CA1333811C - Polyether thickeners for water-based hydraulic fluids - Google Patents
Polyether thickeners for water-based hydraulic fluidsInfo
- Publication number
- CA1333811C CA1333811C CA000430029A CA430029A CA1333811C CA 1333811 C CA1333811 C CA 1333811C CA 000430029 A CA000430029 A CA 000430029A CA 430029 A CA430029 A CA 430029A CA 1333811 C CA1333811 C CA 1333811C
- Authority
- CA
- Canada
- Prior art keywords
- oxide
- percent
- copolymer
- polyether polyol
- lower alkylene
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2654—Aluminium or boron; Compounds thereof
Abstract
Alpha olefin oxide-capped polyether polyols are prepared by reacting a substantially anhydrous heteric or block copolymer of ethylene oxide and a lower alkylene oxide with an alpha olefin oxide in the presence of a catalyst. The capped polyether polyols are useful as thickeners for aqueous systems, such as water-based hydraulic fluids.
Description
-This invention pertains to novel alpha olefin oxide-capped polyether polyols which are particularly suitable for use as thickeners for aqueous systems, such as water-based hydraulic fluids.
Water-soluble or water-dispersible thickeners of a variety of chemical types are used in aqueouQ
liquids to increase their viscosity. In recent years, by reason of their lower cost, as compared to petroleum oils, efforts have been made to provide water-based hydraulic fluids of acceptable properties. Because of the substantially lower viscosity of water-based hydraulic fluids, as compared to those based on petroleum oils, various types of polyether polyols have been ~uggested ~or used therein as thickeners.
However, in order to obtain hydraulic fluids having a viscosity of at least 200 Sabolt Universal Seconds (SUS) at 100 F., it has been necessary to use substantial amounts of polyether polyol thickeners of relatively high molecular weight. In addition to the cost disadvantages due to the substantial quantities of such thickeners which must be used to obtain the desired viscosity, su~h thickeners in use evidence a reduction in molecula~ weight by reason of the shearing forces to which they ~re subjected, whereby a significant decrease .n the viscosity of the hydraulic fluid occurs.
This invention relates to novel thickeners for aqueous-based hydraulic fluids. The thickeners are polyether polyols which have been capped with an aliphatic alpha olefin oxide containing from about 10 11333~
to about 30 carbon atom~. The polyether polyols which are capped are obtained by reacting ethylene oxide and a lower alkylene oxide having 3 to 4 carbon atoms with an active hydrogen compound which is a polyhydric alcohol to form a heteric or block copolymer. The reaction by which such copolymers may be capped may be illustrated as follows:
HOCH2CH2[ (cH3)cHcH2o]x[cH2cH2o]ycH2cHcH3oH
C/O\
+ H2-CH-R
HocH2cH2[(cH3)cHcH2o]x[cH2cH2o]ycH2cHcH2o-cH2cHoH -R
in which x and y are integers and R is an aliphatic chain containing from 8 to 28, preferably from 12 ot 20 carbon atoms.
Surpri~ingly, it wa~ discovered that such capped polyether polyols have considerably greater thickening power than similar high molecular weight uncapped polyether polyols. Thus, a much lesser quantity of the new polyols is required to provide aqueous-based hydraulic fluids of a given viscosity. In addition, and of equal importance, was the discovery that the new capped polyether polyols are ~hear stable as a result of which hydraulic fluids in which they are employed undergo only relatively small reductions in viscosity even after hundreds of hours of use.
In preparing the capped polyether polyol thickeners of this invention, the polyether polyols are first prepared by reacting ethylene oxide, at least one lower alkylene oxide having 3 to 4 carbon atoms, and an active hydrogen compound which is a polyhydric alcohol.
~ ~3~ ~
Method~ for preparing these polyether polyols are well known, and good results may be obtained by bringing a mixture containing the ethylene oxide and the lower alkylene oxide into intimate contact with the aliphatic polyhydric alcohol active hydrogen compound in the liquid phase, throughout which a suitable catalyst is uniformly disper~ed. As catalysts, sodium and pota~sium hydroxide are preferred. The reaction is carried out at temperatures on the order of 50 to 160 C., under a pressure of from about 20 to about 100 psig.
The concentration of the catalyst may vary from about 0.1 to about 5 percent by weight of the active hydrogen compound.
Besides ethylene oxide, the lower alkylene oxides used in the reaction include l,2-propylene oxide, and butylene oxide. The percentages by weight of these components vary from about 10 to about 90 percent of ethylene oxide, to from about 90 to 10 percent of another lower alkylene oxide or mixture thereof. Preferably the copolymers, which may be either heteric or block, contain about 65 to about 85 percent ethylene oxide and about 35 to about 15 percent lower alkylene oxide containing 3 to 4 carbon atoms. A
particularly preferred polyether polyol is a block copolymer comprising 75 percent ethylene oxide and 25 percent l,2-propylene oxide.
The reactive hydrogen compounds or initiators employed in preparing the polyether polyols which are then capped with an aliphatic alpha olefin oxide are selected from the group consisting of alkane polyols, ~33~ ~
-alkene polyols, alkyne polyols and oxyalkylene polyols.
