Polyester-polyether modified polybutadiene and method for producing the same

Abstract

To provide a compound based on a polyether-modified polybutadiene, and a method for preparing the same.SOLUTION: A polyether-modified polybutadiene includes a repeat unit selected from the group consisting of divalent radicals including, for example, a divalent radical illustrated below, where the radical B is at least one ester group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to polybutadiene modified with polyester-polyether in a comb-like (pendantly) position, a method for preparing the same, and its use. [Background technology]

[0002] Polybutadienes having pendant polyether radicals are known and, according to the prior art, are prepared, for example, by the reaction of reactive functionalized polybutadiene with a polyether. For example, Non-Patent Document 1 describes an amphiphilic polymer comb structure prepared by inserting (grafting) polyethylene glycol into the main polybutadiene chain. According to Patent Document 1, polybutadiene functionalized with maleic anhydride units reacts with an amino-terminated polyether. The result is a maleated polybutadiene having polyether radicals at the comb positions, linked via amide or imide groups. In a similar process, according to Non-Patent Document 2, polyethylene glycol is added to polybutadiene with a high proportion of 1,2-butadiene monomer units to form ester bonds. High molecular weight graft polymers having a comb structure are obtained by the process disclosed in Patent Document 2 by adding an OH-functionalized polyether to epoxidized polybutadiene. According to Non-Patent Document 3, the addition of isocyanate-terminated polyethylene glycol to hydroxy-functionalized polybutadiene is used.

[0003] Processes for preparing polyether-modified polybutadienes by reacting hydroxy-functionalized polybutadienes with epoxy compounds are also known. For example, the prior art discloses the alkoxylation of OH-terminated polybutadienes.

[0004] Patent document 3 describes, for example, the alkoxylation of hydroxy-terminated polybutadienes with ethylene oxide and propylene oxide in the presence of tetramethylammonium hydroxide. Patent document 4 states that alkali-catalyzed alkoxylation of OH-terminated polybutadienes is virtually impossible due to structural reasons and the low solubility of alkali catalysts, and that a double metal cyanide (DMC) catalyst is preferable instead. According to Patent document 4, this block structure is the cause of poor miscibility with other reactants in the preparation of polyurethanes.

[0005] Similar to the alkoxylation of OH-terminated polybutadienes, the alkoxylation of pendant hydroxy-functional polybutadienes is also known. For example, Non-Patent Literature 1 describes the preparation of pendant polyether-modified polybutadiene by alkoxylation of pendant hydroxy-functional polybutadiene with ethylene oxide. The pendant hydroxy-functional polybutadiene used here is prepared by first epoxidation of polybutadiene, followed by the reaction of the epoxidized polybutadiene with a lithium-polybutadiene compound, and finally protonation of the reaction product with methanolic HCl. This process yields a polybutadiene having both pendant polyether radicals and pendant polybutadiene radicals. Since a polybutadiene radical is always present for all polyether radicals, this process produces a polyether-modified polybutadiene with a low HLB value (HLB-hydrophilic / lipophilic balance).

[0006] Furthermore, polyether-modified polybutadiene is branched at the polybutadiene moiety. Polyether-modified polybutadiene with higher HLB values ​​and / or unbranched polybutadiene moieties cannot be prepared by this process. A further drawback of this process is the use of organometallic compounds (n-BuLi and lithium-polybutadiene). This imposes special requirements on the process region (regime) due to its high sensitivity to air and moisture. This makes it difficult to implement this process industrially. Prior art has not disclosed a process for preparing preferably linear polybutadiene having a pendant polyether chain by a simple direct alkoxylation reaction of pendant hydroxy-functional polybutadiene with an alkylene oxide, where the pendant hydroxy-functional polybutadiene is prepared from epoxy-functional polybutadiene without the use of organometallic compounds such as lithium polybutadiene. In summary, it can be said that the prior art has not disclosed any process for preparing linear polybutadienes having polyether chains in a comb-like position by a simple direct alkoxylation reaction with alkylene oxide.

[0007] Chemical modifications of polybutadiene with the aid of epoxidation and further reactions are known from the literature. Ring-opening of epoxy usually occurs by reaction with amines. Patent documents 5 and 6 describe the addition of ethanolamine or diethanolamine, and patent documents 7 and 8 describe the reaction of epoxy groups with dimethylamine. Patent document 9 discloses the addition of primary and secondary amines having 4 to 20 carbon atoms to epoxidized polybutadiene in a polar solvent. Modification of polybutadiene with fatty acids is also known. For example, patent document 10 describes the addition of C6-C to epoxidized polybutadiene. 22 The addition of carboxylic acids is described. These documents do not disclose further alkoxylation of the reaction product.

[0008] In the context of the present invention, amine-functionalized polybutadiene is not very suitable as a starting compound for alkoxylation because it often imparts undesirable basic properties to the product, causes discoloration, or inhibits alkoxylation catalysts such as, for example, double metal cyanides.

[0009] According to the prior art, the addition of alcohol and water to epoxidized polybutadiene seems to be much more difficult than the addition of amines and carboxylic acids. Non-Patent Document 4 describes the addition of water to epoxidized polybutadiene in THF using a trifluoromethanesulfonic acid catalyst. The object of Patent Document 11 is the preparation of a glassy polymer by adding water or an alcohol having 1 to 4 carbon atoms to the epoxy group of polybutadiene, and is limited to the preparation of OH-functionalized polybutadiene having a low molar mass of 300 to 2000 g / mol and a high content of 50% to 80% of 1,2-vinyl double bonds and 1,2-cyclovinyl double bonds.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

[0011] Polybutadienes and modified polybutadienes are often used as reactive or compounding components, for example, to make polymers hydrophobic or to make them flexible and improve their mechanical properties. However, the possible uses of alkoxylated polyether-modified polybutadienes are often limited as a result of the current limitation to a small number of available triblock structures. Therefore, there is no way to significantly alter the chemical composition of polyether-modified polybutadienes. Furthermore, there is no simple preparation process for such polymers.

[0012] The yet-to-be-published European patent application EP19212066.5 or PCT / EP2020 / 083013 is dedicated to the preparation of polyether-modified polybutadiene and the preparation of polyether-modified polybutadiene that can be prepared according to the said process, which includes the following steps: a) Reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C), b) At least one epoxy-functionalized polybutadiene (C) is reacted with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E). c) At least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0013] Therefore, the polyether-modified polybutadiene according to the present invention is obtained by direct alkoxylation of a pendantly hydroxy-functionalized polybutadiene and has a polyether radical at the pendant position.

[0014] The polyether-modified polybutadiene pendant (comb position) prepared according to this instruction was found to be ideally suited as an antifoaming agent and / or adhesion promoter for lacquers and paints.

[0015] Therefore, the question arises as to whether it is possible to optimize the polyether-modified polybutadiene to improve its use in the field of paints and lacquers. [Means for solving the problem]

[0016] Based on the teachings of European Patent Application EP19212066.5 or PCT / EP2020 / 083013, the present invention proposes compounds based on polyether-modified polybutadiene, the polyether-modified polybutadiene comprising repeating units selected from the group consisting of divalent radicals. [ka] [ka] [ka] [ka] [ka] [ka] Here, A is independently a monovalent organic radical or a hydrogen radical. Preferably, in each case, independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms, More preferably, in each case, independently selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, In all cases, B is independently selected from the group consisting of radicals of equation (4a). [ka] …Equation (4a), Preferably, in each case, a radical is independently selected from the group consisting of radicals of formula (4b). [ka] ...Equation (4b), R 1In each case, it is independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 16 carbon atoms, Preferably, in each case, independently, an alkyl radical or phenyl radical having 1 to 16 carbon atoms, More preferably, in each case, independently, a methyl radical, an ethyl radical, or a phenyl radical, R 2 is formula -CH2-OR 3 It is a radical of, R 3 In each case, these are independently selected from the group consisting of monovalent hydrocarbon radicals having 3 to 18 carbon atoms. Preferably, in each case, a phenyl radical may be independently substituted with a monovalent radical selected from an allyl radical, a butyl radical, an alkyl radical having 8 to 15 carbon atoms, or a hydrocarbon radical having 1 to 4 carbon atoms. More preferably, a tert-butylphenyl radical or an o-cresil radical; R 4 It is hydrogen, m, n, o, p, and q are each independently between 0 and 300, preferably between 0 and 200, more preferably between 0 and 100, provided that the sum of m, n, o, p, and q is greater than 1, preferably greater than 5, and more preferably greater than 10;

[0017] This includes all permutations of repeating units (U), (V), (W), (X), (Y), (Z), and B radical repeating units, provided 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%, where, Radical B has at least one ester group.

[0018] Surprisingly, it has been found that the performance of the esterified polyether-modified polybutadiene according to the present invention can be further enhanced, for example, as an adhesion promoter. The ester group is preferably formed by reacting a B radical with a compound selected from the group consisting of cyclic anhydrides, dilactides, lactones, or cyclic carbonates as a monomer or comonomer.

[0019] After the reaction, the compound preferably contains repeating units selected from the group consisting of radicals. [ka]

[0020] The cyclic anhydrides in pure form or in any desired mixture are preferably selected from the group consisting of saturated, unsaturated, or aromatic cyclic dicarboxylic acid anhydrides, preferably succinic anhydride, octonyl-decanyl-dodecanyl-succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, trimellitic anhydride, phthalic anhydride, hexahydro-tetrahydro-dihydro-methylhexahydro-methyltetrahydrophthalic anhydride.

[0021] The lactone, in its pure form or in any desired mixture, is preferably selected from the group consisting of valerolactone, caprolactone, and butyrolactone, which may be unsubstituted or substituted with alkyl groups, preferably methyl groups, preferably ε-caprolactone or δ-valerolactone.

[0022] The compounds and polyester-polyether modified polybutadienes according to the present invention should be understood as synonyms herein.

[0023] The polyester-polyether modified polybutadiene is preferably a linear polybutadiene modified at the comb position (pendantly) with a polyether radical modified with at least one ester group. Thus, the polyester-polyether modified polybutadiene preferably has a linear polybutadiene backbone and pendant polyether radicals having at least one ester group.

[0024] Radical R 1 , R 2 and R 3 can each independently be linear or branched, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted.

[0025] R of formula (4a) = R 1 or R 2 or the general notation where R of formula (4b) = CH3

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0026] The general notation of formula (4a)

Chemical formula

Chemical formula

[0027]

Chemical formula

[0028] Here, in at least one polyester-polyether modified polybutadiene (G), the value obtained by dividing the sum of all repeating units (U), (V), and (W) by all repeating units (U), (V), (W), (X), (Y), and (Z) is >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and particularly preferably 4% to 20%.

[0029] This means that >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and especially preferably 4% to 20% of the entire repeating units (U), (V), (W), (X), (Y), and (Z) are modified with polyester-polyether.

