DEFOAMER EMULSION

Abstract

The present invention relates to a defoamer emulsion, which comprises at least one alkyl ether sulfate or sulfonate, at least one defoamer and water, wherein the alkyl in the alkyl ether sulfate or sulfonate is C.sub.6-C.sub.22 alkyl and the average droplet diameter of the emulsion is less than 300 nm. The present invention also provides a process for producing it, a polycarboxylate ether formulation comprising the defoamer emulsion and a cement composition comprising the polycarboxylate ether formulation. The defoamer emulsion of the present invention possesses high transmittance and excellent stability. The polycarboxylate ether formulation comprising the defoamer emulsion also shows excellent stability. The cement composition comprises the polycarboxylate ether formulation according to the present invention has a low air content.

Claims

1. A defoamer emulsion, comprising at least one alkyl ether sulfate or sulfonate, at least one defoamer, and water, wherein the alkyl in the alkyl ether sulfate or sulfonate is C.sub.6-C.sub.22 alkyl and an average droplet diameter of the emulsion is less than 300 nm.

2. The defoamer emulsion according to claim 1, wherein the alkyl in the alkyl ether sulfate or sulfonate is C.sub.8-C.sub.18 alkyl.

3. The defoamer emulsion according to claim 1, wherein the alkyl ether sulfate or sulfonate is a sulfate or sulfonate of a polyethoxylated alkanol.

4. The defoamer emulsion according to claim 3, wherein the sulfate or sulfonate of the polyethoxylated alkanol has 4 to 80 oxyethylene units.

5. The defoamer emulsion according to claim 1, wherein the defoamer is a water-insoluble defoamer.

6. The defoamer emulsion according to claim 1, wherein the defoamer is selected from the group consisting of a silicon oil, a silicon containing emulsion, a fatty acid, a fatty acid ester, an organic modified polysiloxane, a borate ester, a polyalkoxylate, a polyoxyalkylene copolymer, an acetylenic diol having defoaming properties and a phosphoric ester having a formula P(O)(OR.sub.8).sub.3-x(OR.sub.9).sub.x wherein P represents phosphorus, O represents oxygen, R.sub.8 and R.sub.9, are independently C.sub.2-C.sub.20 alkyl or C.sub.6-C.sub.14 aryl group, and x is 0, 1 or 2, and a mixture thereof.

7. The defoamer emulsion according to claim 1, further comprising at least one additive selected from the group consisting of polyvinylpyrrolidone, diethanol amine, triethanol amine, ethylene glycol, urea, and a carbonate salt, and a mixture thereof.

8. The defoamer emulsion according to claim 7, wherein the at least one additive is used in an amount of from 5 to 15 wt % when the additive is polyvinylpyrrolidone, or in an amount of from 1 to 8 wt % when the additive is selected from the group consisting of diethanol amine, triethanol amine, ethylene glycol, urea, a carbonate salt, and a mixture thereof, based on a total weight of the emulsion.

9. The defoamer emulsion according to claim 7, wherein the at least one additive comprises polyvinyl-pyrrolidone, which has a number average molecular weight ranging from 5,000 to 20,000.

10. The defoamer emulsion according to claim 1, wherein the average droplet diameter of the emulsion is from 80 to 300 nm.

11. The defoamer emulsion according to claim 1, wherein a concentration of the alkyl ether sulfate or sulfonate in the defoamer emulsion is from 5 to 20 wt %.

12. The defoamer emulsion according to claim 1, wherein a weight ratio of the alkyl ether sulfate or sulfonate to the defoamer is from 0.15:1 to 0.8:1.

13. A process for producing the defoamer emulsion according to claim 1, the process comprising a) preparing a mixture comprising the alkyl ether sulfate or sulfonate, the defoamer and water; b) optionally subjecting the mixture to a low shear; and c) shearing the mixture at a shear rate of at least 25,000 s.sup.1, for at least 10 minutes.

14. The process according to claim 13, wherein a) is carried out by dissolving the alkyl ether sulfate or sulfonate in the water to obtain a solution and adding the defoamer to the solution or a) is carried out by adding the alkyl ether sulfate or sulfonate and the defoamer to the water simultaneously.

15. A defoamer emulsion, obtained by the process according to claim 13.

16. A polycarboxylate ether formulation, comprising at least one polycarboxylate ether and the defoamer emulsion according to claim 1.

17. The polycarboxylate ether formulation according to claim 16, wherein the polycarboxylate ether comprising a polycarboxylate moiety and an ether moiety.

18. The polycarboxylate ether formulation according to claim 17, wherein the polycarboxylate moiety is a carbon containing backbone bearing carboxylic acid group and/or an ester and/or a salt thereof, and optional sulfonic acid group and/or a salt thereof.

19. The polycarboxylate ether formulation according to claim 17, wherein a weight ratio between the polycarboxylate moiety and the ether moiety is from 3:7 to 99:1.

20. The polycarboxylate ether formulation according to claim 16, wherein a content of the polycarboxylate ether in the polycarboxylate ether formulation is from 5 to 40 wt % and a content of the defoamer emulsion is from 0.1 to 5 wt %, based on a total weight of the formulation.

