Aminofunctional polybutadienes having polyether residues at the comb position and methods for their preparation

Abstract

The subject of the present invention is a method for producing polyether-modified amino-functional polybutadienes as well as polyether-modified amino-functional polybutadienes which can be produced by this method, comprising the steps of a) reacting at least one polybutadiene (A) with at least one epoxidizing agent (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).

Description

[Technical field]

[0001] The present invention relates to a process for preparing polyether-modified amino-functional polybutadienes and to the polyether-modified amino-functional polybutadienes which can be prepared by this process.

[0002] Polybutadienes with pendant polyether residues are known and are prepared according to the prior art, for example, by reacting 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 the polybutadiene backbone (Pfropfen). According to JP 2011038003, polybutadienes functionalized with maleic anhydride units are reacted with amino-terminated polyethers. Maleated polybutadienes are obtained with polyether residues in the comb position, said residues being linked via amide or imide groups. In a similar method, according to J. Wang, Journal of Applied Polymer Science (2013), 128(4), 2408-2413, polyethylene glycol is added to polybutadiene having a high proportion of 1,2-butadiene monomer units, forming ester bonds. High molecular weight graft polymers with comb structures are obtained by addition of epoxidized polybutadiene with OH-functional polyethers according to the method disclosed in JP 2002105209. H. Decher et. al., according to Polymer International (1995), 38(3), 219-225, utilize the addition of isocyanate-terminated polyethylene glycol to hydroxy-functional polybutadiene.

[0003] Furthermore, methods are known for the preparation of polyether-modified polybutadienes by reacting hydroxy-functional polybutadienes with epoxy compounds, and from the prior art, for example, the alkoxylation of OH-terminated polybutadienes is known.

[0004] US 4994621 A describes, for example, 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 exclusively in a polyether-polybutadiene-polyether triblock structure. This block structure, according to EP 2003156 A1, is the cause of poor compatibility with other reactants in the production of polyurethanes.

[0005] In addition to the alkoxylation of hydroxy-terminated polybutadienes, the alkoxylation of pendant hydroxy-functional polybutadienes is also known. For example, Q. Gao et. al., in Macromolecular Chemistry and Physics (2013), 214(15), 1677-1687, describe the preparation of pendant polyether-modified polybutadienes by alkoxylation of pendant hydroxy-functional polybutadienes with ethylene oxide. The pendant hydroxy-functional polybutadienes used here are prepared by first epoxidizing polybutadiene, followed by reaction of the epoxidized polybutadiene with a lithium-polybutadiene compound, and finally protonating the reaction product with methanolic HCl. This method results in polybutadienes that have not only pendant polyether residues, but also pendant polybutadiene residues. According to the method disclosed in the still unpublished document PCT / EP2020 / 083013, polybutadienes modified in the comb position with polyether residues are prepared by alkoxylation, preferably with an alcohol, of a pendant hydroxy-functional polybutadiene previously obtained by ring-opening of an epoxy-functional polybutadiene.

[0006] Chemical modification of polybutadiene by epoxidation followed by epoxide ring-opening by reaction with amines is known. JP 63288295 discloses the reaction of epoxy-functional polybutadiene with dimethylamine and subsequent protonation of the amine functions with acetic acid. The method described in JP 57205596 includes, in addition to the epoxide ring-opening with dimethylamine, a further quaternization of the amine functions with epichlorohydrin. A method for epoxide ring-opening of hydrogenated polybutadiene with amines is disclosed in DE 2554093. DE 2943879, DE 2732736 and JP 49055733 describe the addition of diethanolamine. JP 48051989 likewise describes the addition of diethanolamine followed by a crosslinking reaction in the presence of dibenzoyl peroxide. JP 53117030, DE 2734413 and DE 2943879 describe the addition of ethanolamine, JP 05117556 the reaction with diisopropanolamine and EP 0351135, EP 0274389 and DE 3305964 the reaction of epoxy groups with dimethylamine. DD 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] Thus, from the prior art, a process for preparing preferably linear amino-functional polybutadienes having pendant polyether chains by a simple direct alkoxylation reaction of a pendant amino-functional polybutadiene with an alkylene oxide, said pendant amino-functional polybutadiene being prepared from an epoxy-functional polybutadiene by a ring-opening reaction with an amine, is hitherto unknown.

[0008] 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, the possible uses of polyether-modified polybutadienes are often limited by being limited to only a few available triblock structures. There has not been the possibility to vary the chemical structure of said polyether-modified polybutadienes in a wide range so far. Moreover, there is no simple manufacturing method for such polymers.

[0009] The object of the present invention was to overcome at least one of the disadvantages of the prior art.

[0010] In particular, the object was to provide an improved process for the preparation of preferably linear polybutadienes which are modified with polyether residues via amino groups at the comb position (pendant, lateral). The process should furthermore enable a process-technologically very simple route to preferably linear polybutadienes having pendant polyether residues. The polyether-modified polybutadienes should then furthermore be obtainable by direct alkoxylation of pendant amino-functional polybutadienes. The object was then, moreover, to provide pendant amino-functional polybutadienes suitable for the process as precursors and chain initiators for the alkoxylation.

[0011] Surprisingly, it has now been found that a method for producing polyether modified amino-functional polybutadiene solves this problem, 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 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-functional and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G).

[0012] Surprisingly, it has further been found that polybutadienes, in particular those having a high proportion of 1,4-units and a low proportion of vinyl 1,2-units, can be converted, after epoxidation with hydrogen peroxide, by ring opening with primary or secondary amines to pendant hydroxy- and amino-functional polybutadienes, which can then be alkoxylated with alkylene oxides.

[0013] The object of the present invention is therefore achieved by the subject matter of the independent claims. Advantageous embodiments of the invention are set out in the dependent claims, the examples and the detailed description.

[0014] The subject matter of the present invention is described below by way of example, without the present invention being limited to these exemplary embodiments. If ranges, general formulae or compound groups are described below, these are intended to include not only the corresponding ranges or groups of compounds explicitly listed, but also any subranges and subgroups of compounds that can be obtained by removing individual values ​​(ranges) or compounds. If documents are cited within the present specification, their contents are fully incorporated into the disclosure of the present invention.

[0015] Where average values ​​are stated below, they are number averages, unless otherwise stated. Where measurements, parameters or material properties determined by measurement are stated below, they are, unless otherwise stated, measurements, parameters or material properties measured at 25° C. and preferably at a pressure of 101325 Pa (standard pressure).

[0016] Number average molecular weight M n , weight average molecular weight M w and polydispersity (M w / M n ) is, within the scope of the present invention, unless expressly stated otherwise, preferably determined by gel permeation chromatography (GPC), as described in the examples.

[0017] When numerical ranges are described below in the form "X to Y," where X and Y represent the limits of said numerical range, this is equivalent to the statement "at least X to Y, inclusive," unless otherwise stated. Thus, the description of a range includes the limits X and Y of the range, unless otherwise stated.

[0018] The terms pendant, lateral and comb-position are used synonymously.

[0019] Whenever a molecule or molecular fragment has one or more stereocenters or can be differentiated into isomers on the basis of symmetry or other effects, such as restricted rotation, all possible isomers are encompassed by the present invention.

[0020] The following formulae (1) to (5) describe compounds or residues that are composed of repeating units, for example repeating fragments, blocks or monomer units, and can have a molecular weight distribution. The frequency of said repeating units is described by subscripts. The subscripts used in the formulae should be considered as statistical average values ​​(number averages), unless expressly stated otherwise. The subscript values ​​used as well as the ranges of subscript values ​​described are understood to be the average values ​​of the possible statistical distributions of the actual existing structures and / or their mixtures, unless expressly stated otherwise. The various fragments or repeating units of the compounds described in the following formulae (1) to (5) can be statistically distributed. The statistical distribution can be block-like, with any number of blocks and any sequence, or randomly distributed, alternating, or else form a gradient on the molecular chain, if present, and in particular any mixed type, where groups of different distributions may follow one another if appropriate. In the following formulae, all permutations of the repeating units are included together. Thus, within the scope of the present invention, when compounds that may have a plurality of different units are described, such as polybutadienes (A), epoxy-functional polybutadienes (C), hydroxy- and amino-functional polybutadienes (E), polyether-modified amino-functional polybutadienes (G) or polyether-modified amino-functional polybutadienes containing end-capped polyether residues (K), these units may occur in these compounds randomly, e.g., statistically distributed, or in an orderly manner. Any description of the number or relative frequency of units in such compounds should be understood to be an average value averaged over all corresponding compounds (number average). Particular embodiments may result in the statistical distribution being limited by the embodiments. For all ranges not affected by the limitations, the statistical distribution remains unchanged.

