CA2116536A1

CA2116536A1 - A process for the production of epoxide ring opening products

Info

Publication number: CA2116536A1
Application number: CA 2116536
Authority: CA
Inventors: Peter Daute; Johann Klein; Roland Gruetzmacher; Rainer Hoefer
Original assignee: Individual
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-08-29
Filing date: 1992-08-20
Publication date: 1993-03-18
Also published as: AU660486B2; ES2085030T3; EP0600958B1; DE59205777D1; BR9206415A; JPH06510053A; DE4128649A1; EP0600958A1; WO1993005008A1; AU2437592A

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.

Description

211~S3~

wo 93/05008 PCT/BP92/019OS

A proc~ss for t~e product~on of epoxid~ ri~g opening proaucts Fiel~ o~ the I~vent~o~

This invention relates to epoxide ring opening products obtainable by reaction of epoxide compounds with nucleophiles in the presence of lithium salts and option-ally transesterification of the hydroxy compounds formed S 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 aci~ic catalysts (Fett~, S~ife~, A~trich~itt., 89, 147 (1987)).
U8 4,057,589 for example describes a process for the production o~ ~.etrols, in which unsaturated diols are reacted with peracetic acid and the epoxides formed are subsequently hydrolyzed at temperatures of at least 12~C. --EP O 127 810 A1 describes the sulfuric-acid-cata-lyzed-ring opening of epoxides of unsaturated fatty acid esters-wi~h alcohols and their su~sequent saponification.
D~ 32 4S 612 A1 describes a process for the produc-tion of modified triglycerides in which epoxidized fats or-oils are reacte~ with monohydric or polyhydric al-cohols in the presence or sulfuric acid, phosphoric acid or sulfonic acids.
Finally, EP 0 257 332 B1 describes a process for the S 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 ac-cumulating have to be removed with considerable effort because otherwise ~hey can cause clouding of the products or may lead to an undesirably violent reaction between polyol and diisocyanate.
lS Accordingly, the problem addressed by the present invention was to provide a process for the production of epoxide ring opening products which would be freP from the disadvantages described above.

De cription of the Invention The present invention relates to a process for theproduction of epoxide ring opening products, charac-terized in that a) epoxide compounds are r~acted with nucleophiles in the presence of lithium~salts and !: l b) the hydroxy compounds formed are optionally trans-esterified with fatty acid glyceride esters.

- It has surprisingly--~een found that the ring opening of epoxides takes place-quickly and substantially quanti-tatively even in the presence of very small quantities of lithium hydroxide and/or lithium fatty acid salts. In 211~.~36 3 PCT/E:P92/01905 - 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 inven-S tion 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.
loEpoxide 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 (D~ 857 ~64) or with perfo~mic;acid formed in situ from formic acid and hydrogen peroxide (~8 2,~85,160). 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 accord-- - ing to the invention.
~ poxl~e compounds in the context of the invention ; 25 are , _ .
~-al) ethylene oxi~e, propylene o~ide and/or butyleno - oxl~

3~- a2) epoxides of olefins corresponding to formula (I):
,, - .~, Rl--C~=C~-R~

. , , in which R' is a linear or branched aliphatic hydro-- 3S carbon radical containing 1 to 18 carbon atoms and 2116~3S

wo 93/05008 4 PCT/EP92/01905 R2 is hydrogen or a linear or branched hydrocarbon radical containing 1 to 8 carbon atoms. T~pical examples are the epoxides of oct-1-ene, dec-1-ene, dodec-1-ene, tetradec-l-ene, octadec-l-ene or octadec-9-ene. Epoxides of olefins corresponding to formula (I), in which the sum total of Rl and R2 is a number of 8 to 16, are preferred.
a3) Epox~des of e~t~r~ corresponding to ~ormula R3Co-o~4 ~II) in which R'CO is an aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and is a linear or branched alkyl radical containing 1 to 4 carbon atoms. Typical examples are the epox-ides of palmitoleic~ acid methyl ester, oleic acid ; methyl ester, elaidic acid methyl ester, petroselic aaid methyl ester, linoleic acid methyl ester or erucic acid methyl ester. Epoxides of esters corre-sponding to formula ~II), in which R'CO is an ali-phatic hydrocarbon radical containing 18 to 22 carbon atoms and 1 or`2 double bonds and R~ is a methyl group, are preferred.
a4) Epox~de~ of e~ters corresponding to formula ~III):

