ORGANOPOLYSILOXANES, COMPOSITIONS AND POWDER FORMULATIONS CONTAINING THE SAME AND USES THEREOF AS A DEFOAMER

Abstract

The present disclosure relates to organopolysiloxanes, compositions and powder formulations containing the same and uses thereof as a defoamer. The organopolysiloxane contains at least 50 mol % of trifunctional siloxane units and at least one trifunctional siloxane unit has a polyether group. The composition and powder formulation containing the same have excellent anti-foaming and defoaming performances, and can be used as a defoamer in cement-based materials or coatings.

Claims

1-17. (canceled)

18. An organopolysiloxane, containing at least 50 mol % of trifunctional siloxane units and at least one trifunctional siloxane unit having a polyether group, selected from (i) polysiloxane containing units of formula (I) ##STR00026## where R.sup.1 is independently at each occurrence a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.2 is independently at each occurrence hydrogen or a monovalent, optionally substituted hydrocarbon radical, R.sup.3 is independently at each occurrence a radical of formula OR.sub.a(OR.sub.b).sub.jOR.sub.e wherein R.sub.a is a divalent, optionally substituted hydrocarbon radical, R.sub.b is independently at each occurrence a divalent, optionally substituted hydrocarbon radical, R.sub.e is hydrogen, a monovalent organic radical or has a structure fragment of ##STR00027## wherein R* is independently at each occurrence R.sup.1, OR.sup.2 or O, j is an integer of from 1 to 200, a is 0, 1, 2 or 3, b is 0, 1,2or 3,and c is 0, 1 or 2, with the proviso that at least 50 mol % of all of the units of formula (I) a is 1 and the sum b+c is 0, 1 or 2, of which at least 1 unit c is different from 0; or (ii) polysiloxane containing units of formula (II) ##STR00028## where R.sup.1 is independently at each occurrence a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.3 is independently at each occurrence a radical of formula R.sub.a(OR.sub.b)jOR.sub.c wherein R.sub.a is a divalent, optionally substituted hydrocarbon radical, R.sub.b is independently at each occurrence a divalent, optionally substituted hydrocarbon radical, R.sub.c is hydrogen, a monovalent organic radical or has a structure fragment of ##STR00029## wherein R* is independently at each occurrence R.sup.1 or O and r is an integer of from 1 to 6, j is an integer of from 1 to 200, d is 0or 1,and e is 0 or 1, with the proviso that at least 50 mol % of all of the units of formula (II) the sum d+e is 1, of which at least 1 unit e is different from 0.

19. The organopolysiloxane of claim 18, wherein the radical R.sup.3 is of formula (III) ##STR00030## where x is an integer of from 1 to 10, m is an integer of from 0 to 200, n is an integer of from 0 to 200, the sum m+n is an integer of from 1 to 200, R.sub.c is hydrogen, a C.sub.1C.sub.30 alkyl, a C.sub.1C.sub.30 alkenyl, a radical of C(O)R.sub.a wherein R.sub.d is a C.sub.1C.sub.20 alkyl or has a structure fragment of ##STR00031## wherein R* is independently at each occurrence a C.sub.1C.sub.18alkyl, a C.sub.6 C.sub.9 aryl, hydroxyl, a C.sub.1C.sub.4 alkoxy or O, and the units (OC.sub.2H.sub.4) and (OC.sub.3H.sub.6) may be present in random distribution or else as blocks in the radical of formula (III); the radical R.sup.3 is of formula (V) ##STR00032## where x is an integer of from 1 to 10, m is an integer of from 0 to 200, n is an integer of from 0 to 200, the sum m+n is an integer of from 1 to 200, R.sub.c is hydrogen, a CC.sub.30 alkyl, a C.sub.1C.sub.30 alkenyl or a radical of C(O)R.sub.d wherein R.sub.a is a C.sub.1-C.sub.20 alkyl, or has a structure fragment of ##STR00033## wherein R* is independently at each occurrence a C.sub.1-C.sub.18 alkyl, a C.sub.6-C.sub.9 aryl or O and r is an integer of from 1 to 6; and the units (OC.sub.2H.sub.4) and (OC.sub.3H.sub.6) may be present in random distribution or else as blocks in the radical of formula (V).