[0021] Thus, a first subject of the present invention is a process for preparing one or more polyether-modified amino-functional polybutadienes, 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 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-functional and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G).

[0022] The method according to the invention preferably further comprises at least one of the following steps: d) reacting said at least one polyether modified amino-functional polybutadiene (G) with at least one end-capping reagent (H) to obtain at least one polyether modified amino-functional polybutadiene (K) containing end-capped polyether residues; e) lightening the color of said at least one polyether modified amino-functional polybutadiene (G) or (K); f) reacting at least a portion of the amino groups of said at least one polyether modified amino-functional polybutadiene (G) or (K) with an acid and / or a quaternizing agent to obtain quaternary ammonium groups.

[0023] The steps a), b), c), d), e) and f) are carried out in the order given, where one or more of the steps d), e) and f) can be omitted. The steps can follow one another directly. However, the method can have further upstream, intermediate or downstream steps, such as purification of the starting material, intermediate product and / or final product.

[0024] 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 hydroxy groups. Depending on the reaction conditions in step c), addition of the epoxy-functional compound (F) is effected to the amino groups, the hydroxy groups or preferably both reactive groups.

[0025] In this case, it is preferable to use stabilizers or antioxidants to stabilize the starting materials, intermediates and products during the process according to the invention in order to prevent undesired polymerization reactions of the double bonds. For this purpose, for example, sterically hindered phenols known to those skilled in the art are suitable, for example Anox (登録商標) 20. Irganox (登録商標) 1010 (BASF), Irganox (登録商標) 1076 (BASF) and Irganox (登録商標) It is commercially available as 1135 (BASF).

[0026] It is further preferred to carry out one or more or all of the process steps under an inert atmosphere, for example under nitrogen. Also preferably, the unmodified starting material, i.e. said at least one polybutadiene (A), as well as the polyether-modified final product according to the invention, i.e. said at least one polyether-modified polybutadiene (G) or (K), should be stored under the exclusion of air as far as possible.

[0027] The process according to the invention makes it possible for the first time to modify linear polybutadienes with polyether residues in the comb position by simple direct alkoxylation of the pendant amino and hydroxy groups. The chain length and monomer sequence in the polyether residues can be varied within wide limits. The average number of polyether residues attached to the polybutadiene can be deliberately adjusted through its degree of epoxidation and functionalization with amino and hydroxy groups, opening up a large structural diversity in the hydroxy- and amino-functional polybutadienes (E).

[0028] The amino-functional polybutadienes with polyether residues at the comb positions obtainable according to the invention are preferably essentially free of residual epoxy groups. The products of the process according to the invention preferably contain essentially no free polyether moieties. Preferably, essentially the polyethers are chemically bonded to the polybutadiene via nitrogen atoms and / or via oxygen atoms.

[0029] 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).

[0030] During this reaction, the double bonds of the polybutadiene (A) are converted into epoxy groups.Various methods of 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 2004346310, DD 253627 and WO 2016 / 142249 A1.Performic acid is particularly suitable for producing epoxy-functional polybutadiene (C) with a high proportion of 1,4-units, which can also be formed in situ from formic acid in the presence of hydrogen peroxide. The epoxidation is preferably carried out in a solvent, such as toluene or chloroform, which is removed by distillation after the reaction and after washing away any peroxide residues that may be present.

[0031] The polybutadiene (A) is a polymer of buta-1,3-diene. The polymerization of the buta-1,3-diene monomers takes place essentially with 1,4- and / or 1,2-bonds. The 1,4-bonds result in so-called 1,4-trans-units and / or 1,4-cis-units, which are also collectively called 1,4-units. The 1,2-bonds result in so-called 1,2-units. The 1,2-units carry a vinyl group and are also called vinyl 1,2-units. The 1,2-units are also called "(X)", the 1,4-trans-units "(Y)" and the 1,4-cis-units "(Z)" within the scope of the present invention: [ka]

[0032] The double bonds contained in said units are similarly referred to as 1,4-trans-double bonds, 1,4-cis-double bonds or 1,2-double bonds or 1,2-vinyl double bonds. The 1,4-trans-double bonds and 1,4-cis-double bonds are also collectively referred to as 1,4-double bonds.

[0033] Therefore, the polybutadienes (A) are unmodified polybutadienes. The polybutadienes (A) and their preparation methods are known to those skilled in the art. The preparation is preferably carried out by radical chain polymerization, anionic chain polymerization or coordination chain polymerization.

[0034] The radical chain polymerization is preferably carried out as an emulsion polymerization. This results in the statistical generation of the three units. At low reaction temperatures (about 5° C.), the proportion of vinyl groups decreases. The initiation is preferably carried out with potassium peroxodisulfate and iron salts, or else with hydrogen peroxide.

[0035] In the case of the anionic chain polymerization, the initiation of the chain polymerization is preferably carried out with butyllithium. The polybutadiene (A) thus obtained contains about 40% 1,4-cis-units and 50% 1,4-trans-units.

[0036] In the case of the coordination chain polymerization, preferably Ziegler-Natta catalysts are used, in particular stereospecific Ziegler-Natta catalysts, which give polybutadienes (A) having a high proportion of 1,4-cis units.

[0037] During the polymerization of 1,3-butadiene, branched polybutadienes (A) may also be formed by side or subsequent reactions, for example subsequent reactions of the double bonds of the resulting 1,2- and 1,4-units of the polybutadiene. However, the polybutadienes (A) used according to the invention are preferably linear, i.e. unbranched, polybutadienes. It is also possible for the polybutadienes to have 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 the at least one polybutadiene (A), i.e. based on the total weight of all polybutadienes (A) used, is at least 80%, preferably at least 90%, in particular at least 99%.

[0038] For the process according to the invention, polybutadienes (A) are preferably used which have, based on the total of 1,2- and 1,4-units, 0% to 80% of 1,2-units and 20% to 100% of 1,4-units, more preferably 0% to 30% of 1,2-units and 70% to 100% of 1,4-units, even more preferably 0% to 10% of 1,2-units and 90% to 100% of 1,4-units, and most preferably 0% to 5% of 1,2-units and 95% to 100% of 1,4-units.

[0039] Therefore, of all the double bonds in the polybutadiene (A) used, it is preferred 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.

[0040] Accordingly, for the inventive preparation of said products, it is preferable to use a compound of formula (1) [ka] Polybutadienes (A) of the above formula are used with a content of 0% to 80% 1,2-vinyl double bonds (index x) and 20% to 100% 1,4-double bonds, more preferably 0% to 30% 1,2-vinyl double bonds and 70% to 100% 1,4-double bonds, even more preferably 0% to 10% 1,2-vinyl double bonds and 90% to 100% 1,4-double bonds, and most preferably 0% to 5% 1,2-vinyl double bonds and 95% to 100% 1,4-double bonds. The ratio of 1,4-trans-double bonds (index y) and 1,4-cis-double bonds (index z) is arbitrary.

[0041] The subscripts x, y and z then represent the number of said respective butadiene units in said polybutadiene (A), which are numerical averages (number averages) across all polybutadiene polymers of said at least one polybutadiene (A).

[0042] The polybutadiene (A) according to formula (1) used may have any average molecular weight and polydispersity.

[0043] The number average molecular weight M of the at least one polybutadiene (A) nis 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.

[0044] Optionally, the number average molecular weight M of the 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.

[0045] It is further preferable that the at least one polybutadiene (A) has, on a number 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.

[0046] Alternatively, the at least one polybutadiene (A) preferably has, on a number 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.

[0047] It is further preferred that the polybutadiene (A) used has a viscosity of 50 to 50000 mPas, more preferably 100 to 10000 mPas, most preferably 500 to 5000 mPas (determined in accordance with DIN EN ISO 3219:1994-10).

[0048] The polybutadiene most preferably used is the commercially available product Polyvest® from Evonik Industries AG / Evonik Operations GmbH, having the following typical property data: (登録商標) 110 and Polyvest (登録商標) 130 is: Polyvest (登録商標)110: 1,2-vinyl double bonds approx. 1%, 1,4-trans double bonds approx. 24%, 1,4-cis double bonds approx. 75%, number average molecular weight M n Approx. 2600 g / mol, viscosity (20°C) 700-860 mPas (according to DIN EN ISO 3219:1994-10), Polyvest (登録商標) 130: 1,2-vinyl double bonds approx. 1%, 1,4-trans-double bonds approx. 22%, 1,4-cis-double bonds approx. 77%, number average molecular weight M n Approximately 4600 g / mol, viscosity (20 °C) 2700-3300 mPas (according to DIN EN ISO 3219:1994-10).

[0049] The polybutadienes most preferably used are the products Lithene ultra AL and Lithene ActiV 50 available from Synthomer PLC, further having the following typical property data: Lithene ultra AL: 1,2-vinyl double bonds approx. 40%, 1,4-double bonds approx. 60% Lithene ActiV 50: Approximately 70% 1,2-vinyl double bonds, approximately 30% 1,4-double bonds.

[0050] The degree of epoxidation can be, for example, 13 It is quantitatively determined using C-NMR spectroscopy or epoxy value titration (determination of the epoxy equivalent in accordance with DIN EN ISO 3001:1999) and can be deliberately and reproducibly adjusted via the process conditions, in particular via the amount of hydrogen peroxide used relative to the double bonds in the charged amount of polybutadiene.

[0051] In step a) of the process according to the invention, more than 0% (ie from more than 0% to 100%) of all double bonds of said at least one polybutadiene (A) are epoxidized.

[0052] In step a) of the process according to the present invention, it is preferred that more than 0% to less than 100%, more preferably more than 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% of all double bonds of said at least one polybutadiene (A) are epoxidized.

[0053] As the epoxidizing reagent (B), in principle any epoxidizing agent known to the skilled artisan can be used. The epoxidizing reagent (B) is selected from the group of peroxycarboxylic acids (percarboxylic acid, peracid), preferably from the group consisting of meta-chloroperbenzoic acid, peroxyacetic acid (peracetic acid) and peroxyformic acid (performic acid), and is particularly preferably peroxyformic acid (performic acid). The peroxycarboxylic acid is preferably formed in situ from the corresponding carboxylic acid and hydrogen peroxide.

[0054] Most preferably, said at least one epoxidation reagent (B) comprises performic acid, said performic acid being preferably formed in situ from formic acid and hydrogen peroxide.

[0055] The epoxidation of the at least one polybutadiene (A) is carried out statistically distributed over the polybutadiene chain, preferably at the 1,4-double bonds. The epoxidation of the 1,2-double bonds can be carried out in the same way and is carried out at these double bonds in the same way, statistically distributed over the polybutadiene chain. However, the epoxidation of the 1,2-double bonds is disadvantageous compared to the epoxidation of the 1,4-double bonds. The reaction products therefore contain epoxy-functional polybutadiene polymers with different degrees of epoxidation. All degrees of epoxidation stated are therefore to be understood as average values.

[0056] Step b) In step b) of the process according to the invention, said 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).

[0057] During this reaction, the addition (addition reaction) of the at least one amino-functional compound (D) to the at least one epoxy-functional polybutadiene (C) is carried out. Thus, the reaction is carried out while forming one or more covalent bonds between the at least one amino-functional compound (D) and the at least one epoxy-functional polybutadiene (C). The reaction preferably includes (at least idealized) a reaction step in which the nucleophilic attack of the at least one amino group of the at least one amino-functional compound (D) on the at least one epoxy group of the at least one epoxy-functional polybutadiene (C) is carried out while ring-opening the at least one epoxy group.

[0058] 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. Within the scope of the present invention, these amino-functional compounds (D) also include ammonia. However, it is more 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 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 at least one primary amino group and / or at least one secondary amino group. It is further preferred that the amino functional compound (D) has exactly one primary or secondary amino group, thereby reducing or preventing undesired crosslinking reactions. It is further preferred that the amino functional compound (D) is not an aromatic amine, especially not a primary aromatic amine, because some primary aromatic amines are known human carcinogens. Aromatic amines are understood within the scope of the present invention as amines in which the nitrogen atom of at least one amino group is bound to a carbon atom, which is also part of an aromatic ring system.

[0059] It is further preferred that said at least one amino-functional compound (D) is selected from the group consisting of ammonia, alkylamines, cycloalkylamines, dialkylamines, monoalkanolamines and dialkanolamines. The aliphatic residue attached to the nitrogen can also have an aromatic residue or a heteroatom, such as nitrogen or oxygen. It is therefore equally preferred that said at least one amino-functional compound (D) is selected from the group consisting of diamines, polyamines, polyetheramines and hydroxy-functional aliphatic amines. More preferably, said 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 exactly one primary or secondary amino group. Even more preferably, said at least one amino-functional compound (D) is selected from the group consisting of alkylamines, monoalkanolamines, dialkanolamines and trialkanolamines, each having 1 to 12 carbon atoms and exactly one primary or secondary amino group. Most preferably, said 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. In this case, any mixture of these amines can also be used.The term "trialkanolamine" is understood within the scope of the present invention to mean only trialkanolamines which carry primary and / or secondary amino groups, such as tris(hydroxymethyl)aminomethane.

[0060] The molar ratio of 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 within wide limits. However, it is preferred to use the at least one amino-functional compound (D) and the at least one epoxy-functional polybutadiene (C) in a molar ratio of NH groups to epoxy groups such that a conversion as quantitative 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) to the total number of epoxy groups of all epoxy-functional polybutadienes (C) is 0.8:1 to 20:1, more preferably 0.9:1 to 10:1, even more preferably 1:1 to 5:1, most preferably 1:1 to 3:1. Excess compound (D) can be removed after the reaction, for example by distillation, and can be reused if necessary. In this connection it should be noted that the ammonia molecule has exactly three, one primary amino group, exactly two and one secondary amino group, and exactly one NH group.

[0061] The epoxide ring opening with an amine can optionally be carried out in a solvent such as ethanol, propanol, isopropanol or THF. Preferably, the solvent is omitted.

[0062] Preferably, 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.

[0063] 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 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.

[0064] The type and amount of the catalyst used are selected so as to obtain the most rapid and quantitative addition possible of the at least one amino-functional compound (D) to the epoxy groups of the at least one epoxy-functional polybutadiene (C).Preferably, lithium bromide is used as a solid or dissolved in water in a mass proportion of 0.05% to 15.0%, preferably 0.2% to 10.0%, most preferably 0.5% to 7.0%, based on the mass of the at least one amino-functional compound (D).

[0065] The reaction of said at least one epoxy-functional polybutadiene (C) with said at least one amino-functional compound (D), optionally in the presence of a catalyst, is preferably carried out at a temperature between 50°C and 250°C, more preferably between 80°C and 200°C.

[0066] The components are stirred for several hours until the epoxy groups are converted as completely as possible. Analysis of the epoxy groups can optionally be carried out by NMR spectroscopy or by known methods of epoxy value titration (as described in the examples).

[0067] The reaction conditions in step b) are preferably selected such that more than 90% of the epoxy groups formed in step a) are converted with ring opening. Most preferably, no epoxy groups can be detected anymore in the product of step b), i.e. in said at least one hydroxy- and amino-functional polybutadiene (E).

[0068] After the reaction, any excess amino-functional compound (D) and optionally the solvent, water and the catalyst are removed, preferably by distillation, and the precipitated salts are filtered off if necessary.

[0069] From each one of the epoxy groups of the epoxy-functional polybutadiene (C), after ring opening with an amino-functional compound (D) of formula A1-NH-A2, a compound of formula (2a), (2b) or (2c): [ka] This results in a repeating unit of

[0070] In formulae (2a), (2b) and (2c), the residues A1 and A2 are preferably each independently of the other an organic residue which may bear further amine or hydroxyl groups, or a hydrogen radical. Thus, the residues A1 and A2 may bear heteroatoms, such as nitrogen and oxygen, and may be bridged to each other via an organic residue, for example in the case of morpholine or piperidine. The amino functional compound (D) of formula A1-NH-A2 may be ammonia. In the case of ammonia, both A1 and A2 are hydrogen radicals. If, for example, ethanolamine is used as the amino functional compound (D), then in formulae (2a), (2b) and (2c), the residue A1 is, for example, a hydroxyethyl residue, and the residue A2 is then a hydrogen radical, i.e. A2=H. At least one pendant OH group is generated from each epoxy group reacted.

[0071] 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 be added to another epoxy group in a subsequent reaction via said NH group, and thus two epoxy-functional polybutadienes (C) can be bonded to each other. The reaction conditions in step b) are preferably selected such that this bonding reaction is largely suppressed.

[0072] In the case of polybutadienes (A) having a predominant proportion of 1,4-units, which are preferred according to the invention, among the repeating units of the formulae (2a), (2b) and (2c), the repeating units of the formula (2a) predominate.

[0073] It is preferred that said at least one hydroxy-functional and amino-functional polybutadiene (E) has 20% to 100%, more preferably 70% to 100%, even more preferably 90% to 100%, and most preferably 95% to 100% of repeating units of formula (2a), based on the total number of all repeating units of formulae (2a), (2b) and (2c).

[0074] The percentage of repeat units of formulae (2a), (2b) and (2c) taken together is greater than 0% (i.e., greater than 0% to 100%), based on the total number of all repeat units of said at least one hydroxy-functional and amino-functional polybutadiene (E).

[0075] Accordingly, the degree of amination is greater than 0% (ie, greater than 0% to 100%).

