WO2016094812A1

WO2016094812A1 - Liquid surfactant composition comprising a blend of 2 nonionic surfactants

Info

Publication number: WO2016094812A1
Application number: PCT/US2015/065271
Authority: WO
Inventors: Elvira Stesikova; Ryan WAIER; Gregory W. Drewno
Original assignee: Basf Se
Priority date: 2014-12-11
Filing date: 2015-12-11
Publication date: 2016-06-16

Abstract

A liquid surfactant composition has a solids content of from 30 to 70 weight percent. In one embodiment, the surfactant composition comprises an alkyl alkoxylate surfactant, a gel breaker, and water. The alkyl alkoxylate surfactant has the formula R-(AO)_x wherein R is an alkyl group having 10 to 20 atoms, wherein AO represents at least one alkylene oxide, and wherein x represents a number of moles of alkylene oxide and is from 20 to 50. The alkyl alkoxylate surfactant and the gel breaker are miscible in the water. The gel breaker minimizes or prevents gel formulation and typically also acts as a surfactant itself, thereby further enhancing the performance of the alkyl alkoxylate surfactant, even at high solids contents.

Description

LIQUID SURFACTANT COMPOSITION COMPRISING A BLEND OF 2

NONIONIC SURFACTANTS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The subject patent application claims priority to and all the benefits of U.S. Provisional Patent Application No. 62/090,449, filed on December 1 , 2014, the disclosure of which is expressly incorporated by reference in its entirety.

FIELD OF THE DISCLOSURE

[0002] The disclosure generally relates to a liquid surfactant composition. More specifically, this disclosure relates to a liquid surfactant composition that includes an alkyl alkoxylate surfactant and a particular gel-breaker.

BACKGROUND

[0003] A liquid form of a surfactant is typically typical over a solid form by most formulation chemists. The liquid form allows ease of handling, control in dosage and convenience of testing. When a natural state of non-ionic surfactants, such as alkyl alkoxylates, is solid due to the nature of their composition and structure, aqueous solutions offer an alternative way to liquidize the surfactant. However, this approach comes with its own set of challenges. For example, aqueous solutions having high surfactant concentrations are difficult to formulate but are required in order to optimize the economy of logistics. Freeze-thaw stability is another issue that typically must be addressed for many aqueous systems, especially those with high solids contents. Another unique challenge is derived from the nature of aqueous solutions of high molecular weight nonionic surfactants that form extensive hydrogen bond networks producing unusable gels in a wide range of compositions. To overcome the aforementioned problems and to formulate a liquid, gel breakers are typically used. Gel breakers are compounds that prevent or minimize gel formation and maintain a solution's liquid form in a wide range of compositions and temperatures. Usually, gel breakers are expensive additives that have no other value in a formulation. Therefore, there remains an opportunity for improvement.

BRIEF DESCRIPTION OF THE FIGURES

[0004] Other advantages of the present disclosure will be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:

[0005] Figure 1 is a line graph showing approximate viscosity as a function of concentration %/percent solids of various surfactant compositions set forth in the Examples.

SUMMARY OF THE DISCLOSURE

[0006] This disclosure provides a liquid surfactant composition having a solids content of from 30 to 70 weight percent. The surfactant composition includes an alkyl alkoxyiate surfactant, a tri-block gel breaker, and water. The alkyl alkoxvlate surfactant has the formula R-(AO)x wherein R is an alkyl group having 10 to 20 atoms, wherein AO represents at least one alkyiene oxide, and wherein x represents a number of moles of alkyiene oxide and is from 20 to 50. The tri-block gel breaker has the formula (EO)_a(PO)b(EO)c wherein each EO represents ethylene oxide and PO represents propylene oxide, each of a and c represent a number of moles of ethylene oxide, b represents a number of moles of propylene oxide, each of a and c is from 9 to 12 and b is from 13 to 15. The alkyl alkoxyiate surfactant and the tri- block gel breaker are miscible in the water. The gel breaker minimizes or prevents gel formulation and typically also acts as a surfactant itself, thereby further enhancing the performance of the alkyl alkoxyiate surfactant, even at high solids contents.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0007] This disclosure provides a liquid surfactant composition. The liquid surfactant composition is not particularly limited and may be used in any industry. For example, the liquid surfactant composition may be utilized in emulsion polymerization processes. In various embodiments, the liquid surfactant composition is used in latex paints and coatings, adhesives, and/or industrial coatings, and/or in emulsion polymerization processes involving the same.

[0008] The liquid surfactant composition typically resists gelling. In other words, the liquid surfactant composition typically tends to be a liquid and resists forming into a solid or semi-solid gel, as would be understood in the art. The terminology "liquid" typically describes that the liquid surfactant composition is a liquid at a temperature of 1 to 3, 1 to 5, 1 to 10, 1 to 15, 1 to 20, 1 to 25, or 1 to 30, °C. Typically, the liquid surfactant composition is determined to be a "liquid" and not a "gel" if it is pourable at room temperature, e.g. about 25°C. These determinations may be made using a pour point measurement according to ASTM D97. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated.

[0009] The liquid surfactant composition has a solids content of from 30 to 70 weight percent. The liquid surfactant composition typically includes, is, consists essentially of, or consists of an alkyl alkoxylate surfactant, a gel breaker, and water. In various embodiments, the gel breaker is more particularly described below.

[0010] The terminology "solids content" may alternatively be described as a "percent active" and describes the weight percent of the alkyl alkoxylate surfactant and the gel breaker in the liquid surfactant composition. In other words, the liquid surfactant composition includes from 30 to 70 weight percent of the alkyl alkoxylate surfactant and the gel breaker together based on a total weight of the liquid surfactant composition. In various embodiments, the liquid surfactant composition includes from 30 to 65, from 35 to 65, from 40 to 60, from 45 to 55, from 45 to 50, from 50 to 55, from 40 to 65, from 45 to 65, from 50 to 65, from 55 to 65, or from 60 to 65, weight percent of the alkyl alkoxylate surfactant and the gel breaker based on a total weight of the liquid surfactant composition, in one embodiment, the solids content is further defined as 65 wt % ±3 wt %. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated. Any one of the aforementioned values may vary by ± 1, 2, 3, 4, or 5, wt %.

[0011] In various embodiments, the alkyl alkoxylate surfactant itself is present in an amount of from about 1 to about 69, from 5 to 65, from 10 to 60, from 15 to 55, from 15 to 25, from 20 to 50, from 25 to 45, from 30 to 35, from 45 to 55, from 40 to 60, from 45 to 50, or from 50 to 55, weight percent based on a total weight of the liquid surfactant composition so long as the total weight percent of the alkyl alkoxylate surfactant and the gel breaker is from 30 to 80 weight percent based on a total weight of the liquid surfactant composition, [0012] Similarly, in other embodiments, the gel breaker is present in an amount of from about 1 to about 69, from 5 to 65, from 10 to 60, from 15 to 55, from 20 to 50, from 25 to 45, from 30 to 35, from 45 to 55, from 40 to 60, from 45 to 50, from 50 to 55, from 15 to 25, from 15 to 30, from 10 to 30, from 10 to 25, or from 10 to 20, weight percent based on a total weight of the liquid surfactant composition so long as the total weight percent of the alkyl alkoxylate surfactant and the gel breaker is from 30 to 80 weight percent based on a total weight of the liquid surfactant composition. In still other embodiments, the weight ratio of the alkyl alkoxylate surfactant to the gel breaker is from 2: 1 to 4: 1 , from 2.25: 1 to 3.7: 1, from 2.25: 1 to 3 : 1 , from 2.25: 1 to 2.75: 1.

[0013] Similarly, the water is typically present in an amount the balances the solids content of the liquid surfactant composition, e.g. in an amount of from 70 to 30 weight percent. The water is not particularly limited and may be any kind, e.g. purified or unpurified. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated, [0014] As first introduced above, the liquid surfactant composition typically includes, is, consists essentially of, or consists of, the alkyl alkoxylate surfactant, the gel breaker, and water. The terminology "consists essentially of describes that the liquid surfactant composition is free of other components, such as reactive components (e.g. monomers, polymers, or any other component that reacts to form a polymeric structure), other surfactants not described herein, non-water solvents, additional additives present in typical polymerization systems, and the like. However, in various embodiments, the liquid surfactant composition may consist essentially of, consist of, or be, two or more alkyl alkoxylate surfactants, the water, and the gel breaker, or the alkyl alkoxylate surfactant, the water, and two or more gel breakers, as each are described herein. However, even in these embodiments, the liquid surfactant composition is typically free of the aforementioned other components such as the reactive components, other surfactants (not described herein) and additional additives.

[0015] In various embodiments, the liquid surfactant composition complies with or passes regulations set forth in one or more of 21 CFR §§176.170, 176.180; 177.2260; and/or 175.105 and/or BFR 13/16. In other embodiments, the liquid surfactant composition has a cloud point of from 60 to 80, from 65 to 75, from 70 to 75, °C. In one embodiment, the liquid surfactant composition has a cloud point of about 73°C ± 5°C and/or a melting/pour point of 7°C ± 3°C, e.g. when diluted to a 1 wt% solution in water. In other embodiments, ail values and ranges of values between and including the aforementioned values are herein expressly contemplated.

Alkyl Alkoxylate Surfactant:

[0016] The alkyl alkoxylate surfactant may be a single alkyl alkoxylate surfactant or a combination of two or more alkyl alkoxylate surfactants. The alkyl alkoxylate surfactant has the formula R-(AO)_x wherein R is an alkyl group having 10 to 20 atoms, wherein AO represents at least one alkylene oxide, and wherein x represents a number of moles of alkylene oxide and is from 20 to 50. One or more aikyl aikoxylate surfactants of this formula may be utilized herein,

[0017] More specifically, R can be an alkyl group having 10, 1 1, 12, 13, 14, 1 5, 16, 1 7, 18, 19, or 20 carbon atoms. Alternatively, R may include or be a mixture of alkyl groups with such a number of carbon atoms. The alkyl group can be saturated or unsaturated and may be cyclic, branched, or linear. In various embodiments, R is a Ci₂-C₁₄ alkyl group and may be, for example, derived from lauryl alcohol. In such an embodiment, there may be carbon chains of varying length, e.g. from 6 to 18 carbons. However, these are typically present in very small amounts. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated, [0018] Referring back to AO, the at least one alkylene oxide may be further defined as ethylene oxide, propylene oxide, butyl ene oxide, etc. Typically, AO is ethylene oxide, propylene oxide, or a combination of ethylene oxide and propylene oxide. The AO group may be bonded to the R group as is understood in the art. The terminology x represents a number of moles of the alkylene oxide that are bonded to the R group. In various embodiments, x is from 20 to 50, from 25 to 45, from 30 to 40, or from 35 to 40. In other embodiments, x is from 25 to 35, from 30 to 35, from 25 to 30, or from 28 to 32, In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated. In various embodiments, the alkyl aikoxylate surfactant is commercially available from BASF Corporation under the trade name of Disponil*. Gel Breaker:

[0019] Referring back to the gel breaker, the gel breaker may be a single gel breaker or a combination of two or more gel breakers. In various embodiments, the gel breaker is typically chosen from one of the three set forth below but may include a combination of two of those below or all three of those below:

1. a tri -block gel breaker having the formul a;

(EO)a(PO)b(EO)c wherein each EO represents ethylene oxide and PO represents propylene oxide, each of a and c independently represent a number of moles of ethylene oxide, b represents a number of moles of propylene oxide, each of a and c is independently from 9 to 12 and b is from 13 to 15;

2. a gel breaker composition that is a combination of; (B 1) a first gel breaker having the formula;

R'-(AO)e wherein R' is a linear alky! group having 10 to 16 atoms, wherein AO represents at least one alkylene oxide, and wherein e represents a number of moles of alkylene oxide and is from 5 to 25, and

(B2) a second gel breaker having the formula;

R"-(AO> wherein R" is a non -linear alkyl group having 13 carbon atoms, wherein AO represents at least one alkylene oxide, and wherein f represents a number of moles of alkylene oxide and is from 5 to 15, and

3. a starfactant gel breaker that is the reaction product of epichlorohydrin and R (EO)n(PO)mOH, wherein R³ is a substituted or unsubstituted, saturated or unsaturated aliphatic group, substituted alkyl group, or alkenyl group, having from 4 to 22 carbon atoms; wherein n is a number from 0 to 50 and m is a number from 0 to 10; and wherein the mole ratio of epichlorohydrin to Rⁱ(EO)_n(PO)mOH is from about 0.60: 1 to about 2: 1.

[0020] In various embodiments, the weight average molecular weight of the gel breaker is about 1,900 g/mol ± 200, g/moi. In other embodiments, the polydispersity of the alkyl alkoxylate surfactant and the gel breaker, i.e., the differences in the weight average molecular weight of the aikyi alkoxylate surfactant and the gel breaker is sufficient to disrupt an ability of the liquid surfactant composition to form a gel,

[0021] Typically, the alkyl alkoxylate surfactant and the tri-block gel breaker, the gel breaker composition (e.g. the first and second gel breakers) and/or the starfactant gel breaker are miscible in the water. Miscibility is typically determined optically or visually. For example, when the alkyl alkoxylate surfactant is combined with the water and the tri-block gel breaker, the gel breaker composition (e.g. the first and second gel breakers) and/or the starfactant gel breaker, the resulting liquid is typically clear or approximately clear, as determined visually by one of skill in the art. Alternatively, the terminology "miscible" may be used to describe that a mixture of the aforementioned compounds is determined to be homogeneous, as would be understood by one of skill in the art. Tri-Block Gel Breaker:

[0022] Referring now to the tri-block gel breaker, this gel breaker has the formula (EO)_a(PO)b(EO)c. In this formula, each EO represents ethylene oxide and PO represents propylene oxide. Moreover, each of a and c independently represent a number of moles of ethylene oxide and b represents a number of moles of propylene oxide. In addition, each of a and c is independently from 9 to 12 and b is from 13 to 15. For example each of a and/or c can be 9, 10, 11, or 12. Moreover, b can be 13, 14, or 15. To be clear, a and c can be the same or different from each other and each may independently be the same or different from b. In one embodiment, the total weight average molecular weight of the (EO)_a and (EO)_c blocks is the same as the weight average molecular weight of the (PO)b block ± 5%. In another embodiment, the total weight average molecular weight of the tri-block gel breaker is 2,000 ± 100, g/mol.

[0023] This tri-block gel breaker is typically present in an amount as generally described above as related to the generically described "gel breaker" above. In one embodiment, the tri-block gel breaker is present in an amount of from 19.5 ± 1 weight percent based on a total weight of the liquid surfactant composition. In other embodiments, ail values and ranges of values between and including the aforementioned values are herein expressly contemplated. Gel Breaker Composition:

[0024] Referring now to the gel breaker composition, this composition can be, include, consist essentially of, or consist of, two individual gel breakers (B l) and (B2), Typically, the gel breaker composition is 95, 96, 97, 98, 99, or 100% by weight of (Bl) and (B2). [0025] (B l) and (B2) are not particularly limited in their weight amounts relative to the gel breaker composition itself. In various embodiments, (B l) is present in an amount of from 15 to 35, from 20 to 30, or from 25 to 30, weight percent based on a total weight of the gel breaker composition. In other embodiments, (B2) is present in an amount of from 65 to 85, from 70 to 80, or from 75 to 80, weight percent based on a total weight of the gel breaker composition. In other embodiments, each of the (B l) and/or (B2) is independently present in an amount of from 1 to 20, 2 to 19, 3 to 18, 4 to 17, 5 to 16, 6 to 15, 7 to 14, 8 to 13, 9 to 12, 10 to 1 1, 1 to 10, 1 to 5, 5 to 10, 10 to 15, 15 to 20, 4 to 6, or 13.5 to 15.5, weight percent based on a total weight of the liquid surfactant composition. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated,

[0026] (Bl) is the first gel breaker and has the formula R'-(AO)_e wherein R' is a linear alkyl group having 10 to 16 atoms. The linear alkyl group can have 10, 1 1, 12, 13, 14, 15, or 16 carbon atoms, or any range thereof. In various embodiments, the linear alkyl group is a C12-C1 alkyl group and may be, for example, derived from lauryl alcohol. In such an embodiment, there may be carbon chains of varying length, e.g. from 6 to 18 carbons. However, these are typically present in very small amounts.

[0027] Moreover, AO represents at least one alkyl ene oxide, e.g. ethylene oxide, propylene oxide, butylene oxide, etc. AO can represent a single alkyl ene oxide or more than one, e.g. a mixture, of alkylene oxides, e.g. ethylene oxide and propylene oxide. In addition, e represents a number of moles of alkylene oxide and is from 15 to 25, e.g. 18 to 22. In other words, e can be 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, or 25, or any range thereof. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated.

[0028] (B2) is the second gel breaker and has the formula R"-(AO)f wherein R" is a nonlinear aiky! group having 13 carbon atoms. Typically, this non-linear alkyl group is a tridecyl alcohol group or any isomer thereof. Moreover, just as above, AO represents at least one alkylene oxide, e.g. ethylene oxide, propylene oxide, butvlene oxide, etc. AO can represent a single alkylene oxide or more than one, e.g. a mixture, of alkylene oxides, e.g. ethylene oxide and propylene oxide. Furthermore, f represents a number of moles of alkylene oxide and is from 5 to 15, e.g. 8 to 12. In other words, f can be 5, 6, 7, 8, 9, 10, 1 , 12, 13, 14, or 15, or any range thereof. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated,

[0029] The terminology "non-linear" can be further described as branched. For example, R" can have varying degrees of branching, e.g. 1, 2, 3, or 4. The degree of branching may be actual or averaged. For example, numerous R" groups may be present each having a different degree of branching of 1, 2, 3, or 4 such that an average degree of branching is anywhere from 1 ,0 to 4.0, e.g. 3 to 4, or any value or range of values therebetween, to the tenth decimal place, e.g. 3. 1 to 3.9. All such ranges between 1.0 and 4.0 are expressly contemplated herein in various non-limiting embodiments. The terminology "degree of branching" is understood in the art and is typically calculated by H-NMR analysis. In various embodiments, the degree of branching is based on an isomeric mixture of highly branched synthetic alcohols, such as C13 synthetic alcohols. [0030] in varying embodiments, R" has the structure set forth below wherein structure (1) has a degree of branching of 1; structure (2) has a degree of branching of 2; structure (3) has a degree of branching of 3; and structure (4) has a degree of branching of 4:

In one embodiment, R" has an average degree of branching of from 3 to 4.

[0031] This gel breaker composition is typically present in an amount as generally described above as related to the generic-ally described "gel breaker" above. The gel breaker composition may be present in the gel breaker composition is present in an amount of from 18.5 to 20.5 parts by weight per 100 parts by weight of said liquid surfactant composition. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated.

Starfactant Gel Breaker:

[0032] The starfactant gel breaker is the reaction product of epichlorohydrin and

R³(EO)a(PO)mOH. In this formula, R³ is a substituted or unsubstituted, saturated or unsaturated aliphatic group, substituted alkyl group, or alkenyl group, having from 4 to 22 carbon atoms or any value or range of values therebetween. In addition, n i s a number from 0 to 50 and m is a number from 0 to 10. Alternatively, m and/or n can independently be any value or range of values therebetween the aforementioned values. In various embodiments, n is from 2 to 50 or from 4 to 50. Moreover, the mole ratio of epichlorohydrin to R³(EO)n(PO)mOH is from about 0.60: 1 to about 2: 1 . Alternatively, the ratio is 0.80: 1 to 2: 1. Ail values and ranges of values therebetween are expressly contemplated in various non- limiting embodiments.

[0033] R³ can be any substituted or un substituted, saturated or unsaturated aliphatic moiety having from 4 to 22 carbon atoms. Thus R³ can be a linear or branched alkyl group, a linear or branched alkenyl or alkenyl group, a saturated carbocyclic moiety, an unsaturated carboeyclic moiety having one or more multiple bonds, a saturated heterocyclic moiety, an unsaturated heterocyclic moiety having one or more multiple bonds, a substituted linear or branched alkyl group, a substituted linear or branched alkenyl or alkynyl group, a substituted saturated carbocyclic moiety, a substituted unsaturated carbocyclic moiety having one or more multiple bonds, a substituted saturated heterocyclic moiety, a substituted unsaturated heterocyclic moiety having one or more multiple bonds. Examples of the above include but are not limited to an alkyl group having from 4 to 22 carbon atoms, an alkenyl group having from 4 to 22 carbon atoms, an alkynyl group having from 4 to 22 carbon atoms. R³ can also be an arenyl group, Arenyl groups are alkyl-substituted aromatic radicals having a tree valence at an alkyl carbon atom such as a benzylic group. The typical value of R³ is an alkyl group having from 4 to 22 carbon atoms and most typically an alkyl group having from 8 to 10 carbon atoms. The degree of ethoxylation is typically from 2 to 50 or from 4 to 50 while the degree of propoxvlation can vary from 0 to 10. The degree of propoxvlation can be determined by the desired degree of water solubility or miscibility. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated. [0034] In one embodiment, R³ is an alkyl group having from 4 to 12 carbon atoms. Alternatively, R^J is an alkyl group having from 8 to 10 carbon atoms. Still further, R³ may be an alkyl group having from 4 to 12 carbon atoms while n is a number from 2 to 50. Alternatively, R^J may be an alkyl group having from 8 to 10 carbon atoms wherein n is a number from 4 to 50. The starfactant gel breaker may be as described in any one or more of U.S. Pat. Nos. 5,827,453, 5,895,605, and/or 6,472,440, each of which is expressly incorporated herein by reference in their entirety in one or more non-limiting embodiments. In other embodiments, all values and ranges of values between and including the aforementioned values are herein expressly contemplated.

[0035] The liquid surfactant composition may be formed by any method. For example, the liquid surfactant composition may be formed by combining each of the components described above. In one embodiment, the method includes the step of providing the alkyl alkoxyiate surfactant, the gel-breaker (or any more specific species thereof) and the water and also the step of combining these components to form the liquid surfactant composition. Alternatively, the method may further include one or more steps of forming each of the alkyl alkoxyiate surfactant and/or any one or more of the gel -breakers.

[0036] This disclosure also provides compositions that include the liquid surfactant composition. For example, an emulsion may include the liquid surfactant composition of this disclosure. The emulsion itself is not particularly limited and may be any known in the art, e.g. a water in oil emulsion, and oil in water emulsion, etc.

[0037] Moreover, this disclosure provides an emulsion polymerization process. This process typically includes the steps of forming an emulsion including at least one monomer and the liquid surfactant composition. This process also typically includes the step of polymerizing the at least one monomer in the presence of the liquid surfactant composition to form a polymer in the emulsion. The at least one monomer may be further defined as one monomer, two monomers, or any number of additional monomers. The monomers are not particularly limited and may be any known in the arts of latex paints and coatings, adhesives, and/or industrial coatings. The monomers are typically organic monomers but are not limited as such. Moreover, the polymer formed in the emulsion may be further defined as a latex paint, coating, adhesive, and/or industrial coating.

EXAMPLES

[0038] An alkyl alkoxylate surfactant is made by ethoxylating lauryl alcohol with 30 moles of EO. This ethoxyiated lauryl alcohol (45.5 parts) is then blended with a control gel breaker (19.5 parts) and diluted by adding 35 parts of water. This control gel breaker is a C12-C14 secondary alcohol ethoxyiated with 9 moles of EO. A series of gel -breakers are then utilized to replace the aforementioned comparative gel breaker and form a series of surfactant compositions. The viscosity of each of the surfactant compositions is then evaluated using a Brookfield Viscometer (LVTDV-II), Spindle #2, RPM adjusted to achieve 50% torque. The gel point of each of the surfactant compositions is evaluated using the Anton Paar method (Physica MCR 301) utilizing Spindle PP50-SN27594, equilibration at 25°C for 120 seconds, a Shear Rate of 1 1/sec, a linear ramp from 25°C to 0°C for 8.5 minutes, and a measurement of 100 data points over the temperature ramp. The results are set forth in the Table below. In the Table, the terminology "gel" indicates that the surfactant composition is not pourable at

Gel Breaker 10 700 < 0

Gel Breaker 11 720 < 0

Gel Breaker 12 446 < 0

Gel Breaker 13 35,000 1.5

Gel Breaker 14 Gel > 25

Gel Breaker 15 4060 < 0

Gel Breaker 16 404 < 0

Gel Breaker 17 675 < 0

Gel Breaker 18 5300 < 0

Gel Breaker 19 3360 < 0

Gel Breaker 20 5810 < 0

Gel Breaker 21 10,000 4.2

Gel Breaker 22 Gel > 25

[0039] Gel Breaker 1 is the reaction product of 2-propyl heptanol, 1 mole of propylene oxide, and 5 moles of ethylene oxide.

[0040] Gel Breaker 2 is the reaction product of 2-propyl heptanol, 1 mole of propylene oxide, and 8 moles of ethylene oxide,

[0041] Gel Breaker 3 is the reaction product of 2-propyl heptanol, 1 mole of propylene oxide, and 10 moles of ethylene oxide.

[0042] Gel Breaker 4 is the reaction product of 2-propyl heptanol, 3 mole of propylene oxide, and 14 moles of ethylene oxide.

[0043] Gel Breaker 5 is the reaction product of 2-propyl heptanol and 20 moles of ethylene oxide.

[0044] Gel Breaker 6 is the reaction product of 2-propyl heptanol and 30 moles of ethylene oxide.

[0045] Gel Breaker 7 is the reaction product of tridecanol and 8 moles of ethylene oxide, [0046] Gel Breaker 8 is the reaction product of tridecanol and 9 moles of ethylene oxide. [0047] Gel Breaker 9 is the reaction product of tridecanol and 10 moles of ethylene oxide. [0048] Gel Breaker 10 is Starfactant 20 which is a dendrimer polymer commercially available from BASF Corporation. [0049] Gel Breaker 1 1 is Starfactant 30 which is a dendrimer polymer commercially available from BASF Corporation.

[0050] Gel Breaker 12 is Tetronic 304 which is a tetrafunctional block copolymer.

[0051] Gel Breaker 13 is Tetronic 901 which is a tetrafunctional block copolymer.

[0052] Gel Breaker 14 is Tetronic 904 which is a tetrafunctional block copolymer.

[0053] Gel Breaker 15 is Tetronic 908 which is a tetrafunctional block copolymer.

[0054] Gel Breaker 16 is Pluronic L31 which is a block copolymer,

[0055] Gel Breaker 17 is Pluronic L35 which is a block copolymer.

[0056] Gel Breaker 18 is Pluronic L61 which is a block copolymer.

[0057] Gel Breaker 19 is Pluronic L62 which is a block copolymer.

[0058] Gel Breaker 20 is Pluronic L.64 which is a block copolymer.

[0059] Gel Breaker 21 is Pluronic L81 which is a block copolymer.

[0060] Gel Breaker 22 is the reaction product of a C12-C14 alkanol with 20 moles of EO.

[0061] The data set forth above shows that the majority of the samples exhibited elevated viscosity and gel point whereas some, e.g. Gel Breakers 1 , 4, 5, and 17, had viscosity and gel points similar to the control gel breaker.

[0062] Additional compositions are also formed. More specifically, these compositions include 45.5 weight percent of the alkyl alkoxylate surfactant that is made by ethoxylating lauryl alcohol with 30 moles of EO. These compositions also include 40-45 weight percent of water and varying amounts of the Gel Breaker 17. These compositions further include varying amount of Gel Breakers 10 and 11. Just as above, these compositions are evaluated to determine viscosity and gel point and the results are set forth in the Table below.

0063] This data shows that all compositions at 14.5% loading were gel free. The compositions at 9.5% had a higher viscosity and a gel point above 0°C.

[0064] Additional compositions are further fonned. More specifically, these compositions include 45.5 weight percent of the alkyl alkoxylate surfactant that is made by ethoxylating iauryl alcohol with 30 moles of EO. These compositions also include about 35 weight percent of water and varying amounts of the Gel Breakers set forth below. Just as above, these compositions are evaluated to determine viscosity and gel point and the results are set forth in the Table below.

25 Gel 75 1650 9.3

50 Breaker 50 Gel > 25

75 4 25 Gel > 25

25 Gel 75 4510 18.4

50 Breaker 50 Gel > 25

75 5 25 Gel > 25

25 Gel 75 Gel > 25

50 Breaker 50 1180 < 0

75 6 25 2300 16.9

25 Gel 75 Gel > 25

50 Breaker 50 1210 < 0

75 25 Gel 22.3

25 Gel 75 1060 < 0

50 Breaker 50 1 170 2

75 8 25 Gel > 25

[0065] This data shows that a blended approach can produce a gel free composition. In fact, gel free compositions are produced even when each individual component is ineffective on its own.

[0066] Additional compositions are further formed. More specifically, these compositions include 45.5 weight percent of the alkyl alkoxylate surfactant that is made by ethoxylating iauryl alcohol with 30 moles of EO. These compositions also include about 35 weight percent of water and varying amounts of the Gel Breakers set forth below. Just as above, these compositions are evaluated to determine viscosity and gel point and the results are set forth in the Table below.

[0067] This data shows that by using combinations of branched surfactants based on 2- propylheptanol, gel free formulations are made despite many of the individual components being unable to break a gel on their own. This data also shows that Mw distribution as well as branching affects gel behavior.

[0068] One or more of the values described above may vary by ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described herein.

[0069] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0,4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

Claims

CLAIMS What is claimed is:

1. A liquid surfactant composition that resists gelling, has a solids content of from 30 to 70 weight percent, and comprises:

A. an alky! alkoxylate surfactant having the formula;

R-(AO)_x

wherein R is an alkyl group having 10 to 20 atoms, wherein AO represents at least one alkylene oxide, and wherein x represents a number of moles of alkylene oxide and is from 20 to 50;

B. a tri-block gel breaker having the formula;

(EO)a(PO>₀(EO)c

wherein each EO represents ethylene oxide and PO represents propylene oxide, each of a and c independently represent a number of moles of ethylene oxide, b represents a number of moles of propylene oxide, each of a and c is independently from 9 to 12 and b is from 13 to 15; and

C. water,

wherein said alkyl alkoxylate surfactant and said tri-block gel breaker are miscible in said water.

2. The liquid surfactant composition of claim 1 consisting essentially of (A), (B), and (C).

3. The liquid surfactant composition of claim 1 or 2 wherein a and c are the same.

4. The liquid surfactant composition of any one of claims 1-3 wherein R is a C₁₂- Ci4 alkyl group.

5. The liquid surfactant composition of any one of claims 1-4 wherein AO is further defined as a combination of ethylene oxide and propylene oxide.

6. The liquid surfactant composition of any one of claims 1 -4 wherein AO is further defined as ethylene oxide.

7. The liquid surfactant composition of any one of claims 1-6 wherein x is from 28 to 32.

8. The liquid surfactant composition of any one of claims 1-7 that is liquid at a temperature of 1-10°C as determined using a pour point measurement according to ASTM D97.

9. The liquid surfactant composition of any one of claims 1 -8 that has a melting/pour point of 7°C ± 3°C, and a cloud point of 73°C ± 5°C, when diluted to a lwt % solution in water.

10. The liquid surfactant composition of any one of claims 1-9 wherein the total weight average molecular weight of the (EO)_a and (EO)_c blocks is the same as the weight average molecular weight of the (PG)b block ± 5%.

11. The liquid surfactant composition of any one of claims 1-10 wherein the total weight average molecular weight of the tri -block gel breaker is 2,000 ± 00, g/mol.

12. The liquid surfactant composition of any one of claims 1-11 wherein the solids content is further defined as 65 wt % ±3 wt %.

13. The liquid surfactant composition of any one of claims 1 -1.2 wherein the tri- block gel breaker is present in an amount of from 15 to 25 weight percent based on a total weight of the surfactant composition.

14. The liquid surfactant composition of any one of claims 1 -12 wherein the tri- block gel breaker is present in an amount of 19.5 ± 1 weight percent based on a total weight of the surfactant composition.

15. An emulsion polymerization process comprising the steps of: forming an emulsion comprising at least one monomer and the liquid surfactant composition of any one of claims 1-14; and

polymerizing the at least one monomer in the presence of the liquid surfactant composition to form a polymer in the emulsion.

16. A liquid surfactant composition that resists gelling, has a solids content of from 30 to 70 weight percent, and comprises:

A. an alkyl alkoxylate surfactant having the formula;

R-(AO)d

wherein R is an alkyl group having 10 to 20 atoms, wherein AO represents at least one alkylene oxide, and wherein d represents a number of moles of alkylene oxide and is from 20 to 50;

B. a gel breaker composition that is a combination of;

(B 1) a first gel breaker having the formula;

R'-(AO)_e

wherein R' is a linear alkyl group having 10 to 16 atoms, wherein AO represents at least one alkylene oxide, and wherein e represents a number of moles of alkylene oxide and is from 15 to 25, and

(B2) a second gel breaker having the formula;

R"-(AO)_f

wherein R" is a non-linear alkyl group having 13 carbon atoms, wherein AO represents at least one alkylene oxide, and wherein f represents a number of moles of alkylene oxide and is from 5 to 15; and

C. water,

wherein said alkyl alkoxylate surfactant and said gel breaker composition are miscible in said water.

17. The liquid surfactant composition of claim 16 consisting essentially of (A), (B), and (C).

18. The liquid surfactant composition of claim 16 or 17 wherein R is a CH-CM alkyl group.

19. The liquid surfactant composition of any one of claims 16-18 wherein AO of the alkyl alkoxylate surfactant is iurther defined as a combination of ethylene oxide and propylene oxide.

20. The liquid surfactant composition of any one of claims 16-18 wherein AO of the alkyl alkoxylate surfactant is further defined as ethylene oxide.

21. The liquid surfactant composition of any one of claims 16-20 wherein d is from 28 to 32.

22. The liquid surfactant composition of any one of claims 16-21 wherein R' is a linear C₁₂-C₁₄ alkyl group.

23. The liquid surfactant composition of any one of claims 16-22 wherein AO of the first gel breaker is further defined as a combination of ethylene oxide and propylene oxide.

24. The liquid surfactant composition of any one of claims 16-22 wherein AO of the first gel breaker is further defined as ethylene oxide.

25. The liquid surfactant composition of any one of claims 16-24 wherein e is 18-

26. The liquid surfactant composition of any one of claims 16-25 wherein R" has an average degree of branching of from 3 to 4.

27. The liquid surfactant composition of any one of claims 16-26 wherein AO of the second gel breaker is further defined as a combination of ethylene oxide and propylene oxide.

28. The liquid surfactant composition of any one of claims 16-26 wherein AO of the second gel breaker is further defined as ethylene oxide.

29. The liquid surfactant composition of any one of claims 16-28 wherein f is 8- Ι Δ.

30. The liquid surfactant composition of any one of claims 16-29 that is liquid at a temperature of 1-10°C as determined using a pour point measurement according to ASTM D97.

31. The liquid surfactant composition of any one of claims 16-30 that has a melting/pour point of 7°C ± 3°C, and a cloud point of 73°C ± 5°C, when diluted to a lwt % solution in water.

32. The liquid surfactant composition of any one of claims 16-31 wherein the solids content is further defined as 65 wt % ±3 wt %.

33. The liquid surfactant composition of any one of claims 16-32 wherein the gel breaker composition is present in an amount of from 18,5 to 20.5 parts by weight per 100 parts by weight of said surfactant composition.

34. The liquid surfactant composition of any one of claims 16-33 wherein the first gel breaker is present in an amount of from 4 to 6 parts by weight per 100 parts by weight of said surfactant composition.

35. The liquid surfactant composition of any one of claims 16-34 wherein the second gel breaker is present in an amount of from 13.5 to 15.5 parts by weight per 100 parts by weight of said surfactant composition.

36. An emulsion polymerization process comprising the steps of:

forming an emulsion comprising at least one monomer and the liquid surfactant composition of any one of claims 16-35, and polymerizing the at least one monomer in the presence of the liquid surfactant composition to form a polymer in the emulsion.

37. A liquid surfactant composition that resists gelling, has a solids content of from 30 to 70 weight percent, and comprises:

A. an alkyi alkoxylate surfactant having the formula: wherein R is an alkyi group having 10 to 20 atoms, wherein AO represents at least one alkylene oxide, and wherein x represents a number of moles of alkylene oxide and is from 20 to 50:

B. a starfactant gel breaker that is the reaction product of epichlorohydrin and 3(EO)n(PO)mOH, wherein R is a substituted or un substituted, saturated or unsaturated aliphatic group, substituted alkyi group, or alkenyl group, having from 4 to 22 carbon atoms; wherein n is a number from 0 to 50 and m is a number from 0 to 10; and wherein the mole ratio of epichlorohydrin to R³(EO)_n(PO)_mOH is from about 0.60: 1 to about 2: 1; and

C. water,

wherein said alkyi alkoxylate surfactant and said starfactant gel breaker are miscible in said water.

38. The liquid surfactant composition of claim 37 consisting essentially of (A), (B), and (C).

39. The liquid surfactant composition of claim 37 or 38 wherein R^J is an alkyi group having from 4 to 12 carbon atoms.

40. The liquid surfactant composition of claim 37 or 38 wherein R³ is an alkyi group having from 8 to 10 carbon atoms.

41. The liquid surfactant composition of any one of claims 37-40 wherein n is a number from 4 to 50.

42. The liquid surfactant composition of any one of claims 37-41 wherein the mole ratio of epichlorohydrin to R³(EO)_n(PO)_tnOH is from 0.80: 1 to 2: 1.

43. The liquid surfactant composition of claim 37 wherein R is an alky! group having from 4 to 12 carbon atoms and n is a number from 2 to 50.

44. The liquid surfactant composition of claim 37 wherein R^J is an aikyi group having from 8 to 0 carbon atoms and n is a number from 4 to 50.

45. The liquid surfactant composition of any one of claims 37-44 wherein R is a CO-C M alkyi group.

46. The liquid surfactant composition of any one of claims 37-45 wherein AO is further defined as a combination of ethylene oxide and propylene oxide.

47. The liquid surfactant composition of any one of claims 37-45 wherein AO is further defined as ethylene oxide.

48. The liquid surfactant composition of any one of claims 37-47 wherein x is from 28 to 32.

49. The liquid surfactant composition of any one of claims 37-48 that is liquid at a temperature of 1-10°C as determined using a pour point measurement according to ASTM D97,

50. The liquid surfactant composition of any one of claims 37-49 that has a melting/pour point of 7°C ± 3°C, and a cloud point of 73°C ± 5°C, when diluted to a lwt % solution in water.

51. An emulsion polymerization process comprising the steps of:

forming an emulsion comprising at least one monomer and the liquid surfactant composition of any one of claims 37-50; and

polymerizing the at least one monomer in the presence of the liquid surfactant composition to form a polymer in the emulsion,