Defoamer oil compound, production method therefor, and defoamer composition

Abstract

The present invention relates to a defoamer oil compound that contains an organopolysiloxane (A), a fine silica powder (B), and a group (C) that is represented by the organopolysiloxanes of formulas (I) and/or (II) ##STR00001##
(in the formulas, c, d, and e are each an integer of 0 or more, and at least one of X.sup.1 to X.sup.3 is the group represented by formula (i)). The component (C) is used as a surface treatment agent for the component (B). The present invention makes it possible to obtain a silicone-based defoamer composition that imparts good initial defoaming properties even in an alkaline foaming liquid, that exhibits very little loss in performance over time, and that has excellent defoaming performance.

Claims

1. An oil compound for a defoamer, comprising: (A) 100 parts by weight of an inherently hydrophobic organopolysiloxane having a viscosity at 25 C. of from 10 to 100,000 mm.sup.2/s, (B) from 1 to 30 parts by weight of a fine silica powder having a specific surface area of at least 50 m.sup.2/g, and (C) from 0.001 to 5 parts by weight of an organopolysiloxane of general formula (I) and/or (II) below ##STR00022## (wherein X is an organic group selected from R.sup.1 and YO; Y is an organic group represented by SiR.sup.1.sub.3-a(OR.sup.2).sub.a; R.sup.1 and R.sup.2are methyl; a is 2 or 3; and m is an integer of 2 or more) ##STR00023## [wherein each R.sup.1 is as defined above, X.sup.1 and X.sup.2 are each independently R.sup.1 or a group of formula (i) below ##STR00024## (wherein R.sup.1 and R.sup.2 are as defined above; a is 2 to 3;and b is an integer of 2 or more), each Y is independently a group of formula (ii) below ##STR00025## (wherein R.sup.1 and X.sup.2 are as defined above, X.sup.3 is the same as X.sup.1, and f is an integer of 0 or more), and c, d and e are each integers of 0 or more, with the proviso that at least one of X.sup.1 to X.sup.3 is a group of formula (i)], wherein component (C) serves as a surface treatment agent for component (B).

2. A defoamer composition characterized by comprising the oil compound of claim 1.

3. The defoamer composition of claim 2 which is a solution type composition.

4. The defoamer composition of claim 3, comprising: 5 to 80 wt% of the oil compound; and a solvent.

5. The defoamer composition of claim 2 which is a self-emulsifying composition comprising the oil compound together with a polyoxyalkylene group-modified organopolysiloxane.

6. The defoamer composition of claim 5, comprising: 5 to 80 wt% of the oil compound; and 20 to 95 wt% of a polyoxyalkylene group-modified organopolysiloxane having a following general formula (III):
R.sup.4.sub.2R.sup.6SiO(R.sup.4.sub.2SiO).sub.0(R.sup.4R.sup.5SiO).sub.pSiR.sup.4.sub.2R.sup.6 (III) wherein each R.sup.4 is the same or different, unsubstituted or substituted monovalent hydrocarbon group of 1 to 18 carbon atoms, R.sup.5 is a polyoxyalkylene group of the following general formula (IV):
R.sup.7O(CH.sub.2CH.sub.2O).sub.q(CH.sub.2(CH.sub.3)CHO).sup.rR.sup.8 (IV) wherein R.sup.7 is a divalent hydrocarbon group of 2 to 6 carbon atoms, R.sup.8 is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an acetyl group or an isocyanate group, q and r are positive numbers wherein the degree of polymerization (q+r) satisfies the conditions 3q+r 80 and q/r =2/8 to 8/2, R.sup.6 is a hydroxyl group, an alkoxy group of 1 to 6 carbon atoms, or a group similar to R.sup.4 or R.sup.5, o is an integer from 5 to 200, and p is an integer from 1 to 30.

7. The defoamer composition of claim 2 which is an emulsion type composition.

8. The defoamer composition of claim 7, comprising: 5 to 50 wt% of the oil compound; and an emulsifying agent selected from the group consisting of polyoxyalkylene group-modified organopolysiloxane, polyoxyalkylene polymer, and nonionic surfactant or a mixture of two or more of said emulsifying agents; and water.

9. The defoamer composition of any one of claims 2, 3, 5, or 7 which is for an alkaline foaming liquid.

10. The oil compound of claim 1, wherein component (A) is a linear or branched organopolysiloxane having average compositional formula (II):
R.sup.3.sub.gSiO.sub.(4-g)/2 (II) wherein each R.sup.3 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 18 carbon atoms, wherein each R.sup.3 may be the same or different, and g is a positive number between 1.9g 2.2.

