in a 500 ml reaction flask, coupled with a reflux condenser, a heating surface to achieve a temperature of 50 C., and magnetic agitation to 800 rpm. The reaction was started and 22.11 grams of hydrogen peroxide were added drop by drop, with agitation constant during 90 minutes. The reaction was allowed to continue during 2 hours. The formation reaction of epoxidized oil was evidenced by a change of color from orange to clear yellow.

(42) Hot water washes were then is conducted until a pH close to 5. A wash was performed with a solution of 5% sodium bicarbonate and with a 5% sodium chloride solution. The aqueous phase was discarded through a separation funnel of and the organic phase transferred to a lateral release Erlenmeyer, drying in a vacuum during 3 hours at 80 C. The glycerolysis was then carried out with 100 grams of epoxidized oil, 25.72 grams of glycerin and 0.03 grams of PbO in a 500 ml reaction flask coupled with a reflux condenser, temperature at 215 C., and agitation of 1300 rpm during 45 minutes. The polyol obtained was analyzed, resulting in hydroxyl numbers of between 60 and 110 mg KOH/g sample.

Example 7Obtaining Polyol Using Routes 2 and 4 (Epoxidation and Glycerolysis) from of the Olein Phase of Crude Palm Oil and Using Sodium Hydroxide as Catalyst

(43) 200 grams of the olein phase of crude palm oil and 9.97 grams of formic acid were placed in a 500 ml reaction flask coupled with a reflux condenser, a heating surface to reach a temperature of 50 C. and magnetic agitation to 800 rpm. The reaction was initiated and 22.11 grams of hydrogen peroxide were added drop by drop, with constant agitation during 90 minutes. The reaction continued during 2 additional hours. The reaction of formation of epoxidized oil was evidenced by a change of color from orange to clear yellow.

(44) Hot water washes were then carried out up to a pH close to 5. A wash was performed with a of 5% sodium bicarbonate solution and with a 5% sodium chloride solution. The aqueous phase was discarded through a separating funnel and the organic phase was transferred to a lateral release Erlenmeyer, drying in a vacuum during 3 hours at 80 C. Subsequently the glycerolysis was performed with 100 grams of epoxidized oil, 25.72 grams of glycerin and 1 gram of NaOH in a 500 ml reaction flask coupled with a reflux condenser, temperature of 180 C. and agitation at 1300 rpm for 45 minutes.

(45) The catalyst was neutralized with drops of phosphoric acid, thus avoiding the formation of soaps. Finally, the polyol obtained was analyzed. It yielded hydroxyl numbers between 400 and 440 mg KOH/g sample.

Example 8Obtaining Polyol Using Routes 2 and 4 (Epoxidation and Glycerolysis) from the Olein Phase of Refined Bleached Deodorized Crude Palm Oil and Using Sodium Hydroxide as Catalyst

(46) 200 grams of the olein phase of crude palm oil and 9.97 grams of formic acid were placed in a 500 ml reaction flask, coupled with a reflux condenser, a heating surface to achieve a temperature of 50 C., and magnetic agitation to 800 rpm. The reaction was initiated and 22.11 grams of hydrogen peroxide were added drop by drop, with constant agitation during 90 minutes. The reaction continued during 2 additional hours. The reaction of formation of epoxidized oil was evidenced by a change of color from orange to clear yellow.

(47) Hot water washes were then carried out up to a pH close to 5. A wash was performed with a of 5% sodium bicarbonate solution and with a 5% sodium chloride solution. The aqueous phase was discarded through a separating funnel and the organic phase was transferred to a lateral release Erlenmeyer, drying in a vacuum during 3 hours at 80 C. Subsequently the glycerolysis was performed with 100 grams of epoxidized oil, 25.72 grams of glycerin and 1 gram of NaOH in a 500 ml reaction flask coupled with a reflux condenser, temperature of 180 C. and agitation at 1300 rpm for 45 minutes.

(48) The catalyst was neutralized with drops of phosphoric acid, thus avoiding the formation of soaps. Finally, the polyol obtained was analyzed. It yielded hydroxyl numbers between 370 and 420 mg KOH/g sample.

Example 9Obtaining Polyol Using Routes 2 and 4 (Epoxidation and Glycerolysis} from the Olein Phase of Refined Bleached Deodorized Crude Palm Oil and Using Lead Oxide as Catalyst

(49) 200 grams of the olein phase of crude palm oil and 9.97 grams of formic acid were placed in a 500 ml reaction flask, coupled with a reflux condenser, a heating surface to achieve a temperature of 50 C., and magnetic agitation to 800 rpm. The reaction was initiated and 22.11 grams of hydrogen peroxide were added drop by drop, with constant agitation during 90 minutes. The reaction continued during 2 additional hours. The reaction of formation of epoxidized oil was evidenced by a change of color from orange to clear yellow.

(50) Hot water washes were then carried out up to a pH close to 5. A wash was performed with a of 5% sodium bicarbonate solution and with a 5% sodium chloride solution. The aqueous phase was discarded through a separating funnel and the organic phase was transferred to a lateral release Erlenmeyer, drying in a vacuum during 3 hours at 80 C. Subsequently the glycerolysis was performed with 100 grams of epoxidized oil, 25.72 grams of glycerin and 0.3 grams of PbO in a 500 ml reaction flask coupled with a reflux condenser, temperature of 180 C. and agitation at 1300 rpm for 45 minutes.

(51) Finally, the polyol obtained was analyzed. It yielded hydroxyl numbers between 80 and 90 mg KOH/g sample.

Example 10Preparation of a Polyurethane Varnish from Polyol Obtained by Route 1 of the First Method

(52) The pre-polymer was formed taking 30 g of polyol, 76.92 g surfactant and 20 ml of MEK (Methyl ethyl ketone) in a 250 ml reaction flask at 50 C. during 30 minutes. The pre-polymer was then transferred to a precipitate flask of 1000 ml and 14.88 grams of TDI (Toluene diisocyanate) were added, and stirred mechanically for 3 hours maintaining temperature at 70 C. Once the reaction was completed the pre-polymer was cooled to 50 C. and 4.96 grams of MEKO (Methyl ethyl ketoxima) were added to block the free NCO groups. This reaction took place during 2 hours. Finally, 2.88 grams of TEA (Triethylamine) were added during 30 minutes with vigorous agitation maintaining the temperature at 50 C. An amount of 50% w/w of water was then added drop by drop to form an emulsion.

Example 11Preparation of a Polyurethane Varnish from Polyol Obtained by Route 1 of the Second Method

(53) The pre-polymer was formed taking 12 g of polyol, 50 g surfactant and 10 ml of MEK (methyl ethyl ketone) in a 250 ml reaction flask at 50 C. during 30 minutes. The pre-polymer was then transferred to a precipitate flask of 1000 ml and 12.52 grams of TDI (Toluene diisocyanate) were added, and stirred mechanically for 3 hours maintaining temperature at 70 C. Once the reaction was completed the pre-polymer was cooled to 50 C. and 5 grams of MEKO (methyl ethyl ketoxima) were added to block the free NCO groups. This reaction took place during 2 hours. Finally, 2.2 grams of TEA (Triethylamine) were added during 30 minutes with vigorous agitation maintaining the temperature at 50 C. An amount of 50% w/w of water was then added drop by drop to form an emulsion.

Example 12Preparation of a Polyurethane Foam from Polyol Obtained by Route 2

(54) 13 g of palm polyol were taken and a mixture 50:50 performed with diethylene glycol, placed on a heating surface with magnetic agitation to 800 rpm, and then 0.04 g of surfactant, 0.02 g of DBTL (Dibutilin dilaurate) as catalyst and 0.2 g of water were added. Finally, 3.8 g of TDI (Toluene diisocyanate) were added and rapidly stirred manually. This reaction this is highly exothermic.

Example 13Preparation of a Foam of Polyurethane to from of Polyol Obtained with the Route 3

(55) 10 g of palm polyol were taken and a mixture 50:50 performed with diethylene glycol, placed on a heating surface with magnetic agitation to 800 rpm, and then 0.27 g of surfactant, 0.19 g of DBTL (Dibutilin dilaurate) as catalyst and 2.69 g of water were added. Finally, 13.2 g of TDI (Toluene diisocyanate) were added and rapidly stirred manually. This reaction this is highly exothermic.

Example 14Preparation of Polyurethane Foam from Polyol Obtained by Route 4

(56) 10 g of palm polyol and 10 g of DEG (diethylene glycol) were weighed, then 0, 19 g of DBTL (Dibutyltin dilaurate) catalyst were added, followed by 2.69 g of water and 0.27 g of surfactant. This premix was stirred at room temperature for a few minutes and then 13.24 g of MDI were added. This reaction is highly exothermic.

Example 15Preparation of a Polyurethane Foam from Polyol Obtained from Example 6

(57) 9 grams of polyol and 1 gram of 1,6 butanediol were premixed and submitted to heating in case that the polyol was in a solid state. 0.15 grams of silicone 193C and 0.03 grams DBTL (Dibutyltin dilaurate) were then added and mixed for homogeneity; and finally 1.98 grams of TDI (Toluene diisocyanate) were added and stirred vigorously. The reaction this is highly exothermic.

Example 16Preparation of Rigid Polyurethane from Polyol Obtained in Example 7

(58) 9 grams of polyol and 1 gram of SDR (Diethylene glycol) are mixed. The mixture, which is solid, is heated. 0.15 grams of silicone 193C and 0.03 grams of DBTL (Dibutyltin dilaurate) were added and mixed to achieve homogeneity, and finally 10.5 grams of polymeric MDI (Methylene diisocyanate) are added and stirred vigorously. The reaction is highly exothermic.

Example 17Preparation of Rigid Polyurethane from Polyol Obtained in Example 8

(59) 9 grams of polyol and 1 gram of SDR (Diethylene glycol) are mixed. The mixture, which is solid, is heated. 0.15 grams of silicone 193C and 0.03 grams of DBTL (Dibutyltin dilaurate) were added and mixed to achieve homogeneity, and finally 10.5 grams of polymeric MDI (Methylene diisocyanate) are added and stirred vigorously. The reaction is highly exothermic.

Example 18Preparation of Flexible Polyurethane from Polyol Obtained in Example 9

(60) 8.5 grams of polyol and 1.5 grams of butanediol are mixed. The mixture, which is solid, is heated. 0.15 grams of silicone 193C, 0.1 grams of water, and 0.03 grams of DBTL (Dibutyltin dilaurate) were added and mixed to achieve homogeneity, and finally 4.28 grams of polymeric TDI (toluene diisocyanate) are added and stirred vigorously. The reaction is highly exothermic.

(61) A feature of polyols and of products obtained from these, in view of the previous examples, has yielded the following ranges of properties:

(62) Polyols with molecular weights between 314 and 3366 and with a hydroxyl number between 50 and 450 mgKOH/g sample.

(63) The rigid foams resulting were tested regarding density (according to ASTM C373-88) with results between 0.284 and 0.658 g/cm.sup.3, Young module (according to ASTM 0695-10) with results between 8.94522 and 54.92330 MPa, and maximum effort (according to ASTM 0695-10) with results between 0.92037 and 8.29101 MPa.

(64) The semi-rigid foams resulting were tested regarding density (according to ASTM C373-88) with results between 0.120 and 0.158 g/cm3, Young module (according to ASTM 0695-10) with results between 0.78727 and 1.54311 MPa, and maximum effort (according to ASTM 0695-10) with results between 0.07012 and 0.09753 MPa.

Example 19Additional Experimental Runs

(65) Initially we start from the 4 mother routes (Routes 1-4, considering that Route 1 comprises Methods I and II). From these routes other routes are derived in the order below:

(66) TABLE-US-00003 Mother Derived Route Route 1 1 5 9 13 17 21 25 2 2 6 10 14 18 22 26 3 3 7 11 15 19 23 27 4 4 8 12 16 20 24 28

(67) In the following table the different experimental runs are summarized, defined by the following parameters: Route Number Polyol preparation: reagents operating conditions evaluation results Preparation of polyurethane: reagents operating conditions product characteristics evaluation results

(68) The abbreviation NA indicates that the indicated procedure was not carried out, as it did not become of interest for the inventors.

