Patent Application
20080020948
156 g of water, 49 g of maltodextrin (Cargill MD™ 01918 maltodextrin, DE 18) and 0.0039 g of ferrous ammonium sulfate hexahydrate (FAS) were heated to 98° C. in a reactor. A mixed solution of 81.6 g of acrylic acid (AA) and 129.2 g of a 50% solution of sodium 2-acrylamido-2-methyl propane sulfonate (AMPS) was added to the reactor over a period of 45 minutes. An initiator solution of 13 g of 35% strength hydrogen peroxide in 78 g of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour, neutralized by adding 27.2 g of a 50% solution of sodium hydroxide, and cooled. The final product was a clear yellow solution. The number average molecular weight of this polymer was 68,940 and a pH of 5.1.
This sample remained a clear solution with no sign of precipitation even after 6 months. However a blend of Alcosperse 545 (AA-AMPS copolymer) and Cargill MD™ 01918 maltodextrin phase separates within a day. This is similar to the phase separation seen in Comparative Example 5 of '941 when a maltodextrin of DE 20 (even though this a lower molecular weight than that used in our recipe) is used. This indicates that the '941 Comparative Example 5 has very little graft copolymer due to the presence of mercaptan, resulting in lots of synthetic copolymer.
Further, a blend of Alcosperse 545 and saccharose or sucrose is phase stable. This is due to the fact that the latter is a small molecule and is very compatible. This supports our assertion that the materials of Examples 1, 2 and 12 of '941, due to the presence of mercaptans and organic amine initiators used in their formation, are mostly synthetic copolymers blended with the saccharose. The performance of these polymers in the Table 1 above supports this assertion.
Example 1 was repeated with the exception that 0.39 g of FAS was used. The final product was a clear amber solution.
160 g of water, 207.8 g of Cargill Sweet Satin Maltose (80% solution) and 0.00078 grams of copper sulfate pentahydrate were heated in a reactor to 98° C. A mixed solution containing 16.4 g of AA and 25.9 grams of a 50% solution of sodium 2-acrylamido-2-methyl propane sulfonate (AMPS) was added to the reactor over a period of 45 minutes. The saccharide was 85 weight percent of the total weight of saccharide and monomer (acrylic acid+AMPS). An initiator solution comprising 13 grams of 35% hydrogen peroxide solution in 78 grams of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour. The polymer was then neutralized by adding 8 grams of a 50% solution of NaOH. The final product was a clear yellow solution. This sample has been a clear solution and shows no sign of precipitation even after 6 months.
180 g of water and 146 g of maltodextrin (Cargill MD™ 01960 maltodextrin, DE 11) and 0.0013 g of copper sulfate pentahydrate were heated in a reactor to 98° C. A mixed solution containing 27.3 g of acrylic acid and 43.2 g of a 50% solution of AMPS was added to the reactor over a period of 45 minutes. (The saccharide comprised 75 wt % of the total wt % of saccharide and monomer (acrylic acid+AMPS).) An initiator solution of 13 g of 35% hydrogen peroxide solution in 78 g of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour. The polymer was then neutralized by adding 27 g of a 50% solution of NaOH to a pH of about 7. The final product was a clear yellow solution. This sample remained a clear solution with no sign of precipitation even after 6 months.
Testing was conducted in a full scale washing machine using 3 cotton and 3 polyester/cotton swatches. The soil used was 17.5 g rose clay, 17.5 g bandy black clay and 6.9 g oil blend (75:25 vegetable/mineral). The test was conducted for 3 cycles using 100 g powder detergent per wash load. The polymers were dosed in at 1.0 weight % of the detergent. The wash conditions used a temperature of 33.9° C. (93° F.), 150 ppm hardness and a 10 minute wash cycle.
L (luminance) a (color component) b (color component) values before the first cycle and after the third cycle were measured as L1, a1, b1, and L2, a2, b2, respectively, using a spectrophotometer. Delta whiteness index is calculated using the L, a, b values above. Lower Delta WI (whiteness index) numbers are indicative of better performance.
90 g of water and 65 g of maltodextrin (Cargill MD™ 01960 maltodextrin, DE 11) and 0.00075 g of ferrous ammonium sulfate hexahydrate (FAS) were heated in a reactor to 98° C. A solution containing 100 g of sodium styrene sulfonate dissolved in 500 g of water was added over 150 minutes. An initiator solution comprising 3.6 g of 35% hydrogen peroxide solution in 30 grams of deionized water was simultaneously added to the reactor over a period of 165 minutes. The reaction product was held at 98° C. for an additional hour. The final product was a clear water white solution. The number average molecular weight of this polymer was 4,202. This sample has been a clear solution and shows no sign of precipitation even after 4 months.
80 g of water, 15 g of glycerol and 0.0012 g of ferrous ammonium sulfate hexahydrate (FAS) were heated in a reactor to 98° C. A mixed solution containing 16.3 g of acrylic acid and 25.9 g of a 50% solution of sodium 2-acrylamido-2-methyl propane sulfonate (AMPS) was added to the reactor over a period of 45 minutes. An initiator solution comprising 13 g of 35% hydrogen peroxide solution in 30 g of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour. The reaction product was cooled and neutralized with 6 g of a 50% NaOH solution.
263 g of water, 31.9 g of maleic anhydride, 51.5 g of sodium methallyl sulfonate, 47 g of maltodextrin (Cargill MD™ 01960 maltodextrin, DE 11) and 0.0022 g of copper sulfate pentahydrate were heated in a reactor to 98° C. A solution containing 178 g of acrylic acid dissolved in 142 g of water was added over 150 minutes. An initiator solution comprising 23.8 g of 35% hydrogen peroxide solution in 37 g of deionized water was simultaneously added to the reactor over a period of 180 minutes. The reaction product was held at 98° C. for an additional hour. The reaction product was cooled and neutralized with 90 g of a 50% NaOH solution. The final product was a clear yellowish amber solution.
263.1 g of water, 80 g of maltodextrin (Cargill MD™ 01960, soluble component 90%, DE value of 11 to 14), 63.8 g of maleic anhydride, 0.00075 g (3.5 g of a 0.1% strength) aqueous FAS solution and 94 g of 50% strength aqueous sodium hydroxide solution are heated to a boil in a reactor equipped with stirrer, reflux condenser, thermometer, feed devices, and nitrogen inlet and outlet. The degree of neutralization of maleic acid produced from the maleic anhydride in aqueous solution is 90.2%. Once the reaction mixture has started boiling, a solution of 178.2 g of acrylic acid in 141.9 g of water is added over the course of 5 hours, and a solution of 16.6 g of 50% strength hydrogen peroxide in 44.4 g of water is added at a constant rate over the course of 6 hours at the boil. When the addition of acrylic acid is complete, the degree of neutralization of the maleic acid and acrylic acid units present in the polymer is 31.1%. When the addition of hydrogen peroxide is complete, the reaction mixture is heated at a boil for an additional hour, neutralized to a pH of 7.2 by adding 180 g of 50% strength aqueous sodium hydroxide solution, and cooled.
290 g of maltodextrin having a DE value of from 11 to 14, 470 g of water, 4.2 ml of a 0.1% strength aqueous solution of FAS, 101.38 g of maleic anhydride and 74.52 g of sodium hydroxide are introduced into a reactor and heated to boil. The degree of neutralization of the resultant maleic acid is 90%. Immediately after boiling commences, a mixture of 120 g of acrylic acid and 114.4 g of a 58% strength aqueous solution of the sodium salt of acrylamido methyl propane sulfonic acid is added over the course of 5 hours, and 80 g of 30% hydrogen peroxide and a solution of 24 g of sodium persulfate in 72 g of water are added over the course of 6 hours, in each case at a constant rate and the mixture is polymerized at the boiling point. After the addition of initiator is complete, the reaction mixture is heated at boil for a further 1 hour. The degree of neutralization of the acid groups is 53.5%. After the polymerization is complete, the reaction mixture is neutralized by adding 155 g of 50% strength aqueous sodium hydroxide solution.
The polymers in Example 2 and Comparative Example 1 were compared in this test. Phosphate inhibition data is based upon using 20 ppm orthophosphate and 150 ppm polymer in the aqueous treatment system.
Phosphate Inhibition Test Protocol
Solution “A”
Using sodium hydrogen phosphate and sodium tetraborate decahydrate, Solution A was prepared containing 20 mg/L of phosphate, and 98 mg/L of borate at a pH of from 8.0-9.5.
Solution “B”
Using calcium chloride dihydrate and ferrous ammonium sulfate, Solution B was prepared containing 400 mg/L of calcium and 4 mg/L of iron at a pH of from 3.5-7.0.
Anti-Scalant Preparation
The total solids or activity for anti-scalant(s) to be evaluated was determined as follows. The weight of anti-scalant necessary to provide a 1.000 g/L (1000 mg/L) solids/active solution was determined using the following formula:
(% solids or activity)/100%=“X”
wherein “X”=decimal solids or decimal activity. (1.000 g/L)/“X”=g/L anti-scalant required to yield a 1000 mg/L anti-scalant solution.
Sample Preparation
Fifty (50) ml of Solution “B” was dispensed into a 125 ml Erlenmeyer flask using a Brinkman dispensette. Using a graduated piper, the correct amount of anti-scalant polymer solution was added to give the desired treatment level (i.e., 1 ml of 1000 mg/L anti-scalant solution=10 mg/L in samples). Fifty (50) ml of Solution “A” was dispensed into the 125 ml Erlenmeyer flask. At least three blanks (samples containing no anti-scalant treatment) were prepared by dispensing 50 ml of Solution “B” and 50 ml of Solution “A” into a 125-ml Erlenmeyer flask. The flasks were then stoppered and placed in a water bath set at 70° C., ±5° C., for 16 to 24 hours.
