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Dokumentenidentifikation EP1200531 06.06.2002
EP-Veröffentlichungsnummer 1200531
Titel VERFAHREN ZUR HERSTELLUNG VON POLYOLEN UND POLYOLE FÜR POLYURETHAN
Anmelder Polymermann (Asia) PVT Ltd., Mumbai, IN;
Shah, Ashvin, Mumbai, IN;
Shah, Tilak, Cary, N.C., US
Erfinder SHAH, Ashvin, Mumbai 400026, IN;
SHAH, Tilak, Cary, US
Vertreter derzeit kein Vertreter bestellt
Vertragsstaaten AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LI, LU, MC, NL, PT, SE
Sprache des Dokument EN
EP-Anmeldetag 12.07.2000
EP-Aktenzeichen 009552431
WO-Anmeldetag 12.07.2000
PCT-Aktenzeichen PCT/US00/18895
WO-Veröffentlichungsnummer 0000104225
WO-Veröffentlichungsdatum 18.01.2001
EP-Offenlegungsdatum 02.05.2002
Veröffentlichungstag im Patentblatt 06.06.2002
IPC-Hauptklasse C09F 7/06
IPC-Nebenklasse C09F 7/10   C11B 3/00   C11B 7/00   C08G 18/68   

Beschreibung[en]
BACKGROUND OF THE INVENTION

The invention relates to a process for production of polyols for use in production of polyurethane foam systems. More specifically, the invention relates to the use of renewable agricultural resources being at least one vegetable oil, and more particularly castor oil, for the manufacture of polyester useful in production of foam polyurethane.

Most of the polyols (polyester/polyether) used for manufacture of polyurethane foams systems are based on petroleum feed stock. More specifically, current processes for preparation of polyols for foamed polyurethane involves propoxylation, ethoxylation and estrification of multifunctional hydroxyl (OH) precursors until a required hydroxyl (OH) value is achieved. The desired product is then purified to remove catalyst therefrom, as well as other undesirable components. Thus, as may be appreciated, polyols, in particular polyester and/or polyether are important reactants for the manufacturer of commercially useful polyurethane foams.

WO-A-9912987 relates to a foamable composition comprising at least two parts. The first part comprises at least one polyol, at least one gelling agent and at least one blowing agent wherein the first part also comprises an effective amount of hydrophobic ingredients and the second part comprises at least one isocyanate.

EP-A-0568388 relates to novel polyurethane formulations especially useful as a coating for the protection of ductile cast iron types.

US-A-3248349 relates to polyurethane plastics and more particularly to cellular polyurethane plastics which tend to have a rigid structure with good physical properties.

EP-A-0672697 relates to the preparation of closed-cell, rigid foams containing urethane, urea and biuret groups and having high adhesion to solid surfaces by reacting a polyisocyanate with a modified castor oil in the presence of catalyst, water and optionally a low boiling hydrocarbing blowing agent.

While presenting a useful source for the manufacture of such polyols, petroleum feed stock is generally considered non-renewable and a source of feed stock will eventually be depleted. Thus, in accordance with the invention, it becomes desirable to minimize the use of a non-renewable feed stock such as petroleum. Further, current environmental considerations place great importance on the use of "green technologies", in particular, with respect to the use of such technologies for the manufacture of polyols useful in producing polyurethane foam. Thus, in accordance with the invention, the problems of using a non-renewable feed stock such as petroleum feed stock is avoided., by providing a method of manufacturing commercially useful polyols from renewable feed stock.

SUMMARY OF THE INVENTION

In accordance with one aspect of the invention, there is provided a process for the production of polyol for use in production of polyurethane foam. In particular, the invention relates to a process for the production of polyol for use in production of polyurethane foam, comprising reacting under agitation:

  • a mixture of a predetermined quantity of agricultural origin feed stock in a ratio of 100 parts wherein said feed stock is at least one vegetable oil, with a multifunctional hydroxyl component in a ratio of from 10 to 200 parts, and at least one dibasic acid in a ratio of up to 100 parts of the mixture;
   said reaction being conducted in the presence of a catalyst suitable for esterification and polymerisation in an amount of from 0.01 percent to 2 percent by weight of the mixture; and

   said reaction conducted at a temperature from 150°C to 250°C and for a time effective to result in a polyester polyol having from 2 to 5 hydroxyl functionality useful for producing polyurethane foam.

