CA2146236A1 - Internal hydroxy mixed ethers - Google Patents
Internal hydroxy mixed ethersInfo
- Publication number
- CA2146236A1 CA2146236A1 CA002146236A CA2146236A CA2146236A1 CA 2146236 A1 CA2146236 A1 CA 2146236A1 CA 002146236 A CA002146236 A CA 002146236A CA 2146236 A CA2146236 A CA 2146236A CA 2146236 A1 CA2146236 A1 CA 2146236A1
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- Canada
- Prior art keywords
- epoxides
- hydroxy mixed
- fatty acid
- ring opening
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Internal hydroxy mixed ethers are obtained by a process in which epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
Description
21~623~
HENKEL KGaA
Dr. Fabry/189 6th January, 1993.
Patent Application Internal hydroxy mixed ethers RA~R~.R~UND OF THE lNV r.~ ON
1. Field of the Invention This invention relates to internal hydroxy mixed ethers obtained by ring opening of epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers, to a process for their production and to their use as an auxiliary in the dewatering of solids.
HENKEL KGaA
Dr. Fabry/189 6th January, 1993.
Patent Application Internal hydroxy mixed ethers RA~R~.R~UND OF THE lNV r.~ ON
1. Field of the Invention This invention relates to internal hydroxy mixed ethers obtained by ring opening of epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers, to a process for their production and to their use as an auxiliary in the dewatering of solids.
2.STATEMENT OF RELATED ART
There are many branches of industry, for example mining or sewage treatment, where large quantities of fine-particle solids of high water content accumulate and have to be dewatered before subsequent processing or disposal as waste. For example, the dewatering of hard coal or coke is a key process in the cleaning of coal-based fuels. The upper limits to the water content of these materials as required by the market are often difficult to adhere to, for example because mine-run coal accumulates in very fine-particle form due to the extensive mechanization of underground coal mining. At the present time, around 38% of the gross output con-sists of fine coal with a particle diameter in the range from 0.5 to 10 mm. Another 14~ consists of ultrafine coal with even smaller particle diameters.
It is known that certain surfactants are suitable as auxiliaries for the dewatering of water-containing fine-particle solids suspensions, particularly iron ore concentrates or hard coals, by which their residual moisture content can be reduced. For example, dialkyl sulfosuccinates (US 2,266,954) and nonionic surfactants of the fatty alcohol polyglycol ether type (Erzmetall 30, 292 (1977)) have been described as surface-active dewatering aids of the type mentioned above. However, these surfactants are attended by the disadvantage of high foaming which leads to serious problems, particularly during the recirculation of water typical of cleaning plants.
214623~
DE-A1-39 18 274 (Henkel) describes alkyl-end-capped ~-hydroxyalkyl ethers, so-called hydroxy mixed ethers, which are produced by ring opening of ~-olefin epoxides with fatty alcohol ethoxylates and which are used as low-foaming auxiliaries in the dewatering of solids suspensions. Although good results are obtained with these auxiliaries in the dewatering of solids, they are attended by the disadvantage of unsatisfactory low-temperature behavior. Crystals can form at temperatures of only 10 to 15C, particularly where the suspensions are stored outdoors, which adversely affects the pumping and flow behavior of the products and hence seriously impairs their intended use.
Accordingly, the problem addressed by the present invention was to provide new hydroxy mixed ethers which would show improved low-temperature behavior for otherwise the same performance properties.
DESCRIPTION OF THE lNv~NllON
The present invention relates to internal hydroxy mixed ethers which are obtained by subjecting epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
R1O-(CH2CHO)nH (I) in which Rl is a linear or branched, aliphatic C422 hydrocarbon radical and R2 is hydrogen or a methyl group, to ring opening.
It has surprisingly been found that the internal hydroxy mixed ethers according to the invention show distinctly better low-temperature behavior than the known t~rm;nA1 hydroxy mixed ethers according to DE-A-39 18 274, more particularly lower pour points, for equally good and, in some cases, slightly improved performance properties.
