Hydrogenated polyether modified amino-functional polybutadiene and its preparation method

Abstract

The subject of the present invention is a method for producing hydrogenated polyether-modified amino-functional polybutadienes and the hydrogenated polyether-modified amino-functional polybutadienes which can be produced by said method, comprising the steps of: a) reacting at least one polybutadiene (A) with at least one epoxidation reagent (B) to obtain at least one epoxy-functional polybutadiene (C); b) reacting at least one epoxy-functional polybutadiene (C) with at least one amino-functional compound (D) to obtain at least one hydroxy- and amino-functional polybutadiene (E); c) reacting at least one hydroxy- and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G); and d) hydrogenating the at least one polyether-modified amino-functional polybutadiene (G) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H).

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of hydrogenated polyether-modified amino-functional polybutadienes and to the hydrogenated polyether-modified amino-functional polybutadienes producible by this process.

[0002] Polybutadienes with pendant polyether groups are known and, according to the prior art, are prepared, for example, by reaction of reactively functionalized polybutadienes with polyethers. For example, Q. Gao et al., in Macromolecular Chemistry and Physics (2013), 214(15), 1677-1687, describe amphiphilic polymer comb structures prepared by grafting polyethylene glycol onto a polybutadiene backbone. According to JP 2011-038003, polybutadiene functionalized with maleic anhydride units is reacted with an amino-terminated polyether. As a result, maleic acid modified polybutadienes are obtained with comb-shaped polyether groups linked via amide or imide groups. In a similar manner, according to J. Wang, Journal of Applied Polymer Science (2013), 128(4), 2408-2413, polyethylene glycol is added to polybutadiene with a high proportion of 1,2-butadiene monomer units to form ester bonds. High molecular weight graft polymers with comb structures are obtained by addition of epoxidized polybutadienes with OH-functional polyethers according to the method disclosed in JP 2002-105209 A. H. Decher et al., Polymer International (1995), 38(3), 219-225, use a method in which isocyanate-terminated polyethylene glycols are added to hydroxy-functional polybutadienes.

[0003] Also known are processes for reacting hydroxy-functional polybutadienes with epoxy compounds to produce polyether-modified polybutadienes. For example, the alkoxylation of OH-terminated polybutadienes is known from the prior art.

[0004] For example, US Patent No. 4,994,621 describes the alkoxylation of hydroxy-terminated polybutadiene with ethylene oxide and propylene oxide in the presence of tetramethylammonium hydroxide. The use of hydroxy-terminated polybutadiene in the alkoxylation results in a exclusively polyether-polybutadiene-polyether triblock structure. According to EP 2003156 A1, this block structure is responsible for the poor compatibility with other reactants in the production of polyurethanes.

[0005] In addition to the alkoxylation of hydroxy-terminated polybutadiene, the alkoxylation of pendant hydroxy-functional polybutadiene is also known. For example, Q. Gao et al., Macromolecular Chemistry and Physics (2013), 214(15), 1677-1687, describes the preparation of pendant polyether-modified polybutadienes by alkoxylating pendant hydroxy-functional polybutadienes with ethylene oxide. The pendant hydroxy-functional polybutadienes used in this case are prepared by first epoxidizing polybutadiene, then reacting the epoxidized polybutadiene with a lithium polybutadiene compound, and finally protonating the reaction product with methanolic hydrochloric acid. This method results in polybutadienes having both pendant polyether and pendant polybutadiene groups.

[0006] Chemical modification of polybutadiene by epoxidation and subsequent epoxide ring-opening by reaction with amines is known. JP-A-63-288295 discloses the reaction of epoxy-functional polybutadiene with dimethylamine and subsequent protonation of the amine functions with acetic acid. The method according to JP-A-57-205596 includes, in addition to the epoxide ring-opening with dimethylamine, a further quaternization of the amine functions with epichlorohydrin. A method for the epoxide ring-opening of hydrogenated polybutadiene with amines is disclosed in DE-A-2554093. In DE-A-2943879, DE-A-2732736 and JP-A-49-055733, the addition of diethanolamine is described. JP 48-051989 also describes the addition of diethanolamine followed by a crosslinking reaction in the presence of dibenzoyl peroxide. JP 53-117030, FR 2734413 and FR 2943879 describe the addition of ethanolamine, JP 05-117556 describes the reaction with diisopropanolamine, and EP 0351135, EP 0274389 and FR 3305964 describe the reaction of epoxy groups with dimethylamine. EG 296286 discloses the addition of primary and secondary amines having 4 to 20 carbon atoms to epoxidized polybutadiene in a polar solvent. Further alkoxylation of the amino-functional polybutadiene is not disclosed in any of these documents.

[0007] Polybutadienes and modified polybutadienes are often used as reactive or compounding components, for example to make the polymer hydrophobic or flexible and to improve mechanical properties. However, currently, polyether-modified polybutadienes are often limited in their possible applications because they are limited to a small number of available triblock structures. Until now, there has been no method to significantly change the chemical structure of polyether-modified polybutadienes. Furthermore, there is no easy method to produce such polymers.

[0008] The hydrogenation of unsaturated compounds in general, and in particular unsaturated polymers such as polybutadiene polymers and polybutadiene-isoprene copolymers, is known in principle and can be carried out with heterogeneous or homogeneous catalysis.

[0009] Hydrogenation catalysts commonly used by those skilled in the art are, for example, of the nickel type, such as Raney nickel, or even palladium. Nickel-catalyzed reactions are usually characterized by low reaction rates, whereas with palladium catalysis, significantly faster reactions usually occur.

[0010] For example, DE-A-2 459 115 describes the hydrogenation of polybutadiene in the presence of a supported ruthenium catalyst, and DE-A-1 248 301 describes the use of cobalt, nickel, manganese, molybdenum and tungsten compounds as efficient heterogeneous hydrogenation catalysts, which are applied to an inert support material by means of an aluminum reducing agent.Furthermore, DE-A-2 457 646 describes efficient cobalt-based hydrogenation catalysts prepared by reduction of cobalt(II) chloride with lithium, sodium or potassium salts of lactams.

[0011] Furthermore, German Patent Application No. 2 637 767 also describes triphenylphosphine salts of rhodium (Wilkinson's catalyst), triphenylphosphine salts of iridium and triphenylphosphine salts of ruthenium as selective catalysts for the hydrogenation of the 1,2-vinyl moiety of polybutadiene polymers. Furthermore, Wilkinson's catalyst is also advantageously used as a polymer-bound catalyst in European Patent Application No. 0 279 766.

[0012] EP 0 545 844 A1 describes titanocene catalysts as homogeneous catalysts, which are converted to the active form by in situ reduction with organometallic compounds.

[0013] However, hydrogenated polyether modified amino-functional polybutadiene is not known from the prior art, and therefore also the process for its preparation is not known.

[0014] It was therefore an object of the present invention to provide hydrogenated polyether-modified amino-functional polybutadienes.

[0015] In particular, it was an object of the present invention to provide a method for the preparation of comb-shaped (pendant, side-chain) hydrogenated polybutadienes, advantageously linear, which are modified with polyether groups via amino groups.

[0016] Surprisingly, a method for producing hydrogenated polyether modified amino-functional polybutadiene is now disclosed, comprising the steps of: a) reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functional polybutadiene (C); b) reacting at least one epoxy-functional polybutadiene (C) with at least one amino-functional compound (D) to obtain at least one hydroxy- and amino-functional polybutadiene (E); c) reacting at least one hydroxy- and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G); d) hydrogenating the at least one polyether-modified amino-functional polybutadiene (G) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H); It has been found that this problem is solved by a method comprising the steps of:

[0017] Further subject matter of the invention and its advantageous embodiments can be derived from the claims, the examples and the detailed description of the invention.

[0018] The subject matter of the present invention is described below in an exemplary manner, but it is not intended that the present invention is limited to these exemplary embodiments. When ranges, general formulas or compound classes are given below, they are intended to include not only the corresponding ranges or compound groups explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by selecting individual values ​​(ranges) or compounds. When documents are cited in the present specification, their entire contents are intended to be part of the disclosure of the present invention.

[0019] Where average values ​​are given below, these are numerical averages, unless otherwise stated. Where measured values, parameters or material properties determined by measurement are given below, these are measured values, parameters or material properties measured at 25° C., preferably at a pressure of 101325 Pa (normal pressure), unless otherwise stated.

[0020] In the scope of the present invention, the number average molecular weight M n , weight average molecular weight M w and polydispersity (M w / M n ) is advantageously determined by gel permeation chromatography (GPC) as described in the examples, unless expressly stated otherwise.

[0021] Below, when a numerical range is given in the format "X to Y," where X and Y represent the limits of the numerical range, this is equivalent to saying "at least X to Y (including the endpoints)," unless otherwise stated. Thus, the stated range includes the range limits X and Y, unless otherwise stated.

[0022] The terms "pendant," "side chain," and "comb" are used interchangeably.

[0023] Where a molecule / molecular fragment has one or more stereocenters or can be differentiated into isomers by symmetry or other effects, e.g. restricted rotation, all possible isomers are encompassed by the present invention.

[0024] The following formulae represent compounds or groups that are composed of randomly repeated units (repeating units), such as repeating fragments, blocks or monomer units, and may have a molecular weight distribution. The frequency of the units is indicated by the subscripts, unless expressly stated otherwise. The subscripts used in the formulae are considered to be statistical averages (numerical averages), unless expressly stated otherwise. The subscript values ​​used and the ranges of the subscripts indicated are therefore understood to be the averages of the possible statistical distributions of the structures and / or mixtures thereof that actually exist, unless expressly stated otherwise. The various fragments or units of the compounds described in the following formulae may be statistically distributed. The statistical distributions may have a block-like structure with any number of blocks and any order, or follow a random distribution, they may also have an alternating structure or form a gradient along the chain, if a chain is present, and in particular they may also form any mixed form in which groups with different distributions may be optionally adjacent to each other. The following formulae encompass all combinations of the respective units. Thus, when compounds that may have a plurality of different units, such as polybutadiene (A), epoxy-functional polybutadiene (C), hydroxy- and amino-functional polybutadiene (E), polyether-modified amino-functional polybutadiene (G) or hydrogenated polyether-modified amino-functional polybutadiene (H), are described within the scope of the present invention, they may be present in these compounds in a disordered or orderly manner, such as a statistical distribution. The data on the number or relative frequency of units in such compounds should be understood to be the average value (numerical average) of all corresponding compounds. A particular embodiment may lead to the statistical distribution being limited by that embodiment. For any ranges without such limitations, the statistical distribution remains unchanged.

[0025] The first subject of the present invention is therefore a process for the preparation of one or more hydrogenated polyether-modified amino-functional polybutadienes, comprising: a) reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functional polybutadiene (C); b) reacting at least one epoxy-functional polybutadiene (C) with at least one amino-functional compound (D) to obtain at least one hydroxy- and amino-functional polybutadiene (E); c) reacting at least one hydroxy- and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G); d) hydrogenating the at least one polyether-modified amino-functional polybutadiene (G) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H); The method includes:

[0026] It is preferred that the process according to the invention further comprises exactly one of the following two optional steps cc) and dd): cc) reacting at least one polyether-modified amino-functional polybutadiene (G) not containing end-capped polyether groups with at least one end-capping reagent (I) to obtain at least one polyether-modified amino-functional polybutadiene (G) containing end-capped polyether groups; dd) reacting at least one hydrogenated polyether-modified amino-functional polybutadiene (H) not containing end-capped polyether groups with at least one end-capping reagent (I) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H) containing end-capped polyether groups.

