Antifoaming agent composition based on polybutadiene modified with organic functional groups

Abstract

To provide a silicone-free defoamer composition which allows broad adjustment of the defoamer performance and compatibility.SOLUTION: A defoamer composition comprises a compound based on a polybutadiene having at least one repeat unit selected from the group consisting of divalent radicals (U), (V) and (W) illustrated below. (-A is a monovalent organic group or hydrogen group, and -B is an organic group having a polybutadiene structure terminating in a hydroxy group or an ether).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antifoaming agent composition comprising a polybutadiene-based compound. [Background technology]

[0002] In this specification, the term "defoaming agent" encompasses both products and formulations that prevent foaming and products and formulations that break down foam and enable degassing. In practice, the boundaries between these product characteristics are ambiguous, so we use the general term "defoaming agent" here.

[0003] In many industrial processes, especially when operations are performed in aqueous media, it is necessary to suppress or completely prevent the formation of unwanted foam during manufacturing or processing operations. This is because foam or foam heads formed during stirring and dispersion operations, or in containers during filling operations, can prolong manufacturing time, reduce the effective volume of the plant, and hinder the proper operation of the plant, as they can cause the mixture to overflow from the mixing tank and discolor upon application.

[0004] This can be achieved by adding an antifoaming agent that can avoid or eliminate unwanted bubbles even at very low application concentrations of approximately 0.001% by weight, while simultaneously preventing surface defects after application of the system and suppressing air incorporation into the paint. In practice, these aspects must be considered at least as much as good antifoaming properties.

[0005] Surface defects should be understood as undesirable characteristics for the user, such as pinholes, craters, loss of gloss, orange peel, wrinkles, and loss of adhesion in coating systems. However, since products such as paints are often not used up immediately but only after being stored for a relatively long period, the proper long-term stability of the defoamer in the formulation is also very important for the user. When stored under extreme climatic conditions (heat and sunlight), the effectiveness of the defoamer formulation may be lost in a short time.

[0006] Typical active ingredients for formulating antifoaming agents are polysiloxanes, mineral oils, vegetable oils, or polymers. It is known that by combining these active ingredients, as well as by adding fine hydrophobic solids (e.g., silica), particularly effective antifoaming agents tailored to specific applications can be formulated.

[0007] Defoamers for defoaming aqueous and non-aqueous media, containing polyoxyalkylene polysiloxane polymers as active ingredients that significantly influence defoaming properties, exhibit specific efficacy and storage stability. These include foam suppression, defoaming properties, excellent long-term stability, and superior compatibility with aqueous and non-aqueous media. All of these properties are crucial for modern paint applications.

[0008] Therefore, it is known to those skilled in the art that polyether-modified siloxanes are highly effective antifoaming agents. These may be used in pure form or in compound form. Polyethersiloxanes are under increasing regulatory pressure due to the presence of trace amounts of cyclic siloxanes associated with their manufacture. This is because, recently in Europe, cyclic siloxanes have been classified as "Substances of Very High Concern" (SVHC) by ECHA due to their persistence, bioaccumulative and toxicity (PBT), as well as their high persistence and high bioaccumulativeness (vPvB). Therefore, the presence of cyclic siloxanes at concentrations of 0.1% by weight or higher requires appropriate labeling and significantly limits sales opportunities in Europe. Based on experience, other international regulations are expected to align with European views, further restricting the market scope.

[0009] The popularity of siloxane-based defoamers is based on the wide range of adjustability regarding (physical) chemical properties. This brings about a wide variety of material diversity due to the topological effect of siloxanes, but also results from the selection of organic polymer modification and the density of its functional groups on the siloxane main chain. In the simplest model representation of the defoaming agent action, the defoaming agent must be incompatible with the surrounding matrix. Due to its surface activity potential, the defoaming agent moves to the nearest "liquid-gas bubble" interface, penetrates it, and when spreading along the interface, can force the gas bubble to rupture. Therefore, in this model representation, the (in)solubility of the defoaming agent in the surrounding medium plays an important role. The specific preparation ability of hydrophilicity (by polyethers) and the specific adjustment ability of hydrophobicity (by siloxane structure) enable the individual adjustment of the defoaming agent capacity of each matrix system. Furthermore, the compatibility between the defoaming agent and other substances present in its application is essential. For example, within the scope of coloring and painting applications, the defoaming agent should not be so incompatible as to cause coating defects that adversely affect the applied image, but rather should bring about a satisfactory final result in terms of the application technology.

[0010] Defoamers that do not contain silicone, such as polybutadiene, are also known from the prior art. Their drawback is the limited adjustability of compatibility.

Summary of the Invention

Problems to be Solved by the Invention

[0011] Therefore, it is desirable to provide a defoaming agent composition that does not contain silicone, which can widely adjust the performance and compatibility of the defoaming agent and overcome at least one drawback of the prior art.

Means for Solving the Problems

[0012] Therefore, in order to achieve this object, a defoaming agent composition containing a compound based on polybutadiene having at least one repeating unit selected from the group consisting of divalent groups (U), (V), and (W) is proposed.

[0013] [ka]

[0014] (In the formula, -A is independently a monovalent organic group or hydrogen group in any case, preferably independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 6 carbon atoms, and more preferably independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms. - In all cases, B is independent of equation (4a):

[0015] [ka]

[0016] Selected from the group consisting of the following groups, preferably independently in each case, formula (4b):

[0017] [ka]

[0018] Selected from the group consisting of the following groups, more preferably independently in each case, formula (4c):

[0019] [ka]

[0020] Selected from a group consisting of the following elements, In formula (4a), formula (4b), and formula (4c), R 1 In each case, independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 16 carbon atoms, preferably independently in each case an alkyl group or phenyl group having 1 to 16 carbon atoms, and more preferably independently in each case a methyl group, an ethyl group or a phenyl group. R 2 is, formula -CH 2- Ure 3 It is the basis of, R 3 In each case, these are independently selected from the group consisting of monovalent hydrocarbon groups having 3 to 18 carbon atoms, preferably allyl groups, butyl groups, alkyl groups having 8 to 15 carbon atoms, or phenyl groups, each of which may be independently substituted with a monovalent group selected from hydrocarbon groups having 1 to 4 carbon atoms, more preferably tert-butylphenyl groups or o-cresyl groups. R 4 Each of these is independently a monovalent organic group having 1 to 18 carbon atoms, or hydrogen, preferably hydrogen. m, n, o, p, and q are each independently between 0 and 300, preferably between 0 and 200, more preferably between 0 and 100, and the sum of m, n, o, p, and q is greater than 1, preferably greater than 5, more preferably greater than 10. - The B group is as follows:

[0021] [ka]

[0022] (It has at least one repeating unit, and all sequences of that repeating unit.)