Description

EXAMPLES

(1) Examples and Comparative Examples are given below to more concretely illustrate the invention, although the invention is not limited by these Examples. In the following Examples, the viscosity is a value measured at 25 C. with an Ostwald viscometer, and the average degree of polymerization is a value determined as the polystyrene-equivalent number-average degree of polymerization in gel permeation chromatographic (GPC) analysis. In the formulas below, Me stands for a methyl group and OMe stands for a methoxy group.

Example 1

(2) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 10,000 mm.sup.2/s, 5 parts by weight of AEROSIL 300 (from Nippon Aerosil Co., Ltd.; specific surface area, 300 m.sup.2/g) as a fine silica powder, 0.3 part by weight of a terminal trialkoxy-modified organopolysiloxane (in formula (I), R.sup.1 and R.sup.2 are CH.sub.3, X is YO, Y is Si(OR.sup.2).sub.3, and m is 10) as a silica surface treatment agent, and 0.3 part by weight of water. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 2 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. Next, the kneaded material was raised to a temperature of 150 C., then held at that level and kneaded for a total of 4 hours after raising the temperature. The material was cooled to not more than 100 C., then neutralized by adding succinic acid and kneading for 3 hours, giving Silicone Oil Compound (a-1).

(3) Self-Emulsifying Defoamer Composition (A) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (a-1): 70 parts by weight of Polyoxyalkylene-Modified Organosiloxane (a-2) having an average composition expressed by the formula
R.sup.4.sub.2R.sup.6SiO(R.sup.4.sub.2SiO).sub.x(R.sup.4R.sup.5SiO).sub.ySiR.sup.4.sub.2R.sup.6
(wherein R.sup.1 and R.sup.6 are CH.sub.3, R.sup.5 is C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.21(C.sub.3H.sub.6O).sub.21CH.sub.3, x is 135 and y is 15) and a viscosity of 2,500 mm.sup.2/s.

Example 2

(4) Emulsion-Type Defoamer Composition (B) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (a-1) in Example 1, 4 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 70 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

Example 3

(5) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 8,000 mm.sup.2/s, 12 parts by weight of AEROSIL 200 (from Nippon Aerosil Co., Ltd.; specific surface area, 200 m.sup.2/g) as a fine silica powder, and 0.72 part by weight of a terminal trialkoxy-modified organopolysiloxane (in formula (I), R.sup.1 and R.sup.2 are CH.sub.3, X is R.sup.1, Y is Si(OR.sup.2).sub.3, and m is 30) as a silica surface treatment agent. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 3 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. The kneaded material was raised to a temperature of 150 C. and kneaded for 2 hours at 150 C. The material was cooled to not more than 100 C., then neutralized by adding succinic acid and kneading for 3 hours, giving Silicone Oil Compound (c-1).

(6) Self-Emulsifying Defoamer Composition (C) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (c-1): 50 parts by weight of Polyoxyalkylene-Modified Organosiloxane (c-2) having an average composition expressed by the formula
R.sup.4.sub.2R.sup.6SiO(R.sup.4.sub.2SiO).sub.x(R.sup.4R.sup.5SiO).sub.ySiR.sup.4.sub.2R.sup.6
(wherein R.sup.4 and R.sup.6 are CH.sub.3, R.sup.5 is C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.25.5(C.sub.3H.sub.6O).sub.8.5C.sub.4H.sub.9, x is 30 and y is 5) and a viscosity of 1,000 mm.sup.2/s, and 20 parts by weight of Polyoxyalkylene Polymer (c-3) having an average composition expressed by the formula below.
HO(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.35H

Example 4

(7) Emulsion-Type Defoamer Composition (D) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (c-1) in Example 3, 6 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 68 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

Example 5

(8) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 10,000 mm.sup.2/s, 5 parts by weight of AEROSIL 300 (from Nippon Aerosil Co., Ltd.; specific surface area, 300 m.sup.2/g) as a fine silica powder, 0.3 part by weight of a terminal trialkoxy-modified organopolysiloxane (in formula (I), R.sup.1 and R.sup.2 are CH.sub.3, X is R.sup.1, Y is SiR(OR.sup.2).sub.2, and m is 30) as a silica surface treatment agent, and 0.3 part by weight of water. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 3 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. Next, the kneaded material was raised to a temperature of 150 C. and kneaded for 2 hours at 150 C. The material was cooled to not more than 100 C., then neutralized by adding succinic acid and kneading for 3 hours, giving Silicone Oil Compound (e-1).

(9) Self-Emulsifying Defoamer Composition (E) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (e-1): 70 parts by weight of Polyoxyalkylene-Modified Organosiloxane (e-2) having an average composition expressed by the formula
R.sup.4.sub.2R.sup.6SiO(R.sup.4.sub.2SiO).sub.x(R.sup.4R.sup.5SiO).sub.ySiR.sup.4.sub.2R.sup.6
(wherein R.sup.4 and R.sup.6 are CH.sub.3, R.sup.5 is C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.21 (C.sub.3H.sub.6O).sub.21CH.sub.3, x is 135 and y is 15) and a viscosity of 2,500 mm.sup.2/s.

Example 6

(10) Emulsion-Type Defoamer Composition (F) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (e-1) in Example 5, 4 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 70 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

(11) The following were kneaded using a planetary mixer for 3 hours at 150 C. and under a nitrogen gas atmosphere: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 10,000 mm.sup.2/s, 5 parts by weight of AEROSIL 300 (from Nippon Aerosil Co., Ltd.; specific surface area, 300 m.sup.2/g) as a fine silica powder, and 2 parts by weight of, as an alkaline catalyst, potassium siliconate containing 3 wt % of potassium hydroxide. The system was cooled to not more than 100 C. and neutralized with succinic acid, giving Silicone Oil Compound (g-1).

(12) Self-Emulsifying Defoamer Composition (G) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (g-1): 70 parts by weight of Polyoxyalkylene-Modified Organosiloxane (g-2) having an average composition expressed by the formula
R.sup.4.sub.2R.sup.6SiO(R.sup.4.sub.2SiO).sub.x(R.sup.4R.sup.5SiO).sub.ySiR.sup.4.sub.2R.sup.6
(wherein R.sup.4 and R.sup.6 are CH.sub.3, R.sup.5 is C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.21 (C.sub.3H.sub.6O).sub.21CH.sub.3, x is 135 and y is 15) and a viscosity of 2,500 mm.sup.2/s.

Comparative Example 2

(13) Emulsion-Type Defoamer Composition (H) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (g-1) in Comparative Example 1, 4 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 68 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

(14) Defoamer Compositions (A) to (H) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are presented in Table 1.

(15) [Evaluation Methods]

(16) A 100 mL glass bottle was charged with 50 g of softwood sulfite waste liquor adjusted to a nonvolatiles content of 8 wt %, and this was pre-heated at 80 C.

(17) Defoaming Ability (Initial):

(18) The defoamer composition was added in an amount corresponding to 0.1 wt % of the active ingredient (silicone oil compound) to the test liquid preheated at 80 C., following which the bottle was shaken for 30 seconds on a shaker to induce foaming, and the defoaming ability was evaluated by measuring the foam height (liquid level+foam) and the time until foam knockdown.

(19) Defoaming Ability (Persistence):

(20) The mixtures obtained by adding various defoamer compositions in amounts corresponding to 0.1 wt % of the active ingredient (silicone oil compound) to the above sulfite waste liquor were stored at 80 C., following which these were shaken for 30 seconds on a shaker at predetermined times (after 30 minutes and after 120 minutes) to induce foaming, and the defoaming ability was evaluated by measuring the foam height (liquid level+foam) and the time until foam knockdown.

(21) TABLE-US-00001 TABLE 1 Immediately After 30 minutes After 120 minutes Volume Time Volume Time Volume Time after until after until after until Defoamer shaking knockdown shaking knockdown shaking knockdown composition (mL) (seconds) (mL) (seconds) (mL) (seconds) Working (A) 65 4 65 6 70 15 Example 1 Working (B) 60 3 60 5 65 12 Example 2 Working (C) 60 4 65 5 70 18 Example 3 Working (D) 60 3 60 4 65 14 Example 4 Working (E) 65 3 65 12 70 24 Example 5 Working (F) 60 2 60 10 65 20 Example 6 Comparative (G) 65 4 80 45 85 65 Example 1 Comparative (H) 60 4 70 25 75 45 Example 2

Example 7

(22) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 10,000 mm.sup.2/s, 5 parts by weight of AEROSIL 300 (from Nippon Aerosil Co., Ltd.; BET specific surface area, 300 m.sup.2/g) as a fine silica powder, 0.3 part by weight of a dimethylpolysiloxane which is trimethoxy-modified at both ends and has the formula

(23) ##STR00016##
as a silica surface treatment agent, and 0.3 part by weight of water. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 2 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. Next, the kneaded material was raised to a temperature of 150 C., then held at that level and kneaded for a total of 4 hours after raising the temperature. The material was cooled to not more than 100 C., then neutralized by adding 0.1 part by weight of succinic acid and kneading for 3 hours, giving Silicone Oil Compound (a-1).