[0027] It is therefore preferred that the process according to the invention comprises either step cc) or step dd), or neither of these two steps.

[0028] The polyether-modified amino-functional polybutadiene (G) that does not contain an end-capped polyether group is also referred to as (G1) below. The polyether-modified amino-functional polybutadiene (G) that contains an end-capped polyether group is also referred to as (G2) below. Both (G1) and (G2) are polyether-modified amino-functional polybutadiene (G).

[0029] The hydrogenated polyether-modified amino-functional polybutadiene (H) that does not contain an end-capped polyether group is also referred to as (H1) below. The hydrogenated polyether-modified amino-functional polybutadiene (H) that contains an end-capped polyether group is also referred to as (H2) below. Both (H1) and (H2) are hydrogenated polyether-modified amino-functional polybutadiene (H).

[0030] It is preferred that the method according to the invention further comprises at least one of the following steps: e) bleaching the at least one hydrogenated polyether modified amino-functional polybutadiene (H); f) converting at least a portion of the amino groups of the at least one hydrogenated polyether-modified amino-functional polybutadiene (H) into quaternary ammonium groups using an acid and / or a quaternizing agent.

[0031] Steps a), b), c), cc), d), dd), e) and f) are carried out in the order shown, i.e. a), b), c), cc), d), dd), e) and f), where one or more of steps cc), dd), e) and f) are optional and may be omitted, including either step cc) or dd), or neither of these two steps. These steps may directly follow each other. However, the method may have further upstream, intermediate or downstream steps, such as purification of reactants, intermediates and / or final products.

[0032] The polybutadiene (E) prepared from the epoxy-functional polybutadiene (C) by epoxide ring-opening with an amine is characterized by having both pendant amino and hydroxyl groups. Depending on the reaction conditions of step c), the addition of the epoxy-functional compound (F) occurs at the amino groups, the hydroxyl groups or advantageously at both reactive groups.

[0033] The process according to the invention makes it possible for the first time to obtain hydrogenated polyether-modified polybutadienes, in particular linear hydrogenated polybutadienes with comb-shaped polyether groups. The chain length and monomer sequence of the polyether groups can be varied in a wide range. The average number of polyether groups attached to the polybutadiene can be tailored by the degree of epoxidation and the functionalization with amino and hydroxy groups, which opens up a great structural versatility for the hydrogenated polyether-modified amino-functional polybutadienes (H).

[0034] The hydrogenated amino-functional polybutadienes with comb-shaped polyether groups obtained according to the invention are advantageously substantially free of residual epoxy groups. The process products according to the invention are preferably substantially free of free polyether components. Advantageously, the polyethers are substantially chemically bonded to the (hydrogenated) polybutadiene via nitrogen and / or oxygen atoms.

[0035] Here, in the process according to the invention, it is preferred to stabilize the reactants, intermediates and products with stabilizers or antioxidants in order to avoid undesired polymerization reactions of double bonds.Suitable for this purpose are sterically hindered phenols known to those skilled in the art, for example, commercially available as Anox® 20, Irganox® 1010 (BASF), Irganox® 1076 (BASF) and Irganox® 1135 (BASF).

[0036] It is further preferred to carry out one or more or all of the process steps under an inert atmosphere, for example under nitrogen. It is also preferred to store reactant (A), as well as intermediates (C), (E) and (G), and final product (H), if they are not fully hydrogenated but only partially hydrogenated, under the exclusion of air as far as possible.

[0037] Process a) In step a) of the process according to the invention, at least one polybutadiene (A) is reacted with at least one epoxidizing reagent (B) to obtain at least one epoxy-functional polybutadiene (C).

[0038] In this reaction, the double bonds of polybutadiene (A) are converted into epoxy groups. Various methods for epoxidizing polybutadiene, for example with percarboxylic acid and hydrogen peroxide, are known to those skilled in the art and are disclosed, for example, in CN 101538338, JP 2004-346310, GDR Economic Patent No. 253627 and WO 2016 / 142249. Particularly suitable for the preparation of epoxy-functional polybutadienes (C) with a high proportion of 1,4 units is performic acid, which can also be formed in situ from formic acid in the presence of hydrogen peroxide. Epoxidation is preferably carried out in a solvent such as toluene or chloroform, which is distilled off after the reaction and washing away any residual peroxides present.

[0039] Polybutadiene (A) is a polymer of buta-1,3-diene, where the polymerization of the buta-1,3-diene monomers takes place substantially with 1,4 and / or 1,2 bonds. The 1,4 bonds give rise to so-called 1,4-trans and / or 1,4-cis units, which are also collectively called 1,4 units. The 1,2 bonds give rise to so-called 1,2 units. The 1,2 units, which carry a vinyl group, are also called vinyl 1,2 units. Within the scope of the present invention, the 1,2 units are also called "(X)", the 1,4-trans units are also called "(Y)" and the 1,4-cis units are also called "(Z)": [ka]

[0040] The double bonds contained in the units are also called 1,4-trans double bonds, 1,4-cis double bonds, or 1,2 double bonds or 1,2 vinyl double bonds. 1,4-trans double bonds and 1,4-cis double bonds are collectively called 1,4 double bonds.

[0041] Polybutadiene (A) is therefore an unmodified polybutadiene. Polybutadiene (A) and its methods for preparation are known to those skilled in the art. The preparation is advantageously carried out by radical, anionic or coordination chain polymerization.

[0042] The radical chain polymerization is preferably carried out as an emulsion polymerization. This results in the statistical formation of the three aforementioned units. At low reaction temperatures (approximately 5° C.), the proportion of vinyl groups decreases. Initiation is advantageously carried out with potassium peroxodisulfate and iron salts, or even hydrogen peroxide.

[0043] In the case of anionic chain polymerization, initiation of the chain polymerization is advantageously carried out with butyllithium. The polybutadiene (A) thus obtained contains about 40% 1,4-cis units and 50% 1,4-trans units.

[0044] In the case of coordination chain polymerization, Ziegler-Natta catalysts, in particular stereospecific Ziegler-Natta catalysts, are advantageously used, which give polybutadienes (A) with a high proportion of 1,4-cis units.

[0045] In the case of polymerization of 1,3-butadiene, side or subsequent reactions, for example subsequent reaction of the double bonds of the 1,2 and 1,4 units of the resulting polybutadiene, may result in branched polybutadienes (A). However, preferably, the polybutadienes (A) used according to the invention are linear, i.e. unbranched, polybutadienes. It is also possible for the polybutadienes to contain small proportions of units other than 1,2, 1,4-trans or 1,4-cis units. However, it is preferred that the total weight proportion of 1,2, 1,4-trans and 1,4-cis units, based on the total weight of at least one polybutadiene (A), i.e. based on the total weight of all polybutadienes (A) used, is at least 80%, advantageously at least 90%, in particular at least 99%.

[0046] In the process according to the invention, advantageously polybutadienes (A) are used which have, relative to the total of 1,2 and 1,4 units, from 0% to 80% of 1,2 units and from 20% to 100% of 1,4 units, more preferably from 0% to 30% of 1,2 units and from 70% to 100% of 1,4 units, even more preferably from 0% to 10% of 1,2 units and from 90% to 100% of 1,4 units, most preferably from 0% to 5% of 1,2 units and from 95% to 100% of 1,4 units.

[0047] Therefore, of all the double bonds in the polybutadiene (A) used, it is preferable that 0% to 80% are 1,2 vinyl double bonds and 20% to 100% are 1,4 double bonds, more preferably 0% to 30% are 1,2 vinyl double bonds and 70% to 100% are 1,4 double bonds, even more preferably 0% to 10% are 1,2 vinyl double bonds and 90% to 100% are 1,4 double bonds, and most preferably 0% to 5% are 1,2 vinyl double bonds and 95% to 100% are 1,4 double bonds.

[0048] Thus, for the preparation of the product according to the invention, polybutadienes (A) of formula (1) are advantageously used, [ka] Here, the content of 1,2 vinyl double bonds (subscript x) is 0% to 80%, the content of 1,4 double bonds is 20% to 100%, more preferably, the content of 1,2 vinyl double bonds is 0% to 30%, the content of 1,4 double bonds is 70% to 100%, even more preferably, the content of 1,2 vinyl double bonds is 0% to 10%, the content of 1,4 double bonds is 90% to 100%, and most preferably, the content of 1,2 vinyl double bonds is 0% to 5%, and the content of 1,4 double bonds is 95% to 100%. The ratio of 1,4-trans double bonds (subscript y) and 1,4-cis double bonds (subscript z) is arbitrary.

[0049] Here, the subscripts x, y, and z indicate the number of the respective butadiene units in polybutadiene (A). The subscripts are number averages (numerical averages) across all polybutadiene polymers of at least one polybutadiene (A).

[0050] The polybutadiene (A) of formula (1) used may have any average molecular weight and polydispersity.

[0051] The number average molecular weight M of at least one polybutadiene (A) n is preferably 200 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and most preferably 700 g / mol to 5,000 g / mol.

[0052] Also, the number average molecular weight M of at least one polybutadiene (A) n is preferably 2100 g / mol to 20000 g / mol, more preferably 2200 g / mol to 10000 g / mol, and most preferably 2300 g / mol to 5000 g / mol.

[0053] It is further preferable that at least one polybutadiene (A) has, on a numerical average, 5 to 360 units selected from the group consisting of 1,2 units, 1,4-cis units and 1,4-trans units, more preferably 10 to 180 units, and most preferably 15 to 90 units.

[0054] It is also preferred that at least one polybutadiene (A) has, on average, 35 to 360 units selected from the group consisting of 1,2 units, 1,4-cis units and 1,4-trans units, more preferably 40 to 180 units, and most preferably 45 to 90 units.

[0055] It is further preferred that the polybutadiene (A) used has a viscosity (determined in accordance with DIN EN ISO 3219:1994-10) of 50 to 50 000 mPas, more preferably 100 to 10 000 mPas, most preferably 500 to 5000 mPas.

[0056] The polybutadienes most advantageously used are the commercial products Polyvest® 110 and Polyvest® 130 from Evonik Industries AG / Evonik Operations GmbH, which have the following typical specifications: Polyvest® 110: about 1% 1,2 vinyl double bonds, about 24% 1,4-trans double bonds, about 75% 1,4-cis double bonds, number average molecular weight M n Approximately 2600 g / mol, viscosity (20°C) 700-860 mPas (according to DIN EN ISO 3219:1994-10), Polyvest® 130: about 1% 1,2 vinyl double bonds, about 22% 1,4-trans double bonds, about 77% 1,4-cis double bonds, number average molecular weight M n Approximately 4600 g / mol, viscosity (20 °C) 2700-3300 mPas (according to DIN EN ISO 3219:1994-10).

[0057] The polybutadienes most advantageously used are furthermore the products Lithene ultra AL and Lithene ActiV 50 available from Synthomer PLC, having the following typical specifications: Lithene ultra AL: Approximately 40% 1,2 vinyl double bonds, approximately 60% 1,4 vinyl double bonds, Lithene ActiV 50: Approximately 70% 1,2 vinyl double bonds, approximately 30% 1,4 vinyl double bonds.