[0023] In the context of this invention, the terms “medium,” “coating system,” “coating or paint formulation,” “coating recipe,” and “coating composition” should be understood to be synonymous. These are systems to be defoamed. The subject matter of the present invention will be described below with reference to examples, but the invention is not intended to be limited to these exemplary embodiments. Where ranges, general formulas, or groups of compounds are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subcompound groups obtained by excluding individual values ​​(ranges) or compounds. Where references to literature are cited in the context of this specification, their entire contents are intended to be part of the disclosures of the present invention.

[0024] Where average values ​​are listed below, these values ​​are numerical averages unless otherwise specified. Where measured values, parameters, or material properties are listed below, these are measured values, parameters, or material properties measured at 25°C and preferably at a pressure of 10¹-325 Pa (standard pressure), unless otherwise specified.

[0025] When a numerical range is described below in the form "X~Y," and X and Y represent the boundaries of that range, unless otherwise specified, this is equivalent to the description "X or greater and Y or less." Therefore, unless otherwise specified, the stated range includes X and Y, which are the boundaries of the range.

[0026] Whenever a molecule / molecular fragment has one or more stereocenters, or can differentiate into isomers due to symmetry, or can differentiate into isomers due to other effects, such as restricted rotation, all that can be isomerized are included in the present invention.

[0027] All formulas represent compounds or groups that consist of repeating units (e.g., repeating fragments), blocks, or monomer units and may have a molar mass distribution. The frequency of repeating units is expressed in exponential form. The exponents used in formulas must be considered statistical mean (numerical mean). Thus, the exponents used and the range of reported exponential values ​​must be considered the mean of the possible statistical distributions of the structures and / or mixtures thereof that actually exist. The various fragments or repeating units of the compounds described in the formulas may be statistically distributed. The statistical distributions may have a block structure with any number of blocks and any order, or they may be random distributions. They may also have alternating structures or form gradients along the chain. In particular, they may also give rise to any mixed forms in which groups with different distributions may arbitrarily follow one another. The following formulas contain all permutations of repeating units. Where compounds that may have multiple instances of different units (e.g., polybutadiene (A) containing end-capped polyether groups, epoxy-functionalized polybutadiene (C), hydroxy-functionalized polybutadiene (E), polyether-modified polybutadiene (G), or polyether-modified polybutadiene (K)) are described in the context herein, the multiple instances of different units may arise in a disordered manner (e.g., a statistical distribution) or in a regular manner in these compounds. The number of units or the numerical value of the relative frequency in such compounds should be considered the average (numerical mean) of all corresponding compounds. Certain embodiments may impose limitations on the statistical distribution as a result of that embodiment. In all areas unaffected by such limitations, the statistical distribution remains unchanged.

[0028] It is understood that "antifoaming agent" and "active ingredient in antifoaming agents" are synonymous.

[0029] Surprisingly, it was found that the antifoaming compositions according to the present invention can advantageously include non-silicone-based compounds and allow for adjustment of antifoaming effect and compatibility. First, the versatility of polybutadiene could be utilized. Second, compatibility could be improved by combining specific topologically different polyethers with their functional group densities on the polybutadiene skeleton.

[0030] Surprisingly, in order to achieve both sufficient defoaming effect and sufficient compatibility of the composition according to the present invention, at least one B group is present, as follows:

[0031] [ka]

[0032] It was also proven that it has at least one repeating unit.

[0033] The term "defoaming" is often used to describe the removal of gas bubbles from a coating. However, in some cases, it is necessary to distinguish between "defoaming" and "deaerating." Gas bubbles always reach the surface first. The removal of bubbles that then occur on the surface is called defoaming. Defoaming agents are only effective on the surface where they remove existing bubbles. In contrast, deaerating agents must be active throughout the entire coating. Bubbles on the surface. Defoaming agents destabilize the bubbles. Air is incorporated into the coating. Deaerating agents facilitate the movement of bubbles to the surface.

[0034] The compositions according to the present invention preferably contain a compound in which m, n, o, p, and q are each independently 0 to 300, preferably 0 to 200, more preferably 0 to 100, and the sum of m, n, o, p, and q is greater than 1, preferably greater than 5, and more preferably greater than 10.

[0035] The composition according to the invention particularly preferably contains a compound in which m, n, o, p and q are each independently from 0 to 200, preferably from 0 to 100, more preferably from 0 to 50, and the sum of m, n, o, p and q is greater than 1, preferably greater than 5, more preferably greater than 10.

[0036] The compound for the composition according to the invention preferably has a number-average molar mass M n of from 200 g / mol to 20,000 g / mol, preferably from 500 g / mol to 10,000 g / mol, more preferably from 700 g / mol to 5,000 g / mol for the polybutadiene portion.

[0037] In the case of the composition according to the invention, the polybutadiene portion of the compound has double bonds present as 1,2 vinyl double bonds of from 0% to 80%, preferably from 0% to 30%, more preferably from 0% to 10%, particularly preferably from 0% to 5%, and double bonds present as 1,4 double bonds of from 20% to 100%, preferably from 70% to 100%, more preferably from 90% to 100%, particularly preferably from 95% to 100%. <00OO209> In the case of the composition according to the invention, the compound is preferably prepared on the basis of linear polybutadiene.