The present invention also relates to a process for the production of internal hydroxy mixed ethers, in which epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
RlO-(CH2CHO)nH (I) 21~236 in which R1 is a linear or branched, aliphatic C422 hydrocarbon radical and R2 is hydrogen or a methyl group, are subjected to ring opening.
In the context of the invention, epoxides of unsaturated fatty acid esters are, for example, addition products of oxygen with the double bonds of mono- or polyunsaturated fatty acid lower alkyl esters corresponding to formula (II):
R3Co-oR4 (II) in which R3Co is an unsaturated acyl radical containing 16 to 22 carbon atoms and R4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms. Typical examples are epoxidized methyl, ethyl, propyl or butyl esters of palmitoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid and technical mixtures thereof. The epoxides used may be present in completely epoxidized form, although they may even contain double bonds. The degree of epoxidation, based on the double bonds available, is 50 to 100% and, more particularly, 70 to 95%. Since technical cuts of unsaturated fatty acid lower alkyl esters still containing saturated components are normally used to produce the epoxidized fatty acid esters, the starting epoxides may therefore also contain small amounts of saturated fatty acid lower alkyl esters. The preferred starting material is oleic acid methyl ester epoxide having an epoxide oxygen content of 4.5 to 5.1% by weight.
In addition to the epoxides of unsaturated fatty acid lower alkyl esters, epoxidized unsaturated fatty acid glycerol esters corresponding to formula (III):
CH2o-CoR4 CH-O-CORs (III) I
in which R4Co, R5Co and R5Co independently of one another represent unsaturated acyl radicals cont~;n;ng 16 to 24 carbon atoms, may also be used as starting materials.
Typical examples are epoxides of unsaturated triglycerides of vegetable or animal origin, for example soybean oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, beef tallow or fish oil. These starting materials may also contain saturated components. However, epoxides of fatty acid glycerol esters having an iodine value of 50 to lS0 and preferably 85 to 115 are normally used. As mentioned above, both completely 21~623~
and partly epoxidized esters may be used as starting materials. The preferred starting material is epoxidized soybean oil having an epoxide oxygen content of 4 . 5 to 6.5~ by weight.
Fatty alcohol polyglycol ethers corresponding to formula (I) are suitable as the nucleophile for the ring opening of the starting epoxides mentioned. Typical examples are adducts of 1 to 30 and preferably 2 to 10 mol ethylene and/or propylene oxide with butanol, pentanol, caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and technical mixtures there-of such as are formed, for example, in the hydrogenation of fatty acid methyl ester fractions or aldehydes from Roelen's oxo synthesis. Adducts of 2 to 8 mol ethylene oxide with butanol and technical C12~14 or C12~18 coconut oil fatty alcohol cuts are preferably used.
The epoxides and the fatty alcohol polyglycol ethers may normally be used in a molar ratio of 1:0.5 to 1:1.5 and preferably in a molar ratio of 1:0.9 to 1:1.1, based on the epoxide content.
In order to ensure a short reaction time, it is advisable to carry out the ring opening reaction in the presence of basic catalysts, such as sodium methylate for example, which may be used in quantities of 0.1 to 5~ by weight, based on the epoxide.
Similarly, it is of advantage to carry out the ring opening reaction at temperatures in the range from 80 to 150C and preferably at temperatures in the range from 100 to 130C.
Industrial Applications The internal hydroxy mixed ethers to be used in accordance with the invention support the dewatering of solids suspensions, are readily biodegradable and are distinguished by low pour points.
Accordingly, the present invention also relates to their use as auxiliaries in the dewatering of fine-particle solids suspensions, such as for example iron ore concentrates, quartz sand, hard coal or coke. Another important application is the use of the internal hydroxy mixed ethers to be used in accordance with the invention as auxiliaries in the dewatering of the solids suspensions which accumulate in the recycling of wastepaper, for example in the deinking process or at the filler flotation stage.
