AU660486B2 - Epoxy ring opening using lithium salts - Google Patents

Description

OPI DATE 05/04/93 APPLN. ID 24375/92 IIfIIfIII AOJP DATE 10/06/93 PCT NUMBER PCT/EP92/01905 IlhlIIIIiINI1I AU9224375 (51) Internationale Patentklassiikation 5 C07C 67/31, 69/708, 691675 C07C 29/10, 41/03, 31/20 C07C 43/13 (11) Internationale Veriiffentlichungsnummer: Al (43) lntenionales Veriiffentlichungsdatumn: 18 WO 93/05008 Mi~rz 1993 (18.03.93) 1 (21) Internationales Aktenzeichen: PCT/EP92/0 1905 (22)InternationalesAnmeldedatum: 20. August 1992 (20,08.92) Prioritiitsdaten: P 4128 649.9 29. August 1991 (29.08.9 1) DE (74) Gemeinsamer Vertretcr: H ENKEL KOMMAN DITGE- SELLSCHAFT AUF AKTIEN; TFP/Patentabteilung, Postfach 10 11 00, D-4000 D~isseldorf 1 (D311).

(81) Bestimmungsstnaten: AU, BR, CA, JP, US, europflisches Patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU', NL, SE).

Veriiffentlicht Mit internaionalemn Recherchenberichi.

(71) Anmelder (flr alle Bestirnmungssten ausser US): HEN- KEL KOMMANDITGESELLSCHAFT AUF AXTIEN [DE/DE]; Henkelstrage 67, D-4000 Dosseldorf 13 (DE).

(72) Erfinder; und Erfinder/Anmelder (nur fir US) DAUTE, Peter [DE/DE]; Kreuzeskirchstra~e 5, D-4300 Essen I KLEIN, Johann [DE/DE]; Beethovenstralle 1, D-4000 Dflsseldorf I GRDTZMACHER Roland JDE/DE]; Zur Krakau 12, D-5603 Wilfrath HO FER, Rainer [PE/ DE]; KleverStrage 31, D-4000 D~sseldorf 30 (DE).

(54) Title: MET-HOD OF PRODUCING EPOXY-RING OPENING PRODUCTS (54) Bezeichnung: VERFAHREN ZUR HERSTELLUNG VON EPOXIDRINGOFFNUNGSPRODUKTEN (57) Abstract Epoxy-ring opening products may be produced by a) reacting epoxy compounds with nucleophilic agents in the presence of lithium salts and b) subjecting the hydroxy compounds thus formed to transesterification reaction, optionally using fatty-acid glyderide esters.

(57) Zusammenfassung Epoxidring6ffnungsprodukte lassen sich herstellen, indemn man a) Epoxidverbindungen mit Nucleophilen in Gegenwart von Lithiumsalzen umsetzt und b) die entstehenden 1-ydroxyverbindungen gegebenenfalls mit Fettsfiureglyceridestern einer Umnesterung unterwirft.

WO 93/05008 PCT/EP92/01905 Method of Producing Epoxy-Ring Opening Products Field of the Invention This invention relates to epoxide ring opening products obtainable by reaction of epoxide compounds with nucleophiles in the presence of lithium salts and optionally transesterification of the hydroxy compounds formed as intermediate products with fatty acid glyceride esters, to a process for their production and to their use for the production of polymers.

Prior Art To produce polyurethane foams, diisocyanates are reacted with substances which contain at least two free hydroxyl groups. Hydroxy compounds particularly suitable for the production of such plastics are normally produced by ring opening of epoxide compounds with nucleophiles, for example alcohols, in the presence of alkaline or acidic catalysts [Fette, Seifen, Anstrichmitt., 89, 147 (1987)].

US 4,057,589 for example describes a process for the production of tetrols, in which unsaturated diols are reacted with peracetic acid and the epoxides formed are subsequently hydrolyzed at temperatures of at least 120*C.

EP 0 127 810 Al describes the sulfuric-acid-catalyzed ring opening of epoxides of unsaturated fatty acid esters with alcohols and their subsequent saponification.