[0039] For the composition according to the invention, the compound preferably does not have pendant polybutadiene (at the comb positions).

[0040] The compound preferably has exclusively pendant repeating units (U), (V) and / or (W) (at the comb positions).

[0041] The average molar mass of the B groups of the compound is preferably from 40 g / mol to 20,000 g / mol, preferably from 100 g / mol to 15,000 g / mol, more preferably from 200 g / mol to 10,000 g / mol.

[0042] Group R 1 、R 2 、R 3 and R4 Each of these elements may independently be linear or branched, saturated or unsaturated, aliphatic or aromatic, and substituted or unsubstituted.

[0043] In equation (4a), R = R 1 Or R 2 The general notation is that R=CH3 in equations (4b) and (4c):

[0044] [ka]

[0045] The formula is:

[0046] [ka]

[0047] The unit or formula:

[0048] [ka]

[0049] It represents the unit, but preferably, the formula:

[0050] [ka]

[0051] It is the unit of measurement.

[0052] General notation for equation (4a):

[0053] [ka]

[0054] The formula is:

[0055] [ka]

[0056] The unit or formula:

[0057] [ka]

[0058] It represents the unit, but preferably, the formula:

[0059] [ka]

[0060] It is the unit of measurement.

[0061] More preferably, R 4 In each case, the group is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, an acyl group -C(=O)R 5 , urethane group -C(=O)NH-R 6 , carbonate group -C(=O)OR 7 R is selected from the group consisting of hydrogen. 4 More preferably, in any case independently, an alkyl group having 1 to 18 carbon atoms, an alkylene group having 1 to 18 carbon atoms, or an acyl group -C(=O)R 5 , urethane group -C(=O)NH-R 6 , carbonate group -C(=O)OR 7 Selected from the group consisting of and hydrogen. More preferably, R 4 It is hydrogen.

[0062] R 5 In each case, independently, is an alkyl group or alkenyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably a methyl group.

[0063] R 6In each case, these are independently alkyl or aryl groups having 1 to 18 carbon atoms, preferably 6 to 18 carbon atoms.

[0064] R 7 Each of these is an alkyl group having 1 to 18 carbon atoms, preferably 1 or 2 carbon atoms.

[0065] The compound is preferably as follows:

[0066] [ka]

[0067] It also includes repeating units (Y) and (Z).

[0068] Preferably, in at least one polyether-modified polybutadiene (G) or (K), the value obtained by dividing the sum of all repeating units (U), (V), and (W) by the sum of all repeating units (U), (V), (W), (X), (Y), and (Z) is greater than 0% and less than or equal to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and particularly preferably 4% to 20%.

[0069] This means that more than 0% and up to 70% of the total repeating units (U), (V), (W), (X), (Y), and (Z), preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and particularly preferably 4% to 20%, are polyether-modified.

[0070] Number-average molar mass M of the polybutadiene portion of polyether-modified polybutadiene (G) or (K) n , weight average molar mass M w The polybutadiene and polydispersity can be freely modified. The polybutadiene moiety is understood to mean the polyether-modified polybutadiene (G) or (K) component derived from the polybutadiene (A) used in this method.

[0071] Preferably, the number-average molar mass M of the polybutadiene portion of the polyether-modified polybutadiene (G) or (K). n The concentration is 200 g / mol to 20,000 g / mol, preferably 500 g / mmol to 10,000 g / mol, and more preferably 700 g / mol to 5,000 g / mol.

[0072] Alternatively, preferably, the number-average molar mass M of the polybutadiene portion of the polyether-modified polybutadiene (G) or (K). n The amount is 2,100 g / mol to 20,000 g / mol, more preferably 2,200 g / mol to 10,000 g / mol, and most preferably 2,300 g / mol to 5,000 g / mol.

[0073] Number-average molar mass M of the polybutadiene portion n The number-average molar mass M of polybutadiene (A) below is n It is defined as follows.

[0074] More preferably, the polyether-modified polybutadiene (G) or (K) has 5 to 360, more preferably 10 to 180, and most preferably 15 to 90 repeating units, the repeating units being selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0075] Alternatively, preferably, the polyether-modified polybutadiene (G) or (K) has 35 to 360 repeating units, more preferably 40 to 180, and most preferably 45 to 90, and the repeating units are selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0076] More preferably, the polyether-modified polybutadiene (G) or (K) is characterized in that 0% to 80%, preferably 0% to 30%, more preferably 0% to 10%, and particularly preferably 0% to 5% of the present double bonds are 1,2-vinyl double bonds, and 20% to 100%, preferably 70% to 100%, more preferably 90% to 100%, and particularly preferably 95% to 100% of the present double bonds are 1,4-vinyl double bonds.

[0077] Particularly preferred are the polyether-modified polybutadienes (G) or (K) derived from Polyvest® 110 and Polyvest® 130 from Evonik Industries AG / Evonik Operations GmbH, and Lithene ultra AL and Lithene ActiV 50 from Synthomer PLC.

[0078] The molar mass and polydispersity of group B can be freely changed. However, preferably, the average molar mass of group B is 100 g / mol to 20,000 g / mol, preferably 200 g / mol to 15,000 g / mol, and more preferably 400 g / mol to 10,000 g / mol. The average molar mass of group B may be calculated from the starting weight of the monomer used relative to the number of OH groups of the hydroxy-functionalized polybutadiene (E) used. For example, if 40 g of ethylene oxide is used and the amount of hydroxy-functionalized polybutadiene (E) used is 0.05 moles of OH groups, the average molar mass of group B is 800 g / mol.

[0079] Polyether-modified polybutadiene (G) or (K) is liquid, paste-like, or solid, depending on its composition and molar mass.

[0080] Number average molar mass M of polyether-modified polybutadiene (G) or (K) n The amount is preferably 1,000 g / mol to 6,000 g / mol, more preferably 1,500 g / mol to 5,000 g / mol, and particularly preferably 2,000 g / mol to 4,000 g / mol.

