CA1176268A - Polycarbonate type nonionic surfactants - Google Patents
Polycarbonate type nonionic surfactantsInfo
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- CA1176268A CA1176268A CA000403120A CA403120A CA1176268A CA 1176268 A CA1176268 A CA 1176268A CA 000403120 A CA000403120 A CA 000403120A CA 403120 A CA403120 A CA 403120A CA 1176268 A CA1176268 A CA 1176268A
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Abstract
ABSTRACT
A process for preparing polycarbonate type nonionic surfactant compositions comprising monohydroxy alcohols capped with polycarbonate groups. The sur-factant compositions comprise aliphatic, nonaromatic cycloaliphatic or aromatic alcohols which have been capped with block polycarbonate groups formed by the reaction of the alcohols with ethylene carbonate in the presence of an alkali metal salt catalyst. The sur-factant properties are varied by first reacting the alcohols with ethylene oxide to form a block polyether group cap on the alcohols before the reaction with ethylene carbonate or by further reacting the poly-carbonate capped alcohols with ethylene oxide to form a terminal polyether block group. The surfactants are formed by reacting 2-20 moles ethylene carbonate and 3-50 moles ethylene oxide per mole of the alcohols.
27,098A-F
A process for preparing polycarbonate type nonionic surfactant compositions comprising monohydroxy alcohols capped with polycarbonate groups. The sur-factant compositions comprise aliphatic, nonaromatic cycloaliphatic or aromatic alcohols which have been capped with block polycarbonate groups formed by the reaction of the alcohols with ethylene carbonate in the presence of an alkali metal salt catalyst. The sur-factant properties are varied by first reacting the alcohols with ethylene oxide to form a block polyether group cap on the alcohols before the reaction with ethylene carbonate or by further reacting the poly-carbonate capped alcohols with ethylene oxide to form a terminal polyether block group. The surfactants are formed by reacting 2-20 moles ethylene carbonate and 3-50 moles ethylene oxide per mole of the alcohols.
27,098A-F
Description
76;~
PROCESS FOR PREPARING POLYCARBONATE-TYPE
SURFACT~TS FROM ETHYLFNE CARBONATE
AND A MONOHYDROXY ALCOHOL
This invention relates to methods for making nonionic surfactants, with particular reference to making nonionic surfactant compositions comprising monohydroxy alcohols capped with a polycarbonate.
In many industrial and household cleaning applications it is desirable or necessary to use a surfactant in the cleaning formulations to achieve satisfactory wetting and cleansing. Furthermore, in many of these industrial and household applications it is necessary to maintain a low level of foam during the cleaning operation. For example, surfactants that pxoduce excessive foaming may be unsuitable in an industrial spray metal cleaning operation or for use as an active ingredient in detergents and rinse aids for household mechanical dishwashers.
One type of nonionic surfactant known in the art is the fatty acid ester of an alcohol ethoxylate, which estex is produced by condensing ethylene oxide with a detergent range alcohol, and then reacting such ethoxylated alcohol with fatty acids containing from 8 27,098A-F
*
PROCESS FOR PREPARING POLYCARBONATE-TYPE
SURFACT~TS FROM ETHYLFNE CARBONATE
AND A MONOHYDROXY ALCOHOL
This invention relates to methods for making nonionic surfactants, with particular reference to making nonionic surfactant compositions comprising monohydroxy alcohols capped with a polycarbonate.
In many industrial and household cleaning applications it is desirable or necessary to use a surfactant in the cleaning formulations to achieve satisfactory wetting and cleansing. Furthermore, in many of these industrial and household applications it is necessary to maintain a low level of foam during the cleaning operation. For example, surfactants that pxoduce excessive foaming may be unsuitable in an industrial spray metal cleaning operation or for use as an active ingredient in detergents and rinse aids for household mechanical dishwashers.
One type of nonionic surfactant known in the art is the fatty acid ester of an alcohol ethoxylate, which estex is produced by condensing ethylene oxide with a detergent range alcohol, and then reacting such ethoxylated alcohol with fatty acids containing from 8 27,098A-F
*
-2- 1~7~2~8 to 18 carbon atoms, or with the chlorides of such acids. Surfactants produced in this manner are described in U.S. Patent 1,970,578 which teaches such surfactants as having excellent wetting, foaming and cleansing properties. However, surfactants of this type would not be satisfactory for uses where the suppression of foam is important.
Another type of nonionic surfactant known in the art is described in Japanese Patent Publication 56-106,919 which teaches a nonionic surfactant compo-sition prepared in a manner similar to the method of this application. However, the final products are inferior as foam suppressing agents.
