Alkoxylation compounds and their salts from nitrogen-containing polymers and alkylene oxides

Abstract

The present invention relates to alkoxylation compounds and their salts obtainable by reacting polyamines or alkanolamines with poly-(oxy-C 1-6 -alkylenecarbonyl) compounds and alkylene oxides.

Description

[0001] The present application relates generally to alkoxylation compounds and their salts produced from nitrogen-containing polymers and alkylene oxides, and in particular to their use in various industrial and cosmetic fields.

[0002] Dispersants containing one or more poly(oxy-C1-6-alkylenecarbonyl) chains (POAC chains) are known and are usually produced by polymerization of ε-caprolactone. They are generally used to disperse particulate solids in an organic solvent and contain either acidic and / or basic end groups.

[0003] Dispersants containing terminal base groups are described in application WO 94 / 21368 and comprise the reaction products of polyethyleneimine with one or more POAC chains, obtained using ε-caprolactone in the presence of aliphatic and hydroxyaliphatic carboxylic acids as chain-terminating agents. A disadvantage of these dispersants is their strong tendency to crystallize, whether in the presence or absence of solvents, which complicates their practical use. The crystallized dispersants must be heated and then homogenized before use.

[0004] EP 3 222 650 also discloses dispersing agents based on polyamines or polyimines, wherein they contain side chains based on two or more poly-(oxy-C1-6 -alkylenecarbonyl) compounds.

[0005] EP 3 943 526 also describes pigment dispersants that have amine-reactive groups containing primary, secondary, tertiary and quaternary amines.

[0006] WO 99 / 55763 and WO 01 / 21298 describe the production of dispersants based on at least two lactones. The production of such dispersants enables the suppression of crystallization. However, the lactones used are expensive and not always readily available on the market.

[0007] A dispersing resin according to EP 1 685 895 or WO 2008 / 074564 obtainable by a reaction of amino-functional polymers, polyesters and polyethers is also known.

[0008] The unpublished document EP-No. 24192525.4 also describes dispersing resins produced by the reaction of oligoaminoester monomers.

[0009] The dispersants mentioned above are based on polyetherimines. Polyethyleneimines are macromolecules with primary, secondary, and tertiary amino groups that bind nitrite very rapidly over a wide pH range. Since, in addition to its inhibitory efficacy, it also possesses suitable galenic properties and toxicological safety in both its non-nitrosated and nitrosated forms, it is particularly suitable for use in personal care products. However, it is essential to ensure that monomeric ethyleneimine is not present, as this has been described in the literature as sensitizing and allergenic. Polyethyleneimine with a degree of polymerization of 700 to 1000, 30,000 to 40,000 g / mol, was used as a 50% aqueous solution. In an aqueous system under modified NAP conditions, polyethyleneimine inhibits the nitrosation of diethanolamine by 95% in a 10-fold excess (by weight) of sodium nitrite.By measuring the free nitrite and total nitrosamine content in samples containing only polyethyleneimine and nitrite, it was shown that the nitrite is almost completely chemically bound to polyethyleneimine within a few minutes. A statistical distribution of nitrosations at the secondary amino groups of polyethyleneimine results in an N-nitroso derivative that still exhibits the properties of a basic polyamine. No volatile nitrosamines are detectable in the nitrosation reactions (<5 ppb). In the described model emulsion, the nitrosation of diethanolamine by nitrite is also almost completely inhibited. The nitrosamine yield from diethanolamine by nitrogen oxides is reduced by 65%. The nitrosating potential of bronopol and bronidox is reduced by 63% and 50%, respectively.

[0010] This application addresses the problem of developing alkoxylation compounds that exhibit improved functionality and adaptability in various applications. Specifically, the application offers improvements in the synthesis and structure of branched, saturated, nitrogen-containing end-group functionalized polymers that react with poly(oxy-C1-6-alkylenecarbonyl) compounds and alkylene oxides. The challenge lies in creating suitable alkoxylation compounds that possess a controlled molecular structure and specific chemical properties to increase efficiency and effectiveness in applications such as surfactants, emulsifiers, or other chemical products. This application addresses the need to optimize the ratios of reactants and the specific chemical groups in the polymers to achieve the desired properties.

[0011] The problem is solved by providing alkoxylation compounds and their salts obtainable by reacting polyamines or alkanolamines with poly-(oxy-C1-6-alkylenecarbonyl) compounds and alkylene oxides.