[0081] Their polydispersity varies over a wide range. The polydispersity of at least one polyether-modified polybutadiene (G) or (K) by the GPC method relative to PPG is preferably M w / M n = 1.5 to 10, more preferably 2 to 9, and more preferably 3 to 8.

[0082] As described above, approaches to polybutadiene-based compounds having at least one repeating unit selected from the group consisting of divalent groups (U), (V), and / or (W) can be derived from the unpublished European application no. 19212066.5 or the International application no. PCT / EP2020 / 083013.

[0083] An unpublished European application no. 19212066.5 or International application no. PCT / EP2020 / 083013 relates to the preparation of polybutadiene-based compounds suitable for antifoaming compositions according to the present invention. A method comprising the following steps is described: a) A step of reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C); b) A step of reacting at least one epoxy-functionalized polybutadiene (C) with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E); c) A step of reacting at least one hydroxy-functionalized polybutadiene (E) with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0084] Surprisingly, it has been disclosed that polybutadiene with a high proportion of 1,4 units and a low content of vinyl 1,2 units can readily react with OH-functional compounds under acid-catalyzed ring-opening conditions after epoxidation with hydrogen peroxide to produce pendant OH-functional polybutadiene (polybutadienol), which can then be alkoxylated with alkylene oxide.

[0085] Preferably, this method further includes at least one of the following optional steps: d) Reacting at least one polyether-modified polybutadiene (G) with at least one end-capping reagent (H) to obtain at least one polyether-modified polybutadiene (K) containing end-capped polyether groups; e) A step of lightening the color of at least one polyether-modified polybutadiene (G) or (K).

[0086] This method is preferably further characterized in the following respects: - In step a), more than 0% and up to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and particularly preferably 4% to 20% of the double bonds of at least one polybutadiene (A) are epoxidized with performic acid produced in situ from formic acid and H2O2. - In step b), one or more short-chain alcohols having 1 to 6 carbon atoms, particularly isobutanol, are added to the epoxy group of at least one epoxy-functionalized polybutadiene (C) under ring-opening conditions, preferably using one or more acidic catalysts, particularly trifluoromethanesulfonic acid. - In step c), in the alkoxylation reaction, preferably using an additional Zn / Co bimetallic cyanide catalyst or a basic catalyst (e.g., amine, guanidine, amidine, alkali metal hydroxide, or alkali metal alkoxide), one or more epoxy-functional compounds (F) selected from alkylene oxides, and optionally further epoxy-functional monomers, are added to the obtained pendant OH group of at least one hydroxy-functional polybutadiene (E). - In step d), if necessary, at least one polyether-modified polybutadiene (G) is reacted with at least one end-capping reagent (H) selected from the group consisting of carboxylic acids, carboxylic acid anhydrides, halogenated hydrocarbons, isocyanates, and carbonates to obtain at least one polyether-modified polybutadiene (K) containing end-capped polyether groups. - In step e), if necessary, activated carbon and / or hydrogen peroxide are used to lighten at least one polyether-modified polybutadiene (G) or (K).

[0087] The disclosed method makes it possible for the first time to modify linear polybutadiene by simple direct alkoxylation of pendant OH groups with polyether groups at comb-tooth positions. The chain length and monomer sequence of the polyether groups may be modified within a wide range. The average number of polyether groups bonded to polybutadiene can be controlled through the degree of epoxidation and hydroxy-functionalization, resulting in significant structural diversity in hydroxy-functionalized polybutadiene(E).

[0088] The polybutadiene having polyether groups at the comb-tooth positions obtained according to the present invention preferably contains essentially no residual epoxy groups. The process products according to the present invention preferably contain essentially no free polyether components. Preferably, essentially all polyethers are chemically bonded to the polybutadiene via ether bonds. Therefore, the process products according to the present invention are clearly different in their high purity from compounds known from the prior art to the present.

[0089] To avoid repetition of the preferred configuration of the preparation method of the unpublished European application number 19212066.5 or the International application number PCT / EP2020 / 083013, the following descriptions are specific to the headings of the individual steps. Preferred configuration of step a) of the method according to the present invention Preferred configuration of step b) of the method according to the present invention Preferred configuration of step c) of the method according to the present invention DMC catalysis Base catalyst Products as starters Optional process d) Optional process e) reactor

[0090] In the case of the composition according to the present invention, step c) for preparing the above compound is preferably described in detail.

[0091] In step c) of the method according to the present invention, at least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0092] In step b), at least one hydroxy-functional polybutadiene (E) serves as an initiating compound for the reaction with at least one epoxy-functional compound (F) in step c). Under ring-opening conditions, and preferably in the presence of a suitable catalyst, at least one epoxy-functional compound (F) (hereinafter also simply referred to as "monomer," "epoxy monomer," or "epoxide") is added to the OH group of at least one hydroxy-functional polybutadiene (E) in a polyaddition reaction. This forms the polybutadiene according to the present invention having a polyether chain at the comb-tooth position (pendant position). That is, at least one polyether-modified polybutadiene (G) is formed. The polyether-modified polybutadiene (G) is preferably a linear polybutadiene modified with a polyether group at the comb-tooth position (pendant position). Therefore, preferably, the polyether-modified polybutadiene (G) has a linear polybutadiene backbone and a pendant polyether group.

[0093] The reaction in step c) is preferably an alkoxylation reaction, i.e., a polyaddition of an alkylene oxide to at least one hydroxy-functionalized polybutadiene (E). However, the reaction in step c) may be carried out using a glycidyl compound instead of or in addition to the alkylene oxide.

[0094] Therefore, preferably, at least one epoxy-functional compound used in step c) is selected from the group of alkylene oxides, preferably from the group of alkylene oxides having 2 to 18 carbon atoms, more preferably from the group of alkylene oxides having 2 to 8 carbon atoms, and particularly preferably from the group consisting of ethylene oxide, propylene oxide, 1-butylene oxide, cis-2-butylene oxide, trans-2-butylene oxide, isobutylene oxide, and styrene oxide. and / or, at least one epoxy-functional compound used in step c) is selected from the group of glycidyl compounds, preferably from the group of monofunctional glycidyl compounds, more preferably from the group consisting of phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 / C14 fatty alcohol glycidyl ether, and C13 / C15 fatty alcohol glycidyl ether.