The reaction is conducted in the presence of a free radical catalyst suitable for estrification and polymerisation, typically an alkali/alkaline earth/tin based catalyst, in an amount of 0.01 percent to 2 percent by weight of the mixture. The reaction is conducted at a temperature and for a time effective to result in a polyol useful for producing polyurethane foam.

In a more specific aspect, the feed stock is vegetable oil, or a mixture of vegetable oils, and more particularly castor oil. Castor oil is a non drying oil extracted from the castor bean, which after processing, has previously been used as a lubricant among other applications. It is also known as ricinus oil. The reaction is conducted at a temperature of 150°C to 250°C. Yet preferably, the reaction is conducted for a time period of 6 hours to 8 hours to result in different polyester polyols of 2 to 5 (hydroxyl) functionality. In conducting the reaction, preferably the hydroxyl component is a multifunctional hydroxyl component such as glycerin and sorbitol.

Having thus briefly described the invention, the same will become better understood from the following detailed discussion.

Detailed Discussion of the Invention

In accordance with the invention there is provided a process for manufacture of polyols which are useful for manufacturing polyurethane foam. Specifically, the process results in polyester polyols which are prepared from vegetable oils such as castor oil, or other ingredients mostly derived from agricultural sources.

The other vegetable oils considered are unsaturated oils like Soybean oil. Mutifunctional hydroxyl components used as one of the reaction input are the substances like glycerin and sorbitol. A significant source of glycerin is from saponification vegetable oils like Palm oil, whereas Sorbitol is produced using sucrose as the starting material. Sucrose is fully derived from agricultural sources with multifunctional hydroxyl components to produce a polyester polyol of 2 to 5 (hydroxyl) functionality useful for the manufacturer of polyurethane foam. For purposes of this disclosure, it is noted that OH refers to the hydroxyl number of the polyol. The functionality refers to the average number of hydroxyl groups per molecule of polyol and m.w. refers to the molecular weight of the polyol.

The polymer/polyols in accordance with the invention are produced by estrification/trans estrification of a polymerization known quantity of vegetable oil such as castor oil in a mixture with at least one multifunctional hydroxyl component, i.e., OH greater than 1, or a mixture thereof, and di basic acid. The previously mentioned materials are reacted under agitation at a temperature range of 150°C to 250°C in the presence of a catalytically effective amount of a conventional free radical catalyst known to be suitable for the polymerization of the unsaturated monomers in the oil. Specifically, such a catalyst can be an alkali/alkaline earth/tin based catalyst in an amount of anywhere from 0.01 to 2 percent by weight. The reaction is conducted typically for a period of 2 to 8 hours to result in a polyol which can then be purified and standardized. More specifically, depending on the specific ratios, temperatures and time of reaction, different polyols of functionality of 2 to 5 (hydroxyl) value are produced.

In a second step, depending on the desired polyurethane foam system to be prepared from the polyols, the polyols can be blended with appropriate ingredients such as a stabilizer catalyst, blowing agents, etc., to produce formulated polyols useful for achieving a desired performance of the polyurethane foam system to be produced. More specifically, the resultant polyols from the process of invention are typically polyesters which are used to produce foam polyurethane systems.

Comparative Examples I-IV and Examples I-III

A series of polymer/polyols were prepared in batch processes. Comparative examples I-IV and examples I-III below describe the different types of polyols which result from conducting the process with varying constituents of the mixtures, and under varying temperature and time conditions to result in different polyols, i.e. polyesters.

Comparative Example I

400 gms of Soybean oil is reacted with 100 gms Of Glycerin in a stirred glass reactor at a temperature of 200 to 245°C for three hours in the presence of 0.1% of a tin catalyst. The reaction is carried out in a nitrogen atmosphere. The resulting product is a polyol of functionality of approximately 2 and has OH of 280 to 330 mgKOH/gm.

Comparative Example II

218.35 gms of Castor oil is reacted with 281.35 gms of a mixture of diols (PEG 600) in a stirred glass reactor at a temperature of 200 to 240°C for three to four hours in the presence of 0.5.% of alkaline earth catalyst. The reaction is carried out in a nitrogen atmosphere. The resulting product is a polyol of functionality of between 2 to 3 and has OH of 170 to 200 mgKOH/gm.