[0058] The degree of epoxidation can be, for example, 13 It is quantitatively determined by C NMR spectroscopy or epoxy value titration (determination of the epoxy equivalent in accordance with DIN EN ISO 3001:1999) and can be targeted and reproducibly adjusted by the process conditions, in particular the amount of hydrogen peroxide used relative to the amount of double bonds present in the polybutadiene.

[0059] In step a) of the process according to the invention, it is preferred that >0% to <100%, more preferably >0% to 70%, even more preferably 1% to 50%, even more preferably 2% to 40%, even more preferably 3% to 30%, most preferably 4% to 20% of all double bonds of the at least one polybutadiene (A) are epoxidized.

[0060] As the epoxidizing reagent (B), in principle, all epoxidizing agents known to the skilled artisan can be used.The epoxidizing reagent (B) is preferably selected from the group of peroxycarboxylic acids (percarboxylic acids, peracids), advantageously from the group consisting of metachloroperbenzoic acid, peroxyacetic acid (peracetic acid) and peroxyformic acid (performic acid), in particular peroxyformic acid (performic acid).Here, the peroxycarboxylic acid is advantageously formed in situ from the corresponding carboxylic acid and hydrogen peroxide.

[0061] Most preferably, the at least one epoxidation reagent (B) is or comprises performic acid, advantageously formed in situ from formic acid and hydrogen peroxide.

[0062] The epoxidation of at least one polybutadiene (A) occurs statistically distributed on the polybutadiene chain, preferably at the 1,4 double bonds. The epoxidation of 1,2 double bonds can occur as well, and these bonds also occur statistically distributed on the polybutadiene chain. However, the epoxidation of 1,2 double bonds is disadvantageous compared to the epoxidation of 1,4 double bonds. The reaction product therefore includes epoxy-functional polybutadiene polymers with different degrees of epoxidation. Therefore, it should be understood that all the degrees of epoxidation described are average values.

[0063] Step b) In step b) of the process according to the invention, at least one epoxy-functional polybutadiene (C) is reacted with at least one amino-functional compound (D) to obtain at least one hydroxy- and amino-functional polybutadiene (E).

[0064] In this reaction, the addition (addition reaction) of at least one amino-functional compound (D) to at least one epoxy-functional polybutadiene (C) occurs. Thus, when this reaction is carried out, one or more covalent bonds are formed between the at least one amino-functional compound (D) and the at least one epoxy-functional polybutadiene (C). This reaction advantageously (at least in an idealized case) includes a reaction step in which a nucleophilic attack of at least one amino group of the at least one amino-functional compound (D) on at least one epoxy group of the at least one epoxy-functional polybutadiene (C) is carried out, accompanied by ring-opening of said at least one epoxy group.

[0065] It is preferred that the at least one amino-functional compound (D) is selected from compounds having at least one primary amino group and / or at least one secondary amino group, since primary and secondary amino groups are particularly easily added to the epoxy groups of the polybutadiene. In the scope of the present invention, ammonia is also included among these amino-functional compounds (D). However, it is preferred that the at least one amino-functional compound (D) is selected from organic compounds having at least one primary amino group and / or at least one secondary amino group. It is even more preferred that the at least one amino-functional compound (D) is selected from organic compounds having 1 to 22 carbon atoms and having at least one primary amino group and / or at least one secondary amino group. It is even more preferred that the at least one amino-functional compound (D) is selected from organic compounds having 1 to 12 carbon atoms and having at least one primary amino group and / or at least one secondary amino group. It is even more preferred that the amino-functional compound (D) has exactly one primary or secondary amino group. As a result, undesired crosslinking reactions can be reduced or prevented. It is further preferred that the amino-functional compound (D) is not an aromatic amine, in particular not an aromatic primary amine, since some aromatic primary amines are known to be human carcinogens. Within the scope of the present invention, aromatic amines are understood to be amines in which the nitrogen atom of at least one amino group is bound to a carbon atom that is part of an aromatic ring system.

[0066] It is further preferred that the at least one amino-functional compound (D) is selected from the group consisting of ammonia, alkylamines, cycloalkylamines, dialkylamines, monoalkanolamines and dialkanolamines. The aliphatic group attached to the nitrogen may also have an aromatic group or a heteroatom such as nitrogen or oxygen. It is therefore further equally preferred that the at least one amino-functional compound (D) is selected from the group consisting of diamines, polyamines, polyetheramines and hydroxy-functional aliphatic amines. More preferably, the at least one amino-functional compound (D) is selected from the group consisting of alkylamines, cycloalkylamines, dialkylamines, monoalkanolamines, dialkanolamines and trialkanolamines, each of which has 1 to 22 carbon atoms and has exactly one primary or secondary amino group. Even more preferably, the at least one amino-functional compound (D) is selected from the group consisting of alkylamines, monoalkanolamines, dialkanolamines and trialkanolamines, each having from 1 to 12 carbon atoms and having exactly one primary or secondary amino group. Most preferably, the at least one amino-functional compound (D) is selected from the group consisting of butylamine, isobutylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine, ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, N-methylisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane (tris,2-amino-2-(hydroxymethyl)propane-1,3-diol), morpholine, piperidine, cyclohexylamine, N,N-dimethylaminopropylamine (DMAPA) and benzylamine, where it is also possible to use any mixture of these amines.Within the scope of the present invention, the term "trialkanolamine" is understood to mean only trialkanolamines which have primary and / or secondary amino groups, such as, for example, tris(hydroxymethyl)aminomethane.

[0067] The molar ratio of the NH groups of the at least one amino-functional compound (D) to the epoxy groups of the at least one epoxy-functional polybutadiene (C) can vary over a wide range. However, it is preferred that the at least one amino-functional compound (D) and the at least one epoxy-functional polybutadiene (C) are used in such a molar ratio of NH groups to epoxy groups that as quantitative a conversion as possible of all epoxy groups is achieved. It is therefore preferred that in step b) the total number of NH groups of all amino-functional compounds (D) and the total number of epoxy groups of all epoxy-functional polybutadienes (C) is between 0.8:1 and 20:1, more preferably between 0.9:1 and 10:1, even more preferably between 1:1 and 5:1, most preferably between 1:1 and 3:1. Excess compound (D) can be removed after the reaction, for example by distillation, and reused if necessary. In this connection, it should be noted that an ammonia molecule has exactly 3 NH groups, a primary amino group has exactly 2 NH groups, and a secondary amino group has exactly 1 NH group.

[0068] The epoxide ring opening with the amine can optionally be carried out in a solvent such as ethanol, propanol, isopropanol or THF. Preferably, the solvent is omitted.

[0069] Advantageously, the reaction is carried out in the presence of at least one catalyst, which is optionally homogeneously soluble in the reaction mixture, can be added as an aqueous solution, or is heterogeneously distributed therein as a solid.

[0070] It is preferred that the catalyst is selected from the group consisting of Lewis acids and Bronsted acids; more preferably from the group consisting of water, phenols, alcohols, carboxylic acids, ammonium compounds, phosphonium compounds and lithium bromide; even more preferably from the group consisting of carboxylic acids, phenols, ammonium compounds, phosphonium compounds and lithium bromide, even more preferably from the group consisting of carboxylic acids, phenols and lithium bromide, most preferably from the group consisting of lithium bromide. The catalyst is optionally homogeneously soluble in the reaction mixture, can be added as an aqueous solution or is heterogeneously distributed therein as a solid.

[0071] The type and amount of catalyst used are selected so as to achieve as rapid and quantitative an addition as possible of the at least one amino-functional compound (D) to the epoxy groups of the at least one epoxy-functional polybutadiene (C). Advantageously, lithium bromide is used as a solid or dissolved in water in a weight proportion of 0.05% to 15.0%, preferably 0.2% to 10.0%, most preferably 0.5% to 7.0%, relative to the weight of the at least one amino-functional compound (D).

[0072] The reaction of the at least one epoxy-functional polybutadiene (C) with the at least one amino-functional compound (D) is preferably carried out at temperatures between 50°C and 250°C, more preferably between 80°C and 200°C, optionally in the presence of a catalyst.

[0073] The components are stirred for several hours until the epoxy groups are converted as completely as possible. Analysis of the epoxy groups can be carried out alternatively by known methods of NMR spectroscopy or epoxy value titration (described in the examples).

[0074] The reaction conditions in step b) are advantageously selected such that more than 90% of the epoxy groups generated in step a) are converted into ring-opening. Most preferably, in the product of step b), i.e. the at least one hydroxy- and amino-functional polybutadiene (E), no epoxy groups are detectable anymore.

[0075] After the reaction, any excess amino-functional compound (D) and optionally the solvent, water and catalyst are removed, advantageously by distillation, and the precipitated salts are filtered off, if necessary.

[0076] Each epoxy group of the epoxy-functional polybutadiene (C) gives, after ring-opening with an amino-functional compound (D) of formula A1-NH-A2, a unit of formula (2a), (2b) or (2c): [ka]

[0077] In formulae (2a), (2b) and (2c), the groups A1 and A2 are advantageously each independently of the other an organic group, which may have further amine or hydroxyl groups, or a hydrogen group. Thus, the groups A1 and A2 may contain heteroatoms such as nitrogen and oxygen, and may also be bridged to each other by organic groups, for example in the case of morpholine or piperidine. The amino-functional compound (D) of formula A1-NH-A2 may also be ammonia. In the case of ammonia, A1 and A2 are both hydrogen groups. If, for example, ethanolamine is used as the amino-functional compound (D), then in formulae (2a), (2b) and (2c), the group A1 is, for example, a hydroxyethyl group, and in that case the group A2 is a hydrogen group, i.e. A2=H. At least one pendant OH group is generated from each reacted epoxy group.

[0078] When a primary amine as compound (D) is reacted with an epoxy group of an epoxy-functional polybutadiene (C), a secondary amino group having a reactive hydrogen on the nitrogen atom is always formed. This secondary amino group can add to a further epoxy group via the NH group in a subsequent reaction, thus bonding two epoxy-functional polybutadienes (C) to each other. The reaction conditions in step b) are advantageously selected so that this bonding reaction is sufficiently suppressed.

[0079] In the case of polybutadienes (A) having a predominant proportion of 1,4 units which are preferred according to the invention, among the units of formulae (2a), (2b) and (2c) it is the units of formula (2a) which predominate.

[0080] It is preferred that the at least one hydroxy- and amino-functional polybutadiene (E) has from 20% to 100%, more preferably from 70% to 100%, even more preferably from 90% to 100%, most preferably from 95% to 100%, of units of formula (2a) relative to the total number of all units of formulae (2a), (2b) and (2c).

[0081] It is preferred that the proportion of units of formulae (2a), (2b) and (2c) taken together is >0% to <100%, more preferably >0% to 70%, even more preferably 1% to 50%, even more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20%, based on the total number of all units of the at least one hydroxy- and amino-functional polybutadiene (E).

[0082] Therefore, it is preferable that the degree of amination is >0% to <100%, more preferably >0% to 70%, even more preferably 1% to 50%, even more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20%.

[0083] When the conversion in step b) is complete, the degree of amination of the hydroxy- and amino-functional polybutadiene (E) corresponds to the degree of epoxidation of the corresponding epoxy-functional polybutadiene (C).

[0084] Process c) In step c) of the process according to the invention, at least one hydroxy- and amino-functional polybutadiene (E) is reacted with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G).

