CA1338277C - Process for the production of terminally blocked polyglycol ethers - Google Patents
Process for the production of terminally blocked polyglycol ethersInfo
- Publication number
- CA1338277C CA1338277C CA000586673A CA586673A CA1338277C CA 1338277 C CA1338277 C CA 1338277C CA 000586673 A CA000586673 A CA 000586673A CA 586673 A CA586673 A CA 586673A CA 1338277 C CA1338277 C CA 1338277C
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- Prior art keywords
- formula
- alkali metal
- polyoxyalkylene
- molar ratio
- metal hydroxide
- Prior art date
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Classifications
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Detergent Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In an improved process for the production of terminally blocked alkyl polyalkylene glycol ethers (I), alkyl polyalkylene glycol ethers (IV) are reacted with an organic halide (V) at 60 to 140°C in the presence of 80 to 100% by weight solid, particulate alkali metal hydroxide, the molar ratio of (V) to (IV) being from (1.5 to 2):1 and the molar ratio of alkali metal hydroxide to (IV) being from (1.5 to 2):1.
Description
~- Patent Docket D 7873 1 338~77 A PROCESS FOR THE PRODUCTION OF TERMINALLY BLOCKED POLYGLYCOL
ETHERS
BACKGROUND OF THE INVENTION
.
l. Field of the Invention:
This invention relates to an improved process for the production of terminally blocked-polyglycol ethers.
ETHERS
BACKGROUND OF THE INVENTION
.
l. Field of the Invention:
This invention relates to an improved process for the production of terminally blocked-polyglycol ethers.
2. Statement of Related Art:
German Patent 28 00 710 describes a process for the production of etherified polyoxyalkylene derivatives which are obtained by reaction of polyoxyalkylene alcohols with organic halides in the presence of an aqueous solution of sodium hydroxide or potassium hydroxide having an initial alkali metal hydroxide concentration of at least 30 % by weight. As evidenced by the Examples of German Patent 28 00 710, an only faintly colored or substantially colorless product is obtA;ne~
when the starting material, i.e. the polyoxyalkylene compound, which has been pretreated with hydrogen under the conditions mentioned therein in the presence of the hydrogenation ,~
`~ catalyst, is used for the etherification reaction according to the invention or when the etherification reaction is carried out in the presence of an inorganic reducing agent.
In addition, it can be shown that the process only gives economically satisfactory yields when alkyl halide and alkali metal hydroxide are used in large excesses.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
By contrast, with the process described in the above German patent, an object of the present invention is to provide an improved process for the production of etherified polyoxyalkylene compounds which gives economically acceptable yields despite the use of only relatively small quantities of alkali metal hydroxide and organic halide.
It has now surprisingly been found that terminally blocked polyglycol ethers can be obtained in high yields by reaction of alcohol ethoxylates with very small molar excesses of organic chlorides or bromides and equally small molar excesses of solid alkali metal hydroxide at moderate temperatures.
Accordingly, the present invention relates to a process for the production of polyoxyalkylene compounds corresponding to formula I
R1 _ o - A - CH2 - R2 (I) in which R1 is a linear or branched alkyl radical containing 1 to 20 C atoms, R2 is a hydrogen atom or a radical corresponding to formula II
I
C - R4 (II) I
in which the substituents R3, R4 and R5 independently of one another represent a hydrogen atom or the hydrocarbon radical of an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, the total number of carbon atoms in R2 being from l to 19, and A is a polyoxyalkylene chain corresponding to formula III
[--( CH2CH20 ) X ( CH2CHO ) Yl ( I I I ) in which x is a number of 2 to 50 and y is a number of O to lO; and where y is other than 0, A can be formed both by random polymerization and by block polymerization. In the radical of formula II, the alkyl group or groups can be straight or branched chain, such as methyl, ethyl, n-propyl, n-butyl, n-2 5 amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-propyl, iso butyl, 2,2-dimethylpropyl, 1,3-dimethylbutyl, 1,3,3-trimethylbutyl, 2,4-dimethylpentyl, 4-methylhexyl; the alkenyl groups can be straight or branched chain such as 7-hexadecenyl; examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and alkyl substituted cycloalkyl groups such as methylcyclohexyl and ethylcyclohexyl; the aryl group is preferably a phenyl or naphthyl group; the `~ aralkyl group is preferably phenylalkyl such as benzyl or phenyethyl, and the alkaryl group is preferably phenyl substituted with one or more C1-C4 alkyl groups.
