CA2092951C - Surfactant compositions - Google Patents
Surfactant compositionsInfo
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- CA2092951C CA2092951C CA002092951A CA2092951A CA2092951C CA 2092951 C CA2092951 C CA 2092951C CA 002092951 A CA002092951 A CA 002092951A CA 2092951 A CA2092951 A CA 2092951A CA 2092951 C CA2092951 C CA 2092951C
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- siloxane
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Classifications
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- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3738—Alkoxylated silicones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/06—Protein or carboxylic compound containing
Abstract
Synergistic surfactant compositions.
Polysiloxane-polyoxyalkylene copolymers in which the polyether pendants bear carboxylic acid groups or salts of carboxylic acid groups are demonstrated to have synergystic interactions with anionic and cationic organic surfactants to improve the surface characteristics of a solution, requiring unexpectedly low concentrations to obtain specific surface tension values or to attain critical micelle concentrations in aqueous solutions. Compositions containing an organic surfactant and a polysiloxane-polyoxyalkylene copolymer bearing carboxyl groups are claimed. A method for modifying the surface properties of an aqueous system by employing such compositions as components of the system is also claimed.
Polysiloxane-polyoxyalkylene copolymers in which the polyether pendants bear carboxylic acid groups or salts of carboxylic acid groups are demonstrated to have synergystic interactions with anionic and cationic organic surfactants to improve the surface characteristics of a solution, requiring unexpectedly low concentrations to obtain specific surface tension values or to attain critical micelle concentrations in aqueous solutions. Compositions containing an organic surfactant and a polysiloxane-polyoxyalkylene copolymer bearing carboxyl groups are claimed. A method for modifying the surface properties of an aqueous system by employing such compositions as components of the system is also claimed.
Description
~ D-16636 .
SURFACTANT COMPOSITIONS
Field This application relates to surfactants, and more particularly, to combinations of organic surfactants and carboxylated siloxane-polyoxyalkylene copolymers which exhibit synergistic surfactant properties.
8ackground A surfactant has been defined as a solute which, when dissolved in a designated liquid, will alter the surface or interfacial characteristics of the solution in some manner, such as lowering the surface tension.
Surfactants have utility, for example, as detergents, emulsifiers, foamers, wetting agents, dispersants, flocculants and penetrants. They are particularly useful in producing detergent foams of high stability and high foaming power in aqueous systems. Other specific uses include foam stabilization and emulsification of water-organic solvent mixtures.
Synergystic interactions between surfactants, defined rigorously below, occur when two surfactants used in concert provide unexpected surface characteristics beyond those which would be predicted based on the sum of the surface properties of the individual components. Synergystic surfactant mi~tures not only have the areas of utility as described above for single surfactants, but also have the added advantage of being able to effect these utilities at lower concentrations. This ` ` 2092951 advantage may be exploited in a variety of ways such as the improved economics of using less material to achieve the same performance, or by extending the effective lifetime of a surfactant solution at a given concentration.
U.S. patent 3,562,786 of Bailey, et al., first suggested using organosilicone-o~yalkylene block copolymers in combination with organic surfactants to improve the properties of the water soluble organic surfactants for use in aqueous systems. This patent does not deal with the carboxyl group-containing siloxane-polyoxyalkylene copolymers which are the subject of this application, and does not indicate that the disclosed compositions exhibit synergism.
U.S. patent 4,784,799 of Petroff discloses surfactant compositions comprising a silicone sulfobetaine surfactant and an alkylbenzenesulfonate anionic surfactant, and states that these exhibit synergism. The experimental data presented in this patent show surface tensions produced by 0.1~ levels of blends of 2 surfactants, and surface tensions produced by various levels of each surfactant separately, the concentration in each case being that of the particular surfactant in the surfactant blend. Synergism is traditionally expressed as the whole being greater than the sum of the parts.
Somewhat more rigorously, it can be defined as two or more agents operating together to cause an effect which is greater than that which would have been expected based on the sum of the effects of the agents operating separately. Petroff provides no indication of the surface tensions which would have L3--lbb ~b __ ~ 3 ~ 20 9 2 9 5 1 been expected based on the sum of the effects of the several surfactants operating separately. He merely showed that each surfactant, considered separately at the level employed for the particular material in the surfactant blend, produced a surface tension higher than that of the corresponding blend of surfactants containing the given level of the surfactant under consideration. Thus, this reference does not describe synergystic surface tension lowering behavior, or suggest a method of achieving synergystic interactions between any silicone surfactants and anionic surfactants.
Rosen has published on ~Molecular Interaction and Synergism in Binary Mixtures of Surfactants~, setting forth theoretical and test protocols for ascertaining when synergism exists in mixtures of surfactants. See M.J. Rosen, Phenomena in Mixed Surfactant Systems, (J.F. Scamehorn, Ed.), ACS Symp. Ser., Vol. 311, p. 149 (1986).
Synergism in mixed micelle formation is defined by Rosen as being present when the critical micelle concentration of any mi~ture is lower than that of either pure surfactant. To treat this concept mathematically, a mixed micelle parameter, Bm, is derived which expresses the extent of interaction between two given surfactants in a solution. Thus, according to Rosen:
ln(aCml2 / XmCml) (l-Xm)2 where * cml2 is the critical micelle concentration for the mixture;
-- ~ 4 ~ 2 0 92 9 5 ~
* Cml is the critical micelle concentration of surfactant l;
* a is the weight fraction of surfactant 1 in the initial surfactant solution;
and xm is the weight fraction of surfactant 1 in the surfactant of the mixed micelle.
The value of Xm is derived from the iterative solution to the equation (xm)2 ln (acml2 / XmC 1) , 1 (l-Xm)2 ln ((1-)Cml2 / (1-Xm)Cm2) here * Cm2 is the critical micelle concentration of surfactant 2.
With these mathematical relationships established, synergism in mixed micelle formation is defined mathematically as e~isting when ~m is negative, and ¦ln(cml/cm2)¦<¦Bm¦.
Similarly, synergism in surface tension reduction efficiency is defined by Rosen as being present when a given surface tension can be attained at a total mi~ed surfactant concentration lower than that required of either surfactant by itself. To treat this concept mathematically, a parameter B~ is derived which expresses the extent of the interaction between the two given surfactants in a solution.
Thus, according to Rosen: ~
ln(aCal2 / XCl) Ba (l-X)2 here ~ cal2 is the concentration of the mi~ture required to achieve a specific surface tension;
v--~c~ u * cal is the concentration of surfactant 1 required to achieve a specific surface tension;
* a is the weight fraction of surfactant 1 in the initial surfactant solution;
and * X~ is the weight fraction of surfactant 1 in the surfactant in the mixed monolayer.
The value of X~ is derived from the iterative solution to the e~uation (xa)2 ln (~Cal2 / X C 1) - 1 (l-X~)2 ln ((l-a)C~12 / (1-X~)C~2) here ~ CG2 is the concentration of surfactant 2 required to achieve a specific , surface tension.
With these mathematical relationships established, synergism in mixed monolayer formation is defined mathematically as existing when B~ is negative, and ¦ln(C~l/C2)¦< ¦B~¦ .
It is always desirable to have new surfactant compositions which afford unexpectedly good surfactant properties, for the reasons discussed above. Such compositions are the subject of the present application.
Summary This invention addresses the above-identified needs and provides surfactant compositions which afford unexpectedly good surfactant properties.
The surfactant compositions which are the subject of this application are compositions of V--l b t~
_ -- 6 --matter which comprise an organic surfactant and a carboxyl-containing polysiloxane-polyoxyalkylene copolymer. A method for modifying the surface properties of an aqueous system comprises employing as components of the system an organic surfactant and a carboxyl-containing polysiloxane-polyoxyalkylene copolymer. The addition of the acid functional groups provides a silicone-polyether copolymer which not only has surfactant properties, but which also synergistically interacts with anionic and cationic organic surfactants to provide reduction of surface tension to lower than expected values, lowering of critical micelle concentration and other desirable surface or interfacial properties.
Description of the Drawing The invention will be more fully understood from a consideration of the following detailed description, together with the drawing, in which:
Fig. 1 is a plot of log CMC vs. weight fraction of ARQUAD~ T-50 cationic surfactant in blends with an acid-grafted siloxane-po.lyoxyalkylene copolymer;
Fig. 2 is a plot of log CMC vs. weight fraction of the anionic surfactant sodium dodecyl sulfate in ~lends with an acid-grafted siloxane-polyoxyalkylene copolymer;
Fig. 3 is a plot of log [y40] vs. weight fraction of ARQUADR T-50 cationic surfactant in blends with an acid-grafted siloxane-polyoxyalkylene copolymer; and D--16b3~
Fig. 4 is a plot of log ty90] vs. weight fraction of the anionic surfactant sodium dodecyl sulfate in blends with an acid-grafted siloxane-polyoxyalkylene copolymer.
Detailed Description In the present invention, polysiloxane-polyoxyalkylene copolymers functionalized with carboxylic acids, or salts of carboxylic acids, have shown synergistic interactions in mixed micelle formation with both cationic and anionic organic surfactants. The mixtures have been shown to form micelles at lower concentrations than those required by either of the components. Further, calculations of the mixed micelle parameter (Bm) and comparison with the component critical micelle concentrations ¦~m¦>¦ln(Cml/Cm2)¦ demonstrate that these mixtures fit the mathematical definition for synergistic interactions in the formation of mi~ed micelles.
In addition, these carbo~yl group-containing polysiloxane-polyoxyalkylene copolymers have show synergistic interactions in surface tension reduction efficiency with both cationic and anionic organic surfactants. The mixtures have been shown to reduce the surface tension to a specific value (40 mN/m), at lower concentrations than those required by either of the components. Further, calculations of the mixed monolayer parameter and comparison with the component mised monolayer concentrations 1~1 > ¦ ln(C~l/C~2) ¦
v - l u u ~ u _ - 8 - 2092951 demonstrate that these mixtures fit the mathematical definition for synergistic interactions in the mised monolayer.