[0095] In place of, or in addition to, the alkylene oxides or glycidyl compounds described above, cyclic anhydrides, lactones, dilactines, or cyclic carbonates may also be used as monomers or comonomers with the alkylene oxides or glycidyl compounds described above.

[0096] All cyclic anhydrides known to those skilled in the art may be used in their pure form or as any mixture. Saturated, unsaturated, or aromatic cyclic dicarboxylic acid anhydrides are preferably succinic anhydride, octenyl-, decenyl-, and dodecenyl succinic anhydrides, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, trimellitic anhydride, phthalic anhydride, hexahydro-, tetrahydro-, dihydro-, methylhexahydro-, and methyltetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, phthalic anhydride, and hexahydrophthalic anhydride are preferred, with maleic anhydride and phthalic anhydride being particularly preferred.

[0097] All lactones known to those skilled in the art may be used as lactones in their pure form or in any mixture. Valerolactone, caprolactone, and butyrolactone are preferred, all of which may be substituted or unsubstituted with organic groups, preferably methyl groups. ε-Caprolactone or δ-Valerolactone are preferred, with ε-Caprolactone being particularly preferred.

[0098] As cyclic carbonates, it is generally possible to use all cyclic carbonates known to those skilled in the art, which are available via CO2 insertion into epoxides, in their pure form or in any mixture. It is preferable to use carbonates derived from glycidyl ethers, with propylene carbonate and ethylene carbonate being particularly preferred.

[0099] The monomers may be added individually in their pure form, alternately and sequentially in any metrical order, or simultaneously in a mixture. Consequently, the arrangement of monomer units in the resulting polyether chain will be a block distribution, a statistical distribution, or a gradient distribution in the final product.

[0100] The method according to the present invention forms a pendant polyether chain on polybutadiene. This exemplifies the ability to prepare the pendant polyether chain in a controlled and reproducible manner with respect to its structure and molar mass.

[0101] The sequence of monomer units can be altered over a wide range by changing the order of addition.

[0102] The molar mass of the pendant polyether group may be changed within a wide range by the method according to the present invention and may be specifically and reproducibly controlled by the molar ratio of the added monomer to the OH group of at least one hydroxy-functional polybutadiene (E) initially filled in step b).

[0103] The polyether-modified polybutadiene (G) prepared according to the present invention is preferably characterized by containing B groups bonded to the polybutadiene skeleton via ether groups according to formulas (3a), (3b), and (3c).

[0104] [ka]

[0105] As described above for step B), the A group in formulas (3a), (3b), and (3c) originates from compound A-OH, i.e., the hydroxy-functional compound (D) used in step b). As mentioned above, in step b), two cases must be distinguished: A≠H or A=H. In the first case, i.e., A≠H, the A group in formulas (3a), (3b), and (3c) is the same as the A group in formulas (2a), (2b), and (2c). In the second case, i.e., A=H, the A group in formulas (3a), (3b), and (3c) is independently either an H or a B group in each case. For example, when a monofunctional aliphatic alcohol having 1 to 6 carbon atoms is used as the hydroxy-functional compound (D), A is an alkyl group having 1 to 6 carbon atoms. For example, when a carboxylic acid is used as the hydroxy-functional compound (D), A is an acyl group. However, when water is used as the hydroxyl-functional compound (D), A in formulas (3a), (3b), and (3c) is a B group for the reaction with one or more epoxy-functional compounds (F). If there is no reaction, A remains hydrogen. Thus, each converted pendant hydroxyl group becomes exactly one pendant-OB group. The B group is similarly composed of one or more monomers, preferably two or more monomers, of at least one epoxy-functional compound (F) used.

[0106] In the context of this specification, in principle, all alkoxylation catalysts known to those skilled in the art, such as basic catalysts (e.g., alkali metal hydroxides, alkali metal alkoxides, amines, guanidines, amidines, phosphorus compounds such as triphenylphosphine), as well as acidic and Lewis acidic catalysts (e.g., SnCl4, SnCl2, SnF2, BF3, and BF3 complexes), and bimetallic cyanide (DMC) catalysts can be used.

[0107] Before supplying the epoxide, i.e., before adding at least one epoxy-functional compound (F) to be used, the reactor, partially filled with the starter and catalyst, is inactivated, for example, with nitrogen. This is achieved, for example, by repeatedly alternating between evacuating and supplying nitrogen. After the final nitrogen injection, it is advantageous to evacuate the reactor to less than 200 millibars. This means that it is preferable to add the first amount of epoxy monomer in the evacuated reactor. The monomer is added with stirring and, if necessary, cooling to remove the released reaction heat and maintain the pre-set reaction temperature. The starter to be used is at least one hydroxy-functional polybutadiene (E). Alternatively, a polyether-modified polybutadiene (G) prepared by the method of the present invention may be used as the starter, as will be further described below.

[0108] Further additives, such as polyethers, oils of natural and synthetic origin, organic polymers, organically modified silicone polymers, and solids, may be added to the compositions according to the present invention. Examples of such suitable micronized solids include highly dispersible pyrolysis or wet chemical-derived silica, which is commercially available as Aerosil or Sipernat and may be hydrophobized by treatment with organosilicon compounds. Even more suitable solids include metal soaps such as magnesium, aluminum, and calcium soaps, as well as polyethylene and amide waxes or urea.

[0109] It is preferable to use the compound in an amount of 2 to 100% by weight, preferably 5 to 70% by weight, and more preferably 5 to 30% by weight, relative to the total composition.