(69) TABLE-US-00004 Preparation of polyol Preparation of Polyurethane Experiment Operational Operational Evaluation Route No. Reagents conditions Evaluation Results Reagents conditions Product Features Results 1- 1 Palm Oil Maleinisation: T = 0.23 mgKOH/g Prepolymer (polyol), Isocyanate reaction: The varnish is Method 1 maleic anhydride 180 C.; nitrogen t = sample MEKO, TEA, HDI t = 3 h, T = 70 C. separated into two 3 h Blocking with MEKO: phases. Silicone T = 50 C., t = 2 h. varnish Neutralization with intermediately is TEA: T = 50 C., t = observed, appears 30 min, to be in excess. constant stirring. Dark brown initially, but eventually turns light brown. Opaque appearance. Appearance is that of a dispersion (bubbles are observed). 1- 1 Palm Oil t = 30 min. 2 Pre-polymer (polyol) Isocyanate reaction: Method 2 Maleic anhydride Rotoevaporation: T = HDI t = 3 h, T 70 C. Glycerin (99.5% 80 C., 800 rpm, MEKO Blocking with MEKO: purity) vacuum conditions. T = 50 C., t = 2 h. Sodium Hydroxide 3. Blocking MEK: T = TEA Neutralization with Sodium Chloride 90 c., t = 2 h. 4. TEA: T = 50 C., t = Sulfuric acid (99.5% Blocked 30 min, purity) monoglyceride: T = constant stirring. Methyl ethyl ketone 90 C., t = 3.5 h, 200 rpm. (MEK) 5. Rotoevaporation: Sulfonic Toluene T = 80 C., 800 rpm, Acid vacuum conditions. Toluene 6. Maleinization: T = maleic anhydride 200 C.; nitrogen t = TDI (toluene 3 h. Rotoevaporation: diisocyanate) T = 80 C., 800 rpm, Methyl ethyl vacuum condition, t = ketoxime (MEKO, 1.5 h. 99.5% purity). Ethanol 1- 1 Palm Oil Maleinisation: T = Prepolymer (polyol), Isocyanate reaction: It is a viscous Method 1 Maleic anhydride 180 C.; nitrogen t = MEKO, TEA, HDI t = 3 h, T = 70 C. mixture in which the 3 h Blocking with MEKO: silicone is T = 50 C., t = 2 h. completely Neutralization with separated. Color TEA: T = 50 C., t = dark brown. 30 min, It contains lots of constant stirring. granules. Freshly prepared separately is much eventually improves the homogeneity of the mixture. 1- 2 Palm Oil Maleinisation: T = 1.32 mgKOH/g NA NA NA NA Method 1 maleic anhydride 180 C.; nitrogen t = sample 3 h 1- 3 Palm Oil Maleinisation: T = 1.43 mgKOH/g NA NA NA NA Method 1 maleic anhydride 180 C.; nitrogen t = sample 3 h 1- 1 Palm Oil Maleinisation: T = 2.41 mgKOH/g Prepolymer (polyol), Isocyanate reaction: Smooth varnish. Method 2 maleic anhydride 180 C.; nitrogen t = sample TDI t = 3 h, T = 70 C. Beige Color. Glycerin (99.5% 3 h MEKO Blocking with MEKO: Medium viscosity. purity) T = 50 C., t = 2 h. Strong odor. Sodium Hydroxide TEA Neutralization with Sodium Chloride TEA: T = 50 C., t = Sulfuric acid (99.5% 30 min, purity) constant stirring. Ethyl methyl ketone (MEK) Sulfonic Acid Toluene Toluene Maleic anhydride Toluene diisocyanate (TDI) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 1- 2 Palm Oil Maleinisation: T = 27.13 mgKOH/g NA NA NA Method 2 Maleic anhydride 180 C.; nitrogen t = sample Glycerin (99.5% 3 h purity) Sodium Hydroxide Sodium Chloride Sulfuric acid (99.5% purity) Methyl ethyl ketone (MEK) Sulfonic Toluene Acid Toluene maleic anhydride TDI (toluene diisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 1- 3 Palm Oil Maleinisation: T = 15.03 mgKOH/g NA NA NA Method 2 Maleic anhydride 180 C.; nitrogen t = sample Glycerin (99.5% 3 h purity) Sodium Hydroxide Sodium Chloride Sulfuric acid (99.5% purity) Methyl ethyl ketone (MEK) Sulfonic Toluene Acid Toluene maleic anhydride TDI (toluene diisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 6 1 Palm Oil Glycerolysis: T = 90 C., 19.33 mgKOH/g Diethylene T, P atmospheric, Yellow. Solid Glycerol t = 2 h. Roto- sample TDI vigorous manual appearance, it Sodium Hydroxide evaporation at low Surfactant shaking appears greasy. Terbutanol. (20 ml) temperature, Dibutyltin Dilaurate Not observed porous according to the (DBTDL). Hydrochloric Acid volatility of hexane. water n-Hexane. (40 ml) Ddid not form a foam. 6 2 Palm oil Glycerolysis: T = 90 C., polyethylene glycol T, P atmospheric, When reacting Glycerol t = 2 h. Roto- TDI vigorous manual remained gritty and Sodium hydroxide evaporation at low Surfactant shaking when put in the soft Terbutanol (20 ml) temperature, Dibutyltin Dilaurate mold it becomes soft according to the (DBTDL) to the touch, with Hydrochloric Acid volatility of hexane. water time it hardened. n-Hexane. (40 ml) Its color is pale yellow. 20 1 Palm oil Methanolysis: Palm Polyol T, P atmospheric, Porous foam. methanol Temperature: 70 C., diethylene glycol vigorous manual Initially its color was Sodium Hydroxide t = 1.5 h, agitation: surfactant shaking white, but was Phosphoric acid 1000 rpm. catalyst oxidized and a clear (H3PO4) Rotoevaporation: T = yellow was taken. Hydrogen Peroxide 80 C., t = 3 h, water It is solid but (H202) vacuum conditions. appears liquid on the benzene Epoxidation: T = 40 C., IPDI surface, seems diethylene glycol agitation 800 rpm, excess reagent, (DEG) t = 3 h. possibly is Formic acid Rotoevaporation: T = isocyanate. Sodium Chloride 90 C., t = 4 h. Feels stiff to the touch. 20 2 Palm oil Methanolysis: Palm Polyol T, P atmospheric vigorous manual It is a color foam. Methanol Temperature: surfactant shaking. White pores was Sodium Hydroxide 70 C., t = 1.5 h, catalyst observed. Phosphoric acid agitation: 1000 rpm. water Wet, it appears a bit (H3P04) Rotoevaporation: T = greasy. Hydrogen peroxide 80 C., t = 3 h, IPDI It is a consistent (H202) vacuum conditions. solid. benzene Epoxidation: T = 40 C. Diethylene glycol Agitation: 800 rpm, (DEG). t = 3 h. formic acid Rotoevaporation: T = Sodium Chloride 90 C., t = 4 h. 2 1 Palm oil. Glycerolysis: T = 90 C. diethylene glycol T, P atmospheric, Orange. Glycerol t = 2 h. Roto- HDI vigorous manual Homogeneous. Sodium Hydroxide evaporation at low Surfactant shaking. Played more rigid Terbutanol. (20 mi) temperature, Dilaurate dibutyltin than others. according to the (DBTDL) Initially it looks like a Hydrochloric Acid volatility of hexane. water slurry. n-Hexane. (40 mi) It takes a little time to become solid. 