R5Co-oR~ ~III) in which *CO is an aliphatic acyl radical containing 1 to 24 carbon atoms and 0 or 1 to 5 double bonds and R~ is a linear or branched aliphati¢ hydrocarbon radical containing 16 to 24 carbon atoms and 1 to 5 double bonds. Typical examplas are epoxides of acetic acid oleyl ester, oleic acid oleyl ester or .-:

, ~

2116~.6 WO g3/05008 5 PCT~EP92/01905 erucic acid oley~ ester. Epoxide~ of esters corre-sponding to formula ~ , in which R5Co is an aliphatic acyl radical containing 18 to 22 carbon atoms and 1 or 2 double bonds and R6 is an aliphatic hydrocarbon radical containing 16 to 22 carbon atoms and l or 2 double bonds, are preferred.

a5) Epoxide~ of fatty acid glyceride Q~t2r3 correspond-ing to formula (IV):

C}I20-CO-R7 C~-o_co-~8 (I~) CH2O-CO-R~

in which R7Co is a linear or branched aliphatic acyl radical containing 16 to 24 carbon atoms and l to 5 double bonds and R8C0 and R9Co independently of one another represent a linear or branched aliphatic acyl radical containing 6 to 22 carbon atoms and 0 or l to 5 double bonds and mixtures thereof.
Typical examples are epoxides of peanut oil, cori-ander oil, cottonseed oil, olive ~il, linseed oil, 25 - beef tallow, fish oil or, more particularly, soybean oil. Epoxides of glycerol fatty acid esters corre-sponding to formula ~IV), in which R7C~ CO and R9Co independently of one another represent aliphatic acyl radicals containing 18 to 22 carbon atoms and predominantly 1 or 2 double bonds, ar~ preferably used.

The following compounds may be used as the nucleo-phile~ required for the ring opening of the epoxide compounds:

21lSS3~

bl) ~ater b2) Alcohol~ corresponding to formula (V):

Rl90H (V) in which R' is a linear or branched aliphatio hydrocarbon radical containing 1 to 22 carbon atoms and 0 or 1 to 3 double bonds. Typical examples are ~0 methanol, ethanol, l-propanol, 2-propanol, n-butan~
ol, 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 consist-ing of ethylene glycol, diethylene glycol, polyethy-lene glycols with number average molecular weigh~s in the range from 300 to 1,500, propane-1,2-diol, propane-1,3-diol, glycerol, oligoglycerols having degrees of condensation of on average 2 to 10, trimethylol propane, pentaerythritol, sorbitol and sorbitan.

b4) Fatty alcohol polyglycol ether~ corresponding to formula tVI):
R~ ~ ~~-~
, R"0-~C~C~O),H tVI) in which R" is a linear or branched aliphatic hydrocarbon radical containing 6 to 22 carbon atoms ; and 0 or ~~-to 3 double bonds, Rl2 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 .

211653~

~0 93/OS008 7 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 ~I) r in which Rl1 is a C6la alkyl radical, Rl2 is hydrogen and n is a number of 1 to 10, are preferab-ly used.