[0076] It is preferred that the combined proportion of the repeat units of formulae (2a), (2b) and (2c) is from more than 0% to less than 100%, more preferably from more than 0% to 70%, even more preferably from 1% to 50%, even more preferably from 2% to 40%, even more preferably from 3% to 30% and most preferably from 4% to 20%, based on the total number of all repeat units of said at least one hydroxy-functional and amino-functional polybutadiene (E).

[0077] Accordingly, it is preferable that the degree of amination is more than 0% to less than 100%, more preferably more than 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%.

[0078] When fully converted in step b), the degree of amination of said hydroxy- and amino-functional polybutadiene (E) corresponds to the degree of epoxidation of the corresponding epoxy-functional polybutadiene (C).

[0079] Process c) In step c) of the process according to the invention, said 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).

[0080] At least one hydroxy- and amino-functional polybutadiene (E) from step b) is used in step c) as a starting compound (initiator) to react with said at least one epoxy-functional compound (F). While ring-opening and preferably in the presence of a suitable catalyst, said at least one epoxy-functional compound (F) (hereinafter also simply referred to as "monomer" or "epoxy monomer" or "epoxide") is added to the NH and / or OH groups of said at least one hydroxy- and amino-functional polybutadiene (E) in a polyaddition reaction. This results in the formation of an amino-functional polybutadiene with (pendant) polyether chains in comb position, i.e., said at least one polyether-modified amino-functional polybutadiene (G). Preferably, said monomer is added to (at least essentially) all OH groups and (at least essentially) all NH groups. Preferably, said polyether-modified amino-functional polybutadiene (G) is a linear polybutadiene modified at the comb positions (pendant) with polyether residues, so that said polyether-modified amino-functional polybutadiene (G) preferably has a linear polybutadiene backbone and pendant polyether residues.

[0081] The reaction in step c) is preferably an alkoxylation reaction, i.e. the polyaddition of an alkylene oxide to said at least one hydroxy- and amino-functional polybutadiene (E). However, the reaction in step c) can also be carried out with a glycidyl compound instead of or in addition to said alkylene oxide.

[0082] Thus, the at least one epoxy-functional compound used in said 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 said 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 ethers and C 13 / C 15 - fatty alcohol glycidyl ethers.

[0083] The monomers can alternatively be added individually pure, one after the other in any dosage order, or else simultaneously in admixture, so that the sequence of the monomer units in the resulting polyether chain follows a block-like or statistical or gradient distribution in the final product.

[0084] By the process according to the invention, pendant polyether chains are constructed on the polybutadiene, which are distinguished by the fact that they can be produced in a targeted and reproducible manner with regard to structure and molecular weight.

[0085] The order of the monomer units can be varied within wide limits depending on the order of addition.

[0086] The molecular weight of the pendant polyether residues can be varied within wide limits by the process according to the invention and can be controlled purposefully and reproducibly through the molar ratio of the added monomers with respect to the NH and OH groups of the at least one hydroxy- and amino-functional polybutadiene (E) charged from step b).

[0087] The polyether-modified amino-functional polybutadienes (G) produced according to the present invention preferably have the formulae (3a), (3b) and (3c): [ka] and containing a residue B attached to the polybutadiene backbone via an amino group and / or an ether group according to the formula:

[0088] Residues A1 and A2 are each independently an organic residue, preferably having 1 to 22 carbon atoms, most preferably having 1 to 12 carbon atoms, whereby said residues A1 and A2 may be covalently bonded to each other, said residues A1 and A2 may then contain heteroatoms, preferably nitrogen and oxygen.

[0089] 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, most preferably between 0 and 4. Furthermore, the subscripts l1 and l2 in formula (3a), (3b) or (3c) are integers and each, independently of one another, are either 0 or 1. Thus, the residue B resulting from alkoxylation may be present k1 or k2 times bonded to said residue A1 or A2, where this chemical bond is made via a nitrogen atom or via an oxygen atom which is part of A1 and A2. However, the residue B resulting from alkoxylation may also be present bonded directly to the indicated nitrogen atom. If the residue A1 or A2 in formula (2a), (2b) or (2c) is a hydrogen radical, then the subscript l1 or l2 in formula (3a), (3b) or (3c) is equal to 0 and k1 or k2 is equal to 1, i.e. the corresponding residue A1 or A2 is absent in formula (3a), (3b) and (3c), so that the polyether residue B is directly bonded to the indicated nitrogen atom. Thus, the NH group in formula (2a), (2b) or (2c) is replaced by an NB group. If the residue A1 or A2 in formula (2a), (2b) or (2c) is an organic residue, then the subscript l1 or l2 in formula (3a), (3b) or (3c) is equal to 1. When both A1 and A2 in formula (2a), (2b) or (2c) are hydrogen radicals, then in formula (3a), (3b) or (3c) the subscripts l1 and l2 are equal to 0 and k1 and k2 are equal to 1, i.e., the residues A1 and A2 in formula (3a), (3b) or (3c) are absent and the polyether residue B is directly bonded to the indicated nitrogen atom. Thus, both NH groups in formula (2a), (2b) or (2c) are replaced by NB groups, respectively.

[0090] For example, if a primary alkylamine is used as amino-functional compound (D) in step b) and said alkyl residue does not have further groups reactive towards epoxides, such as OH or NH groups, then for example l1=1, k1=0, l2=0 and k2=1.

[0091] For example, when the primary amine ethanolamine is used as amino-functional compound (D) in step b), A1 is, for example, a divalent residue of formula -CH2CH2O-, which is linked to the nitrogen atom of the amino group via the carbon atom on the left side of the scheme and to residue B via the oxygen atom on the right side, i.e., for example, l1=1, k1=1, l2=0 and k2=1.

[0092] 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 residue of the formula -C(CHO-) which is bonded to the nitrogen atom of the amino group on the left side via the carbon atom and to one residue B (and thus to all three residues B) on the right side via the three oxygen atoms, i.e., for example, l=1, k=3, l=0 and k=1.

[0093] For example, when the secondary amine diethanolamine is used as amino-functional compound (D) in step b), A1 and A2 are, for example, divalent residues of formula -CH2CH2O-, which are linked on the left side in this scheme to the nitrogen atom of the amino group via the carbon atom and on the right side to residue B via the oxygen atom, i.e. l1=1, k1=1, l2=1 and k2=1.

[0094] 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 residue of the formula -CH2CH2O-, which is bonded to the nitrogen atom of the amino group via the carbon atom on the left side of the scheme and to the residue B via the oxygen atom on the right side, i.e. l1=1, k1=0, l2=1 and k2=1.

[0095] For example, when the 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 residue -CH2CH2CH2CH2CH2-, both the left and right sides of which are bonded to the nitrogen atom of the amino group, i.e. l1=1, k1=0, l2=1 and k2=0.

[0096] Thus, preferably, during the alkoxylation reaction, each (at least approximately) pendant OH and NH group of the at least one hydroxy- and amino-functional polybutadiene (E) gives rise to exactly one pendant residue B. The residue B is also composed of one or more monomers, preferably several monomers, of the at least one epoxy-functional compound (F) used. It is possible, but less preferred, that during the alkoxylation reaction, each OH or NH group of the hydroxy- and amino-functional polybutadiene (E) does not give rise to pendant residue B, but rather that only a portion, but preferably the majority, of the OH and NH groups are reacted in step c).

[0097] In the sense of the present invention, any alkoxylation catalyst known to those skilled in the art can be used in principle, such as basic catalysts, such as alkali hydroxides, alkali metal alcoholates, amines, guanidines, amidines, phosphorus compounds, such as triphenylphosphine, as well as Bronsted acidic and Lewis acidic catalysts, such as SnCl4, SnCl2, SnF2, BF3 and BF3 complexes, and double metal cyanide (DMC) catalysts. The addition of catalysts can be omitted if desired.

[0098] Before the epoxide feed, i.e. before the addition of the at least one epoxy-functional compound (F) used, the reactor partially filled with the initiator and optionally the catalyst is inerted, for example with nitrogen. This is done, for example, by repeated alternating evacuation and nitrogen feeding. It is advantageous to evacuate the reactor to less than 200 mbar after the final injection of nitrogen. The addition of the first amount of epoxy monomer is therefore preferably carried out in the evacuated reactor. The metering of the monomer is carried out with stirring and optionally with cooling to remove the released reaction heat and maintain a preselected reaction temperature. As initiator, the at least one hydroxy- and amino-functional polybutadiene (E) described above is used, or, as further described below, a polyether-modified amino-functional polybutadiene (G) already prepared according to the method according to the invention can also be used as initiator.