[0085] The at least one hydroxy- and amino-functional polybutadiene (E) obtained in step b) serves as an initiating compound (starter) for the reaction with at least one epoxy-functional compound (F) in step c). Under ring-opening, advantageously in the presence of a suitable catalyst, the at least one epoxy-functional compound (F) (hereinafter also simply referred to as "monomer" or "epoxy monomer" or "epoxide") is added in a polyaddition reaction to the NH- and / or OH-groups of the at least one hydroxy- and amino-functional polybutadiene (E). This results in the formation of an amino-functional polybutadiene with comb-shaped (pendant) polyether chains, i.e. at least one polyether-modified amino-functional polybutadiene (G). Preferably, the monomer is added to (at least substantially) all the OH-groups and (at least substantially) all the NH-groups. Advantageously, the polyether-modified amino-functional polybutadiene (G) is a linear polybutadiene modified with comb-shaped (pendant) polyether groups. Therefore, it is preferred that the polyether-modified amino-functional polybutadiene (G) has a linear polybutadiene backbone and pendant polyether groups.

[0086] The reaction of step c) is advantageously an alkoxylation reaction, i.e. the polyaddition of an alkylene oxide to at least one hydroxy- and amino-functional polybutadiene (E). However, the reaction of step c) can also be carried out with a glycidyl compound instead of or in addition to the alkylene oxide.

[0087] Thus, the at least one epoxy-functional compound used in step c) is selected from the group of alkylene oxides, more preferably from the group of alkylene oxides having 2 to 18 carbon atoms, even more preferably from the group of alkylene oxides having 2 to 8 carbon atoms, most 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 the at least one epoxy-functional compound used in step c) is selected from the group of glycidyl compounds, more preferably from the group of monofunctional glycidyl compounds, most preferably phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 12 / C 14 Fatty alcohol glycidyl ether and C 13 / 15 It is preferably selected from the group consisting of fatty alcohol glycidyl ethers.

[0088] The monomers can alternatively be added individually in pure form, alternately in succession in any metered order, or simultaneously in admixture, so that the sequence of the monomer units in the resulting polyether chain follows a block-like, statistical or graded distribution in the final product.

[0089] By means of the process according to the invention, pendant polyether chains are built up on polybutadiene, which are characterised by the fact that they can be produced in a targeted and reproducible manner with regard to structural configuration and molecular weight.

[0090] The sequence of the monomer units can be configured in a wide range and with variable order of addition.

[0091] The molecular weight of the pendant polyether groups can be varied within wide limits by the process according to the invention and can be controlled in a targeted and reproducible manner by the molar ratio of the added monomers to the NH and OH groups of the at least one hydroxy- and amino-functional polybutadiene (E) obtained in step b) and charged.

[0092] The polyether-modified amino-functional polybutadienes (G) and likewise the hydrogenated polyether-modified amino-functional polybutadienes (H) prepared therefrom are advantageously characterized in that they contain groups B linked to the polybutadiene backbone by amino and / or ether groups according to formulae (3a), (3b) and (3c). [ka]

[0093] The groups A1 and A2 are each independently of one another an organic group having preferably 1 to 22, most preferably 1 to 12 carbon atoms, where the groups A1 and A2 can be covalently linked to one another, in which case the groups A1 and A2 can contain heteroatoms, advantageously nitrogen and oxygen.

[0094] The subscripts k1 and k2 in formula (3a), (3b) or (3c) are each, independently of one another, an integer between 0 and 8, preferably between 0 and 6, and most preferably between 0 and 4. Furthermore, the subscripts l1 and l2 in formula (3a), (3b) or (3c) are integers, each, independently of one another, either 0 or 1. Thus, the group B formed by alkoxylation can be bonded to the group A1 or A2 at k1 or k2 sites, where the chemical bond is formed by the nitrogen or oxygen atoms that are part of A1 and A2. However, the group B formed by alkoxylation can also be bonded directly to the nitrogen atom shown. In formula (2a), (2b) or (2c), if the group A1 or A2 is a hydrogen group, then in formula (3a), (3b) or (3c), the subscript l1 or l2 is 0 and k1 or k2 is 1, i.e., in formula (3a), (3b) and (3c), the corresponding group A1 or A2 does not exist, and thus the polyether group B is directly bonded to the indicated nitrogen atom. Thus, the NH group in formula (2a), (2b) or (2c) is replaced with an NB group. In formula (2a), (2b) or (2c), if the group A1 or A2 is an organic group, then in formula (3a), (3b) or (3c), the subscript l1 or l2 is 1. When both A1 and A2 in formula (2a), (2b) or (2c) are hydrogen groups, then in formula (3a), (3b) or (3c), the subscripts l1 or l2 are 0 and k1 or k2 are 1, i.e., in formula (3a), (3b) and (3c), the groups A1 and A2 are absent and the polyether group B is directly bonded to the nitrogen atom shown. Thus, the two NH groups in formula (2a), (2b) or (2c) are each replaced by a NB group.

[0095] For example, if a primary alkylamine is used as amino-functional compound (D) in step b), in which the alkyl group does not have other epoxide-reactive groups, such as OH or NH groups, then, for example, l1=1, k1=0, l2=0 and k2=1.

[0096] For example, when a primary amine, ethanolamine, is used as the amino-functional compound (D) in step b), A1 is, for example, a divalent group of formula -CH2CH2O-, which in this structural formula is bonded to the nitrogen atom of the amino group by a carbon atom on the left side and to the group B by an oxygen atom on the right side, i.e., for example, l1=1, k1=1, l2=0 and k2=1.

[0097] For example, when the primary amine tris(hydroxymethyl)aminomethane (tris,2-amino-2-(hydroxymethyl)propane-1,3-diol) is used as the amino-functional compound (D) in step b), A1 is, for example, a tetravalent group of the formula -C(CHO-) which is bonded to the nitrogen atom of the amino group on the left side in this structural formula by a carbon atom and to one group B each (hence to three groups B in total) on the right side by three oxygen atoms, i.e., for example, l=1, k=3, l=0 and k=1.

[0098] For example, when diethanolamine, a secondary amine, is used as amino-functional compound (D) in step b), A1 and A2 are, for example, divalent groups of formula -CH2CH2O-, which in this structural formula are bonded to the nitrogen atom of the amino group by a carbon atom on the left side and to group B by an oxygen atom on the right side, i.e. l1=1, k1=1, l2=1 and k2=1.

[0099] For example, when the secondary amine N-methylethanolamine is used as the amino-functional compound (D) in step b), A1 is, for example, a methyl group and A2 is a divalent group of formula -CH2CH2O-, which is bonded to the nitrogen atom of the amino group by a carbon atom on the left side in this structural formula and to the group B by an oxygen atom on the right side, i.e., l1=1, k1=0, l2=1 and k2=1.

[0100] For example, when a secondary amine piperidine is used as the amino-functional compound (D) in step b), A1 and A2 are covalently bonded to each other and together form a divalent group -CH2CH2CH2CH2CH2-, which is attached to the nitrogen atom of the amino group on both the left and right sides in this structural formula, i.e., l1=1, k1=0, l2=1 and k2=0.

[0101] Thus, advantageously, in the alkoxylation reaction, (at least almost) all the pendant OH and NH groups of the at least one hydroxy- and amino-functional polybutadiene (E) give rise to exactly one pendant group B, respectively. Group B is composed of one or more monomers, advantageously several monomers, of the at least one epoxy-functional compound (F) used. Less preferably, it is also possible that in the alkoxylation reaction, not all the OH or NH groups of the hydroxy- and amino-functional polybutadiene (E) give rise to pendant groups B, but that only a portion, advantageously the major portion, of the OH and NH groups are converted in step c).

[0102] In the sense of the present invention, in principle, all alkoxylation catalysts known to those skilled in the art can be used, for example, basic catalysts such as alkali metal hydroxides, alkali metal alkoxides, amines, guanidines, amidines, phosphorus compounds such as phosphines (e.g. triphenylphosphine), as well as Bronsted acid catalysts and Lewis acid catalysts such as SnCl4, SnCl2, SnF2, BF3 and BF3 complexes, and double metal cyanide (DMC) catalysts. The addition of catalysts can be omitted at any time.

[0103] Before feeding the epoxide, i.e. before the addition of the at least one epoxy-functional compound (F) used, the reactor, which is partially filled with the starter and optionally the catalyst, is inerted, for example with nitrogen. This is achieved, for example, by alternating between evacuation and feeding nitrogen several times. It is advantageous to evacuate the reactor to less than 200 mbar after the last nitrogen injection. The addition of the first amount of epoxy monomer is then advantageously carried out in the evacuated reactor. The metering of the monomer is carried out under stirring, optionally under cooling, in order to remove the released reaction heat and to maintain a preselected reaction temperature. It is also possible to utilize at least one hydroxy- and amino-functional polybutadiene (E) as starter or to use as starter a polyether-modified amino-functional polybutadiene (G) already prepared according to the method according to the invention, as described below.

[0104] In a particular embodiment, the addition of catalyst can be omitted when starting the addition of monomer. This is the case, for example, when the amino group attached to polybutadiene is sufficiently reactive. If there is a sufficient number of nucleophilic NH functional groups on polybutadiene, the starter itself will catalyze the alkoxylation reaction. The reaction rate usually decreases with increasing polyether chain length. To obtain higher molecular weight polyether group B, it may be necessary or beneficial to add any of the aforementioned catalysts to the alkoxylation reaction at a later time.

[0105] DMC catalyst Advantageously, zinc / cobalt DMC catalysts are used, in particular catalysts containing zinc hexacyanocobaltate (III).Advantageously, DMC catalysts as described in US Pat. No. 5,158,922, US Pat. App. Pub. No. 20030119663, WO 01 / 80994 are used. The catalysts may be amorphous or crystalline.

[0106] It is preferred that the catalyst concentration is >0 ppmw to 1000 ppmw, more preferably >0 ppmw to 700 ppmw, most preferably >10 ppmw to 500 ppmw, based on the total weight of product formed.

[0107] Advantageously, the catalyst is metered into the reactor only once. The catalyst is advantageously clean, dry and free of basic impurities that may inhibit the DMC catalyst. The amount of catalyst should advantageously be set so as to provide sufficient catalytic activity for the process. The catalyst can be metered in as a solid or in the form of a catalyst suspension. If a suspension is used, a starter is particularly suitable as a suspending agent.

[0108] To initiate the DMC catalysis, it may be advantageous to first activate the catalyst with a portion of at least one epoxy-functional compound (F), advantageously selected from the group of alkylene oxides, in particular propylene oxide and / or ethylene oxide. After the alkoxylation reaction has proceeded, the continuous addition of monomers can be started.

[0109] In the case of the DMC catalytic reaction in step c), the reaction temperature is preferably 60°C to 200°C, more preferably 90°C to 160°C, and most preferably 100°C to 140°C.

[0110] The pressure inside the reactor in the case of the DMC catalytic reaction in step c) is preferably 0.02 bar to 100 bar, more preferably 0.05 bar to 20 bar, most preferably 0.1 bar to 10 bar (absolute pressure).

[0111] Most preferably, the DMC catalysis of step c) is carried out at a temperature between 100° C. and 140° C. and a pressure between 0.1 bar and 10 bar.