The organic surfactant employed in the surfactant compositions of the invention are cationic or anionic surfactants, which are well known in the art and are commercially available. These organic surfactants are generally considered as comprising hydrophilic and hydrophobic functional groups.
The anionic organic surfactants can contain, for example, hydrophilic groups such as phosphates, sulfosuccinates, carbo~ylates, sulfates and sulfonates, and hydrophobic groups such as alkyl, aromatic, and arylalkyl hydrocarbons. The specific anionic organic surfactant demonstrated in this application is sodium dodecylsulfate, which will be discussed ~elow.
The cationic organic surfactants can contain, for example, hydrophilic groups such as quaternary amine salts of chlorides, sulfates, sulfonates, and carbo~ylates, and hydrophobic groups such as alkyl, aromatic, and arylalkyl hydrocarbons.
The specific cationic organic surfactant demonstrated in this application is trimethyltallowammonium chloride, which will be discussed below.
The carboxyl-containing polysilo~ane-polyoxyalkylene copolymers employed in the surfactant compositions of the invention are materials having the average general formula RaR~3-asio(Me2sio)b(MeRsio)csiRaR 3-a V--~bb~b wherein R~ stands for an alkyl group of 1-3 carbon atoms; and R stands for (CdH2dO)(CeH2eO)i(R CfH2f_lo) jRn ~; wherein Rn stands for -(cgH29-h(co2Q)h)yH ; and R ~ stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or Rn;
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R"CfH2f_lO);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of ~+, alkali metal ions, and quaternary ammonium salts.
The group R is a polyoxyalkylene chain which includes, on average, 0.1 to 5 carbo~yl-containing moieties R" and may be capped or uncapped. The subscript y represents the number of acid-containing monomer units. The polyoxyalkylene chain may be made up of ethyleneo~y groups, propyleneoxy groups, or both.
The group R' is preferably methyl. The subscript "a" is preferably 0-1, and most preferably -0. The subscript "b" is preferably 0-10, and most preferably 0-5. The subscript "c" is preferably 0.5-5, and most preferably 1-3. The subscript "d" is preferably 3. The subscript "g" is preferably 2-5, and most preferably 2-3. The subscript "h" is preferably 1-3, and most preferably 1-2. The subscript "y" is preferably 1-3, and most preferably 1. The group R'n is preferably an alkyl or acyl group of 1-4 carbon atoms, and most preferably an alkyl group. The sum of subscripts "i" and "j" is preferably 1-20 and most preferably 1-10. The subscript "j" is preferably 1-2, and most preferably 1.
The carboxyl-containing polysiloxane-polyoxyalkylene copolymers used in this invention may be prepared by introducing carboxylic acid-containing moieties into the polyether chains of a siloxane-polyalkylene copolymer in any of the ways known to the art.
Procedures for synthesizing nonhydrolyzable silicone surfactants having polyalkylene oxide pendant groups are well known. Representative disclosures are provided in U.S. Patents 3,741,917; 4,147,847; and 4,855,379.
The desired polysiloxane starting material may be prepared by causing a polyhydridosiloxane of generalized average formula M**DXD'~M** to react with allyl-started oxyalkylene polymer in the conventional manner, typically by means of a platinum catalyzed hydrosilylation of the unsaturated polyoxyalkylene with a polydialkyl-siloxane having SiH units, as taught by V.S. patent 4,031,044 for instance.
In the formula for the polyhydridosilo~ane, M is (CH3)2(H)siOl/2 or (cH3)3SiOl~2~ D is -(CH3)2SiO2/2, and D' represents (CH3)(H)SiO2/2. The allyl-started o~yalkylene polymers are polyethers havinq a terminal vinyl group, which may optionally be 2-substituted, and containing multiple units derived from ethylene oxide, propylene oxide, or ~oth. The reagents are mi~ed, generally in a solvent such as toluene or dipropylene glycol, heated to about 70-85 C, then the catalyst is added, a temperature rise of about 10-15 C is observed, and the mixture is finally sampled and analyzed for SiH groups ~y adding an alcohol and base and measuring evolved hydrogen. If a volatile solvent was used, this is removed under vacuum, and the mi~ture is generally neutralized with a weak base such as NaHCO3, then filtered.
The polyhydridosilo~anes of generalized average formula M%~DXD'yM~ are prepared in the manner known to the art. For the case in which M**
is (CH3)3SiOl~2, an alkyldisiloxane such as hexamethyldisiloxane, a polyhydridosiloxane polymer, and an alkyl cyclosiloxane such as octamethyl-cyclotetrasilo~ane are reacted in the presence of a strong acid such as sulfuric acid. For the case in which M%% is (H)(CH3)2siO2/2~ a hydridoalkyldisiloxane such as dihydridotetra-methyldisilo~ane, a polyhydridosilo~ane polymer, and an alkyl cyclosiloxane such as octamethylcyclo-tetrasiloxane are reacted in the presence of a strong acid such as sulfuric acid.
- 12 - 20~2951 The desired unsaturated polyoxyalkylene starting materials are likewise prepared in the manner known to the art, by reacting an unsaturated alcohol starter with a strong base to make an -alkoxide, which is subsequently reacted with with ethylene oxide, propylene o~ide, or both, and ultimately capped as taught by U.S. patents 2,425,755; 2,448,664; and 3,507,923. The capping involves further reaction of the initially formed terminal hydro~yl group with an alkylating or acylating agent such as a methyl halide or acetic anhydride, respectively. Other end caps may of course be employed.
The carbo~ylic acid functional groups may be introduced into the intermediate siloxane-polyoxyalkylene copolymer using any of several known methods. The method used in this application is taught in U.S. patent 3,418,354 and involved slowly and simultaneously adding (a) an olefin and (b) a peroxide containing a peroxide group linked to a tertiary carbon atom to (c) a polyo~yalkylene compound which was maintained at a temperature sufficiently elevated to cause a graft copolymer of the olefin and the polyoxyalkylene compound to be - produced. Using this method, unsaturated carbo~ylic acids were attached to the above prepared siloxane-polyoxyalkylene copolymers. Alternative methods include such methods as selective oxidation of the terminal alcohol on the polyether chain as describe in the ~ritish patent 807,666 or U.S.
patent 4,256,916, or addition to unsaturated acids or nitriles as described in U.S. patent 3,544,615 followed by conversion to the desired form.
The compositions of the invention can be prepared in various ways. The organic surfactant and the carboxylated siloxane-polyoxyalkylene copolymer can be mi~ed. Alternatively, one of these materials can be mi~ed with water and then the resulting mixture combined with the other ingredient. Similarly, one of these materials could be mixed with some third material with which the ultimate surfactant composition is to be used and then the other of these materials combined with the resulting mixture. The skilled in the art will appreciate that there are other modes of combination.
The organic surfactant and the carboxylated siloxane may be employed in any ratio which provides a mixture suitable for one's purpose. The weight ratio of organic surfactant to carboxylated siloxane-polyo~yalkylene copolymer is generally from about 95:5 to 5:95, preferably from 90:10 to 50:50, and most preferably from 90:10 to 70:30.
The surfactant compositions of the invention have typical surfactant applications, namely, as detergents, emulsifiers, foamers, wetting agents, dispersants, flocculants, penetrants, etc.
In aqueous solutions they are generally employed at a level of 0.001 to 10 percent by weight, preferably 0.01 to 5 percent, based on the total weight of the aqueous solution.
Glossary LUPERSOL~ 101 is a free radical-generating catalyst, 2,5-dimethyl-2,5-di(t-butylperoxy)he~ane, and is available from Pennwalt Corporation.
~ L u ~ u ~_ 2092951 ARQUAD~ T-S0 is a cationic surfactant, trimethyltallowammonium chloride, and is available from Akzo Chemicals.
M stands for (CH3)3SiOl/2 .
D stands for (CH3)2SiO2/2 -D' stands for (CH3)(H)SiO2/2 .
D* stands for (CH3)(polyether)SiO2/2 .
~perimental The invention will be further clarified bya consideration of the following e~amples, which are intended to be purely exemplary and not a limitation of the invention.
Surface tension measurements were made using the Wilhelmy Plate method. A sand blasted platinum blade was used as a sensor. All measurements were made at 25C. Deionized water further treated with a Millipore filtration system was used to prepare 5 x 10-3M sodium chloride which was then used to prepare all surfactant solutions.
Surface tension results are given in units of milliNewtons per meter (mN/m).
Critical micelle concentrations were determined in the normal way, by plotting surface tensions versus concentrations and noting the change in slope.
Example 1 This example shows the preparation and surface tension properties of neutralized acrylic acid grafted siloxane polyether copolymers.
150 gms of Me3SiOMeRSiOSiMe3 (MD~l oM) ~
where R is (CH2)3O(CH2CH2O)6 5Me, was placed in a - 15 _ ~ ~295 L
~00 ml flask and heated to 160C. 2.2 gms of LUPERSOLG) 101 free radical catalyst was added very slowly. After allowing for a short initiation time, 7.5 gms of acrylic acid was added slowly in concert with LUPERSOL<9 101 catalyst. When the addition of the two components was complete, the solution was allowed to stir under heating for an additional 30 minutes, and then allowed to cool.
Samples taken for surface measurements were adjusted to pH 7.0 by titrating with 1.0 N NaOH.
Table 1 shows the structure and surface properties for silo~ane polyether copolymers functionalized and neutralized in the manner described above.
Table 1 Surface Propertie~ for Acrylic Acid Functionalized Siloxane polyether Copolymers (pH=7) Siloxane/ Acrylic Acid CMC(wt%) Log [y40]C Log[y40]d polyetherGraftin~ (%) CMC
MD*l oM a 5.0 2.5x10-2 -1.60 4.1x10-4 -3.39 MD l.oM 10.0 1.05x10-1 -0.98 5.6x10-3 -2.25 MD 1.5M 10.0 1.4x10-2 -1.85 1.2x10-3 -2.92 MD13D*5 5M b 10.0 3.0x10-2 -1.52 5.6x10-3 -2.25 Footnotes for Table 1:
a. D~ is Me(O)Si(CH2)3O(cH2cH2o)6.5Me -b. D* is Me(O)Si(cH2)3O(cH2cH2o)ll.2H -c. concentration that gives surfacetension of 90 mN/m.
d. Log concentration that gives surface tension of 40 mN/m.