20. The organopolysiloxane of claim 19, characterized by formula (III) where x is 3, m is 0 and n is an integer of from 5 to 100; or formula (V) where x is 3, m is 0 and n is an integer of from 5 to 100.

21. The organopolysiloxane of claim 18, characterized by a R.sup.3 or R.sup.3 content of from 5 wt % to 95 wt % based on the total weight of the organopolysiloxane.

22. The organopolysiloxane of claim 18, wherein the organopolysiloxane (i) is of formula (R.sup.1SiO.sub.3/2)x (R.sup.1(R.sup.2O)SiO.sub.2/2)y (R.sup.1R.sup.3SiO.sub.2i2)z (R.sup.1(R.sup.2O)R.sup.3SiO.sub.1/2).sub.t (R.sup.1(R.sup.2O).sub.2SiO.sub.1/2).sub.w (IV) where the sum of z+t is greater than 0.

23. The organopolysiloxane of claim 22, wherein the x units (R.sup.1SiO.sub.3/2) are in an amount of from 10 mol % to 60 mol %, the sum of y units (R.sup.1(R.sup.2O)SiO.sub.2i2) and z units (RiR.sup.3SiO.sub.2/2) are in an amount of from 20 mol % to 70 mol %, and the sum of t units (R.sup.1(R.sup.2O)R.sup.3SiOi/.sub.2) and w units (Ri(R.sup.2O).sub.2SiOi/.sub.2) are in an amount of from 5 mol % to 30 mol %, based on the total number of moles of the siloxane units.

24. The organopolysiloxane of claim 18, wherein the organopolysiloxane (i) is derived from reaction of a mixture comprising a polysiloxane containing units of formula (VI) ##STR00034## where R.sup.1 is independently at each occurrence a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.2 is independently at each occurrence hydrogen or a monovalent, optionally substituted hydrocarbon radical, f is 0 or 1, and g is 0, 1,2or 3, with the proviso that at least 50 mol % of all of the units of formula (VI) f is 1, of which at least 1 unit g is different from 0; and a polyether compound of formula (VII) ##STR00035## where R.sup.4 is hydrogen or a monovalent organic radical, R.sup.5 is hydrogen or a C.sub.1-C.sub.3 alkyl, R.sup.6 is independently at each occurrence a divalent, optionally substituted hydrocarbon radical, k is an integer of from 1 to 200.

25. A composition comprising: (a) at least one organopolysiloxane of claim 18, and (b) at least one additive selected from (b1) filler particles and/or (b2) organopolysiloxane resins comprising units of formula (X) ##STR00036## where R.sup.7 is independently at each occurrence hydrogen or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R.sup.8 is independently at each occurrence hydrogen or a monovalent, optionally substituted hydrocarbon radical, u is 0, 1,2or 3 and v is 0, 1, 2 or 3, with the proviso that the sum u+v?3 and in less than 50 mol % of all of the units of formula (X) in the organopolysiloxane resin the sum u+v is 2.

26. The composition of claim 25, further comprising (c) a polyether compound of formula (XI) ##STR00037## where R.sup.9 is independently at each occurrence hydrogen or a monovalent organic radical, R.sup.10 is independently at each occurrence a divalent, optionally substituted hydrocarbon radical, k is an integer of from 1 to 200.

27. The composition of claim 26, characterized in that component (c) is a compound of formula ##STR00038## where R.sup.9 is independently at each occurrence hydrogen, a C.sub.1-C.sub.30 alkyl, a C.sub.1-C.sub.30 alkenyl or a radical of C(O)R.sub.a wherein R.sub.d is a C.sub.1-C.sub.2o alkyl, s is an integer of from 0 to 200, t is an integer of from 0 to 200, the sum s+t is an integer of from 10 to 200, and the units (OC.sub.2H.sub.4) and (OC.sub.3H.sub.6) may be present in random distribution or else as blocks in the polymer of formula (XII).

28. The composition of claim 27, characterized by formula (XII) where s is 0 and t is an integer of from 20 to 200.

29. The composition of claim 26, wherein a mass ratio of component (a) to component (c) is 1:(0.1-100).

30. The composition of claim 25, wherein a mass ratio of component (a) to component (b) is (5-30): 1.

31. The composition of claim 25, comprising (a) 0.1 wt % to 90 wt % of at least one organopolysiloxane, (d) 0.01 wt % to 5 wt % of at least one additive, (c) 5 wt % to 98 wt % of at least one polyether, and optionally (d) 0 wt % to 50 wt % of at least one hydrocarbon oil.

32. A powder formulation, comprising the composition of claim 25 and a solid carrier.

33. The powder formulation of claim 32, wherein a mass ratio of the composition to the solid carrier is 2: (1-15).

34. Use of the composition of claim 25 as a defoamer in cement-based materials or coatings.

35. Use of the powder formulation of claim 32 as a defoamer in cement-based materials or coatings.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0147] The present invention is further illustrated by the following examples, but is not limited to the scope thereof. Any experimental methods with no conditions specified in the following examples are selected according to the conventional methods and conditions, or product specifications.

[0148] Characterization of molecular structure The structure of resins was analyzed by .sup.1H NMR and.sup.29Si NMR using Bruker Avance Ill HD 400 spectrometer equipped with a 5 mm BBO probe head.

[0149] Characterization of molecular weight and distribution thereof

[0150] The molecular weight and its distribution of resins was analyzed by PSS SECcurity gel permeation chromatography using toluene as a solvent and PLgel 5 ?m MiniMIX-C columns from Agilent at an oven temperature of 45? C.

[0151] Evaluation of anti-foaming/defoaming effects

[0152] Preparation of foaming liquid: 8 g of sodium allyl sulfonate was dissolved in 192 mL of water and mixed well to give a 200 mL of foaming liquid.

[0153] In each case, the defoamer composition was added to 200 mL of foaming liquid as prepared in an amount specified in Table 2 and 4, then was subjected to stirring at 1000 rpm for 1 min by a double-rod stirrer. The initial foam height and the change of foam height with time were recorded by a light sensor, thus a foam height-time curve was collected. The initial foam height reflects the anti-foaming property of the composition. And the lower the initial height, the better the anti-foaming performance. The integrated area bounded by the height-time curve, height-axis and time-axis, i.e. the integrated area of the curve from the initial height to the height of zero (more accurately the minimum value of foam height that the light sensor could detect, generally a value extremely close to zero), is called AKZ (activity value). The AKZ comprehensively reflects the anti-foaming property and defoaming speed of the composition. And the smaller the AKZ value, the better the overall anti-foaming/defoaming performance.

[0154] Determination of Air Content

[0155] It was carried out according to standard JC/T 601-2009 Methods for determining air content in cement mortar.

[0156] Determination of Fluidity

[0157] It was carried out according to standard GB/T 2419-2005 Test method for fluidity of cement mortar.

[0158] Details of the raw materials used in the Examples and Comparative Examples were as follows.

[0159] A2:polyether-modified silicone oil, with a formula of P030((CH3).sub.2SiO.sub.2/2)1.sub.5-PO30 determined by.sup.29Si NMR where P030 represents a polyether group having 30 propoxy radicals, and a polyether content of 76 wt % determined by .sup.1H NMR.

[0160] A3: alkoxy-T resin, consisting essentially of CH.sub.3SiO.sub.3/2, C.sub.2H.sub.5O (CH3)SiO.sub.2/2 and (C.sub.2H.sub.5O).sub.2(CH3)SiO.sub.12 units, having 30.5 mol % of CH.sub.3SiO.sub.3/2 units, 46.3 mol % of C.sub.2H.sub.5O (CH3)SiO.sub.2/2 units and 20.3 mol % of (C.sub.2H.sub.5O).sub.2(CH3)Si.sub.12units determined by.sup.29Si NMR.

[0161] B1: fumed silica, trade name HDK? H.sub.2000, provided by Wacker Chemie AG.

[0162] B2: fumed silica, trade name HDK? H.sub.15, provided by Wacker Chemie AG.

[0163] C1: hydroxy-terminated polypropylene glycol, trade name PPG 2000, commercially available.

[0164] C2: hydroxy-terminated polypropylene glycol, trade name PPG 1000, commercially available.

[0165] C3: hydroxy-terminated polypropylene glycol, trade name PPG 350, commercially available.

[0166] D1: hydrotreated light distillates (petroleum), commercially available.

[0167] F1: silica fume: implementation standard GB/T27690-2011, commercially available.

[0168] F2: precipitated silica, trade name Evonik sipernat? 22, provided by Evonik.

[0169] Cement (42.5 grade): benchmark cement for concrete admixture inspection, implementation standard GB8076-2008, commercially available.

[0170] Sand: ISO standard sand, implementation standard GB/T1761-1999, commercially available.

[0171] Redispersible polymer powder: trade name VINNAPAS? 5010 N, provided by Wacker Chemie AG.

[0172] Cellulose ether: trade name Tylose? MH 10007P4, provided by Shin-Etsu.

[0173] Water reducer: trade name MELMENT? F10, provided by BASF.

[0174] Synthesis Example 1 Polyether-T resin

[0175] Alkoxy-T resin A3 and polypropylene glycol C1 were mixed with an effective amount of acid activated clay catalyst and a very small amount of water. The mass ratio of alkoxy-T resin A3 to polypropylene glycol C1 was controlled at (1-3):1 and that for alkoxy-T resin A3 to water was controlled at (4x103-6x103):1. The resulting mixture was heated up to 80-100? C. and stirred at 80-100? C. for 50-80 min for condensation. Then vacuum (100-300 mbar) was applied to distill off distillate (mainly ethanol) at 80-100? C. After the vacuum step, the mixture continued to be stirred for 20-40 min at 80-100? C. Afterwards an appropriate amount of sodium carbonate and water were added and mixed well under stirring at 80-100? C. for 50-80 min. Vacuum (100 200 mbar) was continued until the distillate flux decreased. Then the resulting mixture was cooled down, followed by filtering off solids.

[0176] The resulting reaction product was determined to have a polyether content of 31.63 mol % (equal to 33.00 wt % calculated by weight) by .sup.1H NMR. Compared with the .sup.1H NMR result of the raw material polypropylene glycol C.sub.1, it was found that about 74.56 mol % of hydroxyl from polypropylene glycol C.sub.1 reacted with alkoxy-T resin A3, indicating that most of the charged polypropylene glycol C.sub.1 took part in the condensation reaction and was bonded to alkoxy-T resin A3 via SiO bonds, and part of the polypropylene glycol C.sub.1 was condensed through hydroxyl radicals at one end only, and part was condensed through hydroxyl radicals at both ends. Hereinafter, polyether-T resin A1 was used to refer to this reaction product.

[0177] The polyether-T resin A1 was determined to have a formula of (CH.sub.3SiO.sub.3i2)x (C.sub.2H.sub.5O (CH3)SiO.sub.2i2)y(PO30(CH3)SiO.sub.2/2)z((C.sub.2H.sub.5O)(PO30)(CH3)SiOi2)t((C.sub.2H.sub.50).sub.2(CH3)SiO,i2).sub.wby.sup.21Si NMR, where x was 36.3 mol %, the sum y+z was 49.5 mol %, the sum t+w was 14.2 mol %, and P030 represented a polyether group having 30 propoxy radicals.

[0178] As measured by PSS SECcurity gel permeation chromatography, the raw material alkoxy-T resin A3 had a weight-average molecular weight (Mw) of 3,548 g/mol (using polystyrene standards) and a polydispersity index Mw/Mn of 3.65; the reaction product polyether-T resin A1 had a weight-average molecular weight (Mw) of 13,020 g/mol (using polystyrene standards) and a polydispersity index Mw/Mn of 8.15.

Examples 1-4 and Comparative Examples 1-3 Defoamer Composition

[0179] The ingredients in each example listed in Table 1 were mixed well to give a defoamer composition.

TABLE-US-00001 TABLE 1 Parts by Comparative Comparative Comparative Weight Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 A1 5.74 5.74 5.74 5.74 / / / A2 / / / / 5.74 / / A3 / / / / / 5.74 / B1 0.18 0.18 0.18 0.18 0.20 0.16 / B2 0.18 0.18 0.18 0.18 0.20 0.16 / C1 93.90 / / 69.30 93.87 93.90 100 C2 / 93.90 / / / / / C3 / / 93.90 / / / / D1 / / / 24.6 / / /

[0180] Table 2 displayed the evaluation results of each defoamer composition in Examples 1-4 and Comparative Examples 1-3. The defoamer compositions of Examples 1-4 had a AKZ value less than 400, showing a good overall anti-foaming/defoaming performance. By comparing Example 1 and Comparative Example 1, it was found the overall anti-foaming/defoaming performance of defoamer composition containing the polyether-T resin was significantly better than that of defoamer composition containing a polyether modified silicone oil. And by comparing Example 1 and Comparative Example 2, it was seen the polyether-T resin compounding with polypropylene glycol and fumed silica had an obviously better anti-foaming/defoaming performance than the physical mixture of alkoxy-T resin and polypropylene glycol.

TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Amount of defoamer 200 200 200 200 200 200 200 composition/?l AKZ 10 205 362 155 912 577 9999* Initial height/mm 15 35 76 55 76 76 90 *9999 means the measured AKZ was so big that it exceeded the range of the light sensor.

Example 5 and Comparative Examples 4-5 Defoamer Composition

[0181] The ingredients in each example listed in Table 3 were mixed well to give a defoamer composition.

TABLE-US-00003 TABLE 3 Parts by Comparative Comparative Weight Example 5 Example 4 Example 5 A1 94.15 / / A2 / 77.50 / A3 / / 94.70 B1 2.93 2.66 2.61 B2 2.93 2.66 2.61 C1 / 17.20 /

[0182] Table 4 displayed the evaluation results of each defoamer composition in Example 5 and Comparative Examples 4-5. It was seen form Table 4 that the polyether-T resin compounding with fumed silica had an obviously better anti-foaming/defoaming performance than the polyether modified silicone oil compounding with fumed silica and polypropylene glycol, and than the alkoxy-T resin compounding with fumed silica.

TABLE-US-00004 TABLE 4 Comparative Comparative Example 5 Example 4 Example 5 Amount of defoamer 12 15 12 composition/?l AKZ 255 1515 937 Initial height/mm 84 83 81

Example 6 and Comparative Examples 6-7 Powder Defoamer

[0183] In each example listed in Table 5, ingredients A-D were mixed well and then blended with ingredient F to give a powder defoamer.

TABLE-US-00005 TABLE 5 Parts by Comparative Comparative Weight Example 6 Example 6 Example 7 A1 1.44 / / B1 0.04 / / B2 0.04 / / C1 23.48 46.20 66.00 D1 / 19.80 / F1 75.00 / / F2 / 34.00 34.00

Application Example Use of Powder Defoamer in Dry Mortar

[0184] The powder defoamer in each case listed in Table 6 was added to cement and then mixed well with sand, redispersible polymer powder, cellulose ether and water reducer to give dry mortar. Dry mortar containing no powder defoamer was used as blank control.

[0185] Afterwards the obtained dry mortar in each case was blended with 200 parts by weight of water, and was set and hardened to give a hardened mortar disk. During the blending and hardening process, no oil precipitation was observed for the powder defoamers of Example 6 and Comparative Example 7, while oil precipitation occurred for that of Comparative Example 6.

TABLE-US-00006 TABLE 6 Comparative Comparative Parts by Application Application Application Blank Weight Example 1 Example 1 Example 2 Control Cement 1080 1080 1080 1080 Sand 1255.2 1255.2 1255.2 1255.2 Redispersible 48 48 48 48 polymer powder Cellulose ether 2.4 2.4 2.4 2.4 Water reducer 4.8 4.8 4.8 4.8 Powder defoamer 4.8 / / / of Example 6 Powder defoamer / 4.8 / / of Comparative Example 6 Powder defoamer / / 4.8 / of Comparative Example 7
Table 7 summarized the air content and fluidity of each application example and blank control. The dry mortar containing the powder defoamer of the present invention had an obviously reduced air content and an improved fluidity in comparison with blank control. And the dry mortar containing inventive powder defoamer of the present invention also outperformed that containing non-inventive powder defoamer in air content and fluidity.

TABLE-US-00007 TABLE 7 Comparative Comparative Application Application Application Blank Example 1 Example 1 Example 2 Control Air content 3.00% 4.2% 3.4% 18.2% Fluidity 22.85% 21.85% 3.4% 21.55%