Linear silicone-polyether copolymers and processes for preparing and using the copolymers

Abstract

A two-step hydrosilylation reaction process for preparing linear silicone polyether copolymers is provided. Both steps can be carried out in the same reactor. The resulting silicone-polyether copolymers are useful as defoamers, particularly in clear liquid laundry detergents.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 443,733, filed February 7, 2023. U.S. Provisional Patent Application No. 63 / 443,733 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates to linear silicone-polyether copolymers, a process for preparing the copolymers, and the use of the copolymers as antifoam agents. More specifically, the linear silicone-polyether copolymers can be used as antifoam agents in clear liquid laundry detergents.

[0003] (Introduction) Liquid laundry detergents require antifoaming agents to prevent excessive foaming during use in the laundry wash cycle. The clarity of liquid laundry detergents is a characteristic valued by customers. Existing antifoaming technologies have the disadvantage of requiring expensive stabilization systems that reduce the clarity of the liquid laundry detergent. International Patent Publication No. 2020 / 263379(A1) discloses silicone polyether block copolymers that can be used as foam control agents in liquid laundry detergents.

[0004] When silicone polyether block copolymers are used as foam control agents in liquid laundry detergents, increasing the degree of polymerization (DP) of the silicone block can improve defoaming performance and prevent over-foaming. However, increasing the DP of the silicone block can also reduce the transparency of the liquid laundry detergent. There is a need in the industry for defoamers that have both good foam control properties and good transparency in liquid laundry detergents. Summary of the Invention

[0005] Silicone-polyether block copolymers and processes for their preparation are provided. The silicone-polyether block copolymers are useful as antifoam agents in clear liquid laundry detergents, and can provide foam control properties while maintaining clarity in the clear liquid laundry detergent. DETAILED DESCRIPTION OF THE INVENTION

[0006] The silicone-polyether block copolymers introduced above are 1) under conditions for carrying out a hydrosilylation reaction; I) Aliphatically unsaturated diorganosiloxanes of the formula:

[0007] [ka] In the formula, each R U are independently selected aliphatic unsaturated monovalent hydrocarbon radicals, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each subscript y independently has a value from 1 to 99; II) Organohydrogensiloxanes of the formula:

[0008] [ka] wherein each R is as defined above and each subscript m independently has a value from 1 to 65; wherein I) the aliphatically unsaturated diorganosiloxane and II) the organohydrogensiloxane are present in a molar ratio sufficient to provide a silicon-bonded hydrogen content / aliphatically unsaturated monovalent hydrocarbon radical content (SiH / Vi ratio) >1; and III) by combining starting materials comprising a hydrosilylation catalyst in an amount sufficient to catalyze the hydrosilylation reaction of II) silicon-bonded hydrogen atoms from the organohydrogensiloxane with I) aliphatically unsaturated monovalent hydrocarbon groups from the aliphatically unsaturated diorganosiloxane; Copolymer of formula (1)

[0009] [ka] wherein each D is an independently selected divalent hydrocarbon radical, each R is an independently selected monovalent hydrocarbon radical free of aliphatic unsaturation, each subscript m independently has a value from 1 to 65, each subscript o independently has a value from 1 to 99, and subscript x is an odd number having a value of 3 or greater, with the proviso that subscripts x, m, and o have values ​​such that the copolymer has 200 or fewer silicon atoms per molecule; 2) under conditions for carrying out a hydrosilylation reaction; A) formula

[0010] [ka] wherein Y' is an aliphatic unsaturated organic group; X is selected from a linking bond or a divalent hydrocarbon group having from 2 to 22 carbon atoms; each R' is an independently selected divalent hydrocarbon group having from 2 to 6 carbon atoms; Z is selected from hydrogen and a monovalent hydrocarbon group having from 1 to 30 carbon atoms; and each subscript n independently has a value from 2 to 60; B) the copolymer prepared in step 1) above; optionally, by combining starting materials with C) additional aliphatic unsaturated compounds; preparing a (second) reaction product comprising a silicone-polyether copolymer mixture.

[0011] Step 1) of the process described herein is carried out under conditions for carrying out the hydrosilylation reaction of starting materials I) and II) described above. Step 1) may be carried out by any convenient means, such as mixing and heating in a reactor. The reactor may be, for example, a batch kettle equipped with a mixing means, such as an impeller, and a heating and cooling means, such as a jacket. Steps 1) and 2) of the process described herein may be carried out in the same reactor. For example, step 1) may be carried out, and then step 2) may be carried out by adding the other starting materials to the reactor after the copolymer of formula (1) is formed, as described below. Steps 1) and 2) may be carried out, for example, with heating at 30°C to 125°C, alternatively at least 40°C, alternatively at least 50°C, or alternatively at least 60°C, while steps 1) and 2) may be carried out simultaneously at temperatures up to 120°C, up to 110°C, up to 150°C, alternatively at most 100°C, alternatively at most 80°C, or alternatively at most 60°C. Alternatively, steps 1) and 2) may be carried out with heating at 30°C to 150°C. Pressure is not critical, and steps 1) and 2) may be carried out at ambient pressure or under vacuum; i.e., steps 1) and 2) may be carried out at 0 mmHg (0 kPa) to 760 mmHg (101.325 kPa). The reaction time for steps 1) and 2) depends on various factors, including the type of each starting material and the temperature selected. However, when the reaction is carried out in batch mode, the reaction time for step 1) may be 5 minutes to 5 hours, or 2 to 3 hours. Alternatively, in step 1), starting materials including I) an aliphatically unsaturated organosiloxane and III) a hydrosilylation reaction catalyst may be combined and heated, followed by the addition of starting material II) an organohydrogensiloxane, which may be added continuously or intermittently in one or more aliquots. The conditions, such as temperature and reaction time, selected for step 1) may be the same as or different from those selected for step 2).

[0012] The process described herein can be carried out in one reactor, e.g., steps 1) and 2) can be carried out in the same reactor. Alternatively, steps 1) and 2) can be carried out in different reactors. The process may optionally further include one or more additional steps. For example, the process may optionally further include a purification step, such as stripping under reduced pressure or distillation, either after step 1), after step 2), or both. Alternatively, steps 1) and 2) may be carried out continuously, i.e., step 2) may be carried out after step 1) without an intermediate purification step. Without being bound by theory, it is believed that one advantage of the present process is that an intermediate purification step (between steps 1) and 2) is unnecessary and can be omitted. Alternatively, the process may further include step 3): removing residual catalyst after step 2). Removal of residual catalyst can be carried out by any convenient means, such as those described above for the purification step, or by filtration. The process may optionally further comprise the additional step of adding additional hydrosilylation catalyst to the reactor after step 1) and before and / or during step 2). The additional hydrosilylation catalyst may be an additional amount of the same type of hydrosilylation catalyst as the hydrosilylation catalyst used in step 1), or a different type of hydrosilylation catalyst may be selected.

[0013] The starting materials introduced above are described in detail below.

[0014] I) Aliphatic unsaturated diorganosiloxanes The starting material I) used in the process described herein is an aliphatically unsaturated diorganosiloxane, which may include or be a polydiorganosiloxane. The aliphatically unsaturated diorganosiloxane has the formula (I-1):

[0015] [ka] In the formula, each R Uare independently selected aliphatic unsaturated monovalent hydrocarbon groups, each R is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, and each subscript y independently has a value from 1 to 99.

[0016] In formula (I-1), each R U may be the same or different. U is an aliphatically unsaturated monovalent hydrocarbon group capable of undergoing a hydrosilylation reaction with silicon-bonded hydrogen atoms of the starting material II) polyorganohydrogensiloxane. Suitable aliphatically unsaturated monovalent hydrocarbon groups include alkenyl and alkynyl groups. The aliphatically unsaturated monovalent hydrocarbon group may have 2 to 18 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 8 carbon atoms, or alternatively 2 to 6 carbon atoms. Alternatively, the alkenyl group may be selected from the group consisting of vinyl, allyl, and hexenyl, alternatively vinyl or allyl, or vinyl and hexenyl. Alternatively, the alkynyl group may be selected from ethynyl and propynyl. Alternatively, each R U can be an alkenyl group. Alternatively, each R U can be a vinyl group. Alternatively, each R U can be an allyl group. Alternatively, each R U may be a hexenyl group.

[0017] In formula (I-1), each R may be the same or different. Each R is independently selected from the group consisting of monovalent hydrocarbon groups free of aliphatic unsaturation and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation. Examples of monovalent hydrocarbon groups for R include, but are not limited to, alkyl such as methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 or more carbon atoms), cycloalkyl such as cyclopentyl and cyclohexyl, and aryl such as phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl, and 2-phenylethyl. Examples of monovalent halogenated hydrocarbon groups for R include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Alternatively, each R may be an alkyl group such as methyl, or an aryl group such as phenyl. Alternatively, each R may be methyl.

[0018] In formula (I-1), the subscript y represents the average number of difunctional siloxane units per molecule. The subscript y has a value of at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5, alternatively at least 10, alternatively at least 14, alternatively at least 20, alternatively at least 29, alternatively at least 30, while simultaneously, the subscript y can have a value of up to 99, alternatively up to 49, alternatively up to 46, alternatively up to 45, alternatively up to 40, alternatively up to 35, alternatively up to 30. Alternatively, the subscript y can have a value from 1 to 99, alternatively from 1 to 49, alternatively from 3 to 49, alternatively from 5 to 49, alternatively from 5 to 45, alternatively from 29 to 45.

[0019] The starting material I) may be one or more polydiorganosiloxanes, for example i) α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane; ii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), iii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), iv) α,ω-phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane; v) α,ω-dimethylhexenylsiloxy-terminated polydimethylsiloxane, and vi) a combination of two or more of i) to v).

[0020] Methods for preparing polydiorganosiloxanes suitable for use as starting material I), such as the hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or the equilibration of cyclic polydiorganosiloxanes, are well known in the art; see, for example, U.S. Pat. Nos. 4,772,515 and 5,317,072, which disclose the preparation of polydiorganosiloxanes having monovalent hydrocarbon groups with terminal aliphatic unsaturation. Examples of polydiorganosiloxanes having monovalent hydrocarbon groups with terminal aliphatic unsaturation are commercially available from a variety of sources, including Dow Silicones Corporation (Midland, Michigan, USA) and Gelest, Inc. (Morrisville, Pennsylvania, USA). The aliphatically unsaturated diorganosiloxane starting material I) may be a single aliphatically unsaturated diorganosiloxane, or may be prepared by varying the value of the subscript y, R U It may also be a combination of two or more aliphatically unsaturated diorganosiloxanes that differ in at least one property, such as the selection of groups and / or the selection of R groups.

[0021] II) Organohydrogensiloxane The starting material II) used in the process described herein is an organohydrogensiloxane, which may include or be a polyorganohydrogensiloxane. The organohydrogensiloxane has the formula (II-1):

[0022] [ka] wherein each R is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation or a monovalent halogenated hydrocarbon group free of aliphatic unsaturation, and each subscript m independently has a value from 1 to 65. In formula (II-1), each R can be the same or different, and each R is independently selected from the group consisting of monovalent hydrocarbon groups free of aliphatic unsaturation and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation, as described above for formula (I-1). In formula (II-1), the subscript m represents the average number of siloxane units per molecule. The subscript m has a value of at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5, alternatively at least 10, while the subscript y can have a value of up to 65, alternatively at most 49, alternatively at most 45, alternatively at most 40, or alternatively at most 35. Alternatively, the subscript m may have a value from 1 to 65, alternatively from 1 to 49, alternatively from 1 to 45, alternatively from 1 to 40, alternatively from 1 to 35, alternatively from 1 to 10, alternatively from 1 to 4.

[0023] Suitable polyorganohydrogensiloxanes for use herein are exemplified by the following: (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated poly(dimethyl / methyl,phenyl)siloxane; (iii) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / diphenyl)siloxane; (iv) 1,1,3,3-tetramethyldisiloxane, (v) heptamethyltrisiloxane (e.g., 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, or both), and (vi) A combination of two or more of these.

[0024] Linear polyorganohydrogensiloxanes are also commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA) or Gelest, Inc. (Morrisville, Pennsylvania, USA). Methods for preparing linear polyorganohydrogensiloxanes suitable for use herein, such as the hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified by U.S. Pat. No. 3,957,713 to Jeram et al. and U.S. Pat. No. 4,329,273 to Hardman et al. The organohydrogensiloxane starting material II) can be a single organohydrogensiloxane or a combination of two or more organohydrogensiloxanes that differ in at least one property, such as the DP and / or selection of R groups.

[0025] Starting materials I), the aliphatically unsaturated diorganosiloxane, and II), the organohydrogensiloxane, are used in amounts that depend on various factors, but are sufficient to provide a hydrosilylation reaction product comprising a copolymer having a silicon-bonded hydrogen atom at each end. The amounts of starting materials I) and II) are sufficient to provide a SiH / Vi ratio of >1. Alternatively, these amounts can be sufficient to provide a SiH / Vi ratio of >1 to 2, alternatively 1.1 to 2, alternatively >1 to 1.1.

[0026] III) Hydrosilylation Reaction Catalyst The starting material III) used in step 1) of the process described herein is a hydrosilylation catalyst. Hydrosilylation catalysts are known in the art and commercially available. Hydrosilylation catalysts include III-1) platinum group metal catalysts. Such hydrosilylation catalysts can be metals selected from platinum, rhodium, ruthenium, palladium, osmium, or iridium. Alternatively, the hydrosilylation catalyst may be III-2) a compound of such a metal, for example, chloridetris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), a rhodium diphosphine chelate such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, or platinum dichloride; or III-3) a complex of the above compounds with an organopolysiloxane; or III-4) a compound or complex of the above compounds microencapsulated in a matrix or core-shell structure. Complexes of platinum with aliphatically unsaturated organopolysiloxanes include a platinum complex with 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst) and a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby's complex). Exemplary hydrosilylation catalysts are described in International Patent Publication No. 2021 / 081822 and the references cited therein. Hydrosilylation catalysts are commercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™ 2700, available from Dow Silicones Corporation (Midland, Michigan, USA).

[0027] The amount of hydrosilylation catalyst used herein will vary depending on a variety of factors, including the selection of starting materials and their respective silicon-bonded hydrogen atom and aliphatic unsaturated monovalent hydrocarbon radical content, as well as the platinum group metal content in the selected catalyst. However, the amount of hydrosilylation catalyst will be sufficient to catalyze the hydrosilylation reaction of SiH with aliphatic unsaturated monovalent hydrocarbon radicals, or the amount of catalyst will be sufficient to provide 1 ppm to 6,000 ppm of platinum group metal, or 1 ppm to 1,000 ppm, or 1 ppm to 100 ppm of platinum group metal, based on the combined weight of the starting materials containing silicon-bonded hydrogen atoms and aliphatic unsaturated hydrocarbon radicals, on the same basis.

[0028] IV) Solvent The processes described herein may further include the use of a solvent to aid in the mixing and / or delivery of one or more of the starting materials, such as the hydrosilylation catalyst. For example, III) the hydrosilylation catalyst may be dissolved and / or dispersed in a solvent such as a monohydric alcohol, exemplified by methanol, ethanol, propanol (e.g., isopropanol), or butanol; an aliphatic hydrocarbon, such as hexane or heptane; or an aromatic hydrocarbon, such as benzene, toluene, or xylene. Alternatively, the solvent may be omitted, and III) the hydrosilylation catalyst may be dissolved and / or dispersed in an aliphatically unsaturated diorganosiloxane, such as that described above as starting material I).

[0029] V) Additional Starting Materials (Optional) The processes described herein may further include adding one or more additional starting materials during step 1) or step 2), or both. For example, a processing aid may be added in step 1), such as sodium acetate, optionally. Alternatively, a hydrosilylation reaction catalyst promoter may be added in step 1) and / or step 2).

[0030] Step 1) of the process described herein produces a hydrosilylation reaction product comprising a copolymer of formula (1):

[0031] [ka] wherein each D is an independently selected divalent hydrocarbon radical, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation (as described above), each subscript m independently has a value from 1 to 65 (as described above for starting material II), each subscript o independently has a value from 1 to 99, and subscript x has a value of 3 or greater, with the proviso that subscripts x, m, and o have values ​​such that the copolymer has 200 or fewer silicon atoms per molecule.

[0032] In formula (1), the divalent hydrocarbon group D is R U The divalent hydrocarbon radical D is represented by the empirical formula (C a H 2a ), where the subscript a is 2 to 18. The divalent hydrocarbon group D may be, for example, C2H4, C3H6, C4H8, or C6H 12 Alternatively, each R U When is vinyl, the divalent hydrocarbon group D may have the empirical formula C2H4,

[0033] [ka] or a combination thereof. Formula (1) has at least four Ds per molecule.

[0034] In formula (1), the subscript o has a value of 1 to 99. Each instance of subscript o has a value corresponding to subscript m or subscript y above. When two or more molecules of I) aliphatically unsaturated polydiorganosiloxane and two or more molecules of II) polyorganohydrogensiloxane form a copolymer of formula (1), there are at least two instances where o = y and at least three instances where o = m. The subscript x in the formula above has a value of at least 3, alternatively at least 5, alternatively at least 7, while simultaneously, the subscript x can have a value up to 11, alternatively up to 9, alternatively up to 7. Alternatively, the subscript x can be 3 to 11, alternatively 3 to 9, alternatively 5 to 7.

[0035] In step 1) of the above process, I) the aliphatically unsaturated polydiorganosiloxane and II) the polyorganohydrogensiloxane and the amounts thereof are selected so that the copolymer of formula (1) has 200 or fewer silicon atoms per molecule, alternatively less than 200 silicon atoms per molecule, alternatively up to 150 silicon atoms per molecule, alternatively up to 120 silicon atoms per molecule, while simultaneously the copolymer of formula (1) may have at least 25 silicon atoms per molecule, alternatively at least 50 silicon atoms per molecule, alternatively at least 60 silicon atoms per molecule, alternatively at least 80 silicon atoms per molecule. Alternatively, the copolymer of formula (1) may have 80 to 200 silicon atoms per molecule, alternatively 80 to less than 200 silicon atoms per molecule, alternatively 80 to 150 silicon atoms per molecule.

[0036] In step 2) of the above process, A) Polyether of Formula A-1:

[0037] [ka] wherein Y′, O, X, R′, Z, and subscript n are as described herein; B) the copolymer prepared in step 1), and Optionally, the starting material comprises C) an additional aliphatic unsaturated compound (different from the polyether of A), Starting materials A) are combined under conditions to effect a hydrosilylation reaction of the aliphatically unsaturated groups of the polyether (and, if present, starting material C)) and B) the silicon-bonded hydrogen atoms of the copolymer prepared in step 1). Optionally, in step 2), III) a hydrosilylation reaction catalyst may be added.

[0038] A) Polyether The starting material A) used in the processes described herein is represented by the formula A-1)

[0039] [ka] wherein Y' is an aliphatic unsaturated monovalent hydrocarbon group, X is selected from a linking bond or a divalent organic group having 2 to 22 carbon atoms, each R' is an independently selected divalent hydrocarbon group having 2 to 6 carbon atoms, Z is selected from hydrogen and a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the subscript n has a value of 2 to 60. Alternatively, Y' can be selected from R U Y' may be an alkenyl or alkynyl group, as described and exemplified above for Y. Alternatively, Y' may be selected from the group consisting of vinyl, allyl, and hexenyl.

[0040] In formula A-1, each R' is an independently selected divalent hydrocarbon group. The divalent hydrocarbon group R' is represented by the empirical formula (C b H 2b ), where the subscript b is 2 to 6. The divalent hydrocarbon group R' may be, for example, C2H4, C3H6, C4H8, or C6H 12 Alternatively, the divalent hydrocarbon group of R' may comprise ethylene, propylene, or a combination thereof.

[0041] In formula A-1), X is a connecting bond or a divalent organic group having 2 to 22 carbon atoms. The divalent organic group of X may be a divalent hydrocarbon group having 2 to 18 carbon atoms, or alternatively, 2 to 6 carbon atoms, as described and exemplified above for R'. Alternatively, X may be a different divalent organic group, for example, an alkylene substituted with one or more heteroatoms, such as oxygen. Alternatively, X may be a connecting bond.

[0042] In formula A-1), Z is selected from the group consisting of hydrogen, monovalent hydrocarbon groups having 1 to 30 carbon atoms, hydrocarbonoxy groups such as alkoxy groups having 1 to 30 carbon atoms, and acyl groups. The monovalent hydrocarbon group of Z may be a monovalent hydrocarbon group as described and exemplified above for R. Alternatively, the monovalent hydrocarbon group of Z may have 1 to 8 carbon atoms. Alternatively, Z may be an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryloxy group such as phenoxy. Alternatively, Z may be methyl, ethyl, or phenyl.

[0043] In formula A-1), the subscript n represents the average number of divalent radicals of formula (R'-O) (e.g., hydrocarbylene oxide) groups per molecule. The subscript n is an integer having a value from 2 to 60, alternatively from 2 to 30, alternatively from 2 to 25, alternatively from 2 to 20, alternatively from 2 to 15, alternatively from 2 to 10, alternatively from 2 to 7, or alternatively from 7 to 10. Alternatively, the subscript n may be an integer having a value of at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5, alternatively at least 6, or alternatively at least 7, while at the same time, the subscript n may have a value up to 60, alternatively up to 30, alternatively up to 25, alternatively up to 20, alternatively up to 15, alternatively up to 10, or alternatively up to 7.

[0044] Polyethers of formula A-1) are known in the art and are commercially available, for example, as described in International Patent Publication No. 2020 / 263379(A1), paragraphs

[0019] -

[0020] . For example, polyethylene glycol allyl methyl ether is commercially available as AM350 from Clariant. Starting material A) may be a single polyether or a combination of two or more polyethers that differ in at least one property, such as the selection of each R', the number of units of formula (R'-O) per molecule, the selection of aliphatic unsaturated hydrocarbon groups, and / or the selection of Z. For example, starting material A) may comprise a first polyether of formula A-1) and a second polyether of formula A-1), where one or more of the variables Y', X, R', Z, or subscript n are different in the first polyether and the second polyether. For example, when Y', X, R', and Z are each the same, the subscript n in the first polyether may be smaller than the subscript n in the second polyether. Alternatively, one or more R's in the first polyether may be different from one or more R's in the second polyether. For example, R' in the first polyether may have two carbon atoms, and R' in the second polyether may have more than two carbon atoms, e.g., 3 to 6 carbon atoms. Without being bound by theory, it is believed that when variables such as R' in the first polyether are selected to be more polar than variables such as R' in the second polyether, the resulting copolymer of formula (ABC), described below, has improved foam control and clarity in clear liquid laundry detergents. Alternatively, in addition to the polyether starting material A), the process may include the use of C), an additional aliphatically unsaturated compound different from the starting material A).

[0045] C) Additional aliphatic unsaturated compounds The starting material C) used in the processes described herein is optional. For example, if two or more different polyethers of Formula A-1) are used in the processes described herein, starting material C) can be omitted. Alternatively, starting material C) can be present and can be selected from the group consisting of C1) aliphatically unsaturated trialkoxysilanes, C2) aliphatically unsaturated hydrocarbons, such as alkenes of 2 to 18 carbon atoms or alkenyl-functional aromatic compounds having 8 to 18 carbon atoms, and C3) a combination of both C1) and C2).

[0046] Aliphatically unsaturated trialkoxysilanes which can be used as starting materials C1) are those of the formula R 1 Si(OR 2 ) 3, wherein R 1 is an aliphatic unsaturated monovalent hydrocarbon group of 2 to 12 carbon atoms, and each R 2 R is an independently selected alkyl group of 1 to 12 carbon atoms. 1 The aliphatic unsaturated monovalent hydrocarbon group of R can be an alkenyl group such as vinyl, allyl, or hexenyl, or vinyl and hexenyl, or vinyl. 2 The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 or more carbon atoms). Aliphatically unsaturated trialkoxysilanes include alkenyl-functional trialkoxysilanes such as allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltris(methoxyethoxy)silane. All of these alkenyl-functional silanes are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA). Furthermore, alkenyl-functional silanes can be prepared by known methods, such as those disclosed in U.S. Pat. No. 4,898,961 to Baile et al.

[0047] The alkenes that can be used as starting material C2) can be branched, linear, or a combination thereof, such as ethylene, propylene, butylene, hexylene, or alkenes having 7 to 18 carbon atoms per molecule, and their branched isomers. Alternatively, the alkenes can be cyclic, such as cyclopentene, cyclohexene, or norbornadiene. Alternatively, the alkenes can have 2 to 18, alternatively 3 to 16, alternatively 4 to 14, alternatively 5 to 12, or alternatively 6 to 12 carbon atoms per molecule.

[0048] The alkenyl-functional aromatic compounds that can be used as starting material C2) can have 8 to 18 carbon atoms per molecule, or alternatively 8 to 12 carbon atoms per molecule. For example, the alkenyl-functional aromatic compound can be styrene, α-methylstyrene, or 2,4-dimethylstyrene, which are commercially available, for example, from Sigma Aldrich Inc. (St. Louis, Missouri, USA).

[0049] The amounts of starting material A) and, if present, starting material C) are sufficient to react the silicon-bonded hydrogen atoms of the B) copolymer prepared in step 1) with the aliphatic unsaturated groups of starting material A) (and, if present, starting material C). When starting material C) is not present, the amounts of starting materials A) and B) are sufficient to provide a molar ratio of silicon-bonded hydrogen atoms of the B) copolymer to aliphatic unsaturated groups of the A) polyether (B / A ratio) of >0 to 1, alternatively >0 to <1. Alternatively, when starting material C) is not present, the amount of starting material A) is sufficient to provide a B / A ratio of at least 0.1. Alternatively, when starting material C) is present, the combined amount of starting materials A) and C) is sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated groups [B / (A+C) ratio] of at most 1, alternatively >0 to <1. Alternatively, equimolar amounts of starting materials A) and C) may be used.

[0050] Silicone-Polyether Copolymer The above process forms a reaction product comprising a silicone-polyether copolymer mixture, the silicone-polyether mixture having the formula:

[0051] [ka] Copolymer species of wherein D and R and the subscripts m, o, and x are as defined above. In the above formula, A' represents a group derived from the starting material A), a polyether of formula A-1). The group A' has the following formula:

[0052] [ka] wherein Y is a divalent hydrocarbon group, each X is independently selected from a connecting bond or a divalent hydrocarbon group having 2 to 22 carbon atoms, each R' is independently selected from a divalent hydrocarbon group having 2 to 6 carbon atoms, Z is selected from hydrogen and a monovalent hydrocarbon group having 1 to 30 carbon atoms, and each subscript n independently has a value from 2 to 60, wherein X, R', Z, and subscript n are each as described above for starting material A). In the formula for group A', group Y is formed from the hydrosilylation reaction of an aliphatically unsaturated group Y' (as described above for starting material A)) with a silicon-bonded hydrogen atom (from the starting material B) copolymer), and Y is a divalent hydrocarbon group, which may be as described and exemplified above for D in formula (1). Alternatively, R' in group A' may have two carbon atoms.

[0053] In the formulae (ABC), (ABA) and (CBC) of the copolymer mixtures, C' represents a group that can be derived from the starting material C) above (if starting material C) is present) and / or from starting material A) if, for example, more than one polyether of formula A-1) is used in the process. For example, if more than two different polyethers of formula A-1) are used in the above process, A' and C' can each be a group of formula

[0054] [ka] where one or more of the variables Z, R', X, Y, and subscript n are different between groups A' and C'. For example, subscript n in group A' may have a smaller value than subscript n in group C'. Alternatively, if two different polyethers are used, in group A', R' may have 2 carbon atoms and in group C', R' may have 3 to 6 carbon atoms.

[0055] Alternatively, C1) when an aliphatically unsaturated trialkoxysilane is used in the above process, C' is a compound of the formula -R 3 Si(OR 2 )3, wherein R 3 is a divalent hydrocarbon group, and R 2 Alternatively, when C2) an alkene is used in the above process, C' may be, for example, an alkenyl group of the empirical formula -C c H (2c+1) where the subscript c has a value of 2 to 12.

[0056] Without being bound by theory, it is believed that the copolymers of formula (ABC) provide good defoaming performance and good clarity benefits in clear liquid laundry detergents, however, silicone-polyether copolymer mixtures comprising copolymers of formulas (ABC), (ABA), and (CBC) may be used as defoamers in clear liquid laundry detergents, i.e., it is not necessary to isolate the copolymers of formula (ABC) from the copolymer mixture prior to using the copolymers in the clear liquid laundry detergent.

[0057] How to use The silicone-polyether copolymers of formula (ABC) and / or silicone-polyether copolymer mixtures containing copolymers of formulas (ABC), (ABA), and (CBC) prepared as described above are useful as defoamers. These defoamers can be included in a variety of products, such as foam control compositions. The defoamers and foam control compositions containing the defoamers can provide effective foam control in liquid laundry detergents, such as clear liquid laundry detergents.

[0058] Without being bound by theory, it is believed that the antifoaming agent is "self-emulsifying." As a result, the antifoaming agent can be dispersed and stabilized in a variety of liquids. For example, the antifoaming agent can be utilized by adding it directly to a foaming liquid, such as a cleaning composition such as a liquid laundry detergent. Alternatively, the antifoaming agent may be combined with one or more additional ingredients to form a foam control composition. Exemplary ingredients include linear polydiorganosiloxanes, such as trimethylsiloxy endblocked polydimethylsiloxane (PDMS), available from TDCC under the trade name DOWSIL™ 200 Fluid. When combined with a target antifoaming agent as part of a foam control formulation, the weight ratio of PDMS to antifoaming agent can be 1:3 to 3:1. Other exemplary ingredients include mineral oil and / or organic solvents. When combined with additional ingredients, the combination can be mixed to form an organic liquid mixture. Alternatively, the mixture can be combined with a water-dispersible carrier, such as a silicone glycol or alkyl glycol or mineral oil, as described in U.S. Pat. No. 5,908,891. Alternatively, the antifoaming agent, optionally along with a suitable surfactant (e.g., a fatty acid ester and / or a polyalkylene oxide), and an optional thickener and water under shear, may be combined with such ingredients to form an oil-in-water emulsion. Methods for preparing such emulsions are known and are described, for example, in U.S. Patent No. 6,521,586.

[0059] Traditionally, foam control compositions have included one or more of inorganic fillers, cyclic siloxanes, and siloxane resins. Common inorganic fillers include finely divided particles of silica. Silica typically fumes or precipitates. Other inorganic fillers include silicates, zeolites, Al2O3, TiO2, ZrO2, and combinations thereof. The particles are typically 50-300 m 2 / g specific surface area. Cyclic siloxanes (e.g., D4, D5, and D6) are also commonly present in foam control compositions but are now restricted in many jurisdictions. Siloxane resins are also commonly used in foam control compositions. See, for example, U.S. Pat. Nos. 4,145,308, 5,082,590, and 6,207,722. Such resins, commonly referred to as "MQ" resins, are composed of primarily monofunctional (MeSiO) compounds in a relative molar ratio of 0.25 to 0.75 to 1. 1 / 2 ) and tetrafunctional (SiO 4 / 2 ) units.

[0060] Alternatively, the foam control compositions of the present invention exclude or minimize the traditional inclusion of one or more of inorganic fillers, cyclic siloxanes, and siloxane resins. For example, the subject foam control compositions may contain less than 1 wt. % inorganic filler, alternatively less than 0.5 wt. %, alternatively less than 0.1 wt. %, or even 0 wt. % inorganic filler. Compositions containing less than 0.1 wt. % inorganic filler are characterized herein as being "substantially free" of inorganic filler.

[0061] Alternatively, the foam control composition may contain less than 0.5 wt.%, alternatively less than 0.1 wt.%, alternatively less than 0.01 wt.%, or alternatively 0 wt.% cyclic siloxanes. Formulations containing less than 0.01 wt.% cyclic siloxanes are characterized herein as being "substantially free" of cyclic siloxanes. Alternatively, the subject foam control composition may contain less than 1 wt.%, alternatively less than 0.5 wt.%, alternatively less than 0.1 wt.%, or alternatively 0 wt.% siloxane resins. Formulations containing less than 0.1 wt.% siloxane resins are characterized herein as being "substantially free" of siloxane resins. Alternatively, the foam control composition may be substantially free of one, two, or three of inorganic fillers, cyclic siloxanes, and siloxane resins.

[0062] The subject foam control agents and their formulations can be incorporated into cleaning compositions of the present invention. Such cleaning compositions can be provided in a variety of forms, including, but not limited to, liquid, gel, paste, bar, granular, and powder forms. In addition to personal care such as body and hair washing, such compositions can be used in a variety of cleaning applications, including, but not limited to, laundry, cookware, and tableware (including dishes and plates), and hard surfaces. Alternatively, the cleaning composition can be a liquid laundry detergent composition. Typical liquid laundry detergent formulations include at least one surfactant. Suitable surfactants include nonionic (e.g., polysaccharides, oxylates, amine oxides, fatty acid amides), amphoteric, zwitterionic, cationic (alkylammonium salts), and anionic (e.g., sulfonates, polyalkoxylated carboxylates) surfactants. Applicable liquid laundry detergent compositions may optionally include one or more of soaps (i.e., fatty acid carboxylates), carriers, builders, perfumes, structurants, adjuvants, brighteners, enzymes, dyes, hydrotropes, solvents, dispersants, hueing agents, and rheology modifiers. Alternatively, the liquid laundry detergent composition may include at least one surfactant and 0.001 to 4.0 wt. % (alternatively 0.01 to 2.0 wt. %) of an antifoam agent.

[0063] Alternatively, the defoamers may be used in addition to or in place of the defoamers described in known liquid laundry detergent compositions, such as those disclosed in U.S. Patent Application Publication No. 2017 / 0233681 or International Patent Publication No. 2020 / 263379. Alternatively, the defoamers described herein may be used in addition to or in place of silicone polyethers in cleaning compositions, such as those described in U.S. Patent No. 3,933,672, U.S. Patent No. 8,492,325, U.S. Patent No. 9,133,421, U.S. Patent No. 10,005,110, U.S. Patent Application Publication No. 2017 / 0218312, or U.S. Patent Publication No. 2017 / 0233681.

[0064] Alternatively, the defoaming agent may be used in a clear liquid laundry detergent composition. For example, a clear liquid laundry detergent composition may contain, in addition to the defoaming agent described herein, water, a surfactant such as an anionic surfactant, a nonionic surfactant, or a combination thereof, a stabilizer such as an alkylene glycol (e.g., propylene glycol and / or ethylene glycol from TDCC), and a neutralizer such as an alkanolamine (e.g., triethanolamine). Suitable anionic surfactants include alkylbenzene sulfonates, such as linear C10-C13 alkylbenzene sulfonate sodium salt, commercially available from BASF as DISPONIL™ LDBS 55, sodium laureth sulfate, such as MARLINAT™ 242 / 28 from Sasol Chemicals, and combinations thereof. Suitable nonionic surfactants include polyalkylene glycol ethers, such as alkyl polyethylene glycol ethers made from C12-C18 alcohols and ethylene oxide, such as DEHYDOL™ LT 7 from BASF. The amount of antifoam agent in the clear liquid laundry detergent composition will depend on various factors, including the type and amount of silicone-polyether copolymer of formula (ABC) above, as well as the types and amounts of other ingredients in the clear liquid laundry detergent, but the amount of antifoam agent may be at least 0.001 wt. %, alternatively at least 0.01 wt. %, alternatively at least 0.1 wt. %, alternatively at least 0.5 wt. %, while at the same time, the amount may be up to 4 wt. %, alternatively at most 2 wt. %, alternatively at most 1 wt. %, alternatively at most 0.5 wt. %, each based on the weight of the clear liquid laundry detergent composition. [Example]

[0065] The following examples are provided to illustrate the present invention to one of ordinary skill in the art and should not be construed as limiting the invention as claimed. The starting materials used herein are listed in Table 1.

[0066] [Table 1]

[0067] Example 1: A 2-liter jacketed glass reactor equipped with a heating unit, mechanical stirrer, nitrogen purge, and condenser was charged with 719.3 g of bis-vinyl-terminated polydimethylsiloxane DP=46. The reactor contents were heated to 30°C with mixing. 48.1 g of 1,1,3,3-tetramethyldisiloxane was added to the reactor. 2 ppm of Karstedt catalyst diluted in bis-vinyl-terminated polydimethylsiloxane DP=46 was added. The reaction was allowed to exotherm and then held at 40°C for 2 hours. A sample was taken and the SiH content was measured using FTIR (SiH=350 ppm). The reactor was then charged with 35.1 g of allyl / methyl-terminated polypropylene oxide DP=2 and 63.8 g of allyl / methyl-terminated polyethylene oxide DP=7 and heated to 105°C. 8 ppm of Karstedt catalyst in IPA was added. The reactor was held at 105°C for 2 hours and then cooled. No SiH content was detected by FTIR.

[0068] Example 2: A 250 mL round-bottom flask equipped with a heating mantle, magnetic stir bar, nitrogen purge, and condenser was charged with 41.3 g of bis-vinyl-terminated polydimethylsiloxane DP=30 and 3.6 g of 1,1,3,3-tetramethyldisiloxane. 4 ppm of Karstedt catalyst diluted in bis-vinyl-terminated polydimethylsiloxane DP=30 was added. The mixture was heated to 40°C and held for 3 hours. The reactor was then charged with 1.7 g of allyl / methyl-terminated polypropylene oxide DP=2 and 3.0 g of allyl / methyl-terminated polyethylene oxide DP=7 and heated to 100°C. 4 ppm of Karstedt catalyst in IPA was added. The reactor was held at 100°C for 3 hours and then cooled. The SiH content was determined to be less than 5 ppm by NMR.

[0069] Example 3: A 2-liter jacketed glass reactor equipped with a heating unit, mechanical stirrer, nitrogen purge, and condenser was charged with 747.2 g of bis-vinyl-terminated polydimethylsiloxane DP=46. The reactor contents were heated to 30°C with mixing. 44.0 g of 1,1,3,3-tetramethyldisiloxane was added to the reactor. 2 ppm of Karstedt catalyst diluted in bis-vinyl-terminated polydimethylsiloxane DP=46 was added. The reaction was allowed to exotherm and then held at 40°C for 2 hours. A sample was taken and the SiH content was measured using FTIR (SiH=280 ppm). The reactor was then charged with 26.5 g of allyl / methyl-terminated polypropylene oxide DP=2 and 47.9 g of allyl / methyl-terminated polyethylene oxide DP=7 and heated to 105°C. 8 ppm of Karstedt catalyst in IPA was added. The reactor was held at 105°C for 2 hours and then cooled. No SiH content was detected by FTIR.

[0070] Example 4: A 250 mL round-bottom flask equipped with a heating mantle, magnetic stir bar, nitrogen purge, and condenser was charged with 41.5 g of bis-vinyl-terminated polydimethylsiloxane DP=30 and 3.4 g of 1,1,3,3-tetramethyldisiloxane. 4 ppm of Karstedt catalyst diluted in bis-vinyl-terminated polydimethylsiloxane DP=30 was added. The mixture was heated to 40°C and held for 3 hours. The reactor was then charged with 1.7 g of allyl / methyl-terminated polypropylene oxide DP=2 and 3.0 g of allyl / methyl-terminated polyethylene oxide DP=7 and heated to 100°C. 4 ppm of Karstedt catalyst in IPA was added. The reactor was held at 100°C for 3 hours and then cooled. The SiH content was determined to be less than 5 ppm by NMR.

[0071] Comparative Example 5 (DP > 200): A 250 mL round-bottom flask equipped with a heating mantle, magnetic stir bar, nitrogen purge, and condenser was charged with 44.6 g of bis-vinyl-terminated polydimethylsiloxane DP = 30 and 3.2 g of 1,1,3,3-tetramethyldisiloxane. 4 ppm of Karstedt catalyst diluted in bis-vinyl-terminated polydimethylsiloxane DP = 30 was added. The mixture was heated to 40°C and held for 3 hours. The reactor was then charged with 1.7 g of allyl / methyl-terminated polypropylene oxide DP = 2 and 3.0 g of allyl / methyl-terminated polyethylene oxide DP = 7 and heated to 100°C. 4 ppm of Karstedt catalyst in IPA was added. The reactor was held at 100°C for 3 hours and then cooled. The SiH content was determined to be less than 5 ppm by NMR.

[0072] Comparative Example 6 - (Equilibration) Comparison with Examples 1 and 2: A 100 mL round-bottom flask equipped with a heating mantle, magnetic stir bar, nitrogen purge, and condenser was charged with 30 g of bis-hydride terminated polydimethylsiloxane DP=80 and 1.1 g of allyl / methyl terminated polypropylene oxide DP=2. The contents of the reactor were mixed at room temperature until a homogeneous mixture was obtained. The reactor was heated to 85°C. 3 ppm of IPA and Karstedt catalyst were added. The reactor was then held at 85°C for 5 hours before being cooled to ambient temperature. 3.19 g of allyl / methyl terminated polyethylene oxide DP=7 and 1 mL of IPA were added to the flask. The reactor was heated to 85°C. 4 ppm of Karstedt catalyst in IPA was added. The reactor was held at 85°C for 7 hours. The IPA was removed by distillation before being cooled to room temperature. The SiH content was determined to be less than 5 ppm by NMR.

[0073] Comparative Example 7 (Equilibration): Comparison with Examples 3 and 4: A 2-liter jacketed glass reactor equipped with a heating unit, mechanical stirrer, nitrogen purge, and condenser was charged with 776 g of bis-hydride terminated siloxane DP=100, 26 g of allyl / methyl terminated polypropylene oxide DP=2, and 47 g of allyl / methyl terminated polyethylene oxide DP=7. The system was purged with nitrogen, and the reactor contents were heated to 105°C with mixing. 8 ppm of Karstedt catalyst in IPA was added. The reactor was held at 105°C for 2 hours and then cooled. No SiH content was detected by FTIR.

[0074] Comparative Example 8 (Equilibration): (Comparison with Example 5): A 250 mL round-bottom flask equipped with a heating mantle, magnetic stir bar, nitrogen purge, and condenser was charged with 45 g of bis-hydride terminated polydimethylsiloxane DP=200, 0.7 g of allyl / methyl terminated polypropylene oxide DP=2, and 1.3 g of allyl / methyl terminated polyethylene oxide DP=7. The reactor contents were mixed at room temperature until a homogeneous mixture was obtained. The reactor was heated to 90°C. 6 ppm of Karstedt catalyst in IPA was added. The reactor was held at 90°C for 3 hours and then cooled. The SiH content was determined to be less than 5 ppm by NMR.

[0075] To demonstrate the effect of various SPEs on foaming, several cleaning composition samples were prepared by mixing various SPEs prepared as described in the above examples as foam control agents into a model cleaning composition (liquid detergent) using a Hauschild Speedmixer. The ingredients of the cleaning compositions are listed in Table 2 below. The foam control performance of each cleaning composition sample was measured by adding 0.7 g of the cleaning composition (containing the SPE prepared as described in the above examples as a foam control agent) to 300 mL of tap water in a graduated cylinder. The cylinder was then rotated for 9 minutes at 30 revolutions per minute, after which the foam height was measured.

[0076] A summary of the results is shown in Table 3. The clarity of the cleaning compositions was measured using % transmittance, the percentage of light transmitted through the sample, measured using a Turbiscan™ from Formulaction (www.formulaction.com). A light source (880 nm) was sent through a glass tube containing the cleaning composition containing the SPE. A detector acquired a transmission signal (T). The higher the transmittance value, the more transparent the cleaning composition. A summary of the results is shown in Table 3.

[0077] [Table 2]

[0078] [Table 3]

[0079] The data in Table 3 show that Examples 1 and 2 have improved clarity compared to Example 6 without sacrificing foam control performance. Example 1 contains a silicone-polyether copolymer having an average of 5.1 ethylene groups per molecule (divalent hydrocarbon group D shown in formulas ABA, ABC, and CBC), and Example 2 contains a silicone-polyether copolymer having an average of >5.1 ethylene groups per molecule. Examples 1 and 2 demonstrate that increasing the number of divalent hydrocarbon groups D can improve clarity when silicone-polyether copolymers are used in liquid detergent formulations. Table 3 also shows that Examples 3 and 4, which contain antifoam agents according to the present invention, have better clarity than Example 7, which contains a comparative silicone polyether made by an equilibration process that does not contain the divalent hydrocarbon group D of the antifoam agents of the present invention. Comparative Example 5 demonstrates that using a silicone-polyether copolymer having more than 200 silicon atoms per molecule results in poor foam control performance and poor clarity in the tested liquid laundry detergents. [Industrial Applicability]

[0080] The above examples show that the silicone-polyether copolymers prepared by the process described herein provide both good foam control and good clarity in liquid laundry detergent compositions.Without being bound by theory, it is believed that this process also avoids the formation of cyclic polydiorganosiloxanes such as D4, D5, and D6, compared to previous equilibration processes for making silicone polyether copolymers.

[0081] Definitions and Usage of Terms All amounts, ratios, and percentages herein are by weight unless otherwise specified. The Summary and Abstract are incorporated herein by reference. Unless the context of the specification dictates otherwise, the articles "a," "an," and "the" each refer to one or more. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in sections §2111.03 I, II, and III of the Manual of Patent Examining Procedure, Ninth Edition, Revision 08.2017, Last Revised January 2018. The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples. Abbreviations used herein have the definitions in Table 4.

[0082] [Table 4]

[0083] The present invention has been described in an illustrative manner, and it should be understood that the terminology used is intended to be in the nature of terms of description rather than of limitation. With respect to any Markush group on which a description of a particular feature or aspect herein relies, different, unusual, and / or unexpected results may be obtained from each element of the respective Markush group, independent of all other elements of the Markush group. Each element of a Markush group may be relied upon individually and / or in combination to provide sufficient support for specific embodiments within the scope of the appended claims.

[0084] Furthermore, any ranges and subranges relied upon in describing the invention are understood to independently and inclusively fall within the scope of the appended claims and to describe and contemplate the entire range encompassing every and / or portion thereof, even if that whole and / or portion thereof is not expressly set forth herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the invention, and that such ranges and subranges can be further delineated into relevant halves, thirds, quarters, fifths, and any other subranges contained within the ranges. By way of example only, the range "1 to 99" may be further divided into a lower third (i.e., 1 to 33), a middle third (i.e., 34 to 66), and an upper third (i.e., 67 to 99), or the range "1 to 99" may include the subranges "1 to 10," "2 to 49," and "3 to 46," each of which, individually and collectively, are within the scope of the appended claims and may individually and / or collectively depend on and provide appropriate justification for particular embodiments within the scope of the appended claims. Additionally, with respect to terms defining or modifying ranges, such as "at least," "greater than," "less than," "less than or equal to," etc., such terms should be understood to include subranges and / or upper or lower limits.

[0085] Test Method The silicon-bonded hydrogen (Si—H) content of polyorganohydrogensiloxanes can be determined using FTIR or NMR as follows.

[0086] FTIR Samples were characterized by FTIR as follows: All samples were diluted to 10 wt% in tetrachloroethylene and loaded into 0.5 mm pathlength liquid cells with calcium fluoride windows. Measurements were performed on a Perkin Elmer Spectrum 100 FTIR spectrometer between 4000 and 500 cm with a resolution of 8 cm.

[0087] To quantify the SiH content of the experimental samples, a calibration curve of absorbance at approximately 2120 cm was constructed using samples with known SiH content ranging from 0 to 825 ppm SiH. This calibration curve was used to quantify the SiH content of the experimental samples used to determine DP.

[0088] NMR The samples were characterized by NMR as follows: All samples were dissolved in deuterated chloroform / chromium(III) acetylacetonate and measured by 29Si NMR on a 400 AVANCE III or 600 AVANCE NEO NMR spectrometer from BRUKER. A 10 mm BB probe was used. The pulse sequence zgig was used. Silicon species were identified based on chemical shifts. DP is the M group (-Me2Si(O 1 / 2 )CH2CH2Si(O 1 / 2 )Me2-) and D groups.

[0089] The silicon-bonded hydrogen to alkenyl and / or alkynyl ratio (abbreviated "SiH / Vi ratio") can be determined by calculating the total weight percent of aliphatically unsaturated monovalent hydrocarbon groups, e.g., vinyl [V], in the composition and the total weight percent of silicon-bonded hydrogen [H] in the composition; if the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, then the molar ratio of silicon-bonded hydrogen to vinyl is 27[H] / [V].

[0090] Embodiments of the present invention In a first embodiment, a process for preparing a clear liquid laundry detergent composition comprises: 1) under conditions for conducting a first hydrosilylation reaction; I) Aliphatically unsaturated diorganosiloxanes of the formula:

[0091] [ka] In the formula, each R U are independently selected aliphatic unsaturated monovalent hydrocarbon radicals, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each subscript y independently has a value from 1 to 99; II) Organohydrogensiloxanes of the formula:

[0092] [ka] wherein each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation; and each subscript m independently has a value from 1 to 65; wherein I) the aliphatically unsaturated polydiorganosiloxane and II) the polyorganohydrogensiloxane are present in a molar ratio sufficient to provide a silicon-bonded hydrogen content / aliphatically unsaturated monovalent hydrocarbon group content (SiH / Vi ratio) >1; and III) by combining starting materials comprising a hydrosilylation catalyst in an amount sufficient to catalyze the hydrosilylation reaction of II) silicon-bonded hydrogen atoms from the polyorganohydrogensiloxane with I) aliphatically unsaturated monovalent hydrocarbon groups from the aliphatically unsaturated polydiorganosiloxane; A copolymer of the formula

[0093] [ka] wherein each D is an independently selected divalent hydrocarbon radical, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, each subscript m independently has a value from 1 to 65, each subscript o independently has a value from 1 to 99, and subscript x has a value of 3 or greater, with the proviso that subscripts x, m, and o have values ​​such that the copolymer has 200 or fewer silicon atoms per molecule; 2) under conditions for carrying out a second hydrosilylation reaction; A) Formula (A-1)

[0094] [ka] wherein Y' is an aliphatic unsaturated organic group; X is selected from a linking bond or a divalent hydrocarbon group having from 2 to 22 carbon atoms; each R' is an independently selected divalent hydrocarbon group having from 2 to 6 carbon atoms; Z is selected from hydrogen and a monovalent hydrocarbon group having from 1 to 30 carbon atoms; and each subscript n independently has a value from 2 to 60; B) the copolymer prepared in step 1) above; Optionally, C) an additional aliphatic unsaturated compound selected from the group consisting of C1) silanes, C2) alkenes, and C3) combinations thereof. (provided that when one polyether of formula A-1) is used as starting material A), C) additional aliphatic unsaturated compounds are present), by combining starting materials including preparing a second reaction product comprising a silicone-polyether copolymer mixture; Optionally, 3) forming a foam control composition by combining the silicone-polyether copolymer mixture with at least one additional ingredient; 4) forming a clear liquid laundry detergent by combining the silicone-polyether copolymer mixture or the foam control composition with one or more additional ingredients selected from the group consisting of water, surfactants, stabilizers, and neutralizing agents.

[0095] In a second embodiment, in the process of the first embodiment, each R is a methyl group, each D has the empirical formula (C2H4), and the subscripts x, m, and o have values ​​such that the copolymer has 80 to 150 silicon atoms per molecule.

[0096] In a third embodiment, in the process of the second embodiment, the process further comprises the step of removing residual catalyst from the second reaction product after step 2) and before step 3).

[0097] In a fourth embodiment, in the process of any one of the first to third embodiments, A) in the polyether, Y' is an alkenyl group of 2 to 6 carbon atoms, each R' is independently ethylene or propylene, X is a connecting bond, and Z is hydrogen or an alkyl group of 1 to 8 carbon atoms.

[0098] In a fifth embodiment, in the process of any one of the first to fourth embodiments, in step 2), C) an additional aliphatic unsaturated compound is present; C1) Formula R 1 Si(OR 2 )3(wherein, R 1 is an aliphatic unsaturated monovalent hydrocarbon group of 2 to 12 carbon atoms, and each R 2 are independently selected alkyl groups of 1 to 12 carbon atoms, C2) aliphatic unsaturated hydrocarbons of 2 to 18 carbon atoms, and C3) is selected from the group consisting of a combination of both C1) and C2).

[0099] In a sixth embodiment, in the process of the first embodiment, the silicone-polyether copolymer mixture is a silicone-polyether copolymer having the formula:

[0100] [ka] Copolymer species of wherein D and R and the subscripts m, o, and x are as defined above, A' is a group derived from a polyether, and has the formula

[0101] [ka] wherein each X is independently selected from a connecting bond or a divalent hydrocarbon group having 2 to 22 carbon atoms; each R' is independently a divalent hydrocarbon group having 2 to 6 carbon atoms; Z is selected from hydrogen and a monovalent hydrocarbon group having 1 to 30 carbon atoms; each subscript n independently has a value from 2 to 60; and C' is -R 3 Si(OR 2 )3(wherein, R 3 is a divalent hydrocarbon group, and R 2 is as above), -R 4 (In the formula, R 4 is an alkyl group), and

[0102] [ka] A' has a formula selected from the group: wherein Z, R', X, Y, and subscript n are as described above for A', except that at least one of Z, R', X, Y, and subscript n is different from that of A'.

[0103] In a seventh embodiment, in the process of the sixth embodiment, each R is a methyl group, each D has the empirical formula (C2H4), and the subscripts x, m, and o have values ​​such that each copolymer in the silicone-polyether copolymer mixture has from 80 to 150 silicon atoms per molecule.

[0104] In an eighth embodiment, in the process of the sixth or seventh embodiment, each Y is an independently selected alkylene group of 2 to 6 carbon atoms, each R' is independently ethylene or propylene, each X is a connecting bond, and each Z is hydrogen or an alkyl group of 1 to 8 carbon atoms.

[0105] In a ninth embodiment, in the process of any one of the first to eighth embodiments, step 3) is present, and the additional component is selected from the group consisting of a linear polydiorganosiloxane, a mineral oil, an organic solvent, a water-dispersible carrier, or a combination thereof.

[0106] In a tenth embodiment, in the process of the ninth embodiment, the foam control composition does not include at least one of a cyclic siloxane, an inorganic filler, and a siloxane resin.

[0107] In an eleventh embodiment, in the process of any one of the first to tenth embodiments, in step 4), a stabilizer is present and the stabilizer comprises an alkylene glycol.

[0108] In a twelfth embodiment, in the process of any one of the first to eleventh embodiments, in step 4), a surfactant is present, and the surfactant is selected from an anionic surfactant, a nonionic surfactant, or a combination thereof.

[0109] In a thirteenth embodiment, in the process of any one of the first to twelfth embodiments, a neutralizing agent is present and the neutralizing agent comprises an alkanolamine.

[0110] In a fourteenth embodiment, in the process of any one of the sixth to thirteenth embodiments, A' is a group represented by the formula

[0111] [ka] where Z, X, Y, and subscript n are as defined above, and R' has 2 carbon atoms.

[0112] In a fifteenth embodiment, in the process of the fourteenth embodiment, C' is a compound of the formula

[0113] [ka] where X, Y, and subscript n are as defined above, and R' has 3 to 6 carbon atoms.

[0114] In a sixteenth embodiment, the process of any one of the first to fifteenth embodiments further comprises forming a foam control formulation by combining starting materials including the copolymer mixture and at least one additional ingredient prior to forming the clear liquid laundry detergent.

[0115] In a seventeenth embodiment, in the process of the sixteenth embodiment, the additional component is selected from the group consisting of linear polydiorganosiloxane, mineral oil, organic solvent, water-dispersible carrier, surfactant, thickener, water, and combinations thereof.

[0116] In an eighteenth embodiment, a clear liquid laundry detergent is prepared by the process described in any one of the first to seventeenth embodiments.

Claims

1. A process comprising: 1) under conditions for carrying out a hydrosilylation reaction; I) Aliphatically unsaturated diorganosiloxanes of the formula: 【Chemistry 1】 In the formula, each R Ｕ are independently selected aliphatically unsaturated monovalent hydrocarbon radicals, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each subscript y independently has a value from 1 to 99; II) Organohydrogensiloxanes of the formula: 【Chemistry 2】 wherein each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation; and each subscript m independently has a value from 1 to 65; wherein I) the aliphatically unsaturated polydiorganosiloxane and II) the polyorganohydrogensiloxane are present in a molar ratio sufficient to provide a silicon-bonded hydrogen content / aliphatically unsaturated monovalent hydrocarbon group content (SiH / Vi ratio) > 1; and III) by combining starting materials comprising a hydrosilylation catalyst in an amount sufficient to catalyze the hydrosilylation reaction of II) silicon-bonded hydrogen atoms from the polyorganohydrogensiloxane with I) aliphatically unsaturated monovalent hydrocarbon groups from the aliphatically unsaturated polydiorganosiloxane; A copolymer of the formula 【Transformation 3】 wherein each D is an independently selected divalent hydrocarbon radical, each R is independently selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation and monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, each subscript m independently has a value from 1 to 65, each subscript o independently has a value from 1 to 99, and subscript x has a value of 3 or greater, with the proviso that subscripts x, m, and o have values ​​such that the copolymer has 200 or fewer silicon atoms per molecule; 2) under conditions for carrying out a hydrosilylation reaction; A) Formula (A-1) 【Chemistry 4】 wherein Y' is an aliphatically unsaturated organic group; X is selected from a connecting bond or a divalent hydrocarbon group having from 2 to 22 carbon atoms; each R' is an independently selected divalent hydrocarbon group having from 2 to 6 carbon atoms; Z is selected from hydrogen and a monovalent hydrocarbon group having from 1 to 30 carbon atoms; and each subscript n independently has a value from 2 to 60; B) the copolymer prepared in step 1) above; Optionally, C) an additional aliphatically unsaturated compound selected from the group consisting of C1) a silane, C2) an alkene, and C3) combinations thereof. (provided that when one polyether of formula A-1) is used as starting material A), C) additional aliphatic unsaturated compounds are present), by combining starting materials including preparing a second reaction product comprising a silicone-polyether copolymer mixture.

2. Each R is a methyl group, and each D is a group having the empirical formula (C ２ H ４ 2. The process of claim 1, wherein the copolymer has a silicon atom content of 80 to 150 silicon atoms per molecule.

3. The process comprises: adding additional hydrosilylation reaction catalyst after step 1), before step 2) and / or during step 2); After step 2), removing residual catalyst from the second reaction product; 3. The process of claim 1 or claim 2, further comprising one or more additional steps selected from the following after step 2): purifying the second reaction product.

4. A) The process of any one of claims 1 to 3, wherein in the polyether, Y' is an alkenyl group of 2 to 6 carbon atoms, each R' is independently ethylene or propylene, X is a connecting bond, and Z is hydrogen or an alkyl group of 1 to 8 carbon atoms.

5. 4. The process of any one of claims 1 to 3, wherein a combination comprising a first polyether and a second polyether is used, wherein in the first polyether, R' has 2 carbon atoms and in the second polyether, R' has 3 to 6 carbon atoms.

6. C) the additional aliphatically unsaturated compound is present; C1) Formula R １ Si(OR ２ ) ３ (In the formula, R １ is an aliphatic unsaturated monovalent hydrocarbon radical of 2 to 12 carbon atoms, and each R ２ and R is an independently selected alkyl group of 1 to 12 carbon atoms; C2) aliphatic unsaturated hydrocarbons of 2 to 18 carbon atoms, and C3) A process according to any one of claims 1 to 4, wherein C3) is selected from the group consisting of a combination of both C1) and C2).

7. 7. The process of claim 6, wherein the aliphatic unsaturated hydrocarbon is an alkene of 6 to 12 carbon atoms.

8. 8. A silicone-polyether copolymer mixture prepared by the process of any one of claims 1 to 7, wherein the silicone-polyether copolymer mixture has the formula: 【Transformation 5】 Copolymer species of wherein D and R and the subscripts m, o, and x are as defined above, A′ is a group derived from a polyether, and has the formula 【Transformation 6】 wherein each X is independently selected from a connecting bond or a divalent hydrocarbon having from 2 to 22 carbon atoms; each R' is independently a divalent hydrocarbon group having from 2 to 6 carbon atoms; Z is selected from hydrogen and a monovalent hydrocarbon group having from 1 to 30 carbon atoms; each subscript n independently has a value from 2 to 60; and C' is -R ３ Si(OR ２ ) ３ (In the formula, R ３ is a divalent hydrocarbon group, and R ２ is as above), -R ４ (In the formula, R ４ is an alkyl group), and 【Transformation 7】 wherein Z, R', X, Y, and subscript n are as described above for A', with the proviso that at least one of Z, R', X, Y, and subscript n is different from that of A'.

9. Each R is a methyl group, and each D is a group having the empirical formula (C ２ H ４ 9. The copolymer mixture of claim 8, wherein the subscripts x, m, and o have values ​​such that each copolymer in the silicone-polyether copolymer mixture has from 80 to 150 silicon atoms per molecule.

10. 10. The copolymer mixture of claim 8 or claim 9, wherein each Y is an independently selected alkylene group of 2 to 6 carbon atoms, each R' is independently ethylene or propylene, each X is a connecting bond, and each Z is hydrogen or an alkyl group of 1 to 8 carbon atoms.

11. A foam control formulation comprising the copolymer mixture of any one of claims 6 to 10 and at least one additional ingredient.

12. 12. The foam control formulation of claim 11, wherein the additional component is selected from the group consisting of a linear polydiorganosiloxane, a mineral oil, an organic solvent, a water-dispersible carrier, a surfactant, a thickener, water, and combinations thereof.

13. Use of a copolymer mixture according to any one of claims 8 to 10 or a foam control formulation according to claim 11 or claim 12 as an antifoam agent.

14. Use of a copolymer mixture according to any one of claims 8 to 10 or a foam formulation according to claim 11 or claim 12 as an antifoam agent in a clear liquid detergent.

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