[0112] The reaction can be carried out in a suitable solvent, for example to reduce the viscosity. The end of the epoxide addition is advantageously followed by a post-reaction to complete the conversion. The post-reaction can be carried out, for example, by continuing the reaction under reaction conditions (i.e., for example, maintaining the temperature) without adding reactants. The DMC catalyst usually remains in the reaction mixture.

[0113] After the reaction has taken place, unreacted epoxide and possibly other volatile components can be removed by vacuum distillation, steam or gas stripping or other deodorizing methods. The final product is then filtered at <100° C. to remove any turbidity materials that may be present.

[0114] Base catalysis As an alternative to DMC catalyst, it is also possible to use basic catalysts in step c).Suitable are, in particular, alkali metal alkoxides, such as sodium methoxide and potassium methoxide, which are added as solids or in the form of their methanolic solutions.Furthermore, it is possible to use all alkali metal hydroxides, in particular sodium hydroxide and / or potassium hydroxide, both as solids, for example as aqueous or alcoholic solutions.Furthermore, it is also possible according to the present invention to use basic nitrogen compounds, preferably amines, guanidines and amidines, most preferably tertiary amines, such as trimethylamine and triethylamine.

[0115] The basic catalyst is preferably used at a concentration of >0 mol % to 100 mol %, more preferably >0 mol % to 50 mol %, most preferably 3 mol % to 40 mol %, based on the total of OH groups and NH groups of the starter.

[0116] In the case of the basic catalytic reaction in step c), the reaction temperature is preferably 80°C to 200°C, more preferably 90°C to 160°C, and most preferably 100°C to 160°C.

[0117] The pressure inside the reactor in the case of the basic catalytic reaction in step c) is preferably 0.2 bar to 100 bar, more preferably 0.5 bar to 20 bar, most preferably 1 bar to 10 bar (absolute pressure).

[0118] Most preferably, the base catalyzed reaction of step c) is carried out at a temperature between 100° C. and 160° C. and a pressure between 1 bar and 10 bar.

[0119] The reaction can be carried out in any suitable solvent. The completion of the epoxide addition is preferably followed by a post-reaction to complete the conversion. The post-reaction can be carried out, for example, by continuing the reaction under reaction conditions without adding reactants. After the reaction has taken place, the unreacted epoxide and possibly other volatile components can be removed by vacuum distillation, steam or gas stripping or other deodorizing methods. In this case, volatile catalysts such as volatile amines are removed.

[0120] For neutralization of the basic crude product, an acid, such as phosphoric acid or sulfuric acid, or a carboxylic acid, such as acetic acid or lactic acid, is added. The use of aqueous phosphoric acid or lactic acid is preferred. The amount of the respective acid used depends on the amount of basic catalyst previously used. The basic polybutadiene with pendant polyether groups is stirred in the presence of the acid, advantageously at 40° C. to 95° C., and then dried by vacuum distillation at 80° C. to 130° C. at <100 mbar. The neutralized product is finally filtered, advantageously at <100° C., to remove precipitated salts.

[0121] It is preferred that the final product according to the invention has a moisture content (defined as a percentage by weight of the total weight of the final product) of <0.2% and an acid value of <0.5 mg KOH / g, and is substantially free of phosphate.

[0122] Starter product It is not always possible to achieve the desired molecular weight of the final product in a single reaction step, especially only the alkoxylation step. In particular, if long polyether side chains are aimed for and / or if the starter obtained in step b), i.e. the at least one hydroxy- and amino-functional polybutadiene (E), has a high functionality of OH and NH groups, the addition of large amounts of epoxy monomer is necessary. This may not be allowed depending on the geometry of the reactor. The polyether-modified amino-functional polybutadienes (G) obtained in step c) are suitable as starters for building up higher molecular weight conversion products, since they have OH groups at the ends of their pendant polyether groups, respectively. In the sense of the present invention, they are precursors and starter compounds for the synthesis of polybutadienes with longer polyether groups. The reaction of at least one epoxy-functional compound (F) can therefore be carried out in several partial steps in step c).

[0123] The product produced by DMC catalysis according to step c) can, according to the invention, optionally have its alkoxylation level increased by new addition of epoxy monomers, either by DMC catalysis or using either the abovementioned basic or acidic catalysts. It is optionally possible to add further DMC catalyst, for example to increase the reaction rate during chain extension.

[0124] Similarly, the product produced under basic catalysis in step c) can be selectively alkoxylated to higher molecular weight under basic conditions, acidic conditions or DMC catalysis.When it is intended to further react the basic precursor with monomer under basic catalysis, neutralization is advantageously omitted in step c).For example, it is optionally possible to add additional DMC catalyst to increase the reaction rate during chain extension.

[0125] Step d) In process step d) according to the invention, at least one polyether-modified amino-functional polybutadiene (G) is hydrogenated to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H).

[0126] Here, the CC double bonds of the polyether-modified amino-functional polybutadiene (G) are partially or completely hydrogenated, and thus the CC double bonds are partially or completely converted into CC single bonds.

[0127] Unit (X) is converted to unit (V) when hydrogenated, and units (Y) or (Z) are converted correspondingly to unit (W): [ka]

[0128] In this case, advantageously, at least 30%, more preferably at least 60%, even more preferably at least 90%, particularly preferably at least 95% of the double bonds contained in the polyether-modified polybutadiene (G) are hydrogenated. The degree of hydrogenation is advantageously, as described in particular in the examples, 1 Determined using H-NMR spectroscopy.

[0129] Hydrogenated polyether-modified amino-functional polybutadiene (H) usually has a high viscosity, so it is further preferred to use a solvent during hydrogenation. Advantageously usable solvents are, for example, water, alkanes, isoalkanes, cycloalkanes, alkyl aromatic compounds, alcohols, ethers and / or esters, which can be used alone or in mixtures. Advantageously usable alkanes are, for example, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane and / or n-dodecane. Advantageously usable cycloalkanes are, for example, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane and / or decalin. Advantageously usable alkyl aromatic compounds are, for example, toluene, xylene, cumene, n-propylbenzene, ethylmethylbenzene, trimethylbenzene, solvent naphtha and / or all alkylbenzenes available on an industrial scale. Advantageously usable alcohols are, for example, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol. Advantageously usable ethers are, for example, tetrahydrofuran, advantageously usable esters are, for example, ethyl acetate and butyl acetate. Particularly advantageously usable are aromatic solvents such as toluene, xylene and cumene, or high-boiling esters such as butyl acetate, with particular preference being given to using xylene and / or butyl acetate. The amount of advantageously usable solvent can be easily adapted to the particular application by the skilled person. Preferably, 0-90% by weight of solvent is used, more preferably 10-85%, even more preferably 30-80%, most preferably 50-75%, based on the total weight of polyether-modified amino-functional polybutadiene (G) and solvent.

[0130] The hydrogenation can advantageously be carried out in a pressure autoclave, where a positive pressure, i.e. a pressure higher than atmospheric pressure, is generated by adding hydrogen to a closed reaction vessel. The preferred pressure is between 1 bar and 100 bar, more preferably between 2 bar and 50 bar, most preferably between 3 bar and 10 bar.

[0131] Furthermore, hydrogenation can also be carried out advantageously in the so-called bubble process, in which the reaction mixture is passed into an open reaction vessel, with hydrogen being continuously introduced below the liquid surface, the hydrogenation being carried out under atmospheric pressure.

[0132] Whether the hydrogenation is carried out at atmospheric or positive pressure, care should be taken to ensure that the reaction system is adequately well mixed.

[0133] The hydrogenation temperature can vary over a wide range and is adjusted to suit the individual reaction system consisting of the catalyst and the polyether-modified amino-functional polybutadiene (G). The temperature is preferably 25°C to 200°C, more preferably 60°C to 175°C, and most preferably 100°C to 150°C.

[0134] Preferably, the hydrogenation is carried out with hydrogen in the presence of at least one hydrogenation catalyst.

[0135] As catalyst, in principle, all hydrogenation catalysts known to those skilled in the art can be used, either alone or in a mixture of several catalysts. The use of homogeneous and / or heterogeneous catalysts can be advantageous, but the use of heterogeneous catalysts is preferred due to their easy removal after hydrogenation.

[0136] Preferable noble metal catalysts are, for example, those based on platinum, palladium, rhodium, iridium and ruthenium. Advantageous non-noble metal catalysts are, for example, those based on nickel, copper, cobalt, manganese, molybdenum, tungsten and / or titanium. All catalysts can be used in supported or pure (i.e. unsupported) form.

[0137] Further preferred are hydrogenation catalysts based on nickel, palladium, rhodium and / or ruthenium. Even more preferred are Raney nickel, palladium on activated carbon, ruthenium on activated carbon or rhodium as Wilkinson's catalyst (chloridotris(triphenylphosphine)rhodium(I)). Particularly preferred are Raney nickel, palladium on activated carbon and / or Wilkinson's catalyst as hydrogenation catalyst. When a mixture of two or more of the aforementioned hydrogenation catalysts is used, a mixture of Raney nickel and palladium on activated carbon is preferred.

[0138] The amount of catalyst used can be adapted to each application. The amount used is selected so that at least hydrogenation occurs. The amount of catalyst used is preferably 0.1% to 10% by weight, more preferably 0.2% to 7% by weight, most preferably 0.3% to 5% by weight, based on the amount of polyether-modified amino-functional polybutadiene (G) to be hydrogenated.

[0139] After completion of the hydrogenation, the reaction mixture is advantageously filtered in order to remove any entrained solids, such as, for example, the heterogeneous catalyst. Depending on the viscosity of the reaction mixture, it may be advantageous to dilute the reaction mixture with a suitable solvent, preferably butyl acetate or xylene, before filtration.

[0140] Finally, the filtrate obtained after filtration is distilled to remove highly volatile components, such as the solvents contained, and the pure hydrogenated polyether modified amino-functional polybutadiene (H) according to the present invention is isolated.

[0141] Optional steps cc) and dd) In an optional step cc), at least one polyether-modified amino-functional polybutadiene (G) not containing an end-capped polyether group can be reacted with at least one end-capping reagent (I) to obtain at least one polyether-modified amino-functional polybutadiene (G) containing an end-capped polyether group.

[0142] Thus, in step cc), at least one polyether-modified amino-functional polybutadiene (G1) not containing end-capped polyether groups can be reacted with at least one end-capping reagent (I) to obtain at least one polyether-modified amino-functional polybutadiene (G2) containing end-capped polyether groups.

[0143] As an alternative to the optional step cc), in an optional step dd), at least one hydrogenated polyether-modified amino-functional polybutadiene (H) not containing end-capped polyether groups can be reacted with at least one end-capping reagent (I) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H) containing end-capped polyether groups.

[0144] Thus, in step dd), at least one hydrogenated polyether-modified amino-functional polybutadiene (H1) not containing end-capped polyether groups can be reacted with at least one end-capping reagent (I) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H2) containing end-capped polyether groups.

[0145] By "end-capped polyether group" is understood a polyether group that does not contain a hydroxyl group.

[0146] In steps cc) and dd), the groups B of the polybutadiene (G1) or (H1) having terminal hydroxyl groups are reacted to advantageously give ester, ether, urethane and / or carbonate groups. End-capping of polyethers is known to the person skilled in the art and is, for example, esterification with carboxylic acids or carboxylic anhydrides, acetylation, in particular with acetic anhydride, etherification with halogenated hydrocarbons, in particular methylation with methyl chloride according to the principle of the Williamson ether synthesis, urethanization by reaction of OH groups with isocyanates, in particular monoisocyanates such as stearyl isocyanate, and carbonation by reaction of dimethyl carbonate with diethyl carbonate.