DE 32 46 612 Al describes a process for the production of modified triglycerides in which epoxidized fats

'C,

WO 93/05008 PCT/EP92/01905 or oils are reacted with monohydric or polyhydric alcohols in the presence or sulfuric acid, phosphoric acid or sulfonic acids.

Finally, EP 0 257 332 B1 describes a process for the continuous production of 1,2-diols, in which epoxides are subjected to pressure hydrolysis with water in the presence of acidic catalysts.

All these known processes are attended by the disadvantage that the acidic or alkaline catalysts have to be neutralized after the reaction. The salts accumulating have to be removed with considerable effort because otherwise they can cause clouding of the products or may lead to an undesirably violent reaction between polyol and diisocyanate.

Accordingly, the problem addressed by the present invention was to provide a process for the production of epoxide ring opening products which would be free from the disadvantages described above.

Description of the Invention The present invention relates to a process for the production of epoxide ring opening products, characterized in that a) epoxide compounds are reacted with nucleophiles in the presence of lithium salts and b) the hydroxy compounds formed are optionally transesterified with fatty acid glyceride esters.

It has surprisingly been found that the ring opening of epoxides takes place quickly and substantially quantitatively even in the presence of very small quantities of lithium hydroxide and/or lithium fatty acid salts. In WO 93/05008 PCT/EP92/01905 addition, the quantities of lithium still present in the epoxide ring opening products are sufficient to catalyze any transesterification with fatty acid glyceride esters.

Another advantage of the process according to the invention is that there is no need for neutralization and/or removal of the lithium salts because the small quantities used do not adversely affect either the properties of the products or their behavior in subsequent processing steps.

Epoxide compounds are known substances and may be obtained in known manner by epoxidation of unsaturated starting materials. Examples of relevant methods are the reaction of olefins with peracetic acid in the presence of acidic catalysts [DE 857 364] or with performic acid formed in situ from formic acid and hydrogen peroxide [US 2,485,160]. If the process according to the invention is to be successfully carried out, a substantial percentage content, for example 2 to 40% by weight and preferably 4 to 8.5% by weight, of epoxide oxygen must be present in the epoxide compounds. This includes the observation that not only completely epoxidized, but also partly epoxidized substances may be used in the process according to the invention.

Epoxide compounds in the context of the invention are al) ethylene oxide, propylene oxide and/or butylene oxide, a2) epoxides of olefins corresponding to formula Ri-CH=CH-R 2

(I

in which R 1 is a linear or branched aliphatic hydrocarbon radical containing 1 to 18 carbon atoms

*I"

WO0 93/05008 PCT/EP92/01905 and R 2 is hydrogen or a linear or branched hydrocarbon radical containing 1 to 8 carbon atoms.

Typical examples are the epoxides of oct-l-ene, dec- 1-ene, dodec-l-ene, tetradec-l-ene, octadec-l-ene or octadec-9-ene. Epoxides of olefins corresponding to formula in which the sum total of R 1 and R 2 is a number of 8 to 16, are preferred.

a3) Epoxides of esters corresponding to formula (II):

R

3

CO-OR

4

(II)

in which R 3 CO is an aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R 4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms. Typical examples are the epoxides of palmitoleic acid methyl ester, oleic acid methyl ester, elaidic acid methyl ester, petroselic acid methyl ester, linoleic acid methyl ester or erucic acid methyl ester. Epoxides of esters corresponding to formula in which R 3 CO is an aliphatic hydrocarbon radical containing 18 to 22 carbon atoms and 1 or 2 double bonds and R 4 is a methyl group, are preferred.

a4) Epoxides or esters corresponding to formula (III):

R'CO-OR

6

(III)

in which R 5 CO is an aliphatic acyl radical containing 1 to 24 carbon atoms and 0 or 1 to 5 double bonds and R 6 is a linear or branched aliphatic hydrocarbon radical containing 16 to 24 carbon atoms and 1 to double bonds. Typical examples are epoxides or acetic acid oleyl ester, oleic acid oleyl ester or

V)

WO 93/05008 5 PCT/EP92/01905 erucic acid oleyl ester. Epoxides of esters corresponding to formula (III), in which R 5 CO is an aliphatic acyl radical containing 18 to 22 carbon atoms and 1 or 2 double bonds and R 6 is an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and 1 or 2 double bonds, are preferred.

