Dimethicone copolyol composition and its application as an additive in detergent composition to enhance foamability and cleaning effect

Abstract

The invention to provide an foamable silicone composition, that would easily integrate or mix with the powder or liquid detergent composition having reduced active ingredient having enhanced or similar detergency effect i.e. foaming and dirt removal characteristics and having no negative effect on the detergency and the preferred foaming nature of the detergent during the washing cycle. The foamable silicone composition comprising a silicone composition comprising a siloxane comprising a polyoxyalkylene group having 19 to 30 oxyalkylene group, with the proviso that the siloxane contain at least one oxyalkylene radical per molecule.

Claims

1. A solid foamable silicone composition comprising: a) 10 to 35% of a silicone composition comprising: a siloxane comprising a polyoxyalkylene group represented by the following general formula:
(R.sup.1.sub.3-aY.sub.aSiO.sub.1/2).sub.j(R.sup.3.sub.2-bY.sub.bSiO.sub.2/2).sub.k(R.sup.2.sub.2SiO.sub.2/2).sub.p,  (I) wherein, R.sup.1 is the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, or mixtures thereof, Y is a polyoxyalkylene group having 19 to 30 oxyethylene groups, R.sup.2 and R.sup.3 are the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, wherein, a is 0 or 1, b is 0 or 1 or 2, where if a is 0 then p is 0 or an integer from 1 to 3, and if a is 1 then p is 0 or an integer from 1 to 50, j and k are independent of each other and are 0 or an integer from 1 to 50, where either j or k or both is at least 1, with the proviso that the siloxane contains at least one Y radical per molecule, b) 55 to 90% of a filler, wherein the filler is a carrier filler selected from the group consisting of sodium carbonate, sodium sulfate, aluminum silicate, potassium carbonate, potassium sulfate, sodium bicarbonate, potassium bicarbonate, and zeolite, wherein when b is 1 or 2 and a is 0, the siloxane has at least a pendant polyoxyalkylene group, and a number of silicon units in the siloxane with the pendant polyoxyalkylene group is 3 to 6; and when b is 0 and a is 1, the siloxane has at least a terminal polyoxyalkylene group, and a number of silicon units in the siloxane with the terminal polyoxyalkylene group is 15 to 20.

2. A liquid foamable silicone composition comprising: a) 10 to 35% of a silicone composition comprising: a siloxane comprising a polyoxyalkylene group represented by the following general formula:
(R.sup.1.sub.3-aY.sub.aSiO.sub.1/2).sub.j(R.sup.3.sub.2-bY.sub.bSiO.sub.2/2).sub.k(R.sup.2.sub.2SiO.sub.2/2).sub.p,  (I) wherein, R.sup.1 is the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, or mixtures thereof, Y is a polyoxyalkylene group having 19 to 30 oxyethylene groups, R.sup.2 and R.sup.3 are the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, wherein, a is 0 or 1, b is 0 or 1 or 2, where if a is 0 then p is 0 or an integer from 1 to 3, and if a is 1 then p is 0 or an integer from 1 to 50, j and k are independent of each other and are 0 or an integer from 1 to 50, where either j or k or both is at least 1, with the proviso that the siloxane contains at least one Y radical per molecule, b) 55 to 90% of a protic solvent, wherein when b is 1 or 2 and a is 0, the siloxane has at least a pendant polyoxyalkylene group, and a number of silicon units in the siloxane with the pendant polyoxyalkylene group is 3 to 6; and when b is 0 and a is 1, the siloxane has at least a terminal polyoxyalkylene group, and a number of silicon units in the siloxane with the terminal polyoxyalkylene group is 15 to 20.

3. The liquid foamable silicone composition of claim 2, wherein the liquid foamable silicone composition further comprises a surfactant or emulsifier.

4. The liquid foamable silicone composition of claim 2, further comprising a linear alkyl benzene sulfonic acid.

5. The liquid foamable silicone composition of claim 2, further comprising greater than 0 to 10% of an additive that improves the foamability of the silicone composition, wherein the additive is an alkyl or alkylene ester of a C6-C22 fatty acid.

6. The liquid foamable silicone composition of claim 2, further comprising an additive that improves the foamability of the silicone composition, wherein the additive is a methyl ester of a C6-C22 fatty acid.

7. The solid foamable silicone composition of claim 1 further comprising greater than 0 to 10% of an additive that improves the foamability of the silicone composition, wherein the additive is an alkyl or alkylene ester of a C6-C22 fatty acid.

8. The solid foamable silicone composition of claim 1 further comprising an additive that improves the foamability of the silicone composition, wherein the additive is a methyl ester of a C6-C22 fatty acid.

9. The solid foamable silicone composition of claim 1, wherein the siloxane containing a polyoxyalkylene group is represented by the formula:
Y.sub.aR.sup.1.sub.3-aSiO(R.sup.2.sub.2SiO).sub.p(YR.sup.3SiO).sub.mSiR.sup.1.sub.3-aY.sub.a  (IV) wherein, R.sup.1 is the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, or an alkoxy, or a hydroxyl group or mixtures thereof, Y is a polyoxyalkylene group having 19 to 30 oxyethylene group, R.sup.2 and R.sup.3 are the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, wherein, a is 0 or 1, where if a is 0 then p is 0 or an integer from 1 to 3, and if a is 1 then p is 0 or an integer from 1 to 50, m is 0 or an integer from 1 to 50, with the proviso that the siloxane contains at least one Y radical per molecule.

10. The liquid foamable silicone composition of claim 2, wherein the siloxane containing a polyoxyalkylene group is represented by the formula:
Y.sub.aR.sup.1.sub.3-aSiO(R.sup.2.sub.2SiO).sub.p(YR.sup.3SiO).sub.mSiR.sup.1.sub.3-aY.sub.a  (IV) wherein, R.sup.1 is the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, or an alkoxy, or a hydroxyl group or mixtures thereof, Y is a polyoxyalkylene group having 19 to 30 oxyethylene group, R.sup.2 and R.sup.3 are the same or different and is an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms, or an alkyl, alkenyl or aryl alkyl group having 1-20 carbon atoms and comprising a functional group, wherein, a is 0 or 1, where if a is 0 then p is 0 or an integer from 1 to 3, and if a is 1 then p is 0 or an integer from 1 to 50, m is 0 or an integer from 1 to 50, with the proviso that the siloxane contains at least one Y radical per molecule.