The process of the invention is carried out by reacting a polyoxyalkylene derivative corresponding to formula IV
R1 _ o - A - H (IV) in which R1 and A are as defined above, with an organic halide corresponding to formula V
R2 _ CH2 - Hal (V) in which R2 is as defined above and Hal is a chlorine or bromine atom, at 60 to 140C in the presence of 80 to 100% by weight of solid, particulate alkali metal hydroxide, the molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) being from (1.5 to 2):1 and the molar ratio of alkali metal hydroxide to polyoxyalkylene derivative (IV) is from (1.5 to 2):1.
In contrast to the known prior art, therefore, it is possible by the process according to the invention to work at temperatures far below 100C and with a smaller excess of alkali metal hydroxide. Accordingly, the process according to the invention is distinctly superior in terms of economy to the prior art processes.
In addition, it is possible in accordance with the invention to obtain faintly colored or substantially colorless products without the starting material, i.e. the polyoxyalkylene compound (IV), having to be pretreated in the presence of a hydrogenation catalyst or the etherification reaction having to be carried out in the presence of an inorganic reducing agent. In addition, the process according to the invention does not have to be carried out in the presence of organic solvents.
The alkali metal hydroxide can be present in the form of flakes, tablets, pills, or as powder. In one embodiment of ~ the present invention, sodium hydroxide and/or potassium hydroxide is used as the alkali metal hydroxide.
In another embodiment of the present invention, polyoxyalkylene derivatives of formula (IV), of which the glycol ether groups are derived only from ethylene oxide, are usçd for the production of polyoxyalkylene compounds corresponding to formula (I). This means that, in formula (III), y is 0. In another preferred embodiment of the present invention, polyoxyalkylene derivatives of formula (IV), in which x is a number of 2.5 to 20 and y is 0, are employed therein.
The preferred reaction temperature for the process according to the invention for the production of polyoxyalkylene derivatives corresponding to formula (I) is in the range of from 80 to 120-C.
A molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) of approximately 2:1 is preferred.
The polyoxyalkylene derivatives produced in accordance with the invention are useful as foam-inhibiting additives in low-foam cleaning preparations. They are added to low-foam cleaninq preparations in quantities of from 0.01 to 1.0% by weight, based on the ready-to-use cleaning compositions.
The invention will be illustrated but not limited by the following examples.
EXAMPLES
2105 g (5.63 mol) of an addition product of 7 mol equivalents ethylene oxide with a C1218-fatty alcohol mixture and 770 g (11.25 mol) 82% flake-form potassium hydroxide were introduced into a three-necked flask equipped with a XPG
stirrer, internal thermometer and reflux condenser. The flask was evacuated twice and purged with nitrogen. After addition of 1042 g (11.26 mol) n-butyl chloride, the mixture was heated with stirring to 80-C and stirred for 8 hours at that h `~ temperature. Excess butyl chloride was then distilled off at 1 bar and at a maximum sump temperature of 200C, nitrogen being used as the purging gas. The reaction mixture was cooled to 60C and neutralized with 2N sulfuric acid. Water was added with stirring to the crude reaction product in a quantity corresponding to its volume, the mixture then being left to stand at 50C until phase separation occurred. A
product having a hydroxyl value (OHV) of 5 was obtained by separating off the aqueous phase.
620 g (1 mol) of an addition product of 9 mol equivalents ethylene oxide with a C1218 fatty alcohol mixture, 137 g (2 mol) 82% flake-form potassium hydroxide and 185 g (2 mol) n-butyl chloride were reacted with one another over a period of4 hours at 80C according to the procedure of Example 1. The reaction mixture was worked up in the same way as Example 1 except that excess n-butyl chloride was distilled off in a water jet vacuum and at a maximum sump temperature of 60C.
A product having an OHV of 4.8 was obtained.