[0099] In a particular embodiment, the addition of catalyst can be omitted at the beginning of the monomer addition.This is the case, for example, when the amino group attached to the polybutadiene is sufficiently reactive.When there are, for example, a sufficiently large number of nucleophilic NH functional groups on the polybutadiene, the initiator itself catalyzes the alkoxylation reaction.The reaction rate usually decreases with the polyether chain length.To achieve higher molecular weight polyether residue B, it may be necessary or beneficial to add one of the catalysts to the alkoxylation reaction at a later time point.

[0100] DMC catalysis Preferably, zinc / cobalt DMC catalysts are used, especially those containing zinc hexacyanocobaltate(III).Preferably, DMC catalysts described in US 5,158,922, US 2003 / 0119663, WO 01 / 80994 are used.The catalysts can be amorphous or crystalline.

[0101] The catalyst concentration is preferably from more than 0 ppm to 1000 ppm by mass, more preferably from more than 0 ppm to 700 ppm by mass, and most preferably from more than 10 ppm to 500 ppm by mass, based on the total mass of the product produced.

[0102] Preferably, the catalyst is dosed into the reactor only once. The reactor should preferably be clean, dry and free of basic impurities that may inhibit the DMC catalyst. The amount of catalyst should preferably be adjusted so that the process is provided with sufficient catalytic activity. The catalyst can be dosed as a solid or in the form of a catalyst suspension. When a suspension is used, the initiator is particularly suitable as a suspending agent.

[0103] To initiate the DMC catalysis, it may be advantageous to first activate the catalyst with a portion of the at least one epoxy-functional compound (F), preferably selected from the group of alkylene oxides, in particular propylene oxide and / or ethylene oxide. After the alkoxylation reaction has commenced, continuous monomer addition can be started.

[0104] The reaction temperature in the case of the DMC catalytic reaction in step c) is preferably 60°C to 200°C, more preferably 90°C to 160°C and most preferably 100°C to 140°C.

[0105] The internal pressure of the reactor in 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).

[0106] Most preferably, the DMC catalysis in step c) is carried out at a temperature between 100° C. and 140° C. and a pressure between 0.1 bar and 10 bar.

[0107] The reaction can be carried out in a suitable solvent, for example to reduce the viscosity. The end of the epoxide addition is preferably followed by a post-reaction to complete the reaction. The post-reaction can be carried out, for example, by further reaction under reaction conditions (i.e., for example, maintaining the temperature) without adding starting materials. The DMC catalyst usually remains in the reaction mixture.

[0108] Unreacted epoxide and possibly further volatile components can be removed after the reaction has taken place by vacuum distillation, steam or gas stripping or other deodorizing methods. The finished product is finally filtered below 100° C. to remove any cloudy material that may be present.

[0109] Base catalysis Instead of the DMC catalyst, a basic catalyst can also be used in step c). Particularly suitable are alkali metal alcoholates, such as sodium and potassium methoxide, which are added as solids or in the form of their methanolic solutions.Furthermore, any alkali hydroxide can be used, especially sodium hydroxide and / or potassium hydroxide, and not only as solids, but also, for example, as aqueous or alcoholic solutions.Furthermore, according to the invention, basic nitrogen compounds can also be used, preferably amines, guanidines and amidines, most preferably tertiary amines, such as trimethylamine and triethylamine.

[0110] The basic catalyst is preferably used at a concentration of more than 0 mol % to 100 mol %, more preferably more than 0 mol % to 50 mol %, and most preferably 3 mol % to 40 mol %, based on the total of OH groups and NH groups of the initiator.

[0111] 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.

[0112] The internal pressure of the reactor in case of the base catalysis 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).

[0113] Most preferably, the base catalysis in step c) is carried out at a temperature between 100° C. and 160° C. and a pressure between 1 bar and 10 bar.

[0114] The reaction can be carried out in a suitable solvent if desired.After the end of the epoxide addition, a post-reaction is preferably carried out to complete the reaction.The post-reaction can be carried out, for example, by further reaction under reaction conditions without adding starting material.Unreacted epoxide and possibly further volatile components can be removed after the reaction is carried out by vacuum distillation, steam stripping or gas stripping or other deodorization methods.Volatile catalysts, such as volatile amines, are then removed.

[0115] To neutralize the basic crude product, an acid, such as phosphoric acid or sulfuric acid, or a carboxylic acid, such as acetic acid and lactic acid, is added. Preference is given to the use of aqueous phosphoric acid and aqueous lactic acid. The amount of each acid used depends on the amount of basic catalyst previously used. The basic polybutadiene with pendant polyether residues is stirred in the presence of the acid, preferably at 40°C to 95°C, and subsequently distilled to dryness in a vacuum distillation below 100 mbar and 80°C to 130°C. The neutralized product is finally filtered, preferably below 100°C, to remove precipitated salts.

[0116] It is preferred that the final product according to the invention has a moisture content (expressed as a percentage by weight based on the total weight of the final product) of less than 0.2% and an acid number of less than 0.5 mg KOH / g and is virtually free of phosphates.

[0117] Initiator product It is not always possible to achieve the desired molecular weight of the final product in only one reaction step, especially in the alkoxylation step. In particular, if long polyether side chains are intended and / or the initiator from step b), i.e. the at least one hydroxy- and amino-functional polybutadiene (E), has a high functionality of OH and NH groups, a large amount of epoxy monomer must be added. This is sometimes not allowed by the reactor geometry. The polyether-modified amino-functional polybutadienes (G) from step c) produced according to the invention have one OH group at the end of each of their pendant polyether residues and are therefore also suitable as initiators for the synthesis of higher molecular weight subsequent products. They are precursors and starting compounds for the synthesis of polybutadienes with longer polyether residues in the sense of the present invention. The reaction of the at least one epoxy-functional compound (F) can be carried out in step c), i.e. in several substeps.

[0118] The product produced with DMC catalysis according to step c) can optionally be further alkoxylated according to the invention by new addition of epoxy monomers, either with DMC catalysis or using one of the abovementioned basic or acidic catalysts. Optionally, further DMC catalyst can be added, for example to increase the reaction rate during chain extension.

[0119] Similarly, the base-catalyzed product from step c) can be selectively alkoxylated to higher molecular weights by basic, acidic or DMC catalysis. If in step c) the basic precursor is to be further reacted with monomers under base catalysis, the neutralization is advantageously omitted. Optionally, additional basic catalyst can be added, for example to increase the reaction rate during chain extension.

[0120] Optional step d) In an optional further step d), the at least one polyether-modified amino-functional polybutadiene (G) is reacted with at least one end-capping reagent (H) to obtain at least one polyether-modified amino-functional polybutadiene (K) containing end-capped polyether residues. In this case, the terminal hydroxyl-containing residues B of the polyether-modified polybutadiene (G) are further converted at the ends into ester, ether, urethane and / or carbonate groups. End-capping of the polyethers is known to those skilled in the art, for example, esterification with carboxylic acids or carboxylic anhydrides, acetylation, especially with acetic anhydride, etherification with halogenated hydrocarbons, methylation, especially with methyl chloride according to the principle of Williamson ether synthesis, urethanization by reaction of the OH groups with isocyanates, especially monoisocyanates, such as stearyl isocyanate, and carbonation by reaction with dimethyl carbonate and diethyl carbonate.

[0121] Optional step e) In optional step e), the at least one polyether-modified amino-functional polybutadiene (G) or (K) is lightened in terms of color. If optional step e) follows optional step d), then the at least one polyether-modified amino-functional polybutadiene (K) containing end-capped polyether residues is lightened in terms of color. If optional step d) is omitted, on the other hand, optional step e) follows step c) of the method according to the invention and the at least one polyether-modified amino-functional polybutadiene (G) is lightened in terms of color. The lightening can be carried out, for example, by the addition of activated carbon, preferably in a suitable solvent, or by treatment with hydrogen peroxide.

[0122] Optional step f) In optional step f), at least a portion of the amino groups of said at least one polyether modified amino-functional polybutadiene (G) or (K) is reacted with an acid or a quaternizing agent, such as alkyl and benzyl halides, dimethyl sulfate or chloroacetic acid or sodium chloroacetate, to obtain quaternary ammonium groups. Step f) can alternatively be carried out after step c) or after any of said steps d) or after any of said steps e). After said quaternization, the product can be dissolved or dispersed, for example, in water or an organic solvent.

[0123] Reactor As the reactor for the process according to the invention, any suitable type of reactor can be used in principle, which can control the reactions and their possibly present heat content.The reaction operation can be carried out continuously, semi-continuously or batchwise in a manner known from process engineering, and can be flexibly adapted to existing production technology equipment.In addition to conventional stirred tank reactors, jet loop reactors with gas phase and internal heat exchange tubes, as described in WO 01 / 062826, can also be used.Furthermore, loop reactors without gas phase can also be used.