Epoxides of fatty acid glyceride esters corresponding to formula (IV): CHzO-CO-R

I

CH-O-CO-R

B

(IV)

I

CHzO-CO-R 9 in which R 7 CO is a linear or branched aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to double bonds and R 8 CO and R 9 CO independently of one another represent a linear or branched aliphatic acyl radical containing 6 to 22 carbon atoms and 0 or 1 to 5 double bonds and mixtures thereof.

Typical examples are epoxides of peanut oil, coriander oil, cottonseed oil, olive oil, linseed oil, beef tallow, fish oil or, more particularly, soybean oil. Epoxides of glycerol fatty acid esters corresponding to formula (IV) in which R'CO, R 8 CO and R 9

CO

independently of one another represent aliphatic acyl radicals containing 18 to 22 carbon atoms and predominantly 1 or 2 double bonds, are preferably used.

The following compounds may be used as the nucleophiles required for the ring opening of the epoxide compounds: .4 WO 93/05008 PCT/EP92/01905 bl) Water b2) Alcohols corresponding to formula RIOH

(V)

in which R 10 is a linear or branched aliphatic hydrocarbon radical containing 1 to 22 carbon atoms and 0 or 1 to 3 double bonds. Typical examples are methanol, ethanol, l-propanol, 2-propanol, n-butanol, pentanol, hexanol, octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol or erucyl alcohol. Methanol and ethanol are preferably used.

b3) Polyhydric alcohols selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycols with molecular weights in the range from 300 to 1,500, propane-l,2-diol, propane-1,3diol, glycerol, oligoglycerols having degrees of condensation of on average 2 to 10, trimethylol propane, pentaerythritol, sorbitol and sorbitan.

b4) Fatty alcohol polyglycol ethers corresponding to formula (VI):

R

1 2

I

RO- (CH 2 CHO) H (VI) in which R" is a linear or branched aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 1 2 is hydrogen or a methyl group and n is a number of 1 to 30. Typical examples are adducts of on average 1 to 30 moles of 4.

WO 93/05008 PCT/EP92/01905 ethylene and/or propylene oxide with 1 mole of hexanol, octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol or erucyl alcohol. Fatty alcohol polyglycol ethers corresponding to formula in which R" is a C-_ 1 8 alkyl radical, R 12 is hydrogen and n is a number of 1 to 10, are preferably used.

The epoxide compounds and the nucleophiles may be used in molar ratios of 1:10 to 10:1 and preferably in molar ratios of 1:3 to 3:1.

Besides lithium hydroxide, suitable lithium salts include lithium soaps, i.e. salts of lithium with optionally hydroxyfunctionalized fatty acids containing 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples are the lithium salts of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, 12hydroxystearic acid, ricinoleic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. The lithium salts may be used in the form of an aqueous or alcoholic solution. Because they readily lend themselves to metering, the lithium salts of unsaturated fatty acids, which are liquid in any event, are preferably used. the lithium soaps may be directly added to the reaction mixture. However, they may also be formed in situ, for example from lithium hydroxide and a fatty acid ester.

The lithium salts may be used in quantities of 0.001 to 0.1% by weight, preferably in quantities of 0.002 to 0.05% by weight and more preferably in quantities of 0.005 to 0.01% by weight, based on the starting materials. Since lithium ions are capable of exchange with the alkali metal ions present in glasses, which can lead to WO 93/05008 PCT/EP92/01905 a reduction in the concentration of lithium ions, it is advisable to carry out the process in reactors of steel or similarly inert materials.

The ring opening reaction may be carried out in known manner. It has proved to be of advantage to carry out the reaction at the boiling temperature of the nucleophile used or at a temperature in the range from 100 to 250*C. It is not absolutely essential for the ring opening reaction to be complete. Instead, epoxide ring opening products which still have a defined residual epoxide oxygen content, for example 1 to 3% by weight, may also be produced.