[0030] Number-average molar mass M of the polybutadiene portion of polyester-polyether modified polybutadiene n , weight average molar mass M w , and polydispersity can change freely. The polybutadiene portion is understood to mean the polyester-polyether modified polybutadiene component derived from the polybutadiene used in the process.

[0031] Number-average molar mass M of the polybutadiene portion of polyester-polyether modified polybutadiene n The concentration is 200 g / mol to 20,000 g / mol, preferably 500 g / mol to 10,000 g / mol, and particularly preferably 700 g / mol to 5,000 g / mol.

[0032] Alternatively, the number-average molar mass M of the polybutadiene portion of polyester-polyether modified polybutadiene. n The concentration is 2100 g / mol to 20000 g / mol, more preferably 2200 g / mol to 10000 g / mol, and particularly preferably 2300 g / mol to 5000 g / mol.

[0033] Number-average molar mass M of the polybutadiene portion n Here, the number-average molar mass M of the polybutadiene below is... n It is defined as follows.

[0034] The polyester-polyether modified polybutadiene has a numerical average of 5 to 360 repeating units, more preferably 10 to 180, and particularly preferably 15 to 90, where the repeating units are selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0035] Alternatively, the polyester-polyether modified polybutadiene has an average of 35 to 360 repeating units, more preferably 40 to 180, and particularly preferably 45 to 90, the repeating units being selected from the group consisting of (U), (V), (W), (X), (Y), and (Z).

[0036] Polyester-polyether modified polybutadiene is characterized in that 0% to 80%, preferably 0% to 30%, more preferably 0% to 10%, and especially preferably 0% to 5% of the present double bonds are 1,2 vinyl double bonds, and 20% to 100%, preferably 70% to 100%, particularly preferably 90% to 100%, and especially preferably 95% to 100% of the present double bonds are 1,4 double bonds.

[0037] Particularly preferred are the polybutadienes Polyvest® 110 and Polyvest® 130 from Evonik Industries AG / Evonik Operations GmbH, as well as polyester-polyether modified polybutadienes derived from the above-mentioned LitheneultraAL and LitheneActiV50 from SynthomerPLC.

[0038] The molar mass and polydispersity of B radicals vary freely. However, the average molar mass of B radicals is between 100 g / mol and 20,000 g / mol, preferably between 200 g / mol and 15,000 g / mol, and more preferably between 400 g / mol and 10,000 g / mol. The average molar mass of B radicals can be calculated from the starting weight of the monomer used, based on the number of OH groups in the hydroxy-functionalized polybutadiene (E) used. For example, if 40 g of ethylene oxide is used and the amount of hydroxy-functionalized polybutadiene (E) used is 0.05 moles of OH groups, the average molar mass of B radicals is 800 g / mol.

[0039] Polyester-polyether modified polybutadiene is liquid, paste-like, or solid, depending on its composition and molar mass.

[0040] Number average molar mass M of polyester-polyether modified polybutadiene n Preferably, the concentration is 1000 g / mol to 6000 g / mol, more preferably 1500 g / mol to 5000 g / mol, and particularly preferably 2000 g / mol to 4000 g / mol.

[0041] Their polydispersity varies over a wide range. The polydispersity of at least one polyester-polyether modified polybutadiene by the GPC method relative to the PPG standard is preferably M w / M n = 1.5 to 10, more preferably between 2 and 9, and more preferably between 3 and 8.

[0042] The present invention further provides a process for preparing preferably linear polybutadienes modified in a comb-like (suspended) position with a polyether radical having at least one ester group. Based on European Patent Application EP19212066.5 or PCT / EP2020 / 083013, this process should, from a process technology standpoint, allow very easy access to linear polybutadienes having pendant polyether radicals and be feasible, for example, without the use of organolithium compounds. Polyether-modified polybutadienes should also be obtainable by direct alkoxylation of pendant hydroxy-functional polybutadienes. An additional problem addressed here was to provide improved pendant hydroxy-functional polybutadienes as precursors and chain starters for alkoxylation in the process.

[0043] Based on the teachings of European Patent Application EP19212066.5 or PCT / EP2020 / 083013, a process for preparing polyester-polyether modified polybutadiene has been found to include the following steps: a) Reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C), b) Reacting at least one epoxy-functionalized polybutadiene (C) with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E), c) Reacting at least one hydroxy-functionalized polybutadiene (E) with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G), d) At least one polyether-modified polybutadiene (G) is reacted with at least one compound (I) to obtain at least one polyether-polyester-modified polybutadiene (H).

[0044] Surprisingly, it has been found that polybutadiene, which has a high proportion of 1,4 units and a low content of vinyl 1,2 units after epoxidation with hydrogen peroxide, can readily react with OH-functional compounds to produce pendant OH-functional polybutadiene (polybutadienol) under acid-catalyzed ring-opening conditions, and can be alkoxylated with alkylene oxide.

[0045] The subject matter of the present invention is described in the independent claims. Advantageous configurations of the present invention are identified in the dependent claims, examples, and description.

[0046] The subject matter of the present invention is described below by example, but the invention is not intended to be limited to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by deleting individual values ​​(ranges) or compounds. Where any document is referenced in the context of this specification, its entirety is intended to be part of the disclosure of the present invention.

[0047] Where average values ​​are listed below, these values ​​are numerical averages unless otherwise specified. Where measured values, parameters, or material properties are listed below, these are measured values, parameters, or material properties measured at 25°C and preferably at a pressure of 101 to 325 Pa (standard pressure), unless otherwise specified.

[0048] When a numerical range in the form "X to Y" is listed below, X and Y represent the limits of the range, and unless otherwise specified, this is equivalent to "including at least X to Y". Therefore, the listed range includes the range limits X and Y unless otherwise specified.

[0049] If a molecule / molecular fragment has one or more stereocenters, if it can be distinguished as an isomer due to symmetry, or if it can be distinguished as an isomer due to other effects, such as restricted rotation, then all possible isomers are included in the present invention.

[0050] The formulas detailed in this invention describe compounds or radicals constructed from repeating units, e.g., repeating fragments, blocks, or monomer units, which may have a molar mass distribution. The frequency of repeating units is expressed in the form of an index. The index used in the formulas should be considered a statistical mean (numerical mean). The index used and the range of reported index values ​​are considered the mean of the possible statistical distributions of the structures that actually exist and / or mixtures thereof. The various fragments or repeating units of the compounds described in the following formulas (1) to (5) may be statistically distributed. The statistical distribution may have a block unit structure with any number of blocks and any sequence, or be subject to a randomized distribution. They may also have alternating structures or form gradients along a chain, where gradients exist. In particular, they may also give rise to any mixed forms in which groups having different distributions may arbitrarily follow one another. The following formulas contain all permutations of repeating units. Therefore, if multiple examples of different units of a compound such as polybutadiene (A), epoxy-functionalized polybutadiene (C), hydroxy-functionalized polybutadiene (E), polyether-modified polybutadiene (G), or polyether-polyester-modified polybutadiene (H) are described in the context of the present invention, these may occur in an unordered manner, for example, in a statistical distribution, or in an ordered manner. The number of units or the numerical value of the relative frequency of such compounds should be considered as the average (numerical mean) of all corresponding compounds. Certain embodiments may, as a result of the embodiment, lead to limitations on the statistical distribution. For all parts not affected by such limitations, the statistical distribution remains unchanged.

[0051] Therefore, the present invention further provides a process for preparing one or more polyester-polyether modified polybutadienes, comprising the following steps: a) Reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C), b) Reacting at least one epoxy-functionalized polybutadiene (C) with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E), c) At least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G). d) At least one polyether-modified polybutadiene (G) is reacted with at least one compound (I) to obtain at least one polyether-polyester-modified polybutadiene (H). In step d), the catalyst may preferably function as an initiator for anionic ring-opening polymerization. A general catalyst can be used.

[0052] Preferably, a base or acid, a metal salt, a metal alkoxide, or a metal compound can be used as a catalyst.

[0053] Examples of metal alkoxides include zirconium butoxide, tetraisopropyl titanate, tetrabutyl titanate, or titanium(IV) 2-ethylhexyl oxide.

[0054] Examples of metal salts include zinc acetate, potassium acetate, lithium acetate, sodium acetate, calcium acetate, barium acetate, magnesium acetate, copper acetate, cobalt acetate, or zinc carboxylate / bismuth. The acid catalyst is, for example, toluenesulfonic acid or trifluoroacetic acid. It is also possible to use tin chloride, tin octanoate, dibutyltin dilaurate, or monobutyltin oxide.

[0055] The method according to the present invention preferably further includes at least one of the following optional steps. e) Color lightening of at least one polyether-modified polybutadiene (G), This process is preferably, In step a), >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and especially preferably 4% to 20% of the double bonds of at least one polybutadiene (A) are epoxidized with the help of performic acid produced in situ from formic acid and H2O2. In step b), one or more short-chain alcohols having 1 to 6 carbon atoms, particularly isobutanol, are added to the epoxy group of at least one epoxy-functionalized polybutadiene (C) under ring-opening conditions, preferably using one or more acidic catalysts, particularly trifluoromethanesulfonic acid. In step c), one or more epoxy-functional compounds (F) selected from alkylene oxides and optionally further epoxy-functional monomers are added to the obtained pendant OH group of at least one hydroxy-functional polybutadiene (E) in the alkoxylation reaction, preferably using a Zn / Co bimetallic cyanide catalyst or a basic catalyst such as an amine, guanidine, amidine, alkali metal hydroxide, or alkali metal alkoxide. In step d), optionally, at least one polyether-modified polybutadiene (G) is reacted with at least one compound (I) selected from the group consisting of cyclic anhydrides, lactones, or cyclic carbonates as a monomer or comonomer to obtain at least one polyester-polyether-modified polybutadiene (H). In step e), optionally, lightening of at least one polyether-modified polybutadiene (G) is performed using activated carbon and / or hydrogen peroxide.

[0056] The process according to the present invention enables the modification of linear polybutadiene for the first time by simple direct alkoxylation of a pendant OH group having a polyether radical at the comb position. The chain length and monomer sequence of the polyether radical can vary over a wide range. The average number of polyether radicals bonded to polybutadiene can be controlled by the degree of epoxidation and hydroxy-functionalization, opening up structural diversity for hydroxy-functionalized polybutadiene(E).

[0057] The grafting of polyethers into polybutadiene, as known in the prior art, is rarely quantitative in practice, and the reaction product usually contains a free proportion of polyether and possibly unfunctionalized polybutadiene. The above addition of OH-functionalized polyethers to epoxidized polybutadiene via their OH groups is similarly usually incomplete, and the product contains residual unconverted epoxy groups. While using an excess of polyether can reduce the residual epoxy group content, the excess polyether cannot be removed by distillation and therefore remains in the product.