[0124] Polyether modified amino-functional polybutadiene The subject of the invention is furthermore amino-functional polybutadienes modified with polyether residues at the comb positions (pendant, lateral), as can be prepared by the process according to the invention. A further subject of the present invention is therefore the polyether-modified amino-functional polybutadienes (G) or (K) obtainable by the process according to the invention.

[0125] Preferably, said polyether modified amino-functional polybutadiene (G) or (K) is a linear polybutadiene modified with polyether residues at the comb positions (pendant, lateral), so it is preferred that said polyether modified amino-functional polybutadiene (G) or (K) has a linear polybutadiene backbone and pendant polyether residues.

[0126] A further subject of the present invention are likewise polyether-modified amino-functional polybutadienes (G) or (K), which are preferably obtainable by the process according to the invention, and which contain the divalent residue [ka] and wherein the repeat unit is selected from the group consisting of: Where: A1 and A2 are each independently an organic residue, preferably having 1 to 22 carbon atoms, most preferably having 1 to 12 carbon atoms, wherein said residues A1 and A2 may be covalently bonded to each other; B is, independently of each other, a residue of formula (4a), [ka] Preferably, each independently of the others, is a residue of formula (4b): [ka] Most preferably, each independently of the others, is a residue of formula (4c): [ka] R 1 are each independently a monovalent hydrocarbon residue having 1 to 16 carbon atoms, Preferably, each independently of the other, is an alkyl residue having 1 to 16 carbon atoms or a phenyl residue, Most preferably, each independently of the others is a methyl, ethyl or phenyl residue, R 2 is the formula -CH2-OR 3 is a residue of R 3 are each independently a monovalent hydrocarbon residue having 3 to 18 carbon atoms, Preferably, each independently of the others is a phenyl residue which may be substituted by a monovalent residue selected from an allyl residue, a butyl residue, an alkyl residue having 8 to 15 carbon atoms, or a hydrocarbon residue having 1 to 4 carbon atoms, Most preferably, it is a tert-butylphenyl residue or an o-cresyl residue. R 4 are each independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogen, preferably hydrogen, and k1 and k2 each independently represent an integer of 0 to 8, preferably 0 to 6, and most preferably 0 to 4; l1 and l2 are integers and each independently is either 0 or 1; m, n, o, p and q are each independently 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 sum of all repeat units (U), (V) and (W) divided by the sum of all repeat units (U), (V), (W), (X), (Y) and (Z) is greater than 0%; and all permutations of said repeating units (U), (V), (W), (X), (Y) and (Z) and said repeating units in said residue B are included together.

[0127] residue R 1 , R 2 , R 3 and R 4 may here, independently of one another, be linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted.

[0128] General notation [ka] [where R=R in formula (4a) 1 or R 2 or in formulae (4b) and (4c) where R=CH3, [ka] Units and formulas [ka] but preferably represents a unit of the formula [ka] The general notation in formula (4a) [ka] In that case, the formula [ka] Units and formulas [ka] but preferably represents a unit of the formula [ka] Represents the unit of .

[0129] The residue R 4 each independently represents a monovalent hydrocarbon residue having 1 to 18 carbon atoms, an acyl residue -C(=O)R 5 , urethane residue -C(=O)NH-R 6 , carbonate residue -C(=O)OR 7 and hydrogen, more preferably R 4 are each independently an alkyl residue having 1 to 18 carbon atoms, an alkylene residue having 1 to 18 carbon atoms, or an acyl residue -C(=O)R 5 , urethane residue -C(=O)NH-R 6 , carbonate residue -C(=O)OR 7 and hydrogen, most preferably R 4 is hydrogen, where the nomenclature "hydrogen" is intended to represent hydrogen residue / radical.

[0130] R 5 are each independently an alkyl or alkenyl residue having 1 to 18 carbon atoms, preferably having 1 to 10 carbon atoms, most preferably a methyl residue.

[0131] R 6are each independently an alkyl or aryl residue having 1 to 18 carbon atoms, preferably 6 to 18 carbon atoms.

[0132] R 7 are each independently an alkyl residue having 1 to 18 carbon atoms, preferably 1 to 2 carbon atoms.

[0133] According to the present invention, the sum (total number) of all repeating units (U), (V) and (W) divided by the sum (total number) of all repeating units (U), (V), (W), (X), (Y) and (Z) of said at least one polyether-modified amino-functional polybutadiene (G) or (K) is greater than 0%, i.e., greater than 0% to 100%.

[0134] Conversely, this means that the sum (total number) of all repeating units (X), (Y) and (Z) divided by the sum (total number) of all repeating units (U), (V), (W), (X), (Y) and (Z) of the at least one polyether-modified amino-functional polybutadiene (G) or (K) is less than 100% (i.e., less than 100% to 0%).

[0135] This means that more than 0% (i.e., from more than 0% to 100%) of the total of the repeating units (U), (V), (W), (X), (Y) and (Z) are polyether modified.

[0136] This further means that less than 100% (i.e., less than 100% to 0%) of the total of the repeating units (U), (V), (W), (X), (Y) and (Z) are not polyether modified.

[0137] This further means that said polyether modified amino-functional polybutadiene (G) or (K) comprises at least one repeat unit selected from the group consisting of (U), (V) and (W).

[0138] In this case, the sum (total number) of all repeating units (U), (V), and (W) divided by the sum (total number) of all repeating units (U), (V), (W), (X), (Y), and (Z) of the at least one polyether-modified amino-functional polybutadiene (G) or (K) is preferably more than 0% to less than 100%, more preferably more than 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%.

[0139] This means that preferably more than 0% to less than 100%, even more preferably more than 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% of the total of the repeating units (U), (V), (W), (X), (Y) and (Z) are polyether modified.

[0140] In this case, it is further preferred that the sum (total number) of all repeating units (X), (Y) and (Z) divided by the sum (total number) of all repeating units (U), (V), (W), (X), (Y) and (Z) of the at least one polyether-modified amino-functional polybutadiene (G) or (K) is less than 100% to more than 0%, more preferably less than 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%.

[0141] This means that preferably less than 100% to more than 0%, more preferably less than 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 repeating units (U), (V), (W), (X), (Y) and (Z) are not polyether-modified.

[0142] It is preferred that the combined weight percentage of all repeating units (U), (V), (W), (X), (Y) and (Z) is at least 80%, more preferably at least 90%, even more preferably at least 99%, and most preferably 100%, based on the total weight of said polyether-modified amino-functional polybutadiene (G) or (K).

[0143] It is preferred that said polyether modified amino-functional polybutadiene (G) or (K) consists essentially or completely of said repeat units (U), (V), (W), (X), (Y) and (Z).

[0144] The polyether-modified amino-functional polybutadiene (G) or (K) is preferably a polybutadiene with pendant polyether moieties of formula (5): [ka] Here, the proportion of the polyether-modified repeating unit described in formula (5) is greater than 0% (i.e., greater than 0% to 100%), more preferably greater than 0% to less than 100%, even more preferably greater than 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 of all repeating units described in formula (5), and said proportion is calculated by [(d+e+f) / (a+b+c+d+e+f)]×100%.

[0145] This means that the proportion of the non-polyether-modified repeating units described in formula (5) is less than 100% (i.e., less than 100% to 0%), preferably less than 100% to more than 0%, more preferably less than 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%, based on the total of all repeating units described in formula (5), and said proportion is calculated by [(a+b+c) / (a+b+c+d+e+f)]×100%.

[0146] The repeating units with the subscripts a, b, c, d, e and f are optional and are statistically distributed throughout the polybutadiene chain, therefore all the subscript values ​​given should be understood as average values.

[0147] It is preferred that the combined weight percentage of all repeat units having the subscripts a, b, c, d, e and f is at least 80%, more preferably at least 90%, even more preferably at least 99%, and most preferably 100%, based on the total weight of said polyether-modified amino-functional polybutadiene (G) or (K).

[0148] It is preferred that said polyether modified amino-functional polybutadiene (G) or (K) consists essentially or entirely of repeat units having the subscripts a, b, c, d, e and f.

[0149] It is further preferred that the polyether-modified amino-functional polybutadiene (G) or (K) is characterized in that 0% to 80%, more preferably 0% to 30%, even more preferably 0% to 10% and most preferably 0% to 5% of the double bonds contained therein are 1,2-vinyl double bonds, and 20% to 100%, more preferably 70% to 100%, even more preferably 90% to 100% and most preferably 95% to 100% of the double bonds contained therein are 1,4-double bonds.