Suitable fatty acid glyceride esters with which the ring opening products may optionally be transesterified are triglycerides corresponding to formula (VIz): CHO2-CO-R 1 3

I

CH-O-CO-R

4

(VII)

I

1 in which R 13 CO is a linear or branched, optionally hydroxy- and/or alkoxy-substituted aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R1CO and R CO independently of one another represent a linear or branched aliphatic acyl radical containing 6 to 24 carbon atoms and 0 or 1 to 5 double bonds. Typical examples are natural fatty acid glyceride esters of vegetable or animal origin based on rapeseed oil, castor oil, palm oil, soybean oil or coconut oil and also chemically modified triglycerides of the soya polyol type which are obtained by epoxidation of soybean oil and subsequent opening of the oxirane rings with suitable nucleophiles, for example alcohols.

j WO 93/05008 PCT/EP92/01905 The molar ratio between epoxides and fatty acid glyceride esters may also be from 10:1 to 1:10 and is preferably from 3:1 to 1:3. The transesterification may be carried out in known manner at temperatures in the range from 100 to 250*C. As mentioned above, the concentration of lithium remaining in the ring opening product is sufficient to catalyze the transesterification reaction also. Accordingly, there is no need for other catalysts to be added. The transesterification reaction may be carried out completely or partly, for example to between 10 and 90% by weight and, more particularly, to between 20 and 70% by weight, based on the fatty acid glyceride ester.

In one preferred embodiment of the invention, the ring opening and transesterification are carried out in one step rather than successively. If unreacted nucleophile still present in the product adversely affects the performance properties of the ring opening products or interferes with their subsequent processing, it may be removed, for example by distillation. It does not matter whether distillation is carried out after the ring opening reaction or after the transesterification reaction.

The present invention also relates to epoxide ring opening products obtainable by a) reacting epoxide compounds with nucleophiles in the presence of lithium salts and b) optionally subjecting the hydroxy compounds formed to transesterification with fatty acid glyceride esters.

WO 93/05008 PCT/EP92/01905 Industrial Applications The epoxide ring opening products obtainable by the process according to the invention are suitable as raw materials for the production of polymers. For example, they may be incorporated in alkyd resins by condensation both by way of the hydroxyl functions and by way of epoxide groups still present in the molecule and represent polyfunctional polycondensation units which are of particular importance for the development of polyurethane foams.

Accordingly, the present invention relates to the use of the epoxide ring opening products according to the invention for the production of polymers i. which they may be present in quantities of 1 to 90% by weight and preferably in quantities of 10 to 70% by weight, based on the polymers.

The following Examples are intended to illustrate the invention without limiting it in any way.

Examples Example 1: A mixture of 260 g of soybean oil epoxide, epoxide oxygen content 6.68% by weight corresponding to 1.08 mole of epoxide, 741 g (0.83 mole) of new rapeseed oil, oleic acid content 80% by weight and 299 g (3.25 moles) of glycerol was introduced into a 2-liter three-necked flask equipped with a stirrer, after which 0.13 g (0.0054 mole) of lithium hydroxide, corresponding to 0.01% by weight 1s V( WO 93/05008 PCT/EP92/01905 (based on the starting materials), was introduced with stirring. The reaction mixture was heated to 220"C. The course of the ring opening reaction was followed on the basis of the change in the concentration of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

Example 2: As in Example 1, 260 g of soybean oil epoxide, 741 g of rapeseed oil and 299 g of glycerol were reacted at 240°C in the presence of 0.03 g of lithium hydroxide, corresponding to 0.002% by weight (based on the starting materials). The course of the ring opening reaction was followed on the basis of the change in the concentration of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

Example 3: As in Example 1, 390 g of soybean oil epoxide, corresponding to 1.6 mole of epoxide, 611 g (0.7 mole) of new rapeseed oil and 299 g of glycerol were reacted at 220 to 240°C in the presence of 0.13 g of lithium hydroxide, corresponding to 0.01% by weight, based on the starting materials. The course of the ring opening reaction was followed on the basis of the change in the concentration of epoxide oxygen in the reaction mixture.

The results are set out in Table 1.