A number of other mixed ethers were prepared as in Examples 1 and 2, the chain length of the alcohol component in the alkoxylates and their degree of alkoxylation being varied over wide ranges. Representative Examples are summarized in Table 1. This Table sets forth the starting materials, the reaction parameters and the OHV of the particular end product. The molar ratio of alkoxylate to alkyl halide to KOH was 1 : 2 : 2 in each case. In addition to sulfuric acid, acetic acid or phosphoric acid was used to neutralize the products.
The following abbreviations are used in Table 1:
FA = fatty alcohol mixture OA = oxoalcohol mixture 1 338~77 EO = ethylene oxide PO = propylene oxide For example, the abbreviation C1218- FA + 2 PO + 7.5 EO
stands for an addition product of 2 mol equivalents propylene oxide and 7.5 mol equivalents ethylene oxide with a C12l8 fatty alcohol mixture while the abbreviation C1213 -OA + 10 EO stands for an addition product of 10 mol equivalents ethylene oxide with a C1213 oxoalcohol mixture.
1 33~77 .,. ~.
, , ~ ~ .. , ~o o .~ ,, oo o o,~, .. ..... ..
~ 1` In t~O OD ~ O 1`
5 .C
O ~
.
~_ oo ooooo ooo t~ co t~l co t~ OD 0~ CO 0 o ,1 , -~ ^
.C ~
co t~o ~ ~ t~ r~ 1` t~ tJO 0 t ~ , , P
a C .~
dP O O O O O O O ~ t~ U~
-- tn tn ~n tn tn tn tn oo t~o o~
o c - l u ~
N I I C~ I V
t~ ~ ~ ~ ~ _ ~t ~ ~ ~ ~
C~ C~ V C.) t~ U O V O C) O O O
O O 1~ 0 1i3 0 0 1~ ~
P~ ~ '' ~1 In o ~ c n t~ m ~I t~ t~
~1 >1 + ~1 + + + + + ~ + +
1 +
~ ~ >. C ~ ~ ~ ~ ~ O ~
~ I I I I 1 1~ 1 0 ~ O
N J ~o ~o o N N + N . ,~ o o c~ o t~
o td ~ t~l t~ D r t~o tn X
E~ t'~ tr~ t'~ ~ t~ t~t t~
German Patent 28 00 710 describes a process for the production of etherified polyoxyalkylene derivatives which are obtained by reaction of polyoxyalkylene alcohols with organic halides in the presence of an aqueous solution of sodium hydroxide or potassium hydroxide having an initial alkali metal hydroxide concentration of at least 30 % by weight. As evidenced by the Examples of German Patent 28 00 710, an only faintly colored or substantially colorless product is obtA;ne~
when the starting material, i.e. the polyoxyalkylene compound, which has been pretreated with hydrogen under the conditions mentioned therein in the presence of the hydrogenation ,~
`~ catalyst, is used for the etherification reaction according to the invention or when the etherification reaction is carried out in the presence of an inorganic reducing agent.
In addition, it can be shown that the process only gives economically satisfactory yields when alkyl halide and alkali metal hydroxide are used in large excesses.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
By contrast, with the process described in the above German patent, an object of the present invention is to provide an improved process for the production of etherified polyoxyalkylene compounds which gives economically acceptable yields despite the use of only relatively small quantities of alkali metal hydroxide and organic halide.
It has now surprisingly been found that terminally blocked polyglycol ethers can be obtained in high yields by reaction of alcohol ethoxylates with very small molar excesses of organic chlorides or bromides and equally small molar excesses of solid alkali metal hydroxide at moderate temperatures.