[0150] Therefore, preferably, in the sense of the present invention, the compound of formula (5) has a content of 0% to 80% of 1,2-vinyl double bonds (suffix a) and 20% to 100% of 1,4-double bonds (suffix b and c) based on the total number of repeating units containing said double bonds (sum of a+b+c), more preferably 0% to 30% of 1,2-vinyl double bonds and 70% to 100% of 1,4-double bonds, even more preferably 0% to 10% of 1,2-vinyl double bonds and 90% to 100% of 1,4-double bonds, and most preferably 0% to 5% of 1,2-vinyl double bonds and 95% to 100% of 1,4-double bonds. The ratio of 1,4-trans-double bonds (suffix b) and 1,4-cis-double bonds (suffix c) is arbitrary.

[0151] Most preferably, the compound of formula (5) has a content of repeat units having the subscript d of greater than 95%, based on the sum of said repeat units d+e+f. The repeat units e and f may be in any ratio to each other.

[0152] The number average molecular weight M of the polybutadiene portion of the polyether-modified amino-functional polybutadiene (G) or (K) n , weight average molecular weight M w and polydispersity are optional. The polybutadiene portion is then understood to be a portion of the polyether-modified amino-functional polybutadiene (G) or (K) derived from the polybutadiene (A) used by the present method. In formula (5), the polybutadiene portion of the polyether-modified amino-functional polybutadiene (G) or (K) is obtained by cleaving the residue [B] from the polyether-modified amino-functional polybutadiene (G) or (K). k1 (A1) l1 -N-(A2) l2 -[B] k2 and BO are to be understood as the portion of said polymer obtained by excluding them. Accordingly, this also applies to the above-mentioned polyether-modified amino-functional polybutadienes (G) or (K) comprising repeating units selected from the group consisting of the above-mentioned divalent repeating units (U), (V), (W), (X), (Y) and (Z).

[0153] The number average molecular weight M of the polybutadiene portion of the polyether-modified polybutadiene (G) or (K) 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.

[0154] Optionally, the number average molecular weight M of the polybutadiene portion of the polyether-modified polybutadiene (G) or (K) 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.

[0155] The number average molecular weight M of the polybutadiene portion n In this case, the number average molecular weight M of the parent polybutadiene (A) is n It is defined as:

[0156] It is further preferred that the polyether modified amino-functional polybutadiene (G) or (K) has a number average of 5 to 360, preferably 10 to 180, and most preferably 15 to 90 repeat units, wherein the repeat units are selected from the group consisting of (U), (V), (W), (X), (Y) and (Z).

[0157] Alternatively, the polyether modified amino-functional polybutadiene (G) or (K) has a number average of 35 to 360, preferably 40 to 180, most preferably 45 to 90 repeat units, wherein the repeat units are selected from the group consisting of (U), (V), (W), (X), (Y) and (Z).

[0158] Most preferably, the polybutadiene (A) is Polyvest® from Evonik Industries AG / Evonik Operations GmbH. (登録商標) 110 and Polyvest(登録商標) 130 and polyether modified amino-functional polybutadienes (G) or (K) derived from Lithene ultra AL and Lithene ActiV 50 from Synthomer PLC.

[0159] The molecular weight and polydispersity of the residue B are arbitrary. However, the average molecular weight of the residue B is preferably 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 residue B can be calculated based on the weighted amount of the monomers used and the number of OH groups and NH groups of the hydroxy-functional and amino-functional polybutadiene (E) used. Thus, for example, when 40 g of ethylene oxide is used and the total amount of all OH groups and NH groups of the hydroxy-functional and amino-functional polybutadiene (E) used is 0.05 mol, the average molecular weight of the residue B is 800 g / mol.

[0160] The polyether modified amino-functional polybutadienes (G) or (K) are liquid, pasty or solid, depending on the composition and molecular weight.

[0161] The number average molecular weight (M 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.

[0162] Their polydispersity (M w / M nThe polydispersity of the at least one polyether-modified polybutadiene (G) or (K) is preferably 1.5-10, more preferably 2-8, and most preferably 3-5.

[0163] In the examples described below, the present invention is described by way of example, but the present invention is not limited to the embodiments given in the examples, and the scope of the present invention can be obtained from the entire specification and the claims. EXAMPLES

[0164] Common methods: Gel Permeation Chromatography (GPC): The polydispersity (M w / M n ), weight average molecular weight (M w ) and number average molecular weight (M n The GPC measurements for determining the polydispersity (M) of the polybutadiene (A) were carried out under the following measurement conditions: column combination SDV 1000 / 10000 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 ) can be carried out in a similar manner.

[0165] The polydispersity (M w / M n ), weight average molecular weight (M w ) and number average molecular weight (M nThe GPC measurements to determine the polydispersity (M) of the end-capped polyether modified amino-functional polybutadiene (K) were carried out 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 ) can be carried out in a similar manner.

[0166] Determination of the content of 1,4-cis-, 1,4-trans- and 1,2-units in polybutadiene: The content of 1,4-cis-, 1,4-trans- and 1,2-units is determined by: 1 This can be done using H-NMR spectroscopy, which methods are well known to those skilled in the art.

[0167] Determination of the content of epoxy groups in the epoxy-functional polybutadiene (C) (epoxy content, degree of epoxidation): Determination of the epoxy group content, 13 C-NMR spectroscopy was used. A Bruker Avance 400 NMR spectrometer was used. The samples were dissolved in deuterated chloroform for this purpose. The epoxy content is defined as the proportion of epoxidized butadiene units in mol %, based on the totality of all repeat units contained in the sample. It corresponds to the number of epoxy groups of the epoxy-functional polybutadiene (C) divided by the number of double bonds of the polybutadiene (A) used.

[0168] Determination of Acid Number: The acid number determination was carried out by titration according to DIN EN ISO 2114.

[0169] Synthesis example: Step a): Preparation of epoxidized polybutadiene Example A1: To prepare the epoxidized polybutadiene, a polybutadiene of formula (1) having the structure x=1%, y=24% and z=75% was used (Polyvest (登録商標) 110) According to the prior art, Polyvest in 1500 g of chloroform was dissolved in 1 L of nitrogen in a 5 L reactor. (登録商標) 1500 g of 110 and 146.3 g of concentrated formic acid were charged at room temperature. Then 540 g of a 30% H2O2 solution (30% by weight of H2O2, based on the total weight of the aqueous solution) were 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, the organic phase was separated and washed four more times with distilled H2O. Excess chloroform and residual water were distilled off. 1481 g of product was obtained, which was then mixed with Irganox (登録商標) 1135 1000 ppm and stored under nitrogen. 13 C-NMR indicated a degree of epoxidation of the double bonds of about 15.8%. GPC indicated the following: w = 4690 g / mol, M n = 1982 g / mol, M w / M n =2.4.

[0170] 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%, the degree of amination being 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 its preparation, 800 g of the epoxidized polybutadiene was charged in a 1 L four-neck flask under a nitrogen atmosphere with 136.3 g of ethanolamine and 6.8 g of lithium bromide and heated to 180° C. with stirring. The mixture was stirred at this temperature for 15 hours. During the reaction, the viscosity increased. After the reaction was over, the volatile constituents were removed by distillation at 180° C. and 20 mbar. The product was cooled to 60° C. 908 g of a yellowish product was obtained and stored under nitrogen. 13 C-NMR evaluation showed complete conversion of all epoxy groups, resulting in a degree of amination of about 15.8%.

[0171] Step c), Alkoxylation of the Amino-Functional Polybutadiene Example C1: In a 1.5 L autoclave, 151 g of the hydroxy- and amino-functional polybutadiene prepared in Example B1 were charged under nitrogen and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile constituents present were removed by distillation. 15.9 g of ethylene oxide were fed at 115° C. within 5 minutes. The internal reactor pressure rose to a maximum of 3.4 bar (absolute) and decreased continuously in the course of the reaction. After 5.5 h, a constant pressure of 0.6 bar (absolute) had been reached. Volatile constituents were removed at 115° C. and 20 mbar, the reactor was depressurized to standard pressure with N2 and the reaction mixture was cooled to 40° C. Subsequently, 26.9 g of a 30% sodium methanolate solution (30% by weight of sodium methanolate in methanol, based on the total weight of the solution) were added and the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. The internal reactor pressure was then reduced to 20 mbar and methanol was removed by distillation. 164.7 g of ethylene oxide were added at 115° C. with stirring and cooling within 1.5 h at a maximum internal pressure of 3.4 bar. During the post-reaction at 115° C. for 3 h, the internal pressure was continuously reduced to a constant pressure of 0.5 bar (absolute). Volatiles, e.g. residual ethylene oxide, were distilled off in a vacuum. The product was cooled to below 80° C. and neutralized with 14.9 g of 90% lactic acid (90% by weight of lactic acid in water, based on the total weight of the solution) to an acid number of 0.1 mg KOH / g and dissolved in Irganox (登録商標) 1135 1000 ppm and discharged. 317 g of a viscous orange-red slightly hazy polyether modified amino-functional polybutadiene was discharged and stored under nitrogen. The total amount of ethylene oxide corresponded to an average of 3.8 ethylene oxide units per reactive NH / OH group. GPC evaluation was as follows: M w = 19484 g / mol, M n = 4474 g / mol, M w / M n =3.45.