[0110] Similarly, the defoaming activity may be further enhanced by adding other solids, such as silica, wax, and solids. Such additives are known to those skilled in the art. At least one solid, preferably silica which may exist in a modified or unmodified form, or (alkaline earth) / alkali metal soaps (e.g., calcium stearate) and mixtures thereof, may be used.

[0111] It is also preferable to add an emulsifier to prepare an antifoaming emulsion starting from the composition according to the present invention. It is preferable to use a commercially available emulsifier, preferably anionic, cationic, or nonionic emulsifier, or a mixture thereof. Specific emulsifier systems that may be used are also known.

[0112] Preferably, an emulsifier system having a viscosity of 50 to 5000 mPa·s, preferably 100 to 2000 mPa·s, and more preferably 100 to 1000 mPa·s, as measured in a 5% aqueous solution according to DIN 53015, is suitable for preparing the antifoaming emulsion according to the present invention.

[0113] Preferably, the composition comprises at least one thickener, preferably an associative thickener such as modified polyacrylate, modified cellulose ether, modified polyacrylamide, modified polyether, and associative polyurethane thickener; modified cellulose; organic polymers such as polyvinyl alcohol, polyacrylic acid and polymethacrylic acid and their copolymers, (modified) polyacrylamide, polyvinylpyrrolidone, and polyethylene glycol; natural thickeners such as starch, gelatin, casein or konjac powder, and chemically modified forms thereof; and organic thickeners such as metal soaps, hydrogenated castor oil and its alkoxylates, and chemically modified fat derivatives; or an inorganic compound selected from the group consisting of (which may be modified) layered silicates (bentonite, hectorite) or (hydrated) SiO2 particles.

[0114] Representative examples of ASE (alkali swelling emulsion) type acrylate thickeners are available from companies such as DOW under the brand name ACRYSOL (trademark) TT, from Munzing under the brand name TAFIGEL (registered trademark) AP, and from BASF under the brand name Rheovis (registered trademark) AS.

[0115] Known anionically modified acrylamides are manufactured by Solenis, Yixing Bluwat, or BASF.

[0116] An additional aspect of the present invention is the use of the composition as an antifoaming additive, a flow control additive, and / or a substrate wetting additive.

[0117] A further aspect of the present invention is the use of compositions for preparing dispersions, mill bases, paints, coating or printing inks, inkjet printers, grind resins, pigment concentrates, colorant preparations, pigment preparations, filler preparations, or coating compositions.

[0118] The coating composition may be solvent-based, solvent-free, or water-based coating or printing ink.

[0119] The present invention further provides the use of polybutadiene-based compounds for preparing antifoaming compositions. For specific selection criteria for polyether-modified polybutadienes, please refer to the above.

[0120] The following examples are provided solely to illustrate the present invention to those skilled in the art and do not in any way limit the subject matter or method of claiming the patent. [Examples]

[0121] I. Preparation example General method Gel permeation chromatography (GPC) Polydispersity (M w / M n ), weight average molar mass (M w ), and number-average molar mass (M n GPC measurements were performed to determine the following: SDV1000 / 10000Å column combination (length 65cm), temperature 30℃, THF as mobile phase, flow rate 1mL / min, sample concentration 10g / L, RI detector, evaluation against polypropylene glycol standard.

[0122] Measurement of epoxy group content in polybutadiene (epoxy content, epoxidation level) The epoxy group content 13 Measurements were performed using 13C-NMR. A Bruker Avance 400 NMR spectrometer was used. For this purpose, the sample was dissolved in deuterated chloroform. Epoxy content is defined as the percentage of epoxidized butadiene units in mole percent relative to the total number of repeating units present in the sample. This corresponds to the number of epoxy groups in the epoxidized polybutadiene divided by the number of double bonds in the polybutadiene used.

[0123] Measurement of acid value The acid value was measured by titration in accordance with DIN EN ISO2114.

[0124] Preparation of the defoaming agent composition of the present invention Steps a) to c) were carried out based on the unpublished European application number 19212066.5 or the International application number PCT / EP2020 / 083013 1.1. For example, the first example in each case is described with respect to the weight of the components. The weights and parameters of the intermediate and final products can be seen from each table.

[0125] Step a) Preparation of epoxidized polybutadiene Using epoxidized polybutadiene, we prepared polybutadiene with the structure x=1%, y=24%, and z=75%, trade name Polyvest® 110 (Evonik).

[0126] General explanation of Experiment Example A1 In a 2L four-necked glass flask, 725g of Polyvest® 110 and 39.2g of concentrated formic acid in 1500g of chloroform were first added at room temperature under a nitrogen atmosphere. Subsequently, 145g of a 30% H2O2 solution (30% by weight of H2O2 relative to the total mass of the aqueous solution) was slowly added dropwise, and the solution was then heated to 50°C for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, the organic phase was removed, and washed four times with distilled water (dist H2O). Excess chloroform and residual water were removed by distillation. 689g of product was obtained, which was mixed with 1000ppm Irganox® 1135 and stored under nitrogen. 13 ¹³C NMR analysis revealed an epoxidation level of approximately 8.8% of the double bond. M w = 4596g / mol; M n = 1972g / mol; M w / M n =2.3 For other experimental examples, the weight, reaction conditions, and evaluation are shown in Table 1. For ease of reading, the names of experiments A1 to A3 are listed in Table 2.