Sample Evaluation
All of the flasks were removed from the water bath and allowed to cool to touch. A vacuum apparatus was assembled using a 250-ml side-arm Edenmeyer flask, vacuum pump, moisture trap, and Gelman filter holder. The samples were filtered using 0.2-micron filter paper. The filtrate from the 250-ml side-arm Erlenmeyer flask was transferred into an unused 100-ml specimen cup. The samples were evaluated for phosphate inhibition using a HACH DR/3000 Spectrophotometer, following the procedure set forth in the operator's manual.
Calculation of Percent Inhibition for All Samples
The percent inhibition for each treatment level is determined by using the following calculation—
% Phosphate inhibition=(S/T)*100
wherein S=mg/L Phosphate for Sample and T=mg/L Total Phosphate added.
The data indicates that polymers of this invention are superior to those of U.S. Pat. No. 5,227,446 in minimizing scale, especially ortho phosphate scale.
The polymers of Example 2 and Comparative Example 1 were tested in the following autodish formulation below for filming and spotting in an automatic dishwasher using ASTM D3556. The formulation used was—
The test used a mixture of glasses and plastic tumblers. The soil was 80% margarine and 20% dry milk, which was blended and then smeared on to the surface of the glasses. Soil loading was 40 grams per load. Detergent loading was 40 grams per wash. Water hardness was 350 ppm with a Ca to Mg ratio of 2:1. The test used 4% active polymers of Example 1 and Comparative Example 1. Filming and spotting were visually rated on a scale of 1 to 5, with 1 being the worst and 5 being the best. The visual results of the testing after a total of 3 wash cycles are listed in Table 4.
The polymers of Example 2 and Comparative Example 2 were tested for calcium phosphate inhibition according to the inhibition test detailed in Example 9.
The data above indicates that the sulfonated polymers of this invention are far superior to the dicarboxylic-containing sulfonated polymer of the '446 patent.
One-cycle soil anti-redeposition test using the test procedure of Example 5 under the following conditions
Acid Cleaner
Alkaline Cleaner
Automatic Dishwash Powder Formulation
Once prepared, water-soluble polymers are incorporated into a water treatment composition comprising the sulfonated graft copolymer and other water treatment chemicals. Other water treatment chemicals include corrosion inhibitors such as orthophosphates, zinc compounds and tolyl triazole. The level of inventive polymer utilized in water treatment compositions is determined by the treatment level desired for the particular aqueous system treated. Water soluble polymers generally comprise from 10 to 25 percent by weight of the water treatment composition. Conventional water treatment compositions are known to those skilled in the art, and exemplary water treatment compositions are set forth in the four formulations below. These compositions containing the polymer of the present invention have application in, for example, the oil field.
where HEDP is 1-hydroxyethylidene-1,1 diphosphonic acid and TKPP is tri-potassium polyphosphate.
The polymers of Example 4 and a sulfonated synthetic polymer Aquatreat AR 545 (commercially available from Alco Chemical, Chattanooga, Tenn.) were tested for calcium phosphate inhibition according to the inhibition test detailed in Example 9.
Example 1 was repeated with the exception that the 49 g of maltodextrin (Cargill MD™ 01918 maltodextrin, DE 18) was replaced by Sweet Satin maltose 65% (from Cargill).
Example 1 was repeated with the exception that the 49 g of maltodextrin (Cargill MD™ 01918 maltodextrin, DE 18) was replaced by Sweet Satin maltose 65% (from Cargill).
Brine compatibility of a number of polymers were tested in Brine 3, the composition of which is listed in Table 1. The data shown for these compatibility tests are shown below.
The above data indicates that sulfonated graft copolymers produced from maltodextrin are more compatible in brines than those produced from maltose. This is evident by comparing the brine compatibility of Examples 1 and 24, and Examples 4 and 25.
156 g of water, 90 grams of a 50% solution of NaOH, 20 g of Sweet Satin maltose 65% (available from Cargill) and 0.0039 g of ferrous ammonium sulfate hexahydrate (‘FAS’) were heated to 98° C. in a reactor. A mixed solution of 81.6 g of acrylic acid (AA) and 129.2 g of a 50% solution of sodium 2-acrylamido-2-methyl propane sulfonate (AMPS) was added to the reactor over a period of 45 minutes. An initiator solution of 13 g of 35% strength hydrogen peroxide in 78 g of deionized water was simultaneously added to the reactor over a period of 60 minutes. The reaction product was held at 98° C. for an additional hour.
The graft copolymer of this Example with low levels of saccharide functionality (less than 10 weight percent) was tested for brine compatibility in Brine 3. This polymer was found to be insoluble in Brine 3 when dosed at 250, 1,000, 5,000, 25,000 and 100,000 ppm levels.
Although the present invention has been described and illustrated in detail, it is to be understood that the same is by way of illustration and example only, and is not to be taken as a limitation. The spirit and scope of the present invention are to be limited only by the terms of any claims presented hereafter.
The present application is a continuation-in-part of U.S. Ser. No. 11/459,225, filed 21 Jul. 2006.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11459225 | Jul 2006 | US |
| Child | 11780493 | US |