Description

DETAILED DESCRIPTION

(1) It has surprisingly found that the use of the current silicone composition, which is a foamable silicone composition comprising a silicone composition comprising a siloxane comprising a polyoxyalkylene group represented by the following general formula:
(R.sup.1.sub.3-aY.sub.aSiO.sub.1/2).sub.j(R.sup.3.sub.2-bY.sub.bSiO.sub.2/2).sub.k(R.sup.2.sub.2SiO.sub.2/2).sub.p,  (I)

(2) wherein, R.sup.1 is same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, or mixtures thereof,

(3) Y is a polyoxyalkylene group having 19 to 30 oxyalkylene group,

(4) R.sup.2 and R.sup.3 are same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group,

(5) wherein, a is 0, 1 or 2, b is 1 or 2, p is 0 to 20 preferably 0, 1, 2 or 3, j, k, are independent of each other and is 0 or an integer from 1 to 50, where either j or k or both is at least 1, where, if a is 0 then p is 0, 1, 2 or 3, and if a is 1 or 2 then p is 0 or an integer from 1 to 50, with the proviso that the siloxane contain at least one Y radical per molecule.

(6) In one of the embodiment, when k is at least 1 and b is 1 or 2, a is 0 and j is 2 then p is 0, 1, 2 or 3.

(7) In one of the embodiment, when a is 1 j is 2, and k is 0 then p is an integer from 1 to 30. In another embodiment, when a is 1 j is 2 and k is 0 then p is 0.

(8) This foamable silicone composition when mixed in a reduced active detergent composition gives an appropriate desired foam height after reduction of active content from the detergent composition. This foam after attaining the desired height is also stable for a longer time and gives a better cleaning effect.

(9) Preferably R.sup.2 and R.sup.3 are same or different and is a C.sub.1 to C.sub.20 alkyl radical. Examples of alkyl radicals R are the methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical. For R.sup.1, R.sup.2 and R.sup.3 the preferred group is the alkyl group. Preferably R.sup.2, R.sup.3 is a methyl radical.

(10) In one of the embodiments, Y is a polyoxyalkylene group having 19 to 30 oxyalkylene group of the formula —R.sup.5(OR.sup.4).sub.gOR′, where R.sup.4 is same or different and is a C.sub.1 to C.sub.10 alkylene radical and preferably a C.sub.2 alkylene radical, R.sup.5 is same or different and is a C.sub.1 to C.sub.10 alkylene radical, R′ are same or different and are a hydrogen atom or a C.sub.1 to C.sub.6 alkyl group, preferably a hydrogen atom, and g is from 19 to 30.

(11) The foamable silicone composition may be termed different from silicone composition as the foamable silicone composition may contain optional additive that improves foamability of the silicone composition and is selected from but not limited to an alkyl ester of fatty acid.

(12) In the foamable silicone composition the weight ratio of the siloxane to additive is from 1 part to about 10 parts by weight of the siloxane (in silicone composition) per each part of the additive, i.e. the ratio of siloxane:additive is 1:1 to 10:1.

(13) According to a basic aspect of the invention, there is provided a foamable silicone composition used in fluid-base and powder-based detergent formulation where the foamable silicone composition where the siloxane containing a polyoxyalkylene group represented by the formula:
Y.sub.aR.sup.1.sub.3-aSiO(R.sup.2.sub.2SiO).sub.p(YR.sup.3SiO).sub.mSiR.sup.1.sub.3-aY.sub.a  (IV)

(14) wherein, R1 is same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, alkoxy, and hydroxyl group or mixtures thereof,

(15) Y is a polyoxyalkylene group having 19 to 30 oxyalkylene group of the formula
—R.sup.5(OR.sup.4).sub.gOR′

(16) R.sup.2 and R.sup.3 are same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, R.sup.4 is same or different and is a C.sub.1 to C.sub.10 alkylene radical, R.sup.5 is same or different and is a C.sub.1 to C.sub.10 alkylene radical, R′ are same or different and are a hydrogen atom or a C.sub.1 to C.sub.6 alkyl group, preferably a hydrogen atom, where, a is 0 or an integer from 1 to 2, p is 0 or an integer from 1 to 3, m is 0 or an integer from 1 to 50, g is from 19 to 30, with the proviso that the siloxane contain at least one Y radical per molecule. R.sup.4 is same or different and is a C.sub.2 alkylene radical. Where, if a is 0 then p is 0, 1, 2 or 3, and if a is 1 or 2 then p is 0 or an integer from 1 to 50, with the proviso that the siloxane contain at least one Y radical per molecule.

(17) In one of the embodiment, when k is at least 1 and b is 1 or 2, a is 0 and j is 2 then p is 0, 1, 2 or 3.

(18) In one of the embodiment, when a is 1 j is 2, and k is 0 then p is an integer from 1 to 30. In another embodiment, when a is 1 j is 2 and k is 0 then p is 0.

(19) In one of the other embodiments, the polyoxyalkylene group is polyoxyethylene group. In one of the embodiments, the number of Silicon units the in the siloxane with pendant polyoxyalkylene group is 3-6 Si units, and for siloxane with terminal polyoxyalkylene group is 15-20 Si units.

(20) In one of the embodiments, the solid foamable silicone composition comprising:

(21) a) 10 to 35% of a silicone composition comprising:

(22) a siloxane containing a polyoxyalkylene group represented by the following general formula:
(R.sup.1.sub.3-aY.sub.aSiO.sub.1/2).sub.j(R.sup.3.sub.2-bY.sub.bSiO.sub.2/2).sub.k(R.sup.2.sub.2SiO.sub.2/2).sub.p,  (I)

(23) wherein, R.sup.1 is same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, or mixtures thereof, Y is a polyoxyalkylene group having 19 to 30 oxyalkylene group, R.sup.2 and R.sup.3 are same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, wherein, a is an integer from 0 to 2, b is an integer from 1 to 2, p is an integer from 0 to 3, j, k, are independent of each other and are integers from 0 to 50, where either j or k or both is at least 1, and b) 0 to 10% of an additive that improves foamability of the silicone composition, c) 55 to 90% of filler. In one of the embodiments, the solid could be in the form of powder, flakes, tablets, granules having different bulk densities.

(24) In one of the embodiments, the additive that improves foamability of the silicone composition is selected from but not limited to an alkyl ester of fatty acid. Specifically it improves foamability with the siloxane containing a polyoxyalkylene group i.e. the Y group at the terminal. The alkyl ester of fatty acid is selected from but not limited to fatty acid alkyl or alkylene esters based on C6-C22 fatty acids and in one embodiment specifically methyl ester of fatty acid. Fatty acid alkyl esters e.g. methyl or ethyl esters of vegetable oils (Agnique ME 18 RD-F, Agnique ME 18 SD-F, Agnique ME 12C-F, Agnique ME1270, all products of Cognis GmbH, Germany now BASF) fatty acid alkyl or alkylene esters based on C6-C22 fatty acids. Other suitable may be selected from esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols. Also suitable are esters of linear C6-C22-fatty acids with branched alcohols, esters of C18-C38-alkylhydroxy carboxylic acids with linear or branched C6-C22-fatty alcohols, and/or branched fatty acids with polyhydric alcohols.

(25) Filler is carrier filler selected from the group consisting of sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolite.

(26) The solid foamable silicone composition where the polyoxyalkylene group is a polyoxyethylene group.

(27) In one of the embodiments, the liquid foamable silicone composition comprising:

(28) a) 10 to 35% of a silicone composition comprising:

(29) a siloxane containing a polyoxyalkylene group represented by the following general formula:
(R.sup.1.sub.3-aY.sub.aSiO.sub.1/2).sub.j(R.sup.3.sub.2-bY.sub.bSiO.sub.2/2).sub.k(R.sup.2.sub.2SiO.sub.2/2).sub.p,  (I)

(30) wherein, R.sup.1 is same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group, or mixtures thereof,

(31) Y is a polyoxyalkylene group having 19 to 30 oxyalkylene group,

(32) R.sup.2 and R.sup.3 are same or different and is selected from an alkyl, alkenyl or aryl alkyl group from 1-20 C atom, or alkyl, alkenyl or aryl alkyl group from 1-20 C atom comprising a functional group,

(33) where, a is an integer from 0 to 2, b is an integer from 1 to 2, p is an integer from 0 to 3, k, are independent of each other and are integers from 0 to 50, where either j or k or both is at least 1,

(34) b) 0 to 10% of an additive that improves foamability of the silicone composition,

(35) c) 55 to 90% of a protic solvent.

(36) In one of the embodiments, a protic solvent means solvents capable of producing proton(s) by dissociating themselves. The non-limiting example of the protic solvent is water; alcohols such as methanol and ethanol; carboxylic acids such as acetic acid; phenol; and liquid ammonia, preferably the protic solvent is water.

(37) In one of the embodiments, the liquid foamable composition is composed of primarily of linear alkyl benzene sulfonic acid approx. from 15 to 25 wt % in addition to some alcohol, stabilizers, and perfume and balanced with water with or without a surfactant. Here, surfactant may act as an emulsifier if the liquid foamable silicone composition is not soluble in water at room temperature (25° C.). Particularly suitable surfactant is a non-ionic emulsifiers include alkyl polyglycol ethers, alkylated fatty alcohol alkyl aryl polyglycol ethers, ethylene oxide/propylene oxide (EO/PO) block polymers, fatty acids, natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkylcelluloses, saturated and unsaturated alkoxylated fatty amines. Preferable non-ionic emulsifier is an alkylated fatty alcohol a non-limiting example of alkylate fatty alcohol is polyoxyether of lauryl alcohol (CH.sub.3(CH.sub.2).sub.10CH.sub.2OH).

(38) The viscosity of the siloxane containing a polyoxyalkylene group in the form of wax and semisolid is heated to 50° C. to be measured at 50° C. and viscosity of silicone fluid is measured at 25° C. The viscosity is measured at 25° C. or at 50° C. by Anton Paar Rheometer; model MCR101, geometry single gap cylinder: CC 27 spindle or cone plate of 60 mm diameter and 2° and shear rate 1 s.sup.−1. The measurement is repeated thrice. MCR Rheometer Series products work as per USP (US Pharmacopeia Convention) 912—Rotational Rheometer methods.

(39) The foamable silicone composition may be 100% pure or may further contain some amount of side products. The foamable silicone composition may further contain some small quantity of silicon material may be due to the side product of the fluid preparation by the hydrosilylation reaction. Such silicone material are like cyclosiloxane, small chain polydimethyl siloxane, or polyoxyalkylene siloxane having less than 19 polyoxyalkylene group, or polyoxyalkylene siloxane having more than 30 polyoxyalkylene group, alkyl silanes. The quantity of such silicon material will be less than 5% of the foamable silicone composition.

(40) During the preparation step of the siloxane for the silicone composition, In the second step of the process of the present invention the allyloxy(polyethylene oxide) (available as Polymeg brand from IGL, India) is taken in 10% excess to that of the rearranged H-siloxane obtained from the first step.

(41) Allyloxy(polyethylene oxide) or olefinic unsaturated polyether is preferably selected from polyethylene glycol allyl methyl ether CH.sub.2═CHCH.sub.2(OC.sub.2H.sub.4).sub.nOH; CH.sub.2═CHCH.sub.2(OC.sub.3H.sub.6).sub.nOH; polyalkylene glycol allyl methyl ether (EO/PO random) CH.sub.2═CHCH.sub.2O(C.sub.2H.sub.4O).sub.l(C.sub.3H.sub.6O).sub.kH, here l and k are integers from 2 to 100, preferably from 19 to 40 and more preferably from 19 to 30. Non-limiting example of a preferred olefinic unsaturated polyether is allyloxy(polyethylene oxide) (EO 25) available as Polymeg brand from IGL, India. The olefinic unsaturated polyether is used in an amount of from 1 to 1.1 mol of the olefinic unsaturated radical (C═C) in the polyether per 1 mol Si-bonded hydrogen in the hydrogen siloxane.

(42) In the step 1 for the synthesis of rearranged H-siloxane, the H-siloxane used where H-atom could be at the terminal or branch or both (having 0.01% to 99.9% of Hydrogen concentration). The disiloxane used is used as an end-stop material in excess for the rearrangement reaction and other trialkylterminated siloxane may be used along with the H-siloxane to obtain the desired mole of the invention material. The catalyst used is a PNCl.sub.2 catalyst. The reaction temperature varies from batch to batch basis depending on the starting material and as per the required conditions of the reaction. The usual temperature of the reaction varies from 10 to 300° C., preferably from 80 to 150° C. Some of the reaction may have exotherm and required monitoring and controls are required for control within the reaction temperature. The reaction time also may vary depending upon the type of reactants, in one of the embodiments the reaction time may vary from 1 hour to 24 hours, the reaction time is usually from 1 hour to 10 hours. The reaction process may further have an optional distillation step which if present may be after or before the step 2 of the hydrosilylation reaction. The catalyst used in the rearrangement process may further be neutralized by using basic material (e.g. preferably but not limited to soda ash) to stop the further rearrangement reaction. Yield is 75 to 99% of the rearranged product of Rearranged H-siloxane.