[0147] Optional step e) In an optional step e), the at least one hydrogenated polyether modified amino-functional polybutadiene (H) can be lightened.

[0148] The hydrogenated polyether-modified amino-functional polybutadiene (H) may in this case be a polyether-modified amino-functional polybutadiene (H1) without end-capped polyether groups and / or a polyether-modified amino-functional polybutadiene (H2) with end-capped polyether groups. Lightening can be carried out, for example, advantageously by adding activated carbon in a suitable solvent or by treatment with hydrogen peroxide. Lightening can preferably be determined by the Gardner color number (determined according to DIN EN ISO 4630). Here, it is preferred that the Gardner color number of the hydrogenated polyether-modified amino-functional polybutadiene (H) is reduced by at least 1, advantageously by at least 2, upon lightening.

[0149] Optional step f) In optional step f), at least a portion of the amino groups of the at least one polyether-modified amino-functional polybutadiene (G) can be converted to quaternary ammonium groups using acids or quaternizing agents such as alkyl halides, benzyl halides, dimethyl sulfate or chloroacetic acid or sodium chloroacetate.

[0150] Here, the hydrogenated polyether-modified amino-functional polybutadiene (H) may be a polyether-modified amino-functional polybutadiene (H1) that does not contain an end-capped polyether group and / or a polyether-modified amino-functional polybutadiene (H2) that contains an end-capped polyether group.

[0151] Step f) can alternatively be carried out after step d) or after optional step e).After quaternization, the product can be dissolved or dispersed, for example, in water or an organic solvent.

[0152] Hydrogenated polyether modified amino-functional polybutadiene The subject of the invention is furthermore amino-functional hydrogenated polybutadienes modified with comb-type (pendant, side chain) polyether groups, which can be prepared by the process according to the invention.

[0153] A further subject of the present invention is therefore the hydrogenated polyether-modified amino-functional polybutadienes (H) obtainable by the process according to the invention.

[0154] The hydrogenated polyether-modified amino-functional polybutadiene (H) is advantageously a linear, at least partially hydrogenated polybutadiene modified in the form of a comb (pendant, side chain) with polyether groups. It is therefore preferred that the hydrogenated polyether-modified amino-functional polybutadiene (H) has a linear, at least partially hydrogenated polybutadiene backbone and pendant polyether groups.

[0155] A further subject of the present invention is likewise the hydrogenated polyether-modified amino-functional polybutadienes (H) which are advantageously obtainable by the process according to the invention, said hydrogenated polyether-modified amino-functional polybutadienes (H) being characterized in that: The group consisting of divalent groups (S), (T) and (U): [ka] and the group consisting of divalent groups (V) and (W): [ka] and optionally the group consisting of divalent groups (X), (Y) and (Z): [ka] wherein: A1 and A2 are each independently an organic group having preferably 1 to 22 carbon atoms, most preferably 1 to 12 carbon atoms, where the groups A1 and A2 can be covalently linked to each other; B is, independently of one another, a group of formula (4a), [ka] Preferably, each independently of the other, is a radical of formula (4b), [ka] Most preferably, each independently of the other, is a group of formula (4c): [ka] R 1 are each independently a monovalent hydrocarbon group having 1 to 16 carbon atoms; preferably are each independently an alkyl group or a phenyl group having 1 to 16 carbon atoms; most preferably are each independently a methyl group, an ethyl group, or a phenyl group; R 2is the formula -CH2-OR 3 is the basis of; R 3 are each independently a monovalent hydrocarbon group having 3 to 18 carbon atoms; preferably each independently a phenyl group optionally substituted with a monovalent group selected from an allyl group, a butyl group, an alkyl group having 8 to 15 carbon atoms, or a hydrocarbon group having 1 to 4 carbon atoms; most preferably a tert-butylphenyl group or an o-cresyl group; R 4 are each independently a monovalent organic group having 1 to 18 carbon atoms or hydrogen, preferably hydrogen; k1 and k2 each independently represent an integer of 0 to 8, preferably an integer of 0 to 6, and most preferably an integer of 0 to 4; l1 and l2 are integers, each independently of the other, being either 0 or 1; m, n, o, p and q are each, independently of one another, a rational number from 0 to 300, preferably from 0 to 200, and most preferably from 0 to 100, provided that the sum of m, n, o, p and q is greater than 1, preferably greater than 5, and most preferably greater than 10; The hydrogenated polyether-modified amino-functional polybutadiene (H) is characterized in that all combinations of the units of the group B, whose numbers are indicated by the subscripts m, n, o, p, or q, are included.

[0156] The term "hydrogen" of the group refers to a hydrogen group / radical.

[0157] Here, the group R 1 , R 2 , R 3 , R 4 may each, independently of the other, be linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted.

[0158] Here, the general notation [ka] [Here, in equation (4a), R = R 1 or R 2 and in formulas (4b) and (4c) R=CH3] is represented by the formula [ka] In addition to the units of formula [ka] but advantageously also represents the unit of formula [ka] Represents the unit of .

[0159] Here, the general notation of equation (4a) [ka] is the formula [ka] In addition to the units of formula [ka] but advantageously also represents the unit of formula [ka] Represents the unit of .

[0160] base R 4 each independently represents 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 and hydrogen; more preferably, R 4 are each 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 and hydrogen; most preferably, R 4 is hydrogen; here the term "hydrogen" is intended to represent a hydrogen group / radical.

[0161] R 5 are each independently an alkyl or alkenyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and most preferably a methyl group.

[0162] R 6 are each independently an alkyl or aryl group having 1 to 18 carbon atoms, preferably 6 to 18 carbon atoms.

[0163] R 7 are each independently an alkyl group having 1 to 18 carbon atoms, preferably 1 to 2 carbon atoms.

[0164] According to the present invention, it is preferred that the sum (total number) of all units (S), (T) and (U) of at least one hydrogenated polyether-modified amino-functional polybutadiene (H) divided by the sum (total number) of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is >0% to <100%.

[0165] Conversely, this means that the sum (total number) of all units (V), (W), (X), (Y) and (Z) in at least one hydrogenated polyether-modified amino-functional polybutadiene (H) divided by the sum (total number) of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is <100% ->0%.

[0166] This means that >0% to <100% of the total units (S), (T), (U), (V), (W), (X), (Y) and (Z) are polyether modified.

[0167] This also means that <100% to >0% of the total of units (S), (T), (U), (V), (W), (X), (Y) and (Z) are not polyether modified.

[0168] Here, it is preferred that the value obtained by dividing the sum (total number) of all units (S), (T) and (U) of at least one hydrogenated polyether-modified amino-functional polybutadiene (H) by the sum (total number) of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is >0% to 70%, more preferably 1% to 50%, even more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20%.

[0169] This means that preferably >0% to 70%, more preferably 1% to 50%, even more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20% of the total of the units (S), (T), (U), (V), (W), (X), (Y) and (Z) are polyether modified.

[0170] Here, it is further preferred that the value obtained by dividing the sum (total number) of all units (V), (W), (X), (Y) and (Z) of at least one hydrogenated polyether-modified amino-functional polybutadiene (H) by the sum (total number) of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is <100% to 30%, more preferably 99% to 50%, even more preferably 98% to 60%, even more preferably 97% to 70%, and most preferably 96% to 80%.

[0171] This means that preferably <100% to 30%, even more preferably 99% to 50%, even more preferably 98% to 60%, even more preferably 97% to 70%, and most preferably 96% to 80% of the total of the units (S), (T), (U), (V), (W), (X), (Y) and (Z) are not polyether modified.

[0172] The hydrogenated polyether modified amino-functional polybutadiene (H) may be partially or fully hydrogenated.

[0173] Therefore, it is further preferred that the sum (total number) of all units (V) and (W) of at least one hydrogenated polyether modified polybutadiene (H) divided by the sum (total number) of all units (V), (W), (X), (Y) and (Z) is at least 30%, more preferably at least 60%, even more preferably at least 90%, particularly preferably at least 95%. This means that at least 30%, more preferably at least 60%, even more preferably at least 90%, particularly preferably at least 95% of the total of units (V), (W), (X), (Y) and (Z) are saturated, and less than 30%, more preferably less than 40%, even more preferably less than 10%, particularly preferably less than 5% of the total of units (V), (W), (X), (Y) and (Z) are unsaturated. This is advantageous, in particular as described in the examples, 1 Determined using H-NMR spectroscopy.

[0174] The polyether group B can be, for example, R 1 and / or R 3 It is noted that when is a phenyl group, it may be unsaturated, however the aromatic group is advantageously not hydrogenated and remains unchanged after hydrogenation.

[0175] The number average molecular weight M of the polybutadiene portion of hydrogenated polyether modified amino-functional polybutadiene (H) n , weight average molecular weight M w and polydispersity are optional. Here, the polybutadiene portion is understood to be the portion of the hydrogenated polyether-modified amino-functional polybutadiene (H) that originates from the polybutadiene (A) used by the method. Thus, the number average molecular weight M of the polybutadiene portion of the hydrogenated polyether-modified amino-functional polybutadiene (H) n , weight average molecular weight M wand polydispersity is the number average molecular weight M of the polybutadiene (A) from which the hydrogenated polyether-modified amino-functional polybutadiene (H) is produced. n , weight average molecular weight M w and is identical to the polydispersity.

[0176] The number average molecular weight M of the polybutadiene portion of hydrogenated polyether modified amino-functional polybutadiene (H) n is preferably 200 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and most preferably 700 g / mol to 5,000 g / mol.

[0177] In addition, the number average molecular weight M of the polybutadiene portion of the hydrogenated polyether modified amino-functional polybutadiene (H) n is preferably 2100 g / mol to 20000 g / mol, more preferably 2200 g / mol to 10000 g / mol, and most preferably 2300 g / mol to 5000 g / mol.

[0178] Here, the number average molecular weight M of the polybutadiene part n is the number average molecular weight M of the base polybutadiene (A). n It is defined as:

[0179] It is further preferred that the hydrogenated polyether modified amino-functional polybutadiene (H) has a numerical average of 5 to 360, preferably 10 to 180, most preferably 15 to 90 units, wherein the units are selected from the group consisting of (S), (T), (U), (V), (W), (X), (Y) and (Z).

[0180] It is also preferred that the polyether modified amino-functional polybutadiene (H) has a numerical average of 35 to 360, preferably 40 to 180, and most preferably 45 to 90 units, wherein the units are selected from the group consisting of (S), (T), (U), (V), (W), (X), (Y) and (Z).

[0181] It is preferred that the combined weight proportion of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) relative to the total weight of the at least one hydrogenated polyether-modified amino-functional polybutadiene (H) is at least 50%, more preferably still at least 60%, more preferably still at least 70%, preferably at least 80%, more preferably still at least 90%, more preferably still at least 95%, more preferably still at least 99% and particularly preferably 100%.

[0182] It is preferred that the hydrogenated polyether-modified amino-functional polybutadiene (H) consists essentially or completely of units (S), (T), (U), (V), (W), (X), (Y) and (Z). It is particularly preferred that the hydrogenated polyether-modified amino-functional polybutadiene (H) consists essentially or completely of units (S), (T), (U), (V) and (W).