The alkane polyol~ should contain from about 2 to about 10 carbon atoms from about 2 to about 6 hydroxyl group~. Exampleq of such alkane polyols are ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, trimethylol propane, pentaerythritol and the like. The alkene polyols, like the alkane polyols, may have from 2 to 10 carbon atom~ and 2 to 6 hydroxyl groupY. Useful alkene polyol~ include 2-butene-1,4-diol, 2-hexene-1,4,6-triol, 1,5-hexadiene-3,4-diol, and the like. Example~ of alkyne polyols, which may al~o contain the same number of carbon atoms and hydroxyl groups aq the alkane and alkene polyol~, are 2-butyne-1,4-diol, 2-hexyne-1,4,6-triol and 4-octyne-1,2,7,8-tetrol. Of the oxyalkylene polyol~, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol are preferred active hydrogen compound~.
Generally a relatively minor amount of initiator or active hydrogen compound, e.g. on the order of 10 percent or les~, by weight, ba~ed on the combined weight of the alkylene oxide monomers and initiator need be used to prepare the polyether polyolq which are capped according to the invention.
The polyether polyol~ which are to be capped generally will have a molecular weight of about 5000 to about 75,000, preferably from about 10,000 to about 15,000.
Such polyether polyol~ in which the active 1 3338 1 ~
~ hydrogen compound is a polyol and the proces3 for their preparation are described in detail in U.S. Patent No.
2,425,845, For ~urther details on the preparation of block copolymers see U.S. Patent No. 3,535,307, The aliphatic alpha olefin oxides which are used to cap the polyether polyols described hereinabove, are those containing on the order of from about 10 to about 30 carbon atomq, preferably from about 12 to about 18 carbon atoms. The amount Or alpha olefin oxide required to obtain the improved thickeners Or thiq invention is generally from about 1 to about 20 percent, preferably from about 1 to about 10 percent, by weight Or the capped polyether polyol. Examples of preferred alpha olefin oxides are 1,2-epoxy hexadecane, 1,2-epoxy heptadecane, 1,2-epoxy octadecane, and mixtures thereof.
In capping the polyether polyols, it is preferred that such reactant first be rendered substantially anhydrous. This may be accomplished by heating the polyether polyol in the presence of an organic solvent, such as toluene or xylene, under reflux conditions for several hours, following which the solvent is stripped to remove water. BF3 catalyst, preferably in ether, is added to the reaction vessel under a blanket of an inert gas such as nitrogen. In the alternative, an alkaline catalyst such a~ sodium hydroxide, sodium methoxide or potassium hydroxide may be used in place of BF3. Such alkaline cataly~t may be an anhydrous solid or in the form of a concentrated aqueou~ ~olution. However, where the catalyYt i3 in the form of an aqueous ~olution, the catalyst and polyol ~hould be combined following which water 1s removed to provide anhydrous reactants a~ hereinabove described. The alpha olefin oxide i~ then added and the reaction take~ place over a period of ~everal hour~
in the absence of heat. ~uring the reaction, reaction temperatures should be maintained in the range of from about 45 to about 50 C., although such temperature~
may be as high as 155 C., particularly where an alkaline catalyst is employed.
In order that the invention may be better understood several example~ thereof will now be described, purely by way of illu~tration, without suggestion that the ~cope Or the invention is limited to the details thereGf.
Example I
1400 grams of a liquid diol started polyether polyol comprising 75 percent, by weight of ethylene oxide and 25 percent l,2-propylene oxide and having two terminal hydroxyl groups and a molecular weight of 12,000-15,000, a density of -1.035 g/cc at 210F, and a viscosity of 2620 cs (12,100SUS) at 210 F and of 19,500 cs (90,OOOSUS) at 100F (Ucon 75H
90,000, Union Carbide Corp.) and 100 grams of xylene were placed in a 2 liter, three neck flask and heated under reflux for about five and a half hours, following which the xylene was stripped under a vacuum of 24" mercury to remove sub-stantially all of the water initially present in the copolymer.
The flask was blown with nitrogen for 10 seconds and after cooling the contents of the flask to 72C., 5 ml. Or a mixture of BF3 (47~) in ether were added and the contents of the flask were stirred for one hour.
The heat source wasremoved and 130 grams of a mixture of aliphatic alpha olefin oxides containing from 16 to 18 carbon atoms were added, and the reaction mixture was stirred for five hours to produce the capped polyether polyol thickener.
Example II
A hydraulic fluid was prepared by combining the following constituents:
TABLE I
Constituents Weight Percent Thickener of Example I 9.0 Ethylene glycol 33.0 . *
Lubricant additive 2.0 Copper corrosion inhibitor 0.5 ***
Vapor phase corrosion inhibitor 0.5 Soft water 55.0 * Dibutylamine caprate ** Sodium mercaptobenzothiazole *** Morpholine The hydraulic fluid, whlch had a hazy opaque appearance, had a viscosity of 420 SUS at 100F., a pH
of 9.2 and a specific gravity of about 1.07 at 60 F.
