AU614054B2 - Calcined hydrotalcite catalysts - Google Patents

Calcined hydrotalcite catalysts Download PDF

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AU614054B2
AU614054B2 AU33349/89A AU3334989A AU614054B2 AU 614054 B2 AU614054 B2 AU 614054B2 AU 33349/89 A AU33349/89 A AU 33349/89A AU 3334989 A AU3334989 A AU 3334989A AU 614054 B2 AU614054 B2 AU 614054B2
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hydrotalcites
calcined
ethoxylation
propoxylation
fatty
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AU3334989A (en
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Ansgar Dr. Behler
Helmut Dr. Endres
Klaus Dr. Friedrich
Klaus Herrmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C08G65/2657—Aluminosilicates; Clays; Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polyethers (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The use of calcined hydrotalcites as catalysts for ethoxylation or propoxylation of compounds having active hydrogen atoms results in a narrow bandwidth of the distribution of homologues among the ethoxylated and propoxylated products. <IMAGE>

Description

S FR 4: 82077 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name and Address of Applicant: Henkel Kommanditgesellschaft auf Aktien Henkelstrasse 67 4000 Dusseldorf FEDERAL REPUBLIC OF GERMANY Address for Service: Spruson 9, Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete SpeciFication for the invention entitled: Calcined Hydrotalcite Catalysts The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3
L--
D 8567 The use of calcined hydrotalcites as ethoxylation or propoxylation catalysts Abstract As catalysts for the ethoxylation or propoxylation of compounds containing active H atoms, calcined hydrotalcites provide for a narrow homolog distribution range in the ethoxylation or propoxylation products.
C C C V 21.12.1988 This invention relates to the use of calcined hydrotalcites as catalysts for the ethoxylation or propoxylation of compounds containing active H atoms.
Hydrotalcite is a natural mineral having the ideal formula Mg6Al2(OH) 1 6C0 3 .4HO of which the structure is derived from that of brucite S(Mg(OH) 2 Brucite crystallizes in a layer structure with the metal ions in octahedral vacancies between two layers of close-packed hydroxyl ions, only every second layer of the octahedral vacancies being occupied. In hydrotalcite, some magnesium ions are replaced by aluminium ions so that the layer pack receives a positive charge. This is compensated by the anions which are situated in the intermediate layers together with zeolitic water of crystallization.
The layer structure is clearly visible in the X-ray powder diagram (ASTM Card No. 14-191) which may be used for identification.
o o20 Synthetic hydrotalcites are also known, cf. for example DE-C 1 592 126, DE-A 3 346 943, DE-A 3 306 822 and EP-A 0 207 811.
In natural and synthetic products, the Mg":Al" 3 ratio can vary between about 1 and 5. The OH :C0 3 2 is also variable. Natural and synthetic hydrotalcites may be represented in approximate terms by general formula I MgAl(OH)y(C0 3 n HzO (I) D 8567 2 where the conditions 1 x 5, y z, (y 2 2x 3 and 0 n 10 apply. Differences in the composition of the hydrotalcites, particularly in regard to their water content, lead to line shifts in the X-ray diffractogram.
Natural or synthetic hydrotalcites continuously give off water on heating or calcination. Dehydration is complete at 200"C; it can be shown by X-ray diffraction that the structure of the hydrotalcite has remained intact. Any further increase in temperature leads to degradation of the structure with elimination of hydroxyl groups (as water) and carbon dioxide. Natural hydrotalcites and synthetic hydrotalcites produced by various methods, for example in accordance with the publications cited above, show generally similar behavior on calcination.
1"5 Calcined hydrotalcites have already been used for o.o various purposes, for example as absorbents and in reactions of alkylene oxides with alkyl acetates for the production of mono-, di- and triethylene glycol ethyl ether acetates, cf. JP-A 56/36 431, reported in C.A. 95(11)97 099m (1981).
In the context of the invention, compounds containing active H atoms are, for example, fatty alcohols, fatty acids and amines which form nonionic detergents on ethoxylation or propoxylation. A typical example of this is the reaction of fatty alcohols normally containing 10 to 18 carbon atoms with ethylene oxide and/or propylene oxide in the presence of catalysts, the fatty alcohols reacting with several molecules ethylene oxide and/or propylene oxide.
The following compounds inter alia have been used as catalysts for the polyalkoxylation reaction mentioned above: calcium and strontium hydroxides, alkoxides and phenoxides (EP-A 00 92 256), calcium alkoxides (EP-A 00 91 146), barium hydroxide (EP-B 0 115 083), basic magnesium compounds, for example alkoxides (EP-A 00 82 569), .4 =3r 3 magnesium and calcium fatty acid salts (EP-A 085 167).