21. A process for producing the polycarboxylate ether formulation according to claim 16, the process comprising mixing the defoamer emulsion with the polycarboxylate ether.

22. The process according to claim 21, further comprising: adding at least one additive selected from the group consisting of polyvinylpyrrolidone, diethanol amine, triethanol amine, ethylene glycol, urea, and a carbonate salt.

23. A cement composition, comprising at least one cement and the polycarboxylate ether formulation according to claim 16.

24. The cement composition according to claim 23, wherein the cement is selected from the group consisting of portland cement, masonry cement, alumina cement, refractory cement, magnesia cement, calcium sulfoaluminate cement, oil well cement, and a mixture thereof.

25. The cement composition according to claim 23, wherein the cement composition comprises 0.05 to 1 wt %, of the polycarboxylate ether formulation.

26. A process for producing the cement composition according to claim 23, the process comprising mixing the cement, water, and the polycarboxylate ether formulation.

Description

EXAMPLES

A) Substances Used

[0100] SLES1 (Sodium lauryl ether sulfate, 50 EO, 32 wt % in water);

[0101] SLES2 (Sodium lauryl ether sulfate, 30 EO, 32 wt % in water);

[0102] SLES3 (Sodium lauryl ether sulfate, 12 EO, 30 wt % in water);

[0103] Calfax DB45 (diphenyl oxide disulfonate, 45 wt % in water, DOW);

[0104] SLS (sodium lauryl sulfate, 30 wt % in water);

[0105] AE030 (C13-Oxo alcohol ethoxylate, 30 EO, 70 wt % in water)

[0106] AE040 (C13-Oxo alcohol ethoxylate, 40 EO, 70 wt % in water);

[0107] Defoamer HS-568 (Propoxylated C.sub.7-C.sub.20 alcohol mixture, about 20 PO, 100%, San Nopco);

[0108] POPDMS (Modified silicone, a,w-modified propoxylated polydimethyl siloxane, molar mass of the polydimethyl siloxane=1000 g mol.sup.1, about 35PO, 100%);

[0109] PES (an aqueous polycarboxylate ether solution, 50 wt %, wherein the polycarboxylate ether is a copolymer of polyacrylic acid and allyl polyethylene glycol (weight ratio=3:1), 45 EO, number average molar mass=20,000 g mol.sup.1)

B) Test Method

Light Transmittance

[0110] 0.05 g of defoamer emulsion prepared in the following examples or comparative examples is dispersed in 49.95 g of deionized water. The sample is transferred to the cuvette. The transmittance of the sample is measured with light at 600 nm by using DR/2010 from HACH. The results are shown in table 1.

[0111] To test the stability of the defoamer emulsions, the defoamer emulsions prepared in the following examples and comparative examples are stored over a period of 6 months at room temperature (RT) after preparation. Then, the light transmittances of the resulted defoamer emulsions are tested according to the above procedure. The results are shown in table 1.

Formulation Stability Test

[0112] The polycarboxylate ether formulations prepared below are put in the oven (at 50 C.) and the fridge (at 5 C.) to observe phase separation visibly. The results are shown in table 2.

Air Content Test

[0113] Air content of concrete prepared below is measured according to ASTM C 185(1995) and the results are shown in table 4.

Average Droplet Diameter Test

[0114] The test sample is prepared by adding 0.2 g of the defoamer emulsion obtained in the following examples or comparative examples to 99.8 g deionized water. The average droplet diameter is measured by using the Malvern Nanosizer ZS 90 and is shown in table 1.

Examples 1 to 10 and Comparative Examples 1 to 4

Preparation of the Defoamer Emulsion

Example 1

[0115] 28.125 g of SLES2 is dissolved in 44.875 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 2

[0116] 30 g of SLES3 is dissolved in 43 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 3

[0117] 30 g of SLES1 is dissolved in 43 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 4

[0118] 33.75 g of SLES2 is dissolved in 39.25 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 5

[0119] 42.18 g of SLES2 is dissolved in 30.81 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 6

[0120] The procedure of Example 1 was repeated with the difference that the rough emulsion is subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 10000 rpm (corresponding to shear rate of 30,000 s.sup.1) for 30 minutes.

Example 7

[0121] The procedure of Example 1 was repeated with the difference that the rough emulsion is subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 40000 rpm (corresponding to shear rate of 120,000 s.sup.1) for 30 minutes.

Example 8

[0122] 28.125 g of SLES2 is dissolved in 44.875 g water. Then, 27 g of POPDMS is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 9

[0123] 28.125 g of SLES2 and 27 g of HS-568 are added in 44.875 g deionized water simultaneously and stirred with a propeller at 200 rpm for 10 minutes, which results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 10

[0124] 28.125 g of SLES2 is dissolved in 44.875 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 60 minutes, which then results in a fine emulsion.

Example 11

[0125] 28.125g of SLES2 is dissolved in 44.875 g deionized water. Then, 27 g of HS-568 is added. The mixture is then directly subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Example 12

[0126] 28.125g of SLES2 and 4g of diethanol amine is dissolved in 40.875 g deionized water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes, which then results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes, which then results in a fine emulsion.