- . 2092951 -Example 2 E~ample 2 shows the preparation and sur~ace tension properties for a siloxane polyether copolymer functionalized with a dicarboxylic acid and neutralized to pH 7Ø
200 gms of Me3SiOMeRSiOSiM3 (MD l.oM), where R is (CH2)3OtCH2CH2O)6 5OMe, was placed in a 500 ml flask and heated to 160C. 3.3 gms of LUPERSOLg 101 free radical catalyst was added very slowly. After a short initiation time, 80 gms of a solution made from 20 gms of itaconic acid and 60 gms of methanol was slowly added in concert with the LUPERSOL~ 101 catalyst. After the addition was completed, the solution was heated for an additional 30 minutes and then cooled. A sample was take from this product and adjusted to pH 7.0 with lN NaOH. The sample was then used for the surface tension measurements.
Table 2 shows the results for the itaconic acid grafted siloxane polyether copolymer.
Table 2 Surface Propertie~ of Itaconic Functionalized Siloxane polyether Copolymer6 (pH=7) Siloxane/ Itaconic Acid CMC Log [y40]b Log polyether Grafting (a) (wt%) CMC ly40]C
.
MD l.oM 10.0 6.4x10-3 -2.19 5. x10-4 -3.24 Footnotes for Table 2:
a. D* is Me(o)si(cH2)3o(cH2cH2o)6.5oMe -b. concentration that gi~es surfacetension of 40 mN/m.
c. log concentration that gives surface tension of 40 mN/m.
.
20929~1 Example 3 Example 3 demonstrates the favorable synergistic interaction in mixed micelle formation for anionic functionalized silo~ane polyether copolymers with A~QUAD~ T-50 cationic organic surfactant.
Table 3 shows the results of blending ARQUAD~ T-50 cationic surfactant with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the ARQUAD~ T-50 cationic surfactant with no added cosurfactant. The remainder of the table lists the Log CMC's and mi~ed micelle parameter values for several ARQUAD~ T-50 cationic surfactant /
neutralized, carboxylic acid grafted siloxane `
polyether copolymers. A comparison of each mixed surfactant and its components (listed in Table 1, 2 or 3), shows that the value of the e~perimental CMC
is lower for the mixed surfactant than for the components. Further, since Bm is negative for each mixture, and ¦Bm¦ is >¦ln~Cml/Cm2)¦, the neutralized, carboxylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mi~ed micelle interaction with the cationic organic surfactant.
Figure 1 graphically illustrates the above synergistic interaction for 10% acrylic acid grafted MD~l oM where D is (CH2)3O(CH2CH2O)6.sOMe- A
straight line between the Log CMC's of the component surfactants represents what would be e~pected for an ideal mi~in~ of the two. A horizontal line at the level of the lowest Log CMC for the individual D~
~ - 18 - 2092951 components indicates the limit of the target range for true synergistic interactions. Points below this line lie in the region of synergistic interaction.
As seen in the Figure 1, the interaction of 10%
acrylic acid grafted MD~l oM with ARQUAD3 T-50 cationic surfactant is clearly in the synergistic region for most of the tested blends.
Table 3 Synergi6tic Mixed Micelle Interactions Anionic Siloxane~ / Cationic Organic Surfactant (ARQUADC T-50) Cosurfactanta~b Weight Fraction Log ~m ¦ln(Cml/Cm2)¦
Silicone CMC
ARQUAD~ T-50 -2.34 5ZAA/-MD*1 oM 0.50 -2.51 -4.53 1.69 10% M -MD*l oM O . 25 -3.62 -18.5 3.10 lOZ M -MD*l oM O .75 -3.70 -18.5 3.10 10% M -MD*l 5M 0.50 -2.74 -5.82 1.11 1o2AA-MDl3 sM*5 5M O.50 -2.96 -9.15 1.88 10%IA-MD*1 ~ O.50 -2.68 -3.78 0.33 Footnotes for Table 3:
a. ~AA indicates the amount of acrylic acid grafted onto the siloxane polyether copolymer.
b. %IA indicates the amount of itaconic acid grafted onto the siloxane polyether copolymer.
L~--10~0 - 19 _ 2092951 Example 4 - Example 4 demonstrates the synergistic mi~ed micelle interaction for an carbo~y functionalized siloxane-polyoxyalkylene copolymer and the anionic organic surfactant sodium dodecylsulfate. Table 4 shows the CMC measurements for mixtures of the cationic organic surfactant sodium dodecylsulfate with several neutralized, acid grafted siloxane polyether copolymers. The first row of data is for sodium dodecylsulfate for comparison purposes. The remainder of Table 4 shows the CMC and mixed micelle parameter values for several surfactant mixtures. A
comparison of each mixed surfactant and its components (listed in Table 1 or 4), shows that the value of the experimental CMC is lower for the mixed surfactant than for the components. Further, since ~m is negative for each mixture, and ¦~ml is >¦ln(Cml~Cm2)¦, the neutralized, car~oxylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mixed micelle interaction with the anionic organic surfactant.
Figure 2 graphically illustrates the above synergistic interaction for 10% acrylic acid grafted MD~l oM where D is (CH2)3O(CH2CH2O)6.sOMe- A
between the Log CMC's of the component surfactants represents what would be expected for an ideal mixing of the two. A line at the level of the lowest Log CMC for the individual components indicates the limit of the target range for true synergistic interactions. Points below this line lie in the region of synergistic interaction. As seen in the Figure 2, the interaction of 10% acrylic acid grafted MD~l oM with sodium dodecylsulfate is clearly in the synergistic region.
Table 4 Synergi~tic Mixed Micelle Interaction6 Anionic Siloxane~ / Anionic Organic Surfact~nt (SDS) Co~urfactanta Weight Fraction Log ~m ¦ln(Cml/Cm2)¦
Siloxane CMC
fiodium dodecyl ~ulfate -0.99 ~2AA-MD*1 ~ 0.50 -2.10 -7.17 1.42 10%AA-MD*1 ~ 0.25 -2.08 -10.5 0.02 AA-MD*1 oM O .75 -2.04 -10.3 0.02 lOZAA-MD*1.5M 0.50 -2.47 -9.31 2.00 Footnote for Table 4:
a. %AA indicate~ the amount of acrylic acid grafted onto the ~iloxane polyether copolymer.
Example 5 Example S demonstrates the favorable synergistic interaction in surface tension reduction efficiency for anionic functionalized silo~ane polyether copolymers with ARQUAD3 t-50 cationic organic surfactant.
Table 5 shows the results of blending ARQUAD3 T-50 cationic surfactant with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the ARQ~AD3 T-50 cationic surfactant with no added cosurfactant. The remainder of the table lists the Log ty40] and mixed monolayer parameter o ~ ~ o . ~ - 21 - 2092951 values for several ARQUAD3 T-~0 cationic surfactant /
neutralized, carbo~ylic acid grafted silo~ane polyether copolymer mi~tures. A comparison of each mixed surfactant and its components (listed in Table 1, 2 or 5), shows that the concentration of the mi~ed surfactant required ta attain a surface tension of 40 mN/m is lower for the mixed surfactant than for the components. Further, since B~ is negative for each mi~ture, and ¦B~¦ is > ¦ln(C~l~C~2)¦, the neutralized, carboxylic acid grafted siloxane polyether copolymers fit the mathematical definition of ~osen, discussed above, for interactions at the mixed monolayer with the cationic organic surfactant.
In some cases ~for example 50/50 10%AA-MD 13.5D*5.5M/ARQUAD3 T-50 cationic surfactant), the concentration required by the experimental mixture is only slightly less than for one component (ARQUAD~ T-S0 cationic surfactant).
However, this is the result of arbitrarily picking a particular blend ratio for e~perimental measurements, the mathematics predict that at an optimum blend ratio the required concentration will be lower than for either component alone. Thus for the e~ample cited, B~ is appropriately negative and ¦~¦ is clearlY > ~ln(C~l/C 2)l Figure 3 graphically illustrates the above synergistic interaction for 10~ acrylic acid grafted MD~l oM where D* is (CH2)3O~CH2CH2O)6 ~OMe. A line between the Log ty40]'5 of the component surfactants represents what would be expected for an ideal mixing of the two. A line at the level of the lowest Log ty40] indicates the limit of the target range for ~~ ~ - 22 - 2092951 synergistic interactions. Points below this line lie in the region of synergistic interaction. As seen in the Figure 3, the interaction of 10% acrylic aci~
grafted MD~l oM with Arquad T-50 is clearly in the -synergistic region for most of the blends.
Table 5 Synergi6tic Surface Ten~ion Reduction Efficiency Anionic Siloxane6 / Cationic Organic Surfactant (ARQUADD T-50) Cosurfactant Weight Fraction Loga ~ ¦ln(C~l/C 2) Siloxane [y40]
ARQUADD T-50 -3.18 5% M -MD*1 ~M O.50 -3.46 -1.52 0.48 10% M -MD*i.oM 0.25 -4.22 -14.4 2.20 AA-MD*1 . oM O . 75 -4.28 -14.3 2.20 0%AA MD 1 5M 0.50 -3.43 -3 47 0.60 10%AA-MD 13.5D 5.5M 0.50 -3.19 -3.59 2.14 10%IA-MD*1 oM 0.50 -3.35 -1.23 0.15 Footnote for Table 5:
a. Log concentration that gives surface tension of 40 mN/m.