The internal hydroxy mixed ethers according to the invention may be used individually. However, it can be of advantage 21~23G
for the dewatering of certaln solids to combine products differing in their chain length or degree of alkoxylation with one another to utilize synergisms of their physicochemical properties. Similarly, it can be of advantage to use combinations of the internal hydroxy mixed ethers with other already known ionic or nonionic dewatering aids.
In one advantageous embodiment of the process according to the invention, the internal hydroxy mixed ethers are used in quantities of 10 to 500 g, preferably in quantities of 50 to 300 g and, more preferably, in quantities of 150 to 250 g, based on the solids content, per ton solids.
The following Examples are intended to illustrate the invention without limiting it in any way.
Exam~les I. Production Exam~les A) Hydroxy mixed ethers based on oleic acid methyl ester epoxide.
374 g (1 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C
to remove the methanol introduced with the catalyst. After addition of 312 g (1 mol) oleic acid methyl ester epoxide (EDENOR~ MeTiOs epoxide, a product of Henkel KGaA, Dusseldorf, FRG), the mixture was heated for 130 minutes to 160C. The hydroxy mixed ether was obtained as a clear liquid in a substantially quantitative yield.
Characteristic data of the product:
Pour point : 9 C
Viscosity (Hoppler) : 60 mPa.s Hydroxyl value : 81 Saponification value : 88 Iodine value : 15.2 Acid value : 1.1 35 Residual epoxide oxygen content : 0.1% by welght B) Hydroxy mixed ether based on soybean oil epoxide As in Example A), 748 g (2 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C to remove the methanol introduced with the catalyst.
After addition of 929 g (1 mol) soybean oil epoxide (EDENOR~ D81, epoxide oxygen content 6.5% by weight, a product of Henkel KGaA, Dusseldorf, FRG), the mixture was heated for 130 minutes to 160C.
The hydroxy mixed ether was obtained as a clear liquid in a substantially quantitative yield.
Characteristic data of the ~roduct:
Pour point : ~7 C
Residual epoxide oxygen content : 0.1% by weight Viscosity (Hoppler) : 33 mPa.s Hydroxyl value : 131 C) Hydroxy mixed ether based on alpha-tetradecene epoxide As in Example A), 374 g (1 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C to remove the methanol introduced with the catalyst.
After addition of 212 g (1 mol) alpha-tetradecene epoxide, the mixture was heated for 130 minutes to 160C. The hydroxy mixed ether was obtained as a cloudy liquid in a substantially quantita-tive yield.
Characteristic data of the product:
Pour point : 13 C
Viscosity (Hoppler) : 70 mPa.s Hydroxyl value : 100 Residual epoxide oxygen content : 0.1% by weight Products A) and B) correspond to the invention, product C) is intended for comparison.
II. Dewaterinq of auartz sand Quartz sand having the following particle size distribution was used for the dewatering tests:
214~236 .
> 125 um : 2.8% by weight 125 to 200 um : 26.4% by weight 200 to 315 ~m : 60.1% by weight > 315 ~m :10.7% by weight The tests were carried out in a bucket centrifuge withwhich centrifugal values of 15 to 2,000 can be obtained. Perforated plates with 0.1 x 2 mm sieve openings were used for the screens.
The dewatering aids were used in aqueous solutions. All concentra-tion figures are based on solids.
After the quartz had to be weighed into the buckets of thecentrifuge, the aqueous solutions of the dewatering aids were poured over the layer. After a drainage time of 1 minute, the solids were dewatered for 30 s at a rotational speed of 500 r.p.m. The moist solids were then weighed out, dried to constant weight at 100C and the residual moisture content and reduction in the residual moisture content in %-rel were determined. All the test results are averages of double determinations. The results are set out in Table 1.