[0172] Example C2: In a 1.5 L autoclave, 181 g of the aminated polybutadiene prepared in Example B1 were charged under nitrogen and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile constituents present were removed by distillation. 25.2 g of propylene oxide were fed at 115° C. within 5 minutes. The internal reactor pressure rose to a maximum of 2.4 bar (absolute) and decreased continuously in the course of the reaction. After 4.5 h, a constant pressure of 0.7 bar (absolute) had been reached. Volatile constituents were removed at 115° C. and 20 mbar, the reactor was depressurized to standard pressure with N2 and the reaction mixture was cooled to 40° C. Subsequently, 32.2 g of a 30% sodium methanolate solution (30% by weight of sodium methanolate in methanol, based on the total weight of the solution) were added, the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. The reactor internal pressure was then reduced to 20 mbar and methanol was removed by distillation. 260 g of propylene oxide were added at 115° C. with stirring and cooling within 1.5 h at a maximum internal pressure of 2.9 bar. During the post-reaction of 2 h at 115° C., the internal pressure was continuously reduced to a constant pressure of 0.3 bar (absolute). Volatiles, e.g. residual propylene oxide, were distilled off in a vacuum. The product was cooled to below 80° C. and neutralized with 17.9 g of 90% lactic acid (90% by weight lactic acid in water, based on the total weight of the solution) to an acid number of 0.1 mg KOH / g and dissolved in Irganox (登録商標) 1135 1000 ppm and discharged. 421 g of a viscous orange slightly hazy polyether modified aminofunctional polybutadiene was discharged and stored under nitrogen. The total amount of propylene oxide corresponded to an average of 3.8 propylene oxide units per reactive NH / OH group. GPC evaluation was as follows: M w = 25386 g / mol, M n = 5226 g / mol, M w / M n =4.86.

[0173] Example C3: (Stoichiometry: 5EO / 5PO per reactive NH / OH group) In a 1.5 L autoclave, 197 g of the aminated polybutadiene prepared in Example B1 were charged under nitrogen and heated to 115° C. with stirring. The reactor was evacuated to an internal pressure of 30 mbar and any volatile constituents present were removed by distillation. 27.4 g of propylene oxide were fed at 115° C. within 5 minutes. The internal reactor pressure rose to a maximum of 2.3 bar (absolute) and decreased continuously in the course of the reaction. After 4 h, a constant pressure of 0.7 bar (absolute) had been reached. At 115° C. and 20 mbar, volatile constituents were removed, the reactor was depressurized to standard pressure with N2 and the reaction mixture was cooled to 40° C. Subsequently, 17.6 g of a 30% sodium methanolate solution (30% by weight of sodium methanolate in methanol, based on the total weight of the solution) were added, the reactor contents were inerted with nitrogen and heated to 115° C. with stirring. The reactor internal pressure was then reduced to 20 mbar and methanol was removed by distillation. A mixture of 382 g propylene oxide and 310 g ethylene oxide was added at 115° C. with stirring and cooling within 6 h at a maximum internal pressure of 3.2 bar. During a post-reaction of 2.5 h at 115° C., the internal pressure was continuously reduced to a constant pressure at 0.4 bar (absolute). Volatiles, such as residual propylene oxide and ethylene oxide, were distilled off in a vacuum. The product was cooled to below 80° C., neutralized with 30% phosphoric acid (30% by weight of phosphoric acid in water, based on the total weight of the solution) to an acid number of 0.1 mg KOH / g, mixed with 500 ppm Irganox® 1135 and discharged through a filter. 881 g of viscous, orange, clear polyether-modified amino-functional polybutadiene was discharged and stored under nitrogen. The total amount of ethylene oxide and propylene oxide corresponded to an average of 5 ethylene oxide units and 5 propylene oxide units per reactive NH / OH group. GPC estimation was as follows: w = 32145 g / mol, M n = 8349 g / mol, M w / M n =3.85.

Claims

1. 1. A method for producing one or more polyether modified amino-functional polybutadienes 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 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-functional and amino-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified amino-functional polybutadiene (G). The method comprising:

2. Furthermore, at least one of the following steps: d) reacting said at least one polyether modified amino-functional polybutadiene (G) with at least one end-capping reagent (H) to obtain at least one polyether modified amino-functional polybutadiene (K) containing end-capped polyether residues; e) lightening the color of said at least one polyether modified amino-functional polybutadiene (G) or (K); f) reacting at least a portion of the amino groups of said at least one polyether modified amino-functional polybutadiene (G) or (K) with an acid and / or a quaternizing agent to obtain quaternary ammonium groups. The method of claim 1 , comprising:

3. 3. The process according to claim 1, wherein, of all the double bonds of the polybutadiene (A) used, 1,2-vinyl double bonds account for 0% to 80% and 1,4-double bonds for 20% to 100%.

4. The number average molecular weight M of the at least one polybutadiene (A) ｎ The method according to claim 1 or 2, characterized in that the molecular weight of the polymer is between 200 g / mol and 20,000 g / mol.

5. 3. The process according to claim 1 or 2, characterized in that more than 0% and less than 100% of the double bonds of said at least one polybutadiene (A) are epoxidized.

6. 3. The process according to claim 1 or 2, characterized in that the at least one epoxidation reagent (B) contains performic acid.

7. 3. The process according to claim 1 or 2, characterized in 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.

8. 3. The process according to claim 1 or 2, characterized in that in step b), the total number of NH groups of all amino-functional compounds (D) to the total number of epoxy groups of all epoxy-functional polybutadienes (C) is from 0.8:1 to 20:

1.

9. 3. The process according to claim 1 or 2, characterized in that in step b) a catalyst is used.

10. At least one epoxy-functional compound used in step c) is a. selected from the group of alkylene oxides having 2 to 18 carbon atoms; and / or 3. The method according to claim 1 or 2, characterized in that the glycidyl compounds are selected from the group consisting of b. glycidyl compounds.

11. 3. The process according to claim 1 or 2, characterized in that in step c) an alkoxylation catalyst is used.

12. 3. Polyether modified amino-functional polybutadiene (G) or (K) obtainable by the process according to claim 1 or 2.

13. A polyether-modified amino-functional polybutadiene (G) or (K), wherein the polyether-modified amino-functional polybutadiene (G) or (K) is a divalent residue 【Chemistry 1】 and comprising a repeat unit selected from the group consisting of: Where: A １ and A ２ are each independently an organic residue, １ and A ２ may be covalently bonded to each other, B is, independently of one another, a residue of formula (4a), 【Chemistry 2】 R １ are each independently a monovalent hydrocarbon residue having 1 to 16 carbon atoms, R ２ is represented by the formula -CH ２ -O-R ３ is a residue of R ３ are each independently a monovalent hydrocarbon residue having 3 to 18 carbon atoms, R ４ are each independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogen, and k1 and k2 each independently represent an integer from 0 to 8; l1 and l2 are integers and each independently is 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 sum of all repeat units (U), (V) and (W) divided by the sum of all repeat units (U), (V), (W), (X), (Y) and (Z) is greater than 0%; and comprising all permutations of the repeating units (U), (V), (W), (X), (Y) and (Z) and the repeating units in residue B.

14. The polyether modified amino-functional polybutadiene (G) or (K) according to claim 13, characterized in that the sum of all repeating units (U), (V) and (W) divided by the sum of all repeating units (U), (V), (W), (X), (Y) and (Z) is greater than 0% and less than 100%.

15. Formula (5) 【Chemistry 3】 is a polybutadiene of 15. The polyether modified polybutadiene (G) or (K) according to claim 13 or 14, characterized in that the proportion of polyether modified repeat units according to formula (5) is greater than 0%, based on the sum of all repeat units according to formula (5), wherein said proportion is calculated by [(d+e+f) / (a+b+c+d+e+f)]×100%.

16. The polyether-modified amino-functional polybutadiene (G) or (K) according to claim 13 or 14, characterized in that 0% to 80% of the double bonds contained therein are 1,2-vinyl double bonds and 20% to 100% of the double bonds contained therein are 1,4-double bonds.

17. - Number average molecular weight of the polybutadiene part (M ｎ ) is from 200 g / mol to 20,000 g / mol, and / or the average molecular weight of said residue B is between 30 g / mol and 20 000 g / mol, and / or - the number average molecular weight (M ｎ ) is 1000 g / mol to 50000 g / mol 15. The polyether modified amino-functional polybutadiene (G) or (K) according to claim 13 or 14, characterized in that

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