Example 6 Example 6 demonstrates the favorable synergistic interaction in surface tension reduction efficiency for anionic functionalized silo~ane polyether copolymers with an anionic organic surfactant (sodium dodecylsulfate). -Table 6 shows the results of blending sodium dodecylsulfate with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the sodium dodecylsulfate (SDS) with no added cosurfactant. The remainder of - 23 - 20929~1 the table lists the Log ty40] and mi~ed monolayer parameter values for several SDS / neutralized, carbo~ylic acid grafted siloxane polyether copolymer mixtures. A comparison of each mi~ed surfactant and its components (listed in Table 1 or 6), shows that the concentration of the mixed surfactant re~uired to attain a surface tension of 40 mN/m is lower for the mi~ed surfactant than for the components. Further, since B~ is negative for each mixture, and ¦B~¦ is >
¦ln(C~l/C~2)¦, the neutralized, carbo~ylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mixed micelle interaction with the cationic organic surfactant.
In some cases (for example 50/50 10%AA-MD*l oM/SDS), the concentration required`by the e~perimental mixture is about the same as one of the components (10%AA-MD*l oM). However, this is the result of arbitrarily picking a particular blend ratio for experimental measurements, the mathematics predict that at an optimum blend ratio the required concentration will be lower than for either component alone. Thus for the example cited, ~ is appropriately negative and 1~1 is clearly >
ln(C~l/C 2)l Figure 4 graphically illustrates the above synergistic interaction for 10~ acrylic acid grafted MD*l oM where D* is (CH2)30(CH2CH20)6 50Me. A line between the Log [y40] of the component surfactants represents what would be e~pected for an ideal mixing of the two. A line at the level of the lowest Log ty40] indicates the limit of the target range for true synergistic interactions. Points below this . 2o9295l line lie in the region of synergistic interaction.
As seen in the Figure 4, the interaction of 10%
acrylic acid grafted with SDS is clearly in the synergistic region.
Table 6 Syner~i6tic Surface Ten~ion Reduction Efficiency Anionic Siloxane6 / Anionic Organic Surfactant (SDS) Cosurfactant Weight Fraction Loga ~c ¦In (C~l/C~2)¦
Siloxane [y40]
Sodium dodecyl- -1.0 ~ulfate 10%AA-MD*1 . oM 0.25 -3.17 -10.4 2.9 10%AA-MD*1 oM O .75 -2.72-13.7 2.9 s%AA-MD*l oM 0.50 -3.00 0.0 5.0 10%AA-MD i.5M 0-50 -2.77-4.54 4.42 Footnote for Table 6:
a. Log concentration that gives surface tension of 40 mN/m.
Other embodiments of the invention will be apparent to the skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.
SURFACTANT COMPOSITIONS
Field This application relates to surfactants, and more particularly, to combinations of organic surfactants and carboxylated siloxane-polyoxyalkylene copolymers which exhibit synergistic surfactant properties.
8ackground A surfactant has been defined as a solute which, when dissolved in a designated liquid, will alter the surface or interfacial characteristics of the solution in some manner, such as lowering the surface tension.
Surfactants have utility, for example, as detergents, emulsifiers, foamers, wetting agents, dispersants, flocculants and penetrants. They are particularly useful in producing detergent foams of high stability and high foaming power in aqueous systems. Other specific uses include foam stabilization and emulsification of water-organic solvent mixtures.
Synergystic interactions between surfactants, defined rigorously below, occur when two surfactants used in concert provide unexpected surface characteristics beyond those which would be predicted based on the sum of the surface properties of the individual components. Synergystic surfactant mi~tures not only have the areas of utility as described above for single surfactants, but also have the added advantage of being able to effect these utilities at lower concentrations. This ` ` 2092951 advantage may be exploited in a variety of ways such as the improved economics of using less material to achieve the same performance, or by extending the effective lifetime of a surfactant solution at a given concentration.
U.S. patent 3,562,786 of Bailey, et al., first suggested using organosilicone-o~yalkylene block copolymers in combination with organic surfactants to improve the properties of the water soluble organic surfactants for use in aqueous systems. This patent does not deal with the carboxyl group-containing siloxane-polyoxyalkylene copolymers which are the subject of this application, and does not indicate that the disclosed compositions exhibit synergism.
U.S. patent 4,784,799 of Petroff discloses surfactant compositions comprising a silicone sulfobetaine surfactant and an alkylbenzenesulfonate anionic surfactant, and states that these exhibit synergism. The experimental data presented in this patent show surface tensions produced by 0.1~ levels of blends of 2 surfactants, and surface tensions produced by various levels of each surfactant separately, the concentration in each case being that of the particular surfactant in the surfactant blend. Synergism is traditionally expressed as the whole being greater than the sum of the parts.
Somewhat more rigorously, it can be defined as two or more agents operating together to cause an effect which is greater than that which would have been expected based on the sum of the effects of the agents operating separately. Petroff provides no indication of the surface tensions which would have L3--lbb ~b __ ~ 3 ~ 20 9 2 9 5 1 been expected based on the sum of the effects of the several surfactants operating separately. He merely showed that each surfactant, considered separately at the level employed for the particular material in the surfactant blend, produced a surface tension higher than that of the corresponding blend of surfactants containing the given level of the surfactant under consideration. Thus, this reference does not describe synergystic surface tension lowering behavior, or suggest a method of achieving synergystic interactions between any silicone surfactants and anionic surfactants.
Rosen has published on ~Molecular Interaction and Synergism in Binary Mixtures of Surfactants~, setting forth theoretical and test protocols for ascertaining when synergism exists in mixtures of surfactants. See M.J. Rosen, Phenomena in Mixed Surfactant Systems, (J.F. Scamehorn, Ed.), ACS Symp. Ser., Vol. 311, p. 149 (1986).
Synergism in mixed micelle formation is defined by Rosen as being present when the critical micelle concentration of any mi~ture is lower than that of either pure surfactant. To treat this concept mathematically, a mixed micelle parameter, Bm, is derived which expresses the extent of interaction between two given surfactants in a solution. Thus, according to Rosen:
ln(aCml2 / XmCml) (l-Xm)2 where * cml2 is the critical micelle concentration for the mixture;
-- ~ 4 ~ 2 0 92 9 5 ~
* Cml is the critical micelle concentration of surfactant l;
* a is the weight fraction of surfactant 1 in the initial surfactant solution;
and xm is the weight fraction of surfactant 1 in the surfactant of the mixed micelle.
The value of Xm is derived from the iterative solution to the equation (xm)2 ln (acml2 / XmC 1) , 1 (l-Xm)2 ln ((1-)Cml2 / (1-Xm)Cm2) here * Cm2 is the critical micelle concentration of surfactant 2.
With these mathematical relationships established, synergism in mixed micelle formation is defined mathematically as e~isting when ~m is negative, and ¦ln(cml/cm2)¦<¦Bm¦.
Similarly, synergism in surface tension reduction efficiency is defined by Rosen as being present when a given surface tension can be attained at a total mi~ed surfactant concentration lower than that required of either surfactant by itself. To treat this concept mathematically, a parameter B~ is derived which expresses the extent of the interaction between the two given surfactants in a solution.
Thus, according to Rosen: ~
ln(aCal2 / XCl) Ba (l-X)2 here ~ cal2 is the concentration of the mi~ture required to achieve a specific surface tension;
v--~c~ u * cal is the concentration of surfactant 1 required to achieve a specific surface tension;
* a is the weight fraction of surfactant 1 in the initial surfactant solution;
and * X~ is the weight fraction of surfactant 1 in the surfactant in the mixed monolayer.
The value of X~ is derived from the iterative solution to the e~uation (xa)2 ln (~Cal2 / X C 1) - 1 (l-X~)2 ln ((l-a)C~12 / (1-X~)C~2) here ~ CG2 is the concentration of surfactant 2 required to achieve a specific , surface tension.
With these mathematical relationships established, synergism in mixed monolayer formation is defined mathematically as existing when B~ is negative, and ¦ln(C~l/C2)¦< ¦B~¦ .
It is always desirable to have new surfactant compositions which afford unexpectedly good surfactant properties, for the reasons discussed above. Such compositions are the subject of the present application.
Summary This invention addresses the above-identified needs and provides surfactant compositions which afford unexpectedly good surfactant properties.
The surfactant compositions which are the subject of this application are compositions of V--l b t~
_ -- 6 --matter which comprise an organic surfactant and a carboxyl-containing polysiloxane-polyoxyalkylene copolymer. A method for modifying the surface properties of an aqueous system comprises employing as components of the system an organic surfactant and a carboxyl-containing polysiloxane-polyoxyalkylene copolymer. The addition of the acid functional groups provides a silicone-polyether copolymer which not only has surfactant properties, but which also synergistically interacts with anionic and cationic organic surfactants to provide reduction of surface tension to lower than expected values, lowering of critical micelle concentration and other desirable surface or interfacial properties.
Description of the Drawing The invention will be more fully understood from a consideration of the following detailed description, together with the drawing, in which:
Fig. 1 is a plot of log CMC vs. weight fraction of ARQUAD~ T-50 cationic surfactant in blends with an acid-grafted siloxane-po.lyoxyalkylene copolymer;
Fig. 2 is a plot of log CMC vs. weight fraction of the anionic surfactant sodium dodecyl sulfate in ~lends with an acid-grafted siloxane-polyoxyalkylene copolymer;
Fig. 3 is a plot of log [y40] vs. weight fraction of ARQUADR T-50 cationic surfactant in blends with an acid-grafted siloxane-polyoxyalkylene copolymer; and D--16b3~
Fig. 4 is a plot of log ty90] vs. weight fraction of the anionic surfactant sodium dodecyl sulfate in blends with an acid-grafted siloxane-polyoxyalkylene copolymer.
Detailed Description In the present invention, polysiloxane-polyoxyalkylene copolymers functionalized with carboxylic acids, or salts of carboxylic acids, have shown synergistic interactions in mixed micelle formation with both cationic and anionic organic surfactants. The mixtures have been shown to form micelles at lower concentrations than those required by either of the components. Further, calculations of the mixed micelle parameter (Bm) and comparison with the component critical micelle concentrations ¦~m¦>¦ln(Cml/Cm2)¦ demonstrate that these mixtures fit the mathematical definition for synergistic interactions in the formation of mi~ed micelles.