Table 1: Dewatering of quartz sand Ex. Aux. Residual moisture Red. in residual moisture %-rel. %-rel 1 A 5.7 4.4 4.4 1.9 2.6 2.7 2 B 5.8 4.8 4.8 1.8 2.3 2.3 C1 None 7.6 7.1 7.1 - - -C2 C 5.4 5.0 4.5 2.2 2.1 2.6 Leqend:
Aux. = Auxiliary E1 = Quantity weighed in 150 g auxiliary/t solid E2 = Quantity weighed in 250 g auxiliary/t solid E3 = Quantity weighed in 350 g auxiliary/t solid III. Dewaterinq of iron ore concentrate The in-plant filter feed of an iron ore concentrate was used for the dewatering tests. the tests were carried out in a pressure filter (60 cm~); pressure difference 2 bar. The filter 214~2~6 feed had a solids content of 65% by weight, the sample volume was 120 ml. The dewatering aids were again used in aqueous solutions.
All concentration figures are based on the solids. After dewatering, the moist solids were weighed out, dried to constant weight at 100C and the residual moisture content determined in %-rel. All the test results are averages of double determinations.
The results are set out in Table 2.
Table 2: Dewatering of iron ore concentrate Ex. Aux. Residual moisture Red. in residual moisture %-rel. %-rel 1 A 7.3 7.1 7.1 0.2 0.4 0.4 2 B 7.5 7.3 6.8 - 0.2 0.7 Cl None 7.5 7.5 7.5 C2 C 7.3 7.1 7.2 0.2 0.4 0.3 21462~G
Leqend:
Aux. = Auxiliary E1 = Quantity weighed in 100 g auxiliary/t solid E2 = Quantity weighed in 150 g auxiliary/t solid E3 = Quantity weighed in 200 g auxiliary/t solid
There are many branches of industry, for example mining or sewage treatment, where large quantities of fine-particle solids of high water content accumulate and have to be dewatered before subsequent processing or disposal as waste. For example, the dewatering of hard coal or coke is a key process in the cleaning of coal-based fuels. The upper limits to the water content of these materials as required by the market are often difficult to adhere to, for example because mine-run coal accumulates in very fine-particle form due to the extensive mechanization of underground coal mining. At the present time, around 38% of the gross output con-sists of fine coal with a particle diameter in the range from 0.5 to 10 mm. Another 14~ consists of ultrafine coal with even smaller particle diameters.
It is known that certain surfactants are suitable as auxiliaries for the dewatering of water-containing fine-particle solids suspensions, particularly iron ore concentrates or hard coals, by which their residual moisture content can be reduced. For example, dialkyl sulfosuccinates (US 2,266,954) and nonionic surfactants of the fatty alcohol polyglycol ether type (Erzmetall 30, 292 (1977)) have been described as surface-active dewatering aids of the type mentioned above. However, these surfactants are attended by the disadvantage of high foaming which leads to serious problems, particularly during the recirculation of water typical of cleaning plants.
214623~
DE-A1-39 18 274 (Henkel) describes alkyl-end-capped ~-hydroxyalkyl ethers, so-called hydroxy mixed ethers, which are produced by ring opening of ~-olefin epoxides with fatty alcohol ethoxylates and which are used as low-foaming auxiliaries in the dewatering of solids suspensions. Although good results are obtained with these auxiliaries in the dewatering of solids, they are attended by the disadvantage of unsatisfactory low-temperature behavior. Crystals can form at temperatures of only 10 to 15C, particularly where the suspensions are stored outdoors, which adversely affects the pumping and flow behavior of the products and hence seriously impairs their intended use.
Accordingly, the problem addressed by the present invention was to provide new hydroxy mixed ethers which would show improved low-temperature behavior for otherwise the same performance properties.