Example 4: As in Example 1, 260 g of epoxystearic acid methyl ester, 910 g (1 mole) of new rapeseed oil and 130 g (1.4 mole) of glycerol were reacted at 220 to 240°C in the presence of 0.13 g of lithium hydroxide, corresponding to 0.01% by weight (based on the starting materials). The course of the ring opening reaction was followed on the V: 0, WO 93/05008 PCT/EP92/01905 basis of the change in the concentration of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

Example 520 g of epoxystearic acid methyl ester, 520 g (0.6 mole) of new rapeseed oil and 260 g (2.8 moles) of glycerol were reacted at 220 to 240*C in the presence of 0.13 g of lithium hydroxide, corresponding to 0.01% by weight (based on the starting materials). The course of the ring opening reaction was followed on the basis of the change in the concentration of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

Comparison Example 1: As in Example 1, 260 g of soybean oil epoxide, 741 g of rapeseed oil and 299 g of glycerol were reacted at 240 0 C in the presence of 0.26 g of potassium hydroxide, corresponding to 0.02% by weight (based on the starting materials). The course of the ring opening reaction was followed on the basis of the change in the concentratxon of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

,I 4 v 7 i WO 93/05008 PCT/EP92/01905 Table 1: Epoxide oxygen contents Ex. Epoxide oxygen content by weight) after h 0 1 2 3 4 5 7 1 1.3 1.3 0.8 0.4 0.2 2 1.3 1.2 0.6 0.3 0.2 3 2.0 1.5 0.8 0.3 0.1 4 0.9 0,9 0.5 0.3 0.1 1.9 1.1 0.6 0.5 0.2 C1 1.3 1.2 0.6 0.6 Example 6: 2400 g (26 moles) of glycerol were introduced into a 4-liter steel autoclave and, after the addition of 0.45 g of lithium hydroxide, were heated to 80*C. Any traces of water remaining were removed by evacuation and purging with nitrogen five times. The reaction mixture was then heated to 150 0 C and 1,500 g (26 moles) of propylene oxide were added in portions so that the pressure in the reactor did not exceed 5 bar. On completion of the reaction (approx. 3 the reaction mixture was cooled to 80 to 100°C and evacuated for about 15 minutes to remove traces of unreacted propylene oxide. Approximately 2900 g of glycerol propoxylate were obtained in the form of a clear colorless liquid which had a hydroxyl value of 1,200.

498 g (3.3 moles) of the glycerol propoxylate containing lithium hydroxide and 1,495 g (1.7 moles) of new rapeseed oil were transesterified with stirring for 6 h at 240*C. Approximately 1,950 g of a clear pale yellow liquid with the following characteristic data were )23 AIIl' 'VT o~r WO 93/05008 obtained: PCT/EP92/01905 Hydroxyl value Saponification value Acid value Li content 280 142 0.8 7. 5 ppm

Claims (21)

1. A process for the production of epoxide ring opening products, characterized in that a) epoxide compounds are reacted with nucleophiles in the presence of 0.001 to 0.01% by weight based on the starting materials of lithium salts and b) the hydroxy compounds formed are optionally trans- esterified with fatty acid glyceride esters.

2. A process as claimed in claim 1, characterized in that ethylene oxide, propylene oxide and/or butylene oxide is/are used as the epoxide compound.

3. A process as claimed in claim 1, characterized in that epoxides of olefins corresponding to formula 1 .2 R -CH=CH-R (I) 20 in which R' is a linear or branched aliphatic hydrocarbon :i radical containing 1 to 18 carbon atoms and R 2 is hydrogen or a linear or branched hydrocarbon radical containing 1 to 8 carbon atoms, *are used as the epoxide compounds. S 25 4. A process as claimed in claim 1, characterized in that epoxides of esters corresponding to formula (II): R* oo RCO-OR 4 (II) in which R 3 CO is an aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R 4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms, are used as the epoxide compounds.

5. A process as claimed in claim 1 characterized in 16 that epoxides of esters corresponding to formula (III): RSCO-OR 6 (III) in which R 5 CO is an aliphatic acyl radical containing 1 to 24 carbon atoms and 0 or 1 to 5 double bonds and R 6 is a linear or branched aliphatic hydrocarbon radical contain- ing 16 to 24 carbon atoms and 1 to 5 double bonds, are used as the epoxide compounds.