The hydraulic fluid was sub~ected to the following pump test:
TABLE II -Pump Vickers V-104-A-10 Vane Pump Pressure, psi 900 Output (theoretical) gpm 5 ~.~
1 ~33~ ~
._ Sump temperature F 120 ~ 5F
Duration, hrs. 168 TEST RESULTS
Ring Wear Lo3s, mgs 175 Wear Rate, mgs/hr. 1.04 vi3c09ity Lo~s, S 12.4 Example III
4582 grams of a liquid diol started polyether polyol comprising 75 percent, by weight of ethylene oxide and 25 per-cent 1,2-propylene oxide and having a molecular weight of 12,000-15,000, a density of 1.035 g/cc at 210F, and a vis-cosity of 2620 cs (12,100SUS) at 2IooF and of 19,500 cs (90,OOOSUS~ at 100F (Ucon 75H 90,000, Union Carbide Corp.) and 400 grams of xylene were placed in a 2 liter, three neck flask and heated under reflux for about six hours, following which the xylene was stripped under a vacuum of 20-24" mercury to remove ~ubstantially all of the water initially present in the copolymer. The flask was blown with nitrogen for 10 ~econds, and after cooling the contents of the flask to 50 C., 15 ml. of a mixture of BF3 (47S) in ether were added, and the contents of the flask were stirred for one hour. The heat source was removed and 382 grams of a mixture of aliphatic alpha olefin oxides containing from 16 to 18 carbon atoms were added, and the reaction mixture was stirred for five hours to provide a capped polyether polyol thickener.
Example IV
A hydraulic fluid was prepared by combining the following constituents:
r A ~ -8-~ 33~
TABLE III
Constituents Weight Percent Thickener of Example III7.5 Ethylene glycol 35.5 Lubricant additive l.o Copper corrosion inhibitor 0.5 ***
Vapor phase corrosion inhibitor 0.5 Soft water 55.0 * Dibutylamine caprate ** Sodium mercaptobenzothiazole *** Morpholine.
The hydraulic fluid, which had a hazy opaque color, had a vi~cosity Or 152 SUS at 100 F., a pH of 9.0-9.4 and a qpecific graYity of about 1.07.
The hydraulic fluid wa~ ~ub~ected to the following teqt:
TABLE IV
Pump Vicker~ V-104-A-10 Vane Pump Presqure, psi 900 Output (theoretical) gpm 5.0 Sump temperature F120 + 5F
Duration, hr~. 212 TEST RESULTS
Ring wear lo~s, mgs.801 Vane wear 1033, mgs.34 Total wear los~, mgs. 835 Wear rate, mg~/hr.3.9 Vi-~cosity losq, ~ 5.3 Example V
To a 3 liter, 3 neck flaqk prepared for _g_ ~.~
- heating and agitation were added 120 g. of a liquid diol started polyether polyol comprising about 75 percent by weight of ethylene oxide and ~5 percent of 1,2-propylene oxide and having a molecular weight of about 2500, a density of 1.027 g/cc at 2looF and a viscosity of 257cs (197SUS) at 210F and of 1980cs (1400SUS) at 100F (Ucon 75H 1400, Union Carbide Corp.), 25 g. of a mixture of aliphatic alpha olefin oxides having from 16 to 18 carbon atoms, and 1 ml. of a mixture comprising sF3 (47~) in éther were added, and the reaction mixture was heated for a period of approximately 25 minutes. A capped polyether polyol thickener for aqueous systems was obtained.
Example VI
To a 250 ml. beaker fitted with a stainles~
steel ~tirrer were introduced 100 g. of a heterlc copolymer of ethylene oxide and 1,2-propylene oxide, 20 g. of a mixture of aliphatic alpha olefin oxideQ
containing from 16 to 18 carbon atoms and 1 mg. of a mixture of BF3 (47~) in ether. The reaction mixture WaQ stirred and the temperature of the mixture increased from 26 C. to 34 C. over the approximately 1 hour reaction time. The resulting capped polyether polyol thickener waQ used to formulate a hydraulic fluid containing 10 percent by weight of the thickener, 25 percent polypropylene glycol and 65 percent water.
Example VII
To a 3 liter, 3 neck fla~k prepared for heating and agitation were added 920 B- Of a block copolymer comprising 75 percent by weight of ethylene oxide and about 25 percent of 1,2-propylene oxide (M.W.
30 15,500), 80 g. of toluene and 218 g. o~ a 45 percent ~,J
aqueoUQ ~olutlon of potassium hydroxide. The mixture wa~ blended and heated at 110 - 115 C. for 3-4 hours under a vacuum of 25-28" Hg., following which a nitrogen purge wa~ u~ed to remove water and toluene.
38 g. of a mixture Or aliphatic olefin oxides having from 16 to 18 carbon atoms were added and the reaction mixture was maintained at 150-155 C for 2 hour~. A
capped polyether polyol thickener for aqueou~ ~y~tem~
wa~ obtained.