[0127] [Table 1]

[0128] Step b) Preparation of hydroxy-functionalized polybutadiene Hydroxylated polybutadiene was prepared using epoxidized polybutadiene A1 from step a). The degree of hydroxylation is the number of OH groups in the hydroxyl-functionalized polybutadiene divided by the number of double bonds in the polybutadiene used in step a). For preparation, 684 g of epoxidized polybutadiene in 684 g of isobutanol and 80 ppmw of trifluoromethanesulfonic acid (relative to the mass of epoxidized polybutadiene) were added to a 2 L four-necked flask under a nitrogen atmosphere with stirring. Subsequently, the mixture was heated to 70°C and stirred at that temperature for 3 hours. The reaction mixture became clear during the reaction. After the reaction was complete, the mixture was cooled to room temperature and the solution was neutralized by adding 10.4 g of saturated NaHCO3 solution. The mixture was heated to 115°C and excess water and excess alcohol were removed by distillation under reduced pressure. The alcohol recovered by distillation and dried as needed may be reused in subsequent synthesis. The isobutanol removed by distillation may be dried, for example, by distillation or by adding a drying agent such as molecular sieves. 724 g of a brownish product was obtained, which was mixed with 1000 ppm of Irganox® 1135 and stored under nitrogen. 13 1C-NMR analysis showed that all epoxy groups were completely converted, and the degree of hydroxylation was approximately 8.8%. M w =9257g / mol;M n =2469g / mol;M w / M n =3.7 This process was carried out similarly for other experimental examples; see Table 2.

[0129] [Table 2]

[0130] Step c) Preparation of the antifoaming agent according to the present invention by alkoxylation of hydroxy-functional polybutadiene First, 196.0 g of hydroxy-functional polybutadiene A1 (from step b) and 11.1 g of a 30% sodium methoxide solution (30% by weight sodium methoxide in methanol relative to the total mass of the solution) were added to a 3 L autoclave under nitrogen, and the mixture was stirred at 50°C for 1 hour. Subsequently, the mixture was heated to 115°C while stirring, and the reactor was evacuated until the internal pressure reached 30 millibars, allowing any excess methanol and other volatile components to be removed by distillation. 540 g of propylene oxide (PO) was continuously weighed and supplied while cooling at 115°C and a maximum reactor internal pressure of 3.5 bar (absolute) for 15 hours. The reaction was continued at 115°C for 30 minutes, after which the mixture was degassed. Residual propylene oxide and other volatile components were removed by distillation under reduced pressure. The product was cooled to 95°C, neutralized with 30% H3PO4 to an acid value of 0.1 mg KOH / g, and mixed with 1000 ppm Irganox® 1135. Water was removed by vacuum distillation, and the precipitated salt was filtered off. 706 g of a medium-viscosity, orange-colored, transparent alkoxylated polybutadiene was isolated and stored under nitrogen. To neutralize with lactic acid, the product was cooled to below 80°C, then vacuum distillation was performed to remove volatile components. The solution was neutralized with lactic acid to an acid value of 0.1 mg KOH / g, mixed with 1000 ppm Irganox(R) 1135, and stored under nitrogen. M w =22850g / mol;M n =3160g / mol;M w / M n =7.2 Another defoaming agent according to the present invention and comparative examples were carried out similarly under the weight and reaction conditions listed in Table 3. The alkoxylation modification is evident from the "Supply Profile" column.

[0131] [Table 3]

[0132] II. Tests of compatibility and antifoaming activity method Viscosity (mPa s) Set the print viscosity to 16 seconds (DIN 4 cups) at 23°C in accordance with DIN EN ISO2431. compatibility Compatibility is visually measured using a coating of the formulation to be tested on a film (Putz Folien's Melinex 401CW) applied with a spiral film applicator (Erichsen K-Stab No. 2). The following grades will be used to evaluate an area of ​​10 x 10 cm. 1 = A surface completely covered with defects 2 = A surface almost completely covered with defects 3 = A surface with a very high number of defects 4 = Surface with numerous defects 5 = Separated defective surfaces (maximum 50) 6 = Separated defective surfaces (up to 30) 7 = Surface with very few separated defects (maximum 20) 8 = Surface with very few isolated defects (maximum 10) 9 = Surface with very few separated defects (1-5) 10 = A surface without defects

[0133] Antifoaming agent activity The defoaming agent activity is measured by a stirring test. For this purpose, 50 g of the formulation and a test amount of defoaming agent (e.g., 0.2 g) are weighed into a plastic beaker. The defoaming agent is incorporated using a stirrer (VMA Getzmann GmbH Dispermat type 60 / 2-457) equipped with a toothed dissolving disc (3 cm in diameter, VMA Getzmann GmbH) at 1500 rpm for 1 minute. Subsequently, the formulation is foamed at 5000 rpm for 2 minutes. Then, 45 g of the formulation is weighed and placed in a 100 mL graduated glass measuring cylinder, and the volume is read. A higher volume indicates lower defoaming agent activity.

[0134] Applicable Each coating composition is applied to the film (Melinex401CW, manufactured by Putz Folien) using a spiral film applicator (Erichsen K-Stab No.2). Drying is performed at room temperature.

[0135] Other conditions In the context of this specification, where values ​​are expressed as %, they are weight percent unless otherwise specified. For compositions, values ​​reported as %, are for the entire composition unless otherwise specified. Where averages are mentioned below, they are number averages unless otherwise specified. Where measured values ​​are mentioned below, these measurements were taken at a pressure of 101325 Pa, a temperature of 23°C, and an ambient relative humidity of approximately 40%, unless otherwise specified.

[0136] Materials and equipment - Dispersant mat type 60 / 2-457, VMA Getzmann GmbH - Melting disc (3 cm in diameter), VMA Getzmann GmbH - Spiral film applicator (K-Stab No.2), Erichsen GmbH - Film (Melinex 401CW), Putz Folien -K100 Static Surface Tension Meter, Kruss -BP50 dynamic surface tension meter, Kruss - Speed ​​mixer DAC150FVZ, Hauschild GmbH & Co.KG

[0137] Comparative Example - For blank flexographic ink K1 blank standards and preparation, please refer to the following. - Polyvest130 Polybutadiene, Evonik

[0138] Preparation of flexographic inks To test compatibility and defoaming activity, flexographic ink K1 was first prepared and set as the blank standard. The paste pigment (mill base) was mixed with let-down and homogenized using a dissolver. By adding distilled water, the blank standard was set to a printing viscosity of 16 seconds (DIN 4 cups, 23°C, DIN EN ISO 2431).