[0012] The use of branched, saturated, nitrogen-containing end-group functionalized polymers, such as polyamines or alkanolamines, enables improved solubility in organic and aqueous media, which increases the processability and application range of the alkoxylation compounds.

[0013] By combining them with poly-(oxy-C1-6-alkylenecarbonyl) compounds and alkylene oxides, as well as polyamines or alkanolamines, tailored properties such as flexibility, hardness and chemical resistance of the resulting polymers can be adjusted, leading to a wide range of industrial applications.

[0014] The formation of salts of the alkoxylation compounds can improve the thermal stability and mechanical strength of the polymers, making them suitable for high-performance applications.

[0015] This invention has the advantage that the alkoxylation compounds have a high liquidity, which facilitates their handling and processing in various industrial applications and thus increases the efficiency of production processes.

[0016] The objects according to the invention are described below by way of example, without the invention being 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 removing individual values ​​(ranges) or compounds. Where documents are cited within the scope of this description, their content, particularly with regard to the subject matter in which the document was cited, is intended to be fully incorporated into the disclosure of the present invention. Where chemical formulas are used in the present invention, the indicated indices may represent both absolute numbers and average values.For polymeric compounds, the indices preferably represent mean values. Unless otherwise stated, percentages are given as weight percent. If measured values ​​are given below, these measurements were carried out under standard conditions (25 °C and 1013 mbar), unless otherwise stated. If mean values ​​are given below, they are weight means, unless otherwise stated.

[0017] Preferably, the poly(oxy-C1-6-alkylenecarbonyl) compounds are lactones, preferably selected from the group consisting of δ-valerolactone, ε-caprolactone or lactide.

[0018] The use of copolymers allows for finer control over the molecular architecture and thus over the physical properties of the final product. Copolymers can contain specific segments that improve adhesion to various substrates, increasing the applicability of alkoxylation compounds in adhesives and coatings.

[0019] Selecting lactones from the poly(oxy-C1-6-alkylenecarbonyl) group can lead to increased biocompatibility and biodegradability of polymers, which is important for medical and environmentally friendly applications. Lactones offer the possibility of synthesizing polymers with unique properties such as elasticity and strength, making them attractive for specialized technical applications like flexible electronics and packaging materials.

[0020] The use of lactones can lead to improved control of polymer chain length and distribution, contributing to higher product consistency and predictability of material properties.

[0021] Valerolactones or caprolactones are preferably used, both of which can be unsubstituted or substituted with alkyl groups, preferably methyl groups. Preferably, ε-caprolactone or δ-valerolactone can be used, in particular ε-caprolactone.

[0022] The specific selection of δ-valerolactone, ε-caprolactone, or lactide enables the synthesis of polycaprolactone-based polymers known for their biodegradability and good mechanical properties. These lactones can lead to polymers exhibiting excellent compatibility with other polymers, facilitating the production of polymer blends and composites with enhanced properties. The use of these lactones can also facilitate the production of polymers with low melting points and good processability, thereby increasing energy efficiency during processing.

[0023] Preferably, the alkylene oxides are selected from the group consisting of identical or different C1 to C10 alkylene oxides, preferably ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide.

[0024] The selection of C1 to C10 alkylene oxides, especially ethylene oxide, propylene oxide, butylene oxide or styrene oxide, allows for fine-tuning of the hydrophilicity and lipophilicity of the polymers, optimizing their application in different environments and for different purposes.

[0025] The use of preferred alkylene oxides such as ethylene oxide and propylene oxide can lead to improved reactivity and faster polymerization rates, thus reducing production times. The ability to use the same or different alkylene oxides allows for the production of polymers with a wide variety of block structures and associated properties, resulting in a high degree of adaptability to specific requirements.

[0026] Preferably the polyamines are polyethyleneimines and diethylenetriamines, and the alkanolamines are poly(triethanolamines) and poly(triisopropanolamines).

[0027] Polyamines, polyimines and polyetheramines offer a wide range of physical and chemical properties that can be tailored by choosing the specific polymer type and its structure.

[0028] These polymers can act as effective crosslinking agents in resins and coatings, resulting in materials with improved mechanical properties and chemical resistance.

[0029] The variety of available polyamines, polyimines and polyetheramines enables the development of polymers with specific solubility profiles required for the formulation of paints, adhesives and other specialty chemicals.