In addition, these carbo~yl group-containing polysiloxane-polyoxyalkylene copolymers have show synergistic interactions in surface tension reduction efficiency with both cationic and anionic organic surfactants. The mixtures have been shown to reduce the surface tension to a specific value (40 mN/m), at lower concentrations than those required by either of the components. Further, calculations of the mixed monolayer parameter and comparison with the component mised monolayer concentrations 1~1 > ¦ ln(C~l/C~2) ¦
v - l u u ~ u _ - 8 - 2092951 demonstrate that these mixtures fit the mathematical definition for synergistic interactions in the mised monolayer.
The organic surfactant employed in the surfactant compositions of the invention are cationic or anionic surfactants, which are well known in the art and are commercially available. These organic surfactants are generally considered as comprising hydrophilic and hydrophobic functional groups.
The anionic organic surfactants can contain, for example, hydrophilic groups such as phosphates, sulfosuccinates, carbo~ylates, sulfates and sulfonates, and hydrophobic groups such as alkyl, aromatic, and arylalkyl hydrocarbons. The specific anionic organic surfactant demonstrated in this application is sodium dodecylsulfate, which will be discussed ~elow.
The cationic organic surfactants can contain, for example, hydrophilic groups such as quaternary amine salts of chlorides, sulfates, sulfonates, and carbo~ylates, and hydrophobic groups such as alkyl, aromatic, and arylalkyl hydrocarbons.
The specific cationic organic surfactant demonstrated in this application is trimethyltallowammonium chloride, which will be discussed below.
The carboxyl-containing polysilo~ane-polyoxyalkylene copolymers employed in the surfactant compositions of the invention are materials having the average general formula RaR~3-asio(Me2sio)b(MeRsio)csiRaR 3-a V--~bb~b wherein R~ stands for an alkyl group of 1-3 carbon atoms; and R stands for (CdH2dO)(CeH2eO)i(R CfH2f_lo) jRn ~; wherein Rn stands for -(cgH29-h(co2Q)h)yH ; and R ~ stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or Rn;
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R"CfH2f_lO);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of ~+, alkali metal ions, and quaternary ammonium salts.
The group R is a polyoxyalkylene chain which includes, on average, 0.1 to 5 carbo~yl-containing moieties R" and may be capped or uncapped. The subscript y represents the number of acid-containing monomer units. The polyoxyalkylene chain may be made up of ethyleneo~y groups, propyleneoxy groups, or both.
The group R' is preferably methyl. The subscript "a" is preferably 0-1, and most preferably -0. The subscript "b" is preferably 0-10, and most preferably 0-5. The subscript "c" is preferably 0.5-5, and most preferably 1-3. The subscript "d" is preferably 3. The subscript "g" is preferably 2-5, and most preferably 2-3. The subscript "h" is preferably 1-3, and most preferably 1-2. The subscript "y" is preferably 1-3, and most preferably 1. The group R'n is preferably an alkyl or acyl group of 1-4 carbon atoms, and most preferably an alkyl group. The sum of subscripts "i" and "j" is preferably 1-20 and most preferably 1-10. The subscript "j" is preferably 1-2, and most preferably 1.
The carboxyl-containing polysiloxane-polyoxyalkylene copolymers used in this invention may be prepared by introducing carboxylic acid-containing moieties into the polyether chains of a siloxane-polyalkylene copolymer in any of the ways known to the art.
Procedures for synthesizing nonhydrolyzable silicone surfactants having polyalkylene oxide pendant groups are well known. Representative disclosures are provided in U.S. Patents 3,741,917; 4,147,847; and 4,855,379.
The desired polysiloxane starting material may be prepared by causing a polyhydridosiloxane of generalized average formula M**DXD'~M** to react with allyl-started oxyalkylene polymer in the conventional manner, typically by means of a platinum catalyzed hydrosilylation of the unsaturated polyoxyalkylene with a polydialkyl-siloxane having SiH units, as taught by V.S. patent 4,031,044 for instance.
In the formula for the polyhydridosilo~ane, M is (CH3)2(H)siOl/2 or (cH3)3SiOl~2~ D is -(CH3)2SiO2/2, and D' represents (CH3)(H)SiO2/2. The allyl-started o~yalkylene polymers are polyethers havinq a terminal vinyl group, which may optionally be 2-substituted, and containing multiple units derived from ethylene oxide, propylene oxide, or ~oth. The reagents are mi~ed, generally in a solvent such as toluene or dipropylene glycol, heated to about 70-85 C, then the catalyst is added, a temperature rise of about 10-15 C is observed, and the mixture is finally sampled and analyzed for SiH groups ~y adding an alcohol and base and measuring evolved hydrogen. If a volatile solvent was used, this is removed under vacuum, and the mi~ture is generally neutralized with a weak base such as NaHCO3, then filtered.
The polyhydridosilo~anes of generalized average formula M%~DXD'yM~ are prepared in the manner known to the art. For the case in which M**
is (CH3)3SiOl~2, an alkyldisiloxane such as hexamethyldisiloxane, a polyhydridosiloxane polymer, and an alkyl cyclosiloxane such as octamethyl-cyclotetrasilo~ane are reacted in the presence of a strong acid such as sulfuric acid. For the case in which M%% is (H)(CH3)2siO2/2~ a hydridoalkyldisiloxane such as dihydridotetra-methyldisilo~ane, a polyhydridosilo~ane polymer, and an alkyl cyclosiloxane such as octamethylcyclo-tetrasiloxane are reacted in the presence of a strong acid such as sulfuric acid.
- 12 - 20~2951 The desired unsaturated polyoxyalkylene starting materials are likewise prepared in the manner known to the art, by reacting an unsaturated alcohol starter with a strong base to make an -alkoxide, which is subsequently reacted with with ethylene oxide, propylene o~ide, or both, and ultimately capped as taught by U.S. patents 2,425,755; 2,448,664; and 3,507,923. The capping involves further reaction of the initially formed terminal hydro~yl group with an alkylating or acylating agent such as a methyl halide or acetic anhydride, respectively. Other end caps may of course be employed.
The carbo~ylic acid functional groups may be introduced into the intermediate siloxane-polyoxyalkylene copolymer using any of several known methods. The method used in this application is taught in U.S. patent 3,418,354 and involved slowly and simultaneously adding (a) an olefin and (b) a peroxide containing a peroxide group linked to a tertiary carbon atom to (c) a polyo~yalkylene compound which was maintained at a temperature sufficiently elevated to cause a graft copolymer of the olefin and the polyoxyalkylene compound to be - produced. Using this method, unsaturated carbo~ylic acids were attached to the above prepared siloxane-polyoxyalkylene copolymers. Alternative methods include such methods as selective oxidation of the terminal alcohol on the polyether chain as describe in the ~ritish patent 807,666 or U.S.
patent 4,256,916, or addition to unsaturated acids or nitriles as described in U.S. patent 3,544,615 followed by conversion to the desired form.
The compositions of the invention can be prepared in various ways. The organic surfactant and the carboxylated siloxane-polyoxyalkylene copolymer can be mi~ed. Alternatively, one of these materials can be mi~ed with water and then the resulting mixture combined with the other ingredient. Similarly, one of these materials could be mixed with some third material with which the ultimate surfactant composition is to be used and then the other of these materials combined with the resulting mixture. The skilled in the art will appreciate that there are other modes of combination.
The organic surfactant and the carboxylated siloxane may be employed in any ratio which provides a mixture suitable for one's purpose. The weight ratio of organic surfactant to carboxylated siloxane-polyo~yalkylene copolymer is generally from about 95:5 to 5:95, preferably from 90:10 to 50:50, and most preferably from 90:10 to 70:30.
The surfactant compositions of the invention have typical surfactant applications, namely, as detergents, emulsifiers, foamers, wetting agents, dispersants, flocculants, penetrants, etc.
In aqueous solutions they are generally employed at a level of 0.001 to 10 percent by weight, preferably 0.01 to 5 percent, based on the total weight of the aqueous solution.
Glossary LUPERSOL~ 101 is a free radical-generating catalyst, 2,5-dimethyl-2,5-di(t-butylperoxy)he~ane, and is available from Pennwalt Corporation.
~ L u ~ u ~_ 2092951 ARQUAD~ T-S0 is a cationic surfactant, trimethyltallowammonium chloride, and is available from Akzo Chemicals.
M stands for (CH3)3SiOl/2 .
D stands for (CH3)2SiO2/2 -D' stands for (CH3)(H)SiO2/2 .
D* stands for (CH3)(polyether)SiO2/2 .
~perimental The invention will be further clarified bya consideration of the following e~amples, which are intended to be purely exemplary and not a limitation of the invention.
Surface tension measurements were made using the Wilhelmy Plate method. A sand blasted platinum blade was used as a sensor. All measurements were made at 25C. Deionized water further treated with a Millipore filtration system was used to prepare 5 x 10-3M sodium chloride which was then used to prepare all surfactant solutions.
Surface tension results are given in units of milliNewtons per meter (mN/m).
Critical micelle concentrations were determined in the normal way, by plotting surface tensions versus concentrations and noting the change in slope.
Example 1 This example shows the preparation and surface tension properties of neutralized acrylic acid grafted siloxane polyether copolymers.
150 gms of Me3SiOMeRSiOSiMe3 (MD~l oM) ~
where R is (CH2)3O(CH2CH2O)6 5Me, was placed in a - 15 _ ~ ~295 L
~00 ml flask and heated to 160C. 2.2 gms of LUPERSOLG) 101 free radical catalyst was added very slowly. After allowing for a short initiation time, 7.5 gms of acrylic acid was added slowly in concert with LUPERSOL<9 101 catalyst. When the addition of the two components was complete, the solution was allowed to stir under heating for an additional 30 minutes, and then allowed to cool.
Samples taken for surface measurements were adjusted to pH 7.0 by titrating with 1.0 N NaOH.
Table 1 shows the structure and surface properties for silo~ane polyether copolymers functionalized and neutralized in the manner described above.
Table 1 Surface Propertie~ for Acrylic Acid Functionalized Siloxane polyether Copolymers (pH=7) Siloxane/ Acrylic Acid CMC(wt%) Log [y40]C Log[y40]d polyetherGraftin~ (%) CMC
MD*l oM a 5.0 2.5x10-2 -1.60 4.1x10-4 -3.39 MD l.oM 10.0 1.05x10-1 -0.98 5.6x10-3 -2.25 MD 1.5M 10.0 1.4x10-2 -1.85 1.2x10-3 -2.92 MD13D*5 5M b 10.0 3.0x10-2 -1.52 5.6x10-3 -2.25 Footnotes for Table 1:
a. D~ is Me(O)Si(CH2)3O(cH2cH2o)6.5Me -b. D* is Me(O)Si(cH2)3O(cH2cH2o)ll.2H -c. concentration that gives surfacetension of 90 mN/m.
d. Log concentration that gives surface tension of 40 mN/m.
- . 2092951 -Example 2 E~ample 2 shows the preparation and sur~ace tension properties for a siloxane polyether copolymer functionalized with a dicarboxylic acid and neutralized to pH 7Ø
200 gms of Me3SiOMeRSiOSiM3 (MD l.oM), where R is (CH2)3OtCH2CH2O)6 5OMe, was placed in a 500 ml flask and heated to 160C. 3.3 gms of LUPERSOLg 101 free radical catalyst was added very slowly. After a short initiation time, 80 gms of a solution made from 20 gms of itaconic acid and 60 gms of methanol was slowly added in concert with the LUPERSOL~ 101 catalyst. After the addition was completed, the solution was heated for an additional 30 minutes and then cooled. A sample was take from this product and adjusted to pH 7.0 with lN NaOH. The sample was then used for the surface tension measurements.
Table 2 shows the results for the itaconic acid grafted siloxane polyether copolymer.
Table 2 Surface Propertie~ of Itaconic Functionalized Siloxane polyether Copolymer6 (pH=7) Siloxane/ Itaconic Acid CMC Log [y40]b Log polyether Grafting (a) (wt%) CMC ly40]C
.
MD l.oM 10.0 6.4x10-3 -2.19 5. x10-4 -3.24 Footnotes for Table 2:
a. D* is Me(o)si(cH2)3o(cH2cH2o)6.5oMe -b. concentration that gi~es surfacetension of 40 mN/m.
c. log concentration that gives surface tension of 40 mN/m.
.
20929~1 Example 3 Example 3 demonstrates the favorable synergistic interaction in mixed micelle formation for anionic functionalized silo~ane polyether copolymers with A~QUAD~ T-50 cationic organic surfactant.
Table 3 shows the results of blending ARQUAD~ T-50 cationic surfactant with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the ARQUAD~ T-50 cationic surfactant with no added cosurfactant. The remainder of the table lists the Log CMC's and mi~ed micelle parameter values for several ARQUAD~ T-50 cationic surfactant /
neutralized, carboxylic acid grafted siloxane `
polyether copolymers. A comparison of each mixed surfactant and its components (listed in Table 1, 2 or 3), shows that the value of the e~perimental CMC
is lower for the mixed surfactant than for the components. Further, since Bm is negative for each mixture, and ¦Bm¦ is >¦ln~Cml/Cm2)¦, the neutralized, carboxylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mi~ed micelle interaction with the cationic organic surfactant.
Figure 1 graphically illustrates the above synergistic interaction for 10% acrylic acid grafted MD~l oM where D is (CH2)3O(CH2CH2O)6.sOMe- A
straight line between the Log CMC's of the component surfactants represents what would be e~pected for an ideal mi~in~ of the two. A horizontal line at the level of the lowest Log CMC for the individual D~
~ - 18 - 2092951 components indicates the limit of the target range for true synergistic interactions. Points below this line lie in the region of synergistic interaction.
As seen in the Figure 1, the interaction of 10%
acrylic acid grafted MD~l oM with ARQUAD3 T-50 cationic surfactant is clearly in the synergistic region for most of the tested blends.
Table 3 Synergi6tic Mixed Micelle Interactions Anionic Siloxane~ / Cationic Organic Surfactant (ARQUADC T-50) Cosurfactanta~b Weight Fraction Log ~m ¦ln(Cml/Cm2)¦
Silicone CMC
ARQUAD~ T-50 -2.34 5ZAA/-MD*1 oM 0.50 -2.51 -4.53 1.69 10% M -MD*l oM O . 25 -3.62 -18.5 3.10 lOZ M -MD*l oM O .75 -3.70 -18.5 3.10 10% M -MD*l 5M 0.50 -2.74 -5.82 1.11 1o2AA-MDl3 sM*5 5M O.50 -2.96 -9.15 1.88 10%IA-MD*1 ~ O.50 -2.68 -3.78 0.33 Footnotes for Table 3:
a. ~AA indicates the amount of acrylic acid grafted onto the siloxane polyether copolymer.
b. %IA indicates the amount of itaconic acid grafted onto the siloxane polyether copolymer.
L~--10~0 - 19 _ 2092951 Example 4 - Example 4 demonstrates the synergistic mi~ed micelle interaction for an carbo~y functionalized siloxane-polyoxyalkylene copolymer and the anionic organic surfactant sodium dodecylsulfate. Table 4 shows the CMC measurements for mixtures of the cationic organic surfactant sodium dodecylsulfate with several neutralized, acid grafted siloxane polyether copolymers. The first row of data is for sodium dodecylsulfate for comparison purposes. The remainder of Table 4 shows the CMC and mixed micelle parameter values for several surfactant mixtures. A
comparison of each mixed surfactant and its components (listed in Table 1 or 4), shows that the value of the experimental CMC is lower for the mixed surfactant than for the components. Further, since ~m is negative for each mixture, and ¦~ml is >¦ln(Cml~Cm2)¦, the neutralized, car~oxylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mixed micelle interaction with the anionic organic surfactant.
Figure 2 graphically illustrates the above synergistic interaction for 10% acrylic acid grafted MD~l oM where D is (CH2)3O(CH2CH2O)6.sOMe- A
between the Log CMC's of the component surfactants represents what would be expected for an ideal mixing of the two. A line at the level of the lowest Log CMC for the individual components indicates the limit of the target range for true synergistic interactions. Points below this line lie in the region of synergistic interaction. As seen in the Figure 2, the interaction of 10% acrylic acid grafted MD~l oM with sodium dodecylsulfate is clearly in the synergistic region.
Table 4 Synergi~tic Mixed Micelle Interaction6 Anionic Siloxane~ / Anionic Organic Surfact~nt (SDS) Co~urfactanta Weight Fraction Log ~m ¦ln(Cml/Cm2)¦
Siloxane CMC
fiodium dodecyl ~ulfate -0.99 ~2AA-MD*1 ~ 0.50 -2.10 -7.17 1.42 10%AA-MD*1 ~ 0.25 -2.08 -10.5 0.02 AA-MD*1 oM O .75 -2.04 -10.3 0.02 lOZAA-MD*1.5M 0.50 -2.47 -9.31 2.00 Footnote for Table 4:
a. %AA indicate~ the amount of acrylic acid grafted onto the ~iloxane polyether copolymer.
Example 5 Example S demonstrates the favorable synergistic interaction in surface tension reduction efficiency for anionic functionalized silo~ane polyether copolymers with ARQUAD3 t-50 cationic organic surfactant.
Table 5 shows the results of blending ARQUAD3 T-50 cationic surfactant with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the ARQ~AD3 T-50 cationic surfactant with no added cosurfactant. The remainder of the table lists the Log ty40] and mixed monolayer parameter o ~ ~ o . ~ - 21 - 2092951 values for several ARQUAD3 T-~0 cationic surfactant /
neutralized, carbo~ylic acid grafted silo~ane polyether copolymer mi~tures. A comparison of each mixed surfactant and its components (listed in Table 1, 2 or 5), shows that the concentration of the mi~ed surfactant required ta attain a surface tension of 40 mN/m is lower for the mixed surfactant than for the components. Further, since B~ is negative for each mi~ture, and ¦B~¦ is > ¦ln(C~l~C~2)¦, the neutralized, carboxylic acid grafted siloxane polyether copolymers fit the mathematical definition of ~osen, discussed above, for interactions at the mixed monolayer with the cationic organic surfactant.
In some cases ~for example 50/50 10%AA-MD 13.5D*5.5M/ARQUAD3 T-50 cationic surfactant), the concentration required by the experimental mixture is only slightly less than for one component (ARQUAD~ T-S0 cationic surfactant).
However, this is the result of arbitrarily picking a particular blend ratio for e~perimental measurements, the mathematics predict that at an optimum blend ratio the required concentration will be lower than for either component alone. Thus for the e~ample cited, B~ is appropriately negative and ¦~¦ is clearlY > ~ln(C~l/C 2)l Figure 3 graphically illustrates the above synergistic interaction for 10~ acrylic acid grafted MD~l oM where D* is (CH2)3O~CH2CH2O)6 ~OMe. A line between the Log ty40]'5 of the component surfactants represents what would be expected for an ideal mixing of the two. A line at the level of the lowest Log ty40] indicates the limit of the target range for ~~ ~ - 22 - 2092951 synergistic interactions. Points below this line lie in the region of synergistic interaction. As seen in the Figure 3, the interaction of 10% acrylic aci~
grafted MD~l oM with Arquad T-50 is clearly in the -synergistic region for most of the blends.
Table 5 Synergi6tic Surface Ten~ion Reduction Efficiency Anionic Siloxane6 / Cationic Organic Surfactant (ARQUADD T-50) Cosurfactant Weight Fraction Loga ~ ¦ln(C~l/C 2) Siloxane [y40]
ARQUADD T-50 -3.18 5% M -MD*1 ~M O.50 -3.46 -1.52 0.48 10% M -MD*i.oM 0.25 -4.22 -14.4 2.20 AA-MD*1 . oM O . 75 -4.28 -14.3 2.20 0%AA MD 1 5M 0.50 -3.43 -3 47 0.60 10%AA-MD 13.5D 5.5M 0.50 -3.19 -3.59 2.14 10%IA-MD*1 oM 0.50 -3.35 -1.23 0.15 Footnote for Table 5:
a. Log concentration that gives surface tension of 40 mN/m.
Example 6 Example 6 demonstrates the favorable synergistic interaction in surface tension reduction efficiency for anionic functionalized silo~ane polyether copolymers with an anionic organic surfactant (sodium dodecylsulfate). -Table 6 shows the results of blending sodium dodecylsulfate with several different neutralized, acid grafted siloxanepolyethers prepared above. The first set of data is for the sodium dodecylsulfate (SDS) with no added cosurfactant. The remainder of - 23 - 20929~1 the table lists the Log ty40] and mi~ed monolayer parameter values for several SDS / neutralized, carbo~ylic acid grafted siloxane polyether copolymer mixtures. A comparison of each mi~ed surfactant and its components (listed in Table 1 or 6), shows that the concentration of the mixed surfactant re~uired to attain a surface tension of 40 mN/m is lower for the mi~ed surfactant than for the components. Further, since B~ is negative for each mixture, and ¦B~¦ is >
¦ln(C~l/C~2)¦, the neutralized, carbo~ylic acid grafted siloxane polyether copolymers fit the mathematical definition of Rosen, discussed above, for having a synergistic mixed micelle interaction with the cationic organic surfactant.
In some cases (for example 50/50 10%AA-MD*l oM/SDS), the concentration required`by the e~perimental mixture is about the same as one of the components (10%AA-MD*l oM). However, this is the result of arbitrarily picking a particular blend ratio for experimental measurements, the mathematics predict that at an optimum blend ratio the required concentration will be lower than for either component alone. Thus for the example cited, ~ is appropriately negative and 1~1 is clearly >
ln(C~l/C 2)l Figure 4 graphically illustrates the above synergistic interaction for 10~ acrylic acid grafted MD*l oM where D* is (CH2)30(CH2CH20)6 50Me. A line between the Log [y40] of the component surfactants represents what would be e~pected for an ideal mixing of the two. A line at the level of the lowest Log ty40] indicates the limit of the target range for true synergistic interactions. Points below this . 2o9295l line lie in the region of synergistic interaction.
As seen in the Figure 4, the interaction of 10%
acrylic acid grafted with SDS is clearly in the synergistic region.
Table 6 Syner~i6tic Surface Ten~ion Reduction Efficiency Anionic Siloxane6 / Anionic Organic Surfactant (SDS) Cosurfactant Weight Fraction Loga ~c ¦In (C~l/C~2)¦
Siloxane [y40]
Sodium dodecyl- -1.0 ~ulfate 10%AA-MD*1 . oM 0.25 -3.17 -10.4 2.9 10%AA-MD*1 oM O .75 -2.72-13.7 2.9 s%AA-MD*l oM 0.50 -3.00 0.0 5.0 10%AA-MD i.5M 0-50 -2.77-4.54 4.42 Footnote for Table 6:
a. Log concentration that gives surface tension of 40 mN/m.
Other embodiments of the invention will be apparent to the skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.
Claims (8)
1. A composition comprising two different surfactants, wherein one surfactant is selected from each of the groups i and ii set forth below:
i) from about 5 to about 95 weight percent of an organic surfactant selected from the group consisting of organic cationic surfactants and organic anionic surfactants; and ii) from about 95 to about 5 weight percent of a different carboxyl-containing siloxane-polyoxyalkyene copolymer surfactant having the general average formula RaR'3-aSiO(Me2SiO)b(MeRSiO)oSiRaR'3-a wherein Me stands for methyl;
R' stands for an alkyl group of 1-3 carbon atoms; and R stands for -(CdH2dO)(CcH2eO)i(R"CfH2f-1O)fR"';
wherein R" stands for - (CgH2g-h (CO2Q)h)yH; and R"' stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or R";
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R"CfH2f-1O);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of H+, alkali metal ions, and quaternary ammonium salts.
i) from about 5 to about 95 weight percent of an organic surfactant selected from the group consisting of organic cationic surfactants and organic anionic surfactants; and ii) from about 95 to about 5 weight percent of a different carboxyl-containing siloxane-polyoxyalkyene copolymer surfactant having the general average formula RaR'3-aSiO(Me2SiO)b(MeRSiO)oSiRaR'3-a wherein Me stands for methyl;
R' stands for an alkyl group of 1-3 carbon atoms; and R stands for -(CdH2dO)(CcH2eO)i(R"CfH2f-1O)fR"';
wherein R" stands for - (CgH2g-h (CO2Q)h)yH; and R"' stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or R";
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R"CfH2f-1O);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of H+, alkali metal ions, and quaternary ammonium salts.
2. A composition of claim 1, wherein:
R' is methyl;
R''' is an alkyl or acyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 1.5;
h = 1-3;
y = 1-3; and j = 0.1-2.
R' is methyl;
R''' is an alkyl or acyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 1.5;
h = 1-3;
y = 1-3; and j = 0.1-2.
3. A composition of claim 1, wherein:
R' is methyl;
R''' is an alkyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 2-3;
h = 1-2;
y = 1; and j = 1.
R' is methyl;
R''' is an alkyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 2-3;
h = 1-2;
y = 1; and j = 1.
4. A method for modifying the surface properties of an aqueous system, comprising:
employing as a component of said system a composition comprising two different surfactants, wherein one surfactant is selected from each of the groups i and ii set forth below:
i) from about 5 to about 95 weight percent of an organic surfactant selected from the group conslsting of organic cationic surfactants and organic anionic surfactants; and ii) from about 95 to about 5 weight percent of a different carboxyl-containing siloxane-polyoxyalkylene copolymer surfactant having the general average formula RaR' 3-aSiO(Me2SiO)b(MeRSiO)cSiRaR'3-a wherein Me stands for methyl;
R' stands for an alkyl group of 1-3 carbon atoms; and R stands for - (CdH2dO)(CeH2eO)i(R''CfH2f-1O)fR''';
wherein R'' stands for -(CgH2g-h(CO2Q)h)yH; and R''' stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or R'';
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R''CfH2f-1O);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of H+, alkali metal ions, and quaternary ammonium salts.
employing as a component of said system a composition comprising two different surfactants, wherein one surfactant is selected from each of the groups i and ii set forth below:
i) from about 5 to about 95 weight percent of an organic surfactant selected from the group conslsting of organic cationic surfactants and organic anionic surfactants; and ii) from about 95 to about 5 weight percent of a different carboxyl-containing siloxane-polyoxyalkylene copolymer surfactant having the general average formula RaR' 3-aSiO(Me2SiO)b(MeRSiO)cSiRaR'3-a wherein Me stands for methyl;
R' stands for an alkyl group of 1-3 carbon atoms; and R stands for - (CdH2dO)(CeH2eO)i(R''CfH2f-1O)fR''';
wherein R'' stands for -(CgH2g-h(CO2Q)h)yH; and R''' stands for H, an alkyl group of 1-4 carbon atoms, an acyl group of 1-4 carbon atoms, or R'';
a is an integer 0-2;
b is 0-20;
c is 0-10;
the sum of a and c is 0.1-10;
d is an integer 1-4;
e is 2 or 3 for each unit (CeH2eO);
f is 2 or 3 for each unit (R''CfH2f-1O);
g is 1-8;
h is 1-4;
y is 1-5;
the sum of i and j is 1-25;
j is 0.1-5; and Q is a cation selected from the group consisting of H+, alkali metal ions, and quaternary ammonium salts.
5. The method of claim 4, wherein in said siloxane-polyloxyalkylene copolymer:
R' is methyl;
R''' is an alkyl or acyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 1.5;
h = 1-3;
y = 1-3; and j = 0.1-2.
R' is methyl;
R''' is an alkyl or acyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 1.5;
h = 1-3;
y = 1-3; and j = 0.1-2.
6. The method of claim 4, wherein in said siloxane-polyoxyalkylene copolymer:
R' is methyl;
R''' is an alkyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 2-3;
h = 1-2;
y = 1; and j = 1.
R' is methyl;
R''' is an alkyl group;
a = 0;
b = 0-10;
c = 0.5-1.0;
d = 3;
g = 2-3;
h = 1-2;
y = 1; and j = 1.
7. The composition of claim 1 wherein said organic anionic surfactants contain hydrophilic moieties selected from the group consisting of phosphates, sulfosuccinates, carboxylates, sulfates, and sulfonates, and said cationic surfactants contain hydrophilic moieties selected from the group consisting of quaternary amine salts.
8. The method of claim 4 wherein said organic anionic surfactants contain hydrophilic moieties selected from the group consisting of phosphates, sulfosuccinates, carboxylates, sulfates, and sulfonates, and said cationic surfactants contain hydrophilic moieties selected from the group consisting of quaternary amine salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7-861,066 | 1992-03-31 | ||
| US07/861,066 US5360571A (en) | 1992-03-31 | 1992-03-31 | Surfactant compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2092951A1 CA2092951A1 (en) | 1993-10-01 |
| CA2092951C true CA2092951C (en) | 1997-07-15 |
Family
ID=25334785
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002092951A Expired - Fee Related CA2092951C (en) | 1992-03-31 | 1993-03-30 | Surfactant compositions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5360571A (en) |
| EP (1) | EP0563881B1 (en) |
| AT (1) | ATE170551T1 (en) |
| BR (1) | BR9301367A (en) |
| CA (1) | CA2092951C (en) |
| DE (1) | DE69320675T2 (en) |
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| US5364633A (en) * | 1994-03-14 | 1994-11-15 | Dow Corning Corporation | Silicone vesicles and entrapment |
| US5958448A (en) * | 1995-01-13 | 1999-09-28 | Dow Corning Corporation | Siloxane MQ resin vesicles and entrapment |
| WO1997032475A1 (en) * | 1996-03-06 | 1997-09-12 | Osi Specialties, Inc. | Organoamine siloxane alkoxylate surfactants |
| US6403548B1 (en) | 1998-10-27 | 2002-06-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| US6376456B1 (en) | 1998-10-27 | 2002-04-23 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Wrinkle reduction laundry product compositions |
| US6426328B2 (en) | 1998-10-27 | 2002-07-30 | Unilever Home & Personal Care, Usa Division Of Conopco Inc. | Wrinkle reduction laundry product compositions |
| US6238684B1 (en) | 1998-12-10 | 2001-05-29 | Osi Specialties, Inc. | Terminally modified, amino, polyether siloxanes |
| US6197876B1 (en) | 1999-02-24 | 2001-03-06 | Ck Witco Corporation | Heterocyclic amine modified siloxanes |
| US6576734B1 (en) * | 1999-12-16 | 2003-06-10 | Chisso Corporation | Modified polyorganosiloxane and method for producing it |
| US6840963B2 (en) | 2000-06-05 | 2005-01-11 | Procter & Gamble | Home laundry method |
| US6930079B2 (en) * | 2000-06-05 | 2005-08-16 | Procter & Gamble Company | Process for treating a lipophilic fluid |
| US6673764B2 (en) | 2000-06-05 | 2004-01-06 | The Procter & Gamble Company | Visual properties for a wash process using a lipophilic fluid based composition containing a colorant |
| US6939837B2 (en) * | 2000-06-05 | 2005-09-06 | Procter & Gamble Company | Non-immersive method for treating or cleaning fabrics using a siloxane lipophilic fluid |
| US6840069B2 (en) | 2000-06-05 | 2005-01-11 | Procter & Gamble Company | Systems for controlling a drying cycle in a drying apparatus |
| US6706076B2 (en) | 2000-06-05 | 2004-03-16 | Procter & Gamble Company | Process for separating lipophilic fluid containing emulsions with electric coalescence |
| US6691536B2 (en) | 2000-06-05 | 2004-02-17 | The Procter & Gamble Company | Washing apparatus |
| US6670317B2 (en) | 2000-06-05 | 2003-12-30 | Procter & Gamble Company | Fabric care compositions and systems for delivering clean, fresh scent in a lipophilic fluid treatment process |
| US6706677B2 (en) | 2000-06-05 | 2004-03-16 | Procter & Gamble Company | Bleaching in conjunction with a lipophilic fluid cleaning regimen |
| US6828292B2 (en) | 2000-06-05 | 2004-12-07 | Procter & Gamble Company | Domestic fabric article refreshment in integrated cleaning and treatment processes |
| US6855173B2 (en) | 2000-06-05 | 2005-02-15 | Procter & Gamble Company | Use of absorbent materials to separate water from lipophilic fluid |
| US6426379B1 (en) | 2000-06-22 | 2002-07-30 | Ashland Inc. | Silicone based defoamer |
| US6564591B2 (en) | 2000-07-21 | 2003-05-20 | Procter & Gamble Company | Methods and apparatus for particulate removal from fabrics |
| US7390415B2 (en) * | 2002-07-22 | 2008-06-24 | Cytec Technology Corp. | Method and compositions for preventing or reducing aluminosilicate scale in alkaline industrial processes |
| US7365043B2 (en) * | 2003-06-27 | 2008-04-29 | The Procter & Gamble Co. | Lipophilic fluid cleaning compositions capable of delivering scent |
| US20050003988A1 (en) * | 2003-06-27 | 2005-01-06 | The Procter & Gamble Company | Enzyme bleach lipophilic fluid cleaning compositions |
| US20050003987A1 (en) * | 2003-06-27 | 2005-01-06 | The Procter & Gamble Co. | Lipophilic fluid cleaning compositions |
| US7345016B2 (en) * | 2003-06-27 | 2008-03-18 | The Procter & Gamble Company | Photo bleach lipophilic fluid cleaning compositions |
| US7297465B2 (en) * | 2003-12-18 | 2007-11-20 | Agfa Graphics Nv | Heat-sensitive lithographic printing plate precursor |
| RU2463258C2 (en) * | 2007-02-05 | 2012-10-10 | Сайтек Текнолоджи Корп. | Silane-substituted polyethylene oxide reagents and method for use thereof to prevent or reduce aluminosilicate scaling in industrial methods |
| DE102011109540A1 (en) * | 2011-08-03 | 2013-02-07 | Evonik Goldschmidt Gmbh | Alkylcarbonate end-capped polyethersilioxanes and process for their preparation |
| US9688944B2 (en) | 2012-04-24 | 2017-06-27 | Stepan Company | Synergistic surfactant blends |
| US8728530B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Anionic micelles with cationic polymeric counterions compositions thereof |
| US8765114B2 (en) | 2012-10-30 | 2014-07-01 | The Clorox Company | Anionic micelles with cationic polymeric counterions methods thereof |
| US8728454B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Cationic micelles with anionic polymeric counterions compositions thereof |
| US8883706B2 (en) | 2012-10-30 | 2014-11-11 | The Clorox Company | Anionic micelles with cationic polymeric counterions systems thereof |
| AU2012393508B2 (en) * | 2012-10-30 | 2018-01-25 | The Clorox Company | Cationic micelles with anionic polymeric counterions compositions, methods and systems thereof |
| US8883705B2 (en) | 2012-10-30 | 2014-11-11 | The Clorox Company | Cationic micelles with anionic polymeric counterions systems thereof |
| CN111468033B (en) * | 2020-05-28 | 2021-08-24 | 陕西科技大学 | Silicon-containing surfactant and preparation method and application thereof |
| CN116004214A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Surfactant composition suitable for oil-gas reservoir water lock unlocking and preparation method and application thereof |
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| US2448664A (en) * | 1944-05-30 | 1948-09-07 | Carbide & Carbon Chem Corp | Polyoxypropylene compounds |
| US2425755A (en) * | 1944-06-01 | 1947-08-19 | Carbide & Carbon Chem Corp | Mixtures of polyoxyalkylene monohydroxy compounds and methods of making such mixtures |
| GB1034782A (en) * | 1962-01-24 | 1966-07-06 | Union Carbide Corp | Organosilicon compositions |
| US3418354A (en) * | 1964-12-29 | 1968-12-24 | Union Carbide Corp | Process for producing graft copolymers |
| US3507923A (en) * | 1967-01-06 | 1970-04-21 | Union Carbide Corp | Method of capping allyl endblocked oxyalkylene polymers |
| US3544617A (en) * | 1967-12-27 | 1970-12-01 | Showa Denko Kk | Process for the manufacture of aromatic nitriles |
| US3560544A (en) * | 1968-04-01 | 1971-02-02 | Dow Corning | Triorganosiloxy endblocked polyoxyalkylene siloxane polymers |
| US3741917A (en) * | 1970-10-26 | 1973-06-26 | Union Carbide Corp | Cold cure high resilience foam |
| US4010110A (en) * | 1971-08-06 | 1977-03-01 | Drew Chemical Corporation | Process for dispersing contaminants in circulating water or polar organic liquid system |
| US4031044A (en) * | 1974-04-15 | 1977-06-21 | Dow Corning Corporation | Polyether based, high resilient polyurethane foam |
| US4139546A (en) * | 1977-09-06 | 1979-02-13 | Witco Chemical Corporation | Anionic silicone defoamer |
| DE2854646A1 (en) * | 1977-12-19 | 1979-06-28 | Eastman Kodak Co | PROCESS FOR THE PRODUCTION OF DICARBONIC ACIDS |
| US4395352A (en) * | 1978-06-29 | 1983-07-26 | Union Carbide Corporation | High efficiency antifoam compositions and process for reducing foaming |
| US4462921A (en) * | 1983-01-24 | 1984-07-31 | Texaco Inc. | Siloxane stabilizers for inorganic silicates in antifreeze/coolant formulations |
| JPS61148184A (en) * | 1984-12-22 | 1986-07-05 | Chisso Corp | Siloxane compound containing carboxyl group |
| US4708807A (en) * | 1986-04-30 | 1987-11-24 | Dow Corning Corporation | Cleaning and waterproofing composition |
| US4784799A (en) * | 1988-01-25 | 1988-11-15 | Dow Corning Corporation | Synergistic surfactant compositions |
| JP2665799B2 (en) * | 1989-05-31 | 1997-10-22 | 花王株式会社 | Ester-modified silicone derivative and cosmetic containing the same |
| US5063044A (en) * | 1990-02-16 | 1991-11-05 | Dow Corning Corporation | Carboxy and carboxy-glycol ether and ester functional siloxane containing hair conditioners and shampoos |
| US4990643A (en) * | 1990-06-22 | 1991-02-05 | General Electric Company | Method for preparing carboxy functional silicones |
-
1992
- 1992-03-31 US US07/861,066 patent/US5360571A/en not_active Expired - Lifetime
-
1993
- 1993-03-30 DE DE69320675T patent/DE69320675T2/en not_active Expired - Fee Related
- 1993-03-30 AT AT93105243T patent/ATE170551T1/en not_active IP Right Cessation
- 1993-03-30 BR BR9301367A patent/BR9301367A/en not_active Application Discontinuation
- 1993-03-30 EP EP93105243A patent/EP0563881B1/en not_active Expired - Lifetime
- 1993-03-30 CA CA002092951A patent/CA2092951C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2092951A1 (en) | 1993-10-01 |
| US5360571A (en) | 1994-11-01 |
| DE69320675T2 (en) | 1999-01-21 |
| DE69320675D1 (en) | 1998-10-08 |
| EP0563881B1 (en) | 1998-09-02 |
| ATE170551T1 (en) | 1998-09-15 |
| BR9301367A (en) | 1993-10-13 |
| EP0563881A2 (en) | 1993-10-06 |
| EP0563881A3 (en) | 1995-05-24 |
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