6. A process as claimed in claim 1, characterized in that epoxides of fatty acid glycerol esters corresponding to formula (IV): CHO 2 -CO-R 7 I CH-O-CO-R 8 (IV) 20 in which R 7 CO is a linear or branched aliphatic acyl •double bonds and R 8 CO and R 9 CO independently of one 2 another represent a linear or branched aliphatic acyl radical containing 6 to 24 carbon atoms and 0 or 1 to 25 double bonds and mixtures thereof, are used as the epoxide compounds.

7. A process as claimed in at least one of claims 1 to 6, characterized in that water is used as the nucleo- phile. 30 8. A process as claimed in at least one of claims 1 to 6, characterized in that alcohols corresponding to formula R 10 0H (V) /4IRc' in which R 10 is a linear or branched aliphatic hydrocarbon radical containing 1 to 22 carbon atoms and 0 or 1 to 3 double bonds, are used as the nucleophiles.

9. A process as claimed in any one of claims 1 to 6, characterized in that polyhydric alcohols selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycols with molecular weights in the range from 300 to 1500, propane-1,2-diol, propane-l,3-diol, glycerol, oligoglycerols having degrees of condensation of on average 2 to 10, trimethylol propane, pentaerythritol, sorbitol and sorbitan, are used as the nucleophiles. A process as claimed in any one of claims 1 to 6, characterized in that fatty alcohol polyglycol ethers corresponding to formula (VI): I WloO-(H2L;Hu)nH (VI) S in which R 11 is a linear or branched aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 12 is hydrogen or a methyl group and n is a number of 1 to 30, are used as the nucleophiles.

11. A process as claimed in any one of claims 1 to 10, characterized in that the epoxide compounds and the nucleophiles are used in a molar ratio of 1:10 to 10:1.

12. A process as claimed in any one of claims 1 to 11, characterized in that lithium hydroxide is used as the lithium salt.

13. A process as claimed in any one of claims 1 to 11, characterized in that 20 lithium soaps of optionally hydroxy-substituted fatty acids containing 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds are used as the lithium salts.

14. A process as claimed in any one of claims 1 to 13, characterized in that the ring opening reaction is carried out at the boiling temperature of the nucleophile used or at a temperature in the range from 100 to 250 0 C.

15. A process as claimed in at least one of claims 1 to 14, characterized in that triglycerides corresponding to formula (VII): CH 2 0-CO-R 1 3 CH-O-CO-R 14 (VI) CH 2 0-CO-R 1 in which R 13 CO is a linear or branched, optionally hydroxy- and/or alkoxy-substituted aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R 14 CO and R 15 CO independently of one another represent a linear or branched aliphatic acyl radical containing 6 to 24 carbon atoms and 0 or 1 to 5 double bonds, are used as the fatty acid glyceride esters in the transesterification reaction.

16. A process as claimed in any one of claims 1 to 15, characterized in that the expoxides and the fatty acid glyceride esters are used in a molar ratio of 10:1 to 1:10. A L"s, [n:\libffj00189:dss

17. A process as claimed in any one of claims 1 to 16, characterized in that the transesterification is carried out at a temperature in the range from 100 to 250 0 C.

18. A process as claimed in any one of claims 1 to 17, characterized in that the ring opening and transesterification reactions are carried out in a single step.

19. Epoxide ring opening products when obtained by reacting epoxide compounds with nucleophiles in the presence of 0.001 to 0.01% by weight based on the starting materials of lithium salts and optionally subjecting the hydroxy compounds formed to transesterification with fatty acid glyceride esters.

20. A method of producing alkyd resins and polyurethane foams, which method comprises using as a raw material at least one epoxide ring opening product obtained by the process as claimed in any one of claims 1 to 18.

21. A meiLud of producing alkyd resins and polyurethane foams, which method comprises using as a raw material at least one epoxide ring opening product as claimed in claim 19.

22. A process for the production of epoxide ring opening products, which process is substantially as herein described with reference to any one of Examples 1 to 6 excluding Comparison Example 1.