2 2 Palm oil Glycerolysis: T = 90 C., Polyethylleneglycol T, P atmospheric, The mixture is Glycerol t = 2 h. Roto- HDI vigorous manual sandy. Dark yellow. Sodium Hydroxide evaporation at low Surfactant shaking. No foam was Terbutanol. (20 ml) temperature, Dilaurate dibutyltin formed. according to the (DBTDL) Hydrochloric Acid volatility of hexane. water n-Hexane. (40 ml) 2 3 Palm oil. Glycerolysis: T = 90 C., polyethylene glycol T, P atmospheric, It was prepared Glycerol t = 2 h. Roto- HDI vigorous manual using an index of sodium hydroxide evaporation at low Surfactant shaking 0.5. Terbutanol. (20 mi} temperature, Dilaurate dibutyltin It is a weak according to the (DBTDL) consistency polymer, Hydrochloric Acid. volatility of hexane. water orange, it breaks n-Hexane. (40 mi) easily. Over time white pieces presented themselvese. 2 4 Palm oil. Glycerolysis: T = 90 C., 23.13 mgKOH/g polyethylene glycol T, P atmospheric, It was prepared Glycerol t = 2 h. Roto- sample HDI vigorous manual using an index of Sodium Hydroxide evaporation at low Surfactant shaking 0.8. Tert-butanol (20 ml) temperature, Dilaurate dibutyltin It is a product a little according to the (DBTDL) harder than the 0.5 Hydrochloric Acid. volatility of hexane water index, however it is n-Hexane. (40 mi) still very fragile. Orange 2 5 Palm oil Glycerolysis: T = 90 C., polyethylene glycol T, P atmospheric, It was developed Glycerol t = 2 h. Roto- HDI vigorous manual with an index of 1. Sodium Hydroxide evaporation at low Surfactant shaking Orange, it is a Terbutanol. (20 mi) temperature, Dilaurate dibutyltin product a little according to the (DBTDL) stronger than the 0.8 Hydrochloric Acid. volatility of hexane water index, however it is n-Hexano. (40 mi) even more fragile than expected. 2 6 Palm oil Glycerolysis: T = 90 C., Polyethyleneglycol T, P atmospheric, Made with an index Glycerol. t = 2 h. Roto- HDI vigorous manual of 12. Orange Sodium Hydroxide evaporation at low Surfactant shaking product, stronger Tert-butanol (20 ml) temperature, Dilaurate dibutyltin that lower indices, as according to the (DBTDL) it consistency is Hydrochloric Acid. volatility of hexane water harder; however, it is n-Hexane. (40 mi) still brittle and does not exhibit the desired rigidity 2 7 Palm oil Glycerolysis: T = 90 C., 523.23 mgKOH/g NA NA NA NA Glycerol. t = 2 h. Roto- sample evaporation at low temperature, according to the volatility of hexane 2 8 Palm oil Glycerolysis: T = Glycerol. 215 C., t = 1 h. Lead Oxide Agitation = 1000 rpm. Tert-butanol (20 ml) Roto- Hydrochloric Acid. evaporation at 60, t = n-Hexane. (40 mi) 5 h. 4 1 Palm oil Methanolysis: T: Palm Polyol T, P atmospheric, White color solid Methanol 70 C.m t = 2.5 h. diethylene glycol vigorous manual with good Sodium Hydroxide Agitation 1000 rpm. Surfactant shaking homogeneity. Phosphoric acid Rotoevaporation: T = Catalyst Observed as (H3PO4) 80 C., t = 3 h., somewhat greasy. Hydrogen vacuum conditions. Water Liquid on the Peroxide (H2O2) Epoxidation: T = 40 C.: surface. Benzene Agitation: 800 rpm, HDI Formic Acid t = 3 h. Sodium Chloride Rotoevaporation: T = 90 C., t = 4 h. 4 2 Palm oil. Methanolysis: T: Palm Polyol T, P atmospheric, Clear yellow color. Methanol 70 C., t = 1.5 h. Diethylene glycol vigorous manual The mixture Sodium Hydroxide Agitation 1000 rpm. Surfactant shaking exhibited good Phosphoric Acid (H3PO4) Rotoevaporation: T = Catalyst homogeneity. Hydrogen Peroxide 80 C., t = 3 h., Water Consistent solid. (H2O2) vacuum conditions. Creamy to the touch. Benzene Epoxidation: T = HDI Diethylene glycol 40 C., Agitation 800 rpm, (DEG). t = 3 h. Formic Acid Rotoevaporation: T) Sodium Chloride 90 C., t = 4 h. 4 3 Palm Oil Methanolysis: T: 2.21 mgKOH/g NA NA NA Methanol 70 C., t = 1.5 h. sample Sodium Hydroxide Agitation 1000 rpm. Phosphoric Acid Rotoevaporation: T = (H3PO4) 80 C., t = 3 h., Hydrogen Peroxide vacuum conditions. (H2O2) Epoxidation: T = Benzene 40 C., Agitation 800 rpm, Diethylene glycol t = 3 h. (DEG). Rotoevaporation: T) Formic Acid 90 C., t = 4 h. Sodium Chloride 4 4 Palm Oil Methanolysis: T: NA NA NA Methanol 70 C., t = 1.5 h. Sodium Hydroxide Agitation 1000 rpm. Phosphoric Acid Rotoevaporation: T = (H3PO4) 80 C., t = 3 h., Hydrogen Peroxide vacuum conditions. (H2O2) Epoxidation: T = Benzene 40 C., Agitation 800 rpm, Diethylene glycol t = 3 h. (DEG). Rotoevaporation: T) Formic Acid 90 C., t = 4 h. Sodium Chloride 3 1 Palm Oil Reaction with T, P atmospheric, Polymer with a PbO pentaerythritol: T = vigorous manual grasslike and brittle Pentaerythritol 200 C., inert shaking consistency. Cream Tert-butanol (20 ml) atmosphere, t = 2 h. colored. Allows mold Hydrochloric Acid. flow. n-Hexane. (40 mi) 3 2 Palm oil Reaction with 11.86 mgKOH/g NA NA NA PbO pentaerythritol: T = sample Pentaerythritol 200 C., inert Tert-butanol (20 ml) atmosphere, t = 2 h. Hydrochloric Acid. n-Hexane. (40 mi) 3 3 Palm oil Reaction with NA NA NA PbO pentaerythritol: T = Pentaerythritol 200 C., inert Tert-butanol (20 ml) atmosphere, t = 2 h. Hydrochloric Acid. n-Hexane. (40 ml) 5- 1 Palm oil Maleinisation: T0 Pre-polymer Reaction with This product did not Method 1 Maleic Anhydride 180 C.; Nitrogen MeKO, HDI, TEA isocyanate: t = 3 hr., yield varnish, as it atmosphere, t = 3 h. T = 70 C. MEKO became a solid. Blockage: T = 50 C., t = 2 hr. Neutralization with TEA: T = 50 C., t = 30 min., constant agitation. 