Comparative Example III

400 gms of Castor oil is reacted with 100 gms of glycerin in a stirred glass reactor at a temperature of 200 to 240°C for three to four hours in the presence of 0.5 to 1% of an alkaline earth catalyst. The reaction is carried out in a nitrogen atmosphere. The product is purified by precipitating the catalyst chemically and filtering it off. The resulting product is a polyol has a functionality of approximately 3 and has OH of 410 to 450 mgKOH/gm.

Comparative Example IV

364 gms of Castor oil is reacted with 135.88 gms of a mixture of glycerin and sorbitol in a stirred glass reactor at a temperature of 200 to 250°C for three to four hours in the presence of 1% of an alkaline earth catalyst. The reaction is carried out in a nitrogen atmosphere. The resulting product is a polyol, which is then purified by removing the catalyst chemically by precipitating the catalyst and filtering it off. The resulting polyol has a functionality of between 3 to 4 and OH of 380 to 400 mgKOH/gm.

Example I

240.6 gms of Castor oil is reacted with 164.1 gms of a mixture of glycerin using 0.5% of the tin catalyst in a stirred glass reactor at a temperature of 200 to 250°C for one to two hours. After two hours, 95.3 gms of Phthalic acid is added and reaction proceeds at 180°C for the next two hours. Thereafter, the reaction temperature is increased to 220°C for another two hours to complete the reaction. The reaction is carried out under nitrogen initially, and a vacuum is applied during the last half hour to complete the reaction and to bring the acid value to less than one. The resulting product is a polyol having a functionality of between 4 to 5 and having OH of 470 to 490 mgKOH/gm.

Example II

146.8 gms of Castor oil is reacted with 69.29 gms of a mixture of Adipic and Phthalic acid in a stirred glass reactor at a temperature of 200 to 250°C for about four hours. Thereafter, 283.9 gms of PEG 600 is added and reaction proceeds further using 0.1% of a tin catalyst at 180°C to 230°C for the next 10 to 12 hours. The reaction is carried out under nitrogen initially and vacuum is applied during last three hours to complete the reaction and to bring the acid value less than one. The resulting product is a polyol with a functionality of approximately 3 and having OH of 30 to 50 mgKOH/gm.

Example III

134.7 gms of Castor oil is reacted with 211.74 gms of a mixture of Adipic and Phthalic acid in a stirred glass reactor at a temperature of 200 to 250°C for about four hours. Thereafter, 153.55 gms of DEG is added and reaction proceeds further using 0.1% of tin catalyst at 180°C to 220°C for next 10 to 12 hours. The reaction is carried out under nitrogen initially and a vacuum is applied during the last three hours to complete the reaction and to bring the acid value to less than one. The resulting product is a polyol with a functionality of between 2 to 3 and having OH of 30 to 45 mgKOH/gm.


Anspruch[de]
  1. Verfahren zum Herstellen von Polyol zur Verwendung bei der Herstellung von Polyurethanschaum, durch Umsetzen unter Rühren

    eines Gemisches aus einer vorgegebenen Menge eines Ausgangsmaterials landwirtschaftlichen Ursprungs in einem Verhältnis von 100 Teilen, wobei das Ausgangsmaterial ein pflanzliches Öl ist, mit einer multifunktionellen Hydroxylkomponente in einem Verhältnis von 10 bis 200 Teilen und wenigstens einer zweibasigen Säure in einem Verhältnis von bis zu 100 Teilen des Gemisches,

    wobei die Reaktion in Anwesenheit eines zur Veresterung und Polymerisation geeigneten Katalysators in einer Menge von 0.01 Gewichtsprozent bis 2 Gewichtsprozent des Gemisches durchgeführt wird,