The epoxide compounds and the nucleophiles may be used in molar ratios of l:10 to 10:1 and preferably in molar ratios of 1:3 to 3:1.
Besides lithium hydroxide, suitable lithium salt~
include lithium soaps, i.e. salts of lithium with option-ally 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, 12-hydroxystearic 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 I example from lithium hydroxide and a fatty acid ester.
- -- 30 The lithium salts may be used in quantities of 0.001 to 0.1% by weight, preferably in quantities of 0.002 to -- O.05% by weight and more preferably in quantities of ~- 0.005 to 0.01% by weight, based on the starting materi-als. Since lithium ions are capable of exchange with the alkali metal ions present in glasses, which can lead to 211~536 a reduction in the concentration of lit-hium 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 250C. 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 glyceri~e ~ter~ with which the ring opening products may optionally be transesterified 15- are triglycerides corresponding to formula ~VII):

CR2o-Co-Rl3 I

C}I-O-CO--Rl~ tVII ) CH2O-co-~l5 in which R13Co is a linear or branched, optionally hy-droxy- and/or alkoxy-substituted aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R1~CO and R15Co 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 vege-table 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.

21 1 6 .~ 3 6 Wo 93/05008 9 PC~tEP92/01905 The molar ratio be~ween the ring opening products and fatty acid glyceride esters may also be from 10:1 to 1:10 and is prefarably from 3:1 to 1:3. The transesteri-fication may be carried out in known manner at tempera-tures in the range from 100 to 250C. As mentioned above, the concentration of lithium remaining in the ring opening product is sufficient to catalyze the transester-ification reaction also. Accordingly, there is no need for other catalysts to be added. The transesterification reaction may be carried out complstely or partly, for example to between 10 and 90% by weight and, more partic-ularly, 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 nucleo-phile 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 reac-- - tion.
The present invention also relates to epoxide ring opening products obtaina~le by -- - a) reacting epoxide compounds with nucleophiles in the - ~ presence of lithium salts and i: , i ' , . !
~30 b) optionally subjecting the hydroxy compounds formed ~ to transesterification with fatty acid glyceride --_- esters.
~ . .

2116 ~ 3 S
~o 93/05008 lo pcT/~s2/olgos ~ u~tr~l Applications The epoxide ring opening products obtainable by the proces~ 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 with polybasic acids, e.g. phthalic anhydride, both by way of the hydroxyl functions and by way of epoxide groups still present in the molecule and represent polyfunctional polycondensation units for reaction with polyisocyanates 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 in which they may be present in quantities o~ 1 to 90% by weight and preferably in quantities of 10 to 70% by weight, based on the polymer~.
The following Examples are intended to illustrate the invention without limiting it in any way.

~xample~

Example~
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 intro~uced 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 211~536 WO 93/05008 11 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 ~ollowed on the basis of` the change in the concentration of epoxide S oxygen in the reaction mixture. The results are set out in Table 1.

Ex~ample 2:
As in Example 1, 260 g of soybean oil epoxide, 741 g of rapeseed oil and 299 g of glycerol were reacted at 240C in the presence of 0.03 g of lithium hydroxide, corresponding to 0.002% by weight tbased on the starting materials). The course of the ring opening reaction was followed on the basis of the change in the concentration lS of epoxide oxygen in the reaction mixture. The resul s 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 hydrox-ide, 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 concen~tration of epoxide oxygen in the reaction mixture.
The results are set out in Table 1.

Example 4: ~
30-- As in Example 1, 260 g of epoxystearic acid methyl estsr, 910 g (1 mole) of new rapeseed oil and 130 g (1.4 mo~e~ o~ glycerol were reacted at 220 to 240C in th~
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 .

2116~36 W0 93~05008 12 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 5:
520 g of epoxystearic acid methyl ester, 520 g (0.6 mole) of new rapeseed oil and ~60 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 240C 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 o~ the change in the concentration of epoxide oxygen in the reaction mixture. The results are set out in Table 1.

. .

I

21116.~36 Table 1: Epoxide oxygen contents Ex. Epoxide oxy~en content ~% by weight) after h 0 1 2 3 ~ 5 7 10 .. __ .. . .
l 1.3 1.3 ~.8 0.4 0.2 2 1.3 1.2 0.6 0.3 0.2 3 2.~ l.S 0.8 0.3 0.1 ~ 0~9 0.9 0.~ 0.3 0.1 S l.g 1.l 0.6 0.5 0.2 C1 1.3 1.2 0.6 _ 0.6 ~xample 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 80C. Any traces of water remaining were removed by evac~ation and purging with nitrogen five times. The reaction mixture was then heated ta 150C and 1,500 g (26 moles) of propylene oxide were~ added in portions so that the pressure in the reac-tor did not exceed 5 bar. on completion of the reaction (approx. 3 h~, the reaction mixture was cooled to 80 to `- ~
100C 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 l,200.-498 g (3.3 moles) of the glycerol propoxylate_containing lithium hydroxide and l,495 g (1.7 moles)=~of_ ~
new rapeseed oil were transesterified with stirring for 6 h at 240C. Approximately 1,950 g of a clear pale yellow liquid with the following characteristic data were .

2116~36 WO 93/05008 14 PC~/EP92/01905 obta ined: - ~

Hydroxyl value : 280 Saponification value : 142 Acid value : 0 . 8 Li content : 7 . 5 ppm

Claims

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 (I):
R1-CH=CH-R2 (I) in which R1 is a linear or branched aliphatic hydrocarbon radical containing 1 to 18 carbon atoms and R2 is hydrogen or a linear or branched hydrocarbon radical containing 1 to 8 carbon atoms, are used as the epoxide compounds.

4. A process as claimed in claim 1, characterized in that epoxides of esters corresponding to formula (II):
R3CO-OR4 (II) in which R3CO is an aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R4 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 that epoxides of esters corresponding to formula (III):
R5CO-OR6 (III) in which R5CO is an aliphatic acyl radical containing 1 to 24 carbon atoms and 0 or 1 to 5 double bonds and R6 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):
(IV) in which R7CO is a linear or branched aliphatic acyl radical containing 16 to 24 carbon atoms and l to 5 double bonds and R8CO and R9CO 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 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.

8. A process as claimed in at least one of claims 1 to 6, characterized in that alcohols corresponding to formula (V):
R10OH (V) in which R10 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 at least 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 1,500, propane-1,2-diol, propane-1,3-diol, glycerol, oligoglycerols having degrees of condensation of on average 2 to 10, trimethylol propane, pentaerythritol, sorbitol and sorbitan, are used as the nucleophiles.

10. A process as claimed in at least one of claims 1 to 6, characterized in that fatty alcohol polyglycol ethers corresponding to formula (VI):
(VI) in which R11 is a linear or branched aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R12 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 at least 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 at least one of claims 1 to 11, characterized in that lithium hydroxide is used as the lithium salt.

13. A process as claimed in at least one of claims 1 to 11, characterized in that 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 at least 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°C.

15. A process as claimed in at least one of claims 1 to 14, characterized in that triglycerides corresponding to formula (VII):
(VII) in which R13CO is a linear or branched, optionally hy-droxy-and/or alkoxy-substituted aliphatic acyl radical containing 16 to 24 carbon atoms and 1 to 5 double bonds and R14CO and R15CO 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 at least one of claims 1 to 15, characterized in that the epoxides and the fatty acid glyceride esters are used in a molar ratio of 10:1 to 1:10.

17. A process as claimed in at least one of claims 1 to

18, characterized in that the transesterification is carried out at a temperature in the range from 100 to 250°C.
18. A process as claimed in at least one of claims 1 to 17, characterized in that in that the ring opening and transesterification reactions are carried out in a single step.

19. Epoxide ring opening products obtainable by a) 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 b) optionally subjecting the hydroxy compounds formed to transesterification with fatty acid glyceride esters.

20. The use of the epoxide ring opening products ob-tained by the process claimed in claims 1 to 18 for the production of alkyd resins and polyurethane foams.

21. The use of the epoxide ring opening products claimed in claim 19 for the production of alkyd resins and polyurethane foams.