[0058] For compound (I) in step d), it is preferable to use the following: -Saturated, unsaturated, or aromatic cyclic dicarboxylic acid anhydrides, preferably succinic anhydride, octonyl(octenyl)-, decanyl(dekenyl)- and dodecanyl(dodekenyl) succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, trimellitic anhydride, phthalic anhydride, hexahydro-, tetrahydro-, dihydro-, methylhexahydro- and methyltetrahydrophthalic anhydride or - Lactones selected from the group consisting of valerolactone, caprolactone, and butyrolactone, which may be unsubstituted or substituted with alkyl groups, preferably methyl groups, preferably ε-caprolactone or δ-valerolactone, in pure form or in any desired mixture.

[0059] In step d), the catalyst may preferably function as an initiator for anionic ring-opening polymerization. A base or acid, a metal salt, a metal alkoxide or a metal compound can be used as the catalyst.

[0060] Examples of metal alkoxides include zirconium butoxide, tetraisopropyl titanate, tetrabutyl titanate, or titanium(IV) 2-ethylhexyl oxide.

[0061] Examples of metal salts include zinc acetate, potassium acetate, lithium acetate, sodium acetate, calcium acetate, barium acetate, magnesium acetate, copper acetate, cobalt acetate, or zinc carboxylate / bismuth. The acid catalyst is, for example, toluenesulfonic acid or trifluoroacetic acid.

[0062] It is also possible to use tin chloride, tin octanoate, dibutyltin dilaurate, or monobutyltin oxide.

[0063] The polybutadiene having polyester-polyether radicals in comb-like positions obtained according to the present invention is preferably essentially free of residual epoxy groups. The process products according to the present invention are preferably essentially free of free polyether components. Preferably, essentially all polyethers are chemically bonded to the polybutadiene via ether bonds. Thus, the process products according to the present invention are clearly different from the compounds known today from the prior art due to their high purity.

[0064] In the case of the composition according to the present invention, the compound was preferably prepared based on linear polybutadiene. In the case of the composition according to the present invention, the compound preferably does not contain pendant (comb-shaped) polybutadiene. The compound preferably has only the repeating units (U), (V), and / or (W) of the pendant (comb-shaped position).

[0065] Preferred configuration of step a) of the method according to the present invention: In step a) of the method according to the present invention, at least one polybutadiene (A) is reacted with at least one epoxidizing reagent (B) to obtain at least one epoxy-functionalized polybutadiene (C).

[0066] In this reaction, the double bonds of polybutadiene (A) are converted to epoxy groups. For example, various methods for epoxidizing polybutadiene using percarboxylic acid and hydrogen peroxide are known to those skilled in the art and are disclosed, for example, in CN 101533838, JP 2004346310, DD 253627 and WO 2016 / 142249 A1. Performic acid is particularly suitable for the preparation of epoxy-functionalized polybutadiene (C) with a high proportion of 1.4 units, and 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 the peroxide residue.

[0067] Polybutadiene (A) is a polymer of buta-1,3-diene. Polymerization of butadiene-1,3-diene monomers is essentially carried out by 1,4 and / or 1,2 linkages. The 1,4 linkages lead to what are called 1,4-trans units and / or 1,4-cis units. These are collectively also called 1,4 units. The 1,2 linkages lead to so-called 1,2 units. The 1,2 units have a vinyl group and are also called vinyl 1,2 units. In the context of this invention, the 1,2 units are also called "(X)", the 1,4-trans units are also called "(Y)", and the 1,4-cis units are also called "(Z)".

[0068] [ka] 1,2 units (X)

[0069] [ka] 1,4-Transformer Unit (Y)

[0070] [ka] 1,4-Sys Unit (Z)

[0071] Double bonds present in a unit are similarly called 1,4-trans double bonds, 1,4-cis double bonds, or 1,2 double bonds or 1,2 vinyl double bonds. 1,4-trans double bonds and 1,4-cis double bonds are collectively called 1,4 double bonds.

[0072] Therefore, polybutadiene (A) is unmodified polybutadiene. Polybutadiene (A) and the processes for preparing them are known to those skilled in the art. Preparation is preferably carried out by free radical, anionic, or coordination chain polymerization.

[0073] Free radical chain polymerization is preferably carried out as emulsion polymerization. This statistically generates the three units mentioned above. At low reaction temperatures (about 5°C), the proportion of vinyl groups decreases. Initiation is preferably carried out using potassium peroxodisulfate and iron salts, or hydrogen peroxide.

[0074] In anionic chain polymerization, the chain polymerization is preferably initiated with butyllithium. The resulting polybutadiene (A) contains about 40% 1,4-cis units and 50% 1,4-trans units.

[0075] In coordination chain polymerization, the use of Ziegler-Natta catalysts, particularly stereospecific Ziegler-Natta catalysts, is preferred, which results in polybutadiene (A) with a high proportion of 1,4-cis units.

[0076] Side reactions or further reactions, such as polymerization of 1,3-butadiene by further reactions of the 1,2 and 1,4 unit double bonds of the resulting polybutadiene, may also result in branched polybutadiene (A). However, the polybutadiene (A) used according to the present invention is preferably linear, i.e., unbranched polybutadiene. Polybutadiene may also contain small amounts of units other than 1,2 units, 1,4-trans units, or 1,4-cis units. However, the mass percentage of the total 1,2 units, 1,4-trans units, and 1,4-cis units is preferably at least 80%, preferably at least 90%, and particularly at least 99%, based on the total mass of at least one polybutadiene (A), i.e., based on the total mass of all polybutadiene (A) used.

[0077] For the method according to the present invention, it is preferable to use polybutadiene (A) having 1.2 units in the sum of 1.2 units and 1.4 units in the sum of 0% to 80% and 1.4 units in the sum of 20% to 100%, preferably 1.2 units in the sum of 0% to 30% and 1.4 units in the sum of 70% to 100%, particularly preferably 1.2 units in the sum of 0% to 10% and 1.4 units in the sum of 90% to 100%, and especially preferably 1.2 units in the sum of 0% to 5% and 1.4 units in the sum of 95% to 100%.

[0078] Therefore, of all the double bonds in polybutadiene (A) used, 0% to 80% are 1,2-vinyl double bonds, 20% to 100% are 1,4 double bonds, preferably 0% to 30% are 1,2-vinyl double bonds, 70% to 100% are 1,4 double bonds, particularly preferably 0% to 10% are 1,2-vinyl double bonds, 90% to 100% are 1,4 double bonds, especially preferably 0% to 5% are 1,2-vinyl double bonds, and 95% to 100% are 1,4 double bonds.

[0079] Therefore, for the preparation of the product of the present invention, it is preferable to use polybutadiene (A) of formula (1).

[0080] [ka] Formula (1)

[0081] Polybutadiene (A) has 0% to 80% 1,2-vinyl double bonds (index x) and 20% to 100% 1,4-double bonds (sum of indices y and z), preferably 0% to 30% 1,2-vinyl double bonds and 70% to 100% 1,4-double bonds, particularly preferably 0% to 10% 1,2-vinyl double bonds and 90% to 100% 1,4-double bonds, and especially 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) to 1,4-cis double bonds (index z) can be freely varied.

[0082] The indices x, y, and z represent the number of butadiene units in each polybutadiene(A). The index is the numerical average (number mean) of all polybutadiene polymers across at least one polybutadiene(A). The average molar mass and polydispersity of polybutadiene (A) in formula (1) used are freely variable.

[0083] The number-average molar mass M of at least one polybutadiene (A) n The concentration is preferably 200 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and more preferably 700 g / mol to 5,000 g / mol.

[0084] Alternatively, the number-average molar mass M of at least one polybutadiene (A). n The concentration is 2100 g / mol to 20,000 g / mol, more preferably 2200 g / mol to 10,000 g / mol, and most preferably 2300 g / mol to 5000 g / mol.

[0085] In the context of the present invention, the number-average molar mass M n , weight average molar mass M wand polydispersity (M w / M n ) is preferably determined by gel permeation chromatography (EPC), as described in the examples.

[0086] Furthermore, it is preferable that at least one polybutadiene (A) has a numerical average of 5 to 360, preferably 10 to 180, and most preferably 15 to 90 units, selected from the group consisting of 1,2 units, 1,4-cis units, and 1,4-trans units.

[0087] Furthermore, it is preferable that at least one polybutadiene (A) has a numerical average of 35 to 360, preferably 40 to 180, most preferably 45 to 90 units, selected from the group consisting of 1,2 units, 1,4-cis units, and 1,4-trans units.

[0088] Furthermore, the viscosity of the polybutadiene (A) used is preferably 50 to 50,000 mPas, more preferably 100 to 10,000 mPas, and particularly preferably 500 to 5,000 mPas (as determined in DIN EN ISO 3219:1994-10).

[0089] The polybutadienes that are particularly preferred are Polyvest® 110 and Polyvest® 130 products, commercially available from Evonik Industries AG / Evonik Operations GmbH, and have the following typical index:

[0090] Polyvest(registered trademark) 110: Approximately 1% 1,2-vinyl double bonds, approximately 24% 1,4-trans double bonds, approximately 75% 1,4-cis double bonds, number-average molar mass M n ca. 2600 g / mol, viscosity (20℃) 700-860 mPas (according to DIN EN ISO 3219:1994-10),

[0091] Polyvest® 130: Approximately 1% 1,2-vinyl double bonds, approximately 22% 1,4-trans double bonds, approximately 77% 1,4-cis double bonds, number-average molar mass M n Ca. 4600 g / mol, viscosity (20°C) 2700-3300 mPas (according to DIN EN ISO 3219:1994-10).

[0092] Polybutadiene used with particular preference is also available from SynthomerPLC as LitheneultraAL and LitheneActiV 50 products, which have the following typical indexes: Lithene ultra AL: ca. 40% 1,2 vinyl double bonds, approximately 60% 1,4 double bonds. Lithene ActiV 50: ca. 70% 1,2 vinyl double bonds, approximately 30% 1,4 double bonds.

[0093] The degree of epoxidation is, for example, 13 The amount of epoxy equivalents can be quantitatively determined using 13C NMR spectroscopy or epoxy value titration (measurement of epoxy equivalents in accordance with DIN EN ISO 3001:1999) and can be adjusted in a controlled and reproducible manner through process conditions, particularly the amount of hydrogen peroxide used in relation to the amount of double bonds in the initial charge of polybutadiene.

[0094] In step a) of the method according to the present invention, >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, particularly preferably 3% to 30%, and 4% to 20% of all double bonds of at least one polybutadiene (A) are epoxidized.

[0095] The usable epoxidizing reagent (B) is, in principle, all epoxidizing agents known to those skilled in the art. The epoxidizing reagent (B) is preferably selected from the group of peroxycarboxylic acids (percarboxylic acids, peracids), preferably from the group consisting of metachloroperbenzoic acid, peroxyacetic acid (peracetic acid), and peroxyformic acid (performic acid), and particularly preferably from peroxyformic acid (performic acid). The peroxycarboxylic acid is preferably formed in situ from the corresponding carboxylic acid and hydrogen peroxide. It is particularly preferable that at least one epoxidizing reagent (B) contains performic acid, which is preferably formed in situ from formic acid and hydrogen peroxide.