Comparative Example 1

[0127] 28.125 g of SLES2 is dissolved in 44.875 g water. Then, 27 g of HS-568 is added and stirred with a propeller at 200 rpm for 10 minutes. No high-shear mixing is applied.

Comparative Example 2

[0128] 10 g of Calfax DB45 and 6.43 g of AE040 are dissolved in 56.57 g water. Then, 27 g of HS568 is added and stirred with a propeller at 200 rpm for 10 minutes. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes.

Comparative Example 3

[0129] 10.0 g of SLS and 8.57 g of AE030 are dissolved in 54.43 g water. Then, 27g of HS568 is added and stirred with a propeller at 200 rpm for 10 minutes. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes

Comparative Example 4

[0130] 27 g of Disponil HS568 is added in 64 g water and stirred with a propeller at 200 rpm for 10 minutes, which results in a rough emulsion. The rough emulsion is then subjected to an IKA Ultra-Turrax high-speed homogenizer with a S50B-G45G dispersing head and a T65 control unit at 20000 rpm (corresponding to shear rate of 60,000 s.sup.1) for 30 minutes.

[0131] The properties of the defoamer emulsions obtained in examples 1 to 10 and comparative 1 to 4 are shown in the following table 1.

TABLE-US-00001 TABLE 1 Transmittance Defoamer average after 6 months emulsion droplet Example No. Transmittance storage at RT stability diameter Example 1 82% 78% + + 120 nm Example 2 83% 79% + + 125 nm Example 3 81% 78% + + 116 nm Example 4 82% 79% + + 119 nm Example 5 82% 77% + 120 nm Example 6 75% 67% + 250 nm Example 7 95% 90% + 95 nm Example 8 85% 82% + + 118 nm Example 9 82% 78% + + 120 nm Example 10 90% 88% + + 101 nm Example 11 82% 78% + + 120 nm Example 12 82% 78% + + 118 nm Comparative 23% Not 1000 nm example 1 measurable Comparative 52% Not 720 nm example 2 measurable Comparative 51% Not 732 nm example 3 measurable Comparative 20% Not 1134 nm example 4 measurable + +: transmittance % decreases less than 5% after the defoamer emulsion is stored over a period of 6 months at room temperature. +: transmittance % decreases by 5-15% after the defoamer emulsion is stored over a period of 6 months at room temperature. : complete phase separation after ~5 days storage at room temperature

Preparation of the Polycarboxylate Ether Formulations

[0132] The PES (aqueous polycarboxylate ether solution, 50 wt %) is diluted to 25 wt % with deionized water. Each defoamer emulsion (0.6 g) prepared in above examples 1 to 10 and comparative examples 1 to 4 is then added to 99.4 g of the diluted aqueous polycarboxylate ether solution and mixed well using a hot plate at room temperature with stirring rate of 100 rpm to obtain the polycarboxylate ether formulation.

[0133] The properties of the polycarboxylate ether formulations are shown in the following table 2.

TABLE-US-00002 TABLE 2 The defoamer emulsion in Formulation Formulation Formulation the Formulation stability stability stability from Example No. at 50 C. at 25 C. at 5 C. Example 1 >6 months >6 months >6 months Example 2 >6 months >6 months >6 months Example 3 >6 months >6 months ~4 months Example 4 >6 months >6 months >6 months Example 5 >6 months >6 months >6 months Example 6 ~3 months ~3 months ~3 months Example 7 >6 months >6 months >6 months Example 8 >6 months >6 months ~2 months Example 9 >6 months >6 months >6 months Example 10 >6 months >6 months >6 months Example 11 >6 months >6 months ~6 months Example 12 >6 months >6 months >10 months Comparative Separation Separation Separation example 1 within 2 days within 2 days within 2 days Comparative Separation Separation Separation example 2 within 5 days within 8 days within 10 days Comparative Separation Separation Separation example 3 within 5 days within 7 days within 10 days Comparative Separation Separation Separation example 4 within 2 days within 2 days within 2 days

Preparation of the Concrete

[0134] Each polycarboxylate ether formulation prepared above (0.042 kg) is mixed with the ingredients shown in table 3 to prepare the concrete.

TABLE-US-00003 TABLE 3 Component Amount/kg Cement (Hailuo cement 425) 4.20 Sand 8.40 Stone (diameter from 5 mm to 15 mm) 9.20 water 1.70

[0135] Air contents in concretes prepared above are shown in the following table 4.

TABLE-US-00004 TABLE 4 The defoamer emulsion in the Formulation from Example No. Air content in concrete Example 1 1.0% Example 2 0.9% Example 3 1.0% Example 4 1.6% Example 5 2.2% Example 6 1.0% Example 7 1.0% Example 8 2.5% Example 9 1.0% Example 10 1.0% Example 11 1.0% Example 12 1.0% Comparative example 1 1.0% Comparative example 2 1.0% Comparative example 3 1.1% Comparative example 4 1.0%