(24) Self-Emulsifying Defoamer Composition (I) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (a-1): 70 parts by weight of Polyoxyalkylene-Modified Methylpolysiloxane (a-2) having an average composition expressed by the formula

(25) ##STR00017##
and a viscosity of 2,500 mm.sup.2/s.

Example 8

(26) Emulsion-Type Defoamer Composition (J) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (a-1) from Example 7, 4 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 70 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

Example 9

(27) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 8,000 mm.sup.2/s, 12 parts by weight of AEROSIL 200 (from Nippon Aerosil Co., Ltd.; BET specific surface area, 200 m.sup.2/g) as a fine silica powder, and 0.72 part by weight of a dimethylpolysiloxane that is trimethoxy-modified at both ends and has the formula

(28) ##STR00018##
as a silica surface treatment agent. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 3 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. Next, the kneaded material was raised to a temperature of 150 C. and kneaded for 2 hours at 150 C. The material was cooled to not more than 100 C., then neutralized by adding 0.15 part by weight of succinic acid and kneading for 3 hours, giving Silicone Oil Compound (c-1).

(29) Self-Emulsifying Defoamer Composition (K) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (c-1): 50 parts by weight of Polyoxyalkylene-Modified Methylpolysiloxane (c-2) having an average composition expressed by the formula

(30) ##STR00019##
and a viscosity of 1,000 mm.sup.2/s, and 20 parts by weight of Polyoxyalkylene Polymer (c-3) having an average composition expressed by the formula below.
HO(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.35H

Example 10

(31) Emulsion-Type Defoamer Composition (L) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (c-1) from Example 9, 6 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 68 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

Example 11

(32) The following were kneaded for one hour using a planetary mixer: 100 parts by weight of, as an inherently hydrophobic organopolysiloxane, a dimethylpolysiloxane capped at both ends of the molecular chain with trimethylsilyl groups and having a viscosity of 10,000 mm.sup.2/s, 5 parts by weight of AEROSIL 300 (from Nippon Aerosil Co., Ltd.; BET specific surface area, 300 m.sup.2/g) as a fine silica powder, 0.3 part by weight of pendant trimethoxy-modified methylpolysiloxane of the formula

(33) ##STR00020##
as a silica surface treatment agent, and 0.3 part by weight of water. The temperature was then raised to 150 C. and kneading was continued for 2 hours. The system was cooled to not more than 100 C., following which 3 parts by weight of potassium siliconate containing 3 wt % of potassium hydroxide was added as an alkaline catalyst and the mixture was kneaded for 0.1 hour at not more than 100 C. Next, the kneaded material was raised to a temperature of 150 C. and kneaded for 2 hours at 150 C. The material was cooled to not more than 100 C., then neutralized by adding 0.15 part by weight of succinic acid and kneading for 3 hours, giving Silicone Oil Compound (e-1).

(34) Self-Emulsifying Defoamer Composition (M) was prepared by mixing the following at room temperature into 30 parts by weight of this Silicone Oil Compound (e-1): 70 parts by weight of Polyoxyalkylene-Modified Methylpolysiloxane (e-2) having an average composition expressed by the formula

(35) ##STR00021##
and a viscosity of 2,500 mm.sup.2/s.

Example 12

(36) Emulsion-Type Defoamer Composition (N) was prepared by heating and dissolving a mixture of 20 parts by weight of Silicone Oil Compound (e-1) from Example 11, 4 parts by weight of sorbitan monostearate and 6 parts by weight of polyoxyethylene (55) monostearate, subsequently adding 70 parts by weight of water, and stirring and emulsifying with a homogenizing mixer.

(37) Defoamer Compositions (I) to (N) obtained in Examples 7 to 12 were evaluated by the methods described above. The results are shown in Table 2. For the sake of reference, the results for Comparative Examples 1 and 2 also are presented in Table 2.

(38) TABLE-US-00002 TABLE 2 Immediately After 30 minutes After 120 minutes Volume Time Volume Time Volume Time after until after until after until Defoamer shaking knockdown shaking knockdown shaking knockdown composition (mL) (seconds) (mL) (seconds) (mL) (seconds ) Working (I) 65 4 65 5.5 70 14.5 Example 7 Working (J) 60 3 60 5 65 11 Example 8 Working (K) 60 4 65 5 70 16 Example 9 Working (L) 60 3 60 4 65 12 Example 10 Working (M) 65 3 65 11 70 22 Example 11 Working (N) 60 2 60 9.5 65 18.5 Example 12 Comparative (G) 65 4 80 45 85 65 Example 1 Comparative (H) 60 4 70 25 75 45 Example 2