5- 1 Palm oil Maleinisation: T = Pre-polymer (polyol) Reaction with This varnish exhibits Method 2 Maleic Anhydride 180 C.; Nitrogen MDI isocyanate: t = 3 hr., phase separation. Glycerin (99.5% atmosphere, t = 3 h. Meko T = 70 C. MEKO purity) Blockage: T = 50 C., Sodium Hydroxide TEA t = 2 hr. Neutralization Sodium Chloride with TEA: T = 50 C., Sulfuric Acid (99.5% t = 30 min., constant purity) agitation. Methyl ethyl ketone (MEK) Sulfonic Toluene Acid Toluene Maleic Anhydride Toluene disiocyanate (TDI) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 7 1 Palm Oil Reaction with Palm Polyol T, P atmospheric, Foam with a greasy PbO pentaerythritol: T = Diethylene glycol vigorous manual aspect. Very sticky. Pentaerythritol 200 C., inert Surfactant shaking Yellow color. Difficult Tert-butanol (20 ml) atmosphere, t = 2 h. Catalyst to remove as a Hydrochloric Acid. Water whole. n-Hexane. (40 ml) HDI 7 2 Palm oil Reaction with Palm Polyol T, P atmospheric, This product is a PbO pentaerythritol: T = Surfactant vigorous manual modification of the Pentaerythritol 200 C., inert Catalyst shaking route initially Tert-butanol (20 ml) atmosphere, t = 2 h. Water planned, because Hydrochloric Acid. the Polyol used iso n-Hexane. (40 ml) TDI nly palm oil polyol. Its consistency is a very brittle foam. Clear yellow color. Does not appear greasy and dries more rapidly thatn the product of this route where the polyol Combined with the DEG. 8 1 Palm oil Methanolysis: T: Palm Polyol T, P atmospheric, A white foam, methanol 70 C., t = 1.5 h. Diethylene glycol vigorous manual appears somewhat Sodium Hydroxide Agitation 1000 rpm. Surfactant shaking porous. Consistent, Phosphoric acid Rotoevaporation: T = Catalyst but appears brittle. (H3PO4) 80 C., t = 3 h., Hydrogen Peroxide vacuum conditions. Water (H202) Epoxidation: T = benzene 40 C., Agitation 800 rpm, MDI diethylene glycol t = 3 h. (DEG) Rotoevaporation: T) Formic acid 90 C., t = 4 h. Sodium Chloride 78 2 Palm oil Methanolysis: T: Palm Polyol T, P atmospheric, White color foam. Its methanol 70 C., t = 1.5 h. Surfactant vigorous manual appearance is Sodium Hydroxide Agitation 1000 rpm. Catalyst shaking similar to gypsum. Phosphoric acid Rotoevaporation: T = Water Very brittle. (H3PO4) 80 C., t = 3 h., Hydrogen Peroxide vacuum conditions. TDI (H202) Epoxidation: T = benzene 40 C., Agitation 800 rpm, diethylene glycol t = 3 h. (DEG) Rotoevaporation: T) Formic acid 90 C., t = 4 h. Sodium Chloride 9 1 Palm oil Methanolysis: T: Pre-polymer (polyol) Reaction with Coffee-colored Maleic Anhydride 180 C., MEKO, TEA, TDI isocyanate: varnish. Nitrogen t = 3 hr., T = 70 C. Easily separated as atmosphere, t = 3 hr. MEKO Blockage: T = it does not have low 50 C., t = 2 hr. stability, when left in Neutralization with repose two phases TEA: T = 50 C., t = 30 min., are observed and a constant semisolid layer at agitation. the bottom. Pores observed in its interior. 9- 1 Palm Oil Methanolysis: T: Prepolymer (polyol) Reaction with This product did not Method 2 Maleic anhydride 180 C.,, Nitrogen TDI isocyanate: t = 3 hr., yield a varnish, as it Glycerin (99.5% atmosphere, t = 3 hr. Meko T = 70 C. MEKO solidified. purity) Blockage: T = 50 C., Coffee colored solid Sodium Hydroxide TEA t = 2 hr. Neutralization paste. Sodium Chloride with TEA: T = 50 C., Sulfuric acid (99.5% t = 30 min., constant purity) agitation. Methyl ethyl ketone (MEK) Sulfonic Toluene Acid Toluene maleic anhydride TDI (toluene diisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol. 5 1. Polyol of Palm Oil Epoxidation: # OH = 105.52 mg Palm polyol Vigorous agitiation Rapid growth of the crude palm Hydrogen Peroxide Temperature = 50 C. KOH/g sample Diethylene glycol Ambient temperature foam which solidified oil using Formic acid Time: 4 hrs. Dibutyltin Dilaureate immediately. Rigid PbO (DBTDL) foam is not greasy to Sodium Bicarnonate Agitation: 800 rpm Silicone 193C the touch. Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Lead Oxide Time = 45 mins. Agitation: 1300 rpm 6 1. Polyol of Crude palm oil Epoxidation: # OH = 202.43 mg Reaction with crude palm Hydrogen Peroxide Temperature = 50 C. KOH/g sample continuous bubbling oil using Formic acid Time: 4 hrs. and release of heat, PbO Sodium Bicarbonate Agitation: 800 rpm after a half hour Sodium Chloride Glycerolysis product has not Glycerin Temp = 215 C. solidified, an excess Sodium Hydroxide Time = 45 mins. of isocyanate is Phosphoric Acid Agitation: 1300 rpm observed. 7 1. Oil RBD Palm Oil Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitation Semi-rigid Polyol Hydrogen Peroxide Temperature = 50 C. KOH/g sample Diethylene glycol Ambient polyurethane, color Of RBD temperature Yellowish, solidified NaOH Formic acid Time: 4 hrs. Dibutyltin Dilauate rapidly. palm. (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 8 1. Polyol of RBD Palm Oil Epoxidation: # OH = 81.59 mg Palm polyol Vigorous agitation The product has a palm oil Hydrogen Peroxide Temperature = 50 C. KOH/g sample Diethylene glycol Ambient grasslike RBD PbO temperature consistence and Formic acid Time: 4 hrs. Dibutyltin Dilauate there was no (DBTDL) evience of reaction, Sodium Bicarbonate Agitation: 800 rpm Silicon 193C such as release of Sodium Chloride Glycerolysis Toluene isocyanate heat. (TDI) Glycerin Temp = 215 C. Lead Oxide Time = 45 mins. Agitation: 1300 rpm Combined 1 Olein Phase of palm Epoxidation: # OH = 105.52 mg Palm polyol Vigorous agitation The mixture begins 2 and 4 oil KOH/g sample to rise instantly Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient forming a low temperature density foam, it Formic acid Time: 4 hrs. Dibutyltin Dilauate Evidence of a very (DBTDL) large pore size and Sodium Bicarbonate Agitation: 800 rpm Silicone 193C low consistency. Sodium Chloride Glycerolysis Toluene isocyanate This product does (TDI) not allow flow, nor Glycerin Temp = 215 