~i . ~ .
Water-soluble or water-dispersible thickeners of a variety of chemical types are used in aqueouQ
liquids to increase their viscosity. In recent years, by reason of their lower cost, as compared to petroleum oils, efforts have been made to provide water-based hydraulic fluids of acceptable properties. Because of the substantially lower viscosity of water-based hydraulic fluids, as compared to those based on petroleum oils, various types of polyether polyols have been ~uggested ~or used therein as thickeners.
However, in order to obtain hydraulic fluids having a viscosity of at least 200 Sabolt Universal Seconds (SUS) at 100 F., it has been necessary to use substantial amounts of polyether polyol thickeners of relatively high molecular weight. In addition to the cost disadvantages due to the substantial quantities of such thickeners which must be used to obtain the desired viscosity, su~h thickeners in use evidence a reduction in molecula~ weight by reason of the shearing forces to which they ~re subjected, whereby a significant decrease .n the viscosity of the hydraulic fluid occurs.
This invention relates to novel thickeners for aqueous-based hydraulic fluids. The thickeners are polyether polyols which have been capped with an aliphatic alpha olefin oxide containing from about 10 11333~
to about 30 carbon atom~. The polyether polyols which are capped are obtained by reacting ethylene oxide and a lower alkylene oxide having 3 to 4 carbon atoms with an active hydrogen compound which is a polyhydric alcohol to form a heteric or block copolymer. The reaction by which such copolymers may be capped may be illustrated as follows:
HOCH2CH2[ (cH3)cHcH2o]x[cH2cH2o]ycH2cHcH3oH
C/O\
+ H2-CH-R
HocH2cH2[(cH3)cHcH2o]x[cH2cH2o]ycH2cHcH2o-cH2cHoH -R
in which x and y are integers and R is an aliphatic chain containing from 8 to 28, preferably from 12 ot 20 carbon atoms.
Surpri~ingly, it wa~ discovered that such capped polyether polyols have considerably greater thickening power than similar high molecular weight uncapped polyether polyols. Thus, a much lesser quantity of the new polyols is required to provide aqueous-based hydraulic fluids of a given viscosity. In addition, and of equal importance, was the discovery that the new capped polyether polyols are ~hear stable as a result of which hydraulic fluids in which they are employed undergo only relatively small reductions in viscosity even after hundreds of hours of use.
In preparing the capped polyether polyol thickeners of this invention, the polyether polyols are first prepared by reacting ethylene oxide, at least one lower alkylene oxide having 3 to 4 carbon atoms, and an active hydrogen compound which is a polyhydric alcohol.
~ ~3~ ~
Method~ for preparing these polyether polyols are well known, and good results may be obtained by bringing a mixture containing the ethylene oxide and the lower alkylene oxide into intimate contact with the aliphatic polyhydric alcohol active hydrogen compound in the liquid phase, throughout which a suitable catalyst is uniformly disper~ed. As catalysts, sodium and pota~sium hydroxide are preferred. The reaction is carried out at temperatures on the order of 50 to 160 C., under a pressure of from about 20 to about 100 psig.
The concentration of the catalyst may vary from about 0.1 to about 5 percent by weight of the active hydrogen compound.
Besides ethylene oxide, the lower alkylene oxides used in the reaction include l,2-propylene oxide, and butylene oxide. The percentages by weight of these components vary from about 10 to about 90 percent of ethylene oxide, to from about 90 to 10 percent of another lower alkylene oxide or mixture thereof. Preferably the copolymers, which may be either heteric or block, contain about 65 to about 85 percent ethylene oxide and about 35 to about 15 percent lower alkylene oxide containing 3 to 4 carbon atoms. A
particularly preferred polyether polyol is a block copolymer comprising 75 percent ethylene oxide and 25 percent l,2-propylene oxide.
The reactive hydrogen compounds or initiators employed in preparing the polyether polyols which are then capped with an aliphatic alpha olefin oxide are selected from the group consisting of alkane polyols, ~33~ ~
-alkene polyols, alkyne polyols and oxyalkylene polyols.
The alkane polyol~ should contain from about 2 to about 10 carbon atoms from about 2 to about 6 hydroxyl group~. Exampleq of such alkane polyols are ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, trimethylol propane, pentaerythritol and the like. The alkene polyols, like the alkane polyols, may have from 2 to 10 carbon atom~ and 2 to 6 hydroxyl groupY. Useful alkene polyol~ include 2-butene-1,4-diol, 2-hexene-1,4,6-triol, 1,5-hexadiene-3,4-diol, and the like. Example~ of alkyne polyols, which may al~o contain the same number of carbon atoms and hydroxyl groups aq the alkane and alkene polyol~, are 2-butyne-1,4-diol, 2-hexyne-1,4,6-triol and 4-octyne-1,2,7,8-tetrol. Of the oxyalkylene polyol~, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol are preferred active hydrogen compound~.
Generally a relatively minor amount of initiator or active hydrogen compound, e.g. on the order of 10 percent or les~, by weight, ba~ed on the combined weight of the alkylene oxide monomers and initiator need be used to prepare the polyether polyolq which are capped according to the invention.