DESCRIPTION OF THE lNv~NllON
The present invention relates to internal hydroxy mixed ethers which are obtained by subjecting epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
R1O-(CH2CHO)nH (I) in which Rl is a linear or branched, aliphatic C422 hydrocarbon radical and R2 is hydrogen or a methyl group, to ring opening.
It has surprisingly been found that the internal hydroxy mixed ethers according to the invention show distinctly better low-temperature behavior than the known t~rm;nA1 hydroxy mixed ethers according to DE-A-39 18 274, more particularly lower pour points, for equally good and, in some cases, slightly improved performance properties.
The present invention also relates to a process for the production of internal hydroxy mixed ethers, in which epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
RlO-(CH2CHO)nH (I) 21~236 in which R1 is a linear or branched, aliphatic C422 hydrocarbon radical and R2 is hydrogen or a methyl group, are subjected to ring opening.
In the context of the invention, epoxides of unsaturated fatty acid esters are, for example, addition products of oxygen with the double bonds of mono- or polyunsaturated fatty acid lower alkyl esters corresponding to formula (II):
R3Co-oR4 (II) in which R3Co is an unsaturated acyl radical containing 16 to 22 carbon atoms and R4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms. Typical examples are epoxidized methyl, ethyl, propyl or butyl esters of palmitoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid and technical mixtures thereof. The epoxides used may be present in completely epoxidized form, although they may even contain double bonds. The degree of epoxidation, based on the double bonds available, is 50 to 100% and, more particularly, 70 to 95%. Since technical cuts of unsaturated fatty acid lower alkyl esters still containing saturated components are normally used to produce the epoxidized fatty acid esters, the starting epoxides may therefore also contain small amounts of saturated fatty acid lower alkyl esters. The preferred starting material is oleic acid methyl ester epoxide having an epoxide oxygen content of 4.5 to 5.1% by weight.
In addition to the epoxides of unsaturated fatty acid lower alkyl esters, epoxidized unsaturated fatty acid glycerol esters corresponding to formula (III):
CH2o-CoR4 CH-O-CORs (III) I
in which R4Co, R5Co and R5Co independently of one another represent unsaturated acyl radicals cont~;n;ng 16 to 24 carbon atoms, may also be used as starting materials.
Typical examples are epoxides of unsaturated triglycerides of vegetable or animal origin, for example soybean oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, beef tallow or fish oil. These starting materials may also contain saturated components. However, epoxides of fatty acid glycerol esters having an iodine value of 50 to lS0 and preferably 85 to 115 are normally used. As mentioned above, both completely 21~623~
and partly epoxidized esters may be used as starting materials. The preferred starting material is epoxidized soybean oil having an epoxide oxygen content of 4 . 5 to 6.5~ by weight.
Fatty alcohol polyglycol ethers corresponding to formula (I) are suitable as the nucleophile for the ring opening of the starting epoxides mentioned. Typical examples are adducts of 1 to 30 and preferably 2 to 10 mol ethylene and/or propylene oxide with butanol, pentanol, caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and technical mixtures there-of such as are formed, for example, in the hydrogenation of fatty acid methyl ester fractions or aldehydes from Roelen's oxo synthesis. Adducts of 2 to 8 mol ethylene oxide with butanol and technical C12~14 or C12~18 coconut oil fatty alcohol cuts are preferably used.
The epoxides and the fatty alcohol polyglycol ethers may normally be used in a molar ratio of 1:0.5 to 1:1.5 and preferably in a molar ratio of 1:0.9 to 1:1.1, based on the epoxide content.
In order to ensure a short reaction time, it is advisable to carry out the ring opening reaction in the presence of basic catalysts, such as sodium methylate for example, which may be used in quantities of 0.1 to 5~ by weight, based on the epoxide.
Similarly, it is of advantage to carry out the ring opening reaction at temperatures in the range from 80 to 150C and preferably at temperatures in the range from 100 to 130C.
Industrial Applications The internal hydroxy mixed ethers to be used in accordance with the invention support the dewatering of solids suspensions, are readily biodegradable and are distinguished by low pour points.
Accordingly, the present invention also relates to their use as auxiliaries in the dewatering of fine-particle solids suspensions, such as for example iron ore concentrates, quartz sand, hard coal or coke. Another important application is the use of the internal hydroxy mixed ethers to be used in accordance with the invention as auxiliaries in the dewatering of the solids suspensions which accumulate in the recycling of wastepaper, for example in the deinking process or at the filler flotation stage.
The internal hydroxy mixed ethers according to the invention may be used individually. However, it can be of advantage 21~23G
for the dewatering of certaln solids to combine products differing in their chain length or degree of alkoxylation with one another to utilize synergisms of their physicochemical properties. Similarly, it can be of advantage to use combinations of the internal hydroxy mixed ethers with other already known ionic or nonionic dewatering aids.
In one advantageous embodiment of the process according to the invention, the internal hydroxy mixed ethers are used in quantities of 10 to 500 g, preferably in quantities of 50 to 300 g and, more preferably, in quantities of 150 to 250 g, based on the solids content, per ton solids.
The following Examples are intended to illustrate the invention without limiting it in any way.
Exam~les I. Production Exam~les A) Hydroxy mixed ethers based on oleic acid methyl ester epoxide.
374 g (1 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C
to remove the methanol introduced with the catalyst. After addition of 312 g (1 mol) oleic acid methyl ester epoxide (EDENOR~ MeTiOs epoxide, a product of Henkel KGaA, Dusseldorf, FRG), the mixture was heated for 130 minutes to 160C. The hydroxy mixed ether was obtained as a clear liquid in a substantially quantitative yield.
Characteristic data of the product:
Pour point : 9 C
Viscosity (Hoppler) : 60 mPa.s Hydroxyl value : 81 Saponification value : 88 Iodine value : 15.2 Acid value : 1.1 35 Residual epoxide oxygen content : 0.1% by welght B) Hydroxy mixed ether based on soybean oil epoxide As in Example A), 748 g (2 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C to remove the methanol introduced with the catalyst.
After addition of 929 g (1 mol) soybean oil epoxide (EDENOR~ D81, epoxide oxygen content 6.5% by weight, a product of Henkel KGaA, Dusseldorf, FRG), the mixture was heated for 130 minutes to 160C.
The hydroxy mixed ether was obtained as a clear liquid in a substantially quantitative yield.
Characteristic data of the ~roduct:
Pour point : ~7 C
Residual epoxide oxygen content : 0.1% by weight Viscosity (Hoppler) : 33 mPa.s Hydroxyl value : 131 C) Hydroxy mixed ether based on alpha-tetradecene epoxide As in Example A), 374 g (1 mol) butyl diglycol-5EO-ether and 5 g sodium methylate (30% solution in methanol) were heated in vacuo to 60C to remove the methanol introduced with the catalyst.
After addition of 212 g (1 mol) alpha-tetradecene epoxide, the mixture was heated for 130 minutes to 160C. The hydroxy mixed ether was obtained as a cloudy liquid in a substantially quantita-tive yield.
Characteristic data of the product:
Pour point : 13 C
Viscosity (Hoppler) : 70 mPa.s Hydroxyl value : 100 Residual epoxide oxygen content : 0.1% by weight Products A) and B) correspond to the invention, product C) is intended for comparison.
II. Dewaterinq of auartz sand Quartz sand having the following particle size distribution was used for the dewatering tests:
214~236 .
> 125 um : 2.8% by weight 125 to 200 um : 26.4% by weight 200 to 315 ~m : 60.1% by weight > 315 ~m :10.7% by weight The tests were carried out in a bucket centrifuge withwhich centrifugal values of 15 to 2,000 can be obtained. Perforated plates with 0.1 x 2 mm sieve openings were used for the screens.
The dewatering aids were used in aqueous solutions. All concentra-tion figures are based on solids.
After the quartz had to be weighed into the buckets of thecentrifuge, the aqueous solutions of the dewatering aids were poured over the layer. After a drainage time of 1 minute, the solids were dewatered for 30 s at a rotational speed of 500 r.p.m. The moist solids were then weighed out, dried to constant weight at 100C and the residual moisture content and reduction in the residual moisture content in %-rel were determined. All the test results are averages of double determinations. The results are set out in Table 1.
Table 1: Dewatering of quartz sand Ex. Aux. Residual moisture Red. in residual moisture %-rel. %-rel 1 A 5.7 4.4 4.4 1.9 2.6 2.7 2 B 5.8 4.8 4.8 1.8 2.3 2.3 C1 None 7.6 7.1 7.1 - - -C2 C 5.4 5.0 4.5 2.2 2.1 2.6 Leqend:
Aux. = Auxiliary E1 = Quantity weighed in 150 g auxiliary/t solid E2 = Quantity weighed in 250 g auxiliary/t solid E3 = Quantity weighed in 350 g auxiliary/t solid III. Dewaterinq of iron ore concentrate The in-plant filter feed of an iron ore concentrate was used for the dewatering tests. the tests were carried out in a pressure filter (60 cm~); pressure difference 2 bar. The filter 214~2~6 feed had a solids content of 65% by weight, the sample volume was 120 ml. The dewatering aids were again used in aqueous solutions.
All concentration figures are based on the solids. After dewatering, the moist solids were weighed out, dried to constant weight at 100C and the residual moisture content determined in %-rel. All the test results are averages of double determinations.
The results are set out in Table 2.
Table 2: Dewatering of iron ore concentrate Ex. Aux. Residual moisture Red. in residual moisture %-rel. %-rel 1 A 7.3 7.1 7.1 0.2 0.4 0.4 2 B 7.5 7.3 6.8 - 0.2 0.7 Cl None 7.5 7.5 7.5 C2 C 7.3 7.1 7.2 0.2 0.4 0.3 21462~G
Leqend:
Aux. = Auxiliary E1 = Quantity weighed in 100 g auxiliary/t solid E2 = Quantity weighed in 150 g auxiliary/t solid E3 = Quantity weighed in 200 g auxiliary/t solid
Claims (9)
1. Internal hydroxy mixed ethers obtainable by subjecting epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
(I) in which R1 is a linear or branched, aliphatic C4-22 hydrocarbon radical and R2 is hydrogen or a methyl group, to ring opening.
(I) in which R1 is a linear or branched, aliphatic C4-22 hydrocarbon radical and R2 is hydrogen or a methyl group, to ring opening.
2. A process for the production of internal hydroxy mixed ethers, in which epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers corresponding to formula (I):
(I) in which R1 is a linear or branched, aliphatic C4-22 hydrocarbon radical and R2 is hydrogen or a methyl group, are subjected to ring opening.
(I) in which R1 is a linear or branched, aliphatic C4-22 hydrocarbon radical and R2 is hydrogen or a methyl group, are subjected to ring opening.
3. A process as claimed in claim 2, characterized in that epoxides of unsaturated fatty acid lower alkyl esters corresponding to formula (II):
R3CO-OR4 (II) in which R3CO is an unsaturated acyl radical containing 16 to 22 carbon atoms and R4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms, are used.
R3CO-OR4 (II) in which R3CO is an unsaturated acyl radical containing 16 to 22 carbon atoms and R4 is a linear or branched alkyl radical containing 1 to 4 carbon atoms, are used.
4. A process as claimed in claim 2, characterized in that epoxides of unsaturated fatty acid glycerol esters corresponding to formula (III):
(III) in which R4CO, R5CO and R6CO independently of one another represent unsaturated acyl radicals containing 16 to 24 carbon atoms, are used.