C. removal from the Lead Oxide Time = 45 mins. mold. Agitation: 1300 rpm 2 Olein Phase of palm Epoxidation: # OH = 202.43 mg Palm Polyol Vigorous agitation No evidence of oil KOH/g sample reaction, a viscous Hydrogen Peroxide Temperature = 50 C. Dibutyltin Dilauate Ambient yellow liquid pours (DBTDL) temperature when emptying the Formic acid Time: 4 hrs. Silicon 193C mold. After 1 day it Sodium Bicarbonate Agitation: 800 rpm Methylene still has not diisocyanate (MDI) solidified. Sodium Chloride Glycerolysis Water Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 3 Olein Phase of palm Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitation Brittle foam that oil KOH/g sample grows rapidly and Hydrogen Peroxide Temperature = 50 C. Water Ambient whose interior is not temperature compact. Formic acid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 4 Olein Phase of palm Epoxidation: # OH = 105.52 mg Palm Polyol Vigorous agitation No evidence of oil KOH/g sample reaction, emptying of Hydrogen Peroxide Temperature = 50 C. Water Ambient the mold yields a temperature viscous yellowish Formic acid Time: 4 hrs. Dibutyltin Dilauate creamy liquid. (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Lead oxide Time = 45 mins. Agitation: 1300 rpm 5 Olein Phase of palm Epoxidation: # OH = 81.59 mg Palm Polyol Vigorous agitation A very compact oil KOH/g sample product was Hydrogen Peroxide Temperature = 50 C. Water Ambient obtained but it is temperature very fragile to Formic acid Time: 4 hrs. Dibutyltin Dilauate contact. (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Lead oxide Time = 45 mins. Agitation: 1300 rpm 6 Olein Phase of palm Epoxidation: # OH = 202.43 mg Palm Polyol Vigorous agitation Material is rigid to oil KOH/g sample the touch, dries Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient quickly, not greasy, temperature pores are smaller Formic acid Time: 4 hrs. Dibutyltin Dilauate than for foams (DBTDL) obtained before, Sodium Bicarbonate Agitation: 800 rpm Silicon 193C medium density. An Sodium Chloride Glycerolysis Methylene excess of isocyanate diisocyanate (MDI) is observed. Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 7 Olein Phase of palm Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitation Rigid foam, higher oil KOH/g sample density and smaller Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient pore size than the temperature prior one. Color is Formic acid Time: 4 hrs. Dibutyltin Dilauate beige, with a (DBTDL) tendency to light Sodium Bicarbonate Agitation: 800 rpm Silicon 193C yellow. Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 8 Olein Phase of palm Epoxidation: # OH = 105.52 mg Palm Polyol Vigorous agitation Rigid foam, of oil KOH/g sample greater density and Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient lesser pore size than temperature the prior one. Color Formic acid Time: 4 hrs. Dibutyltin Dilauate is beige, with (DBTDL) tendency to clear Sodium Bicarbonate Agitation: 800 rpm Silicon 193C yellow. Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Lead oxide Time = 45 mins. Agitation: 1300 rpm 9 Olein Phase of palm Epoxidation: # OH = 81.59 mg Palm Polyol Vigorous agitation Rigid foam, medium oil KOH/g sample density and smaller Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient pore size than the temperature prior one. Color is Formic acid Time: 4 hrs. Dibutyltin Dilauate beige, with tendency (DBTDL) to clear yellow. Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Lead oxide Time = 45 mins. Agitation: 1300 rpm 10 Olein Phase of palm Epoxidation: # OH = 202.43 mg Palm Polyol Vigorous agitation Rigid sandy oil KOH/g sample polyurethane, good Hydrogen Temperature = 50 C. 1,6 butanediol Ambient appearance. Peroxide (BDO) temperature Formic acid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 11 Olein Phase of palm Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitation A rigid white oil KOH/g sample polyurethane was Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient obtained, very hard. (BDO) temperature Does not permit Formic acid Time: 4 hrs. Dibutyltin Dilauate agitation because (DBTDL) the reaction is very Sodium Bicarbonate Agitation: 800 rpm Silicon 193C fast. Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 12 Olein Phase of palm Epoxidation: # OH = 202.43 mg Palm Polyol Vigorous agitation Beige colored oil KOH/g sample polymer, which Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient exhibited good (BDO) temperature consistency. Formic acid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 13 Olein Phase of palm Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitation A white high density oil KOH/g sample foam was obtained, Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient with oval pores, of (BDO) temperature rigid consistence. Formic acid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 14 Olein Phase of palm Epoxidation: # OH = 32.84 mg Palm Polyol Vigorous agitation Manually agitated, oil KOH/g sample however no typical Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient features of rection temperature were evidenced Formic acid Time: 4 hrs. Dibutyltin Dilauate (temperature (DBTDL) changes, bubbling, Sodium Bicarbonate Agitation: 800 rpm Silicone emulsion and growth of foam), Sodium Chloride Glycerolysis Methylene on the contrary, the diisocyanate liquid aspect stayed. (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 15 Olein Phase of palm Epoxidation: # OH = 88.97 mg Palm Polyol Vigorous agitation No formation of foam oil KOH/g sample was witnessed. Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient (BDO) temperature Formic acid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicone 193C Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Ethylenediamine Sodium Hydroxide Time = 45 mins. Water Phosphoric acid Agitation: 1300 rpm 16 Olein Phase of palm Epoxidation: # OH = 88.97 mg Palm Polyol Vigorous agitation Bubbling was oil KOH/g sample observed, as well as Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient an increase in (BDO) temperature temperature and the Formic acid Time: 4 hrs. Dibutyltin Dilauate foam that was seen (DBTDL) solidifying Sodium Bicarbonate Agitation: 800 rpm Silicone 193C completely. Sodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215 C. Ethylenediamine Sodium Hydroxide Time = 45 mins. Water Phosphoric Acid Agitation: 1300 rpm 17 Olein Phase of palm Epoxidation: # OH = 401.4 mg Palm polyol Vigorous agitiation Rigid polyurethane oil KOH/g sample with good Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature consistency although Formic acid Time: 3 hrs. Dibutyltin Dilaureate the pore size is big. (DBTDL) Sodium Bicarnonate Agitation: 950 rpm Silicone emulsion Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 18 Olein Phase of palm Epoxidation: # OH = 401.4 mg Palm polyol Vigorous agitiation Polymer with a small oil KOH/g sample sized pore and good Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature rigidity properties. Formic acid Time: 3 hrs. Dibutyltin Dilaureate (DBTDL) Sodium Bicarbonate Agitation: 950 rpm Silicone emulsion Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 19 Olein Phase of palm Epoxidation # OH = 437.56 mg Palm Polyol Vigorous agitation Polymer with a small Young module = oil KOH/g sample pore size and 33.3293 Mpa Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature Good properties for Maximum Formic acid Time: 3 hrs. Dibutyltin Dilaureate rigidity. Chosen for effort = 3.1673 Mpa (DBTDL) the characterizing Sodium Bicarnonate Agitation: 950 rpm Silicone emulsion range for rigid PU Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 20 Olein Phase of palm Epoxidation: # OH = 433.08 mg Palm polyol Vigorous agitiation Presents oil KOH/g sample homogeneity, good Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature pore size, shows Formic acid Time: 3 hrs. Dibutyltin Dilaureate good rigidity. (DBTDL) Sodium Bicarbonate Agitation: 950 rpm Silicone 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 21 Olein Phase of palm Epoxidation # OH = 263.4 mg Palm Polyol Vigorous agitation Exhibits oil KOH/g sample homogeneity, good Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature pore size and in Formic acid Time: 3 hrs. Dibutyltin Dilaureate general good (DBTDL) physical Sodium Bicarnonate Agitation: 950 rpm Silicone 193C appearance. Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 22 Olein Phase of palm Epoxidation: # OH = 79.97 mg Palm polyol Vigorous agitiation It was found that part oil KOH/g sample of the polyol did not Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature react and remained Formic acid Time: 3 hrs. Dibutyltin Dilaureate in the lower part, a (DBTDL) white foam being Sodium Bicarbonate Agitation: 950 rpm Silicone emulsion found in the upper Sodium Chloride Glycerolysis Methylene part. The reaction diisocyanate (MDI) time was slow. Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 23 Olein Phase of palm Epoxidation # OH = 263.4 mg Palm Polyol Vigorous agitation This polyurethane oil KOH/g sample presents good Hydrogen Peroxide Temperature = 50 C. 1,6 butanediol Ambient temperature features, compared (BDO) with that of the same Formic acid Time: 3 hrs. Dibutyltin Dilaureate Hydroxil number, (DBTDL) with DEG, however, Sodium Agitation: 950 rpm Silicone 193C its rigidity is less. Bicarbonate Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180 C. Sodium Hydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 24 Olein Phase of palm Epoxidation: # OH = 263.4 mg Palm polyol Vigorous agitiation This polyurethane oil KOH/g sample exhibts good Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature features, it is a semi- Formic acid Time: 3 hrs. Dibutyltin Dilaureate rigid product. (DBTDL) Sodium Bicarbonate Agitation: 950 rpm Silicone 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180 C. Sodium Hydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 25 Olein Phase of palm Epoxidation # OH = 263.4 mg Palm Polyol Vigorous agitation Shows good Density = oil KOH/g sample replicability and is 0.133 g/cm3 Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature sent for the Formic acid Time: 3 hrs. Dibutyltin Dilaureate characterization by (DBTDL) density test. Sodium Bicarnonate Agitation: 950 rpm Silicone 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180 C. Sodium Hydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 26 Olein Phase of palm Epoxidation: # OH = 263.4 mg Palm polyol Vigorous agitiation Exhibits good Young module = oil KOH/g sample replicability and is 1.32276 Mpa Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature sent for the test by Maximu effort = Formic acid Time: 3 hrs. Dibutyltin Dilaureate characterization of 0.08760 Mpa (DBTDL) compression. Sodium Bicarbonate Agitation: 950 rpm Silicone 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180 C. Sodium Hydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 27 Olein Phase of palm Epoxidation # OH = 437.66 mg Palm Polyol Vigorous agitation Polymer with a small Density = oil KOH/g sample pore size and good 0.450 g/cm3 Hydrogen Peroxide Temperature = 50 C. Diethylene glycol Ambient temperature velocity features. Formic acid Time: 3 hrs. Dibutyltin Dilaureate Chosen for the rank (DBTDL) of PU Sodium Bicarnonate Agitation: 950 rpm Silicone 193C characterization by Sodium Chloride Glycerolysis Methylene density. diisocyanate (MDI) Glycerin Temp = 215 C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm