Patent Application
20180042221
This invention relates to formulations of tetrakis(hydroxymethyl)phosphonium sulfate (THPS) which do not freeze when stored at low temperatures.
Formulations of biocidal active ingredients often are stored or used under conditions including extremely low temperatures, including, e.g., oil and gas extraction. Compositions containing THPS and various solvents have been reported in the literature, but compositions which are stable at low temperatures are not known. For example, WO2015/017705 discloses compositions containing THPS and various solvents, but this reference does not suggest the compositions claimed herein.
The present invention is directed to a composition comprising:
The present invention is further directed to a composition comprising:
The present invention is further directed to a composition comprising:
Unless otherwise specified, temperatures are in degrees centigrade (° C.), and references to percentages are by weight (wt %). All operations were performed at room temperature (20-25° C.), unless otherwise specified. 1,2-propanediol is also known as propylene glycol (PG). A polygon is a plane figure having at least three sides, with all sides being straight lines.
Compositions of THPS, water and PG within the scope of this invention are those for which the weight percentages are within the polygon defined by the five points, A, B, C, D and E listed above on a ternary phase diagram for THPS, water and PG. In one preferred embodiment of the invention, the composition is within the area defined by the points: (A), (B); (F) 30% THPS/20.5% water/49.5% 1,2-propanediol; and (G) 30% THPS/34% water/36% 1,2-propanediol; or the area defined by the points: (C), (D), (H) 47% THPS/27% water/26% 1,2-propanediol; and (I) 47% THPS/21.5% water/21.5% 1,2-propanediol. Each of the two areas in the preceding description is a trapezoid.
Compositions of THPS, water and ethylene glycol within the scope of this invention are those for which the weight percentages are within the triangle defined by the three points, J, K and L listed above on a ternary phase diagram for THPS, water and ethylene glycol. In one preferred embodiment of the invention, the composition is within the area defined by the points: (M) 20% THPS/39% water /41% ethylene glycol; (N) 24% THPS/18% water/58% ethylene glycol; and (L).
Compositions of THPS, water and glycerine within the scope of this invention are those for which the weight percentages are within the triangle defined by the three points, O, P and Q listed above on a ternary phase diagram for THPS, water and glycerine. In one preferred embodiment of the invention, the composition is within the area defined by the points: (R) 15% THPS/37% water/ 48% glycerine; (S) 15% THPS/28% water/57% glycerine; and (Q)
The composition may contain small amounts of other ingredients, e.g., solvents, process impurities associated with the commercial active ingredient, surfactants, defoamer agents, dispersing agents, brand identification markers; preferably no more than 5 wt % of other ingredients, preferably no more than 4 wt %, preferably no more than 3 wt %, preferably no more than 2 wt %, preferably no more than 1 wt %, preferably no more than 0.5 wt %, preferably no more than 0.3 wt %. A composition containing other ingredients is evaluated by normalizing the total of the weight percentages of THPS, water and 1,2-propanediol to 100%;
the composition is within the scope of the present invention if the point on a ternary phase diagram representing these normalized amounts is within the stated area.
The composition of the present invention is a free-flowing liquid even after storage at −40° C. Known aqueous solutions of THPS are not physically stable under these conditions. The prior art provided no indication that one could make a solution of THPS that would not freeze or phase-separate at −40° C.
To a glass sample vial was added: (i) commercial aqueous solution of bis[tetrakis(hydroxymethyl)phosphonium] sulfate containing 76.5 wt % THPS and (ii) water, or an alcohol selected from methanol, ethanol or isopropanol (IPA), or a combination of water and one of the listed alcohols in an amount sufficient to produce a 20 g sample. Each sample was then placed in a −40° C. freezer. The samples were observed after 24 hours and the physical form was noted in Table 1. Reexamination of the samples after several days revealed them to be unchanged from the original observation. Only those samples diluted with a combination of water and methanol appeared as free flowing homogeneous liquids.
To a glass sample vial was added commercial solution of bis[tetrakis(hydroxymethyl)phosphonium] sulfate solution, water and methanol in an amount sufficient to produce a 20 g sample. The composition of each sample is shown below in table 2. Each sample was then placed in a −40° C. freezer. The samples were observed after 24 hours and the physical form was noted in Table 2. Reexamination of the samples after several days revealed them to be unchanged from the original observation.
10%
10%
80%
15%
25%
60%
30%
35%
35%
40%
45%
15%
28%
22%
60%
27%
13%
To a glass sample vial was added commercial solution of bis[tetrakis(hydroxymethyl)phosphonium] sulfate solution, water and ethylene glycol in an amount sufficient to produce a 20 g sample. The composition of each sample is shown below in Table 3. Each sample was then placed in a −40° C. freezer. The samples were observed after 24 hours and the physical form was noted in Table 3. Reexamination of the samples after several days revealed them to be unchanged from the original observation.
To a glass sample vial was added commercial solution of bis[tetrakis(hydroxymethyl)phosphonium] sulfate solution, water and propylene glycol in an amount sufficient to produce a 20 g sample. The composition of each sample is shown below in Table 4. Each sample was then placed in a −40° C. freezer. The samples were observed after 24 hours and the physical form was noted in Table 4. Reexamination of the samples after several days revealed them to be unchanged from the original observation.
25%
15%
60%
25%
35%
40%
40%
20%
40%
40%
30%
30%
40%
40%
20%
To a glass sample vial was added commercial solution of bis[tetrakis(hydroxymethyl)phosphonium] sulfate solution, water and glycerine in an amount sufficient to produce a 20 g sample. The composition of each sample is shown below in table 2. Each sample was then placed in a −40° C. freezer. The samples were observed after 24 hours and the physical form was noted in table 1. Reexamination of the samples after several days revealed them to be unchanged from the original observation.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US16/22408 | 3/15/2016 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62134801 | Mar 2015 | US |