(III) in which R4CO, R5CO and R6CO independently of one another represent unsaturated acyl radicals containing 16 to 24 carbon atoms, are used.
5. A process as claimed in claim 2, characterized in that the epoxides and the fatty alcohol polyglycol ethers are used in a molar ratio of 1:0.5 to 1:1.15, based on the epoxide content.
6. A process as claimed in claim 2, characterized in that the ring opening reaction is carried out in the presence of basic catalysts.
7. A process as claimed in claim 2, characterized in that the catalysts are used in quantities of 0.1 to 5% by weight, based on the epoxide.
8. A process as claimed in claim 2, characterized in that the ring opening reaction is carried out at temperatures of 80 to 150°C.
9. The use of the internal hydroxy mixed ethers claimed in claim 1 as auxiliaries for dewatering fine-particle solids suspen-sions, particularly in the recycling of wastepaper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4233219.2 | 1992-10-02 | ||
| DE4233219A DE4233219A1 (en) | 1992-10-02 | 1992-10-02 | Internal hydroxymix ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2146236A1 true CA2146236A1 (en) | 1994-04-14 |
Family
ID=6469525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002146236A Abandoned CA2146236A1 (en) | 1992-10-02 | 1993-09-24 | Internal hydroxy mixed ethers |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0662947A1 (en) |
| CA (1) | CA2146236A1 (en) |
| DE (1) | DE4233219A1 (en) |
| FI (1) | FI951552A (en) |
| WO (1) | WO1994007840A1 (en) |
| ZA (1) | ZA937314B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6770679B1 (en) | 1999-06-29 | 2004-08-03 | Akzo Nobel N.V | Compounds from epoxidised nitriles, process for their production and use as cleaning agents |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19526501A1 (en) * | 1995-07-20 | 1997-01-23 | Basf Ag | Hydroxy mixed ethers by ring opening of epoxides of unsaturated fatty acid esters with polyglycol ethers and their use as biodegradable defoamers |
| DE19622967C1 (en) * | 1996-06-07 | 1998-01-29 | Henkel Kgaa | Aqueous pearlescent concentrates |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3318596A1 (en) * | 1983-05-21 | 1984-11-22 | Henkel KGaA, 4000 Düsseldorf | NEW HYDROXYALCOXYCARBONIC ACIDS AND THEIR SALTS, THEIR PRODUCTION AND USE |
| DE4002213A1 (en) * | 1990-01-26 | 1991-08-01 | Henkel Kgaa | Alkoxylation prod. prepd. from epoxide derivs. |
| DE4115146A1 (en) * | 1991-05-08 | 1992-11-12 | Henkel Kgaa | METHOD FOR PRODUCING EPOXY RING OPENING PRODUCTS WITH A DEFINED RESIDUAL EPOXY OXYGEN CONTENT |
-
1992
- 1992-10-02 DE DE4233219A patent/DE4233219A1/en not_active Withdrawn
-
1993
- 1993-09-24 WO PCT/EP1993/002601 patent/WO1994007840A1/en not_active Application Discontinuation
- 1993-09-24 EP EP93920819A patent/EP0662947A1/en not_active Withdrawn
- 1993-09-24 CA CA002146236A patent/CA2146236A1/en not_active Abandoned
- 1993-10-01 ZA ZA937314A patent/ZA937314B/en unknown
-
1995
- 1995-03-31 FI FI951552A patent/FI951552A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6770679B1 (en) | 1999-06-29 | 2004-08-03 | Akzo Nobel N.V | Compounds from epoxidised nitriles, process for their production and use as cleaning agents |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA937314B (en) | 1994-04-05 |
| EP0662947A1 (en) | 1995-07-19 |
| FI951552A0 (en) | 1995-03-31 |
| WO1994007840A1 (en) | 1994-04-14 |
| DE4233219A1 (en) | 1994-04-07 |
| FI951552A (en) | 1995-03-31 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |