Defoaming agent composition

Abstract

The invention relates to a defoamer composition. The invention also relates to a method for reducing or preventing foam in an aqueous composition. The defoamer composition of the present invention comprises at least one hydrophobic liquid; and at least one modified polyacrylate polymer. The modified polyacrylate polymer is obtainable by a process comprising: 1. Reacting at least one selected from the group consisting of substituted or unsubstituted C1-C22 alkyl acrylates, substituted or unsubstituted C4-C22 cycloalkyl acrylates, substituted or unsubstituted C1-C22 acrylamides, esters of acrylic acid with polyalkyl ether alcohols, and substituted or unsubstituted C4-C22 cycloalkyl acrylates; polymerizing acrylate monomers, or a combination of two or more thereof, to obtain at least one polyacrylate polymer; and 2. Modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one alcohol selected from the group consisting of (c1) at least one unsubstituted C8-C36 alcohol, (c2) at least one polyalkyl ether alcohol, or a combination of two or more thereof.

Description

Technical Field

[0001] The present invention relates to a defoamer composition. The present invention also relates to a method for reducing or preventing foam in an aqueous composition. Background Art

[0002] Aqueous compositions in the form of dispersions or emulsions are generally used for multiple purposes, such as coatings. These aqueous compositions generally contain one or more stabilizers, such as surfactants, emulsifiers, dispersants, etc. The presence of such stabilizers results in the risk of foaming during operations such as mixing and applying coatings. Foaming may also occur due to other reasons. The retention of foaming or bubbles in the aqueous composition causes multiple problems. For example, an aqueous coating composition with foam may provide a surface coating with defects such as pits and fish eyes.

[0003] Antifoam agents or antifoam compositions are generally used to reduce foaming in aqueous compositions. Antifoam compounds are known in the prior art and are described, for example, in the following references.

[0004] EP 3210663 B1 discloses a silicone defoamer composition comprising a silicone active material, a polyether-polydiorganosiloxane and a polyether polyol.

[0005] EP 2947103A1 discloses a silyl group-containing polyvinyl alcohol-based resin having defoaming properties and adhesion to inorganic adherends such as glass.

[0006] However, the use of defoamers is associated with various problems. Some defoamers exhibit poor defoaming ability and / or have a transient defoamer effect. Defoamers comprising wax and paraffin oil tend to affect the scrub resistance of surface coatings. Defoamers may be incompatible with one or more components of the aqueous composition, which causes its rheology to change or causes precipitate formation. Some defoamers such as silicones tend to adversely affect the main purpose of the aqueous composition. An effective amount of the defoamer composition may change the characteristics of the aqueous composition to the extent that its normal function is affected, for example, a paint composition may not be able to provide a glossy finish after adding the defoamer composition. Therefore, there is a continuous demand for a defoamer composition that will effectively defoam the aqueous composition without affecting its desired characteristics.

[0007] Accordingly, it is an object of the present invention to provide a defoamer composition that reduces or prevents foam in an aqueous composition. In addition, it is desirable that the defoamer composition is compatible with the aqueous composition. It is also an object of the present invention to provide a method for reducing or preventing foam in an aqueous composition. Summary of the invention

[0008] It was unexpectedly found that the defoamer composition of the present invention exhibits effective defoamer activity in aqueous compositions. In addition, the defoamer composition has high compatibility with aqueous compositions. The present invention provides a method for reducing or preventing foam in aqueous compositions.

[0009] Accordingly, one aspect of the present invention relates to a defoamer composition comprising

[0010] a. at least one hydrophobic liquid; and

[0011] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0012] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 acrylamide, or an acrylate monomer of an ester of acrylic acid and a polyalkyl ether alcohol to obtain at least one polyacrylate polymer; and

[0013] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0014] In some embodiments, the present invention relates to a defoamer composition comprising

[0015] a. at least one hydrophobic liquid; and

[0016] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0017] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 Acrylic acid ester monomer polymerization of acrylamide or ester of acrylic acid and polyalkyl ether alcohol

[0018] to obtain at least one polyacrylate polymer; and

[0019] ii. by using at least one selected from unsubstituted C8-C 36 The alcohol (c1), or the alcohol of the polyalkyl ether alcohol (c2), is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0020] Another aspect of the present invention relates to a method for reducing or preventing foam in an aqueous composition, the method comprising adding a defoamer composition to the aqueous composition in an amount ranging from 0.01 wt.% to 5.0 wt.%, based on 100 wt.% of the total weight of the aqueous composition. DETAILED DESCRIPTION

[0021] Before describing the compositions and formulations of the present invention, it should be understood that the present invention is not limited to the specific compositions and formulations described, as such compositions and formulations may, of course, vary. It should also be understood that the terminology used herein is not intended to be limiting, as the scope of the present invention will be limited only by the appended claims.

[0022] If a group is defined as including at least a certain number of embodiments hereinafter, this means that it also includes a group preferably consisting only of these embodiments. In addition, the terms 'first', 'second', 'third' or 'a', 'b', 'c', etc. in the specification and claims are used to distinguish similar elements, and are not necessarily used to describe sequential or chronological order. It should be understood that the terms used in this way are interchangeable where appropriate, and the embodiments of the present invention described herein can be operated in other sequences except as described or shown herein. In the case of the steps of the methods or uses or tests of the terms 'first', 'second', 'third' or '(A)', '(B)' and '(C)' or '(a)', '(b)', '(c)', '(d)', 'i', 'ii', etc., unless otherwise indicated in the application as described above or below, there is no time or time interval coherence between these steps, that is, these steps can be performed simultaneously or there can be a time interval of seconds, minutes, hours, days, weeks, months or even years between such steps.

[0023] Furthermore, ranges defined throughout this specification also include the endpoints, ie, a range of 1 to 10 means that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalents under applicable law.

[0024] In the following paragraphs, different aspects of the present invention are defined in more detail. Unless explicitly indicated to the contrary, each aspect so defined can be combined with any one or more other aspects. In particular, any feature indicated as preferred or advantageous can be combined with any one or more other features indicated as preferred or advantageous.

[0025] References throughout this specification to 'one embodiment' or 'an embodiment' mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrase 'in one embodiment' or 'in an embodiment' in various places throughout this specification do not necessarily all refer to the same embodiment, but may.

[0026] Furthermore, in one or more embodiments, specific features, structures, or characteristics may be combined in any suitable manner, as will be apparent to those skilled in the art from this disclosure. Furthermore, although some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are also intended to be within the scope of the present invention and form different embodiments, as will be understood by those of ordinary skill in the art. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

[0027] The defoamer composition of the present invention comprises a modified polyacrylate polymer. The modified polyacrylate polymer is amphiphilic in nature. The properties of the modified polyacrylate polymer depend on the monomers used to prepare the polyacrylate polymer and the alcohol used for its transesterification, i.e., polyalkyl ether alcohol, which alcohol is optionally reacted with a C8-C 36 The defoamer composition of the present invention is also compatible with aqueous compositions. In addition, the defoamer composition of the present invention is effective in reducing or preventing foam in aqueous compositions.

[0028] Accordingly, one aspect of the present invention relates to a defoamer composition comprising

[0029] a. at least one hydrophobic liquid; and

[0030] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0031] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 acrylamide, or an acrylate monomer of an ester of acrylic acid and a polyalkyl ether alcohol to obtain at least one polyacrylate polymer; and

[0032] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0033] In some embodiments, the present invention relates to a defoamer composition comprising

[0034] a. at least one hydrophobic liquid; and

[0035] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0036] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 acrylamide, or an acrylate monomer of an ester of acrylic acid and a polyalkyl ether alcohol to obtain at least one polyacrylate polymer; and

[0037] ii. by using at least one selected from unsubstituted C8-C 36 The alcohol (c1), or the alcohol of the polyalkyl ether alcohol (c2), is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0038] In the context of the present invention, as used herein, the term alkyl refers to a non-cyclic saturated aliphatic group, including those of the general formula C n H 2n+1 The alkyl group is a linear alkyl saturated hydrocarbon group represented by alkyl, wherein n is the number of carbon atoms 1, 2, 3, 4, etc. Preferably, alkyl refers to a linear and branched unsubstituted C2 to C 22 The carbon atom is selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, 1-ethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, or 6-ethyloctyl.

[0039] In the context of the present invention, as used herein, the term cycloalkyl refers to monocyclic and bicyclic saturated alicyclic groups, including branched cycloalkyl saturated hydrocarbons. Preferably, cycloalkyl refers to C4 to C22 The carbon atom is selected from cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl, cycloeicosyl, cycloheneicosyl, or cyclodocosyl.

[0040] In the context of the present invention, the term "alcohol" refers to a compound having one or more hydroxyl groups. 36 Alcohol refers to a straight-chain or branched C8-C 36 alkyl.

[0041] In the context of the present invention, the term "mineral oil" refers to an oil selected from a mixture of various colorless, odorless and light higher alkanes obtained from mineral sources, in particular by various processes including the distillation of petroleum. Typically, mineral oil is a liquid obtained from refining crude oil.

[0042] In one embodiment, the composition comprises

[0043] a. at least one hydrophobic liquid; and

[0044] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0045] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0046] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0047] In one embodiment, the composition comprises

[0048] a. at least one hydrophobic liquid; and

[0049] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0050] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0051] ii. by using at least one selected from unsubstituted C8-C 36 The alcohol (c1), or the alcohol of the polyalkyl ether alcohol (c2), is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0052] In one embodiment, the composition comprises

[0053] a. at least one hydrophobic liquid; and

[0054] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0055] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0056] ii. Modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one polyalkyl ether alcohol (c2).

[0057] In one embodiment, the composition comprises

[0058] a. at least one hydrophobic liquid; and

[0059] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0060] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 alkyl esters, or acrylate monomers of esters of acrylic acid and polyalkyl ether alcohols; and

[0061] ii. Modifying the at least one polyacrylate polymer obtained in step (i) by transesterification with at least one polyalkyl ether alcohol (c2).

[0062] In one embodiment, the defoamer composition comprises

[0063] a. 0.1 wt.% to 25.0 wt.% of the at least one modified polyacrylate polymer; and

[0064] b. 75.0 wt.% to 99.9 wt.% of the at least one hydrophobic liquid,

[0065] Based on the total weight of the defoamer composition being 100 wt. %.

[0066] Hydrophobic liquid

[0067] In one embodiment, the at least one hydrophobic liquid is selected from mineral oil, organic modified silicone, vegetable oil, synthetic hydrocarbon, fatty alcohol, alkoxylated fatty alcohol, ester of fatty alcohol, fatty carboxylic acid ester, liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymer, ester of polypropylene oxide, or ester of polypropylene oxide-polyethylene oxide copolymer.

[0068] In one embodiment, the at least one hydrophobic liquid is selected from mineral oils, organomodified silicones, vegetable oils, synthetic hydrocarbons, or alkoxylated fatty alcohols.

[0069] In one embodiment, the at least one hydrophobic liquid is selected from mineral oil, organomodified silicones, vegetable oils, or alkoxylated fatty alcohols.

[0070] In some preferred embodiments, the composition comprises

[0071] a. at least one hydrophobic liquid which is one or more mineral oils and / or one or more organomodified silicones; and

[0072] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0073] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0074] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0075] In one embodiment, the at least one hydrophobic liquid is mineral oil.

[0076] Typically, mineral oil is a hydrocarbon based on refined petroleum.Mineral oil is a hydrocarbon mixture containing paraffinic, cycloparaffinic, or aromatic hydrocarbons.

[0077] In one embodiment, the mineral oil has a 15 To C 50 The number of carbon atoms in the range of .

[0078] In one embodiment, the mineral oil has a Saybolt universal viscosity in the range from 50 and 300 and preferably in the range from 100 to 150 according to ASTM D88.

[0079] In one embodiment, the mineral oil is selected from mineral oils containing low amounts of aromatic hydrocarbons, white oils, or a combination of two or more thereof. Typically, white oils are colorless, odorless, and tasteless hydrocarbons that do not contain any aromatic or sulfur compounds.

[0080] In one embodiment, the mineral oil is a light base oil.

[0081] In one embodiment, the mineral oil is base oil N 150. Base oil SN 150 is a light base oil at the low end of the Class I light base oil specification.

[0082] In one embodiment, when the at least one hydrophobic liquid is mineral oil, the amount of the at least one modified polyacrylate polymer is in the range of from 0.1 wt.% to 25.0 wt.%, preferably in the range of from 0.2 wt.% to 15.0 wt.%, and more preferably in the range of from 0.4 wt.% to 8.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0083] In one embodiment, the at least one hydrophobic liquid is a vegetable oil.

[0084] In one embodiment, the vegetable oil is selected from the group consisting of soybean oil, palm oil, pine oil, olive oil, rapeseed oil, sunflower oil, and combinations of two or more thereof.

[0085] In one embodiment, when the at least one hydrophobic liquid is selected from the group consisting of mineral oil, vegetable oil, and a combination of two or more thereof, the amount of the modified at least one polyacrylate polymer is in the range of from 0.1 wt.% to 25.0 wt.%, preferably in the range of from 0.2 wt.% to 15.0 wt.%, and more preferably in the range of from 0.4 wt.% to 8.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0086] In one embodiment, the defoamer composition comprises

[0087] a. 0.1 wt.% to 25.0 wt.% of the at least one modified polyacrylate polymer; and

[0088] b. 75.0 wt.% to 99.9 wt.% of the at least one hydrophobic liquid selected from the group consisting of mineral oils, vegetable oils, and combinations of two or more thereof,

[0089] Based on the total weight of the defoamer composition being 100 wt. %.

[0090] In one embodiment, the defoamer composition comprises

[0091] a. 0.1 wt.% to 25.0 wt.% of the at least one modified polyacrylate polymer; and

[0092] b. 75.0 wt.% to 99.9 wt.% of at least one hydrophobic liquid selected from mineral oil,

[0093] Based on the total weight of the defoamer composition being 100 wt. %.

[0094] In one embodiment, the defoamer composition comprises

[0095] a. 0.1 wt.% to 25.0 wt.% of the at least one modified polyacrylate polymer; and

[0096] b. 75.0 wt.% to 99.9 wt.% of at least one hydrophobic liquid selected from vegetable oils,

[0097] Based on the total weight of the defoamer composition being 100 wt. %.

[0098] In one embodiment, the at least one hydrophobic liquid is a synthetic hydrocarbon.

[0099] In one embodiment, the at least one synthetic hydrocarbon is hydrogenated polyisobutylene.

[0100] In one embodiment, when the at least one hydrophobic liquid is a synthetic hydrocarbon, the amount of the at least one modified polyacrylate polymer is in the range of from 0.1 wt.% to 25.0 wt.%, preferably in the range of from 0.2 wt.% to 15.0 wt.%, and more preferably in the range of from 0.4 wt.% to 8.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0101] In one embodiment, the defoamer composition comprises

[0102] a. 0.1 wt.% to 25.0 wt.% of the at least one modified polyacrylate polymer; and

[0103] b. 75.0 wt.% to 99.9 wt.% of at least one hydrophobic liquid selected from the group consisting of mineral oils, vegetable oils and synthetic hydrocarbons,

[0104] Based on the total weight of the defoamer composition being 100 wt. %.

[0105] In one embodiment, the at least one hydrophobic liquid is an organomodified silicone.

[0106] In one embodiment, the organo-modified silicone is a polyether-modified polysiloxane. The polyether-modified polysiloxane is derived from a substituted or unsubstituted polyether polymer. In one embodiment, the unsubstituted polyether polymer is selected from the group consisting of polyethylene glycol, polypropylene glycol, and copolymers thereof. In one embodiment, the substituted polyether polymer has a moiety selected from C1-C 22 Alkyl, C6-C 12 Aryl and C1-C 22 The carboxyl group is substituted with the hydroxyl group by a substituent group consisting of the group consisting of the carboxyl group.

[0107] The organo-modified polysiloxane has a structure selected from a comb polymer structure or an α-ω polymer structure.

[0108] In one embodiment, the at least one organomodified silicone is an α-ω-polypropylene glycol-modified polysiloxane.

[0109] In one embodiment, when the at least one hydrophobic liquid is an organic modified silicone, the amount of the at least one modified polyacrylate polymer is in the range of from 1.0 wt.% to 80.0 wt.%; preferably 4.0 wt.% to 50.0 wt.%; and more preferably 5.0 wt.% to 25.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0110] In one embodiment, the defoamer composition comprises

[0111] a. 1.0 wt.% to 80.0 wt.% of the at least one modified polyacrylate polymer; and

[0112] b. 20.0 wt.% to 99.0 wt.% of at least one hydrophobic liquid selected from organomodified silicones,

[0113] Based on the total weight of the defoamer composition being 100 wt. %.

[0114] In one embodiment, the at least one hydrophobic liquid is selected from the group consisting of fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylic acid esters, liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, and esters of polypropylene oxide-polyethylene oxide copolymers.

[0115] In one embodiment, the at least one hydrophobic liquid is a fatty alcohol.

[0116] In one embodiment, the at least one hydrophobic liquid is an alkoxylated fatty alcohol.

[0117] In one embodiment, the at least one hydrophobic liquid is an ester of a fatty alcohol and a carboxylic acid.

[0118] In one embodiment, the at least one hydrophobic liquid is a monoester, a diester, or a combination thereof of a fatty alcohol and a dicarboxylic acid.

[0119] In one embodiment, the at least one hydrophobic liquid is selected from esters of fatty carboxylic acids and alcohols.

[0120] In one embodiment, the at least one hydrophobic liquid is selected from the group consisting of liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymers, and combinations of two or more thereof.

[0121] In one embodiment, the at least one hydrophobic liquid is selected from the group consisting of esters of carboxylic acid and polypropylene oxide, polypropylene oxide-polyethylene oxide copolymers, and combinations of two or more thereof.

[0122] In one embodiment, the at least one hydrophobic liquid is selected from the group consisting of monoesters, diesters, or both of dicarboxylic acids and polypropylene oxide, polypropylene oxide-polyethylene oxide copolymers, and combinations of two or more thereof.

[0123] In one embodiment, when the at least one hydrophobic liquid is selected from the group consisting of fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylates, liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, and esters of polypropylene oxide-polyethylene oxide copolymers, based on 100 wt.% of the total weight of the defoamer composition, the amount of the at least one modified polyacrylate polymer is in the range of from 1.0 wt.% to 80.0 wt.%; preferably 4.0 wt.% to 50.0 wt.%; and more preferably 5.0 wt.% to 25.0 wt.%.

[0124] In one embodiment, the defoamer composition comprises

[0125] a. 1.0 wt.% to 80.0 wt.% of the at least one modified polyacrylate; and

[0126] b. 20.0 wt. % to 99.0 wt. % of at least one hydrophobic liquid selected from the group consisting of fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylates, liquid polypropylene oxides, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, and esters of polypropylene oxide-polyethylene oxide copolymers,

[0127] Based on the total weight of the defoamer composition being 100 wt. %.

[0128] In one embodiment, the at least one hydrophobic liquid is a mixture of two or more hydrophobic liquids.

[0129] In one embodiment, the at least one hydrophobic liquid is a mixture of an organomodified silicone and an alkoxylated fatty alcohol. In some preferred embodiments, the at least one hydrophobic liquid is a mixture of an organomodified silicone and a mineral oil.

[0130] In one embodiment, the defoamer composition comprises

[0131] a. 1.0 wt.% to 80.0 wt.% of the at least one modified polyacrylate;

[0132] b. 5.0 wt.% to 50.0 wt.% of an organo-modified silicone; and

[0133] c. 15.0 wt. % to 94.0 wt. % of at least one hydrophobic liquid selected from the group consisting of fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylates, liquid polypropylene oxides, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, and esters of polypropylene oxide-polyethylene oxide copolymers,

[0134] Based on the total weight of the defoamer composition being 100 wt. %.

[0135] In one embodiment, the defoamer composition comprises

[0136] a. 1.0 wt.% to 80.0 wt.% of the at least one modified polyacrylate;

[0137] b. 5.0 wt.% to 50.0 wt.% of an organo-modified silicone; and

[0138] c. 15.0 wt.% to 94.0 wt.% of alkoxylated fatty alcohols;

[0139] Based on the total weight of the defoamer composition being 100 wt. %.

[0140] In one embodiment, the defoamer composition comprises

[0141] a. 1.0 wt.% to 40.0 wt.% of at least one modified polyacrylate;

[0142] b. 5.0 wt.% to 30.0 wt.% of an organo-modified silicone; and

[0143] c. 30.0 wt.% to 94.0 wt.% of alkoxylated fatty alcohol;

[0144] Based on the total weight of the defoamer composition being 100 wt. %.

[0145] Polyalkyl acrylate

[0146] In one embodiment, the at least one polyacrylate polymer is a homopolymer comprising a substituted or unsubstituted alkyl acrylate; and step (i) comprises polymerizing an acrylate monomer selected from substituted or unsubstituted alkyl acrylates.

[0147] In one embodiment, the alkyl acrylate is selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, linear or branched C 12 -C 16 Alkyl esters, n-octadecyl acrylate, and combinations of two or more thereof.

[0148] In one embodiment, the alkyl acrylate is n-butyl acrylate.

[0149] In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight determined according to DIN 55672-1 in the range of from 1000 to 50000 g / mol; preferably in the range of from 1000 to 25000 g / mol; and more preferably in the range of from 1000 to 15000 g / mol.

[0150] In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight of 5000 g / mol determined according to DIN 55672-1.

[0151] In one embodiment, the at least one polyacrylate polymer is poly-n-butyl acrylate having a number average molecular weight of 9700 g / mol determined according to DIN 55672-1.

[0152] In one embodiment, the ester of acrylic acid and polyalkyl ether alcohol is selected from the group consisting of ethylene glycol acrylate, polyethylene glycol acrylate, polyethylene glycol-polypropylene glycol acrylate, and combinations of two or more thereof.

[0153] In one embodiment, the at least one polyacrylate polymer is a copolymer comprising an acrylate monomer and at least one monomer selected from a methacrylate monomer and a styrene monomer.

[0154] In one embodiment, the at least one polyacrylate polymer is a copolymer selected from a random copolymer or a block copolymer, and step (i) comprises polymerizing an acrylate monomer and at least one monomer selected from a methacrylate monomer or a styrene monomer to obtain the at least one polyacrylate polymer.

[0155] In one embodiment, the at least one polyacrylate polymer is a random copolymer, and step (i) comprises polymerizing a monomer mixture comprising an acrylate monomer and at least one monomer selected from a methacrylate monomer and a styrene monomer.

[0156] In one embodiment, the at least one polyacrylate polymer is a block copolymer, and step (i) comprises two or more sub-steps to prepare the block copolymer, and comprises at least a sub-step of polymerizing an acrylate monomer and at least a sub-step of polymerizing at least one monomer selected from a methacrylate monomer and a styrene monomer.

[0157] In one embodiment, the methacrylate monomer is selected from substituted or unsubstituted methacrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted C1-C22 The group consisting of methacrylamide and esters of methacrylic acid with polyalkyl ether alcohols.

[0158] In one embodiment, the alkyl methacrylate is selected from the group consisting of ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, and combinations of two or more thereof.

[0159] In one embodiment, the ester of methacrylic acid and polyalkyl ether alcohol is selected from the group consisting of polyethylene glycol-polypropylene glycol-methacrylate, polyethylene glycol-methacrylate, and combinations of two or more thereof.

[0160] In one embodiment, the at least one polyacrylate polymer comprises 1.0 wt. % to 20.0 wt. % of methacrylate monomers, based on 100 wt. % of the total weight of the polyacrylate polymer.

[0161] In one embodiment, the styrene monomer is selected from the group consisting of styrene, C1-C4 alkyl-substituted styrene, and combinations of two or more thereof.

[0162] In one embodiment, the at least one polyacrylate polymer comprises 1.0 wt. % to 20.0 wt. % of styrene monomer, based on 100 wt. % of the total weight of the polyacrylate polymer.

[0163] Modification of polyacrylate polymers by transesterification with alcohols

[0164] By using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0165] In some embodiments, the present invention is carried out by using at least one unsubstituted C8-C 36 The at least one polyacrylate polymer obtained in step (i) is modified by transesterification of an alcohol (c1) or an alcohol of a polyalkyl ether alcohol (c2).

[0166] In one embodiment, the unsubstituted C8-C 36 The alcohol (c1) is selected from the group consisting of 2-ethylhexanol, n-decanol, isodecyl alcohol, linear or branched C 12 -C 16 alcohol, n-octadecyl alcohol, oleyl alcohol, and combinations of two or more thereof.

[0167] In one embodiment, the unsubstituted C8-C 36 Alcohol (c1) is selected from linear or branched C 12 -C16 The group consisting of alcohol, oleyl alcohol and combinations of two or more thereof.

[0168] In one embodiment, the unsubstituted C8-C 36 Alcohol (c1) is oleyl alcohol.

[0169] In one embodiment, the at least one polyacrylate polymer is 36 The weight ratio of the alcohol (c1) is in the range from 25:1 to 5:1; preferably in the range from 20:1 to 8:1; and more preferably in the range from 15:1 to 10:1.

[0170] In one embodiment, the at least one polyacrylate polymer obtained in step (i) is modified by transesterification with a polyalkyl ether alcohol (c2).

[0171] In one embodiment, the polyalkyl ether alcohol (c2) is a compound having formula (A)

[0172]

[0173] in

[0174] m is an integer in the range from ≥1 to ≤10;

[0175] n and p are independently integers ranging from ≥0 to ≤2000, wherein n+p is an integer ranging from ≥1 to ≤4000;

[0176] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 The group consisting of alkenyl and substituted or unsubstituted phenyl; and

[0177] R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

[0178] In one embodiment, the polyalkyl ether alcohol (c2) is a compound having formula (A)

[0179]

[0180] in

[0181] m is an integer in the range from ≥1 to ≤10;

[0182] n and p are independently integers ranging from ≥0 to ≤500, wherein n+p is an integer ranging from ≥1 to ≤1000;

[0183] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 The group consisting of alkenyl and substituted or unsubstituted phenyl; and

[0184] R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

[0185] In one embodiment, the polyalkyl ether alcohol (c2) is a compound having formula (A)

[0186]

[0187] in

[0188] m is an integer in the range from ≥1 to ≤10;

[0189] n and p are independently integers ranging from ≥0 to ≤100, wherein n+p is an integer ranging from ≥1 to ≤200;

[0190] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 The group consisting of alkenyl and substituted or unsubstituted phenyl; and

[0191] R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and substituted or unsubstituted phenyl.

[0192] In one embodiment, the polyalkyl ether alcohol (c2) is a compound having formula (A)

[0193]

[0194] in,

[0195] m is an integer in the range from ≥1 to ≤10;

[0196] n and p are independently integers ranging from ≥0 to ≤100, wherein n+p is an integer ranging from ≥1 to ≤200;

[0197] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 The group consisting of alkenyl and substituted or unsubstituted phenyl; and

[0198] R2 It's methyl.

[0199] In one embodiment, the polyalkyl ether alcohol (c2) is

[0200] R 1 -(O-CH2CH2)n-OH...Formula (A1)

[0201] in

[0202] n is an integer in the range from ≥1 to ≤100;

[0203] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 A group consisting of an alkenyl group and a substituted or unsubstituted phenyl group.

[0204] In one embodiment, the polyalkyl ether alcohol (c2) is

[0205] R 1 -(O-CH2CH2)n-OH...Formula (A1)

[0206] in,

[0207] n is an integer in the range from ≥1 to ≤100;

[0208] R 1 is substituted or unsubstituted C1-C 30 alkyl.

[0209] In one embodiment, based on the total weight of 100 wt.% of the polyalkyl ether alcohol, the polyalkyl ether alcohol (c2) is a polyalkyl ether alcohol having 67.0 wt.% of C 13 Oxo alcohol and 33.0 wt.% C 15 Oxo alcohol C 13 -C 15 Ethoxylates of mixtures of oxo alcohols.

[0210] In one embodiment, the polyalkyl ether alcohol (c2) is a C 13 -C 15 Mixture of oxo alcohol ethoxylates.

[0211] In one embodiment, the polyalkyl ether alcohol (c2) is a C 13 -C 15 Mixture of oxo alcohol ethoxylates.

[0212] In one embodiment, the polyalkyl ether alcohol (c2) is a C 13-C 15 Mixture of oxo alcohol ethoxylates.

[0213] In one embodiment, the polyalkyl ether alcohol (c2) is a C 13 -C 15 Mixture of oxo alcohol ethoxylates.

[0214] In one embodiment, the polyalkyl ether alcohol (c2) is a C 10 - Guerbet alcohol ethoxylates.

[0215] In one embodiment, the weight ratio of the at least one polyacrylate polymer to the polyalkyl ether alcohol (c2) is in the range of from 1:6 to 6:1; and preferably in the range of from 1:4 to 4:1, more preferably in the range of from 1:3 to 3:1.

[0216] In one embodiment, the polyalkyl ether alcohol (c2) is a mixture of: (i) C with 7 moles of ethylene oxide; 13 -C 15 A mixture of oxo alcohol ethoxylates and (ii) a C 13 -C 15 Mixture of oxo alcohol ethoxylates.

[0217] In one embodiment, by using an unsubstituted C8-C 36 At least one alcohol of the combination of alcohol (c1) and polyalkyl ether alcohol (c2) is transesterified to modify the polyacrylate polymer obtained in step (i).

[0218] In one embodiment, the unsubstituted C8-C 36 The weight ratio of the alcohol (c1) to the polyalkyl ether alcohol (c2) is in the range from 1:2 to 1:80; and preferably in the range from 1:5 to 1:50; and more preferably in the range from 1:5 to 1:25.

[0219] In one embodiment, the at least one alcohol is a C 12 -C 14 A combination of a fatty alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0220] In one embodiment, the at least one alcohol is a combination of branched tridecyl alcohol ethoxylate (c1) having 6 moles of ethylene oxide and oleyl alcohol (c2).

[0221] In one embodiment, the at least one alcohol is an iso-C 13 H 27A combination of an alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0222] In one embodiment, the at least one alcohol is a C 10 - A combination of a Guerbet alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0223] In one embodiment, the at least one alcohol is a linear C 16 -C 18 A combination of an alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0224] In one embodiment, the at least one alcohol is a C 10 - A combination of oxo alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0225] In one embodiment, the at least one alcohol is a C 13 -C 15 Combination of oxo alcohol ethoxylate (c1) and oleyl alcohol (c2).

[0226] In one embodiment, the weight ratio of the at least one polyacrylate polymer to the at least one alcohol ranges from 1:6 to 6:1; and preferably ranges from 1:4 to 4:1, more preferably ranges from 1:3 to 3:1.

[0227] In one embodiment, the peak molecular weight of the modified polyacrylate polymer is in the range of from 2000 to 100,000 g / mol according to DIN 55672-1; preferably in the range of from 5000 to 60000 g / mol; and more preferably in the range of from 10000 to 40000 g / mol.

[0228] In one embodiment, the modified polyacrylate polymer comprises

[0229] 1. 20.0 wt. % to 70.0 wt. % of at least one polyacrylate polymer; and

[0230] 2. 30.0 wt.% to 80.0 wt.% of at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 Alcohol (c1),

[0231] Based on 100 wt.% of the total weight of the at least one modified polyacrylate polymer.

[0232] In one embodiment, the modified polyacrylate polymer comprises

[0233] 1. 20.0 wt. % to 70.0 wt. % of at least one polyacrylate polymer; and

[0234] 2. 30.0 wt.% to 80.0 wt.% of at least one alcohol selected from unsubstituted C8-C 36 alcohol (c1) or at least one polyalkyl ether alcohol (c2),

[0235] Based on 100 wt.% of the total weight of the at least one modified polyacrylate polymer.

[0236] In one embodiment, the modified polyacrylate polymer comprises

[0237] 1. 20.0 wt. % to 70.0 wt. % of at least one polyacrylate polymer; and

[0238] 2. 30.0 wt.% to 80.0 wt.% of at least one alcohol selected from polyalkyl ether alcohols (c2),

[0239] Based on 100 wt.% of the total weight of the at least one modified polyacrylate polymer.

[0240] In one embodiment, the modified polyacrylate polymer comprises

[0241] 1. 20.0 wt.% to 70.0 wt.% of at least one polyacrylate polymer;

[0242] 2. 29.0 wt.% to 79.0 wt.% of at least one alcohol selected from polyalkyl ether alcohols (c2); and

[0243] 3. 1.0 wt.% to 10.0 wt.% of at least one alcohol selected from unsubstituted C8-C 36 Alcohol (c1),

[0244] Based on 100 wt.% of the total weight of the at least one modified polyacrylate polymer.

[0245] Polymerization of acrylate monomers

[0246] The polymerization of the monomers is carried out by a free radical polymerization process or by a controlled free radical polymerization process.

[0247] In one embodiment, the at least one polyacrylate polymer obtained has a number average molecular weight determined according to DIN 55672-1 in the range from 1000 to 50000 g / mol; preferably in the range from 1000 to 25000 g / mol; and more preferably in the range from 1000 to 15000 g / mol.

[0248] A. Free Radical Polymerization Process

[0249] In one embodiment, step (i) is performed by a free radical polymerization process. The free radical polymerization process is performed using at least one free radical initiator.

[0250] In one embodiment, step (i) is performed in the presence of at least one free radical initiator.

[0251] In one embodiment, the at least one free radical initiator is selected from the group consisting of organic peroxides and azo initiators.

[0252] In one embodiment, the at least one free radical initiator is selected from the group consisting of: 2,4-dimethyl-2,5-dibenzyl peroxyhexane, tert-butyl perbenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl (peroxybutane), tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-bis (peroxybenzoyl) hexane, tert-butyl peroxyacetate, 2,4-pentadiene peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and combinations of two or more thereof.

[0253] In one embodiment, the at least one free radical initiator is selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, and combinations of two or more thereof.

[0254] In one embodiment, the at least one free radical initiator is tert-butyl peroxy-2-ethylhexanoate.

[0255] In one embodiment, step (i) is carried out at a temperature ranging from 60°C to 160°C and preferably ranging from 80°C to 140°C.

[0256] In one embodiment, step (i) is performed in the presence of a solvent selected from the group consisting of isopropanol, 2-butanol, butyl acetate, methoxypropyl acetate, methoxypropanol, xylene, and combinations of two or more thereof.

[0257] In one embodiment, the solvent is 2-butanol.

[0258] B. Controlled Free Radical Polymerization (CFRP) Process

[0259] In one embodiment, step (i) is carried out by a controlled radical polymerization process. Controlled radical polymerization is often referred to as living polymerization, in which free radicals do not exist permanently as free radicals at the ends of growing polymer chains, but exist in equilibrium in a non-radical form and are constantly reformed under polymerization conditions.

[0260] The CFRP process allows for enhanced control over the polydispersity of the polymer and allows for the production of polymers within a narrow molecular weight distribution.

[0261] Controlled free radical polymerization processes by the NMP (nitroxide mediated polymerization) process are preferred. Preferably, the CFRP process is carried out in the presence of at least one nitroxyl ether of the general formula (B).

[0262] In one embodiment, step (i) is carried out in the presence of at least one nitroxyl ether having the general formula (B)

[0263]

[0264] in

[0265] R 11 and R 12 are independently selected from substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted C7-C 18 Aralkyl;

[0266] wherein the substituted alkyl group carries a C1-C4 alkoxy group, a C1-C4 alkoxy-C1-C4 alkoxy group, or a PO3R z 2 substituents, and R z is a C1-C4 alkyl group;

[0267] or

[0268] R 11 and R 12 Together they form a substituted or unsubstituted C2-C 10 Alkylene or substituted or unsubstituted C2-C 10 an alkenylene ring;

[0269] Wherein the substituted C2-C 10 Alkylene or substituted C2-C 10 The alkenylene group has 1, 2, 3, 4 or 5 substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-C1-C4 alkoxy, COOH, or CONH2; and

[0270] Among them, C2-C 10 Alkylene or C2-C 10Alkenylene optionally has one or two CH2 groups replaced independently of each other by O, C=O, C=NOH, CH-OCOCH3 or NRx, and Rx is C1-C4 alkyl or C1-C4 alkoxy;

[0271] R 13 is C1-C4 alkyl or H;

[0272] R 14 , R 15 and R 16 are independently C1-C4 alkyl;

[0273] X is selected from the group consisting of: -CH2-phenyl, -CH(CH3)-phenyl, -C(CH3)2-phenyl, -C(C5-C6-cycloalkyl)2-CN, -C(CH3)2CN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CHR 17 -C(O)-phenyl, -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4 alkyl), -(C1-C4 alkyl)-CHR 17 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)-CHR 17 -C(O)-NH(C1-C4 alkyl) and -(C1-C4 alkyl)-CHR 17 -C(O)-NH2, where

[0274] R 17 It is H or C1-C4 alkyl.

[0275] In one embodiment, step (i) is carried out in the presence of at least one nitroxyl ether having the general formula (B)

[0276]

[0277] in

[0278] R 11 and R 12 Together they form a substituted or unsubstituted C2-C 10 an alkylene ring;

[0279] R 13 is C1-C4 alkyl or H;

[0280] R 14 , R 15 and R 16 are independently C1-C4 alkyl; and

[0281] X is as defined above.

[0282] In one embodiment, step (i) is carried out in the presence of at least one nitroxyl ether having the general formula (B)

[0283]

[0284] in

[0285] R 11 and R 12 Together they form a ring comprising a substituted or unsubstituted C2-C4 alkylene group;

[0286] R 14 , R 15 and R 16 are independently C1-C4 alkyl; and

[0287] X is selected from the group consisting of -CH2-phenyl, -CHCH3-phenyl, -C(CH3)2-phenyl, and -C(C5-C6-cycloalkyl)2-CN.

[0288] In one embodiment, step (i) is carried out in the presence of nitroxyl ether (BI).

[0289]

[0290] In one embodiment, the amount of the compound having formula B ranges from 0.01 wt.% to 20.0 wt.%; and preferably ranges from 0.1 wt.% to 10.0 wt.%, based on the total weight of the at least one alkyl acrylate to be polymerized.

[0291] The at least one nitroxyl ether of the general formula (B) decomposes under the action of heat to form stable nitroxyl free radicals. Alternatively, a free radical polymerization initiator is added to initiate the conversion of the at least one nitroxyl ether of the general formula (B) into the corresponding stable nitroxyl free radicals.

[0292] In one embodiment, the at least one free radical initiator is selected from the group consisting of organic peroxides and azo initiators.

[0293] In one embodiment, the at least one free radical initiator is selected from the group consisting of: 2,4-dimethyl-2,5-dibenzyl peroxyhexane, tert-butyl perbenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl (peroxybutane), tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-bis (peroxybenzoyl) hexane, tert-butyl peroxyacetate, 2,4-pentadiene peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and combinations of two or more thereof.

[0294] In one embodiment, the at least one free radical initiator is selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, and combinations of two or more thereof.

[0295] In one embodiment, the at least one free radical initiator is tert-butyl peroxy-2-ethylhexanoate.

[0296] In one embodiment, the total amount of the at least one free radical initiator ranges from 1.5 wt. % to 7.0 wt. %, based on the total weight of monomers.

[0297] In one embodiment, step (i) is performed in the presence of at least one stable nitroxyl free radical.

[0298] In one embodiment, step (i) is carried out in the presence of at least one stable nitroxyl radical selected from the group consisting of radicals having formula Za, Zb, Zc, Zd, Ze, Zf, Zg, Zh, and combinations of two or more thereof.

[0299]

[0300] In one embodiment, step (i) is carried out at a temperature in the range of from 80°C to 180°C; preferably in the range of from 100°C to 175°C; more preferably in the range of from 100°C to 150°C; and even more preferably in the range of from 110°C to 130°C.

[0301] In one embodiment, the polydispersity of the at least one polyalkyl acrylate obtained by the controlled radical polymerization process is in the range of from 1.2 to 2.0; and preferably in the range of from 1.2 to 1.8.

[0302] In one embodiment, the peak average molecular weight of the at least one modified polyacrylate polymer is in the range of from 2000 to 100,000 g / mol.

[0303] The polydispersity of the at least one modified polyalkyl acrylate ranges from 1.2 to 2.0.

[0304] Defoamer composition

[0305] In one embodiment, the defoamer composition further comprises at least one additive selected from the group consisting of water, nonionic surfactants, anionic surfactants, liquid alkoxylates selected from liquid polypropylene oxide or liquid polypropylene oxide copolymers, liquid polyethers, liquid polyesters, solid particles based on silica or based on synthetic waxes or natural waxes, and combinations of two or more thereof.

[0306] In one embodiment, the at least one additive is water.

[0307] In some preferred embodiments, the composition comprises

[0308] a. at least one hydrophobic liquid which is one or more mineral oils and / or one or more organomodified silicones;

[0309] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0310] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0311] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 alcohol (c1) to modify the at least one polyacrylate polymer obtained in step (i) by transesterification;

[0312] and water.

[0313] In one embodiment, the at least one additive is a wax.

[0314] In one embodiment, the at least one additive is polyethylene wax.

[0315] In one embodiment, the amount of the wax ranges from 1.0 wt.% to 25 wt.% based on the total weight of the defoamer composition which is 100 wt.%.

[0316] Another aspect of the present invention relates to a method for reducing or preventing foam in an aqueous composition, comprising adding a defoamer composition to the aqueous composition in an amount ranging from 0.01 wt.% to 5.0 wt.% based on 100 wt.% of the weight of the aqueous composition.

[0317] In one embodiment, the method includes adding the defoamer composition to the aqueous composition in an amount ranging from 0.1 wt. % to 1.0 wt. % based on 100 wt. % of the total weight of the aqueous composition.

[0318] In one embodiment, the method includes adding 0.5 wt.% of the defoamer composition to the aqueous composition, based on 100 wt.% of the total weight of the aqueous composition.

[0319] In one embodiment, the aqueous composition is selected from the group consisting of water-based paints, coating compositions, inks, and adhesive compositions.

[0320] In one embodiment, the aqueous composition is a coating composition.

[0321] Typically, the aqueous composition is an aqueous submicron dispersion of polymer particles based on acrylic polymers, styrene acrylic copolymers, or vinyl acrylic copolymers.

[0322] Aqueous compositions are designed to be used on different substrates like mineral substrates, wood, metal, paper, or plastic.

[0323] Another aspect of the present invention relates to use of a defoamer composition for reducing or preventing foam in an aqueous composition; wherein the amount of the defoamer composition ranges from 0.01 wt.% to 5.0 wt.% based on 100 wt.% of the total weight of the aqueous composition.

[0324] In one embodiment, the use includes adding the defoamer composition to the aqueous composition in an amount ranging from 0.1 wt.% to 1.0 wt.% based on the total weight of the aqueous composition which is 100 wt.%.

[0325] In one embodiment, the use comprises adding 0.5 wt.% of the defoamer composition to the aqueous composition, based on the total weight of the aqueous composition being 100 wt.%.

[0326] In one embodiment, the aqueous composition is selected from the group consisting of water-based paints, coating compositions, inks, and adhesive compositions.

[0327] In one embodiment, the aqueous composition is a coating composition.

[0328] The present invention provides one or more of the following advantages:

[0329] 1. The defoamer composition of the present invention is compatible with aqueous compositions.

[0330] 2. The defoamer composition of the present invention exhibits high defoaming activity in an aqueous composition.

[0331] 3. Low amounts of the defoamer composition of the present invention provide high defoaming activity.

[0332] In the following, a list of examples is provided to further illustrate the present disclosure without intending to limit the present disclosure to the specific examples listed below.

[0333] 1. A defoamer composition comprising

[0334] a. at least one hydrophobic liquid; and

[0335] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0336] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 Acrylic acid ester monomer polymerization of acrylamide or ester of acrylic acid and polyalkyl ether alcohol

[0337] to obtain at least one polyacrylate polymer; and

[0338] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0339] 2. A defoamer composition comprising

[0340] a. at least one hydrophobic liquid; and

[0341] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0342] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 Acrylic acid ester monomer polymerization of acrylamide or ester of acrylic acid and polyalkyl ether alcohol

[0343] to obtain at least one polyacrylate polymer; and

[0344] ii. by using at least one selected from unsubstituted C8-C 36 The alcohol (c1), or the alcohol of the polyalkyl ether alcohol (c2), is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

[0345] 3. The composition according to embodiment 1 or 2, comprising

[0346] a. at least one hydrophobic liquid; and

[0347] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0348] i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 alkyl esters, or esters of acrylic acid and polyalkyl ether alcohols, preferably at least one substituted or unsubstituted acrylic acid C1-C 22 polymerizing alkyl acrylate monomers; and

[0349] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 alcohol (c1) to modify the at least one polyacrylate polymer obtained in step (i) by transesterification;

[0350] or

[0351] By using at least one selected from unsubstituted C8-C 36 The at least one polyacrylate polymer obtained in step (i) is modified by transesterification of an alcohol (c1) or an alcohol of a polyalkyl ether alcohol (c2).

[0352] 4. The composition of any one of embodiments 1 to 3, wherein the at least one hydrophobic liquid is selected from the group consisting of mineral oils, organomodified silicones, vegetable oils, synthetic hydrocarbons, fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylic acid esters, liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, esters of polypropylene oxide-polyethylene oxide copolymers, and combinations of two or more thereof.

[0353] 5. The composition of any one of embodiments 1 to 4, wherein the at least one hydrophobic liquid is mineral oil.

[0354] 6. The composition of any one of embodiments 1 to 4, wherein the at least one hydrophobic liquid is a vegetable oil.

[0355] 7. The composition according to embodiment 5 or 6, wherein the amount of the at least one modified polyacrylate polymer is in the range of from 0.1 wt.% to 25.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0356] 8. The composition of any one of embodiments 1 to 4, wherein the at least one hydrophobic liquid is an organomodified silicone.

[0357] 9. The composition of embodiment 8, wherein the organo-modified polysiloxane is a polyether-modified polysiloxane.

[0358] 10. The composition according to embodiment 8 or 9, wherein the amount of the at least one modified polyacrylate polymer ranges from 1.0 wt.% to 80.0 wt.%, based on 100 wt.% of the total weight of the defoamer composition.

[0359] 11. The composition according to any one of embodiments 1 to 10, wherein the alkyl acrylate is selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, linear or branched C acrylate, 12 -C 16 alkyl esters, n-octadecyl acrylate, or a combination of two or more thereof.

[0360] 12. The composition of any one of embodiments 1 to 11, wherein the ester of acrylic acid and a polyalkyl ether alcohol is selected from the group consisting of ethylene glycol acrylate, polyethylene glycol acrylate, polyethylene glycol-polypropylene glycol acrylate, or a combination of two or more thereof.

[0361] 13. The composition of any one of embodiments 1 to 12, wherein the at least one polyacrylate polymer is a copolymer selected from the group consisting of random copolymers and block copolymers, and wherein step (i) comprises polymerizing the acrylate monomer and at least one monomer selected from methacrylate monomers and styrene monomers to obtain the at least one polyacrylate polymer.

[0362] 14. The composition of embodiment 13, wherein the at least one polyacrylate polymer is a random copolymer, and wherein step (i) comprises polymerizing a monomer mixture comprising the acrylate monomer and at least one monomer selected from the group consisting of a methacrylate monomer and a styrene monomer.

[0363] 15. A composition according to embodiment 13, wherein the at least one polyacrylate polymer is a block copolymer, and wherein step (i) comprises two or more sub-steps to prepare the block copolymer and comprises at least a sub-step of polymerizing at least one acrylate monomer and at least a sub-step of polymerizing at least one monomer selected from methacrylate monomers and styrene monomers.

[0364] 16. The composition according to any one of embodiments 13 to 15, wherein the methacrylate monomer is selected from substituted or unsubstituted methacrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted C1-C 22 The group consisting of methacrylamide, esters of methacrylic acid and polyalkyl ether alcohols, and combinations of two or more thereof.

[0365] 17. The composition of embodiment 16, wherein the alkyl methacrylate is selected from the group consisting of ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, and combinations of two or more thereof.

[0366] 18. The composition of embodiment 16, wherein the ester of methacrylic acid and polyalkyl ether alcohol is selected from the group consisting of polyethylene glycol-polypropylene glycol-methacrylate, polyethylene glycol-methacrylate, and combinations thereof.

[0367] 19. The composition of any one of embodiments 13 to 18, wherein the at least one polyacrylate polymer comprises 1.0 wt.% to 20.0 wt.% of the methacrylate monomer, based on 100 wt.% of the total weight of the polyacrylate polymer.

[0368] 20. The composition of any one of embodiments 13 to 15, wherein the styrene monomer is selected from the group consisting of styrene, C1-C4 alkyl-substituted styrene, and combinations of two or more thereof; and wherein the at least one polyacrylate polymer comprises 1.0 wt.% to 20.0 wt.% of the styrene monomer, based on 100 wt.% of the total weight of the polyacrylate polymer.

[0369] 21. The composition of any one of embodiments 1 to 20, wherein the unsubstituted C8-C 36 Alcohol (C1) is selected from the group consisting of 2-ethylhexanol, n-decanol, isodecyl alcohol, linear or branched C 12 -C 16 alcohol, n-octadecyl alcohol, oleyl alcohol, and combinations of two or more thereof.

[0370] 22. The composition of any one of embodiments 1 to 21, wherein the unsubstituted C8-C 36 Alcohol is selected from linear or branched C 12 -C 16 The group consisting of alcohol, oleyl alcohol and combinations of two or more thereof.

[0371] 23. The composition of any one of embodiments 1 to 22, wherein the polyacrylate polymer and the unsubstituted C8-C 36 The weight ratio of alcohol (C1) is in the range from 25:1 to 5:1.

[0372] 24. The composition according to any one of embodiments 1 to 23, wherein the polyether alcohol (C2) is

[0373]

[0374] in,

[0375] m is an integer in the range from ≥1 to ≤10;

[0376] n and p are independently integers ranging from ≥0 to ≤2000, wherein n+p is an integer ranging from ≥1 to ≤4000;

[0377] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 The group consisting of alkenyl and substituted or unsubstituted phenyl; and

[0378] R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted and unsubstituted phenyl.

[0379] 25. The composition according to any one of embodiments 1 to 24, wherein the polyether alcohol (c2) is

[0380] R 1 -(O-CH2CH2) n -OH...Formula (A)

[0381] in,

[0382] n is an integer in the range from ≥1 to ≤100; and

[0383] R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted

[0384] C2-C 30A group consisting of an alkenyl group, or a substituted or unsubstituted phenyl group.

[0385] 26. The composition of any one of embodiments 1 to 25, wherein the weight ratio of the polyacrylate polymer to the polyether alcohol (C2) is in the range from 1:4 to 4:1, preferably in the range from 1:3 to 3:1.

[0386] 27. The composition of any of embodiments 1 to 26, wherein the at least one modified polyacrylate polymer has a peak molecular weight in the range of from 2000 to 100,000 g / mol according to DIN 55672-1.

[0387] 28. The composition of any one of embodiments 1 to 27, wherein the modified polyacrylate polymer comprises

[0388] a. 20.0 wt.% to 70.0 wt.% of the at least one polyacrylate polymer; and

[0389] b. 30.0 wt.% to 80.0 wt.% of at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 Alcohol (c1);

[0390] or,

[0391] a. 20.0 wt.% to 70.0 wt.% of the at least one polyacrylate polymer; and

[0392] b. 30.0 wt.% to 80.0 wt.% of the at least one alcohol selected from unsubstituted C8-C 36 Alcohol (c1) or polyalkyl ether alcohol (c2),

[0393] Based on 100 wt.% of the total weight of the at least one modified polyacrylate polymer.

[0394] 29. The composition of any one of embodiments 1 to 28, wherein step (i) is performed in the presence of at least one free radical initiator.

[0395] 30. The composition of embodiment 29, wherein the at least one free radical initiator is selected from the group consisting of organic peroxides, azo initiators, and combinations thereof.

[0396] 31. The composition of embodiment 29 or 30, wherein the at least one free radical initiator is selected from the group consisting of 2,4-dimethyl-2,5-dibenzyl peroxide hexane, tert-butyl peroxybenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl (butane peroxide), tert-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2 , 5-bis(benzoyl peroxide)hexane, tert-butyl peroxyacetate, 2,4-pentadiene peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and combinations of two or more thereof.

[0397] 32. The composition of any one of embodiments 29 to 31, wherein the at least one free radical initiator is selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, and combinations of two or more thereof.

[0398] 33. The composition of any one of embodiments 29 to 32, wherein the at least one free radical initiator is tert-butyl peroxy-2-ethylhexanoate.

[0399] 34. The composition of any one of embodiments 29 to 33, wherein step (i) is performed in the presence of a solvent selected from the group consisting of isopropanol, 2-butanol, butyl acetate, methoxypropyl acetate, methoxypropanol, xylene, and combinations of two or more thereof.

[0400] 35. The composition of embodiment 34, wherein the solvent is 2-butanol.

[0401] 36. The composition according to any one of embodiments 1 to 35, wherein step (i) is carried out in the presence of at least one nitroxyl ether of formula (B).

[0402]

[0403] in

[0404] R 11 and R 12 are independently selected from substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted C7-C 18 A group consisting of aralkyl groups;

[0405] wherein the substituted alkyl group carries a C1-C4 alkoxy group, a C1-C4 alkoxy-C1-C4 alkoxy group, or a PO3R z 2, and Rz is a C1-C4 alkyl group; or

[0406] R 11 and R 12 Together they form a substituted or unsubstituted C2-C 10 Alkylene or substituted or unsubstituted C2-C 10 an alkenylene ring;

[0407] Wherein the substituted C2-C 10 Alkylene or substituted C2-C 10 The alkenylene group has 1, 2, 3, 4 or 5 substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-C1-C4 alkoxy, COOH, or CONH2; and

[0408] Among them, C2-C 10 Alkylene or C2-C 10 Alkenylene optionally has one CH2 group replaced by O, C=O, C=NOH, CH-OCOCH3 or NRx or two CH2 groups replaced independently of the other, and Rx is C1-C4 alkyl or C1-C4 alkoxy;

[0409] R 13 is C1-C4 alkyl or H;

[0410] R 14 , R 15 and R 16 are independently C1-C4 alkyl;

[0411] X is selected from the group consisting of: -CH2-phenyl, -CHCH3-phenyl, -C(CH3)2-phenyl, -C(C5-C6-cycloalkyl)2-CN, -C(CH3)2CN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CHR 17 -C(O)-phenyl, -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4)alkyl, -(C1-C4alkyl)-CHR 17 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)-CHR 17 -C(O)-NH(C1-C4 alkyl) and -(C1-C4 alkyl)-CHR 17-C(O)-NH2, where

[0412] R 17 It is H or C1-C4 alkyl.

[0413] 37. The composition according to embodiment 36, wherein step (i) is carried out in the presence of nitroxyl ether (BI)

[0414]

[0415] 38. The composition of embodiment 36 or 37, wherein step (i) is performed in the presence of at least one free radical initiator selected from the group consisting of organic peroxides, azo initiators, and combinations thereof.

[0416] 39. The composition of any one of embodiments 36 to 38, wherein the at least one free radical initiator is selected from the group consisting of 2,4-dimethyl-2,5-dibenzyl peroxide hexane, tert-butyl peroxybenzoate, di-tert-butyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl peroxycrotonate, 2,2-bis-tert-butyl (peroxide butylene), tert-butyl peroxy isopropyl carbonate, 2,5-dimethyl -2,5-bis(benzoyl peroxide)hexane, t-butyl peroxyacetate, 2,4-pentadiene peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and combinations of two or more thereof.

[0417] 40. The composition of any one of embodiments 36 to 39, wherein the at least one free radical initiator is selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, dibenzoyl peroxide, and combinations of two or more thereof.

[0418] 41. The composition of any one of embodiments 36 to 40, wherein the at least one free radical initiator is tert-butyl peroxy-2-ethylhexanoate.

[0419] 42. The composition of any one of embodiments 36 to 41, wherein the total amount of the free radical initiator ranges from 1.5 wt.% to 7.0 wt.% based on the total weight of the monomers being 100 wt.%.

[0420] 43. The composition of any one of embodiments 36 to 42, wherein the polydispersity of the at least one polyalkyl acrylate ranges from 1.2 to 2.0.

[0421] 44. The composition of any of embodiments 36 to 43, wherein the peak molecular weight of the at least one modified polyacrylate polymer is in the range of from 2000 to 100,000 g / mol.

[0422] 45. The defoamer composition according to any one of embodiments 1 to 44, further comprising at least one additive selected from the group consisting of water, nonionic surfactants, anionic surfactants, liquid alkoxylates selected from liquid polypropylene oxide or liquid polypropylene oxide copolymers, liquid polyethers, liquid polyesters, solid particles based on silica or based on synthetic or natural waxes, and combinations of two or more thereof.

[0423] 46. ​​The defoamer composition according to any one of embodiments 1 to 45, comprising

[0424] a. at least one hydrophobic liquid which is one or more mineral oils and / or one or more organomodified silicones;

[0425] b. at least one modified polyacrylate polymer obtainable by a process comprising:

[0426] i. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and

[0427] ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 alcohol (c1) to modify the at least one polyacrylate polymer obtained in step (i) by transesterification;

[0428] and water.

[0429] 47. A method for reducing or preventing foam in an aqueous composition, the method comprising adding the defoamer composition according to any one of embodiments 1 to 46 to the aqueous composition in an amount ranging from 0.01 wt.% to 5.0 wt.%, based on 100 wt.% of the total weight of the aqueous composition.

[0430] 48. The method of embodiment 47, wherein the aqueous composition is selected from the group consisting of water-based paints, coating compositions, inks, and adhesive compositions.

[0431] 49. Use of the defoamer composition of any one of embodiments 1 to 46 for reducing or preventing foam in an aqueous composition; wherein the amount of the defoamer composition ranges from 0.01 wt.% to 5.0 wt.% based on 100 wt.% of the total weight of the aqueous composition.

[0432] 50. The use according to embodiment 49, wherein the aqueous composition is selected from the group consisting of water-based paints, coating compositions, inks, and adhesive compositions.

[0433] While the invention has been described in terms of specific embodiments thereof, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention.

[0434] Examples

[0435] The invention is illustrated in detail by the non-limiting working examples hereinafter. More particularly, the test methods specified hereinafter are part of the general disclosure of the present application and are not limited to the specific working examples.

[0436] Material

[0437] The following materials are used in the examples:

[0438] 3 is based on C 13 -C 15 Oxo alcohol and 3 mol of ethylene oxide ether, and the oxo alcohol ethoxylate is composed of about 67% C 13 product and about 33% C 15 Product composition;

[0439] 5 is based on C 13 -C 15 Oxo alcohol and 5 mol of ethylene oxide ether, and the oxo alcohol ethoxylate is composed of about 67% C 13 product and about 33% C 15 Product composition;

[0440] 7 is based on C 13 -C 15 Oxo alcohol and 7 mol of ethylene oxide ether, and the oxo alcohol ethoxylate is composed of about 67% C 13 product and about 33% C 15 Product composition;

[0441] 8 is based on C 13 -C 15Oxo alcohol and 8 mol of ethylene oxide ether, and the oxo alcohol ethoxylate is composed of about 67% C 13 product and about 33% C 15 Product composition;

[0442] 70 is based on C 10 - ether of a Guerbet alcohol and 7 mol of ethylene oxide;

[0443] 7 is based on C 13 Oxo alcohol and ether of 7 mol of ethylene oxide;

[0444] LS24 is made of C 12 -C 14 Ether made from fatty alcohol (1 mole), ethylene oxide (2 moles) and propylene oxide (4 moles);

[0445] Available from BASF SE.

[0446] Base oil N150 CAS No. 64741-76-0, a mineral oil available from Wistema GmbH, has a sulfur content of about 0.01 wt-% (determined in accordance with EN ISA 8754), is a hydrocarbon mixture containing paraffins in the range from 65 wt-% to 70 wt-%, cycloparaffins in the range from 27 wt-% to 32 wt-% and aromatic hydrocarbons in the range from 3 wt-% to 6 wt-%.

[0447] Honeywell 629A is a low density oxidized polyethylene (LDOxPE) homopolymer (PE wax) available from Honeywell.

[0448] Ethoxylated C with 7EO 10 -Oxo alcohol, C 12 -C 14 Fatty alcohol, branched tridecanol C 13 H 27 OH, isotridecanol C 13 H 27 OH, oleyl alcohol, C 10 -Guerbet alcohol, straight chain C 16 -C 18 Alcohol, C 10 - oxo alcohols,

[0449] Available from BASF.

[0450] method

[0451] Weight average molecular weight (Mw)

[0452] Mw was determined according to DIN 55672-1 involving gel permeation chromatography using a refractometer as detector. The mobile phase used was tetrahydrofuran (THF, 1 mL / min, 35° C.) and the standard used for determining the molecular weight was polystyrene (PS).

[0453] Number average molecular weight (Mn)

[0454] Mn was determined according to DIN 55672-1 involving gel permeation chromatography using a refractometer as detector. The mobile phase used was tetrahydrofuran (THF, 1 mL / min, 35° C.) and the standard used for determining the molecular weight was polystyrene (PS).

[0455] Peak molecular weight (Mp)

[0456] The peak molecular weight (Mp) is determined from the retention time corresponding to the peak of the elution curve obtained in gel permeation chromatography based on standard polystyrene. The peak of the elution curve is the point where the elution curve is at a maximum value.

[0457] M p The determination was carried out according to DIN 55672-1, involving gel permeation chromatography using a refractometer as detector. The mobile phase used was tetrahydrofuran (THF, 1 mL / min, 35° C.) and the standard used for determining the molecular weight was polystyrene (PS).

[0458] Examples

[0459] Reference Example 1: General Procedure for the Synthesis of Polyalkyl Acrylates by Free Radical Polymerization (FRP) Process

[0460] A 5000 mL polymerization reactor equipped with an overhead stirrer, thermometer, distillation line, vacuum pump, and dosing device was charged with 926.0 g of solvent. The reactor was maintained under a nitrogen atmosphere and the contents were heated to 100° C. A monomer feed of 1900.0 g of alkyl acrylate and a feed of 45.2 g of tert-butyl peroxy-2-ethylhexanoate were started and transferred to the reactor over a period of 300 minutes while the temperature of the reaction mixture was maintained at 100° C.

[0461] After complete addition of the feeds, the solvent and volatiles were removed by distillation at 100° C. under reduced pressure to obtain polyalkyl acrylate as a clear, colorless viscous liquid with a polymer content of >99 wt.%.

[0462] Reference Example 2: General procedure for transesterification of polyalkyl acrylate obtained from Example 1

[0463] Into the reactor maintained under nitrogen atmosphere, polyalkyl acrylate (20-70wt.%) and at least one alcohol (30-80wt.%) are loaded. The contents of the reactor are heated at 100°C under nitrogen atmosphere. 0.1-1.0wt.% of transesterification catalyst (e.g., tetrabutoxy titanate, lithium tert-butoxide or lithium methoxide) is added to the reaction mixture, and the resulting mixture is heated under reduced pressure (<50 mbar). The bath temperature is gradually raised to 160°C. After collecting the expected amount of distillate, the product is cooled to room temperature and discharged from the reactor to obtain a modified polyacrylate polymer.

[0464] Polybutyl acrylate was prepared according to the procedure of Reference Example 1 using n-butyl acrylate as the alkyl acrylate and 2-butanol as the solvent. The modified polyacrylate polymers of Examples 1 to 46 were prepared according to the procedure of Reference Example 2. The amounts of the polyalkyl acrylate polymer and the alcohol(s) and the peak molecular weight of the modified polyacrylate polymer (product) are provided in Tables 1 and 2.

[0465] Table 1 relates to modified polyacrylate polymers obtained by reacting polybutyl acrylate with one or more ethoxylated polyether alcohols.

[0466] Table 2 relates to the reaction of polybutyl acrylate with alkoxylated polyether alcohol and unsubstituted C8-C 36 Modified polyacrylate polymer obtained by reaction with alcohol.

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475] Reference Example 3: General Procedure for the Synthesis of Polyalkyl Acrylates by Controlled Free Radical Polymerization (CFRP)

[0476] A reactor maintained under a nitrogen atmosphere was charged with n-butyl acrylate (n-BA, 1211.13 g, Mw 128.7 g / mol) and nitroxyl ether (BI) (60.00 g, Mw 317.48 g / mol). The reaction mixture was heated at 115° C. for 1.5 h. Feed n-BA (2422.26 g) was fed to the reactor over 3 hours, and the resulting mixture was heated at 125° C. for another 4.5 h. The residual monomers were distilled off at 105° C. and 20 mbar to obtain the product polybutyl acrylate. Yield: 50.36% (Mn=9700 g / mol, PDI=1.21, viscous liquid).

[0477] Reference Example 4: General procedure for transesterification of polyalkyl acrylate obtained from Example 3

[0478] In a 5-neck 2000 mL HWS reactor equipped with an overhead stirrer, thermometer, distillation line, vacuum pump and baffle, polyalkyl acrylate (polybutyl acrylate) and alcohol (polyalkylene ether, unsubstituted C8-C 36 alcohol, or a mixture thereof). The reaction mixture is gradually heated under nitrogen. At 60° C., the mixture is dried under reduced pressure (to remove traces of water). Vacuum distillation is performed for 4 h. 0.1-1.0 wt.% of tetrabutoxytitanate is added and the resulting mixture is heated under reduced pressure until the expected amount of n-butanol is separated. During this vacuum distillation step, the reaction mixture is heated at 100° C. or gradually heated to 145° C., depending on the conversion of the reaction mixture and the alcohol (for transesterification). The final product is cooled to room temperature and discharged from the reactor.

[0479] Polybutyl acrylate was prepared according to Reference Example 3. The following modified polyacrylates of Examples 47 to 56 were prepared from the polybutyl acrylate according to Reference Example 4.

[0480]

[0481]

[0482] Examples 57 to 86

[0483] The polyalkyl acrylates according to Examples 57 to 68 were prepared according to Reference Example 1 using ethyl acrylate or n-butyl acrylate as monomers and using a solvent selected from isopropanol, 2-butanol, 1-methoxy-2-propyl acetate, n-butyl acetate, 2-butanol and xylene. Details on the monomers and solvents used are given in Table 4. From these polyalkyl acrylates, modified polyalkyl acrylates of Examples 69 to 86 were prepared according to Reference Example 2, wherein details on specific polyalkyl acrylates, alcohols and transesterification catalysts are given in Table 5.

[0484]

[0485]

[0486] Part 2: Performance Testing

[0487] Preparation of defoamer composition

[0488] The following defoamer compositions were prepared.

[0489] A) Defoamer composition prepared using polyether-modified polysiloxane as hydrophobic liquid

[0490] Reference Example 5: Synthesis procedure for polyether-modified siloxane:

[0491] Step 1:

[0492] 620.0 g of octamethylcyclotetrasiloxane, 188.0 g of dimethyldiethoxysilane and 0.5 g of trifluoromethanesulfonic acid were charged into a 2 L reactor and the reaction mixture was stirred at 60° C. for 6 hours. After equilibrium was established as determined by increasing the solid fraction of the mixture, the catalyst was neutralized by adding 0.8 g of tri-n-butylamine. The reaction mixture was filtered and unreacted starting materials and low molecular weight oligomers formed as by-products were removed by stripping under reduced pressure. 1 The obtained product was analyzed by H-NMR spectroscopy. The product was found to contain 678.0 g of the corresponding siloxane.

[0493] Step 2:

[0494] The siloxane obtained in step 1 of 45.0g, the n-butyl polypropylene glycol (2000g / mol) of 160.0g and 0.2g methanesulfonic acid are mixed in a round-bottom flask equipped with a distillation bridge. The mixture is heated at 150°C for 6 hours under reduced pressure under stirring. The ethanol formed during the heating process is continuously removed from the reaction mixture by distillation. The process of the reaction is monitored by gel permeation chromatography. After complete conversion, the reaction mixture is cooled to room temperature, and the catalyst is neutralized by adding 0.5g n-tributylamine and the residue is filtered off. The product polypropylene glycol modified siloxane (194.0g) is obtained as a clear liquid and is used for the next step without further purification.

[0495] Step 3:

[0496] 98.0 g of the α,ω-polypropylene glycol-modified siloxane obtained in step 2 was added to a glass jar (250 ml) placed in a water bath. 2.0 g of hydrophobic fumed silica (BET: 90-130 m 2 / g) was added to the polyether-modified siloxane in small portions, and then stirring was continued for another 10 minutes at room temperature. The agitator was then replaced with a high-speed rotor-stator disperser, and the silica was dispersed at 15000 rpm for 5 minutes at room temperature. The obtained product was used for silicone defoamer formulations without further purification.

[0497] Defoamer compositions PS-1 to PS-5 and PS-6 to PS-23

[0498] Defoamer compositions PS-1 to PS-5 and PS-6 to PS-23 were prepared by mixing the α,ω-polypropylene glycol-modified polysiloxane obtained in Example 5 as a hydrophobic liquid (16.0 wt.%), a diluent 24 (64.0 wt.%) and modified polyacrylate polymer (20.0 wt.%) were mixed to prepare it.

[0499] Comparative composition PS-C

[0500] Comparative composition PS-C was prepared by mixing α,ω-polypropylene glycol-modified polysiloxane as a hydrophobic liquid (20.0 wt.%) and a diluent 24 (80.0wt.%) was mixed to prepare.

[0501] B) Stability of the defoamer composition

[0502] Initially, the compatibility of the defoamer compositions (PS-1 to PS-5, and PS-6 to PS-23) was visually checked. The formulations with modified polyacrylate polymers (see Table 4 for examples) were homogeneous and stable, and they did not show any phase separation or sedimentation.

[0503] C) Compatibility of defoamer composition and defoamer activity

[0504] To evaluate compatibility and defoamer activity, the defoamer compositions were added to different latexes used as model test systems for industrial and architectural waterborne coatings and paints.

[0505] Evaluation of Defoamer Composition PS-1

[0506] The defoamer composition PS-1 (0.6 g) was added to a latex binder resin for paint ( 9014) (amount: 120.0 g), and the resulting mixture was stirred with a high-speed mixer (disk diameter: 3 cm) at a high speed (4500 rpm) for 3 minutes to obtain a coating composition CC-PS-1.

[0507] Coating compositions CC-PS-2 to CC-PS-5 and CC-PS-6 to CC-PS-23 were prepared using the above procedure.

[0508] Compatibility test:

[0509] After 24 hours, the coating composition CC-PS-1 (test system with defoamer composition) was applied to the glass plate using a slot coater (100 μm wet) and dried overnight.

[0510] Glass plates coated with coating compositions CC-PS-2 to CC-PS-5 and CC-PS-6 to CC-PS-23 were similarly prepared using the above procedure.

[0511] The compatibility of coating compositions CC-PS-1 to CC-PS-5 and CC-PS-6 to CC-PS-23 was rated on a scale of 5 (best: no defects) to 1 (worst: many pits or other defects) by visual evaluation of surface defects on the coating surfaces.

[0512] Test of defoaming efficiency of sponge roller test:

[0513] The sponge roller was pre-soaked with deionized water and spun dry.The test system CC-PS-1 (approximately 16.0 g) was poured onto a polyester foil (20 cm x 20 cm) and evenly distributed over the total area with a sponge roller in a comparable manner.

[0514] Polyester foils coated with coating compositions CC-PS-2 to CC-PS-5 and CC-PS-6 to CC-PS-23 were similarly prepared using the above procedure.

[0515] The appearance of the dried films was rated from 5 to 1 by visually evaluating the number of bubbles remaining in and on the film (5: no bubbles, 1: many bubbles).

[0516] Table 6:

[0517] Test system Defoaming efficiency and compatibility in 9014:

[0518]

[0519]

[0520] As is apparent from Table 6, the defoamer composition of the present invention shows high defoaming efficiency and high compatibility. Therefore, the defoamer composition of the present invention shows balanced defoaming efficiency and compatibility compared to the comparative composition.

[0521] Comparative composition MO-C

[0522] A comparative composition was prepared using mineral oil as the hydrophobic liquid and wax. The comparative composition did not contain a modified polyacrylate polymer.

[0523] The comparative composition MO-C was prepared by adding a base oil as a hydrophobic liquid. (Wistema GmbH) (mineral oil) (20.8 wt.%) with added wax Honeywell (7.3 wt.%). The mixture was heated to 110°C with stirring until the wax was completely dissolved. The mixture was added to 71.9 wt.% of cold base oil with stirring. , followed by cooling to 50° C. and homogenization with a rotor-stator apparatus during the cooling phase.

[0524] Defoamer composition prepared using mineral oil

[0525] A) Antifoam compositions MO-1 to MO-5 and MO-6 to MO-11

[0526] Defoamer compositions MO-1 to MO-5 and MO-6 to MO-11 were prepared by mixing modified polyacrylate polymers (examples listed in Table 7) (4.0 wt.%) into a mixture containing a base oil. (Wistema GmbH) (mineral oil) as hydrophobic liquid and wax Honeywell The composition MO-C is prepared.

[0527] Therefore, the compositions of MO-1 to MO-5 and MO-6 to MO-11 are as follows: modified polyacrylate polymer (examples listed in Table 7) (4.0 wt.%), wax Honeywell (7.0wt.%), base oil (Wistema GmbH) (mineral oil) (20.0 wt.%) and base oil (69.0wt.%).

[0528] B) Stability of the defoamer composition

[0529] Initially, the compatibility of the defoamer compositions (MO-1 to MO-5, and MO-6 to MO-11) was visually checked. The formulations with modified polyacrylate polymers (see Table 5 for examples) were homogeneous and stable, and they did not show any phase separation or sedimentation.

[0530] C) Compatibility of defoamer composition and defoamer activity

[0531] To evaluate compatibility and defoamer activity, the defoamer compositions were added to different latexes used as model test systems for industrial and architectural waterborne coatings and paints.

[0532] Testing of the novel defoamer composition based on formulation example MO-1:

[0533] The defoamer composition MO-1 (0.6 g) was added to a latex binder resin for paint ( EDGE6283) (amount: 120 g) and stirred at high speed (5000 rpm) for 3 minutes with a high-speed mixer (disk diameter: 4 cm) to obtain a coating composition CC-MO-1.

[0534] Coating compositions CC-MO-2 to CC-MO-5 and CC-MO-6 to CC-MO-11 were prepared using the above procedure.

[0535] Compatibility test:

[0536] After 24 hours, the coating composition CC-MO-1 (test system with defoamer composition) was applied to the glass plate using a slot coater (100 μm wet) and dried overnight.

[0537] Glass plates coated with coating compositions CC-MO-2 to CC-MO-5 and CC-MO-6 to CC-MO-11 were similarly prepared using the above procedure.

[0538] The compatibility of coating compositions CC-MO-1 to CC-MO-5 and CC-MO-6 to CC-MO-11 was rated on a scale of 5 (best: no defects) to 1 (worst: many pits or other defects) by visual evaluation of surface defects on the coating surface.

[0539] Test of defoaming efficiency of sponge roller test:

[0540] The sponge roller was pre-soaked with deionized water and then spin-dried.The test system CC-MO-1 (approximately 16 g) was poured onto a polyester foil (20 cm x 20 cm) and evenly distributed over the total area with a sponge roller in a comparable manner.

[0541] Polyester foils coated with coating compositions CC-MO-2 to CC-MO-5 and CC-MO-6 to CC-MO-11 were similarly prepared using the above procedure.

[0542] The appearance of the dried films was rated from 5 to 1 by visually evaluating the number of bubbles remaining in and on the film (5: no bubbles, 1: many bubbles).

[0543] Table 7:

[0544] Test system Defoaming efficiency and compatibility in EDGE 6283:

[0545]

[0546] As is apparent from Table 7, the defoamer composition of the present invention shows high defoaming efficiency and high compatibility. Therefore, the defoamer composition of the present invention shows balanced defoaming efficiency and compatibility compared to the comparative composition.

Claims

1. A defoamer composition comprising a. at least one hydrophobic liquid; and b. at least one modified polyacrylate polymer obtainable by a process comprising: i. making at least one selected from substituted or unsubstituted acrylic acid C1-C 22 Alkyl esters, substituted or unsubstituted acrylic acid, C4-C 22 Cycloalkyl esters, substituted or unsubstituted C1-C 22 Acrylamide, or acrylic acid ester monomers of esters of acrylic acid and polyalkyl ether alcohols, to obtain at least one polyacrylate polymer; and ii. by using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 The alcohol (c1) is transesterified to modify the at least one polyacrylate polymer obtained in step (i).

2. The composition according to claim 1, wherein The at least one hydrophobic liquid is selected from the group consisting of mineral oils, organomodified silicones, vegetable oils, synthetic hydrocarbons, fatty alcohols, alkoxylated fatty alcohols, esters of fatty alcohols, fatty carboxylates, liquid polypropylene oxide, liquid polypropylene oxide-polyethylene oxide copolymers, esters of polypropylene oxide, or esters of polypropylene oxide-polyethylene oxide copolymers.

3. The composition according to claim 1 or 2, wherein The at least one hydrophobic liquid is mineral oil.

4. The composition according to claim 1 or 2, wherein The at least one hydrophobic liquid is an organomodified silicone.

5. The composition according to any one of claims 1 to 4, wherein The alkyl acrylate is selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, linear or branched C 12 -C 16 alkyl esters, n-octadecyl acrylate, or a combination of two or more thereof.

6. The composition according to any one of claims 1 to 5, wherein The at least one polyacrylate polymer is a copolymer selected from a random copolymer, or a block copolymer, and wherein step (i) comprises polymerizing the acrylate monomer and at least one monomer selected from a methacrylate monomer or a styrene monomer to obtain the at least one polyacrylate polymer.

7. The composition according to any one of claims 1 to 6, wherein The unsubstituted C8-C 36 The alcohol (C1) is selected from the group consisting of 2-ethylhexanol, n-decanol, isodecyl alcohol, linear or branched C 12 -C 16 alcohol, n-octadecyl alcohol, oleyl alcohol, or a combination of two or more thereof.

8. The composition according to any one of claims 1 to 7, wherein The polyether alcohol (c2) is a compound having formula (A) in, m is an integer in the range from ≥1 to ≤10; n and p are independently integers ranging from ≥0 to ≤2000, wherein n+p is an integer ranging from ≥1 to ≤4000; R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 alkenyl, or substituted or unsubstituted phenyl; and R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or substituted or unsubstituted phenyl.

9. The composition according to any one of claims 1 to 8, wherein The polyether alcohol (c2) is a compound having the formula (A1) R 1 -(O-CH2CH2) n -OH...Formula (A1) in, n is an integer in the range from ≥1 to ≤100; and R 1 Selected from substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C2-C 30 A group consisting of an alkenyl group, or a substituted or unsubstituted phenyl group.

10. The composition according to any one of claims 1 to 9, wherein The peak molecular weight of the at least one modified polyacrylate polymer is in the range of from 2000 to 100,000 g / mol according to DIN 55672-1.

11. The composition according to any one of claims 1 to 10, wherein The at least one modified polyacrylate polymer comprises 1. 20.0 wt.% to 70.0 wt.% of at least one polyacrylate polymer; and 2. 30.0 wt.% to 80.0 wt.% of at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 Alcohol (c1); Based on 100 weight-% of the total weight of the at least one modified polyacrylate polymer.

12. The composition according to any one of claims 1 to 11, wherein Step (i) is carried out in the presence of at least one nitroxyl ether having the general formula (B) in R 11 and R 12 are independently selected from substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted C7-C 18 Aralkyl; wherein the substituted alkyl group carries a C1-C4 alkoxy group, a C1-C4 alkoxy-C1-C4 alkoxy group, or a PO3R z 2 substituents, and R z is C1-C4 alkyl; or R 11 and R 12 Together they form a substituted or unsubstituted C2-C 10 Alkylene or substituted or unsubstituted C2-C 10 an alkenylene ring; Wherein the substituted C2-C 10 Alkylene or substituted C2-C 10 The alkenylene group has 1, 2, 3, 4 or 5 substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy-C1-C4 alkoxy, COOH, or CONH2; and Among them, C2-C 10 Alkylene or C2-C 10 The alkenylene group may be optionally substituted by O, C=O, C=NOH, CH-OCOCH3 or NR x A CH2 group replaced or two CH2 groups replaced independently of each other, and R x is C1-C4 alkyl or C1-C4 alkoxy; R 13 is C1-C4 alkyl or H; R 14 , R 15 and R 16 are independently C1-C4 alkyl; X is selected from the group consisting of: -CH2-phenyl, -CHCH3-phenyl, -C(CH3)2-phenyl, -C(C5-C 6- Cycloalkyl)2-CN, -C(CH3)2CN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CHR 17 -C(O)-phenyl, -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)-CHR 17 -C(O)-(C1-C4)alkyl, -(C1-C4alkyl)-CHR 17 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)-CHR 17 -C(O)-NH(C1-C4 alkyl) and -(C1-C4 alkyl)-CHR 17 -C(O)-NH2, where R 17 It is H or C1-C4 alkyl.

13. The composition according to any one of claims 1 to 12, further comprising at least one additive selected from the group consisting of water, nonionic surfactants, anionic surfactants, liquid alkoxylates selected from liquid polypropylene oxide or liquid polypropylene oxide copolymers, liquid polyethers, liquid polyesters, or solid particles based on silica or on synthetic or natural waxes.

14. A composition according to any one of claims 1 to 13, comprising c. at least one hydrophobic liquid which is one or more mineral oils and / or one or more organomodified silicones; d. at least one modified polyacrylate polymer obtainable by a process comprising: j. making at least one substituted or unsubstituted acrylic acid C1-C 22 Alkyl ester polymerization; and jj. By using at least one polyalkyl ether alcohol (c2) and optionally at least one unsubstituted C8-C 36 alcohol (c1) to modify the at least one polyacrylate polymer obtained in step (i) by transesterification; and water.

15. Use of the defoamer composition according to any one of claims 1 to 14 for reducing or preventing foam in an aqueous composition; wherein, The amount of the defoamer composition ranges from 0.01 wt.% to 5.0 wt.% based on the total weight of the aqueous composition which is 100 wt-%, wherein the aqueous composition is preferably selected from the group consisting of water-based paints, coating compositions, inks and adhesive compositions.

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