The present invention is a process for the preparation of a polycarbonate type surfactant com-prising reacting ethylene carbonate and a monohydroxy alcohol in the presence of an alkali metal salt catalyst at a temperature of 130C to 210C.
The present invention is also directed to a process wherein said surfactant is reacted with ethylene oxide in the amount of 3 to 50 moles of oxide per mole of surfactant.
More specifically, the surfactant compositions prepared by the process of the present invention comprise compounds repxesented by the following structural formulas:
R-O-[cH2-cH2-o-c-o-cH2-cH2-o]y~H
27,098A-F -2-~3~ ~7~
R-O-[CH2-CH2-O]X-[CH2-CH2-O-C-O-CH2-CH2-O]y~H
[ 2 2 CH2 CH2 O]y [CH2 CH2 ]x H
where R is an aliphatic, non-aromatic cycloaliphatic or aromatic group, y is a number from 1 to 10 and x is a number from 3 to 50. The monohydroxy alcohol may be capped with ethylene oxide before reacting it with ethylene carbonate or the reaction product of the ethylene carbonate/monohydroxy alcohol reaction may be further reacted with ethylene oxide to provide sur-factants having different physical properties. The hydroxyethylation reaction of the alcohol or poly-carbonate reaction product with ethylene oxide can be easily accomplished by using a basic catalyst, i.e., KOH, at a temperature of about 90C to about 120C.
The reaction of the monohydroxy alcohol or ethoxylated alcohol with ethylene carbonate is represented by the following equations.
CH2 \ H2 o 0-CH2 2 1 /C=O > CO2~ + I \C/
E2 o H2 c) O-CH2 2 \ / 2 "
RO~ + Y ¦ f ~ ~ R-O-[cH2-cH2-o-c-o-cH2-cH2-o]y-H
C~2 O-CH2 The above equations illustrate that 50 percent of the 39 available CO2 in the ethylene carbonate is lost as a 27,098A-F-3--4- 1~'~6Z~
result of the formation of the carbonate intermediate illustrated by the first equation. Thus, the theoretical maximum yield of the polycarbonate block portion in the surfactant compositions is only 50 percent of the CO2 available in the original ethylene carbonate reactant.
Moreover, it is believed that the ethylene carbonate/-alcohol reaction is initiated by an ethoxy ether radical resulting from the decomposition of ethylene carbonate to ethylene oxide and CO2. This ethoxy ether free radical initiation of the polycarbonate/alcohol reaction appears to be accurate since only about 38 percent to 43 percent of the CO2 in the ethylene carbonate is normally retained as a carbonate radical in the final surfactant compositions.
Generally, about 2 to 20 moles, and more preferably about 3 to lO moles, of ethylene carbonate per mole of monohydroxy alcohol or ethoxylated mono-hydroxy alcohol are reacted together to provide the hydrophobic properties in the final surfactant compo-sitions. Also, about 3 to 50 moles, and prefera'oly about 3 to 10 moles, of ethylene oxide per mole of monohydroxy alcohol- or polycarbonate-capped mono-hydroxy alcohol are reacted together to provide the hydrophilic properties in the final surfactant compositions.
The temperature of the ethylene carbonate/-alcohol reaction is maintained between about 130C to about 210C, and preferably between about 140C and about 170C. A reaction temperature below 130C is not desirable since the formation of the polycarbonate bloc~ portion of the surfactant compositions is extremely slow at such low temperatures. Reaction 27,0g8A-F -4--5~ Z ~ ~
temperatures above about 210C are also undesirable since ethylene carbonate will decompose into ethylene oxide and C02 at these elevated temperatures and the more reactive hydroxyethylation or polyether reactions will occur.
In order to form the polycarbonate block portion of the surfactant compositions, it is necessary that the ethylene carbonate/alcohol reaction be run in the presence of an alkali metal salt catalyst. Examples of useful alkali metal salt catalyst are sodium stannate, potassium stannate, sodium carbonate, potassium carbonate, sodium hydroxide, potassiwn hydroxide, the sodium alkoxide of the monohydroxy alcohol and the potassium alkoxide of the monohydroxy alcohol. Sodium stannate has been found to be a particularly effective catalyst since high yields and low reaction time were obtained when it was used.
In view of the preceding discussion, it will be appreciated that the polycarbonate type surfactant products produced by this invention have, in all probability, some random ether radicals disposed within the polycarbonate block portion of the products since the theoretical 50 percent CO2 retention in the products is normally not achieved during the ethylene carbonate/alcohol reaction. Furthermore, it will be appreciated that the surfactant products are not a single compound in each instance, but are a mixture of compounds of different molecular weights characterized by an average molecular weight depending on the ~0 termination point of the ether and/or carbonate ~locks in each molecule.
27,098A-F -5--6- 1~6~1~
The following examples illustrate the prepara-tion of the polycarbonate type surfactants in accordance with the present invention.
Example 1 A stirred reaction mixture of 2640 grams (30 moles) of ethylene carbonate, 558 grams (3 moles) of n-dodecanol and 12.0 grams (0.056 mole) of sodium stannate was heated to 170C for 24 hours in a reaction vessel under a nitrogen atmosphere. The mixture was then cooled to 130C and 30 grams of finely divided magnesium silicate and 60 grams of CELITE brand of diatomaceous earth were added to purify the mixture.
The mixture was continuously stirred at 130C for an additional 21 hours. At this point, the reaction prod-uct mixture was permitted to cool and was then filtered to remove the magnesium silicate and CELITE brand of dia-tomaceous earth. 2000 Grams of a pale yellow, trans-parent, viscous liquid reaction product was obtained which retained about 40 weight percent of the available CO2 in the ethylene carbonate as a carbonate radical in the reaction product as determined by nuclear magnetic resonance spectral analysis.
Example 2 A stirred reaction mixture of 44 grams (0.5 mole) of ethylene carbonate, 18.4 grams (0.1 mole) of cyclododecanol and 0.2 gram (0.001 mole) of sodium stan-nate was heated to 170C for 22 hours in a reaction vessel under a nitrogen atmosphereO The mixture was then cooled to 130C and 0.5 gram of magnesium silicate and 1.0 gram of CELITE brand of diatomaceous earth were added to purify the mixture. The mixture was continuously stirred at 130C for an additonal one hour. The reaction product mixture was permitted to cool and was then filtered to 27,098A-F -6--7~
remove the magnesium silicate and CELITE brand of dia-tomaceous earth. 35.1 Grams of a pale yellow, trans-parent, viscous liquid reaction product was obtained which solidified on standing. About 40 weight percent of the available CO2 in the ethylene carbonate was retained as a carbonate radical in the product.
Example 3 The reaction conditions of Examples 1 and 2 were duplicated except that a mixture of 44 grams (0.5 10 mole) of ethylene carbonate, 20 grams (0.091 mole) of 4-nonylphenol and 0.2 gram (0.001 mole) of sodium stan-nate was reacted at 170C for 18 hours. The temperature of the mixture was reduced to 130C, 1 gram of magnesium silicate and 1 gram of CELITE brand of diatomaceous earth were added to the mixture and stirring was con-tinued for one hour before cooling and filtering the reaction product. About 33 weight percent of the avail-able CO2 in the ethylene carbonate was retained as a carbonate radical in the reaction product.
Example 4 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 4.7 grams (0.025 mole) of n-dodecanol and 0.5 gram (0.002 mole) of 25 sodium stannate was reacted at 150C for 40 hours.
30.3 Grams of a yellow, transparent, viscous liquid reaction product was obtained after purification and filtration as in Example 3. 41 Weight percent of the available CO2 was retained as a carbonate radical in the reaction product.
27,0~8A-F -7-8 i~
Example 5 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 5 grams (0.025 mole) of 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (0.001 mole) of sodium stannate was reacted at 150C
for 20 hours. 26.4 Grams of reaction product was obtained after purification and filtration as in Example 3. 40 Weight percent of the available CO2 was retained as a carbonate radical in the reaction product.
~xample 6 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 6.3 grams (0.034 mole) of n-dodecanol and 0.01 gram (0.001 mole) of potassium carbonate was reacted at 135C for 24 hours.
The temperature of the mixture was then raised to 165C
and reacted for an additional 44 hours. 26.9 Grams of a dark brown, transparent, viscous liquid reaction product was obtained after purification and filtration as in Example 3. 19 Weight percent of the available C2 was retained as a carbonate radical in the reaction product.
Example 7 37.3 Grams ~0.2 mole) of n-dodecanol and about 0.05 gram (0.002 mole) of sodium metal were mixed in a reaction vessel at 100C until the sodium dissolved. 88.1 Grams (1.0 mole) of ethylene carbonate were added to the reaction vessel and the stirred mixture was heated to 200C and maintained at that temperature for 2 hours. 83.2 Grams of a pale yellow, transparent, viscous liquid reaction ~roduct were 27,09~A-F -8--9~ 6r~
obtained after purification and filtration as in Example
Another type of nonionic surfactant known in the art is described in Japanese Patent Publication 56-106,919 which teaches a nonionic surfactant compo-sition prepared in a manner similar to the method of this application. However, the final products are inferior as foam suppressing agents.
The present invention is a process for the preparation of a polycarbonate type surfactant com-prising reacting ethylene carbonate and a monohydroxy alcohol in the presence of an alkali metal salt catalyst at a temperature of 130C to 210C.
The present invention is also directed to a process wherein said surfactant is reacted with ethylene oxide in the amount of 3 to 50 moles of oxide per mole of surfactant.
More specifically, the surfactant compositions prepared by the process of the present invention comprise compounds repxesented by the following structural formulas:
R-O-[cH2-cH2-o-c-o-cH2-cH2-o]y~H
27,098A-F -2-~3~ ~7~
R-O-[CH2-CH2-O]X-[CH2-CH2-O-C-O-CH2-CH2-O]y~H
[ 2 2 CH2 CH2 O]y [CH2 CH2 ]x H
where R is an aliphatic, non-aromatic cycloaliphatic or aromatic group, y is a number from 1 to 10 and x is a number from 3 to 50. The monohydroxy alcohol may be capped with ethylene oxide before reacting it with ethylene carbonate or the reaction product of the ethylene carbonate/monohydroxy alcohol reaction may be further reacted with ethylene oxide to provide sur-factants having different physical properties. The hydroxyethylation reaction of the alcohol or poly-carbonate reaction product with ethylene oxide can be easily accomplished by using a basic catalyst, i.e., KOH, at a temperature of about 90C to about 120C.
The reaction of the monohydroxy alcohol or ethoxylated alcohol with ethylene carbonate is represented by the following equations.
CH2 \ H2 o 0-CH2 2 1 /C=O > CO2~ + I \C/
E2 o H2 c) O-CH2 2 \ / 2 "
RO~ + Y ¦ f ~ ~ R-O-[cH2-cH2-o-c-o-cH2-cH2-o]y-H
C~2 O-CH2 The above equations illustrate that 50 percent of the 39 available CO2 in the ethylene carbonate is lost as a 27,098A-F-3--4- 1~'~6Z~
result of the formation of the carbonate intermediate illustrated by the first equation. Thus, the theoretical maximum yield of the polycarbonate block portion in the surfactant compositions is only 50 percent of the CO2 available in the original ethylene carbonate reactant.
Moreover, it is believed that the ethylene carbonate/-alcohol reaction is initiated by an ethoxy ether radical resulting from the decomposition of ethylene carbonate to ethylene oxide and CO2. This ethoxy ether free radical initiation of the polycarbonate/alcohol reaction appears to be accurate since only about 38 percent to 43 percent of the CO2 in the ethylene carbonate is normally retained as a carbonate radical in the final surfactant compositions.
Generally, about 2 to 20 moles, and more preferably about 3 to lO moles, of ethylene carbonate per mole of monohydroxy alcohol or ethoxylated mono-hydroxy alcohol are reacted together to provide the hydrophobic properties in the final surfactant compo-sitions. Also, about 3 to 50 moles, and prefera'oly about 3 to 10 moles, of ethylene oxide per mole of monohydroxy alcohol- or polycarbonate-capped mono-hydroxy alcohol are reacted together to provide the hydrophilic properties in the final surfactant compositions.
The temperature of the ethylene carbonate/-alcohol reaction is maintained between about 130C to about 210C, and preferably between about 140C and about 170C. A reaction temperature below 130C is not desirable since the formation of the polycarbonate bloc~ portion of the surfactant compositions is extremely slow at such low temperatures. Reaction 27,0g8A-F -4--5~ Z ~ ~
temperatures above about 210C are also undesirable since ethylene carbonate will decompose into ethylene oxide and C02 at these elevated temperatures and the more reactive hydroxyethylation or polyether reactions will occur.
In order to form the polycarbonate block portion of the surfactant compositions, it is necessary that the ethylene carbonate/alcohol reaction be run in the presence of an alkali metal salt catalyst. Examples of useful alkali metal salt catalyst are sodium stannate, potassium stannate, sodium carbonate, potassium carbonate, sodium hydroxide, potassiwn hydroxide, the sodium alkoxide of the monohydroxy alcohol and the potassium alkoxide of the monohydroxy alcohol. Sodium stannate has been found to be a particularly effective catalyst since high yields and low reaction time were obtained when it was used.
In view of the preceding discussion, it will be appreciated that the polycarbonate type surfactant products produced by this invention have, in all probability, some random ether radicals disposed within the polycarbonate block portion of the products since the theoretical 50 percent CO2 retention in the products is normally not achieved during the ethylene carbonate/alcohol reaction. Furthermore, it will be appreciated that the surfactant products are not a single compound in each instance, but are a mixture of compounds of different molecular weights characterized by an average molecular weight depending on the ~0 termination point of the ether and/or carbonate ~locks in each molecule.
27,098A-F -5--6- 1~6~1~
The following examples illustrate the prepara-tion of the polycarbonate type surfactants in accordance with the present invention.
Example 1 A stirred reaction mixture of 2640 grams (30 moles) of ethylene carbonate, 558 grams (3 moles) of n-dodecanol and 12.0 grams (0.056 mole) of sodium stannate was heated to 170C for 24 hours in a reaction vessel under a nitrogen atmosphere. The mixture was then cooled to 130C and 30 grams of finely divided magnesium silicate and 60 grams of CELITE brand of diatomaceous earth were added to purify the mixture.
The mixture was continuously stirred at 130C for an additional 21 hours. At this point, the reaction prod-uct mixture was permitted to cool and was then filtered to remove the magnesium silicate and CELITE brand of dia-tomaceous earth. 2000 Grams of a pale yellow, trans-parent, viscous liquid reaction product was obtained which retained about 40 weight percent of the available CO2 in the ethylene carbonate as a carbonate radical in the reaction product as determined by nuclear magnetic resonance spectral analysis.
Example 2 A stirred reaction mixture of 44 grams (0.5 mole) of ethylene carbonate, 18.4 grams (0.1 mole) of cyclododecanol and 0.2 gram (0.001 mole) of sodium stan-nate was heated to 170C for 22 hours in a reaction vessel under a nitrogen atmosphereO The mixture was then cooled to 130C and 0.5 gram of magnesium silicate and 1.0 gram of CELITE brand of diatomaceous earth were added to purify the mixture. The mixture was continuously stirred at 130C for an additonal one hour. The reaction product mixture was permitted to cool and was then filtered to 27,098A-F -6--7~
remove the magnesium silicate and CELITE brand of dia-tomaceous earth. 35.1 Grams of a pale yellow, trans-parent, viscous liquid reaction product was obtained which solidified on standing. About 40 weight percent of the available CO2 in the ethylene carbonate was retained as a carbonate radical in the product.
Example 3 The reaction conditions of Examples 1 and 2 were duplicated except that a mixture of 44 grams (0.5 10 mole) of ethylene carbonate, 20 grams (0.091 mole) of 4-nonylphenol and 0.2 gram (0.001 mole) of sodium stan-nate was reacted at 170C for 18 hours. The temperature of the mixture was reduced to 130C, 1 gram of magnesium silicate and 1 gram of CELITE brand of diatomaceous earth were added to the mixture and stirring was con-tinued for one hour before cooling and filtering the reaction product. About 33 weight percent of the avail-able CO2 in the ethylene carbonate was retained as a carbonate radical in the reaction product.
Example 4 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 4.7 grams (0.025 mole) of n-dodecanol and 0.5 gram (0.002 mole) of 25 sodium stannate was reacted at 150C for 40 hours.
30.3 Grams of a yellow, transparent, viscous liquid reaction product was obtained after purification and filtration as in Example 3. 41 Weight percent of the available CO2 was retained as a carbonate radical in the reaction product.
27,0~8A-F -7-8 i~
Example 5 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 5 grams (0.025 mole) of 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (0.001 mole) of sodium stannate was reacted at 150C
for 20 hours. 26.4 Grams of reaction product was obtained after purification and filtration as in Example 3. 40 Weight percent of the available CO2 was retained as a carbonate radical in the reaction product.
~xample 6 The reaction conditions of Examples 1 and 2 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 6.3 grams (0.034 mole) of n-dodecanol and 0.01 gram (0.001 mole) of potassium carbonate was reacted at 135C for 24 hours.
The temperature of the mixture was then raised to 165C
and reacted for an additional 44 hours. 26.9 Grams of a dark brown, transparent, viscous liquid reaction product was obtained after purification and filtration as in Example 3. 19 Weight percent of the available C2 was retained as a carbonate radical in the reaction product.
Example 7 37.3 Grams ~0.2 mole) of n-dodecanol and about 0.05 gram (0.002 mole) of sodium metal were mixed in a reaction vessel at 100C until the sodium dissolved. 88.1 Grams (1.0 mole) of ethylene carbonate were added to the reaction vessel and the stirred mixture was heated to 200C and maintained at that temperature for 2 hours. 83.2 Grams of a pale yellow, transparent, viscous liquid reaction ~roduct were 27,09~A-F -8--9~ 6r~
obtained after purification and filtration as in Example
3.
Example 8 A stirred reaction mixture of 22 grams (0.25 mole) of ethyl~ne carbonate, 16.6 grams (0.05 mole) of a mixture of n-dodecyl and n-tetradecyl triethoxylates (approximately 50/50 mole percent mixture) and 0.2 gram (O.001 mole) of sodium stannate was heated to 150C for 17 hours in a reaction vessel under a nitrogen atmosphere. 24.1 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained aft~r purification and filtration as in Example 3.
Example 9 A stirred reaction mixture of 44 grams (0 5 mole) of ethylene carbonate, 23.6 grams ~0.05 mole) of a mixture of n-dodecyl and n-tetradecyl hexaethoxylates (approximately 50/50 mole percent) and 0.2 gram (0.001 mole) of sodium stannate was heated to 150C for 24 hours. 48.1 Grams of a pale yellow, transparent, viscous liguid reaction product were obtained after purification and filtration as in Example 3.
Example 10 27 Grams (0.31 mole) of ethylene carbonate, 53.0 grams (0.10 mole) of 2,4,6,8-tetramethyl-l-nonyl octaethoxylate and 0.2 gram (0.001 mole) of sodium stannate were heated to 150C for 20 hours in a stirred reaction vessel as in Example 8. 64.2 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained after purification and filtration as in Example 3.
27,098A-F -9--lo- ~176Z~8 Example 11 440 Grams (5 moles) of ethylene carbonate, 530 grams (0.96 mole) of 2,4,6,8-tetramethyl-1-nonyl octa-ethoxylate and 2 grams (0.01 mole) of sodium stannate were heated to 160C for 24 hours in a stirred reaction vessel under a nitrogen atmosphere. The mixture was then cooled to 110C, 10 grams of magnesium silicate and 10 grams of CELITE brand of diatomaceous earth were added and the mixture was stirred for one hour. After filtration, 703 grams of a pale yellow, transparent, viscous liquid reaction product were obtained.
Example 12 15.1 Grams (0.17 mole) of ethylene carbonate, 17.1 grams (0.0087 mole) of tertiary-octylphenol capped with 40 moles of ethylene oxide per mole of alcohol and 0.2 gram (0.001 mole) of sodium stannate were heated to 160C for 12 hours in a stirred reaction vessel as in Example 8. 10.7 Grams of a tan solid reaction product were obtained after purification and filtration as in Example 3.
Example 13 The reaction conditions of Example 5 were duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 20 grams (0.1 mole) of 25 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (0.001 mole) of sodium stannate was reacted at 150C for 20 hours. The reaction product was purified and filtered as in Example 3. 20 Grams (0.038 mole) of this reaction product and 0.1 gram (0.0018 mole) of potassium hydroxide were placed in a reaction vessel and heated to 110C. 7.5 Grams (0.17 mole) of ethylene oxide were then added to the reaction vessel and the 27,098A-F -10-mixture was continuously stirred for 16 hours. 23.5 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained after purification and filtration as in Example 3.
Example 14 The reaction conditions of Example 5 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 10 grams (0.05 mole) of 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (O.001 lQ mole) of sodium stannate was reacted at 150C for 20 hours. 20 Grams (0.023 mole) of this reaction product, 5 grams (0.114 mole) of ethylene oxide and 0.1 gram (0.0018 mole) of potassium hydroxide were continuously stirred at 110C for 16 hours in a reaction vessel.
25.5 Grams of a pale yellow, transparent, viscous liguid reaction product were obtained after purification and filtration as in Example 3.
The following Table 1 illustrates the mole ratios of ethylene carbonate and ethylene oxide reacted with each mole of alcohol and the catalyst used for the above examples.
27,098A-F -11--12- ~ ~7~ ;8 Moles Moles Moles Example ROH1 CatalystEG2 EC3 EO
12 Na2SnO3 - 10 2 Cyc-C12OH Na25nO3 - 5 3 Cg ~ OH Na SnO ~ 5 5
Example 8 A stirred reaction mixture of 22 grams (0.25 mole) of ethyl~ne carbonate, 16.6 grams (0.05 mole) of a mixture of n-dodecyl and n-tetradecyl triethoxylates (approximately 50/50 mole percent mixture) and 0.2 gram (O.001 mole) of sodium stannate was heated to 150C for 17 hours in a reaction vessel under a nitrogen atmosphere. 24.1 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained aft~r purification and filtration as in Example 3.
Example 9 A stirred reaction mixture of 44 grams (0 5 mole) of ethylene carbonate, 23.6 grams ~0.05 mole) of a mixture of n-dodecyl and n-tetradecyl hexaethoxylates (approximately 50/50 mole percent) and 0.2 gram (0.001 mole) of sodium stannate was heated to 150C for 24 hours. 48.1 Grams of a pale yellow, transparent, viscous liguid reaction product were obtained after purification and filtration as in Example 3.
Example 10 27 Grams (0.31 mole) of ethylene carbonate, 53.0 grams (0.10 mole) of 2,4,6,8-tetramethyl-l-nonyl octaethoxylate and 0.2 gram (0.001 mole) of sodium stannate were heated to 150C for 20 hours in a stirred reaction vessel as in Example 8. 64.2 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained after purification and filtration as in Example 3.
27,098A-F -9--lo- ~176Z~8 Example 11 440 Grams (5 moles) of ethylene carbonate, 530 grams (0.96 mole) of 2,4,6,8-tetramethyl-1-nonyl octa-ethoxylate and 2 grams (0.01 mole) of sodium stannate were heated to 160C for 24 hours in a stirred reaction vessel under a nitrogen atmosphere. The mixture was then cooled to 110C, 10 grams of magnesium silicate and 10 grams of CELITE brand of diatomaceous earth were added and the mixture was stirred for one hour. After filtration, 703 grams of a pale yellow, transparent, viscous liquid reaction product were obtained.
Example 12 15.1 Grams (0.17 mole) of ethylene carbonate, 17.1 grams (0.0087 mole) of tertiary-octylphenol capped with 40 moles of ethylene oxide per mole of alcohol and 0.2 gram (0.001 mole) of sodium stannate were heated to 160C for 12 hours in a stirred reaction vessel as in Example 8. 10.7 Grams of a tan solid reaction product were obtained after purification and filtration as in Example 3.
Example 13 The reaction conditions of Example 5 were duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 20 grams (0.1 mole) of 25 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (0.001 mole) of sodium stannate was reacted at 150C for 20 hours. The reaction product was purified and filtered as in Example 3. 20 Grams (0.038 mole) of this reaction product and 0.1 gram (0.0018 mole) of potassium hydroxide were placed in a reaction vessel and heated to 110C. 7.5 Grams (0.17 mole) of ethylene oxide were then added to the reaction vessel and the 27,098A-F -10-mixture was continuously stirred for 16 hours. 23.5 Grams of a pale yellow, transparent, viscous liquid reaction product were obtained after purification and filtration as in Example 3.
Example 14 The reaction conditions of Example 5 were again duplicated except that a mixture of 44 grams (0.5 mole) of ethylene carbonate, 10 grams (0.05 mole) of 2,4,6,8-tetramethyl-1-nonanol and 0.2 gram (O.001 lQ mole) of sodium stannate was reacted at 150C for 20 hours. 20 Grams (0.023 mole) of this reaction product, 5 grams (0.114 mole) of ethylene oxide and 0.1 gram (0.0018 mole) of potassium hydroxide were continuously stirred at 110C for 16 hours in a reaction vessel.
25.5 Grams of a pale yellow, transparent, viscous liguid reaction product were obtained after purification and filtration as in Example 3.
The following Table 1 illustrates the mole ratios of ethylene carbonate and ethylene oxide reacted with each mole of alcohol and the catalyst used for the above examples.
27,098A-F -11--12- ~ ~7~ ;8 Moles Moles Moles Example ROH1 CatalystEG2 EC3 EO
12 Na2SnO3 - 10 2 Cyc-C12OH Na25nO3 - 5 3 Cg ~ OH Na SnO ~ 5 5
4 C12H Na2SnO3 - 20 C13H Na2SnO3 - 20 C12H K2CO3 - 14.7 7 C12OH - Na - 5 8 C12/C14-OH Na2SnO3 3 5 9 C12/C14-OH Na2SnO3 6 10 C13H Na2SnO3 8 3 11 C13H Na2SnO3 8 5 15 12 C8 ~ OH Na2SnO3 40 2 13 C13H KOH - 5 4.5 14 C13H KOH - 10 4.9 1 Monohydroxy alcohol 2 Ethylene oxide 2 3 Ethylene carbonate The following Table 2 illustrates the surfactant properties for the reaction products of the above examples.
27,098A-F -12--13~ 6Z~
Inter-Surface facial Foam Height, Wetting Cloud Tension2, Tension3, Cms4 Ti~e5 Point6, Examplel dynes/cm dynes/cm In tlal Final seconds C
Control ~300 1 28.2 1.31.5 0.5>300 <25 2 37.4 1.00.5 0.2>300 c25 3 31.3 9.40.8 0.7>300 Insoluble 4 31.8 1.3*5.5 *3.0*120 <25 32.7 1.6*4.6 *0.8>300 <25 6 33.3 5.819.6 8.9 75 <25 7 28.8 1.05.6 1.8 85 <25 8 31.7 2.2~3.0 ~.6 45 35 9 ~9.8 1.~6.1 2.3 61 27.5 1.18.6 3.8 36 18 11 26.8 1.76.0 1.6 40 24 12 34.3 8.926.9 12.2>300 13 26.8 2.47.6 3.3 ~1 <5 14 29.6 1.28.4 3.8 66 <5 0.1 weight percent concentration in deionized water.
Numbers marked with * are 1.0 weight percent concen-tration in deionized water.
2 ASTM D-1331 test procedure.
2 5 3 ASTM D-1331 test procedure.
4 Foam height was determined by whipping at low speed for one minute in a blender 250 ml of a 0.1 percent by weight surfactant/water solution. The solution and foam were poured into a standard 500 ml graduated cylinder having a 4.7 centimeter diameter. The foam height was measured immediately and after five minutes.
27,09~A-F -13--14~ 7~
27,098A-F -12--13~ 6Z~
Inter-Surface facial Foam Height, Wetting Cloud Tension2, Tension3, Cms4 Ti~e5 Point6, Examplel dynes/cm dynes/cm In tlal Final seconds C
Control ~300 1 28.2 1.31.5 0.5>300 <25 2 37.4 1.00.5 0.2>300 c25 3 31.3 9.40.8 0.7>300 Insoluble 4 31.8 1.3*5.5 *3.0*120 <25 32.7 1.6*4.6 *0.8>300 <25 6 33.3 5.819.6 8.9 75 <25 7 28.8 1.05.6 1.8 85 <25 8 31.7 2.2~3.0 ~.6 45 35 9 ~9.8 1.~6.1 2.3 61 27.5 1.18.6 3.8 36 18 11 26.8 1.76.0 1.6 40 24 12 34.3 8.926.9 12.2>300 13 26.8 2.47.6 3.3 ~1 <5 14 29.6 1.28.4 3.8 66 <5 0.1 weight percent concentration in deionized water.
Numbers marked with * are 1.0 weight percent concen-tration in deionized water.
2 ASTM D-1331 test procedure.
2 5 3 ASTM D-1331 test procedure.
4 Foam height was determined by whipping at low speed for one minute in a blender 250 ml of a 0.1 percent by weight surfactant/water solution. The solution and foam were poured into a standard 500 ml graduated cylinder having a 4.7 centimeter diameter. The foam height was measured immediately and after five minutes.
27,09~A-F -13--14~ 7~
5 In the wetting test, a nine-inch (22.8 cm) strip of unmercerized natural cotton cloth tape was attached to a one-gram hook, which in turn was attached to a forty-gram weight by thread to determine wetting time. The solution concentration was 0.1 percent by weight surfactant in deionized water. The arrange-ment was dropped into 500 ml of the surfactant solu-tion in a graduated cylinder. When the tape was wetted, it dropped to the bottom of the cylinder, indicating the wetting time.
6 ASTM D-2024 test procedure e~cept 0.1 percent con-centration used in place of 1.0 percent concentration.
27,098A-F -14-
27,098A-F -14-
Claims (4)
1. A process for the preparation of a poly-carbonate type surfactant comprising reacting ethylene carbonate and a monohydroxy alcohol in the presence of an alkali metal salt catalyst at a temperature of 130°C
to 210°C.
to 210°C.
2. The process of Claim 1 wherein 2 to 20 moles of ethylene carbonate per mole of said monohydroxy alcohol are reacted.
3. The process of Claim 1 wherein said mono-hydroxy alcohol has the formula:
R-O-[CH2-CH2-O]x-H
wherein R is an aliphatic, non-aromatic cycloaliphatic or aromatic group and x is a number from 3 to 50.
R-O-[CH2-CH2-O]x-H
wherein R is an aliphatic, non-aromatic cycloaliphatic or aromatic group and x is a number from 3 to 50.
4. The process of Claim 1 wherein said surfactant is reacted with ethylene oxide in the amount of 3 to 50 moles of oxide per mole of surfactant.
27,098A-F -15-
27,098A-F -15-
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000403120A CA1176268A (en) | 1982-05-17 | 1982-05-17 | Polycarbonate type nonionic surfactants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000403120A CA1176268A (en) | 1982-05-17 | 1982-05-17 | Polycarbonate type nonionic surfactants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1176268A true CA1176268A (en) | 1984-10-16 |
Family
ID=4122797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000403120A Expired CA1176268A (en) | 1982-05-17 | 1982-05-17 | Polycarbonate type nonionic surfactants |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1176268A (en) |
-
1982
- 1982-05-17 CA CA000403120A patent/CA1176268A/en not_active Expired
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