[0096] Epoxidation of at least one polybutadiene (A) preferentially occurs at the 1,4 double bonds in the statistical distribution of the entire polybutadiene chain. Epoxidation of the 1,2 double bonds can also occur, similarly in the statistical distribution of these bonds across the entire polybutadiene chain. However, epoxidation of the 1,2 double bonds is less favorable than epoxidation of the 1,4 double bonds. Therefore, the reaction products will contain epoxy-functionalized polybutadiene polymers with varying degrees of epoxidation. Thus, all described degrees of epoxidation should be considered averages.

[0097] During the methods according to the present invention, it is even more preferable to stabilize the reactants, intermediates, and products using stabilizers or antioxidants to avoid undesirable polymerization reactions of double bonds. Suitable for this purpose are sterically interfered phenols known to those skilled in the art, commercially available as, for example, Anox® 20, Irganox® 1010 (BASF), Irganox® 1076 (BASF), and Irganox® 1135 (BASF). Furthermore, it is preferable to carry out the entire preparation process under an inert atmosphere, for example, under nitrogen. The unmodified reactants, i.e., at least one polybutadiene (A), and the polyether-modified final product according to the present invention, i.e., at least one polyether-modified polybutadiene (G) or (K), should also preferably be stored with air removed as much as possible.

[0098] Preferred configuration of step b) of the process according to the present invention: In step b) of the method according to the present invention, at least one epoxy-functionalized polybutadiene (C) is reacted with at least one hydroxy-functionalized compound (D) to obtain at least one hydroxy-functionalized polybutadiene (E).

[0099] In this reaction, an addition reaction occurs in which at least one hydroxy-functional compound (D) is added to at least one epoxy-functional polybutadiene (C). Thus, the reaction occurs by forming one or more covalent bonds between at least one hydroxy-functional compound (D) and at least one epoxy-functional polybutadiene (C). The reaction preferably (at least idealized) includes a reaction step in which at least one hydroxyl group of at least one hydroxyl group of at least one hydroxyl group of at least one hydroxyl group of at least one epoxy-functional polybutadiene (C) occurs, accompanied by ring-opening of this at least one epoxy group.

[0100] In principle, in the context of the method according to the present invention, all compounds having at least one hydroxyl group can be added to the epoxy group of polybutadiene. The hydroxy-functional compound (D) can be selected from the group consisting of, for example, alcohols, carboxylic acids, and water. It is preferred to select at least one hydroxy-functional compound (D) from the group consisting of monofunctional alcohols having 1 to 6 carbon atoms, preferably from the group consisting of monofunctional alcohols having 2 to 4 carbon atoms, and more preferably from the group consisting of ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, and isobutanol. Any mixture of these alcohols can also be used here. However, it is particularly preferred not to use methanol as the hydroxy-functional compound (D). Another suitable hydroxy-functional compound (D) is water. Water can be used alone or in mixture with one or more other hydroxy-functional compounds (D). For example, in step b), a mixture of alcohol and water, or a mixture of carboxylic acid and water can be used. Therefore, at least one hydroxy-functional compound (D), for example, an alcohol or carboxylic acid without water, does not need to be dried.

[0101] The molar ratio of OH groups of the hydroxy-functional compound (D) to the epoxy groups of the epoxy-functional polybutadiene (C) can vary over a wide range. However, to achieve quantitative conversion of all epoxy, it is preferable to use a stoichiometrically excess of the hydroxy-functional compound (D) based on the stoichiometric ratio of hydroxyl groups to epoxy groups of the epoxy-functional polybutadiene (C). Therefore, in step b), the total number of hydroxyl groups of all hydroxy-functional compounds (D) to the total number of epoxy groups of all epoxy-functional polybutadiene (C) is preferably >1:1 to 50:1, more preferably 2:1 to 35:1, even more preferably 3:1 to 30:1, and particularly preferably 3:1 to 25:1. The excess compound (D) can be removed, for example, by distillation and reused after the reaction as needed.

[0102] In preferred embodiments, the reaction occurs in the presence of at least one acidic catalyst. The catalyst is either uniformly dissolved in the reaction mixture or heterogeneously distributed therein in solid form, for example, in a sulfonic acid ion exchanger. In the context of the present invention, catalysts such as sulfuric acid, sulfonic acid, and trifluoroacetic acid, more preferably trifluoromethanesulfonic acid, are preferred. Therefore, in step b), it is preferable to use an acid, more preferably sulfuric acid, sulfonic acid, and / or trifluoroacetic acid, and particularly preferably trifluoromethanesulfonic acid, as the catalyst.

[0103] The type and amount of acid used are selected to achieve very rapid and quantitative addition of at least one hydroxy-functional compound (D) to the epoxy group of at least one epoxy-functional polybutadiene (C). Based on the reaction mixture, it is preferable to use trifluoromethanesulfonic acid at a concentration of 1 ppmw to 1000 ppmw (ppmw = mass ppm), more preferably at a concentration of 50 ppmw to 3000 ppmw.

[0104] The reaction between at least one epoxy-functionalized polybutadiene (C) and at least one hydroxy-functionalized compound (D) in the presence of an acidic catalyst preferably occurs within a temperature range of 20°C to 120°C, with the upper limit limited by the boiling point of the hydroxy-functionalized compound (D), or, if multiple hydroxy-functionalized compounds (D) are used, the boiling point of the most volatile hydroxy-functionalized compound (D). It is preferable to carry out the reaction between 50°C and 90°C. The components are stirred for several hours until the epoxy groups are converted as completely as possible. Analysis of the epoxy groups can be carried out by either NMR spectroscopy or known methods of epoxy value titration (as described in the examples). The reaction conditions in step b) are preferably selected so that at least 97% of the epoxy groups generated in step a) are converted under ring-opening conditions. It is particularly preferable that no epoxy groups are detected in the product from step b), i.e., at least one hydroxy-functionalized polybutadiene (E).

[0105] After the reaction, the acidic reaction mixture is neutralized. For this purpose, in principle, any basic neutralizing agent can be added. Neutralization is preferably carried out using sodium bicarbonate in solid form or aqueous solution. Possible excess hydroxy-functional compound (D) and possibly water are preferably removed by distillation, and the precipitated salt is filtered off as needed. In this case, it is preferable to use an aqueous solution of sodium bicarbonate as a lighter colored product is obtained.

[0106] Each epoxy group in the epoxy-functionalized polybutadiene (C) after ring opening by the hydroxy-functionalized compound (D) of formula A-OH becomes a repeating unit of formula (2a), (2b), or (2C).

[0107] [ka] Formula (2a)

[0108] [ka] Formula (2b)

[0109] [ka] Formula (2c)

[0110] Here, preferably, A is a monovalent organic radical or a hydrogen radical that may also have further hydroxyl groups. For example, when a monofunctional aliphatic alcohol having 1 to 6 carbon atoms is used as the hydroxy-functional compound (D), A is an alkyl radical having 1 to 6 carbon atoms. In the case of water as the hydroxy-functional compound (D), A is a hydrogen radical, i.e., A = H. For example, when a carboxylic acid is used as the hydroxy-functional compound (D), A is an acyl radical. Thus, each converted epoxy group results in at least one pendant OH group. In the case of A = H, as in the case of water, each converted epoxy group results in exactly two pendant OH groups. In all other cases, i.e., when A ≠ H, each converted epoxy group results in exactly one pendant OH group.

[0111] In the case of polybutadiene (A) having a preferred 1,4-unit dominant proportion according to the present invention, the one of formula (2a) is dominant among the repeating units of formulas (2a), (2b), and (2C).

[0112] Preferably, at least one hydroxy-functionalized polybutadiene (E) has 20% to 100%, preferably 70% to 100%, more preferably 90% to 100%, and most preferably 95% to 100% of the repeating units of formula (2a), (2b), and (2c) in total.

[0113] The proportion of the combined repeating units of formulas (2a), (2b), and (2c) to the total number of all repeating units of at least one hydroxy-functional polybutadiene (E) is preferably >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20%. Correspondingly, the degree of hydroxylation is preferably >0% to 70%, preferably 1% to 50%, more preferably 2% to 40%, even more preferably 3% to 30%, and most preferably 4% to 20%. Once the conversion in step b) is complete, the degree of hydroxylation of the hydroxy-functional polybutadiene (E) corresponds to the degree of epoxidation of the corresponding epoxy-functional polybutadiene (C).

[0114] Preferred configuration of step c) of the process according to the present invention: In step c) of the method according to the present invention, at least one hydroxy-functionalized polybutadiene (E) is reacted with at least one epoxy-functionalized compound (F) to obtain at least one polyether-modified polybutadiene (G).

[0115] At least one hydroxy-functional polybutadiene (E) from step b) serves as a starter compound for the reaction with at least one epoxy-functional compound (F) in step c). Under ring-opening conditions, preferably in the presence of a suitable catalyst, at least one epoxy-functional compound (F) (hereinafter also simply called "monomer," "epoxy monomer," or "epoxide") is added to the OH group of at least one hydroxy-functional polybutadiene (E) in the polyaddition reaction. This results in the formation of a polybutadiene according to the present invention having a polyether chain at the comb-shaped (pendant) position, i.e., the formation of at least one polyether-modified polybutadiene (G). The polyether-modified polybutadiene (G) is preferably a linear polybutadiene modified with a polyether radical at the comb-shaped (pendant) position. Therefore, the polyether-modified polybutadiene (G) preferably has a linear polybutadiene skeleton and a pendant polyether radical.

[0116] The reaction in step c) is preferably an alkoxylation reaction, i.e., a polyaddition of an alkylene oxide to at least one hydroxy-functionalized polybutadiene (E). However, the reaction in step c) can also be carried out using a glycidyl compound as an alternative or additional to the alkylene oxide.

[0117] Therefore, at least one epoxy-functional compound used in step c) is selected from alkylene oxide groups, preferably from alkylene oxide groups having 2 to 18 carbon atoms, more preferably from alkylene oxides having 2 to 8 carbon atoms from the group consisting of ethylene oxide, propylene oxide, 1-butylene oxide, cis-2-butylene oxide, trans-2-butylene oxide, isobutylene oxide and styrene oxide, and / or at least one epoxy-functional compound used in step c) is selected from the group of glycidyl compounds, preferably from the group of monofunctional glycidyl compounds, more preferably from phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 12 / C 14 Fatty alcohol glycidyl ether and C 13 / C 15 It is particularly preferable to select from the group consisting of fatty alcohol glycidyl ethers.

[0118] Monomers can be added individually in their pure form, alternately and sequentially in any metering sequence, or simultaneously in a mixed form. Therefore, the sequence of monomer units in the resulting polyether chain is affected by the block-unit distribution, statistical distribution, or gradient distribution of the final product.

[0119] The present invention exemplifies a method by which a pendant polyether chain is constructed on polybutadiene, which can be prepared in a reproducible manner with respect to structure and molar mass. The order of monomer units can be changed by the order of addition within a wide range.