    und wobei die Reaktion bei einer Temperatur von 150 °C bis 250°C und während einer Dauer durchgeführt wird, die wirksam ist, um ein Polyesterpolyol mit 2 bis 5 Hydroxylfunktionalitäten zu ergeben, das zur Herstellung von Polyurethanschaum geeignet ist.
  2. Verfahren nach Anspruch 1, worin das pflanzliche Öl Ricinusöl enthält.
  3. Verfahren nach Anspruch 1, worin die Hydroxylkomponente Glycerin enthält.
  4. Verfahren nach Anspruch 1, worin die Hydroxylkomponente Sorbit enthält.
  5. Verfahren nach Anspruch 1, das ferner das Durchführen der Reaktion während 6 bis 8 Stunden beinhaltet.
  6. Verfahren nach Anspruch 1, das ferner das Mischen des erhaltenen Polyols mit einem Stabilisatorkatalysator und Treibmitteln beinhaltet, um ein Polyol zu erhalten, das sich zum Herstellen eines vorbestimmten Polyurethanschaums eignet.
  7. Verfahren nach Anspruch 6, das ferner das Reinigen des erhaltenen Polyols vor dem Durchführen des genannten Mischens mit dem Stabilisatorkatalysator und den Treibmitteln beinhaltet.
Anspruch[en]
  1. A process for the production of polyol for use in production of polyurethane foam, comprising reacting under agitation:
    • a mixture of a predetermined quantity of agricultural origin feed stock in a ratio of 100 parts wherein said feed stock is at least one vegetable oil, with a multifunctional hydroxyl component in a ratio of from 10 to 200 parts, and at least one dibasic acid in a ratio of up to 100 parts of the mixture;
       said reaction being conducted in the presence of a catalyst suitable for esterification and polymerisation in an amount of from 0.01 percent to 2 percent by weight of the mixture; and

       said reaction conducted at a temperature from 150°C to 250°C and for a time effective to result in a polyester polyol having from 2 to 5 hydroxyl functionality useful for producing polyurethane foam.
  2. The process of claim 1, wherein said vegetable oil includes castor oil.
  3. The process of claim 1, wherein said hydroxyl component comprises glycerin.
  4. The process of claim 1, wherein said hydroxyl component comprises sorbitol.
  5. The process of claim 1, further comprising conducting said reaction for 6 to 8 hours.
  6. The process of claim 1, further comprising blending the resultant polyol with stabilizer catalyst and blowing agents to result in a polyol suitable for production of a predetermined polyurethane foam.
  7. The process claim 6, further comprising purifying the resulting polyol before conducting said blending with stabilizer catalyst and blowing agents.
Anspruch[fr]
  1. Procédé de production de polyol pour l'emploi dans la production de mousse de polyuréthane, comprenant la réaction sous agitation :
    • d'un mélange d'une quantité prédéterminée de produit de départ d'origine agricole selon un rapport de 100 parties dans lequel ledit produit de départ est au moins une huile végétale, avec un composant hydroxyle multifonctionnel selon un rapport de 10 à 200 parties, et d'au moins un acide dibasique selon un rapport d'au plus 100 parties du mélange ;
       ladite réaction étant conduite en présence d'un catalyseur approprié à l'estérification et à la polymérisation, en une quantité comprise entre 0,01 pour cent et 2 pour cent en poids du mélange ; et

       ladite réaction étant conduite à une température comprise entre 150°C et 250°C et pendant un temps efficace pour conduire à un polyol polyester ayant une fonctionnalité de 2 à 5 hydroxyles, utile pour la production de mousse de polyuréthane.
  2. Procédé selon la revendication 1, dans lequel l'huile végétale comprend l'huile de ricin.
  3. Procédé selon la revendication 1, dans lequel le dit composant hydroxyle comprend le glycérol.
  4. Procédé selon la revendication 1, dans lequel le dit composant hydroxyle comprend le sorbitol.
  5. Procédé selon la revendication 1, comprenant aussi la conduite de ladite réaction pendant 6 à 8 heures.
  6. Procédé selon la revendication 1, comprenant aussi le mélange du polyol obtenu avec des agents catalyseurs stabilisants et gonflants pour donner un polyol approprié à la production d'une mousse de polyuréthane prédéterminée.
  7. Procédé selon la revendication 6, comprenant aussi la purification du polyol obtenu, avant la mise en oeuvre dudit mélange avec des agents catalyseurs stabilisants et gonflants.






IPC
A Täglicher Lebensbedarf
B Arbeitsverfahren; Transportieren
C Chemie; Hüttenwesen
D Textilien; Papier
E Bauwesen; Erdbohren; Bergbau
F Maschinenbau; Beleuchtung; Heizung; Waffen; Sprengen
G Physik
H Elektrotechnik

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