The catalysts mentioned above are attended inter alia by the disadvantage that they are not easy to incorporate in the reaction system and/or are difficult to produce.
Other typical polyalkoxylation catalysts are potassium hydroxide and sodium methylate.
A narrow range of the degree of polyalkoxylation is of particular importance for fatty alcohol polyalkoxylates, cf. JAOCS, Vol. 63, 691-695 (1986) and HAPPI, 52-54 (1986). Accordingly, the so-called "narrow-range" alkoxylates have above all the following advantages: low flow points, relatively high smoke points, fewer mols alkoxide to achieve solubility in water fewer hydrotropes for introduction into liquid universal detergents, relatively faint odor through the presence of free (unreacted) fatty alcohols, reduction of pluming in the spray-drying of detergent slurries containing fatty alcohol polyalkoxylate surfactants.
It has now been found that, by using calcined hydrotalcites as catalysts in accordance with the invention, compounds containing active H atoms can be polyalkoxylated in high yields and short reaction times and the reaction products can be obtained with a narrow homolog distribution range, the distribution curve coming very close to that calculated in accordance with Poisson.
"2E. According to a first embodiment of the present invention there is provided a process for the ethoxylation or propoxylation of compounds containing active hydrogen atoms characterized in that the process is carried out in the presence of a catalytic amount of a calcined hydrotalcite.
3C Any of the catalysts obtainable by calcination from the natural and/or synthetic hydrotalcites mentioned at the beginning are suitable for the purposes of the invention, although it is preferred to use hydrotalcites which, before calcination, correspond to general formula I MgxAI(OH)y(CO 3 )z n H20 (I) KXW:1499R 1 2 D 8567 4 with the above-mentioned conditions for x, y, z and n; .values of 1.8 to 3 are particularly preferred for x.
The calcined hydrotalcites used in accordance with the invention have the advantage that they may readily be incorporated in the alkoxylation reaction mixture and, because they are insoluble in the reaction mixture, may be removed therefrom by simple measures. However, they may also remain in the reaction mixture providing their presence does not affect the subsequent use of the reaction products.
In one advantageous embodiment of the invention, the compounds containing active H atoms are selected from the group consisting of fatty acids, hydroxyfatty acids, fatty acid amides, alcohols7 alkylphenols, polyglycols, fatty amines, fatty acid alkanolamides or vicinally hydroxy, alkoxy-substituted alkanes.
Examples of compounds which can be alkoxylated in accordance with the invention using calcined hydrotalcites are given in the following: Fatty acids:
C,-C
22 fatty acids of natural or synthetic origin, more particularly linear, saturated or unsaturated fatty acids, including technical mixtures thereof, of the type obtainable by lipolysis from animal and/or vegetable fats and oils, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cottonseed oil, fish oil, beef tallow and lard; special examples are caprylic, capric, lauric, lauroleic, myristic, myristoleic, S palmitic, palmitoleic, oleic,7elaidic, arachic, gadoleic, behenic, brassidic and erucic acid; also methyl-branched, saturated and unsaturated C 10 -Cz 2 fatty acids, of the type formed as secondary products in the dimerization of the corresponding unsaturated fatty acids, and C 1
-C
7 monocarboxylic acids.
Hydroxyfatty acids: <stearic,> D 8567 natural or synthetic hydroxyfatty acids, more especially containing 16 to 22 carbon atoms, for example ricinoleic acid or 12-hydroxystearic acid.
Fatty acid amides: derivatives of the above-mentioned linear, saturated or unsaturated fatty acids with ammonia or primary aliphatic amines containing 1 to 4 carbon atoms in the aliphatic substituent.
Alcohols: saturated or unsaturated aliphatic monoalcohols, more especially fatty alcohols containing 8 to 22 carbon atoms as they can be obtained from the above mentioned linear, saturated or unsaturated fatty acids or from their derivatives, i e.g. their methyl esters or triglycerides, by catalytic hydrogenrtion; aliphatic or cycloaliphatic alcohols containing 2 to 6 carbon atoms, for example ethanol, propanol, butanol, hexanol and cyclohexanol; including the Guerbet alcohols derived from the monoalkanols mentioned above.
Alkylphenols: mono-, di- or trialkylphenols, more particularly containing 4 to 12 carbon atoms in the alkyl groups.
o Polyglycols: 00oo polyethylene or polypropylene glycols (average degree of polymerization 2 to 2000).
ot Fatty amines: 0 c 25 more particularly primary fatty amines obtainable from nitriles of the above-mentioned linear, saturated or unsaturated fatty acids or the corresponding fatty alcohols; also mono- and dialkylamines containing CI-C alkyl groups.
Fatty acid alkanolamides: derivatives of the above-mentioned linear, saturated or unsaturated fatty acids with mono- or dialkanolamines, more particularly mono- or diethanolamine.
Vicinally hydroxy,alkoxy-substituted alkanes: ring-opening products of 1,2-epoxyalkane mixtures j' qm~ I~ D 8567 containing 12 to 22 carbon atoms in the chain with poly- Sfunctional alkanols containing 2 to 12 carbon atoms and 2 to 6 hydroxyl groups.
The derivatives to be produced in accordance with the invention using calcined hydrotalcites are commercially available products so that there is no need for a detailed description. They are all prepared by ethoxylation and/or propoxylation of starting compounds containing active hydrogen atoms. Typical representatives are, for example, an adduct of 9 mol ethylene oxide with coconut oil fatty acid, an adduct of 2 mol ethylene oxide with a C, 12 1 fatty alcohol mixture, an adduct of 3 mol ethylene oxide and 8 mol propylene oxide with a C,12 18 fatty alcohol mixture, an adduct of 10 mol ethylene oxide with nonyl phenol, an adduct of 7.3 mol ethylene oxide with glycerol, an adduct of 10 mol ethylene oxide with a diol mixture obtained by reaction of a 16 1,2-epoxyalkane mixture with ethylene glycol, an adduct of 12 mol ethylene oxide with a C, 10 is fatty amine mixture and an adduct of 4 mol ethylene oxide with a coconut oil fatty acid monoethanolamide.
In another advantageous embodiment of the invention, the calcined hyd:rotalcites are added to the reaction mixtures in a quantity of from 0.1 to 2% by weight, based on the end product of the ethoxylation or propoxylation reaction.
The calcined hydrotalcites to be used in accordance with the invention may be obtained from the natural or synthetic hydrotalcites by heating for several hours at temperatures above 100"C, calcination temperatures in the range from 400 to 600'C being particularly preferred.
The invention is illustrated by the following Examples with reference to the accompanying drawings. The drawings show the homolog distributions obtained in the Examples by comparison with those obtainable using sodium methylate.
L D 8567 7 Example 1 A commercially available synthetic hydrotalcite was calcined for 8 h at 500°C.
To react a commercially available lauryl alcohol with 6 mol ethylene oxide, the lauryl alcohol was introduced into a pressure reactor in which 0.5% by weight, based on expected end product, of the calcined hydrotalcite previously obtained was added to it. The reactor was purged with nitrogen and evacuated for 30 minutes at a temperature of 100'C. The temperature was then increased to 180"C and the desired quantity of ethylene oxide was introduced under a pressure of 4 to 5 bar. On completion of the reaction, the reaction mixture was left to after-react for 1i minutes. After suspended catalyst had been filtered off, the desired reaction mixture was obtained, its characteristic data being shown in Table 1.
Examples 2 to 1'' The compr ids containing active H atoms listed in Table 1 were reacted with ethylene oxide as in Example 1 using calcined synthetic hydrotalcites. The compounds used, the quantities of ethylene oxide reacted, the calcination conditions for the hydrotalcites, the catalyst 125 concentration, the reaction time of the ethoxylation and the OH values of some of the ethcxylation products obtained are shown for some compounds in Table 1. Table 1 also indicates the drawing in which the homolog distributions obtained are shown by comparison with sodium ethylate.
Calcined hydrotalcites in which the atomic ratio of Mg to Al (corresponding to x in the above general formula) was 2.17 were used in Examples 1, 2, 6 and 7. The Mg/.A atomic ratio for the calcined hydrotalcites of Examples 3, 4 and 8 to 13 was 2.17 and, for that of Example 5, 2.08.
D 8567 Table 1 Ethoxylation of H-reactive compounds Ex. Product Hydrotalcite Catalyst Reaction Product OH 1 Homolog No. (calcination concen- time found caic. distribution conditions) tration 1 C 12 6 EQ 8 h/500-C 0.5 8 135.4 125 Figure 1 2 C 12 14 2E0 8 h/500-C 0.5 3 198.2 200 Figure 2 3 C 12 6E0 4 h/500-C 0.5 7.5 132.1 135.7 Figure 3.
4 C 12114 2E0 4 h/500-C 0.5 2 201.8 200 Figure 4
C
12 +EO0 4 h/500-C 0.5 7.5 128.3 125 Figure 6 C 18 1 18 4.6E0 8 h/500-C 0.5 8.5 123.6 117.8 Figure 6 7 C 8 4 EQ 8 h/500 0 C 0.5 9.0 196.3 184.8 Figure 7 8 C 1 2 +6 E0 4 h/600 0 C 0.5 6.5 130.9 131.7 Figure 8 9 2-octyldodecanol+2E0 4 h/500 0 C 0.5 0.75 140.7 145.1 cyclohexanol x 4E0 4 h/500-C 0.5 2 274.9 223.5 11 butanol x 1O x 10PO 4 h/500-C 0.5 3.5 55.3 51.4 12 lauric acid x 6E0 4 h/500-C 0.5 3.5 143.4 132.3 13 coconut amine x 12E0 4 h/500-C 0.5 4 244.7 219.4 1) OH.= hydroxyl value 2) Technical oleyl alcohol (C 1 ,)/stearyl alcohol mixture