[0183] It is particularly preferred that the hydrogenated polyether-modified amino-functional polybutadiene (H) is characterized in that the proportion by weight of units (S) relative to the total weight of all units (S), (T) and (U) is at least 95%.

[0184] Most preferred are the above-mentioned polybutadienes (A) Polyvest® 110 and Polyvest® 130 from Evonik Industries AG / Evonik Operations GmbH, and the hydrogenated polyether-modified amino-functional polybutadienes (H) derived from Lithene ultra AL and Lithene ActiV 50 from Synthomer PLC.

[0185] The molecular weight and polydispersity of the group B are arbitrary. However, it is preferred that the average molecular weight of the group B is 30 g / mol to 20000 g / mol, more preferably 50 g / mol to 10000 g / mol, even more preferably 100 g / mol to 5000 g / mol, and most preferably 150 g / mol to 1000 g / mol. The average molecular weight of the group B can be calculated from the initial weight of the monomers used relative to the number of OH and NH groups of the hydroxy- and amino-functional polybutadiene (E) used. Thus, for example, if 40 g of ethylene oxide is used and the total amount of all OH and NH groups of the hydroxy- and amino-functional polybutadiene (E) used is 0.05 mol in total, the average molecular weight of the group B is 800 g / mol.

[0186] The hydrogenated polyether modified amino-functional polybutadienes (H) are liquid, pasty or solid, depending on the composition and molecular weight.

[0187] The number average molecular weight (M) of at least one hydrogenated polyether modified amino-functional polybutadiene (H) n ) is preferably 1000 g / mol to 50000 g / mol, more preferably 1500 g / mol to 40000 g / mol, even more preferably 2000 g / mol to 30000 g / mol, and most preferably 3000 g / mol to 10000 g / mol.

[0188] Its polydispersity (M w / M n ) can vary within wide limits. The polydispersity of the at least one hydrogenated polyether-modified amino-functional polybutadiene (H) is preferably 1.5-10, more preferably 2-8, most preferably 3-5.

[0189] The following examples are provided to illustratively explain the present invention, and are not intended to limit the present invention to the embodiments set forth in the examples. The scope of application of the present invention is clear from the entire specification and the claims.

[0190] Working Example: General Method: Gel Permeation Chromatography (GPC): Polydispersity (M w / M n ), weight average molecular weight (M w ) and number average molecular weight (M n GPC measurements to determine the polydispersity (M) of polybutadiene (A) were carried out under the following measurement conditions: column combination SDV 1000 / 10,000 Å (length 65 cm), temperature 30° C., THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l, RI detector, evaluation against polypropylene glycol standards. w / M n ), weight average molecular weight (M w ) and number average molecular weight (M n GPC measurements to determine the molecular weight can be carried out as well.

[0191] The polydispersity (M w / M n ), weight average molecular weight (M w ) and number average molecular weight (M n GPC measurements to determine the polydispersity (M) of end-capped polyether modified amino-functional polybutadienes (K) were performed under the following measurement conditions: column combination Jordi DVB 500 Å (length 30 cm), Jordi DVB Mixed Bed (length 30 cm), temperature 30° C., THF / triethylamine as mobile phase, flow rate 0.4 ml / min, sample concentration 3 g / l, RI detector, evaluation against polystyrene standards. w / M n ), weight average molecular weight (M w ) and number average molecular weight (M n GPC measurements to determine the molecular weight can be carried out similarly.

[0192] Determination of the content of 1,4-cis, 1,4-trans and 1,2 units in polybutadiene: Determination of the content of 1,4-cis units, 1,4-trans units and 1,2 units 1 This can be done using H-NMR spectroscopy, which is routinely used by those skilled in the art.

[0193] Determination of the content of epoxy groups (epoxy content, degree of epoxidation) of epoxy-functional polybutadienes (C): Determination of the epoxy group content, 13 C-NMR spectroscopy was used. A Bruker Avance 400 NMR spectrometer was used. For this purpose, the samples were dissolved in deuterated chloroform. The epoxy content is defined as the percentage (mol%) of epoxidized butadiene units relative to the total of all epoxidized and non-epoxidized butadiene units contained in the sample. It corresponds to the number of epoxy groups in the epoxy-functional polybutadiene (C) divided by the number of double bonds in the polybutadiene (A) used.

[0194] Determination of hydrogenation degree: The hydrogenation degree is determined by 1 H-NMR spectroscopy was used. A Bruker Avance 400 NMR spectrometer was used. For this purpose, samples were dissolved in deuterated chloroform.

[0195] First, the double bond content of the polyether-modified amino-functional polybutadiene (G) (i.e., before hydrogenation) was determined, and then the double bond content of the hydrogenated polyether-modified amino-functional polybutadiene (H) after hydrogenation was also determined. For this purpose, the double bond content of 4.8 to 6.3 ppm was determined. 1 The integral value of the H-NMR spectrum was obtained before and after hydrogenation. PB、前 ) or after hydrogenation (I PB、後 ) is proportional to the number of double bonds in polybutadiene ("PB"). For normalization, these integral values ​​are set to 2.8 to 4.2. 1 These integrals were also calculated from the integrals of the H-NMR spectrum before hydrogenation (I PE、前 ) or after hydrogenation (I PE、後The hydrogenation degree is then calculated by the following formula: Degree of hydrogenation=1-[(I PB、後 / I PE、後 ) / (I PB、前 / I PE、前 )] I PB、後 = 4.8-6.3 ppm after hydrogenation 1 H-NMR spectrum integral I PE、後 = 2.8-4.2 ppm after hydrogenation 1 H-NMR spectrum integral I PB、前= 4.8 to 6.3 ppm before hydrogenation 1 H-NMR spectrum integral I PE、前= 2.8-4.2 ppm before hydrogenation 1 H-NMR spectrum integral value.

[0196] Determination of Acid Number: The acid number was determined by titration according to DIN EN ISO 2114.

[0197] Synthesis example: Step a): Preparation of epoxidized polybutadiene Example A1 Epoxidized polybutadiene was produced using polybutadiene of formula (1) with structure x=1%, y=24% and z=75% (Polyvest® 110). According to the prior art, a 5 liter reactor was charged with 1500 g of Polyvest® 110 and 146.3 g of concentrated formic acid in 1500 g of chloroform at room temperature under nitrogen atmosphere. Then, 540 g of 30% H2O2 solution (30% by weight H2O2 with respect to the total weight of the aqueous solution) was slowly added dropwise and the solution was then heated to 50° C. for 7 hours. After the reaction was over, it was cooled to room temperature and the organic phase was separated, which was washed four more times with distilled water. Excess chloroform and residual water were distilled off. 1481 g of product was obtained, which was mixed with 1000 ppm of Irganox® 1135 and stored under nitrogen. 13The degree of epoxidation of the double bonds was estimated to be about 15.8% by C-NMR. The following was obtained by GPC: w = 4690 g / mol; M n = 1982 g / mol;M w / M n =2.4.

[0198] Step b), Preparation of Amino-Functional Polybutadiene Example B1 The epoxidized polybutadiene prepared in Example A1 was used to prepare an amino-functional polybutadiene having a degree of amination of about 15.8%, where the degree of amination is the number of amino groups of the amino-functional polybutadiene divided by the number of double bonds of the polybutadiene used in step a). For the preparation, 800 g of epoxidized polybutadiene, 136.3 g of ethanolamine and 6.8 g of lithium bromide were placed in a 1 liter four-neck flask under nitrogen and heated to 180° C. with stirring. The mixture was stirred at this temperature for 15 hours. The viscosity increased during the reaction. After the reaction was over, the volatile constituents were distilled off at 180° C. and 20 mbar. The product was cooled to 60° C. 908 g of yellowish product was obtained, which was stored under nitrogen. 13 C-NMR evaluation revealed complete conversion of all epoxy groups, from which the degree of amination was about 15.8%.

[0199] Step c), Alkoxylation of Hydroxy- and Amino-Functional Polybutadienes Example C1 (stoichiometry: 5EO / 5PO per reactive NH / OH group) A 1.5 liter autoclave was charged under nitrogen with 197 g of aminated polybutadiene prepared in Example B1 and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile contents present were distilled off. 27.4 g of propylene oxide were fed at 115° C. over 5 minutes. The reactor pressure rose to a maximum of 2.3 bar (absolute) and was continuously reduced during the reaction. After 4 hours, a constant pressure of 0.7 bar (absolute) was reached. The volatile components were removed at 115° C. and 20 mbar, the reactor was depressurized to normal pressure with N2 and the reaction mixture was cooled to 40° C. Then 17.6 g of sodium methoxide solution (30% in methanol) was added, the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. Now the reactor pressure was reduced to 20 mbar and the methanol was distilled off. A mixture of 382 g propylene oxide and 310 g ethylene oxide was added at 115° C. with stirring and cooling over 6 hours at a maximum internal pressure of 3.2 bar. During the post-reaction at 115° C. for 2.5 hours, the internal pressure was continuously reduced until a constant pressure of 0.4 bar (absolute) was reached. Volatiles such as residual propylene oxide and ethylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., neutralized with 30% phosphoric acid to an acid value of 0.1 mg KOH / g, mixed with 500 ppm Irganox® 1135 and discharged through a filter. 881 g of viscous, orange, transparent polyether-modified amino-functional polybutadiene was discharged and stored under nitrogen. Evaluation by GPC gave the following: M w = 32145 g / mol;M n = 8349 g / mol;M w / M n =3.85.

[0200] Example C2 (stoichiometry: 3.8 PO per reactive NH / OH group) A 1.5 L autoclave was charged under nitrogen with 181 g of aminated polybutadiene prepared in Example B1 and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile contents present were distilled off. 25.2 g of propylene oxide were fed at 115° C. over 5 minutes. The reactor pressure rose to a maximum of 2.4 bar (absolute) and was continuously reduced during the reaction. After 4.5 hours, a constant pressure of 0.7 bar (absolute) was reached. The volatile components were removed at 115° C. and 20 mbar, the reactor was depressurized to normal pressure with N2 and the reaction mixture was cooled to 40° C. Then 32.2 g of sodium methoxide solution (30% in methanol) was added and the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. Now the reactor pressure was reduced to 20 mbar and the methanol was distilled off. 260 g of propylene oxide were added at 115° C. with stirring and cooling over 1.5 hours at a maximum internal pressure of 2.9 bar. During the 2-hour post-reaction at 115° C., the internal pressure was continuously reduced until a constant pressure of 0.3 bar (absolute) was reached. Volatiles such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., neutralized with 17.9 g of lactic acid (90% in water) to an acid value of 0.1 mg KOH / g, mixed with 1000 ppm of Irganox® 1135 and discharged. 421 g of viscous orange slightly hazy polyether-modified amino-functional polybutene were discharged and stored under nitrogen. Evaluation by GPC gave the following: M w = 25386 g / mol;M n = 5226 g / mol;M w / M n =4.86.