Accordingly, the present invention relates to a process for the production of polyoxyalkylene compounds corresponding to formula I
R1 _ o - A - CH2 - R2 (I) in which R1 is a linear or branched alkyl radical containing 1 to 20 C atoms, R2 is a hydrogen atom or a radical corresponding to formula II
I
C - R4 (II) I
in which the substituents R3, R4 and R5 independently of one another represent a hydrogen atom or the hydrocarbon radical of an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, the total number of carbon atoms in R2 being from l to 19, and A is a polyoxyalkylene chain corresponding to formula III
[--( CH2CH20 ) X ( CH2CHO ) Yl ( I I I ) in which x is a number of 2 to 50 and y is a number of O to lO; and where y is other than 0, A can be formed both by random polymerization and by block polymerization. In the radical of formula II, the alkyl group or groups can be straight or branched chain, such as methyl, ethyl, n-propyl, n-butyl, n-2 5 amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-propyl, iso butyl, 2,2-dimethylpropyl, 1,3-dimethylbutyl, 1,3,3-trimethylbutyl, 2,4-dimethylpentyl, 4-methylhexyl; the alkenyl groups can be straight or branched chain such as 7-hexadecenyl; examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and alkyl substituted cycloalkyl groups such as methylcyclohexyl and ethylcyclohexyl; the aryl group is preferably a phenyl or naphthyl group; the `~ aralkyl group is preferably phenylalkyl such as benzyl or phenyethyl, and the alkaryl group is preferably phenyl substituted with one or more C1-C4 alkyl groups.
The process of the invention is carried out by reacting a polyoxyalkylene derivative corresponding to formula IV
R1 _ o - A - H (IV) in which R1 and A are as defined above, with an organic halide corresponding to formula V
R2 _ CH2 - Hal (V) in which R2 is as defined above and Hal is a chlorine or bromine atom, at 60 to 140C in the presence of 80 to 100% by weight of solid, particulate alkali metal hydroxide, the molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) being from (1.5 to 2):1 and the molar ratio of alkali metal hydroxide to polyoxyalkylene derivative (IV) is from (1.5 to 2):1.
In contrast to the known prior art, therefore, it is possible by the process according to the invention to work at temperatures far below 100C and with a smaller excess of alkali metal hydroxide. Accordingly, the process according to the invention is distinctly superior in terms of economy to the prior art processes.
In addition, it is possible in accordance with the invention to obtain faintly colored or substantially colorless products without the starting material, i.e. the polyoxyalkylene compound (IV), having to be pretreated in the presence of a hydrogenation catalyst or the etherification reaction having to be carried out in the presence of an inorganic reducing agent. In addition, the process according to the invention does not have to be carried out in the presence of organic solvents.
The alkali metal hydroxide can be present in the form of flakes, tablets, pills, or as powder. In one embodiment of ~ the present invention, sodium hydroxide and/or potassium hydroxide is used as the alkali metal hydroxide.
In another embodiment of the present invention, polyoxyalkylene derivatives of formula (IV), of which the glycol ether groups are derived only from ethylene oxide, are usçd for the production of polyoxyalkylene compounds corresponding to formula (I). This means that, in formula (III), y is 0. In another preferred embodiment of the present invention, polyoxyalkylene derivatives of formula (IV), in which x is a number of 2.5 to 20 and y is 0, are employed therein.
The preferred reaction temperature for the process according to the invention for the production of polyoxyalkylene derivatives corresponding to formula (I) is in the range of from 80 to 120-C.
A molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) of approximately 2:1 is preferred.
The polyoxyalkylene derivatives produced in accordance with the invention are useful as foam-inhibiting additives in low-foam cleaning preparations. They are added to low-foam cleaninq preparations in quantities of from 0.01 to 1.0% by weight, based on the ready-to-use cleaning compositions.
The invention will be illustrated but not limited by the following examples.
EXAMPLES
2105 g (5.63 mol) of an addition product of 7 mol equivalents ethylene oxide with a C1218-fatty alcohol mixture and 770 g (11.25 mol) 82% flake-form potassium hydroxide were introduced into a three-necked flask equipped with a XPG
stirrer, internal thermometer and reflux condenser. The flask was evacuated twice and purged with nitrogen. After addition of 1042 g (11.26 mol) n-butyl chloride, the mixture was heated with stirring to 80-C and stirred for 8 hours at that h `~ temperature. Excess butyl chloride was then distilled off at 1 bar and at a maximum sump temperature of 200C, nitrogen being used as the purging gas. The reaction mixture was cooled to 60C and neutralized with 2N sulfuric acid. Water was added with stirring to the crude reaction product in a quantity corresponding to its volume, the mixture then being left to stand at 50C until phase separation occurred. A
product having a hydroxyl value (OHV) of 5 was obtained by separating off the aqueous phase.