The polyether polyol~ which are to be capped generally will have a molecular weight of about 5000 to about 75,000, preferably from about 10,000 to about 15,000.
Such polyether polyol~ in which the active 1 3338 1 ~
~ hydrogen compound is a polyol and the proces3 for their preparation are described in detail in U.S. Patent No.
2,425,845, For ~urther details on the preparation of block copolymers see U.S. Patent No. 3,535,307, The aliphatic alpha olefin oxides which are used to cap the polyether polyols described hereinabove, are those containing on the order of from about 10 to about 30 carbon atomq, preferably from about 12 to about 18 carbon atoms. The amount Or alpha olefin oxide required to obtain the improved thickeners Or thiq invention is generally from about 1 to about 20 percent, preferably from about 1 to about 10 percent, by weight Or the capped polyether polyol. Examples of preferred alpha olefin oxides are 1,2-epoxy hexadecane, 1,2-epoxy heptadecane, 1,2-epoxy octadecane, and mixtures thereof.
In capping the polyether polyols, it is preferred that such reactant first be rendered substantially anhydrous. This may be accomplished by heating the polyether polyol in the presence of an organic solvent, such as toluene or xylene, under reflux conditions for several hours, following which the solvent is stripped to remove water. BF3 catalyst, preferably in ether, is added to the reaction vessel under a blanket of an inert gas such as nitrogen. In the alternative, an alkaline catalyst such a~ sodium hydroxide, sodium methoxide or potassium hydroxide may be used in place of BF3. Such alkaline cataly~t may be an anhydrous solid or in the form of a concentrated aqueou~ ~olution. However, where the catalyYt i3 in the form of an aqueous ~olution, the catalyst and polyol ~hould be combined following which water 1s removed to provide anhydrous reactants a~ hereinabove described. The alpha olefin oxide i~ then added and the reaction take~ place over a period of ~everal hour~
in the absence of heat. ~uring the reaction, reaction temperatures should be maintained in the range of from about 45 to about 50 C., although such temperature~
may be as high as 155 C., particularly where an alkaline catalyst is employed.
In order that the invention may be better understood several example~ thereof will now be described, purely by way of illu~tration, without suggestion that the ~cope Or the invention is limited to the details thereGf.
Example I
1400 grams of a liquid diol started polyether polyol comprising 75 percent, by weight of ethylene oxide and 25 percent l,2-propylene oxide and having two terminal hydroxyl groups and a molecular weight of 12,000-15,000, a density of -1.035 g/cc at 210F, and a viscosity of 2620 cs (12,100SUS) at 210 F and of 19,500 cs (90,OOOSUS) at 100F (Ucon 75H
90,000, Union Carbide Corp.) and 100 grams of xylene were placed in a 2 liter, three neck flask and heated under reflux for about five and a half hours, following which the xylene was stripped under a vacuum of 24" mercury to remove sub-stantially all of the water initially present in the copolymer.
The flask was blown with nitrogen for 10 seconds and after cooling the contents of the flask to 72C., 5 ml. Or a mixture of BF3 (47~) in ether were added and the contents of the flask were stirred for one hour.
The heat source wasremoved and 130 grams of a mixture of aliphatic alpha olefin oxides containing from 16 to 18 carbon atoms were added, and the reaction mixture was stirred for five hours to produce the capped polyether polyol thickener.
Example II
A hydraulic fluid was prepared by combining the following constituents:
TABLE I
Constituents Weight Percent Thickener of Example I 9.0 Ethylene glycol 33.0 . *
Lubricant additive 2.0 Copper corrosion inhibitor 0.5 ***
Vapor phase corrosion inhibitor 0.5 Soft water 55.0 * Dibutylamine caprate ** Sodium mercaptobenzothiazole *** Morpholine The hydraulic fluid, whlch had a hazy opaque appearance, had a viscosity of 420 SUS at 100F., a pH
of 9.2 and a specific gravity of about 1.07 at 60 F.
The hydraulic fluid was sub~ected to the following pump test:
TABLE II -Pump Vickers V-104-A-10 Vane Pump Pressure, psi 900 Output (theoretical) gpm 5 ~.~
1 ~33~ ~
._ Sump temperature F 120 ~ 5F
Duration, hrs. 168 TEST RESULTS
Ring Wear Lo3s, mgs 175 Wear Rate, mgs/hr. 1.04 vi3c09ity Lo~s, S 12.4 Example III
4582 grams of a liquid diol started polyether polyol comprising 75 percent, by weight of ethylene oxide and 25 per-cent 1,2-propylene oxide and having a molecular weight of 12,000-15,000, a density of 1.035 g/cc at 210F, and a vis-cosity of 2620 cs (12,100SUS) at 2IooF and of 19,500 cs (90,OOOSUS~ at 100F (Ucon 75H 90,000, Union Carbide Corp.) and 400 grams of xylene were placed in a 2 liter, three neck flask and heated under reflux for about six hours, following which the xylene was stripped under a vacuum of 20-24" mercury to remove ~ubstantially all of the water initially present in the copolymer. The flask was blown with nitrogen for 10 ~econds, and after cooling the contents of the flask to 50 C., 15 ml. of a mixture of BF3 (47S) in ether were added, and the contents of the flask were stirred for one hour. The heat source was removed and 382 grams of a mixture of aliphatic alpha olefin oxides containing from 16 to 18 carbon atoms were added, and the reaction mixture was stirred for five hours to provide a capped polyether polyol thickener.
Example IV
A hydraulic fluid was prepared by combining the following constituents:
r A ~ -8-~ 33~
TABLE III
Constituents Weight Percent Thickener of Example III7.5 Ethylene glycol 35.5 Lubricant additive l.o Copper corrosion inhibitor 0.5 ***
Vapor phase corrosion inhibitor 0.5 Soft water 55.0 * Dibutylamine caprate ** Sodium mercaptobenzothiazole *** Morpholine.
The hydraulic fluid, which had a hazy opaque color, had a vi~cosity Or 152 SUS at 100 F., a pH of 9.0-9.4 and a qpecific graYity of about 1.07.
The hydraulic fluid wa~ ~ub~ected to the following teqt:
TABLE IV
Pump Vicker~ V-104-A-10 Vane Pump Presqure, psi 900 Output (theoretical) gpm 5.0 Sump temperature F120 + 5F
Duration, hr~. 212 TEST RESULTS
Ring wear lo~s, mgs.801 Vane wear 1033, mgs.34 Total wear los~, mgs. 835 Wear rate, mg~/hr.3.9 Vi-~cosity losq, ~ 5.3 Example V
To a 3 liter, 3 neck flaqk prepared for _g_ ~.~
- heating and agitation were added 120 g. of a liquid diol started polyether polyol comprising about 75 percent by weight of ethylene oxide and ~5 percent of 1,2-propylene oxide and having a molecular weight of about 2500, a density of 1.027 g/cc at 2looF and a viscosity of 257cs (197SUS) at 210F and of 1980cs (1400SUS) at 100F (Ucon 75H 1400, Union Carbide Corp.), 25 g. of a mixture of aliphatic alpha olefin oxides having from 16 to 18 carbon atoms, and 1 ml. of a mixture comprising sF3 (47~) in éther were added, and the reaction mixture was heated for a period of approximately 25 minutes. A capped polyether polyol thickener for aqueous systems was obtained.
Example VI
To a 250 ml. beaker fitted with a stainles~
steel ~tirrer were introduced 100 g. of a heterlc copolymer of ethylene oxide and 1,2-propylene oxide, 20 g. of a mixture of aliphatic alpha olefin oxideQ
containing from 16 to 18 carbon atoms and 1 mg. of a mixture of BF3 (47~) in ether. The reaction mixture WaQ stirred and the temperature of the mixture increased from 26 C. to 34 C. over the approximately 1 hour reaction time. The resulting capped polyether polyol thickener waQ used to formulate a hydraulic fluid containing 10 percent by weight of the thickener, 25 percent polypropylene glycol and 65 percent water.
Example VII
To a 3 liter, 3 neck fla~k prepared for heating and agitation were added 920 B- Of a block copolymer comprising 75 percent by weight of ethylene oxide and about 25 percent of 1,2-propylene oxide (M.W.
30 15,500), 80 g. of toluene and 218 g. o~ a 45 percent ~,J
aqueoUQ ~olutlon of potassium hydroxide. The mixture wa~ blended and heated at 110 - 115 C. for 3-4 hours under a vacuum of 25-28" Hg., following which a nitrogen purge wa~ u~ed to remove water and toluene.
38 g. of a mixture Or aliphatic olefin oxides having from 16 to 18 carbon atoms were added and the reaction mixture was maintained at 150-155 C for 2 hour~. A
capped polyether polyol thickener for aqueou~ ~y~tem~
wa~ obtained.
~i . ~ .
Claims (21)
1. A polyether polyol particularly useful for thickening aqueous systems, said polyether polyol having a molecular weight of from about 5000 to about 75,000 and having been prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one polyhydric alcohol selected from the group consisiting of alkane polyols, alkene polyols, alkyne polyols and oxyalkylene polyols to prepare a heteric or block copolymer, and further reacting said copolymer with a lower aliphatic alpha olefin oxide having from about 10 to about 30 carbon atoms and wherein said alpha olefin oxide is present in the amount of from about 1 percent to about 20 percent by weight based on the total weight of said copolymer and alpha olefin oxide.
2. A polyether polyol of claim 1 prepared by copolymerizing a mixture of ethylene oxide and said lower alkylene oxide to form a heteric copolymer and subsequently reacting said copolymer with said alpha olefin oxide.
3. A polyether polyol of claim 1 prepared by reacting ethylene oxide with a lower alkylene oxide to form a block copolymer and subequently reacting said copolymer with said alpha olefin oxide.
4. A polyether polyol according to claim 3 in which said lower alkylene oxide is 1,2-propylene oxide.
5. A polyether polyol according to claim 1 in which the proportion of ethylene oxide to lower alkylene oxide employed in preparing said copolymer is from about 65 to about 85 percent by weight of ethylene oxide and from about 35 to about 15 lower alkylene oxide.
6. A polyether polyol according to claim 1 in which said polyhydric alcohol is an alkane polyol.
7. A polyether polyol according to claim 6 in which said polyhydric alcohol is ethylene glycol.
8. A polyehter polyol according to claim 6 in which said polyhydric alcohol is diethylene glycol.
9. A polyether polyol according to claim 1 in which said aliphatic alpha olefin oxide contains from 12 to 18 carbon atoms.
10. A polyether polyol according to claim 1 in which said alpha olefin oxide comprises a mixture of 1,2-epoxy hexadecane, 1,2-epoxy heptadecane and 1,2-epoxy octadecane.
11. A polyether polyol particularly useful for thickening aqueous systems, said polyether polyol having a molecular weight of from about 10,000 to about 15,000 and having been prepared by reacting from about 75 percent, by weight of ethylene oxide, and about 25 percent of l,2-propylene oxide with an alkane polyol selected from the group consisting of ethylene glycol and diethylene glycol to prepare a block copolymer, and further reacting said copolymer with a mixture of 1,2-epoxy hexadecane, 1,2-epoxy heptadecane and 1,2-epoxy octadecane.
12. A process for preparing a polyether polyol particularly suitable for thickening aqueous systems which comprises reacting a substantially anhydrous diol started copolymer of ethylene oxide and a lower alkylene oxide containing 3 to 4 carbon atoms with an aliphatic alpha olefin oxide having about 12 to 18 carbon atoms in the presence of a catalyst selected from the group consisting of boron trifluoride, sodium hydroxide, sodium methoxide and potassium hydroxide, said alpha olefin oxide being present in the amount of from aobut 1 to about 10 percent by weight, based on the total weight of copolymer and alpha olefin oxide.
13. A process according to claim 12 in which said copolymer is prepared by reaction of from about 65 to about 85 percent by weight of ethylene oxide with from about 35 to about 15 percent of lower alkylene oxide.
14. A process according to claim 12 in which said copolymer is a block copolymer containing about 75 percent by weight of ethylene oxide and about 25 percent of 1,2-propylene oxide, and said alpha olefin oxide comprises a mixture of 1,2-epoxy hexadocane, 1,2-epoxy heptadecane and 1,2-epoxy octadecane.
15. The process of thickening aqueous systems comprising the addition of an effective thickening amount of a polyether having a molecular weight of about 5000 to about 75,000 prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen aliphatic compound containing at least two active hydrogens to prepare a heteric or block copolymer and further reacting said copolymer with at least one alpha-olefin oxide having a carbon chain length of about 12 to about 18 aliphatic carbon atoms and wherein said alpha-olefin oxide is present in the amount of about 1 percent to about 20 percent by weight based upon the total weight of said polyether.
16. The process of claim 15 wherein said polyether is prepared by polymerizing a mixture of ethylene oxide and at least one of said lower alkylene oxides to prepare a liquid heteric copolymer intermediate which is subsequently capped with said alpha-olefin oxide.
17. The process of claim 15 wherein said polyether is the reaction product of the sequential polymeriztaion of ethylene oxide and at least one of said lower alkylene oxides to prepare an intermediate block copolymer which is subsequently capped with said alpha-olefin oxide.
18. The process of claims 16 or 17 wherein the ethylene oxide residue is present in said polyether in an amount of at least 10 percent by weight of the weight of said polyether and said lower alkylene oxide is selected from the group consisting of propylene oxide and butylene oxide.
19. The process of claim 18 wherein the proportion of said ethylene oxide residue to the lower alkylene oxide residue in said polyether is in the amount of about 65 to about 85 percent by weight, said lower alkylene oxide residue is present in the amount of about 35 to about 15 percent by weight and said active hydrogen containing aliphatic compound is a polyhydric alcohol having from 2 to 10 carbon atoms and from 2 to 6 hydroxyl groups.
20. The process of claim 19 wherein said polyhydric alcohol is selected from the group consisting of alkane polyols, alkene polyols, alkyne polyols and oxyalkylene polyols.
21. The process of claim 20 wherein said alkane polyol selected from the group consisting of trimethylolpropane, and pentaerythritol.
(22) A polyether polyol thickener for aqueous systems comprising a polyether polyol having a molecular weight of from 5,000 to 75,000 prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen containing polyhydric alcohol initiator having from 2 to 10 carbon atoms and from 2 to 6 hydroxyl groups to prepare a heteric or block copolymer and further reacting said copolymer with at least one alpha-olefin oxide having a carbon chain length of 12 to 18 aliphatic carbon atoms wherein said alpha-olefin oxide is present in an amount of 1 percent to 20 percent by weight based upon the total weight of the polyether polyol thickener.
(23) The process of thickening aqueous systems comprising the addition of an effective thickening amount of a polyether polyol thickening agent having a molecular weight of from 5,000 to 75,000 prepared by reacting ethylene oxide ant at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen containing polyhydric alcohol initiator having from 2 to 10 carbon atoms and from 2 to 6 hydroxyl groups to prepare a heteric or block copolymer and further reacting said copolymer with at least one alpha-olefin oxide having a carbon chain length of 12 to 18 aliphatic carbon atoms wherein said alpha-olefin oxide is present in an amount of 1 percent to 20 percent by weight based upon the total weight of the polyether polyol thickener.
(22) A polyether polyol thickener for aqueous systems comprising a polyether polyol having a molecular weight of from 5,000 to 75,000 prepared by reacting ethylene oxide and at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen containing polyhydric alcohol initiator having from 2 to 10 carbon atoms and from 2 to 6 hydroxyl groups to prepare a heteric or block copolymer and further reacting said copolymer with at least one alpha-olefin oxide having a carbon chain length of 12 to 18 aliphatic carbon atoms wherein said alpha-olefin oxide is present in an amount of 1 percent to 20 percent by weight based upon the total weight of the polyether polyol thickener.
(23) The process of thickening aqueous systems comprising the addition of an effective thickening amount of a polyether polyol thickening agent having a molecular weight of from 5,000 to 75,000 prepared by reacting ethylene oxide ant at least one lower alkylene oxide having 3 to 4 carbon atoms with at least one active hydrogen containing polyhydric alcohol initiator having from 2 to 10 carbon atoms and from 2 to 6 hydroxyl groups to prepare a heteric or block copolymer and further reacting said copolymer with at least one alpha-olefin oxide having a carbon chain length of 12 to 18 aliphatic carbon atoms wherein said alpha-olefin oxide is present in an amount of 1 percent to 20 percent by weight based upon the total weight of the polyether polyol thickener.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39630182A | 1982-07-08 | 1982-07-08 | |
| US396,301 | 1982-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1333811C true CA1333811C (en) | 1995-01-03 |
Family
ID=23566688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000430029A Expired - Fee Related CA1333811C (en) | 1982-07-08 | 1983-06-09 | Polyether thickeners for water-based hydraulic fluids |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0116564A1 (en) |
| KR (1) | KR840005420A (en) |
| CA (1) | CA1333811C (en) |
| IT (1) | IT8348649A0 (en) |
| WO (1) | WO1984000361A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3531915A1 (en) * | 1985-09-07 | 1987-03-19 | Bayer Ag | THICKENING SYSTEMS FOR HIGH-WATER-FUNCTIONAL LIQUIDS AND THE HIGH-WATER-FUNCTIONAL LIQUIDS CONTAINING THESE THICKENING SYSTEMS |
| DE3807235A1 (en) * | 1988-03-05 | 1989-09-14 | Basf Ag | TILE ADHESIVE |
| DE4017688A1 (en) * | 1990-06-01 | 1991-12-05 | Bayer Ag | IMPROVED FUNCTIONAL LIQUIDS AND NEW POLYOXYALKYLENE POLYMERS |
| DE4017687A1 (en) * | 1990-06-01 | 1991-12-05 | Bayer Ag | IMPROVED FUNCTIONAL LIQUIDS |
| AU2015213022B9 (en) * | 2014-01-28 | 2018-05-24 | Basf Se | The use of alkoxylated polyethylene glycols in lubricating oil compositions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3829506A (en) * | 1971-06-01 | 1974-08-13 | Basf Wyandotte Corp | Biodegradable surface active agents having good foam properties and foam stabilizing characteristics |
| US3748276A (en) * | 1971-07-19 | 1973-07-24 | Basf Wyandotte Corp | Aqueous gel composition containing polyether polyol gelling agents |
| US4312775A (en) * | 1979-10-22 | 1982-01-26 | Basf Wyandotte Corporation | Polyether thickeners for aqueous systems containing additives for increased thickening efficiency |
| US4310436A (en) * | 1979-10-22 | 1982-01-12 | Basf Wyandotte | Polyether-based thickeners with additives for increased efficiency in aqueous systems |
| US4312768A (en) * | 1979-10-22 | 1982-01-26 | Basf Wyandotte Corporation | Synergistic polyether thickeners for water-based hydraulic fluids |
| US4381205A (en) * | 1982-04-05 | 1983-04-26 | E. F. Houghton & Company | Metal quenching process |
-
1983
- 1983-06-03 EP EP83902194A patent/EP0116564A1/en not_active Withdrawn
- 1983-06-03 WO PCT/US1983/000857 patent/WO1984000361A1/en unknown
- 1983-06-09 CA CA000430029A patent/CA1333811C/en not_active Expired - Fee Related
- 1983-06-29 KR KR1019830002957A patent/KR840005420A/en not_active Application Discontinuation
- 1983-07-08 IT IT8348649A patent/IT8348649A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR840005420A (en) | 1984-11-12 |
| IT8348649A0 (en) | 1983-07-08 |
| EP0116564A1 (en) | 1984-08-29 |
| WO1984000361A1 (en) | 1984-02-02 |
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