(43) In one of the embodiments, the invention provides a process for preparing the rearranged H-siloxane comprising:

(44) (i) reacting in a first step

(45) a hydrogen siloxane of the formula
HR*.sub.2SiO(R.sub.2SiO).sub.uSiR*.sub.2H OR R*.sub.3SiO(RHSiO).sub.uSiR*.sub.3 OR HR*.sub.2SiO(RHSiO).sub.uSiR*.sub.2H

(46) wherein R* is R or R.sup.6,

(47) R is same or different and a monovalent C.sub.1 to C.sub.20 hydrocarbon radical,

(48) R.sup.6 is same or different and a C.sub.1 to C.sub.6 alkoxy radical or a hydroxyl radical,

(49) u is an integer from 1 to 500,

(50) with

(51) a disiloxane of formula
R.sub.3SiOSiR.sub.3

(52) in the presence of a catalyst at a temperature of 10 to 300° C., preferably from 80 to 150° C. in one embodiment the disiloxane is taken from 10-40% of molar excess than the hydrogen siloxane, to obtain a rearranged H-siloxane of formula
(R.sub.3-aH.sub.aSiO.sub.1/2).sub.j(R.sub.2-bH.sub.bSiO.sub.2/2).sub.k(R.sub.2SiO.sub.2/2).sub.p

(53) ii) reacting in a second step

(54) an olefinic unsaturated polyether or its mixture with the rearranged H-siloxane of the formula CH.sub.2═CH—R.sup.9—(OR.sup.4).sub.gOR′, and in one of the embodiments mixed with CH.sub.2═CH—R.sup.9—(OR.sup.4).sub.g1OR′,

(55) wherein R.sup.9 is C.sub.1 to C.sub.8 alkylene radical, R.sup.4 is same or different and is a C.sub.1 to C.sub.10 alkylene radical and preferably a C.sub.2 alkylene radical, R.sup.5 is same or different and is a C.sub.1 to C.sub.10 alkylene radical, R′ are same or different and are a hydrogen atom or a C.sub.1 to C.sub.6 alkyl group, preferably a hydrogen atom, and g is from 19 to 30, and g1 is 1 to 18

(56) In the presence of a catalyst comprising platinum or its compounds or complexes to form a siloxane comprising a polyoxyalkylene group of formula
(R.sub.3-aH.sub.aSiO.sub.1/2).sub.j(R.sub.2-bH.sub.bSiO.sub.2/2).sub.k(R.sub.2SiO.sub.2/2).sub.p

(57) where, Y is —R.sup.5—(OR.sup.4).sub.gOR′, or mixture of —R.sup.5—(OR.sup.4).sub.gOR′ and —R.sup.5—(OR.sup.4).sub.g1OR′, wherein the g is in average from 19 to 30 in the siloxane comprising a polyoxyalkylene molecule.

(58) The inventive structures of siloxane comprising a polyoxyalkylene group of the current invention are selected from but not limited to the following structures:

(59) ##STR00001##

(60) R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R′ are defined earlier.

(61) where, p is 0 or an integer from 1 to 3,

(62) m′ is an integer from 1 to 50, and preferably g is average from 19 to 30,

(63) and p1 is 0 or an integer from 1 to 50, and preferably from 1 to 30, more preferably from 1 to 20,

(64) with the proviso that the siloxane contain at least one Y radical per molecule.

(65) In the second step of the synthesis (step 2) synthesis of polyoxyalkylene silicone by taking rearranged H-siloxane taken from step 1 or the H-siloxane available in the market with the required specification e.g. H-content, viscosity, refractive index and flash point. The reaction temperature varies from batch to batch basis depending on the starting material and as per the required conditions of the reaction. The usual temperature of the reaction varies from 10 to 300° C., preferably from 80 to 150° C. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile.

(66) In the second step of the process of the present invention more preferably the (olefinic unsaturated) allyloxy (polyethylene oxide) compound is used in an amount of from 0.9 to 1.3 mol of the H-content (Si—H) per 1 mol Si-bonded hydrogen in the hydrogen siloxane and more preferably the unsaturated alkoxy compound is used in an amount of from 1.0 to 1.15 mol per 1 mol Si-bonded hydrogen in the hydrogen siloxane. In one of the non-limiting embodiments, the allyloxy (polyethylene oxide) compound and the Si-bonded hydrogen in the hydrogen siloxane is reacted in the second step either simultaneously or stepwise and also either mixed together or dosed separately either at a predetermined rate or at a predetermined quantity at a predetermined interval.

(67) The catalysts for the hydrosilylation reaction in the step 2 step preferably comprise a metal from the group of the platinum metals, or a compound or a complex from the group of the platinum metals. Examples of such catalysts are metallic and finely divided platinum, which may be present on supports, such as silicon dioxide, aluminum oxide or activated carbon, compounds or complexes of platinum, such as platinum halides, e.g. PtCl.sub.4, H.sub.2PtCl.sub.6*H.sub.2O, Na.sub.2PtCl.sub.4*4H.sub.2O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H.sub.2PtCl.sub.6*H.sub.2O and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complexes with or without detectable inorganically bonded halogen, bis(gamma-picoline)platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentadieneplatinum dichloride, dimethylsulfoxideethyleneplatinum(II) dichloride, cyclooctadiene-platinum dichloride, norbornadiene-platinum dichloride, gamma-picoline-platinum dichloride, cyclopentadiene-platinum dichloride, and also reaction products of platinum tetrachloride with olefin and primary amine or secondary amine, or primary and secondary amine, such as the reaction product of platinum tetrachloride in solution in 1-octene with sec-butylamine, or ammonium-platinum complexes.

(68) Preferably, the reaction is carried out in between 70 to 110° C., more preferably from 80 to 100° C., in the presence of a catalyst, preferably hexachloroplatinic acid, preferably in the range of 500 to 5000 ppm by weight. The reaction is preferably carried out in absence of oxygen, i.e. in nitrogen under N.sub.2 atmosphere.

(69) Effective detergent compositions comprise anionic surfactants, particularly alkyl benzene sulfonate and alkyl sulfate surfactants. It has also been found beneficial for the appearance and cleaning of fabrics for laundry detergents to contain an amount of an enzyme sufficient to improve the appearance and cleaning of such fabrics, particularly after multiple cleaning cycles, but the anionic surfactant is important for cleaning and is an inexpensive source of generating substantial foam in washing. To improve upon the detergent effect of the laundry detergent formulation, further chemicals are often used, for example complex phosphates, non-ionic surfactants, soap noodles, different inorganic salts and other additives used for optimizing detergency effect.

(70) In detergent powders, the main foaming component is an anionic surfactant. According to the present invention, when laundry detergent powder containing anionic surfactant, a large amount of foam is generated due to the anionic surfactant. The foaming nature of the detergent during prewash or in post wash does not change. But, when we reduce the amount of the anionic detergent the foaming and finally the cleaning benefit reduces.

(71) In the rinse cycle, residual detergent transfers into fresh water from the fabric after squeezing the fabrics. Therefore, the rinse liquor foam density reduces significantly due to lesser amount of detergent i.e. the anionic surfactant present in the liquor and hence, as a result, due to very low concentration of the anionic surfactant, thereby loses its foaming nature and hence, foams in the rinse water are eliminated in significant amounts. Specially, in case of hand wash, no foam is observed after 4 rinses.

(72) The details of the invention, its nature and objects are explained hereunder in detail in relation to the following non-limiting examples.

EXAMPLES

(A) Synthesis Examples of Silicone Polymer

Example 1a) Preparation of 25-polyoxyalkylene-siloxane (According to Invention)

(73) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(74) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 7659 g of allyloxy(polyethylene oxide) (EO 25) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 25) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 150 mPa.

Example 1b) Preparation of 24-polyoxyalkylene-siloxane in Average (According to Invention)

(75) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane, the catalyst is then neutralized with soda ash. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(76) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 4865 g of allyloxy (polyethylene oxide) (EO 27) (preheated at 40° C.) (10% excess of 6.081 moles) and 760.64 g of allyloxy (polyethylene oxide) (EO 12) available as Polymeg brand from IGL India, these materials are in two phase, and continue the reaction till all the allyloxy (polyethylene oxide) (EO 27) molecule and allyloxy (polyethylene oxide) (EO 12) to form a 24-polyoxyalkylene-siloxane in average reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 150 mPa.

Example 2) Preparation of 27-polyoxyalkylene-siloxane with 2 D [—OSi(CH.SUB.3.).SUB.2.] Units (According to Invention)

(77) Step 1—Synthesis of H-siloxane: Load 1500 g of H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 3332.34 g of disiloxane (24−3.43=20.57 moles) (Wacker BELSIL® DM 0 65), 4116 g of Wacker Belsil 10 (3.43 moles, as each unit has 14 D units so, 48 moles of D units will be there which will rearrange to form a siloxane chain with 1 Si—H and 2 D units) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(78) Step 2—Synthesis of polyoxyalkylene silicone: 2250 g of Rearranged H-siloxane with 2 D-units (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 8247 g of allyloxy(polyethylene oxide) (EO 27) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 27) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 165 mPa.

Example 3) Preparation of 19-polyoxyalkylene-siloxane (According to Invention)

(79) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(80) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 5819.5 g of allyloxy(polyethylene oxide) (EO 19) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 19) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a semisolid like material. The viscosity of the material at 50 deg C. is 90 mPa.Math.s.

Example 4) Preparation of 30-polyoxyalkylene-siloxane with 3 D Units [—OSi(CH.SUB.3.).SUB.3.] (According to Invention)

(81) Step 1—Synthesis of H-siloxane: Load 1500 g of H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 3332.34 g of disiloxane (24−3.43=20.57 moles) (Wacker BELSIL® DM 0 65), 6171 g of Wacker Belsil 10 (5.143 moles, as each unit has 14 D units so, 72 moles of D units will be there which will rearrange to form a siloxane chain with 1 Si—H and 3 D units) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(82) Step 2—Synthesis of polyoxyalkylene silicone: 2699 g of Rearranged H-siloxane with 3 D-units (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 8233.67 g of allyloxy(polyethylene oxide) (EO 30) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 30) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 150 mPa.Math.s.

Example 5a) Preparation of Tetramethyl Disiloxane with Two 25 Polyoxyalkylene on the Terminal Ends (According to Invention)

(83) Step 2—Synthesis of polyoxyalkylene silicone: Load 160.8 g of tetramethyl-disiloxane (i.e. 2.4 moles of H), is taken in the reactor and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature add epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 2993 g of allyloxy(polyethylene oxide) (EO 25) (10% excess of 2.4 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 25) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 190 mPa.Math.s.

Example 5b) Preparation of Siloxane with 15 D Units [—OSi(CH.SUB.3.).SUB.3.] and with Two 25 Polyoxyalkylene on the Terminal Ends (According to Invention)

(84) Step 2—Synthesis of polyoxyalkylene silicone: Load 1250 g of H-terminal having 15D siloxane (Wacker H-polymer 15 available from Wacker Chemie) (0.17% of H, i.e. 2.125 moles of H), is taken in the reactor and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature add epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 3024 g of allyloxy(polyethylene oxide) (EO 25) (10% excess of 2.3375 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 25) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 190 mPa.Math.s.

Example 6) Preparation of 12-polyoxyalkylene-siloxane (Comparative Example)

(85) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(86) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 3759.3 g of allyloxy(polyethylene oxide) (EO 12) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 12) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 25 deg C. is 130 mPa.Math.s.

Example 7) Preparation of 18-polyoxyalkylene-siloxane (Comparative Example)

(87) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(88) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 5525.2 g of allyloxy(polyethylene oxide) (EO 18) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 18) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a semisolid like material. The viscosity of the material at 50 deg C. is 80 mPa.Math.s.

Example 8) Preparation of 25-polyoxyalkylene-siloxane with 20 D Units [—OSi(CH.SUB.3.).SUB.3.] (Comparative Example)

(89) Step 1—Synthesis of H-siloxane: Load 150 g of H-siloxane (having 1.6% of Hydrogen concentration, i.e. 2.4 moles of H), 333.2 g of disiloxane (2.06 moles) (Wacker BELSIL® DM 0 65), 4116 g of Wacker Belsil 10 (3.43 moles of PDMS having 14 D-units and 2 terminal trimethyl siloxy terminal units) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane which will have 1 Si—H unit and 20 D units. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(90) Step 2—Synthesis of polyoxyalkylene silicone: 1702 g of Rearranged H-siloxane with 20 D-units (1 mole) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 1247 g of allyloxy(polyethylene oxide) (EO 25) (10% excess of 1 mole) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 25) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a semisolid like material. The viscosity of the material at 25 deg C. is 250 mPa.Math.s.

Example 9) Preparation of 31-polyoxyalkylene-siloxane (Comparative Example)

(91) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(92) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 9351.4 g of allyloxy(polyethylene oxide) (EO 31) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 31) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 180 mPa.Math.s.

Example 10) Preparation of 40-polyoxyalkylene-siloxane (Comparative Example)

(93) Step 1—Synthesis of H-siloxane: Load 1500 g of Wacker H-siloxane (having 1.6% of Hydrogen concentration, i.e. 24 moles of H), 4192 g of disiloxane (Wacker BELSIL® DM 0 65) (25.88 moles) and 200 ppm of PNCl.sub.2 catalyst in SS reactor, Set temperature 105° C., Temperature Overshoot to 110-115° C., set temperature 108-110° C. Continue the reaction for 4 h, then start to distilled with 5° C. temperature increment up to 180° C. (time for 10 It reactor 2 h for complete distillation to obtain a Rearranged H-siloxane. Yield is 75 to 80% of the rearranged product of Rearranged H-siloxane.

(94) Step 2—Synthesis of polyoxyalkylene silicone: 1800 g of Rearranged H-siloxane (6.081 moles) (from step 1) and increase the temperature 100-102° C. in a reactor. This reactor is equipped with control stirring and heating with a facility of carry out reaction under vacuum or nitrogen blanketing or pressure and additionally facility of reaction under reflux or stripping out volatile. At this temperature ad epoxycyclohexane and Pt catalyst (0.5% hexachloroplatinic acid in isopropanol) and slowly add drop by drop 12000 g of allyloxy(polyethylene oxide) (EO 40) (10% excess of 6.081 moles) available as Polymeg brand from IGL, India, these materials are in two phase and, and continue the reaction till all the allyloxy(polyethylene oxide) (EO 40) molecule reacts. After 1-2 min exotherm start (max 10° C.) and after 60 min materials become cleared continue for more 60 min. Check IR spectra for the conversion by unreacted H-concentration. Apply 0.2-0.5 kg/cm.sup.2 N.sub.2 purging at 100° C. for 1 h. Cool the reaction mixture to obtain a wax like material. The viscosity of the material at 50 deg C. is 250 mPa.Math.s.

(B) Formulation Examples

(95) Solid Foamable Silicone Composition Formulation Preparation Method:

(96) The methyl ester used in the example for preparation as depicted in Table 1, is a fatty acid alkyl esters e.g. methyl esters of vegetable oils (Agnique ME 18 RD-F). As required to prepare the composition as described in Table 1, the methyl ester can be mixed in a container with the mentioned siloxane in the ratio as mentioned in Table 1 to perform the experiments.

(97) Equipment used: 10 litre volume, Stainless steel plough shear mixer, with one side entry high speed dispersing tool, suitably jacketed for nominal pressure hot water/cold water heating and cooling. All shaft glands were N.sub.2 purged. A suitable dust separator was installed at the loading hopper and the mixer was provided with a standard bottom outlet.

(98) To the mixer was added 3.5 kg of commercial grade sodium carbonate powder having an average particle size of 125 μm, and the powder was stirred and heated to 130° C. under N.sub.2 purge to dry the powder. After drying the powder for about an hour, the foamable composition [inventive (silicone foamable composition) or non-inventive] in fluid form or if is in wax form is heated from 35 to 50° C. to form a fluid (as described as Composition 1-33 as in Table 1) and was added by means of a metering pump at an elevated temperature of 50° C., to ensure uniform dispensing into the stirred mass. The addition of 1.5 kg of above fluid is completed in about 3 hours, while the temperature is maintained at 130° C. Mixing is continued for another hr after fluid addition. The powder is cooled to 40° C. before emptying from the mixer to obtain a solid foamable composition.

(99) The details of the experiment and the protocol used for evaluation disclosed as in the published and granted patent number U.S. Pat. No. 8,481,476B2 from Wacker.

(100) 1) Blank Solid Detergent Formulation for Hand Wash:

(101) Detergent Formulation for Hand Wash: Example (without Foamable Composition) Linear Alkyl benzene sulfonate Salt=14.00 part Sodium tripolyphosphate=26.40 part Soda Ash=47.55 part Sodium Sulphate=4.40 part Sodium Perborate=6.85 part Tetra Acetyl Ethylene Diamine=0.5 part Perfume=0.30 part

(102) 2) Solid Detergent Formulation for Hand Wash with Inventive and Non-Inventive Silicone Composition: Linear Alkyl benzene sulfonate Salt=8.4 part (14−5.6 part) Sodium tripolyphosphate=26.40 part Solid foamable composition [inventive (solid foamable silicone composition) or non-inventive]=1 part Soda Ash=52.15 part (47.55+4.6 parts) Sodium Sulphate=4.40 part Sodium Perborate=6.85 part Tetra Acetyl Ethylene Diamine=0.5 part Perfume=0.30 part

(103) 3) Blank Detergent Formulation for Machine Wash:

(104) Example without Foamable Composition (Inventive or Non-Inventive) Linear Alkyl benzene sulfonate Salt=10.00 part Soap=1.25 part Lauryl alcohol 7 EO=2.00 part Sodium tripolyphosphate=26.40 part Soda Ash=47.9 part Sodium Sulphate=4.40 part Enzyme Protease=0.40 part Sodium Perborate=6.85 part Tetra Acetyl Ethylene Diamine=0.5 part Perfume=0.30 part

(105) 4) Solid Detergent Formulation for Machine Wash with Inventive and Non-Inventive Silicone Composition: Linear Alkyl benzene sulfonate Salt=6.00 part (=10 minus 4 parts) Soap=1.25 part Lauryl alcohol 7 EO=2.00 part Sodium tripolyphosphate=26.40 part Solid foamable silicone composition (inventive or non-inventive)=1 part Soda Ash=50.9 part (47.9+3 parts) Sodium Sulphate=4.40 part Enzyme Protease=0.40 part Sodium Perborate=6.85 part Tetra Acetyl Ethylene Diamine=0.5 part Perfume=0.30 part

(C) Performance Measurements

(106) 1) Performance Evaluation of Foaming without Fabrics (Hand Wash)

(107) The Protocol Used for the Evaluation of the Respective Detergent in Buckets by Hand Washing was as Below: a. 24° fH hard water. b. fabric to liquor ratio was 1:10. c. 4 gpl detergent (gpl=grams per liter). d. lathering was performed for 20 sec e. At the end of 20 seconds immediately note down the height of lather, the type of lather, stability of lather. This is reported as initial lather at time t=0 (H.sub.0). The foam height (H.sub.20) is again taken at 5, 10 or 20 minutes (t=0) intervals.

(108) 2) Performance Evaluation of Foaming with Fabrics (Hand Wash)

(109) The Protocol Used for the Evaluation of the Respective Detergent in Buckets by Hand Washing was as Below a. 24° fH hard water. b. fabric to liquor ratio was 1:10. c. 4 gpl detergent (gpl=grams per liter). d. lathering was performed for 20 sec and the fabrics then immersed into the bucket of water. Water Quantity: 10.6 lit, Plastic Bucket: ˜30 lit Capacity, uniform diameter of 34 cm, height 34.5 cm. e. washing cycle maintained for 15 min or 30 min and the foam height measured, this is reported as initial lather at time t=0 (H.sub.0). The foam height (H.sub.20) is again taken at 5, 10 or 20 minutes (t=0) intervals. f. the fabrics were squeezed to 50% weight pick up. g. rinsing was done in each case in fresh 24° fH hard water in a ratio of part of rinse water 1 to 7 parts fresh water and then 5 seconds agitation the fabrics were then squeezed to 50% weight pick up and the foam height in bucket was measured.

(110) 3) Performance Evaluation (Machine Wash)

(111) The Protocol Used for the Evaluation of Detergent in Top Load Automatic Machine a. 24° fH hard water. b. fabric to liquor ratio was 1:10. c. 4 gpl detergent (gpl=grams per liter). Semiautomatic LG 7.2 Kg capacity Washing machine. d. washing cycle maintained for 15 min or 30 min. The top lid of washing machine was opened just before discharging the washing liquor (as soon as top lid opened, machine stopped in operation automatically) and fabrics were removed by squeezing so that the fabric retained 50% wash liquor. After taking out the fabric, the foam height was measured. e. The top lid was closed and the machine runs again. As soon as the machine discharged the washing liquor, the top lid of the machine was opened and the fabrics were transferred. The top lid of the machine was closed and immediately the machine was operated for the rinsing cycle. The top lid of the machine was opened just before discharged the 1st rinsing liquor. The fabrics were removed by squeezing so that fabrics contained 50% washed liquor. After taking out the fabric, the foam height was measured and noted as the 1st rinsing foam height. f. The top lid was again closed and repeated as step ‘f’ for foam height measurement of the 2nd, 3rd & 4th rinsing.

(112) (a) Foam Height Measurement:

(113) The foam height is measured by using standard procedure take an initial foam height reading at t=0 min followed by 5 min measurements and a final t=20 min reading. Take the reading by measuring the foam production at the bucket at the highest average height to which the rim of the foam has reached, 5 such readings are taken and average done to note the final foam height, the value is noted for each composition and reported in Table 1.

(114) (b) Foam Stability Measurement:

(115) Foam Stability factor (H.sub.0−H.sub.20)*100/H.sub.0 in percentage, is determined by the difference of foam height (already measured) the initial foam height at time, t=0 (H.sub.0) minus the foam height at time, t=20 minutes (H.sub.20) multiplied by 100 and divided by the initial foam height. The lower the value of Foam Stability factor more stable the foam is, means the foam has been stable for longer time and do not settle down thus the difference is lowered and foam stability factor is less in value, which is noted for each composition and reported in Table 1.

(116) (c) Measurement of the Foam Density:

(117) Determination of density is done by Pyknometer method DIN EN ISO 2811-1. A pyknometer is filled with the foam generated under test by using the stated foam generation method. The density is calculated from the mass of the foam in the pyknometer and the known volume of the pyknometer. Metal pyknometer from ERICHSEN Germany is used with a volume of 100 cm.sup.3. the density, ρ, of the product, in grams per cubic centimeter, at the test temperature, 25° C., using Equation
ρ=(m.sub.2−m.sub.1)/V.sub.t

(118) where, m.sub.1 is the mass, in grams, of the empty pyknometer;

(119) m.sub.2 is the mass, in grams, of the pyknometer filled with the product at the test temperature, 25° C.;

(120) V.sub.t is the volume, in cubic centimetres, of the pyknometer at the test temperature.

(121) Test Procedure:

(122) Step 1. Foam is generated by lathering for 20 sec, using 10.6 lit of hard water (24° fH) in a bucket having 4 gpl detergents. Temperature of hard water (24° fH) should be maintained at 25° C. so that foam temperature during lathering is also maintained 25° C. Maintain the room temperature to 25° C. till experiment is completed.

(123) Step 2. Cool the Pycnometer to 25° C. and then the take the weight of the empty Pycnometer (m1) in an electric balance which has maximum capacity 220 gm. Fill the Pycnometer with the foam (generated during lathering) up to top edge of Pycnometer. Filling of foam in the Pycnometer should carry out in such a way, no air from outside is trapped inside the Pycnometer. Pycnometer's lid is then placed on the top of the container and surplus foam escaping through the overflow hole is wiped off. Take the weight of the Pycnometer with foam (m2). Calculate foam density by using the above equation.

(124) 3. The experiment is repeated for 5 times and then take the average density and the result for each composition is noted down in Table 1.

(125) (d) Cleaning Efficiency:

(126) After the washing and rinsing cycle, a panel is formed of 5 people to rate the stain removal efficiency on a scale of 1 to 10. 10 being the highest efficiency and 1 being the lowest efficiency, the rating are noted and then averages of the five ratings are taken for each of the composition and noted down in Table 1.

(127) It is further observed, according to the present invention, that the effects of the inventive silicone composition, when directly incorporated in a liquid laundry detergent with substantial reduced linear alkyl benzene sulfonate salt for the purpose of foam boosting during fabric washing by hand or by machine washing are similar to the effects obtained with blank liquid laundry detergents.

(128) TABLE-US-00001 TABLE 1 Preparation of silicone composition and properties: The foamable composition details in Foam Post Solid Foam Height Stability wash Detergent hand wash (cm) factor = foam Formulation Without Without Initial (H.sub.0- (H.sub.0- height Cleaning Compo- Details of fabric, fabric, Foam H.sub.20) H.sub.20)* hand efficiency sition of Formulation at t = 0 at t = 20 Density (in 100/H.sub.0 wash (scale of No. experiment Difference Example (H.sub.0) (H.sub.20) (g/cc) cm) (In %) (in cm) 1 to 10)  0 Blank 19.5 12.5 0.003 7 35.90 5.5 7  1 Inventive Detergent 19 EO TS 18.5 13.5 0.0025 5 27 6.5 7 Detergent (Ex. 3 fluid)  2a with 25 EO 19.5 15 0.0027 4.5 23 6 7 oxyalkylene TS(Ex. 1a siloxane fluid)  2b (TS) 24 EO 20 15 0.0026 5 25 6 7.5 with average inventive TS(Ex. 1b D Si fluid)  3a range Disiloxane 19.5 14.5 0.0025 5 25.6 6.5 7 with 25 EO (Ex. 5a fluid)  3b 15D siloxane 20 15.5 0.0023 4.5 22.5 6 7.5 with 25 EO terminal group(s) (Ex. 5b fluid)  4 27 EO with 2 19.5 14.5 0.0022 3.5 25.6 6 7.5 D-unit (Ex. 2 fluid)  5 30 EO 3 D- 17.5 13.5 0.0026 4 22.86 6.5 7.5 unit (Ex. 4 fluid)  6 Non Detergent Less 12 EO TS 5 0.2 0.0065 5 100 0 4 Inventive with No. of (Ex. 6 fluid) oxyalkylene EO  7 siloxane No. of 18 EO with 1 7 1 0.007 6 85.71 1 5 less or EO D-unit (Ex. 7 more EO fluid)  8 and More No. 25 EO in 8 1 0.0056 7 87.5 0.5 6 more of D branch with D Si 20 D-units units (Ex. 8 fluid)  9a More No. 31 EO (Ex. 9 12 3 0.0089 9 75 1 7 of EO fluid)  9b More No. 40 EO (Ex. 11 2 0.009 9 81.8 1 7 of EO 10 fluid) 10 Inventive Detergent 19 EO (Ex. 3 19 15 0.0045 2.5 21 6.5 8.5 with fluid) + oxyalkylene methyl ester siloxane (2:1) 11 with 24 EO 20 15.5 0.003 2 22.5 7 10 methyl average ester TS(Ex. 1b with fluid) + the methyl ester inventive (2.75:1) 12 weight 27 EO 2 D- 18.5 15.5 0.0040 3 16.21 7 10 ratio unit (Ex. 2 from fluid) + 1:1 to methyl ester 10: 1 (5:1) 13 30 EO with 3 18 14 0.0035 4 22.22 6.5 8 D-units (Ex. 4 fluid) + methyl ester 14a Disiloxane 19 13 0.0033 6 31.58 7 8 with two terminal EO + methyl ester (2.75:1) 14b 15D 20.5 17 0.003 3.5 17.07 7 10 siloxane with 25 EO terminal groups (Ex. 5b fluid) + methyl ester (2.75:1) 15 Non Detergent Absence only methyl 3 0.5 0.015 2.5 83.33 1 1 Inventive with of EO TS ester 16 Only Ratio 25 EO TS 9 1 0.011 8 88.89 1 5 methy (Ex. 1a ester & fluid): oxyalkylene methyl ester siloxane (1:2) 17 with methyl 25 EO TS 10 1 0.0115 9 90 1.5 5 methyl ester (Ex. 1a ester of fluid) + with different lower alkyl/ non- alkylene inventive (C.sub.5) methyl ratio & TS ester 18 with other other 25 EO TS 11 2 0.015 9 81.82 1.5 6 surfactant additive (Ex. 1a fluid) such as (co- with other (EO)x surfactant) alkyl type polyoxy- alkylene Emulgen grade surfactant 19 other 25 EO TS 7 1 0.015 6 85.71 1 6 additive with other (co- alkyl surfactant) polyglycoside of Triton grade surfactant 20 Non Solid Ratio 7% of (25 7 2 0.009 5 71.43 1 6 Inventive detergent EO TS + with methyl ester Oxyalkylene (3:1)) and siloxane 93% Na.sub.2CO.sub.3 with filler 21 methy Ratio 40% of (25 12 2 0.015 10 83.33 1 5 ester EO TS + with methyl ester the (3:1)) and noninventive 60% Na.sub.2CO.sub.3 ratio filler 22 and Filler 40% of (25 3 1 0.02 2 66.66 1 3 different EO TS + filler methyl ester (3:1)) and 60% water soluble resin filler 23 Non Liquid Ratio 7% of (25 12 4 0.015 8 66.66 3 5 Inventive detergent EO TS + with methyl ester Oxyalkylene (3:1)) and siloxane 93% water with with RH_ 24 methy Ratio 40% of (25 10 1 0.02 9 90 2 5 ester EO TS + with methyl ester the (3:1)) and noninventive 60% water ratio with RH_ 25 Inventive At at 5° C. 25 EO + 17.5 14 0.0065 3.5 20 5 8.5 different methyl ester temperature (2.75:1) 26 and pH at 40° C. 25 EO + 18 15 0.0035 3 75 4 10 methyl ester (2.75:1) 27 at pH 5 25 EO + 18 14 0.0035 4 22.22 3 9 methyl ester (2.75:1) 28 at pH 10 25 EO + 19 16 0.0025 3 15.79 6 10 methyl ester (2.75:1) 29 high 25 EO + 18 14 0.011 4 22.22 6 9 hardness methyl ester of water (2.75:1) 90 fH at 25° C. 30 Liquid 20% (25 EO 19.5 15.5 0.0025 4 20.51 5.5 9 detergent of Ex. 1 a fluid + methyl ester (2.75:1)) and 80% water with RH 31 Non Other Silane bis-peg-18 7 0.5 0.015 6.5 92.85 0.5 5 Inventive compared surfactant methyl ether structures dimethyl and silane compositions available from DKSH 32 only Fatty 8 0.5 0.01 7.5 93.75 1 6 alkyl alcohol polyoxy ethoxylates alkylene as Lutensol surfactant available from BASF 33 molecule 25 PO TS 11 2 0.008 9 81.80 1 5 having prepared by PPG hydrosilylation group with rearranged H-siloxane with POLY (PROPYLENE OXIDE) MONOALLYL ETHER (20-30 PO) from Gelest (Cas No: 9042-19-7)

(129) Observation from the Experiments:

(130) 1) From the above experiments, it is observed that composition no. 14(b) of table 1, having siloxane with 15 D units [—OSi(CH.sub.3).sub.3] and with two 25 polyoxyalkylene on the terminal ends of example 5(b) with the methyl ester gives the best result of foam height and stability and ever better than the blank detergent. This result is followed by the composition no. 3(b) of table 1, having the inventive composition with siloxane of example 5(b) with 15 D units [—OSi(CH.sub.3).sub.3] and with two 25 polyoxyalkylene on the terminal ends. This is followed by the results of composition no. 11 where the inventive composition with 24-polyoxyalkylene-siloxane in average of example 1(b) with the methyl ester and further followed by the results of composition no. 2(b) of example 1(b) with 24-polyoxyalkylene-siloxane in average.

(131) 2) r Polyoxyalkylene siloxane having lower value of oxyalkylene groups (composition 6 & 7) and very high EO siloxane (composition 9A & 9B) also produces foam but does not match the foaming height and stability.

(132) 3) Another disadvantage of the polyoxyalkylene siloxane having higher number of oxyalkylene groups than the claimed range needs high temperature to melt and it breaks at such high temperature, so it is very difficult to process, melt, and spray it on the filler support.

(133) 4) Detergent composition having Pendent polyoxyalkylene in the siloxane having more D units [—OSi(CH.sub.3).sub.3] i.e. Composition 8 with example 8 fluid having high D units do not foam and cleaning efficiency decreases.

(134) 5) Composition 17 showed that 25 polyoxyalkylene siloxane with added lower alkyl/alkylene methyl ester which is outside the claimed range reduces the cleaning efficiency drastically whereas in composition 11, 12, 13 and 14a and 14b we see that the inventive foaming silicone composition with appropriate alkyl/alkylene methyl ester synergistically boost the foaming and cleaning efficiency of the composition.

(135) 6) It is also found from experiments that the detergent with oxyalkylene siloxane having number of oxyalkylene group outside the claimed range of 19 to 30, and more D units from example 6 to 9b do not give the desired foaming and foam stability.

(136) 7) Again, from example 15 to 19, we see that detergent with only methyl ester & oxyalkylene siloxane with methyl ester of different non-inventive ratio, do not give the desired foam height and foam stability results.

(137) 8) For solid detergent composition 20 to 22 and for liquid detergent composition of 23 to 24, the detergent with oxyalkylene siloxane with methyl ester with the non-inventive ratio do not give the proper foaming result.

(138) Also for composition 31 to 33, other compared silicone structures and compositions of the prior art do not give the desired foaming and foam stability properties.

(139) 9) It is also evident that the inventive composition in example 25 to 30, at different temperature and pH do give the desired foaming and foam stability characteristics along with the cleaning efficacy.

(140) This result and experiments are non-limiting and is not restricted to this certain composition.

(141) They may vary and minor variations in composition may give similar result.