[0030] The use of trialkanolamines as starting materials for condensation enables the synthesis of polyetheramines with predictable and reproducible properties, resulting in consistent product quality.

[0031] The condensation of at least two trialkanolamines can lead to polyetheramines with tailored end groups, enabling targeted functionalization and improved reactivity in subsequent chemical reactions.

[0032] By selecting specific alkanolamines, the hydrophilicity or hydrophobicity of the resulting polyetheramines can be controlled, which facilitates adaptation to water-based or organic systems.

[0033] The use of tertiary amino groups in the polymers can lead to increased reactivity towards alkoxylation reagents, enabling more efficient synthesis processes.

[0034] Polymers with tertiary amino groups can exhibit improved solubility in organic and / or aqueous media, expanding their applicability in a wide variety of formulations. The presence of amino groups can enhance the polymers' ability to bind to other molecules, potentially leading to end products with improved properties such as adhesion, viscosity modification, or emulsion stability.

[0035] The combination of hydroxy and / or amino groups as end groups can enhance the functionality of polymers, thereby expanding their potential applications in various chemical reactions and processes. Hydroxy and amino groups can serve as anchor points for the attachment of further functional molecules, enabling the synthesis of tailored polymers for specific applications. These end groups can improve the biocompatibility and environmental friendliness of the polymers, making them attractive for applications in medicine and sustainable technologies.

[0036] Polyethyleneimine offers excellent functionality due to its high density of amino groups, making it an ideal candidate for applications requiring high reactivity and binding capacity. The unique branching structures of polyethyleneimine can lead to high molecular weight polymers without significantly impairing solubility, thus facilitating processing and application. Polyethyleneimine can be effectively used as a flocculant in water treatment, as it promotes the aggregation of suspended particles and thus contributes to wastewater clarification.

[0037] Adjusting the specific mean molecular weight of the polyethyleneimine allows for tailored adaptation of the physical and chemical properties of the alkoxylation compounds, resulting in improved solubility in various solvents and optimized reactivity. Selecting a preferred molecular weight range can enhance compatibility with other components in formulations, thus expanding the application range of the alkoxylation compounds in various industrial processes.

[0038] A particularly preferred molecular weight can improve safety in handling alkoxylation compounds by minimizing dust formation and keeping the viscosity within a manageable range.

[0039] It is conceivable to cap the alkoxylation compounds with functional groups such as sulfate, sulfonate, carboxylate or phosphate groups, which can lead to an increase in the water solubility and surface activity of the alkoxylation compounds, thus improving their applicability in cleaning and washing agents.

[0040] The introduction of these functional groups allows the alkoxylation compounds to serve as effective dispersants, emulsifiers or conditioning agents in various formulations, increasing their versatility in application.

[0041] Capping can also improve the biodegradability of the alkoxylation compounds and thus contribute to a more environmentally friendly product design.

[0042] Another aspect of the invention is a process for producing alkoxylation compounds and their salts by... • presents at least one polyamine or one alkanolamine • the polyamine or the alkanolamine is heated to a temperature within a specified temperature range, • adds at least one alkylene oxide and • adds at least one poly(oxy-C1-6-alkylenecarbonyl) compound.

[0043] The process enables controlled reaction conditions and ensures that the alkoxylated polyamine compound is synthesized with consistent quality and desired properties while maintaining specific temperature and pressure parameters. The method offers the flexibility to use various alkylene oxides, allowing for the tailoring of the final product's properties, such as hydrophilicity, molecular weight, and branching, to specific applications. The reaction setup minimizes side reactions and polyamine degradation, resulting in higher yield and purity of the alkoxylated polyamine compound, which is advantageous for industrial-scale production.

[0044] Preferably, the alkylene oxide and the poly(oxy-C1-6-alkylenecarbonyl) compound are added as a homogeneous mixture.

[0045] The process is preferably carried out in the presence of a catalyst.

[0046] It is also preferred that the alkylene oxide be added multiple times. The selection of ethylene oxide (EO) and propylene oxide (PO) as the alkylene oxides for the alkoxylated polyamine compound offers the advantage of tailoring the hydrophilic-lipophilic equilibrium (HLB) of the compound, which can be beneficial for applications requiring specific solubility or dispersive properties.