23. Epoxide ring opening products when obtained by the process of claim 22. 20 Dated 19 April, 1995 •Henkel Kommanditgesellschaft auf Aktien Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON 0**0 o 'I [n:\libff]00tl 89:ss INTERNATIONAL SEARCH REPORT International application No. PCT/EP 92/01905 A. CLASSIFICATION OF SUBJECT MATTER SCl.5 C07C67/31; CQ7C69/708; C07C69/675; C07C29/10 C07C41/03; C07C31/20; C07C43/13 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C07C Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A WO, A, 9 111 424 (HENKEL) 1 8 August 1991 see page 2, paragraph 4 page 4, Paragraph 1 see page 11 page 13; claims A EP, A, 0 437 001 (STAMICARBON 1 17 July 1991 see column 3, example 1 see column 3- column 4; claims A CH, A, 484 861 (STAMICARBON 1 31 January 1970 see column 1, line 17 line 41 see column 4; claim S Further documents are listed in the continuation of Box C. See patent family annex. Special categories of cited documents: laterdocument published afterthe international filingdateorpriority document defining the general state of the art which is not considered date a n in co with te appliion butcited to understand to be of particular relevance the principle or theory underlying the invention earlier document but published on or after the international filing date document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to involve an inventive document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other special reason (as specified) document of particular relevance; the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined with oneor more othersuch documents. such combination .being obvious to a person skilled in the art document published prior to the international filing date but later than o ou to er the a the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report November 1992 (05.11.92) 23 November 1992 (23.11.92) Name and mailing address of the ISA/ Authorized officer EUROPEAN PATENT OFFICE Facsimile No. Telephone No. Form PCT/ISA/210 (second sheet) (July 1992) ANNLX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION No. EP SA 9201905 63558 Tids annex limt the patent family members relating to the patent documents cited in the above-mentioned international search report. Ile members are as contained in te European Patent Office EDP file on 7he European Patent Office is in no way liable for these particulars which arm merely given for the purpose of information. 05/11/92 Patent document PublicationPaetfmlPuicio citedt in searcia report PuI d on Pae1 famildat WO-A-9111424 08-08-91 DE-A- 4002213 CN-A- 1053608 01-08-91 07-08-91 EP-A-0437001 17-07-91 NL-A- 9000035 01-08-91 CH-A-484861 31-01-70 BE-A- 693292 27-07-67 DE-A- 1643058 15-04-71 FR-A- 1509555 GB-A- 1111024 NL-A- 6601300 02-08-67 US-A- 3522300 28-07-70 M For mom detaik about this annex see Official Journal of the European Patent Office, r4o. 12182 INTERNATIONALER RECHERCHENBERICHT Interrationales Alieazeichen PCT/EP 92/01905 1. KLASSIFIL4TION DES ANMELDUNGSGEGENSTANDS (bei rnabfrem Kimifikatiornsymboien slat alit azugebca)' Nach der Internationalea Patentl1=1fikation (IC ader nach der natjonajen EiusiflkAton un-- der IPC Int.K1. 5 C07C67/31; C07C639/708; C07C691675; C07C29110 C07C41/03; C07C31/20; C07C43/13 U. REMiERMHERTE SAQIGEBIET Recherclerter MlndeStprlftoaff 7 Klassiflicatlonsstern lasslflkationssym bale Int.K1. 5 C07C Racchcrte nit zum Mindestpriffstaff getulrende Vesrlffentlichunme, sowett die unter die recierdilertei Sadigebicte fallen HI. EINSCHIAGIGE VEROFFENTUCHUNGEN 9 ArV Kenazeicbnung der Vertlffatlidhuzog" sowtit erfordexticb unter Angahe der maflebicben Tels L2 Be. Azispruch NrJ3 A WO,A,9 111 424 (HENKEL) 1 8. August 1991 siehe Seite 2, Absatz 4 Seite 4, Absatz 1 siehe Seite 11 Seite 13; AnsprUche A EP,A,0 437 001 (STAMICARBON BYV.) 1 17. Juli 1991 siehe Spalte 3; Beispiel 1 siehe Spalte 3 Spalte AnsprUche A CH,A,484 861 (STAMICARBON 1