[0120] The molar mass of the pendant polyether radical can vary over a wide range by the process according to the present invention and can be specifically and reproducibly controlled via the molar ratio of monomers added to the OH group of at least one initially charged hydroxy-functional polybutadiene (E) from step b).

[0121] The polyether-modified polybutadiene (G) prepared according to the present invention is preferably characterized by containing B radicals bonded to the polybutadiene skeleton via ether groups according to formulas (3a), (3b), and (3c). [ka] Formula (3a) [ka] Formula (3b) [ka] Formula (3c)

[0122] As described in step b) above, the A radical in formulas (3a), (3b), and (3c) originates from compound A-OH, i.e., the hydroxy-functional compound (D) used in step b). As also mentioned above, in step b), it is necessary to distinguish between two cases: A≠H or A=H. In the first case, i.e., A≠H, the radical A in formulas (3a), (3b), and (3c) is identical to the radical A in formulas (2a), (2b), and (2c). In the second case, i.e., A=H, the radical A in formulas (3a), (3b), and (3C) is independently H or radical B, respectively. For example, when a monofunctional aliphatic alcohol having 1 to 6 carbon atoms is used as the hydroxy-functional compound (D), A is an alkyl radical having 1 to 6 carbon atoms. For example, when a carboxylic acid is used as the hydroxy-functional compound (D), A is an acyl radical. However, when water is used as the hydroxyl-functional compound (D), A in formulas (3a), (3b), and (3c) is the B radical in the case of a reaction with one or more epoxy-functional compounds (F), and if there is no reaction, A remains hydrogen. Thus, each converted pendant hydroxyl group becomes exactly one pendant-OB radical. The radical B is then composed of one or more monomers, preferably two or more monomers, of at least one epoxy-functional compound (F) used.

[0123] In the context of the present invention, in principle, all alkoxylation catalysts known to those skilled in the art, such as basic catalysts including alkali metal hydroxides, alkali metal alkoxides, amines, guanidine, amidine, and phosphorus compounds such as triphenylphosphine, and additional acidic and Lewis acidic catalysts such as SnCl4, SnCl2, SnF2, BF3, and BF3 complexes, and bimetallic cyanide (DMC) catalysts can be used.

[0124] Before supplying the epoxide, i.e., before adding at least one epoxy-functional compound (F) to be used, the reactor, partially filled with the starter and catalyst, is inactivated, for example, with nitrogen. This is achieved, for example, by repeatedly alternating between evacuating and supplying nitrogen. After the final injection of nitrogen, it is advantageous to evacuate the reactor to less than 200 mbar. To remove the released reaction heat and maintain a pre-selected reaction temperature, the monomers are administered with stirring and optionally cooling. The starter used is at least one hydroxy-functional polybutadiene (E), or, as further described below, a polyether-modified polybutadiene (G) already prepared by the process of the present invention may be used as the starter.

[0125] DMC catalysis The use of zinc / cobalt DMC catalysts, particularly those containing zinc(III) hexacyanocobaltate, is preferred. The use of DMC catalysts described in US5158922, US20030119663, and WO01 / 80994 is preferred. The catalyst may be amorphous or crystalline.

[0126] Based on the total mass of the products formed, the catalyst concentration is preferably >0 pmpw to 1000 pmpw, preferably >0 pmpw to 700 pmpww, and more preferably 10 pmpw to 500 pmpww.

[0127] The catalyst is preferably metered into the reactor only once. The catalyst is preferably clean and dry and free from basic impurities that could inhibit the DMC catalyst. The amount of catalyst is preferably set to provide sufficient catalytic activity for the process. The catalyst can be metered in solid form or in the form of a catalyst suspension. When using a suspension, OH-functional starters are particularly suitable as suspension agents.

[0128] To initiate the DMC catalytic reaction, it may be advantageous to activate the catalyst with a portion of at least one epoxy-functional compound (F) preferably selected from alkylene oxide groups, particularly propylene oxide and / or ethylene oxide. Once the alkoxylation reaction proceeds, the sequential addition of monomers can be initiated.

[0129] In the case of the DMC catalytic reaction in step c), the reaction temperature is preferably 60°C to 200°C, more preferably 90°C to 160°C, and more preferably 100°C to 140°C.

[0130] In the case of the DMC catalytic reaction in step c), the reactor pressure is preferably 0.02 bar to 100 bar, more preferably 0.05 bar to 20 bar, and more preferably 0.1 bar to 10 bar (absolute). More preferably, the DMC catalytic reaction in step c) is carried out at a temperature of 100°C to 140°C and a pressure of 0.1 bar to 10 bar.

[0131] The reaction can be carried out in a suitable solvent, for example, to reduce viscosity. At the end of the epoxide addition, preferably, a further reaction period is allowed to proceed to completion. The further reaction can be carried out, for example, by continuing the reaction under reaction conditions (i.e., maintaining the temperature) without adding any reactants. The DMC catalyst usually remains in the reaction mixture.

[0132] Once the reaction has occurred, unreacted epoxides and other volatile components can be removed by vacuum distillation, vapor or gas stripping, or other deodorizing methods. To remove any remaining turbidity, the final product is filtered at a temperature below 100°C.

[0133] Base catalysis Similar to DMC catalysts, the present invention also allows the use of basic catalysts in step c). Particularly suitable are alkali metal alkoxides such as sodium methoxide and potassium methoxide, which are added in solid form or in methanol solution form. Furthermore, all alkali metal hydroxides, especially sodium hydroxide and potassium hydroxide, can be used, for example, in solid form or in aqueous or alcohol solution form. In addition, the present invention also allows the use of basic nitrogen compounds, preferably amines, guanidine and amidine, more preferably tertiary amines such as trimethylamine and triethylamine.

[0134] The basic catalyst is preferably used at a concentration of >0 mol% to 100 mol%, preferably >0 mol% to 50 mol%, and more preferably 3 mol% to 40 mol%, based on the amount of OH groups contained in the starter.

[0135] In the case of the base-catalyzed reaction in step c), the reaction temperature is preferably 80°C to 200°C, more preferably 90°C to 160°C, and more preferably 100°C to 160°C.

[0136] In the case of the base-catalyzed reaction in step c), the reactor pressure is preferably 0.2 bar to 100 bar, more preferably 0.5 bar to 20 bar, and more preferably 1 bar to 10 bar (absolute).

[0137] The reaction can optionally be carried out in a suitable solvent. At the end of the epoxide addition, preferably, a further reaction period is allowed to proceed to completion. The further reaction can be carried out, for example, by continuing the reaction under reaction conditions without adding reactants. Once the reaction has occurred, unreacted epoxides and other volatile components can be removed by vacuum distillation, vapor or gas stripping, or other deodorizing methods. Volatile catalysts such as amines are removed at this stage.

[0138] To neutralize the basic crude product, an acid such as phosphoric acid, sulfuric acid, or carboxylic acids such as acetic acid and lactic acid is added. The use of aqueous solutions of phosphoric acid and lactic acid is preferred. The amount of each acid used is determined by the amount of basic catalyst used beforehand. The basic polybutadiene having pendant polyether radicals is stirred in the presence of the acid, preferably at 40°C to 95°C, and then distilled to dryness by vacuum distillation at <100 mbar and 80°C to 130°C. The neutralized product is finally filtered, preferably at less than 100°C, to remove precipitated salts.

[0139] The final product according to the present invention preferably has a water content of <0.2% (specified as a mass ratio based on the total mass of the final product) and an acid value of <0.5 mg KOH / g, and is substantially free of phosphates.

[0140] Products as starters It is not always possible to achieve the desired molar mass of the final product in a single reaction step, particularly the alkoxylation step. In particular, when long polyether side chains are desired and / or when the starter in step b) has high OH-functionality, a large amount of epoxy monomer must be added. This may not be permitted depending on the reactor configuration. The polyether-modified polybutadienes (G) prepared according to the present invention from step c) have OH groups at each end of their pendant polyether radicals and are therefore consequently suitable as starters for constructing high molecular weight conversion products. In the context of the present invention, they are precursor and starter compounds for the synthesis of polybutadienes having relatively long polyether radicals. Thus, at least one epoxy-functional compound (F) can be converted in the steps of multiple components in step c).

[0141] The product prepared in step c) with the help of DMC catalysis may, according to the present invention, have an increased level of alkoxylation due to newly added epoxy monomers, either by DMC catalysis or by use in conjunction with either of the aforementioned basic or acidic catalysts. Optionally, additional DMC catalyst may be added, for example, to increase the reaction rate in chain extension.

[0142] The product prepared under base catalysis from step c) can similarly be alkoxylated to a higher molar mass under basic or acidic conditions, or by DMC catalysis. In step c), neutralization is advantageously omitted if the objective is to further react the basic precursor with the monomer under base catalysis. In some cases, it is possible to add an additional basic catalyst, for example, to increase the reaction rate in chain extension.

[0143] Preferred configuration of step d) of the process according to the present invention: In a further step d), at least one polyether-modified polybutadiene (G) is reacted with at least one compound (I) to obtain at least one polyester-polyether-modified polybutadiene (H).

[0144] In this case, the B radical of polyether-modified polybutadiene (G) having a terminal hydroxyl group reacts further to give a terminal ester group. The dilactines or cyclic anhydrides used herein are in pure form or in any desired mixture, and are selected from the group consisting of saturated, unsaturated or aromatic cyclic dicarboxylic acid anhydrides, preferably succinic anhydride, octonyl(octenyl)-, decanyl(dekenyl)-, and dodecanyl(dodekenyl) succinic anhydride, maleic anhydride, itaconic anhydride, glutaric acid anhydride, adipic acid anhydride, citraconic acid anhydride, trimellitic acid anhydride, phthalic acid anhydride, hexahydro-, tetrahydro-, dihydro-, methylhexahydro-, and methyltetrahydrophthalic acid anhydride and / or lactones, and the lactones are in pure form or in any desired mixture, and are selected from the group consisting of valerolactone, caprolactone and butyrolactone, which may be unsubstituted or substituted with organic radicals, preferably methyl groups, preferably ε-caprolactone or δ-valerolactone.

[0145] As cyclic carbonates, it is possible to use all cyclic carbonates that are generally known to those skilled in the art, accessible in pure form or in any desired mixture via the insertion of CO2 into epoxides. Carbonates derived from glycidyl ethers are preferred, with propylene carbonate and ethylene carbonate being particularly preferred.

[0146] Monomers can be added individually in their pure form, alternately and sequentially in any metering sequence, or simultaneously in a mixed form. Therefore, the sequence of monomer units in the resulting polyester chain is affected by the block unit distribution, statistical distribution, or gradient distribution of the final product.

[0147] Optional step e) In optional step e), at least one polyether-modified polybutadiene (G) becomes lighter in color.

[0148] If the optional step e) follows step d), the color of at least one polyester-polyether modified polybutadiene (H) will be lightened. However, the lightening step may also be carried out after step c) of the method according to the present invention, so that at least one polyether modified polybutadiene (G) is lightened. Lightening can be achieved, for example, by adding activated carbon to a suitable solvent, or by treatment with hydrogen peroxide. The lightening of the color is preferably determined via the Gardner color number (determined according to DIN EN ISO 4630). Here, it is preferable that the Gardner color number of the polyether modified polybutadiene (G) decreases by at least 1, preferably at least 2, with respect to the lightening of the color. The Gardner color number of the polyether modified polybutadiene (G) is at most 3, particularly at most 2.5.

[0149] reactor The reactor used in the method according to the present invention may, in principle, be any suitable reactor type that allows control of the reaction and any heat generated therein. The reaction regime can be carried out continuously, semi-continuously, or in batches, as is known in process technology, and can be flexibly adjusted to suit the available production equipment. In addition to conventional stirred-tank reactors, it is also possible to use jet loop reactors with a gas phase and internal heat exchanger tubes, as described in WO01 / 062826. It is also possible to use loop reactors without a gas phase.

[0150] The present invention further includes at least one repeating unit (U) * , (V) * and / or (W) * The present invention provides a composition comprising a compound having the properties described herein.

[0151] It is preferable to use the compositions according to the present invention for manufacturing coating materials, paints, and lacquers as printing inks or inkjet inks, or as sealants and adhesives.

[0152] The present invention also provides at least one repeating unit (U) as an adhesion promoter, defoamer, dispersion additive, wetting aid, hydrophobic additive, rheological additive, glide additive, plasticizer, or other additive for the lacquer and paint sector. * , (V) * and / or (W) * The present invention provides for the use of compounds having the following properties.

[0153] The compounds according to the present invention can preferably be used in 1K (one-component) or 2K (two-component) coating systems, melamine baking systems, room temperature or high-temperature systems, and UV systems. These are verified for their properties in improving adhesion to various substrates after the addition of the substance according to the present invention.

[0154] The substrate is preferably a composite material such as metal, concrete, wood, and / or glass fiber and / or carbon fiber composite material, a mineral substrate such as steel (variously alloyed and / or post-treated), aluminum, or glass, a dimensionally stable plastic, and / or duromers.

[0155] The term "metal substrate" is understood, though not exhaustive, to mean the following materials: hot-rolled and cold-rolled steel, with or without post-treatment. Untreated steel is degreased before use using a specific cleaner such as GARDOBOND®.

[0156] As the first layer, a chemical solution, for example, Type 26 from GARDOBOND®, can be applied. This is either by spraying (S) or dipping (D). Post-treatment can usually be carried out using an inorganic conversion layer based on phosphate, alkaline passivation, or chromate. This can be carried out by hot-dip galvanizing or electrolytic galvanizing. For example, an aqueous zinc phosphate solution can be used. This forms a layer of tertiary zinc phosphate or zinc iron phosphate.

[0157] However, phosphorylation can also be performed. For example, an aqueous solution containing a primary alkali metal phosphate can be used. These sheets can be obtained, for example, from Q-LAB® as type RI.

[0158] Next, a further chemical rinsing solution is used for passivation to ensure a sealed protective layer on the metal. Typically, this is first demineralized water, or a variety of rinsing solutions such as Gardoline® D60, D86, or D6800.

[0159] Aluminum is typically used in cold rolling corresponding to grade AlMg 1 G 18. For example, GARDOBOND® type AA 5005A or GARDOBOND® grade AlMg 0,4Si 1.2 (automotive specification) type AA6016. Here, the surface is treated with a chromate aqueous solution containing chromic acid. These sheet metals are available, among other things, from Q-LAB® as type AL. However, galvanized steel can also be further processed using this method.

[0160] The term "glass" is understood to mean inorganic silicate glass, such as borosilicate glass or soda-lime glass, which functions as, for example, beverage bottles. These are usually labeled, or more recently, have labels printed directly on them.

[0161] The term "dimensionally stable plastics" is understood to mean, though not exhaustively, the following polymers: acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polycarbonate (PP), polystyrene (PS), polyether ether ketone (PEEK), polypolycarbonate (PVC), polypropylene (PP), polyethylene (PE), and synthetic rubber mixture of ethylene propylene diene (EPDM).

[0162] In a 1K coating system, film formation is due to physical drying; therefore, the film-forming polymer preferably does not contain functional groups, or, if drying occurs through a mixture of oxidative curing and physical drying, it is double-bonded.

[0163] Purely physically drying film-forming polymers are preferably selected from the group of acrylate polymers, such as Degalan, trade name from EVONIK®. When polymers that also cure oxidatively are preferred, they are usually selected from the group of alkyd binders. These are chemically polyesters and are formed by the condensation of alcohols and polyprotic acids with the addition of fatty acids to modify their properties. They are distinguished by the oil content, which controls their drying properties. If the oil content is less than 40%, it is called a short-oil alkyd that dries in the air. If the oil content is between 40% and 60%, it is called a medium-oil alkyd resin and dries in an oven. If the oil content exceeds 60%, a non-drying alkyd is obtained.

[0164] Preferably, in the formulations according to the present invention, for example, a short oily air-drying alkyl resin from WORLEEKyd® is used. Polymerization occurs via double bonds of unsaturated fatty acid esters under the influence of oxygen. Of particular note here is polyunsaturated α-linolenic acid. Desiccants are usually used to accelerate curing. These preferably take the form of octoates, for example, cobalt octoate or calcium octoate. Used in the formulations according to the present invention are a combination of Octa-Soligen® Cobalt 6 and Octa-Soligen® Calcium 10 and the novel desiccant Borchi® OXY Coat from BORCHERS®. However, cobalt octoate trade names Octa-Soligen® Cobalt 10 or Octa-Soligen® Cobalt 12 are also possible. Furthermore, manganese octoate, traded as Octa-Soligen® Manganese 10, or zirconium octoate, traded as Octa-Soligen® Zirconium 18 from Borchers®, are also possible. Manganese octoate (AKDRY Mn Octoate 6%) and zirconium octoate are also available from American Elements®. Calcium octanoate is also available from Patchem® Ltd under the trade name Calcium Octoate 10%. In addition, desiccants based on barium, cerium, lithium, or strontium can be used. Today, modern desiccants based on various carboxylic acid metal soaps are also available. An example based on 2-ethylhexanoic acid is Octa-Soligen® 203 from Borchers®.

[0165] If drying is too rapid, so-called de-peeling inhibitors based on ketoximes, substituted phenols, or aldoximes may be added. These form reversible complexes with the desiccant. Oximes are available, for example, from BODOMOLLER® CHEMIE under the trade names Dura® MEKO or Duroxim P. Alternatively, butanone oximes are available from FISHERSCIENTIFIC® under the trade name AlfaAesar® 2.

[0166] However, to ensure good processability, it is always necessary to dilute with an appropriate organic solvent. Xylene is preferably used in the formulation according to the present invention. The use of aliphatic hydrocarbons is also possible.

[0167] In the case of a 2K coating system, the film-forming polymer preferably contains an isocyanate-containing curing agent, an amine-containing curing agent, or a functional group that is reactive with a catalyst.

[0168] The film-forming polymer is preferably selected from the group consisting of hydroxyl-functionalized acrylate polymers, polyester polymers, polyurethane polymers and / or polyether polymers, polyoxypropylene amines, amino-functionalized acrylate polymers or polyester polymers, and polycarbamates that react with an isocyanate-containing curing agent.

[0169] Such polymers typically have reactive hydroxyl groups. It is particularly preferable to use polymers having multiple hydroxyl functional groups. Hydroxyl-functionalized acrylates are available, among others, from Allnex® under the trade names MACRYNAL® or SETALUX®. Examples of hydroxyl-functionalized polyesters are commercially available, among others, under the trade names DESMOPHEN® or SETAL®. Available and commercially available hydroxyl-functionalized polyethers are available, among others, under the trade names TERATHANE® or POLYMEG®. Preferably, the tested 2K coating according to the present invention comprises a curing agent selected from the group of aliphatic or alicyclic isocyanates.

[0170] Examples of isocyanate-containing curing agents include monomer isocyanates, polymer isocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomer isocyanates due to their lower toxicity. Examples of polyisocyanates include isocyanurates, uretdiones, and biuret based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Examples of commercially available products include Covestro's DESMODUR® trade name or Evonik Industries' VESTANAT trade name. Known products include Covestro's DESMODUR® N3200, DESMODUR® N3300, DESMODUR® N3600, DESMODUR® N75, DESMODUR® XP2580, DESMODUR® Z4470, DESMODUR® XP2565, and DESMODUR® VL. Other examples include Evonik Industries' VESTANAT® HAT2500 LV, VESTANAT® HB 2640 LV, or VESTANAT® T1890E. Examples of isocyanate prepolymers include Covestro's DESMODUR® EXP 2863, DESMODUR® XP 2599, or DESMODUR® XP2406. Further isocyanate prepolymers known to those skilled in the art may be used.

[0171] The use of a catalyst for curing is a possibility. The following catalysts can be used, selected from organic Sn(IV), Sn(II), Zn, Bi compounds, or tertiary amines.

[0172] It is preferable to use a catalyst selected from the group consisting of organotin catalysts, titanates or zirconates, organometallic compounds of aluminum, iron, calcium, magnesium, zinc, or bismuth, Lewis acids or organic acids / bases, linear or cyclic amidines, guanidines, or amines, or mixtures thereof.

[0173] The curing catalyst used is preferably an organotin compound, such as dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, or dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, or dioctyltin oxide, particularly preferably dioctyltin dicarboxylate and dioctyltin dilaurate. Furthermore, zinc salts such as zinc octanoate, zinc acetylacetonate, and zinc 2-ethylcaproate, or tetraalkylammonium compounds such as N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, or choline 2-ethylhexanoate may also be used. The use of zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds is preferred, with zinc octoate being particularly preferred. A bismuth catalyst is even more preferred. Bismuth catalysts include, for example, TIB Kat (TIB Mannheim) or Borchi® catalysts, titanates (e.g., titanium(IV) isopropoxide), iron(III) compounds (e.g., iron(III) acetylacetonate), aluminum triisopropoxide, aluminum trisequbutoxide and other alkoxides, as well as aluminum compounds such as aluminum acetylacetonate, calcium compounds such as calcium disodium ethylenediamine tetraacetate or calcium diacetylacetonate, or amines such as triethylamine, tributylamine, 1,4-diazabicyclo"2.2.2" octane, 1,8-diazabicyclo"5.4.0" undeca-7-ene, 1,5-diazabicyclo"4.3.0" non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, etc.Furthermore, preferred catalysts include acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride, hydrochloric acid, phosphoric acid, and their monoesters and / or diesters, such as organic or inorganic Brønsted acids like butyl phosphate, (iso)propyl phosphate, and dibutyl phosphate. Guanidine-containing organic and organosilicon compounds are also preferred. Of course, it is also possible to use combinations of two or more catalysts. In addition, as described in WO2005 / 100482, it is also possible to use photolatent bases as catalysts.

[0174] The curing catalyst is used in an amount preferably 0.01% to 5.0% by weight, more preferably 0.05% to 4.0% by weight, and particularly preferably 0.1% to 3% by weight, based on the total mass of the curable composition.

[0175] The use of solvents may also be useful. These solvents may, for example, help to reduce the viscosity of non-crosslinked binders or facilitate application to surfaces. In principle, the solvents intended include all solvents and solvent mixtures. The selection of appropriate solvents is made from the group consisting of alkanes, alkenes, alkynes, benzenes, and aromatic compounds with aliphatic and aromatic substituents, carboxylic acid esters, linear and cyclic ethers, and, at high pressure, carbon dioxide as well, halogenated aliphatic or aromatic hydrocarbons, ketones or aldehydes, lactones (γ-butyrolactone), lactams (e.g., N-methyl-2-pyrrolidone), nitriles, nitro compounds, tertiary carboxamides (dimethylformamide), urea derivatives such as tetramethylurea or dimethylpropylene urea (DMPU), sulfoxides such as dimethyl sulfoxide (DMSO), sulfones such as sulfolanes, and carbonate esters such as dimethyl carbonate and ethylene carbonate. Aprotic solvents such as water, methanol, ethanol, n- and isopropanols and other alcohols, primary and secondary amines, carboxylic acids and their esters, as well as primary and secondary amides such as anhydrides and formamides may also be mentioned. Solvents accepted in coating applications are preferred, such as ethers such as t-butyl methyl ether, esters such as ethyl acetate or n-butyl acetate, tert-butyl acetate or diethyl carbonate, alcohols such as ethanol, and propanol and butanol in various positional isomers. Preferred solvents also include aromatic and / or aliphatic solvents such as benzene, toluene, or naphtha-cut.

[0176] If necessary, one or more substances selected from the group consisting of cocrosslinking agents, flame retardants, deaeration agents, curing agents, antimicrobial and preservative agents, dyes, colorants and pigments, antifreeze agents, bactericides, spraying aids, wetting agents, fragrances, light stabilizers, free radical scavengers, UV absorbers and stabilizers, particularly stabilizers to counteract thermal and / or chemical stress and / or stress caused by ultraviolet and visible light.

[0177] The UV stabilizer is preferably a known product based on hindered phenols or benzotriazoles. The light stabilizer used may be, for example, one known as a HALS amine. Available stabilizers include products or combinations of products known to those skilled in the art, such as Tinuvin® stabilizer (BASF), for example Tinuvin® 1130, Tinuvin® 292, or Tinuvin® 400, preferably a combination of Tinuvin® 1130 and Tinuvin® 292. The amount used is determined by the required degree of stabilization.

[0178] Suitable pigments for coloring the coating include titanium dioxide and other white pigment-based pigments, inorganic coloring pigments such as iron oxide, organic coloring pigments such as chromium pigments, ultramarine pigments, and azo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, and carbon black. Typical anticorrosive pigments such as zinc phosphate are also used to improve corrosion protection.

[0179] The fillers are preferably precipitated or pulverized chalk, common inorganic carbonates, precipitated or pulverized silicates, precipitated or pulverized silica, glass powder, hollow glass beads (called bubbles), metal oxides such as TiO2 and Al2O3, natural or precipitated barium sulfate, finely pulverized quartz, sand, aluminum trihydrate, talc, mica, cristobalite powder, reinforcing fibers such as glass fibers or carbon fibers, long or short fiber wollastonite, cork, carbon black, or graphite. These products allow for the advantageous use of hydrophobic fillers because they reduce water penetration and improve the storage stability of the formulation. It is also conceivable that the substance according to the present invention may be used in UV-curable formulations. Here, curing occurs by free radical polymerization.

[0180] The film-forming polymer is preferably selected from the group of acrylates and methacrylates. In most cases, for example, a mixture of BASF's polyether acrylate, trade name LaromerLR8945®, and BASF's polyester acrylate, trade name LaromerLR8799 or LaromerLR8800, is used. Suitable reactive solvents are hexadiol diacrylate or trimethylolpropane triacrylate.

[0181] The present invention is illustrated by the embodiments cited below, and the scope of the application arising from the entire detailed description and the claims is not limited to the embodiments described in the examples. [Brief explanation of the drawing]

[0182] [Figure 1] Figure 1 shows the evaluation of a preliminary test using the Andreascutt test.

[0183] I. Adjustment example General method Gel permeation chromatography (GPC): Polydispersity (M w / M n ), weight average molecular weight (M w ), and number-average molecular weight (M n GPC measurements to determine the following conditions were performed: SDV 1000 / 10000A° column combination (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 standard. Measurement of epoxy group content in polybutadiene (epoxy content, epoxidation level)

[0184] The epoxy group content is, 13The epoxy content was determined using 13C-NMR spectroscopy. A Bruker Avance 400 NMR spectrometer was used. For this purpose, the sample was dissolved in deuterated chloroform. The epoxy content is defined as the percentage in mole percent of epoxidized butadiene units based on the total number of repeating units present in the sample. This corresponds to the number of epoxy groups in the epoxidized polybutadiene divided by the number of double bonds in the polybutadiene used.

[0185] Determination of acid value: The acid value was determined by titration in accordance with DIN ENISO 2114.

[0186] Preparation of an adhesion promoter according to the present invention Steps a) to c) were carried out based on the European patent application EP19212066.5 or PCT / EP2020 / 0830131.1, which has not yet been published. As an example, the first example in each case is described with respect to the weight of the components. The weights used and the parameters of the intermediate and final products are listed in their respective tables.

[0187] Step a) Preparation of epoxidized polybutadiene Epoxidized polybutadiene was prepared using polybutadiene of formula (1) having the structure x=1%, y=24%, and z=75% (Polyvest® 110).

[0188] A typical example of Example A1: Under a nitrogen atmosphere, 1500 g of Polyvest® 110 and 81.0 g of formic acid concentrate in 1500 g of chloroform at room temperature were first placed in a 5 L four-necked glass flask. Subsequently, 300 g of 30% H2O2 solution (30 wt% H2O2 based on the total mass of the aqueous solution) was slowly added dropwise, and the solution was then heated to 50°C for 5.5 hours. After the reaction was complete, the mixture was cooled to room temperature, the organic phase was removed, and the mixture was washed four times with distilled water. Excess chloroform and residual water were removed by distillation. 1440 g of product was obtained, which was mixed with 1000 ppm of Irganox® 1135 and stored under nitrogen. 13 Evaluation by 13C NMR revealed an epoxidation level of approximately 8.5% of the double bond. M w =4597g / mol;M n =1999g / mol;M w / M n =2.3

[0189] For other examples A2-A5, the weight, reaction conditions, and evaluation are shown in Table 1. For readability, the specifications for examples A1-A5 are also retained in Tables 2 and 3. [Table 1-1] [Table 1-2]

[0190] Step b) Preparation of hydroxy-functional polybutadiene Hydroxylated polybutadiene was prepared using epoxidized polybutadiene A1 from step a). The hydroxylation level here is determined by dividing the number of OH groups in the OH-functionalized polybutadiene by the number of double bonds in the polybutadiene used in step a). For preparation, 1400 g of epoxidized polybutadiene and 80 ppmw of trifluoromethanesulfonic acid (based on the mass of epoxidized polybutadiene) in 1400 g of isobutanol were first added to a 5 L four-necked flask under a nitrogen atmosphere with stirring. Subsequently, the mixture was heated to 70°C and stirred at this temperature for 6 hours. The reaction mixture became clear during the reaction. After the reaction was complete, the mixture was cooled to room temperature and the solution was neutralized by adding 21.4 g of saturated (sat.) NaHCO3 solution. The mixture was heated to 115°C and excess water and excess alcohol were removed by distillation under reduced pressure. The alcohol recovered by distillation and dried as needed can be reused in subsequent synthesis. The distilled isobutanol can be dried, for example, by distillation or by adding a drying agent such as molecular sieves. 1455 g of a brownish product was obtained, which was mixed with 1000 ppm Irganox® 1135 and stored under nitrogen.

[0191] 13 ¹ M w =6228g / mol;M n =2196g / mol;M w / M n =2.8 This step was performed as in the other examples. See Table 2.

[0192] [Table 2-1]

[0193] [Table 2-2]

[0194] Step c) Preparation of alkoxylated polybutadiene

[0195] First, a 3-liter autoclave was charged with 334.0 g of hydroxy-functional polybutadiene A2 and 19.2 g of a 30% sodium methoxide solution (30 wt% sodium methoxide in methanol based on the total mass of the solution) under nitrogen from step b). The mixture was stirred at 50 °C for 1 hour. Subsequently, the mixture was heated to 115 °C with stirring, and the reactor was evacuated to an internal pressure of 30 mbar to remove the excess methanol and other volatile components present by distillation. A mixture of 332 g of ethylene oxide (EO) and 306 g of propylene oxide (PO) was continuously metered in and cooled at 115 °C for over 9 hours at a maximum internal reactor pressure of 3.5 bar (absolute). After continuing the reaction at 115 °C for 30 minutes, it was degassed. Volatile components such as residual ethylene oxide and propylene oxide were removed by distillation under reduced pressure. The product was cooled to 95 °C, neutralized with 30% H3PO4 to an acid number of 0.1 mg KOH / g, and mixed with 1000 ppm of Irganox® 1135. Water was removed by distillation under reduced pressure, and the precipitated salts were filtered off. 1076 g of medium-viscosity, orange-colored transparent alkoxylated polybutadiene was isolated and stored under nitrogen. M w = 13481 g / mol; M n = 3209 g / mol; M w / M n = 4.2

[0196] Further examples and comparative examples according to Table 3 were carried out in the same manner as the described weights and reaction conditions. The changes in alkoxylation are evident from the "feed profile" column.

[0197]

Table 3-1

[0198]

Table 3-2

[0199] Step d) Preparation of polyester-polyether modified polybutadiene according to the present invention by esterification of alkoxylated polybutadiene.

[0200] A typical example of PPA1: In a 500 mL four-necked flask under nitrogen, 120 g of alkoxylated polybutadiene from step c), 40 g of ε-caprolactone (Aldrich), and 40 g of δ-valerolactone (Aldrich) were first placed, and the mixture was heated to 40°C. After adding 0.95 g of Tyzor® NBZ (0.5 wt%) based on the total mass of the reaction mixture, the mixture was heated to 160°C and stirred at this temperature for 4 hours. After cooling, 188 g of an orange-brown paste-like product was isolated. Further examples were conducted using the weight (weight %) and reaction conditions listed in Table 4.

[0201] [Table 4]

[0202] II. Application Examples General conditions Where values ​​are expressed as % in the context of this invention, they are weight % unless otherwise specified. In the case of compositions, values ​​reported as % are based on the entire composition unless otherwise specified. Where averages are referred to below, they are numerical averages unless otherwise specified. Where measured values ​​are referred to below, these measurements were taken at a pressure of 101325 Pa, a temperature of 23°C, and an ambient relative humidity of approximately 40%, unless otherwise specified.

[0203] device Hauschild Engineering Speedmixer, Model FAC 150.1 FVZ Drying oven, Binder brand, equipment type FDL 115 E2 Dispermat, manufactured by Getzmann, machine type CV2-SIP Cross-cut tester, DIN EN ISO 2409, CCP cross-cut stencil set Cutter knife, manufactured by HEYCO, model 01664000000 Adhesive tape, manufactured by TESA, 4651 Laboratory balance, Sartorius MSE 6202 S 100 DO Spiral coating bar, manufactured by BYK Gardner, 100 μm

[0204] Method Adhesion test To optimally test the adhesion performance of adhesion promoters, it has been proven useful to perform an initial preliminary test by Andreas cut test. If the sample is evaluated with a value of 1 (no flaking), a cross-cut test according to DIN EN ISO 2409 follows. In this way, time and effort can be minimized. In some cases, it may be sufficient to use only the value of the Andreas cut test.

[0205] a) Preliminary test using Andreas cut test Using a cutter knife, make two scores, each 3 - 4 cm long, perpendicular to each other along a ruler and cut through the coating to the substrate. In the case of a plastic substrate, care should be taken not to cut the substrate as much as possible. Subsequently, cover the scored area with TESA adhesive tape 4651, press firmly, and then peel off. The evaluation is as shown in Figure 1. b) The cross-cut test is carried out in accordance with DIN EN ISO 2409. The conformity test is determined by visual evaluation of the coating film according to a scale (Table 5).

[0206]

Table 5

[0207] Material [Table 6]

[0208] Preparation of coating formulations For application testing, three coating formulations E1 to E3 were first prepared, corresponding to the components and quantities from Table 7.

[0209] Coating formulation E1: The amounts of components (P1 + P8) listed in Table 3 were extrapolated to 2 kg and weighed into a 2.5 L sheet metal container. The mixture was stirred for 20 minutes at a speed of 500 rpm using a Getzmann Dispermat, instrument type CV2-SIP, with an 8 cm diameter dispersion disk.

[0210] Coating formulation E2: The amounts of the components (P2+P5 to P8, P11+P12, and P14+P15) without the hardener (P5) listed in Table 6 were estimated to be 2 kg by extrapolation. First, P2 was weighed into a 2.5 L sheet metal can. Positions P5 to P8 and P11+P12 and P14+P15 were added sequentially while stirring. The mixture was prepared using a Getzmann Dispermat, instrument type CV2-SIP, on an 8 cm diameter dispersion disk at a speed of 500 rpm, and stirred for a further 20 minutes after the addition of the last position. Care was taken to avoid the appearance of smears.

[0211] Coating formulation E3: For coating formulation E2, all components except the hardener (P4) (P3+P4, P7, and P9+P10, P13+P15) were estimated to be 2 kg using the amounts listed in Table 3 and weighed into a 2.5 L volumetric can. The mixture was stirred at a speed of 500 rpm using a Getzmann Dispermat, instrument type CV2-SIP, with an 8 cm diameter dispersion disc. First, the binder (P3) was added, followed by the addition of all other components (P7, and P9+P10, P13+P15) while stirring. After the last addition, the mixture was stirred for a further 20 minutes.

[0212] 1) Preparation of coating formulations for application testing Compounds PPA1 to PPA5.3 of the present invention, comparative examples VGA1, VGA2, VGA4, and PV 110 (Polyvest® 110) were added up to 5% by weight each, based on their respective solid content (E1=30%, E2=57.5%, E3=56.3%). Coating formulations E1 to E3 without polybutadiene were used as blank references. VGA1, VGA2, and VGA4 are alkoxylated polybutadienes without subsequent esterification.

[0213] To incorporate the compounds PPA1 to PPA5.3 of the present invention, 20 g each of coating formulations E1 to E3 (2K system including curing agent) for comparative examples VGA1, VGA2, VGA4, and PV110 (Polyvest® 110) were weighed into a 50 ml PP screw-top jar (Durrmann GmbH & Co KG, 85664 Hohenlinden) and mixed for 2 minutes at 2000 rpm using a speed mixer (Hauschild Engineering, type DAC 150 FVZ). The prepared coating formulations were then applied to various substrates using a 100 μm spiral coating bar to a dry layer thickness of approximately 40 μm. E1 was applied to glass. E2 was applied to glass, ABS, and aluminum. E3 was applied to a steel A36Q panel. The applied substrates were dried and cured overnight at room temperature (23°C), then at 60°C for 2 days.

[0214] [Table 7] The results are shown in the following table. [Table 8]

[0215] Coating formulation E1, used as a blank reference, did not adhere to the glass as expected. Comparative example PV110 showed comparable adhesion, but the coating film was cloudy and had spots and / or pinholes.

[0216] The coating formulations using polyester-polyether modified polybutadiene according to the present invention similarly exhibited good adhesion to glass and, at the same time, very good compatibility. [Table 9]

[0217] Coating formulation E2 of the present invention exhibited better adhesion to glass than that of the comparative example. Its compatibility was at least superior to that of PV110. Coating formulations using non-esterified polyether-modified polybutadiene did not adhere to glass as well as the PPA2 coating formulations.

[0218] [Table 10] All coating formulations according to the present invention exhibited excellent adhesion to ABS. They are also compatible with the known PV110.

[0219] [Table 11]

[0220] Here again, the coating formulations according to the present invention are superior to known PV110 and non-esterified polyether-modified polybutadiene in terms of their adhesive properties.

[0221] [Table 12]

[0222] Here, the coating formulation E3 of the present invention on steel demonstrated its superiority over unesterified polyether-modified polybutadiene and known PV110 in terms of both their adhesive properties and their compatibility.

Claims

1. The polyether-modified polybutadiene is a compound based on polyether-modified polybutadiene that contains repeating units selected from the group consisting of the following divalent radicals: 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 【Chemistry 32】 【Chemical 33】 【Chemical 34】 (In the formula, Each A is independently a monovalent organic radical or a hydrogen radical; B is in each case independently selected from the group consisting of radicals of formula (4a): 【Chemistry 35】 Formula (4a) R １ are independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 16 carbon atoms; R ２ is the formula -CH ２ -O-R ３ is a radical of R ３ are independently selected from the group consisting of monovalent hydrocarbon radicals having 3 to 18 carbon atoms; R ４ is hydrogen, m, n, o, p and q are each independently 0 to 300, with the proviso that the sum of m, n, o, p and q is greater than 1; comprising all permutations of repeat units (U), (V), (W), (X), (Y), (Z), and B radical repeat units, with the proviso that 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 >0%; Characteristically, radical B has at least one ester group.

2. 2. The compound according to claim 1, characterized in that the ester group is formed by reacting a compound (I) selected as a monomer or comonomer from the group consisting of cyclic anhydrides, lactones, dilactides or cyclic carbonates with a radical B, and has a repeating unit selected from the group consisting of the following radicals: 【Chemical 37】

3. 2. Compounds according to claim 1, characterised in that the cyclic anhydrides, in pure form or in any desired mixture, are saturated, unsaturated or aromatic cyclic dicarboxylic acid anhydrides.

4. 2. A compound according to claim 1, characterized in that the lactone, in pure form or in any desired mixture, is unsubstituted or organic radical.

5. 2. The compound according to claim 1, 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 >0% to 70%.

6. 2. The compound according to claim 1, characterized in that the polybutadiene part has a number-average molar mass Mn of from 200 g / mol to 20,000 g / mol.

7. 2. The compound according to claim 1, characterized in that from 0% to 80% of the double bonds present are 1,2 vinyl double bonds and from 20% to 100% of the double bonds present are 1,4 double bonds.

8. 2. Compounds according to claim 1, characterized in that the average molar mass of radical B is from 100 g / mol to 20 000 g / mol.

9. a) reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to obtain at least one epoxy-functional polybutadiene (C); b) reacting at least one epoxy-functional polybutadiene (C) with at least one hydroxy-functional compound (D) to obtain at least one hydroxy-functional polybutadiene (E); c) reacting at least one hydroxy-functional polybutadiene (E) with at least one epoxy-functional compound (F) to obtain at least one polyether-modified polybutadiene (G); d) reacting at least one polyether-modified polybutadiene (G) with at least one compound (I) to obtain at least one polyether-polyester-modified polybutadiene (H); A method for preparing one or more polyether-modified polybutadienes comprising the steps of:

10. e) color lightening of at least one polyether-modified polybutadiene (G); The method of claim 9 further comprising the steps of:

11. 10. The process according to claim 9, characterized in that, of the double bonds of all the polybutadienes (A) used, from 0% to 80% are 1,2 vinyl double bonds and from 20% to 100% are 1,4 double bonds.

12. 10. The process according to claim 9, characterized in that the at least one polybutadiene (A) has a number-average molar mass Mn of from 200 g / mol to 20 000 g / mol.

13. 10. The method of claim 9, wherein >0% to 70% of the double bonds of at least one polybutadiene (A) are epoxidized.

14. 10. The process according to claim 9, characterized in that the at least one epoxidation reagent (B) comprises performic acid.

15. 10. The process according to claim 9, characterized in that the at least one hydroxy-functional compound (D) is selected from the group of monofunctional alcohols having 1 to 6 carbon atoms.

16. 10. The method of claim 9, wherein the total number of hydroxyl groups of all hydroxy-functional compounds (D) in step b) relative to the total number of epoxy groups of all epoxy-functional polybutadienes (C) is >1:1 to 50:

1.

17. 10. The process according to claim 9, characterized in that in step b) an acid is used as catalyst.

18. The 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 b. selected from the group of glycidyl compounds; 10. The method according to claim 9, characterized in that

19. 10. The process according to claim 9, characterized in that the alkoxylation catalyst used in step c) is selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, amines, guanidines, amidines, phosphines, SnCl4, SnCl2, SnF2, BF3, BF3 complexes and double metal cyanide (DMC) catalysts.

20. 10. The process according to claim 9, characterized in that at least one compound (I) used in step d) is selected from the group consisting of cyclic anhydrides, lactones, dilactides or cyclic carbonates as monomers or comonomers.

21. 10. The process of claim 9, characterized in that the initiator catalyst used in step d) is selected from the group consisting of zirconium butoxide, tetraisopropyl titanate, tetrabutyl titanate or titanium(IV) 2-ethylhexyloxide, zinc acetate, potassium acetate, lithium acetate, sodium acetate, calcium acetate, barium acetate, magnesium acetate, copper acetate or cobalt acetate, zinc / bismuth carboxylate, toluenesulfonic acid or trifluoroacetic acid.

22. A composition comprising the compound of claim 1.

23. 23. Use of the composition according to claim 22 for producing printing or inkjet inks or coating materials, paints and lacquers as sealants and adhesives.

24. 10. Use of the compounds of claim 1 as adhesion promoters, defoamers, dispersing additives, wetting aids or glide additives.

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