Claims (8)

1. A process for the ethoxylation or propoxylation of compounds containing active hydrogen atoms characterized in that the process is carried out in the presence of a catalytic amount of a calcined hydrotalcite.
2. The process as claimed in claim 1, characterized in that the compounds containing active hydrogen atoms are selected from the group consisting of fatty acids, hydroxyfatty acids, fatty acid amides, alcohols, alkylphenols, polyglycols, fatty amines, fatty acid alkanolamides or vicinally hydroxy, alkoxy-substituted alkanes.
3. The process as claimed in claim 1 or 2, characterized in that, before calcination, the hydrotalcites correspond in their composition to formula I Mg xA(OH) (C03 n H 2 0 (I) in which the conditions 1 x 5, y z, (y 2 z) 2x 3 and 0 n 10 apply. o
4. The process as claimed in any one of claims 1 to 3, characterized in that, for the hydrotalcites corresponding to general formula I MgxA1(OH)y(CO 3 n H 2 0 x has a value of 1.8 to 3 and y, z and n are as defined above.
The process as claimed in any one of claims 1 to 4, characterized S in that the hydrotalcites are calcined at temperatures of from 400 to 600 0 C.
6. The process as claimed in any one of claims 1 to 5, characterized in that the calcined hydrotalcites are used in a quantity of from 0.1 to 2% o by weight, based on the end product of the ethoxylation or propoxylation.
7. A process for the ethoxylation or propoxylation of compounds containing active hydrogen atoms substantially as hereinbefore described with reference to any one of the Examples.
8. Ethoxylated or propoxylated compounds whenever prepared by a process as claimed in any one of claims 1 to 7. DATED this FIFTEENTH day of MARCH 1989 Henkel Kommanditgesellschaft auf Aktien Patent Attorneys for the Applicant SPRUSON FERGUSON LH/115W
AU33349/89A 1988-04-25 1989-04-24 Calcined hydrotalcite catalysts Ceased AU614054B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3813910 1988-04-25
DE3813910 1988-04-25
DE3843713A DE3843713A1 (en) 1988-04-25 1988-12-23 USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION
DE3843713 1988-12-23

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AU3334989A AU3334989A (en) 1989-10-26
AU614054B2 true AU614054B2 (en) 1991-08-15

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KR (1) KR970003516B1 (en)
AT (1) ATE111429T1 (en)
AU (1) AU614054B2 (en)
BR (1) BR8901932A (en)
DE (2) DE3843713A1 (en)
ES (1) ES2058375T3 (en)
NO (1) NO171630C (en)
TR (1) TR24219A (en)

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DE3843713A1 (en) 1989-11-02
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EP0339426B1 (en) 1994-09-14
ES2058375T3 (en) 1994-11-01
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AU3334989A (en) 1989-10-26
TR24219A (en) 1991-07-02
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EP0339426A3 (en) 1991-03-20
EP0339426A2 (en) 1989-11-02
NO171630C (en) 1993-04-14
DE58908341D1 (en) 1994-10-20
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JPH0271841A (en) 1990-03-12

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