31. Januar 1970 siehe Spalte 1, Zeile 17 -Zeile 41 siehe Spalte 4; Anspruch BaDsondere Kategorlezi van angegebenezi Verllffentlicbunge' 0 Veft atlicbung, die den aligemelnen Stand der Tedinik 'T Spitern Verlffenticu die nacb deta internLmlonsal An- defniert, abet nicht als besonders bedeutsim mnmsehen 1st re1dodatuto odor do cri litsdatum vceloffentiicht warden IV Aters Dkumet, es sdoch e dornachdemlat=-1st und mit der Anmeldung nicht knlilirt, sonder u zu ai tiotee Dokmet ed ocbm ert 1 am 4ct flad s Vcrntindnls de der Erflodung zupimidilegooden Pinxip tlnnkzi nmcledatm vetlffntllht wrdeodotrw der ibr uredeliegeden Theorie angegeben ist WL Vertlffentiichung, die gelnet ist, elnen Prtorititsan ''Vrsralcun o esaudBoetnrdebanpub zwelfeihaft erscheinen zu iwsen, 04cr dumbh die das We~-X Vrlfztlin o eonrrtBduugdebas.ub fectlichungsdatum slowt anderta im Rederdiatbericht go- to Effindung kann nicht Ws neu odor auf orfindeuisdr Titg- nantni Vertlffentlicbung beiqit werden soil 04cr die airs tinem keit beflubei botmcbts werien andereo besondurn Grand angegeben, it (wie aisgefuhrt) 'Y Vetlifentlicirung von besonderer Bodoutg die beans rucb- '0'Verentichngdiesic adein mlndlcheOffnbzun&te Erfndung kazin nicht Lis auf effinderi er TWtI&T tbe- 0 Vellfattlchng ie ech artmin mohndicheOfflbaun&ruhend betmebtet warden, wean die Vertlifentlidaung mit eta. flenutrarag, cine Aussteliung 04cr andere Mailnahmen einer 04cr menrerenaonderen Vaetlffentichung'en dieset Kate- bezimibt gorte in Verbindung lebmdat wini und ties* Icstaltduaj flU 'P Verlfentlichung. die vor des. internationalen Anmeldeda- in Fachmana cabellMgas i st turn, abet nach dern beansprchtea Prioriti1sdatum verat-t Vertlffantilchung, die Mitglled derseben Patentfavail lIt lildt warden ist IV. BESCIIEINIGUNG Datum des Abschlusses der internationalen Recherche Absendedatulo des inot noWR11rchebeichts 1992 Intematonale Rcerhenbebbrde Lnterscbrlft des be-Milmliclttgten Dediensteten EUROPAISCHES PATENTAMT KINZINGER J.M. FeimlmI PCTIISA/210 tO~ot 21 jJa-e ISS ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT ODBER DIE INTERNATIONALE PATENTANMELDLJNG NIL EP SA 9201905 63558 In diese Anhong sind die Mitglcder der Patentflamilien der im obencenannten internationaica Rccerdienbezicht angeffibtesi Paterztdokumente angqgebcn. Die Angahen Oiber die Famifiazmitgfieder entsprechen dem Stand der Datei des Esaropiisdien Patentamtt amm Diese Angahen diacen nur zur Unterricbbmg and erfolgen obne GmWih. 05/11/92 Ims Rcchercbeahericbt Datum der Mitglied(cr) der Ditumi der angeiWirtes Patentdokuminct VerbrYentiichung Patectfalmilie Vacrbffntidaung WO-A-9111424 08-08-91 DE-A- 4002213 CN-A- 1053608 01-08-91 07-08-91 EP-A-0437001 17-07-91 NL-A- 9000035 01-08-91 CH-A-484861 31-01-70 BE-A- 693292 27-07-67 DE-A- 1643058 15-04-71 FR-A- 1509555 GB-A- 1111024 NL-A- 6601300 02-08-67 US-A- 3522300 28-07-70 Hir nibere Finzelbeiten zu diescim Anhang siebe AnitsWatt des Europiischen Patentombi Nr.12182