[0047] The use of EO and PO in the alkoxylated polyamine compound improves the reactivity and compatibility of the compound with a wide range of other chemical substances, thus expanding its applications in various chemical formulations and industrial processes. The incorporation of EO and PO into the polyamine structure can lead to improved viscosity control and lower pour points, which are crucial parameters for processing and applying the compound in various temperature-sensitive environments.

[0048] By carrying out the alkoxylation reaction at a predetermined pressure in the range of 0 to 2 bar (absolute), the reaction can proceed under mild conditions, which minimizes the risk of degradation or unwanted side reactions and thus preserves the integrity of the alkoxylated polyamine compound.

[0049] The specified pressure range facilitates the use of simpler and potentially more cost-effective reaction equipment, as extremely pressure-resistant vessels may not be required, resulting in lower manufacturing costs and increased safety during production.

[0050] Operating within the 0 to 2 bar (absolute) pressure range can improve control over the molecular weight distribution of the alkoxylated polyamine compound, resulting in more consistent product quality and performance in the intended applications.

[0051] Preferably, the polyamine or the alkanolamine is heated to a temperature in the range of 80 °C to 130 °C, preferably 90 °C to 115 °C.

[0052] Preferably, the reaction mixture is neutralized after the reaction.

[0053] Preferred poly(oxy-C 1-6 -alkylenecarbonyl) compounds, alkylene oxides, polyamines and alkanolamines are as written above.

[0054] The use of the alkoxylation compounds and their salts according to the invention as wetting or dispersing agents, as dispersion stabilizers, as anti-settling agents, as rheology additives, as coating agents also constitutes a further invention.

[0055] The present invention is explained in more detail below with reference to examples. Alternative embodiments of the present invention are available in an analogous manner. Measurement methods: GPC measurements

[0056] GPC measurements to determine polydispersity and mean molar masses Mw as polystyrene equivalents were carried out under the following measurement conditions: Column combination JORDI-Gel DVB 5 µm, 500 Å guard column 4.6 x 50 mm, JORDI-Gel DVB 500 Å 4.6 x 250 mm, JORDI-Gel DVB mixed-bed 4.6 x 300 mm, temperature 30 °C, THF / triethyleneamine (1.5 vol%) as mobile phase, flow rate 0.4 ml / min, sample concentration 3 g / l, RI detector. Determination of the OH number:

[0057] Hydroxyl values ​​were determined according to the method DGF CV 17 a (53) of the German Society for Fat Science. Samples were acetylated with acetic anhydride in the presence of pyridine, and the consumption of acetic anhydride was determined by titration with 0.5 N potassium hydroxide in ethanol against phenolphthalein. Determination of viscosity

[0058] Viscosities were measured in accordance with DIN 53019 using a Haake RV12 rotational viscometer at 25°C. Polyamines used: Diethylenetriamine: Sigma Aldrich (CAS 111-40-0), 99% Lupasol PR 8515: Polyethyleneimine from BASF (CAS 25987-06-8) Viscosity (25 °C) 5,000 - 35,000 mPas, average molar mass 2,000 g / mol PTEA: Poly(triethanolamine, Sigma Aldrich) OH number 512 g / mol PTIPA: Poly(triisopropanolamine), Sigma Aldrich, OH number 351 g / mol Examples 1. Preparation of the alkoxylation compounds according to the invention 1.1 Alkoxylation compounds with PTIPA

[0059] 271 g of PTIPA were placed in an autoclave. Subsequently, 11.9 g of potassium methoxide were added, and the reactor contents were inertized by repeated evacuation and depressurization with nitrogen. The reaction mixture was heated to 115 °C, and 650 g of propylene oxide were added over 2.5 h and 1 h at 1 to 2 bar. A homogeneous mixture of 1083 g of propylene oxide and 638 g of caprolactone was then added over 7 h at 1 to 2 bar (absolute). A 60-minute post-reaction at 115 °C followed, after which volatile components were removed by distillation under vacuum at 95 °C. The alkoxylation product was neutralized with lactic acid and filtered from the reactor. The product was yellow and low-viscosity at room temperature. The OH number was 49.0 mg KOH / g, and the acid number was 1.2 mg KOH / g. According to GPC analysis, the product has a weight-average molar mass Mw of 10477 g / mol and a polydispersity Mw / Mn of 2.92. 1.2 Alkoxylation compounds with PEI

[0060] 79 g of Lupasol PR 8515 were placed in an autoclave. The reactor contents were inerted by repeated evacuation and depressurization with nitrogen. The reaction mixture was then heated to 115 °C with stirring. 128 g of propylene oxide were added over 20 min at an internal temperature of 115 °C and an internal pressure of 1 to 2 bar (absolute) while cooling. After 2 h of post-reaction at 115 °C, volatile components were removed by distillation under vacuum at 60 °C. Subsequently, 13.9 g of potassium methoxide were added, and the reactor contents were inerted by repeated evacuation and depressurization with nitrogen. The reaction mixture was heated to 115 °C, and a total of 701 g of PO₄ was added over 2 h. Finally, a homogeneous mixture of 842 g of propylene oxide and 1379 g of caprolactone was added over 2 h at 1 to 2 bar (absolute). This was followed by a 60-minute post-reaction at 115 °C before volatile components were removed by distillation under vacuum at 95 °C.The alkoxylation product was neutralized with lactic acid and drained from the reactor via a filter. The product was yellow and of medium viscosity at room temperature. The OH number was 52.6 mg KOH / g, and the acid number was 2.1 mg KOH / g. According to GPC analysis, the product has a weight-mean molar mass (Mw) of 15684 g / mol and a polydispersity (Mw / Mn) of 5.65. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 94 / 21368

[0003] EP 3 222 650

[0004] EP 3 943 526

[0005] WO 99 / 55763

[0006] WO 01 / 21298

[0006] EP 1 685 895

[0007] WO 2008 / 074564

[0007] EP 24192525.4

[0008]

Claims

Alkoxylation compounds and their salts obtainable by reacting polyamines or alkanolamines with poly-(oxy-C1-6-alkylenecarbonyl) compounds and alkylene oxides. Alkoxylation compounds according to claim 1, characterized in that the poly(oxy-C1-6-alkylenecarbonyl) compounds are lactones. Alkoxylation compounds according to claim 2, characterized in that the lactones are δ-valerolactone, ε-caprolactone or lactide. Alkoxylation compounds according to one of the preceding claims, characterized in that the alkylene oxides are selected from the group consisting of identical or different C1 to C10 alkylene oxides, preferably ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide. Alkoxylation compounds according to one of the preceding claims, characterized in that the polyamines are selected from the group consisting of polyethyleneimines and diethylenetriamines. Alkoxylation compounds according to one of the preceding claims, characterized in that the alkanolamines are selected from the group consisting of poly(triethanolamines) and poly(triisopropanolamines). Method for the preparation of alkoxylation compounds and their salts by: • providing at least one polyamine or an alkanolamine, • heating the polyamine or the alkanolamine to a temperature in a predetermined temperature range, • adding at least one alkylene oxide, and • adding at least one poly(oxy-C1-6-alkylenecarbonyl) compound. The method according to claim 7, characterized in that the alkylene oxide and the poly(oxy-C1-6-alkylenecarbonyl) compound are added as a homogeneous mixture. Method according to one of claims 7 - 8, characterized in that the method is carried out in the presence of a catalyst. Method according to one of claims 7 - 9, characterized in that the alkylene oxide is added multiple times. Method according to one of claims 7-10, characterized in that the polyamine or the alkanolamine is heated to a temperature in the range of 80 °C to 130 °C, preferably 90 °C to 115 °C. Method according to one of claims 7 - 11, characterized in that neutralization takes place after the reaction. Method according to one of claims 7 - 12 , characterized in that the poly-(oxy-C1-6-alkylenecarbonyl) compounds are δ-valerolactone, ε-caprolactone or lactide. Method according to one of claims 7 - 13, characterized in that the alkylene oxides are selected from the group consisting of identical or different C1 to C10 alkylene oxides, preferably ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide. Method according to one of claims 7 - 14, characterized in that the polyamines are selected from the group consisting of polyethyleneimines and diethylenetriamines. Method according to one of claims 7 - 15, characterized in that the alkanolamines are selected from the group consisting of poly(triethanolamines) and poly(triisopropanolamines). Method according to one of claims 7 - 16, characterized in that these are subsequently capped with functional groups such as sulfate, sulfonate, carboxylate or phosphate groups. Method according to one of claims 7 - 15, characterized in that these are subsequently oxidized to N-oxides. Use of the alkoxylation compounds and their salts according to any of the preceding claims 1 - 6 as wetting or dispersing agents, as dispersion stabilizers, as anti-settling agents, as rheology additives, as coating agents.