[0139] To prepare the mill base for flexographic ink K1, the liquid binder was first placed in a grinding container according to Table 4. Another liquid component was incorporated and homogenized using a 012.5cm dissolving disc at 2.6 m / s (400 rpm) for 5 minutes, then the pigment was added. Next, the mixture was pre-dispersed using a 012.5cm dissolving disc at 18-23 m / s (3520 rpm) for 10 minutes at a maximum of 50°C. Finally, after pre-dispersion, the final portion of the liquid binder was weighed and incorporated at 1800 rpm for 5 minutes. The mixture was dispersed using a 013cm double grinding disc and 2.5mm diameter glass beads at 10 m / s (1470 rpm) until the particle size was less than 10 μm. The particle size was tested using a grindometer in accordance with DIN EN ISO 1524. After the particles were finely ground, distilled water was weighed and homogenized. Afterward, the material was sieved using a metal sieve.

[0140] [Table 4]

[0141] [Table 5]

[0142] First, the mill base was added according to Table 2, followed by the addition of the Letdown binder. The mixture was then homogenized in a dissolving machine at a speed of 1500 revolutions per minute for 20 minutes using a 0.10 cm dissolving disc. After homogenization, distilled water was added to adjust the viscosity. The printing viscosity was adjusted to 16 seconds in a DIN 4 cup at 23°C, in accordance with DIN EN ISO 2431. Flexographic ink K1 was used for further testing.

[0143] Preparation of an antifoaming agent emulsion according to the present invention For performance testing, 80.0% by weight of the antifoaming agents EA1.1, EA1.2, EA2, EA3, comparative example VGA2, and Polyvest® 130 according to the present invention were converted into a 20% aqueous antifoaming emulsion using a nonionic emulsifier (a mixture of polyoxyethylene fatty alcohol ether and polyoxyethylene triglyceride having 13 mixed HLBs). In either case, since a thickening agent was added to the antifoaming agent emulsion according to the present invention, the concentration of the thickening agent in the antifoaming agent emulsion is System 1: Commercially available acrylate thickener type ASE (alkaline swelling emulsion), e.g., Dow Corporation, ACRYSOL® ASE-60, 0.8% by weight System 2: Magnafloc anionic acrylamide, manufactured by BASF, 0.25% by weight That was the case.

[0144] Compatibility test Flexographic ink K1 (50g) and 0.2g of a suitable defoaming agent emulsion 1 (system 1) or 2 (system 2) were weighed into a plastic beaker and foamed as described above. The collapse of the bubbles was observed for 90 minutes, and then the mixture was applied to a film as described above and visually evaluated.

[0145] Antifoaming agent activity Flexographic ink K1 (50g) and a suitable defoaming agent emulsion 1 or 2 (0.2g) were weighed into a plastic beaker and foamed as described above. The defoaming effect was then tested accordingly. The results are shown in the table below.

[0146] [Table 6]

[0147] The antifoaming emulsion according to the present invention showed a superior antifoaming effect compared to the comparative example.

[0148] [Table 7]

[0149] The antifoaming emulsion is far superior to the comparative example in terms of both its antifoaming effect and compatibility.

Claims

1. An antifoaming agent composition comprising a polybutadiene-based compound having at least one repeating unit selected from the group consisting of divalent groups (U), (V), and (W). 【Chemistry 1】 (In the formula, - In all cases, A is independently a monovalent organic group or a hydrogen group. - In all cases, B is independently given by equation (4a): 【Chemistry 2】 Selected from a group consisting of the following elements, In formula (4a), R １ In each case, these are independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 16 carbon atoms. R ２ is, formula -CH ２ -O-R ３ It is the basis of, R ３ In each case, these are independently selected from the group consisting of monovalent hydrocarbon groups having 3 to 18 carbon atoms. R ４ Each is independently a monovalent organic group or hydrogen having 1 to 18 carbon atoms. m, n, o, p, and q are each independently between 0 and 300, and the sum of m, n, o, p, and q is greater than 1. - The B group is as follows: 【Transformation 5】 (Having at least one repeating unit, and having all the sequences of said repeating units.)

2. The defoaming agent composition according to claim 1, wherein m, n, o, p, and q are each independently between 0 and 300, and the sum of m, n, o, p, and q is greater than 1.

3. The defoaming agent composition according to claim 1, wherein the number-average molar mass Mn of the polybutadiene portion is 200 g / mol to 20,000 g / mol.

4. The antifoaming agent composition according to claim 1, wherein the polybutadiene portion has double bonds present as 0% to 80% 1,2 vinyl double bonds and double bonds present as 20% to 100% 1,4 double bonds.

5. The defoaming agent composition according to claim 1, wherein the compound is prepared based on linear polybutadiene.

6. The defoaming agent composition according to claim 1, wherein the compound has pendant repeating units (U), (V), and / or (W) exclusively at the comb tooth positions.

7. The defoaming agent composition according to claim 1, wherein the average molar mass of group B is 40 g / mol to 20,000 g / mol.

8. The defoaming agent composition according to claim 1, wherein the compound is used in an amount of 2 to 100% by weight relative to the overall composition.

9. The defoaming agent composition according to claim 1, comprising at least one emulsifier.

10. The defoaming agent composition according to claim 1, wherein the viscosity measured in a 5% aqueous solution at 20°C in accordance with DIN 53015 is 50 to 5000 mPa·s.

11. The defoaming agent composition according to claim 1, comprising at least one thickening agent or selected from the group consisting of a modified layered silicate or an inorganic compound.

12. The defoaming agent composition according to claim 1, comprising at least one solid, an alkaline earth metal soap or an alkali metal soap, and a mixture thereof, selected from the group.

13. Use of the defoaming agent composition according to claim 1 as a defoaming additive, a flow control additive, and / or a substrate wetting additive.

14. Use of the defoaming agent composition according to claim 1 for preparing dispersions, mill bases, paints, coating or printing inks, inkjet printers, grind resins, pigment concentrates, colorant preparations, pigment preparations, filler preparations, or coating compositions.

15. Use of the polybutadiene-based compound for preparing the antifoaming agent composition according to Claim 1.

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