[0201] Example C3 (stoichiometry: 3.8 EO per reactive NH / OH group) A 1.5 liter autoclave was charged under nitrogen with 151 g of hydroxy- and amino-functional polybutadiene prepared in Example B1 and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile contents present were distilled off. 15.9 g of ethylene oxide were fed at 115° C. over 5 minutes. The reactor pressure rose to a maximum of 3.4 bar (absolute) and was continuously reduced during the reaction. After 5.5 hours, a constant pressure of 0.6 bar (absolute) was reached. The volatile components were removed at 115° C. and 20 mbar, the reactor was depressurized to normal pressure with N2 and the reaction mixture was cooled to 40° C. Then 26.9 g of sodium methoxide solution (30% in methanol) was added and the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. Now the reactor pressure was reduced to 20 mbar and the methanol was distilled off. 164.7 g of ethylene oxide were added at 115° C. with stirring and cooling over 1.5 hours with a maximum internal pressure of 3.4 bar. During the post reaction at 115° C. for 3 hours, the internal pressure was continuously reduced until a constant pressure of 0.5 bar (absolute) was reached. Volatiles such as residual ethylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., neutralized with 14.9 g of lactic acid (90% in water) to an acid value of 0.1 mg KOH / g, mixed with 1000 ppm Irganox® 1135 and discharged. 317 g of viscous orange-red slightly hazy polyether modified amino-functional polybutene were discharged and stored under nitrogen. Evaluation by GPC gave the following: M w = 19484 g / mol;M n = 4474 g / mol;M w / M n =3.45.

[0202] Step d), hydrogenation of polyether modified amino-functional polybutadiene Example D1 A 500 ml four-neck flask was charged with 50 g of alkoxylated hydroxylated amino-functional polybutadiene prepared in Example C1 and 150 g xylene. Then, 0.25 g of Rh-100 (Wilkinson's catalyst) was added. After heating to 120° C., 0.025-0.05 lpm (lpm = liters per minute) of hydrogen was introduced with stirring under a strong argon flow for 34 hours. Then, 0.25 g of Rh-100 was again added and 0.025-0.05 lpm of hydrogen was introduced for another 10 hours. After adding 1.5 g of Harbolite 800 filter aid (Alpha Aesar GmbH & Co. KG), the product was hot filtered. After distillation under reduced pressure, a black-brown turbid product was obtained which becomes viscous on cooling. The hydrogenation degree is 64.6%. Evaluation by GPC gave the following: M w = 29189 g / mol;M n = 8156 g / mol;M w / M n =3.58.

[0203] Example D2 A 250 ml four-neck flask is charged with 71 g of alkoxylated hydroxylated amino-functional polybutadiene prepared in Example C1, 3.55 g of Raney nickel (aluminum / nickel 50 / 50) and 0.71 g of palladium catalyst Pd-Kat / C (5% Pd on activated carbon, water content 50%) under argon. After heating to 120°C, 0.025-0.05 lpm (lpm = liters per minute) of hydrogen is introduced with stirring under a strong argon flow for 86 hours. The product is diluted with 28.4 g of butyl acetate and hot filtered after adding 2.1 g of Harbolite 800 filter aid. After distillation under reduced pressure, a black-brown turbid product is obtained which becomes viscous on cooling. The hydrogenation degree is 67.1%. Evaluation by GPC gives the following: M w = 32447 g / mol;M n = 7294 g / mol;M w / M n =4.45.

[0204] Example D3 A 250 ml four-neck flask was charged under argon with 50 g of alkoxylated hydroxylated amino-functional polybutadiene prepared in Example C2 and 50 g of butyl acetate. Then, 0.5 g of palladium catalyst Pd-Kat / C (5% Pd on activated carbon, water content 50%) was added. After heating to 120°C, 0.025-0.05 lpm (lpm = liters per minute) of hydrogen was introduced with stirring under a strong argon flow for 40 hours. The product was diluted again with 20 g of xylene and hot filtered after adding 1.5 g of Harbolite 800 filter aid. After distillation under reduced pressure, a black-brown product is obtained which becomes viscous on cooling. The hydrogenation degree is 49.6%. Evaluation by GPC gave the following: M w = 25649 g / mol;M n = 7038 g / mol;M w / M n =3.64.

[0205] Example D4 A 250 ml four-neck flask was charged under argon with 31.4 g of alkoxylated hydroxylated amino-functional polybutadiene prepared in Example C3 and 31.4 g of butyl acetate. Then, 0.016 g of citric acid, 0.31 g of water, 1.57 g of Raney nickel (aluminum / nickel 50 / 50) and 0.31 g of palladium catalyst Pd-Kat / C (5% Pd on activated carbon, water content 50%) were added. After heating to 120 ° C, 0.025-0.05 lpm (lpm = liters per minute) of hydrogen was introduced with stirring under a strong argon flow for 35 hours. The product was diluted again with 12.5 g of xylene and hot filtered after adding 1 g of Harbolite 800 filter aid. After distillation under reduced pressure, a black-brown turbid product was obtained, which became solid on cooling. The hydrogenation degree was 48.1%. Evaluation by GPC gave the following:M w = 17776 g / mol;M n = 4925 g / mol;M w / M n =3.61.

[0206] Example D5 A 250 ml four-neck flask is charged under argon with 31.8 g of alkoxylated hydroxylated amino-functional polybutadiene prepared in Example C3, 1.59 g of Raney nickel (aluminum / nickel 50 / 50) and 0.32 g of palladium catalyst Pd-Kat / C (5% Pd on activated carbon, water content 50%). After heating to 120°C, 0.025-0.05 lpm (lpm = liters per minute) of hydrogen is introduced with stirring under a strong argon flow for 37 hours. The product is diluted with 30 g of xylene and hot filtered after adding 1 g of Harbolite 800 filter aid. After distillation under reduced pressure, a black-brown product is obtained which becomes viscous on cooling. The hydrogenation degree is 59.2%. Evaluation by GPC gives the following: M w = 18536 g / mol;M n = 4821 g / mol;M w / M n =3.84.

[0207] Example D6 A 500 ml four-neck flask was charged under argon with 50 g of alkoxylated hydroxylated amino-functional polybutadiene WD 1011 prepared in Example C1 and 150 g of xylene. Then 1.5 g of Rh-100 were added. After heating to 120° C., 0.025-0.05 lpm (lpm = liters per minute) of hydrogen was introduced with stirring under a strong argon flow for 20 hours. After adding 1.5 g of Harbolite 800 filter aid, the product was hot filtered. After distillation under reduced pressure, a black-brown turbid product was obtained which became solid on cooling. The hydrogenation degree was 97.9%. Evaluation by GPC gave the following: M w = 32451 g / mol;M n = 9190 g / mol;M w / M n =3.53.

[0208] Example D7 A 500 ml four-neck flask was charged with 50 g of alkoxylated hydroxylated amino-functional polybutadiene WD 995 prepared in Example C3 and 150 g of butyl acetate under argon. Then 1.5 g of Rh-100 were added. After heating to 120° C., 0.025-0.05 lpm (lpm = liters per minute) of hydrogen was introduced with stirring under a strong argon flow for 20 hours. After adding 1.5 g of Harbolite 800 filter aid, the product was hot filtered. After distillation under reduced pressure, a black-brown product was obtained which became viscous on cooling. The hydrogenation degree was 47.0%. Evaluation by GPC gave the following: M w = 24962 g / mol;M n = 6463 g / mol;M w / M n =3.86.

Claims

1. 1. A method for producing one or more hydrogenated polyether-modified amino-functional polybutadienes, comprising: a) reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functional polybutadiene (C); b) reacting said at least one epoxy-functional polybutadiene (C) with at least one amino-functional compound (D) to obtain at least one hydroxy- and amino-functional polybutadiene (E); c) reacting said at least one hydroxy- and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G); d) hydrogenating said at least one polyether-modified amino-functional polybutadiene (G) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H); A method comprising:

2. The following steps cc) and dd): cc) reacting at least one polyether-modified amino-functional polybutadiene (G) not containing end-capped polyether groups with at least one end-capping reagent (I) to obtain at least one polyether-modified amino-functional polybutadiene (G) containing end-capped polyether groups; dd) reacting at least one hydrogenated polyether-modified amino-functional polybutadiene (H) with at least one end-capping reagent (I) to obtain at least one hydrogenated polyether-modified amino-functional polybutadiene (H) containing end-capped polyether groups. and / or at least one of the following steps e) and f): e) brightening said at least one hydrogenated polyether modified amino-functional polybutadiene (H); f) converting at least a portion of the amino groups of said at least one hydrogenated polyether-modified amino-functional polybutadiene (H) into quaternary ammonium groups using an acid and / or a quaternizing agent; The method of claim 1 , further comprising at least one of:

3. 2. The process of claim 1, wherein >0% to <100% of the double bonds of said at least one polybutadiene (A) are epoxidized.

4. The method of claim 1 , wherein the at least one epoxidation reagent (B) comprises performic acid.

5. 2. The process of claim 1, wherein the at least one amino-functional compound (D) is selected from compounds having at least one primary amino group and / or at least one secondary amino group.

6. At least one epoxy-functional compound used in step c) a. from the group of alkylene oxides, and / or b. From the group of glycidyl compounds The method of claim 1 , wherein

7. 2. The process according to claim 1, wherein in process step d) at least 30% of the double bonds of the polyether modified polybutadiene (G) are hydrogenated.

8. 2. The process of claim 1, wherein step d) is carried out with hydrogen in the presence of at least one hydrogenation catalyst.

9. Hydrogenated polyether modified amino-functional polybutadiene (H) obtainable by the process according to any one of claims 1 to 8.

10. A hydrogenated polyether-modified amino-functional polybutadiene (H), comprising: The group consisting of divalent groups (S), (T) and (U): 【Chemistry 1】 and the group consisting of divalent groups (V) and (W): 【Chemistry 2】 and optionally the group consisting of divalent groups (X), (Y) and (Z): 【Chemistry 3】 wherein: A １ and A ２ are each independently an organic group, １ and A ２ can be covalently bonded to each other, B is each independently a group of formula (4a), 【Chemistry 4】 R 1 are each independently a monovalent hydrocarbon group having 1 to 16 carbon atoms; R ２ is represented by the formula -CH ２ -O-R ３ is a group represented by the formula: R ３ are each independently a monovalent hydrocarbon radical having 3 to 18 carbon atoms; R ４ are each independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogen; k1 and k2 are each independently an integer from 0 to 8; l1 and l2 are integers, each independently of the other, being either 0 or 1; m, n, o, p and q are each, independently of one another, rational numbers from 0 to 300, provided that the sum of m, n, o, p and q is greater than 1; The hydrogenated polyether-modified amino-functional polybutadiene (H) includes all combinations of the units of the group B whose numbers are indicated by the subscripts m, n, o, p, or q.

11. 11. The hydrogenated polyether modified amino-functional polybutadiene (H) according to claim 10, wherein the sum of all units (S), (T) and (U) divided by the sum of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is >0% to 70%.

12. The number average molecular weight (M ｎ 12. The hydrogenated polyether modified amino-functional polybutadiene (H) according to claim 10 or 11, wherein the molecular weight of the polybutadiene (H) is 200 g / mol to 20,000 g / mol.

13. The hydrogenated polyether modified amino-functional polybutadiene (H) according to claim 10 or 11, wherein the average molecular weight of the group B is from 30 g / mol to 20000 g / mol.

14. The number average molecular weight (M ｎ 12. The hydrogenated polyether modified amino-functional polybutadiene (H) according to claim 10 or 11, wherein the molecular weight of the polybutadiene (H) is 1000 g / mol to 50000 g / mol.

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