620 g (1 mol) of an addition product of 9 mol equivalents ethylene oxide with a C1218 fatty alcohol mixture, 137 g (2 mol) 82% flake-form potassium hydroxide and 185 g (2 mol) n-butyl chloride were reacted with one another over a period of4 hours at 80C according to the procedure of Example 1. The reaction mixture was worked up in the same way as Example 1 except that excess n-butyl chloride was distilled off in a water jet vacuum and at a maximum sump temperature of 60C.
A product having an OHV of 4.8 was obtained.
A number of other mixed ethers were prepared as in Examples 1 and 2, the chain length of the alcohol component in the alkoxylates and their degree of alkoxylation being varied over wide ranges. Representative Examples are summarized in Table 1. This Table sets forth the starting materials, the reaction parameters and the OHV of the particular end product. The molar ratio of alkoxylate to alkyl halide to KOH was 1 : 2 : 2 in each case. In addition to sulfuric acid, acetic acid or phosphoric acid was used to neutralize the products.
The following abbreviations are used in Table 1:
FA = fatty alcohol mixture OA = oxoalcohol mixture 1 338~77 EO = ethylene oxide PO = propylene oxide For example, the abbreviation C1218- FA + 2 PO + 7.5 EO
stands for an addition product of 2 mol equivalents propylene oxide and 7.5 mol equivalents ethylene oxide with a C12l8 fatty alcohol mixture while the abbreviation C1213 -OA + 10 EO stands for an addition product of 10 mol equivalents ethylene oxide with a C1213 oxoalcohol mixture.
1 33~77 .,. ~.
, , ~ ~ .. , ~o o .~ ,, oo o o,~, .. ..... ..
~ 1` In t~O OD ~ O 1`
5 .C
O ~
.
~_ oo ooooo ooo t~ co t~l co t~ OD 0~ CO 0 o ,1 , -~ ^
.C ~
co t~o ~ ~ t~ r~ 1` t~ tJO 0 t ~ , , P
a C .~
dP O O O O O O O ~ t~ U~
-- tn tn ~n tn tn tn tn oo t~o o~
o c - l u ~
N I I C~ I V
t~ ~ ~ ~ ~ _ ~t ~ ~ ~ ~
C~ C~ V C.) t~ U O V O C) O O O
O O 1~ 0 1i3 0 0 1~ ~
P~ ~ '' ~1 In o ~ c n t~ m ~I t~ t~
~1 >1 + ~1 + + + + + ~ + +
1 +
~ ~ >. C ~ ~ ~ ~ ~ O ~
~ I I I I 1 1~ 1 0 ~ O
N J ~o ~o o N N + N . ,~ o o c~ o t~
o td ~ t~l t~ D r t~o tn X
E~ t'~ tr~ t'~ ~ t~ t~t t~
Claims (9)
1. A process for the production of polyoxyalkylene compounds corresponding to formula I
R1 - O - A - CH2 - R2 (I) in which R1 is a linear or branched alkyl radical containing 1 to 20 C
atoms, R2 is a hydrogen atom or a radical corresponding to formula II
(II) in which the substituents R3, R4 and R5 independently of one another represent a hydrogen atom or the hydrocarbon radical of an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, the total number of carbon atoms in R2 being from 1 to 19 and, A is a polyoxyalkylene chain corresponding to formula III
(III) in which x is a number of 2 to 50 and y is a number of 0 to 10;
where y is other than 0, A is formed by random or by block polymerization, comprising the steps of A. reacting a polyoxyalkyline derivative of the formula R1 - O - A - H (IV) in which R1 and A are as defined above, with an organic halide of the to formula R2 - CH2 - Ha1 (V) in which R2 is as defined above and Hal is a chlorine or bromine atom, at a temperature in the range of from about 60°C to about 140°C in the presence of about 80 to 100% by weight solid, particulate alkali metal hydroxide, wherein the molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) is from about (1.5 to 2):1, and the molar ratio of alkali metal hydroxide to polyoxyalkylene derivative (IV) is from about (1.5 to 2):1, to form a reaction mixture containing a compound of formula I; and B. isolating the compound of formula I from the reaction mixture.
R1 - O - A - CH2 - R2 (I) in which R1 is a linear or branched alkyl radical containing 1 to 20 C
atoms, R2 is a hydrogen atom or a radical corresponding to formula II
(II) in which the substituents R3, R4 and R5 independently of one another represent a hydrogen atom or the hydrocarbon radical of an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, the total number of carbon atoms in R2 being from 1 to 19 and, A is a polyoxyalkylene chain corresponding to formula III
(III) in which x is a number of 2 to 50 and y is a number of 0 to 10;
where y is other than 0, A is formed by random or by block polymerization, comprising the steps of A. reacting a polyoxyalkyline derivative of the formula R1 - O - A - H (IV) in which R1 and A are as defined above, with an organic halide of the to formula R2 - CH2 - Ha1 (V) in which R2 is as defined above and Hal is a chlorine or bromine atom, at a temperature in the range of from about 60°C to about 140°C in the presence of about 80 to 100% by weight solid, particulate alkali metal hydroxide, wherein the molar ratio of organic halide (V) to polyoxyalkylene derivative (IV) is from about (1.5 to 2):1, and the molar ratio of alkali metal hydroxide to polyoxyalkylene derivative (IV) is from about (1.5 to 2):1, to form a reaction mixture containing a compound of formula I; and B. isolating the compound of formula I from the reaction mixture.
2. The process of claim 1 wherein in step A_ the alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
3. The process of claim 1 wherein in formula I, y = 0.
4. The process of claim 1 wherein in formula I, x is a number of from 2.5 to 20.
5. The process of claim 1 wherein in step A the reaction temperature is in the range of from about 80°C to about 120°C.
6. The process of claim 1 wherein in step A the molar ratio of organic halide of formula V to polyoxyalkylene derivative of formula IV is about 2:1.
7. The process of claim 1 wherein in formula I, y = 0 and x is a number of from 2.5 to 20, and in step A the alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and the reaction temperature is in the range of from about 80° to about 120°C.
8. The process of claim 7 wherein in step A the molar ratio of organic halide of formula V to polyoxyalkylene derivative of formula IV is about 2:1.
9. The process of claim 1 wherein ln formula III, y = other than 0.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3744525.1 | 1987-12-30 | ||
| DE3744525A DE3744525C1 (en) | 1987-12-30 | 1987-12-30 | Process for the preparation of end group capped polyglycol ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338277C true CA1338277C (en) | 1996-04-23 |
Family
ID=6343847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000586673A Expired - Fee Related CA1338277C (en) | 1987-12-30 | 1988-12-21 | Process for the production of terminally blocked polyglycol ethers |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0322781B1 (en) |
| JP (1) | JPH01223123A (en) |
| KR (1) | KR890010034A (en) |
| AT (1) | ATE119175T1 (en) |
| BR (1) | BR8806976A (en) |
| CA (1) | CA1338277C (en) |
| DE (2) | DE3744525C1 (en) |
| DK (1) | DK721888A (en) |
| ES (1) | ES2069543T3 (en) |
| FI (1) | FI886028A (en) |
| MX (1) | MX169728B (en) |
| NO (1) | NO173829C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847229A (en) * | 1994-11-02 | 1998-12-08 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of end-capped nonionic surfactants |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3744525C1 (en) * | 1987-12-30 | 1988-12-01 | Henkel Kgaa | Process for the preparation of end group capped polyglycol ethers |
| DE3800490A1 (en) * | 1988-01-11 | 1989-07-20 | Henkel Kgaa | USE OF SELECTED END-GROUP-CONTAINED FAT ALCOHOL ETHHOXYLATES FOR FOAM ARMS, COLD-FRYABLE CLEANING AGENTS |
| DE3800493A1 (en) * | 1988-01-11 | 1989-07-20 | Henkel Kgaa | USE OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS, IN PARTICULAR ALSO SUITABLE FOR COLD CLEANING |
| DE4342214C1 (en) * | 1993-12-10 | 1995-05-18 | Henkel Kgaa | Nonionic detergent mixtures |
| DE4431158C2 (en) * | 1994-09-01 | 1999-10-21 | Henkel Kgaa | Methyl end-capped alkyl and / or alkenyl polyglycol ethers |
| DE19652680A1 (en) * | 1996-12-18 | 1998-06-25 | Clariant Gmbh | Mixtures of alkoxylates with foam-suppressing and disinfecting effects and their use in cleaning agents |
| GB0121580D0 (en) * | 2001-09-06 | 2001-10-24 | Syngenta Ltd | Novel compounds |
| ES2803507T3 (en) * | 2013-03-15 | 2021-01-27 | Croda Inc | Alkyl ethers of alkoxylated fatty alcohols and products containing them |
| CN118043304A (en) | 2021-10-01 | 2024-05-14 | 科莱恩国际有限公司 | End-capped bio-based low foaming surfactants |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959391A (en) * | 1973-03-29 | 1976-05-25 | Nalco Chemical Company | Diethers of polyalkylene glycol |
| DE2800710C2 (en) * | 1978-01-09 | 1989-06-08 | Kuraray Co., Ltd., Kurashiki, Okayama | Process for the preparation of etherified polyoxyalkylene derivatives |
| DE3416289A1 (en) * | 1984-05-03 | 1985-11-07 | Hoechst Ag, 6230 Frankfurt | Method for processing the residue from the reaction of an alkylene oxide with excess water, alkanol or alkanediol |
| US4587365A (en) * | 1984-10-29 | 1986-05-06 | Basf Corporation | Preparing capped polyoxyalkylene polyols |
| DE3744525C1 (en) * | 1987-12-30 | 1988-12-01 | Henkel Kgaa | Process for the preparation of end group capped polyglycol ethers |
-
1987
- 1987-12-30 DE DE3744525A patent/DE3744525C1/en not_active Expired
-
1988
- 1988-12-21 CA CA000586673A patent/CA1338277C/en not_active Expired - Fee Related
- 1988-12-23 ES ES88121574T patent/ES2069543T3/en not_active Expired - Lifetime
- 1988-12-23 DE DE3853202T patent/DE3853202D1/en not_active Expired - Fee Related
- 1988-12-23 DK DK721888A patent/DK721888A/en not_active Application Discontinuation
- 1988-12-23 EP EP88121574A patent/EP0322781B1/en not_active Expired - Lifetime
- 1988-12-23 AT AT88121574T patent/ATE119175T1/en active
- 1988-12-28 MX MX014367A patent/MX169728B/en unknown
- 1988-12-28 JP JP63332694A patent/JPH01223123A/en active Pending
- 1988-12-29 FI FI886028A patent/FI886028A/en not_active Application Discontinuation
- 1988-12-29 NO NO885805A patent/NO173829C/en unknown
- 1988-12-29 BR BR888806976A patent/BR8806976A/en not_active Application Discontinuation
- 1988-12-30 KR KR1019880018032A patent/KR890010034A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847229A (en) * | 1994-11-02 | 1998-12-08 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of end-capped nonionic surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0322781B1 (en) | 1995-03-01 |
| NO885805L (en) | 1989-07-03 |
| JPH01223123A (en) | 1989-09-06 |
| BR8806976A (en) | 1989-09-05 |
| DK721888D0 (en) | 1988-12-23 |
| EP0322781A2 (en) | 1989-07-05 |
| MX169728B (en) | 1993-07-21 |
| NO885805D0 (en) | 1988-12-29 |
| NO173829B (en) | 1993-11-01 |
| DE3853202D1 (en) | 1995-04-06 |
| FI886028A (en) | 1989-07-01 |
| NO173829C (en) | 1994-02-09 |
| DE3744525C1 (en) | 1988-12-01 |
| ATE119175T1 (en) | 1995-03-15 |
| DK721888A (en) | 1989-07-01 |
| ES2069543T3 (en) | 1995-05-16 |
| EP0322781A3 (en) | 1990-06-13 |
| KR890010034A (en) | 1989-08-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |