EP4698297A1 - Use of amine polymers in carbon capturing - Google Patents

Abstract

Use of a nitrogen containing polymer NP in CO2 capturing obtainable by: reaction of (i) a di- or oligoamine A with (ii) a bridging compound BC, BC being (I) phosgene or (II) comprising at least two amine reactive groups ARG, wherein BC is capable of bonding to amine groups of A to provide NP, wherein NP comprises BC bonded to at least two molecular components of A, and wherein the proportion of BC bonded to at least two A in NP is the bridging factor BF, wherein BF is greater than 50%, wherein the sum of the primary amine groups and the secondary amine groups of NP is at least 600 mg KOH/g, and wherein the number average molecular weight of NP is greater than 600 g/mol.

Description

BASF SE 230163 Amine Polymers for Use in Carbon Capturing Field of the Invention The present invention relates to the use of nitrogen-containing polymers (NP) which may optionally be alkoxylated in the field of carbon capturing, for instance in direct air capture (DAC) applications, typically where carbon dioxide is absorbed directly from air. Specifically, the amine-containing polymers are based on condensation products of polyamines, such as tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA), with di- or polyfunctional bridging compounds (BC) which are able to link together polyamine molecules. The di- or polyfunctional bridging compounds (BC) contain two or more amine reactive groups (ARG). These amine-containing polymers may optionally be alkoxylated, for instance by the action of one or more alkylene oxide(s) to produce alkoxylated nitrogen-containing polymers (ANP). Background of the Invention The increasing levels of greenhouse gases in the atmosphere is of growing global concern in view of the predicted impact on climate change. This is particularly so in view of the rising levels of carbon dioxide. It is widely accepted that even the present concentration of carbon dioxide in atmospheric air is responsible for increasing dramatic environmental changes, including droughts, flooding and disruption of ecosystems around the world. It is predicted that as carbon dioxide levels continue to rise that we are predicted see significant increases in the average temperatures of the atmosphere and oceans leading to increasing melting of polar and glacier ice which in turn would bring about rising sea levels with the inevitable flooding of low- lying lands. Increased atmospheric temperatures are also expected to increase the likelihood of powerful cyclonic storms globally. The governments of many countries are aiming to act by legislating with the aim of reducing emissions of greenhouse gases, particularly carbon dioxide, and ultimately limit global warming. Many nations have adopted The Paris Agreement which is a BASF SE 230163 legally binding international treaty on climate change. Its goal is to limit global warming to well below 2, preferably to 1.5°C, compared to preindustrial levels. In recent years there has been a great deal of effort placed in developing technologies that can achieve the goal of reducing carbon dioxide levels from atmospheric air and/or gaseous emissions. Capturing carbon dioxide at source is generally regarded as the most cost-effective. Typically, this could be large carbon- based energy facilities, natural gas processing, synthetic fuel plants, industries with major carbon dioxide emissions, for instance steelmaking and cement production, and hydrogen production plants which employ fossil fuels. One dominant carbon capture technology involves absorption or sequestering of the carbon dioxide. By far the most common active compounds used for absorbing carbon dioxide has relied on amine chemistry. Typical amines used for this purpose include alkanolamines, including monoethanolamine, diethanolamine, diisopropanolamine, pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, tetraethylenetetramine, bis (2-hydroxypropyl) amine, N,N’-bis (2-hydroxy ethyl) ethylene diamine, alkyl amines, methyl amine, linear polyethyleneimine, branched polyethyleneimine, dimethyl amine, diethyl amine, methyl diethanolamine, methyl ethanol amine, polyethylene polyamine, diethylene tri-amine, N,N’-bis-(3-aminopropyl) ethylene diamine. US Patent No 9,084,960 B2 discloses a method for reducing the CO₂ content of a gas and employs CO2 capture agents that may include mono amines (in particular secondary amines, such as diethanolamine), polyamines, monoguanidines and polyguanidines and mixtures of these compounds. US Patent No 9,533,250 B2 concerns CO2 reduction from indoor air from an enclosed space. The reference describes an amine-based compound, and it is suggested that the amine-based compound may comprise any suitable amine, such as a primary or secondary coming, or a combination thereof. The disclosure reveals that the amine-based compound may range from simple single molecules, such as ethanolamine, to large molecule amine polymers such as polyethyleneimine. Suggested in the document are monoethanolamine, ethanol amine, methylamine, BASF SE 230163 branched polyethyleneimine, linear polyethyleneimine, diethanolamine, dimethylamine, diethylamine, diisopropanolamine, tetraethylenepentamine, methyldiethanolamine, methylethanolamine, and any of several polyamines such as polyethyleneimine, or a combination thereof. US Patent No 11,229,897 B2 discloses a gas absorbing material that includes a polyamine produced using a process that is free of formaldehyde as a reaction product and/or a reactant. The disclosure describes producing reaction solution of a first amine compound and a reactant. The reactant is said to comprise a carbonate ester compound or a ketone compound. The first amine compound would react with the reactant to produce a second amine compound. US Patent No 10,010,861 B2 and its corresponding published application US 2018/0008958 A1 describe a polymeric amine in the context of absorbing carbon dioxide. The polymeric amine is said to consist of a polymer skeleton containing nitrogen atoms and branched chains bonded to the nitrogen atoms of the polymer skeleton. Each of the branched chains contains at least one nitrogen and the polymeric amine is modified by substitution of at least one of the nitrogen atoms of the polymer skeleton or the branched chains with a hydroxyl group containing carbon chain. Example 1 describes the synthesis of polyethyleneimines modified by a partial substitution with butylene oxide. This synthesis involves dissolving a polyethyleneimine (MN = 1200, 19 mmol N/g) in methanol. The disclosure reveals adding the butylene oxide to the polyethyleneimine/methanol solution in different amounts such that the mole ratio of the butylene oxide to nitrogen atoms present in the polyethyleneimine were 0.15:1, 0.37:1, and 0.54:1. The disclosure reveals removing the solvent by subjecting the solutions of the modified polyethyleneimine to heating in a vacuum oven. US Patent No 10,751,689 B2 and its corresponding published application US 2016/0199810 A1 disclose a modified polyamine in the context of absorbing carbon dioxide. The modified polyamine is the reaction product of an amine and an epoxide. The amines described are relatively low molecular weight amines such as pentaethylenehexamine (PEHA) and tetraethylenepentamine (TEPA) and such amines are known as oligoamines. Example 1 reveals preparing a modified BASF SE 230163 polyamine species based on pentaethylenehexamine (PEHA) and propylene oxide (PO). The preparation describes dissolving 10 g of the PEHA in 40 mL of water and adding 5 g of PO to the PEHA solution followed by stirring for 20 hours at room temperature. The temperature of the reaction mixture was said to be raised progressively to 60°C which was maintained for two hours. The water was said to be removed by rotary evaporator followed by overnight vacuum at below 1 mmHg. US Patent Application Publication No US 2019/0076820 A1 describes a method and apparatus for removing a volatile component from a mixture in which the method and apparatus employee a cross-linked elastomer with a glass transition temperature ≤+ 25°C as the sorbent. The disclosure describes in paragraph [0029] as one embodiment an alternative in which the VOC may be an organic monomer used in the polymerisation or cross-linking such as ethylene, propylene, and various other hydrophobic vinyl addition monomers and in addition this list includes glycidyl methacrylate, phosgene, isocyanates, amine compounds such as ethylene diamine, epoxy compounds such as oligomeric liquid epoxy resin. It is stated that the VOC may also be a petroleum derived fuel or fuel mixture, such as diesel fuel or alternatively the VOC may be an organic noxious or older causing compound such as organo- sulphur compound. Alternatively, it is stated that the VOC may be CO₂. International Application Publication No WO 2021/168498 A1 describes processes for removing carbon dioxide (CO2) from low CO2 concentration gaseous streams. The process is said to comprise contacting the gaseous stream with a hydrogel for absorbing at least some CO₂ from the gaseous stream. The hydrogel is said to comprise a cross-linked hydrophilic polymer comprising a hydrophilic polymer cross- linked with a cross-linking agent. Example 1 describes the fabrication of polyethyleneimine hydrogel particles which are cross-linked by the addition of 1,3- butadiene diepoxide cross-linking solution with varying concentrations. Example 5 describes direct air capture using PEI hydrogels and the DAC capacity was assessed. US Patent Application Publication No US 2022/0347654 A1 describes methods for generating CHEFS (chemisorption fibre sorbents) from a dope. One or more embodiments relate to a method for generating CHEFS having amine functional groups having the steps of generating a dope containing a BIAS (basic immobilised BASF SE 230163 amine sorbents) with amine groups, at least one polymer, and at least one solvent; and forming CHEFS from the dope. The CHEFS are said to be suitable for capture of CO₂. The disclosure describes in paragraph [0036] the BIAS generally comprising about 60 weight % silica and 40 weight % of a combination of polyamine and a cross-linker in which the cross-linker comprises an epoxy silane, a polyepoxide, an amino silane, and acrylamide based cross-linker, and combinations thereof. The reference describes an exemplary BIAS comprising silica particles having an average particle size of 25 µm and polyethyleneimine were in the polyethyleneimine is a cross-linked polyethyleneimine Mw = 800 and N,N-diglycidyl-4- glycidyloxyaniline. Polyethyleneimines (PEI) and other polyalkyleneimines, such as polypropyleneimines (PPI), are known for their superior performance with respect to stability as CO2 adsorbents in DAC and CO2 capture in post-combustion processes and from CO2 point sources. These sources are typically present in three areas, namely fuel combustion activities, industrial processes and natural gas processing. It is known that linear PEI and linear PPI are better than branched PEI and branched PPI and this is believed to be as a result of the relatively high content of secondary amino groups in the linear products compared to the corresponding branched products. It is known that a low fraction of primary NH functionality is more beneficial for absorbing CO2. This can be improved by alkoxylation of the PEI or PPI by alkoxylation, but such improvement tends to be limited. Lower molecular weight oligoamines, such as tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA), are also known to be good CO₂ sorbents. It has been proposed to use such polyamines for CO₂ capture in various carbon capture applications such as DAC in the patents and literature. However, such low molecular weight polyamines suffer the disadvantage of exhibiting higher vapour pressure and this can be particularly problematic for recycling of the sorbent at elevated temperatures, typically in the CO2 desorption step, where higher polyamine losses are observed. BASF SE 230163 An objective of the present invention was to develop in nitrogen-based product which displays a good or improved capacity for absorbing CO2, and the inventors especially set out to provide such a product which exhibits a more beneficial ratio of secondary to primary NH functionality. A further particular objective was to develop such a product which could be more easily recycled, typically during the CO2 desorption step involving elevated temperatures. Summary of the Invention The present invention provides a use of an optionally alkoxylated nitrogen containing polymer in carbon dioxide capturing, the optionally alkoxylated nitrogen containing polymer being obtainable by a process comprising the following steps: a) reaction of (i) a di- or oligoamine (A) with (ii) a bridging compound (BC), the bridging compound (BC) (I) being phosgene; or (II) comprising at least two amine reactive groups (ARG), wherein the bridging compound (BC) is capable of bonding to amine groups of at least two di- or oligoamine (A) molecules, to provide the nitrogen containing polymer (NP), wherein the nitrogen-containing polymer (NP) comprises bridging compound (BC) molecular components that are bonded to at least two molecular components of di- or oligoamine (A), and wherein the proportion of bridging compound (BC) molecules bonded to at least two di- or oligoamine (A) molecules is the nitrogen-containing polymer (NP) bridging factor (BF), wherein the bridging factor (BF) is greater than 50%, wherein the sum of the primary amine groups and the secondary amine groups of the nitrogen-containing polymer (NP) is at least 600 mg KOH/g, and wherein the number average molecular weight (Mn) of the nitrogen-containing polymer (NP) is greater than 600 g/mol and BASF SE 230163 b) optionally reaction of the nitrogen containing polymer (NP) with an alkylene oxide (AO), preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is no more than 0.25, in order to obtain alkylene oxide side chains (AB) linked to nitrogen atoms of the nitrogen containing polymer (NP) thus providing the alkoxylated nitrogen containing polymer (ANP). The present invention also includes a method of capturing carbon dioxide, comprising contacting a mixture of gases comprising carbon dioxide by an optionally alkoxylated nitrogen containing polymer in carbon dioxide capturing, the optionally alkoxylated nitrogen containing polymer being obtainable by a process comprising the following steps: a) reaction of (i) a di- or oligoamine (A) with (ii) a bridging compound (BC), the bridging compound (BC) (I) being phosgene; or (II) comprising at least two amine reactive groups (ARG), wherein the bridging compound (BC) is capable of bonding to amine groups of at least two di- or oligoamine (A) molecules, to provide the nitrogen containing polymer (NP), wherein the nitrogen-containing polymer (NP) comprises bridging compound (BC) molecular components that are bonded to at least two molecular components of di- or oligoamine (A), and wherein the proportion of bridging compound (BC) molecules bonded to at least two di- or oligoamine (A) molecules is the nitrogen-containing polymer (NP) bridging factor (BF), wherein the bridging factor (BF) is greater than 50%, wherein the sum of the primary amine groups and the secondary amine groups of the nitrogen-containing polymer (NP) is at least 600 mg KOH/g, BASF SE 230163 and wherein the number average molecular weight (Mn) of the nitrogen-containing polymer (NP) is greater than 600 g/mol and b) optionally reaction of the nitrogen containing polymer (NP) with an alkylene oxide (AO), preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is no more than 0.25, in order to obtain alkylene oxide side chains (AB) linked to nitrogen atoms of the nitrogen containing polymer (NP) thus providing the alkoxylated nitrogen containing polymer (ANP), contacting the optionally alkoxylated nitrogen-containing polymer (NP) with carbon dioxide. Detailed Description of the Invention The bridging compound (BC) is a compound that should bond to at least two amine groups i.e. of at least two different di- or oligoamine (A) molecules to form a bridge in order to build the structure of the nitrogen containing polymer (NP). Such a bridging compound (BC) is either phosgene or a compound that comprises at least two amine reactive groups (ARG) and be capable of bonding to at least two amine groups in order to link together at least two molecules of the di- or oligoamine (A). Phosgene will react with a primary amine group of the di- or oligoamine (A) to form an isocyanate group which will further react with an amine group of another molecule of the di- or oligoamine, thereby forming the bridge between molecules of the di- or oligoamine. Preferably, the bridging compound (BC) comprises at least two amine reactive groups (ARG) and is capable of bonding to at least two amine groups of the di- or oligoamine. The bridging compound (BC) desirably may be a reaction product formed by reacting (i) a di- or polyol with (ii) an epihalohydrin, preferably epichlorohydrin. BASF SE 230163 The di- or polyols are organic compounds comprising two or more hydroxyl groups. This includes diols, triols or compounds with four or more hydroxyl groups. Suitable examples of diols include aliphatic compounds containing 2 to 14 carbon atoms. Specific examples include ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,3-diol (trimethylene glycol), butane-1,2-diol, butane- 1,3-diol, butane-1,4-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, cyclopentane-1,2-diol, 4-methylcyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol and 2-ethylhexane- 1,3-diol. Preferred diols are ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,3-diol (trimethylene glycol). Examples of triols include propane-1,2,3-triol (glycerol), butane-1,2,3-triol, butane-1,2,4-triol, pentane-1,2,3- triol, pentane-1,2,4-triol, pentane-1,2,5-triol, pentane-1,3,5-triol. Preferred is propane-1,2,3-triol (glycerol). Other polyols include pentaerythritol. Suitable polyols include sugar alcohols which are typically derived from sugars. They are characterised by having one hydroxyl group attached to each carbon atom. Examples of sugar alcohols include erythritol, xylitol, sorbitol, mannitol, threitiol, arabitol, ribitol, galactitol, fucitol, iditol, inositol and volemitol. Other polyols may include polyethers or polyester polyols carrying at least two hydroxyl groups, generally as terminal groups. Polyethers would generally contain repeating alkylene oxide units with hydroxyl groups as terminal groups. Polyester polyols would generally contain repeating alkylene ester linkages but having terminal hydroxyl groups. Preferably the number of repeating units for both polyethers and polyester polyols would be no more than six, for instance 2 to 6, preferably 2 to 3. Preferred polyethers as polyols include diethylene glycol and triethylene glycol. Preferably, the di- or polyol is selected from the group consisting of 1,4-butandiol, 1,6-hexanediol, 1,3-neopentylglycol, 1,4-cyclohexanedimethanol, glycerine and trimethylolpropane. BASF SE 230163 The epihalohydrin would normally be epichlorohydrin. Epichlorohydrin is also known as (chloromethyl)oxirane, 1-chloro-2,3-epoxypropane, γ-chloropropylene oxide, glycidyl chloride or ECH. The reaction product of (i) the di- or polyol with (ii) epihalohydrin, preferably epichlorohydrin, will contain glycidyl groups and bonded to the di- or polyol radical by an ether linkage typically in place of the hydroxyl groups. Such reaction product comprising at least two glycidyl groups would be an effective bridging compound (BC). Preferably the reaction product of (i) the di- or polyol with (ii) epihalohydrin, preferably epichlorohydrin, will be a reaction product with at least 55 mol% of the reaction product molecules containing two epoxy groups, suitably greater than 60 mol %, preferably greater than 70 mol % and more preferably still greater than 80 mol %. In one more preferred embodiment the reaction product is formed by the reaction of a mixture of (i) diols and triols with (ii) epihalohydrin, preferably epichlorohydrin, and in which the reaction product has greater than 90 mol % of the reaction product molecules containing two epoxy groups. Depending upon the purity of the di- or polyol the reaction product may contain up to 45 mol % one epoxy group, suitably less than 40 mol %, preferably less than 30 mol %, more preferably less than 20 mol %. Particularly preferably less than 10 mol % of the reaction product molecules contain one epoxide group, such as less than 5 mol %, typically less than 1 mol %, for example less than 0.5 mol %, for instance less than 0.1 mol %. Reaction products containing three or more epoxide groups may also be used as the bridging compound (BC) for reacting with the di- or oligoamine. Suitably, the reaction product may comprise a mixture comprising molecules with predominantly two epoxide groups, molecules containing three or more epoxide groups and molecules containing one epoxide group. Desirably, such a reaction product may comprise up to 40 mol % molecules containing three or more epoxide groups, more desirably up to 30 mol % molecules containing three or more epoxide groups. Furthermore, it is particularly preferred that less than 20 mol%, especially preferably less than 10 mol%, of the reaction product molecules contain three or more epoxide groups. BASF SE 230163 The bridging compound (BC) preferably is a compound comprising at least two amine reactive groups (ARG). The amine reactive groups (ARG) in the present invention can be any group which are reactive towards an amine group. Typically, such amine reactive groups (ARG) would include functional groups such as epoxide, isocyanate, blocked isocyanate, ester and acid anhydride. In one preferable form the bridging compound (BC) comprises at least two epoxide groups. The at least two epoxide groups as amine reactive groups (ARG) will readily react with the amine groups, preferentially the primary amine groups, of the di- or oligoamines (A) to form amino alcohol linkages between the di- or oligoamines (A). Suitably the two epoxide groups can be part of an aliphatic molecule, such as 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane and 1,2,7,8- diepoxyoctane. More preferably each epoxide is part of a glycidyl group and more preferably still the at least two glycidyl groups are glycidyl ether groups. Suitable examples of bridging compounds (BC) comprising at least two glycidyl ether groups include diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanedioldiglycidyl ether, neopentyldiglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 5,5-dimethyl-3,7-dioxa-1,9(2)- bis(oxirana)-4,6(2,4)-dibenzenanonaphane. Another suitable group of bridging compounds (BC) are diisocyanates in which the amine reactive groups (ARG) are two isocyanate groups. Isocyanates will readily react with amine groups to give a urea derivative. Therefore, the two isocyanate groups of the diisocyanates can readily react with the amines, preferentially the primary amine groups, of two di- or oligoamine (A) molecules and link them together by a urea linkage. Examples of suitable diisocyanates include methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylene dicyclohexyl diisocyanate or hydrogenated MDI (HMDI) and isophorone (IPDI). It may be desirable to employ blocked diisocyanates in order to control the reaction between the isocyanate groups and the amine groups of the di- or oligoamine (A). This may be to allow the reaction to take place following a particular trigger, for instance at a specific temperature or on exposure to UV light. Examples of blocking BASF SE 230163 agents to be used with the diisocyanates to render them blocked include methyl ethyl ketone oxime. Typically, it may not be necessary to employ blocked diisocyanates. A further suitable group of bridging compounds (BC) are diesters. A suitable example includes carbonate esters which can react with amine groups of two di- or oligoamine (A) molecules by aminolysis to form a urea bridging the di- or oligoamine (A) moieties. A further suitable example includes terephthalic esters which also will react with amine groups of two di- or oligoamine (A) molecules to form a terephthalic diamide bridge between the di- or oligoamine molecules. The bridging compound (BC) may comprise at least two acid anhydride groups as the amine reactive groups (ARG). Acid anhydride groups are reactive towards amines and on reaction with amines form amide linkages. Preferably, the bridging compound (BC) is a compound comprising at least two amine reactive groups (ARG) selected from the group consisting of a compound comprising at least two glycidyl ether groups at least two diisocyanate groups. More preferably the bridging compound (BC) is a compound comprising at least two glycidyl ether groups. More preferably the bridging compound (BC) is a compound comprising at least two glycidyl ether groups is a compound that (i) comprises at least two times a structure according to formula (I) wherein the dotted line indicates bond to the remaining part of the compound comprising at least two glycidyl ether groups, preferably the compound comprising at least two glycidyl ether groups possesses the structure according to formula (I) two times; and/or (ii) is selected from the group consisting of 1,4-butandiol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether, diglycidyl ether, 1,3-neopentylglycol BASF SE 230163 bisglycidyl ether, 1,4-cyclohexanedimethanol bisglycidyl ether, ethylene glycol bisglycidyl ether, glycerine triglycidyl ether and trimethylolpropane triglycidyl ether. The bridging compound (BC) should comprise at least two amine reactive groups (ARG) in order to satisfactorily form molecular bridges between the di- or oligoamine molecules (A). The bridging compound (BC) may comprise a mixture of bridging compound (BC) molecules containing at least two amine reactive groups (ARG) and molecules containing only one amine reactive group (ARG). In general, the amine reactive groups (ARG) of the bridging compound (BC) molecules contained in such a mixture should be the same, same category or at least would not react with each other. Normally, these amine reactive groups (ARG) typically are the same as each other. Suitably the bridging compound (BC) comprises a predominance of bridging compound (BC) molecules comprising at least two amine reactive groups (ARG). In some cases, the bridging compound (BC) may comprise up to 45 mol % mono functional molecules i.e. comprising only one amine reactive group (ARG). This may depend upon the purity of the bridging compound. For instance, bisglycidyl ethers may comprise up to 45 mol % mono functional compounds containing only one epoxide group and at least 55 mol % of the bisglycidyl ether molecules containing two epoxide groups. Preferably the bridging compound (BC) comprises predominantly bridging compound (BC) molecules containing two amine reactive groups (ARG), preferably both of which are epoxide groups. Suitably the bridging compound (BC) comprises greater than 60 mol % compounds having two amine reactive groups (ARG), preferably both being epoxide groups and preferably less than 40 mol % compounds having one amine reactive group (ARG), preferably an epoxide group; and preferably greater than 70 mol % compounds having two amine reactive groups (ARG), preferably both being epoxide groups and preferably less than 30 mol % compounds having one amine reactive group (ARG), preferably an epoxide group; and more preferably greater than 80 mol % compounds having two amine reactive groups (ARG), preferably both being epoxide groups and preferably less than 20 mol % having one amine reactive group (ARG), preferably an epoxide group. Particularly preferably BASF SE 230163 less than 10 mol % of the bridging compound (BC) molecules should contain only one amine reactive group (ARG), preferably an epoxide group. It is especially preferred that the bridging compound (BC) comprises substantially no molecules containing only one amine reactive group (ARG). Thus, it is possible that a relatively small proportion of compounds containing only one amine reactive group (ARG) are present with the bridging compound (BC). Nevertheless, preferably this should be kept to a minimum as higher levels of such compounds containing only one amine reactive group (ARG) could be detrimental to the building of the molecular structure of the nitrogen containing polymer (NP). Generally, the amount of compound containing only one amine reactive group (ARG) should be less than 10 mol %, normally less than 5 mol %, typically less than 1 mol %, preferably less than 0.5 mol %, more preferably less than 0.1 mol %. Especially preferably the bridging compound (BC) should contain substantially no or no compounds containing only one amine reactive group (ARG). Bridging compounds (BC) containing three or more amine reactive groups (ARG), preferably epoxide groups may also be used for reacting with the di- or oligoamine (A). Suitably, the bridging compound (BC) may comprise a mixture of bridging compound (BC) molecules comprising predominantly molecules with two amine reactive groups (ARG) and the remainder made up of molecules containing three or more amine reactive groups (ARG) and/or molecules containing one amine reactive group (ARG). In a preferred form, the mixture should be of bridging compound (BC) molecules comprising predominantly molecules with two epoxide groups and the remainder made up of molecules containing three or more epoxide groups and/or molecules containing one epoxide group. Particularly preferably less than 20%, especially preferably less than 10%, of the bridging compound (BC) molecules have three or more amine reactive groups (ARG). This is to avoid undesirable levels of cross-linking of the nitrogen-containing polymer (NP) which may adversely affect the solubility of the polymer in water. Cross-linking of the nitrogen-containing polymer (NP) can be acceptable provided that the solubility of the nitrogen-containing polymer (NP) in water is not adversely BASF SE 230163 affected. Generally, cross-linking can be tolerated as it may even reduce the volatility of the nitrogen-containing polymer (NP) to offset any small impact on water solubility. The degree of cross-linking may be controlled by adjusting the ratio of reaction product molecules containing two epoxide groups to reaction product molecules containing three or more epoxide groups to reaction product molecules containing only one epoxide group. The di- or oligoamine (A) desirably comprises at least 2 amino groups and more desirably from 2 to 12 amino groups. Preferably the di- or oligoamine (A) comprises from 2 to 8 amino groups, for instance 3, 4, 5, 6, 7 or 8 amino groups, more preferably from 4 to 8 amino groups. Generally, the di- or oligoamine (A) has at least one carbon atom per nitrogen atom, preferably 1 to 5 carbon atoms per nitrogen atom, more preferably 1 to 3 carbon atoms per nitrogen atom. Typically, the nitrogen atoms would be separated from each other by 2 to 6 carbon atoms of at least one saturated hydrocarbyl radical, for instance alkylene or alkanetriyl radicals, preferably alkylene radicals of from 2 to 4 carbon atoms. Desirably the di- or oligoamine (A) has at least two primary and/or secondary amino groups. Preferably the di- or oligoamine (A) has at least two primary amino groups and more preferably has a predominance of secondary amino groups to primary amino groups. The weight average molecular weight (MW) of the di- or oligoamine (A) suitably lies in the range of from 50 to 500 g/mol, preferably 60 to 300 g/mol, more preferably from 80 to 250 g/mol, more preferably still from 120 to 250 g/mol, especially preferably from 150 to 250 g/mol. Preferably the at least one di- or oligoamine (A) (i) has at least 2 amino groups, suitably 2 to 12 amino groups, preferably 2 to 8 amino groups, more preferably 3, 4, 5, 6, 7 or 8 amino groups; and BASF SE 230163 (ii) has at least one carbon atom per nitrogen atom, preferably 1 to 5 carbon atoms per nitrogen atom, more preferably 1 to 3 carbon atoms per nitrogen atom; and (iii) comprises at least two primary and/or secondary amino groups, preferably at least two primary amino groups; and (iv) has a molecular weight (Mw) that lies in the range of 50 to 500 g/mol, preferably in the range of 60 to 300 g/mol, more preferably 80 to 250 g/mol, more preferably still from 120 to 250 g/mol, especially preferably from 150 to 250 g/mol. Independently of or in addition to the above characteristics (i), (ii), (iii) and (iv) the di- or oligoamine (A) preferably is selected from the group consisting of ethylenediamine, hexamethylenediamine, methylcyclohexane diamine (MCDA), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), dipropylene-triamine (DPTA), tripropylene-tetramine (TPTA), tris(2- aminoethyl)amine (TAEA), tetrapropylenpentamine (TPPA), N,N'-Bis-(3- aminopropyl)-ethylenediamine (N4-amine), 3-(2-aminoethylamino)propylamine (N3- amine), spermine, spermidine, triamino nonane, diethylentriamin (DETA), triethylentetramine (TETA), tetraethylenpentamine (TEPA), pentaethylenhexamine (PEHA) and a compounds according to Formulas (II) to (X), BASF SE 230163 (X). In some cases, it may be desirable that the di- or oligoamine (A) contains some degree of alkoxylation. Such alkoxylated di- or oligoamine (A) would then be reacted with the bridging compound (BC) in step (a). Generally, the degree of alkoxylation should only be partial so as not to prevent or adversely affect the reaction of the di- or oligoamine (A) from reacting with the bridging compound (BC) in step (a). For instance, the molar ratio of alkylene oxide (AO) to NH functionality the of the di- or oligoamine (A) is no more than 0.25, suitably from 0.05 to 0.25 and more suitably from 0.05 to 0.20. Preferably the di- or oligoamine (A) is substantially not alkoxylated, for instance having a molar ratio of alkylene oxide (AO) to NH functionality the of the di- or oligoamine (A) of less than 0.05, for instance less than 0.01, especially less than 0.001. Most preferably the di- or oligoamine (A) comprises no alkoxylation. Desirably the molar ratio of bridging compound (BC) to di- or oligoamine (A) may be in the range from 0.35 to 0.85, preferably from 0.4 to 0.8, more preferably from 0.45 to 0.75, particularly from 0.5 to 0.7. It is particularly desirable that the molar ratio of epoxide groups of the bridging compound (BC) to NH function of the di- or oligoamine (A) to form the optionally alkoxylated nitrogen-containing polymer (NP) less than 0.5, preferably up to 0.45, more preferably up to 0.4, for instance from 0.1 to 0.45, desirably from 0.15 to 0.4, and more desirably 0.15 to 0.3. NH function represents the amine number and is calculated by determination of the secondary amino groups and primary amino groups, where NH = (number of secondary amino groups) + (2 x (number of primary amino groups)). NH is BASF SE 230163 determined by titration of the respective polyalkyleneimine with trifluoromethansulphonic acid. In one embodiment of the optionally alkoxylated nitrogen-containing polymer (NP) the proportion of the di- or oligoamine molecular components with less than two amine groups bonded to bridging compound (BC) molecular components is less than 25%. However, it is preferable that the optionally alkoxylated nitrogen-containing polymer (NP) comprises a proportion of di- or oligoamine molecular components with less than two amine groups bonded to bridging compound (BC) molecular components is at least 20%, suitably from 25% to 90%, desirably from 30% to 85%, more desirably from 35% to 80%, typically from 40% to 80%, often from 45% to 75% and preferably from 50% to 75%. The optionally alkoxylated nitrogen-containing polymer (NP) is desirably prepared by reacting the di- or oligoamine compound with the bridging compound (BC) other suitable reaction conditions to form the nitrogen containing polymer (NP). The nitrogen-containing polymer (NP) can be alkoxylated with a suitable alkoxylating agent, typically alkylene oxide, when preparing an alkoxylated nitrogen-containing polymer (NP). Suitably the nitrogen-containing polymer (NP) may be prepared by combining the di- or oligoamine compound with the bridging compound (BC) in a suitable vessel. The reaction may be carried out anhydrously or in the presence of a suitable solvent. When a solvent is employed, it may be aqueous but preferably it is an organic solvent, more preferably a polar organic solvent, for instance methanol, ethanol, isopropanol, acetone, DMF, or chloroform, more preferably still methanol. It may be desirable to use solvents for such reactions where the reaction products would build up more viscosity. When higher ratios of bridging compound to di- or oligoamine (amine compound) are employed, for instance at least 1.3 equivalents bridging compound to 2 equivalents of amine compound, it may be desirable to employ a solvent, particularly an organic polar solvent, most preferably methanol. The reaction may be carried out at any suitable temperature. Suitably, the temperature may be BASF SE 230163 higher than 25°C, typically at least 30°C, for instance from 30°C to 90°C, desirably from 35°C to 85°C. When the reaction is carried out in the presence of a solvent, suitably methanol, the reaction temperature may be for instance from 30°C to 45°C, typically from 30°C to 40°C. When the reaction is carried out in the absence of a solvent, i.e. anhydrously, the reaction temperature may be from 35°C to 90°C, for instance from 45°C to 85°C, suitably from 50°C to 85°C, for instance from 60°C to 85°C, preferably from 70°C to 85°C, more preferably from 75°C to 85°C. The reaction time may depend on the mass of reactants, the presence or absence of a solvent and the reaction temperature. Generally, the reaction may be completed over a period of from one hour to 3 hours, for instance from 1.5 to 2.5 hours. Where a solvent has been employed, particularly an organic solvent, such as methanol, the solvent would typically be removed from the so formed nitrogen-containing polymer (NP) at the end of the reaction. This may be achieved by employing an elevated temperature and/or reduced pressure. Typically, this may employ temperatures of greater than 60°C, for instance from 75°C to 95°C. Reduced pressures where employed may be pressures below 1.0 bar, for instance below 500 mbar, typically below 250 mbar. The nitrogen-containing polymer (NP) employed in the present invention normally would be a liquid at 25°C. The nitrogen-containing polymer (NP) may be alkoxylated as described herein. The use according to the invention includes the use of the nitrogen containing polymer (NP), i.e. the polymer that has not been alkoxylated. In one preferred embodiment the optionally alkoxylated nitrogen-containing polymer is an alkoxylated nitrogen-containing polymer (ANP). Alkoxylation of the nitrogen- containing polymer (NP) is normally achieved by reacting the nitrogen-containing polymer (NP) with an alkylene oxide. Preferably the alkoxylation process is carried out in an aqueous medium. The alkylene oxide (AO) reacts with an NH group of the nitrogen-containing polymer (NP) to provide an alkoxylated substituent bonded to the nitrogen atom. Alternatively, the alkoxylated nitrogen-containing polymer may be derived from the reaction of di- or oligoamine (A) that is already alkoxylated before BASF SE 230163 reaction with the bridging compound (BC). Pre-alkoxylation of the di- or oligoamine (A) may negate any requirement to post alkoxylate nitrogen-containing polymer. In some cases, it may be desirable to further alkoxylated the nitrogen-containing polymer that has been derived from pre-alkoxylated di- or oligoamine (A). Preferably, where alkoxylation of the nitrogen-containing polymer (NP) is desired, the alkoxylation step (b) should take place after formation of the nitrogen-containing polymer (NP) in step (a). Desirably the molar ratio of alkylene oxide (AO) to NH functionality the of the nitrogen-containing polymer (NP) is up to 0.25, preferably in the range from 0.05 to 0.25 and more preferably from 0.05 to 0.2, more preferably from 0.05 to 0.15, for instance from 0.075 to 0.125. As described above, NH represents the amine number and is calculated by determination of the secondary amino groups and primary amino groups, where NH = (number of secondary amino groups) + (2 x (number of primary amino groups)). NH is determined by titration of the respective polyalkyleneimine with trifluoromethansulphonic acid. In a typical representation, the alkoxylated nitrogen containing polymer (ANP) comprises a structural element according to Formula (XI) wherein the dotted lines indicate bonds to the remaining parts of the alkoxylated nitrogen containing polymer; and AB represents one alkylene oxide side chain. The alkylene oxide (AO) may be any suitable alkylene oxide for the alkoxylation of the nitrogen-containing polymer (NP). In one desirable embodiment of the alkylene oxide may be one or mixtures of more than one C₂-C₁₂-alkylene oxide, desirably a BASF SE 230163 C2-C10-alkylene oxide, more desirably a C2-C8-alkylene oxide, preferably ethylene oxide, propylene oxide or butylene oxide, more preferably propylene oxide or butylene oxide. One desirable embodiment the alkylene oxide (AO) is a mixture of alkylene oxides comprising a mixture of C2-C4 alkylene oxides and C8-C12 alkylene oxides, desirably having a molar ratio of C2-C4 alkylene oxides to C8-C12 of from 2:1 to 20:1, more desirably from 5:1 to 10:1. Nevertheless it is most preferred that the alkylene oxide (AO) is substantially only one alkylene oxide, for instance greater than 90% by weight, desirably greater than 95% and more desirably greater than 99% only one alkylene oxide. The optionally alkoxylated nitrogen-containing polymer will usually have a weight average molecular weight (MW) at least 70% greater than the weight average molecular weight (M_W) of the di- or oligoamine (A). Typically, the weight average molecular weight (MW) of the option alkoxylated nitrogen-containing polymer is at least 150% greater, preferably at least 300% greater, than the di- or oligoamine (A). Desirably the number average molecular weight (Mn) of the optionally alkoxylated nitrogen-containing polymer lies in the range of 600 to 50,000 g/mol, for example from 600 to 20,000 g/mol, preferably from 600 to 10,000 g/mol, more preferably from 800 to 5000 g/mol, more preferably from 600 to 2500 g/mol, more preferably still from 1000 to 2500 g/mol. In one preferred embodiment, the fraction of the optionally alkoxylated nitrogen - containing polymer with molecular weight greater than 15,000 g/mol is less than 10%, and more preferably the fraction with molecular weight greater than 10,000 g/mol is less than 10%. The polydispersity index (Mw/Mn) of the nitrogen-containing polymer which is not alkoxylated (this includes the nitrogen-containing polymer (NP) prior to any alkoxylation) may be in the range of up to 7, suitably from 2 to 7, for instance from 3 to 7. BASF SE 230163 The ratio of secondary amine to primary amine in the nitrogen containing polymer either not alkoxylated or prior to alkoxylation may be from 1.3:1 to 2.2:1, for instance 1.4:1 to 2.1:1. The sum of the primary amine groups and the secondary amine groups of the nitrogen-containing polymer (NP) not alkoxylated (including the polymer prior to alkoxylation) is at least 600 mg KOH/g. For example, this may be at least 603 mg KOH/g. The NH function of the nitrogen-containing polymer (NP) not alkoxylated (including the polymer prior to alkoxylation) is at least 800 mg KOH/g. For instance, this may be at least 804 mg KOH/g. The OH number of the nitrogen containing polymer (NP) not alkoxylated (including the polymer prior to alkoxylation) may be from 160 to 260 mg KOH/g, for instance 170 to 250 mg KOH/g. The optionally alkoxylated nitrogen-containing polymer (NP) should be a liquid at 25°C. Preferably the optionally alkoxylated nitrogen-containing polymer is soluble in water. Soluble in water means the optionally alkoxylated nitrogen-containing polymer will be soluble or miscible up to a concentration of 350 g/l of deionised water at a temperature of 25°C. The optionally alkoxylated nitrogen-containing polymer is deemed to be soluble in water if the aqueous solution of the polymer remains clear without any observed opaqueness or phase separation, preferably after storage, for instance after storage for at least seven days. The optionally alkoxylated nitrogen-containing polymer may be linear or branched. In one preferred embodiment the alkoxylated nitrogen-containing polymer is branched. In this preferred embodiment the branched alkoxylated nitrogen-containing polymer is preferably soluble in water. In another preferred embodiment the alkoxylated nitrogen-containing polymer is linear. In this preferred embodiment the linear alkoxylated nitrogen-containing polymer is water-soluble. BASF SE 230163 In one suitable embodiment the optionally alkoxylated nitrogen-containing polymer is substantially unquaternised, for instance where less than 10% of the nitrogen atoms present in the optionally alkoxylated nitrogen-containing polymer are quaternised, preferably less than 5%, more preferably less than 1%, especially preferably less than 0.5%, more especially preferably less than 0.1%. In this embodiment particularly preferably the optionally alkoxylated nitrogen-containing polymer is not quaternised. In one preferred embodiment the optionally alkoxylated nitrogen containing polymer is alkoxylated and the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is <0.25, preferably from 0.05 to 0.24 and more preferably from 0.05 to 0.2, and wherein more than 50 mol% of the alkylene is based on ethylene oxide, propylene oxide and/or butylene oxide, preferably butylene oxide. In the following preferred embodiments, (1) in step a) the di- or oligoamine (A) is TPTA or PEHA and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (2) in step a) the di- or oligoamine (A) is 3-(2-aminoethylamino)propylamine (N3- amine) and the compound comprising at least two glycidyl ether groups is 1,4- butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (3) in step a) the di- or oligoamine (A) is N,N'-Bis-(3-aminopropyl)- ethylenediamine (N4-amine) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether; and BASF SE 230163 in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (4) in step a) the di- or oligoamine (A) is triethylentetramine (TETA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (5) in step a) the di- or oligoamine (A) is tris(2-aminoethyl)amine (TAEA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or1,6-hexanediol bisglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (6) in step a) the di- or oligoamine (A) is diethylentriamine (DETA) and the compound comprising at least two glycidyl ether groups is1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether, 1,3- neopentylglycol bisglycidyl ether or 1,4-cyclohexanedimethanol bisglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (7) in step a) the di- or oligoamine (A) is triamino nonane and the compound comprising at least two glycidyl ether groups is ethylene glycol diglycidyl ether or 1,4- butandiol bisglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (8) in step a) the di- or oligoamine (A) is tetraethylenpentamine (TEPA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,4-butandiol bisglycidyl ether or diglycidyl ether; and BASF SE 230163 in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP); or (9) in step a) the di- or oligoamine (A) is pentaethylenhexamine (PEHA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol bisglycidyl ether; and in step b) no more than 0.25 mol, preferably from 0.05 to 0.25, more preferably from 0.05 to 0.2, of propylene oxide or butylene oxide is employed per mol of NH- functionality of nitrogen containing polymer (NP). The optionally alkoxylated nitrogen-containing polymer can suitably be employed for capturing carbon dioxide from a mixture of gases. By mixture of gases we mean carbon dioxide and at least one other gas. Desirably the mixture of gases is either atmospheric air or any sort of exhaust fumes. Typically, the exhaust fumes may for instance be gases emitted from an industrial process, including power generating plants. Additionally, the exhaust fumes may be produced from various other devices such as heat generating devices, including commercial and domestic boilers, or other devices such a motion generating devices, for instance combustion engines for vehicles. Preferred aspect of the use, the optionally alkoxylated nitrogen containing polymer can be incorporated into a formulation for direct capturing of carbon dioxide, preferably the formulation being the alkoxylated nitrogen containing polymer on a solid support or the optionally alkoxylated nitrogen containing polymer being in a liquid composition, for instance as in aqueous solution. More preferably the optionally alkoxylated nitrogen-containing polymer is supported on a solid inorganic support (SIS). The solid inorganic support (SIS) preferably has a primary particle size of from 5 to 200 nm, for instance in the range from 5 to 50 nm and exhibits a secondary size structure of from 5 to 500 µm, preferably from 30 to 300 µm. Suitably the solid inorganic support (SIS) is either particulate or a macroscopic support. The solid inorganic support (SIS) may be a porous support. Such porous BASF SE 230163 solid inorganic support (SIS) may comprise clay. Typically, such a clay may include one or more of bentonite, attapulgite, kaolinite, montmorillonite, ball clay, Fullers Earth, hectorite, palygorskite, saponite, and sepiolite and halloysite. Desirably the porous solid inorganic support (SIS) may include silica, such as nanosilica, especiallyfumed silica or precipitated silica; titania; magnesia (MgO); alumina, such as gamma alumina; silica-alumina (SiO₂-Al₂O₃); zinc chloride hydrate; calcium sulphate; zeolite, such as natural zeolite or synthetic zeolite. Suitably the solid inorganic support (SIS) may be any of the commercially available silicas, including the fumed silicas, AEROSIL® from Evonik, CAB-O-SIL® from Cabot, and REOLOSIL® from Tokuyama; the precipitated silicas, HI-SIL® from PPG Industries, SIPERNAT® from Evonik and FIESIL® and TOKUSIL® from Tokuyama. The optionally alkoxylated nitrogen-containing polymer may alternatively be supported on an organic solid support, for instance activated carbon, such as activated charcoal; organic non-polymeric supports; or polymeric supports. In a further alternative embodiment, the optionally alkoxylated nitrogen-containing polymer may be supported on an inorganic-organic solid support which comprises both inorganic and organic components, for instance in the combined entity. The solid inorganic support (SIS), solid organic support or solid inorganic-organic solid support can be in the form of a hollow or solid particles, beads, microspheres, sheets, hollow or solid fibres, monolithic structures, films and honeycomb structures. Preferably the solid inorganic support (SIS), organic solid organic support or solid inorganic-organic support is particulate, and this may take the form as a powder or granules. The average particle size (D50) lies in the range from 0.002 and 5 mm, for instance from 0.01 to 4 mm, typically from 0.25 mm to 4 mm. In one embodiment, the solid inorganic support (SIS), solid organic support or solid inorganic-organic solid support, which is preferably a solid inorganic support (SIS), is porous and has a surface area of greater than 50 m²/g. In certain embodiments the surface area is greater than 10 m²/g and less than 5000 m²/g. In certain other embodiments, the surface area is greater than 25 m²/g and less than 1000 m²/g. Other embodiments, the surface area is from 50 m²/g to 500 m²/g, for instance from BASF SE 230163 75 m²/g to 300 m²/g, for instance from 100 m²/g to 120 m²/g. In certain embodiments, the surface area is from 200 m²/g to 400 m²/g, for instance from 200 m²/g to 300 m²/g. The surface area of the porous support may be determined by the Brunauer- Emmett-Teller (BET) method according to DIN ISO 9277:2003-05 (which is a revised version of DIN 66131). The specific surface area can be determined by a multipoint BET measurement in the relative pressure range from 0.05-0.3 p/p0. In another embodiment, the solid inorganic support (SIS), solid organic support or solid inorganic-organic solid support, which is preferably a solid inorganic support (SIS), is porous and has an average pore volume which lies in the range from 0.1 cm³/g to 3.0 cm³/g, for instance from 0.2 cm³/g to 0.8 cm³/g. The average pore volume can be determined according to Barrett-Joyner-Halenda (BGH) method of determining pore volume. Preferred solid inorganic supports (SIS) are selected from silica supports or alumina supports. Preferably the silica support or alumina support may encompass any of the aforementioned embodiments. The optionally alkoxylated nitrogen-containing polymer, in any of its aforementioned embodiments, may be impregnated onto or into the solid support, preferably solid inorganic support (SIS), more preferably where the solid inorganic support (SIS) is porous, especially selected from a silica support or an alumina support by any of the known and conventional techniques for impregnating amines or polyamines onto or into such solid supports. In one embodiment, the optionally alkoxylated nitrogen-containing polymer can be impregnated into a particulate solid support, for instance a porous silica, by introducing the particulate solid support into a suitable vessel, typically used for preparing granules or pellets of porous solid, e.g. silica, impregnated by amine or polyamine. Typically, such a vessel may be a disc pelletiser or a ball pelletiser. The optionally alkoxylated nitrogen-containing can then be introduced into the vessel are mixed with the porous solid, e.g. silica, for instance by rotating the vessel, typically BASF SE 230163 as a pelletising device, for instance by rotating the disc of the disc pelletiser or the drum of the ball pelletiser. Suitably this process would result in the formation of wet granules which can be dried at an elevated temperature, for instance between 40 and 70°C for 1 to 4 hours under an inert atmosphere, typically nitrogen. The so formed granules impregnated by the optionally alkoxylated nitrogen-containing polymer may then be used in the capture of carbon dioxide from a mixture of gases. A particularly preferred embodiment relates to the use of the optionally alkoxylated nitrogen containing polymer in direct air capture (DAC). Direct air capture (DAC) relates to technologies that extract carbon dioxide directly from the atmosphere. Such technology typically relies on employing carbon dioxide sorbents which can initially adsorb the carbon dioxide directly from the air and then later in a controlled environment desorb the carbon dioxide where it can be further processed to produce a more permanent storage for the carbon dioxide. The optionally alkoxylated nitrogen-containing polymer according to the present invention can be used in direct air capture (DAC) as the sorbent for initially capturing the carbon dioxide directly from air. The optionally alkoxylated nitrogen-containing polymer may suitably be used in the form of suitable formulations, for instance in a liquid formulation or preferably in a suitable solid support, more preferably impregnated onto or into a porous solid inorganic sorbent (SIS), for instance in the form of granules. The following examples are an illustration of the invention but do not limit the scope of the invention.

BASF SE 230163 Examples Procedure A With higher ratios of the bridging compound (1.3 equivalents), the amine compound is diluted in Methanol to yield a 50% solution 1 mol of the amine compound was placed in a 500mL 4-neck flask equipped with an anchor stirrer, a reflux condenser and dropping funnel . The solution was warmed to 35°C and stirred at 150 rpm. The bisglycidyl compound is dosed through a funnel within 90 minutes. After another 30 Minutes the viscous liquid was transferred to a rotation evaporator (Büchi) and the solvent was removed at 90°C resulting in viscous liquids

^r _e ^d _im^y _l ^d _{i s} ^u _q ^{o u} _{q s} ^{u u} _{o s s} ⁱ l_p ⁱ l _{o g} ^{s n} _{i u} ^{c c} sⁱ _s ^{i u} v _o ^{u s c} _o ^c _u ^{o n} _{c i} ^{o a} _{c v t} ^s _{h s} ⁱ _s ^{i s} _i ⁿ _{i h} ^{s s} _{i v v} ^v _o ^v _i w _h r w ^{s c} _{- a} ^o _l ^{o l} _l ^l _{i h} ^s w _i w w ^o _l ^{n e} _{l e} ^o _e ^c _e , ^{y y ,} _{, l} ^{l o} _l ^{l l} _e ^{y g} _{e e} ^{g r} _{g g} ^{y y g} _ot _{d d 5} ^. _d ^g _d ^g _{d 5} ^. _i ^l _e ⁱ ₃ ² ₄ ^{i 4} _{u 0} ⁱ _{u 2} ^{i 2} _{u 1} ⁱ _{u 3} N _{Y 2 2} ^q _{i l} ⁶ ₂ ^q _{i l 2} ^q _{i l} ² ₂ ^q _{i l} ² ₂ g g ⁵ _{. g} ^{g 3 8 4} _{g 8 8 1 0 2 2} ^{. .} _l ^{1 1 9} _{2 8} ^y _{d d} ^{i n} _; ^{1 7 7 l} _{; ; ; ; ; o} ^l _o ^l _o ^l _o ^{l l} _c ^y _{u l} ^o _p ^{g m m m m} _o m _o m^g _{s ;} ⁱ m ^l _o ⁵ ₆ ^{4 4 6 6 .} _{5 5 4 5} ⁹ _{3 B} ^o _c m ₀ ^. ₀ ^. ₀ ^. ₀ ^. ₀ ^. _{0 l} ^o _c ^r _e ^{r r} ₎ ^{r r h} _e ^r _{e e e} ^{0 h} _{e 3 l} ^y _{l t} ^{h y E l} _t ^e _l ^{h h} _{d d} ^o _t ^l _t ^e _t ^{h e} _l ^l _t ^{e i} _c ^{n G} _l ^y _u ^e _n ^y _{o d} ⁱ _l ^y _i ^e _l ^{o i} _d ^d _l ^y _o ⁱ _l ^{y y} _o ⁱ _l ^{y e} _d ⁱ _{e d} ⁱ _d ^e _d ⁱ _d ⁱ _{d d} ^{i g} _p ^e _{l c s} ⁱ m ^y _h ^y _{l n c} ^{y n g a} _{t l} ^g _{a c} x ^y _{l n c c} ^{y g a} _t ^y _l ^g _l ^{e g} _{n c i} ^a _t ^y _{l B} ^o _c ^t E _i D ^u B _i D _e H _i D ^u B _i D ^D ₍ ^{u g} B _i D _d ⁿ _u ⁿ _i ^o _{n p} ^o _i m ^{t o} _{u c} ^l _o ⁵ _, ^{5 6 4} _e ^{s g 8} _. ⁸ _. ⁴ _. ^{2 n} _i ^g _{; )} H ⁶ _{7 7 6 0} ⁴ ₉ ^{m l % O} ₀ ^{2 2 2 3 2} o _{0 e} ^{2 ;} ₈ ^; ₈ ^; ₇ ^{; ;} ( M ^; ₁ ^. ₀ ^. _{8 6 A} m ⁵ ₀ ^. ₀ ^. ₀ ^. ₀ -_n -_{n d} ^{) n} _{e u} ⁿ _i ⁾ _e ^{) e} _l ^{y e} _l ^{y o m -} ₎ ⁿ _{e i} ^{- n} _{i h} ^t _{h e e} ^t _e ⁿ _{i p a} ⁱ - _l ^m - _)l ^{m a m}m _r ^o _t ³( ^y _{p a} ^{i 3}( ^y _{p a} ⁱ _r ^{t ) a} _r ^{t )} _a ^t _c ⁿ _{e e} ^l _{e - y} ⁿ _i ^s _i ^{o B} _{r d} p ^e _{e - n} ⁿ _i ^s _i ^o _{d e e} ^{n B} _r ^{p e} _n ^T _{( i e e} T ₍ ⁿ _{i n} ^e _p ⁿ _{i A} ^{m T h} _t ^e m _{- ' o} ^e _l m _{- ' o} ^e _{l i} ^{A N} _, ⁿ _i ^{y A N n} _i ^{y A m} P _a ^t _n ^{A m} P _a ^{t o} n _d ^l _{A E} D ^D _{( 4} N ^N ₍ ^m _{h a} ^t _{e 4 ,} N ^N ₍ ^m _{h a} ^t _e ^E _T ^e _p ^E _T ^e _{p a} C ^. _p ^x _{E 1 5 7} ⁰ ₁ ¹ ₁ ⁸ ₁ BASF SE 230163 Procedure B 1 mol of the amine compound was placed in a 500mL 3-neck flask equipped with an anchor stirrer and a dropping funnel . The amine compound was warmed to 50°C and stirred at 150 rpm while the bisglycidyl compound was dosed through a funnel within 90 minutes, always keeping the temperature below 85°C. The reaction mixture was kept at 80°C for another 1h and is then allowed to cool to room temperature (RT) to yield a viscous product.

^r _d ⁱ e _{u d} ⁱ _{d d} m ^qi y _{l u} ^{i i q} _{u l} ^d _i ^{d i} _u ^{qi qi} _l o ^u _{i p q} ^u _{s l l s} i ^l _q ⁱ l ^u _s ^u _s ^{u u} g ^{s n} _{i u} ^s _{o u} ^c _{s o} i ^c _{o o s} ^{c i c} _s ⁱ _s ^{i n} _i ^{o a} _c ^o t ^{s n} _{i c v v v v} s_{i h} ^s _{h h h} ^s _{i o} ^v _i ^{s r v} w _i ^s _i w c_{- a} ^r _a ^o _l w^o w^{o o} _l n ^e _l ^e _l ^l _e ^l _l ^l _l ^l _{e e} ^{c c y e} _y ^e _y ^{y g} _o ^r _{t d} ^, _g ^, _g ^, _{g g g} ^{g -} i ^l _{e 0 8 8 5 2 8} N ⁱ Y ⁵ ₂ ³ ₂ ⁹ ₂ ⁵ ₂ ⁷ ₂ ⁶ _{2 g} ^{g 8} _. ³ _. ^{g g} _{g g} ⁸ ₀ ⁶ ₂ ^{5 1} _{. 5 1} ^{4 .} l ^{1 y} ₂ ¹ _; ¹ _; ¹ ₀ ¹ ₃ ⁸ d _d i_c ^{n y} _u ¹ _; ^{l l} _o ^l _{o ;} ^l _; ^l _; m m _{o o} ^l _{o l} ^o _p ^g _{o 5 5} ^{m m m g} _s ⁱ m _; ^l m o ₆ ^{2 2 5 2 8 .} ₆ ^. ₆ ^. ₅ ^. ₅ ^. _{4 B} ^o _c m _{0 0 0 0 0} ^. ₀ r _{l ) e} ^{o r h} _{c e} ^{r r r} _l h _e ^{o r h} _e ^h _e ^h _{c e} ^h l^{y l} _t ^{e y} _{l t t t t} ^y d _d ^{G E l e l e l e} _{l t} E ² ₃ i_c ⁿ _o y _u ⁱ _{l d} ^y _l ^y _o ⁱ _l ^y _o ⁱ _l ^y _o ⁱ _l ^{y G} _l ^y l ^{o e} _d ^{i e} _{n d} ⁱ _{d d} ⁱ _{d d} ⁱ _{d d} ^{i e} _{n d} ^{i g} _{p n c s} ⁱ m ^a _t ^y _l ^e _{l c} ^{e y} _{n c} ^{e y} _{n c} ^e _{n c} ^e _{l c} g ^y _{h l} ^a _{t l} ^a _t ^y _l ^a _t ^y _l ^y _h ^y _{l B} ^o _c ^u B _i ^g D ^t E _i D ^{u g} B _i D ^{u g} B _i D ^{u g} B _i D ^{t g} E _i D d ^{g n} e _{u g} ⁶ g _g ^g _g ⁰ _. n ^o ₇ ⁵ i _p ^g _; ^{1 1 4 6 m} m ^l ₃ ¹ ₈ ¹ o ¹ ₃ ¹ ₇ ¹ ₄ ^{; ;} A ^o _c m ^; ₁ ^; ₁ ^{; 1} 1 ^; _{9 1} ^. _{8 0} ^. ₀ -⁾ - ⁾ o ⁾ _e ^{) n} _o ^{n n} _{i e i d} ^m _i ^{) m} _e ⁿ m ^{n a} _i m n _a ^l _a ^{l )} _{i t u y} o ^h _{y e} m ^{n a h n} _{x i} ^a _e ^e p _t ^{e )} _{t e} ^{e )} _e - -_)l ^m _rt ^{p e} _{t n h} e ⁿ m^o _{e o} ^{n n} _{i e o} ^{n n} _{i e} ³(- ^y _{p a} ^{i n} _l ^y _e ^l c ⁿ _{i i} ^{m n} _{i i} ^{m n} _i ^s _i ^o _{r d} ^e _e ^l _h ^t _h ^t eⁿ _i ^m m A ^a _{- a} ^{l m} m^a _{- a} ^{l m B}- ^p _{o n y} ^h _{e e} ^{a m -} ₃ ² _y (- ^p _{o A}-₃ ² _y (- ^p _{o A}- _' N_, ⁿ _i ^e _l ^{y A} _{t h T} ^{ei A a} _{r r P} ^t _{A t e} H ⁿ _e ^B _A N ³ ₍ ^r _p N ³ ₍ ^r _{p 4} N ^N ₍ ^m _a ^t _e ^E _T ^T ₍ ^E _T ^T ₍ ^E P ^P ₍ ^e _l ^{. b} _{a p} ^{x T} _{E 2 3 4 6 9} ² ₁ ^d _i ^d _i ^{d u u} _{i q} ⁱ _q ^{d i} _i ^u l l ^u _q ⁱ _q ⁱ l s ^s l u _u ^{s o s} _{u u} o_{c c} ^{o o s} _i ^s _{i c c} ^s _i v ^{v s} _i ^v w ^v w w w o ^{o l} _{l l} ^{l o o l} _l ^{l e} _{e y} ^y _l ^e _e ^y g ^g _{y 5} ^g 0 ^. _{g 5} ^{. 8} ₃ ⁴ _{7 3 2 2} ⁵ ₂ ² _{2 g g 5 g 8 7} ^. _{3 7} ^{. 9 8 9} _{8 ;} ^{7 3} ₆ ^l _{; o} ^l _{; ; o} ^{l l 1 m m} _o m _{o 0} ^{3 m} ₂ ⁸ ₄ ⁸ ₄ ⁸ ₄ ^{9 . .} ₀ ^. _{3 0 0} ^. ₀ r _{l ) e} ^{o r} _e ^{r r h} _c ^h _{e e t} ^y _t ^h _t ^{h l} _o ^e _{l t} ^{3 i} _l ^{y G E} _l ^l _o ^{e l e i} _{l o} ⁱ _{l 3 d} ^e _d ^{e y} _{d d} ^y _{d d} ^y _{d n} ^{i a} _{c n} ⁱ t ^{y u} _l ^e _{l c} ^{e i y g} _{l n c} ^{e i y} _{n c} ^y B _i ^y _h ^a D ^{t g} E _{i t} D ^u _l ^g B _i ^a _t D ^u _l ^g B _i D g ^{g g 6} _. ^{6 5} _. ⁶ _{. 8} ^{1 1} ₆ ^{4 1} ₆ ^{1 1} ₉ ; ^{; ; 2} 8 ^{; .} ₈ ^. _{8 6 0 0} ^. ₀ ^. ₀ )_e ⁿ _i m^a _x ^e _{e h} ^{n n} _{i e} ^{m l} _{a h e e} ^{t t} _{n e} ⁿ _i ^{n e} A ^a _{i t} m m _p H ^{n E E} _e ^r _e ^r _e ^o _d ^{l P p p} _{a S P ( S S} C _F ^S _A ^B ₄ ^{1 5} ₁ ⁶ ₁ ⁷ _{1 s} ^u _o ^c _s ⁱ _{v s} ^u h _o g_i ^{c h} _s ⁱ , _v w _h o_l ^{g l} _{i e} ^{h y} _{, t} w n_i ^o _l ^{l a} f _e ^y d ^{g l} ₅ ^g e ^. ₁ ^{. i} ₄ ³ _{9 Y 2} ³ ₂ e_t ^a _{g d} ^{5 3} _{6 n} ^g ₇ ^{. 1 a} _y ⁿ _{u 3} ^. _{7 5 0} ^{3 c} _{2 o} ^{o s} _p ^{g 6 5} _; i_i m _; ^l _o ^; ₄ ² D ^o _c m ^. _{3 0} ^. ₀ e ^e _{n t} ^e _{l )} a ^{y e} ₎ ^e n _d a_y ⁿ _h ^t _{t e} ⁿ _t ⁴ _{3 e} ^a _{n e} ^a _n c _{u o} ^o _p ^{m a} a _y ^u _l ^{a c o} _t ⁽ _y ^{c si} _i m _I ^x _o D ^o _c D _e ^s _i H ^h ₍ ⁱ _{I o d} ^{D s} _{i T} ⁱ _{d d} ^{g n} e _{u g} ^{6 n o 0} _{. 7} ⁵ _{8 i p} ^g _; ^{l 1; 1 m} m A ^o _{o 9} ^; _{8 c} m ^. ₀ ^. ₀ )_e ⁿ _i ⁾ _e m ⁿ d ^a _i n _t m u ⁿ _e ^a _x o_p ^p _n ^e _h ⁿ m ^e _{l e} o ^y c _h ^{l t} _h C _{e e} ^{t a} _{e A} ^a _{t e} ⁿ _i ^A P _r ^t H ^{n E r} _{S u} ^{m E} _e T ^E _e P _F ^d _{A T ( P (} ^S _e C ^. _A ^c _e ^B _o ^{l r} _{b p} ^{x 3} P ^a _{T E 8 1 5} BASF SE 230163 Comparative Examples Procedure D 50% aqueous solutions of PEHA and TEPA were dosed into a 1 l autoclave with stirrer. At 40°C the alkylene oxides were dosed within 90 minutes. The reaction temperature was raised to 95°C for 2 hours and then again stirred at room temperature (RT) overnight. The mixture was put into a 2l Büchi-flask and the water was removed at 100 mbar at 80°C. Yellowish liquids were obtained.

-^d _n ^s ₎ o _e ^g c ⁿ _/ e _y ^r _i m _g H ( ^O _{2 8 4 0 S a a} ^m _K ⁰ ₄ ¹ ₄ ¹ ₄ ² _{4 y} ^r _{) a} ^s _e ^{g n} _/ m_i ^r _{i P} ^m _g H a ^m ₍ ^O _{1 K} ⁰ _{3 2} ⁷ _{0 2} ⁷ _{5 2} ⁴ _{2 r} ^{) e} _{) d b} ^g _/ ^r _a ^m H ^d _u ^O _n ^{n a} _{- K t} H _{g 8} ⁸ ₁ ⁰ _{3 5} ^s O ^m _{( 1 2} ⁹ ₁ ⁰ ₂ ^G _E ^P _n M ^h _{/ ti} w ₈ M ^. _{4 3 4 5} ^{. .} ₄ ^. w _{4 4 d} ^e _t ^a _r ⁾ _e ^l i ₀ ⁰ _{5 0} ^{0 b} _{l n / o} M ^g ₍ m ^{9 0 5} ₅ ^{1 a} _{6 1 9 1 c P} ^I _{F e} ^{r H} _u ^{d n} _{i e} ^{c 6} _{3 d} ^e _{o r} ^{r u} _{P A B B B s} ^a _e m _a ^o _# ^t i_{t d a} ^{a d} _{r /} r _e ^{g n} nⁱ _u ^{o 3 C} _{a P} ^l _o ⁿ _{i g p .} m ^d _i ^r m ¹ ₂ ^{5 5} / ^. _{2 1} ^. ₂ ^{. G /} ₁ ^/ ₁ ^/ ₍ M _{A B} ^o _{c 2 2 2 2} ^s _e ^r _{d o} ^{c g n} _{l l n} ⁱ _u ^{e y e y} _l o _n - ^{y e} _l ^y - e _{l d} ⁱ _c ^# _{r n} ^e _{l d} ⁱ _{c r} ^e _d ⁱ _{c n} ^e _{l d} ⁱ _c ^{e f} _{g p l} ^{y o} _c ^y _l ^e _l ^{y o} _c ^y _l ^e _n ^{a y} _{l r l} ^{y o} _c ^y _{l r} ^e _{n o n} ^d _i ^r m _h ^y _l ^{g o} _{i h h} ^y _l ^g _{i h t} ^l _o ^{g e} _{h h} ^y _l ^g _h ^a _t ^l _oi_{t B} ^o _c ^t E G D ^t E ^t E G D ^t E ^u B ⁱ _{d i} D ^t _e ^t E G _i D ^{t u i i} _{E B d s} ^o _p -m _e ^o _c ⁿ _e ^{l )} _{e e} ⁿ _{e e i} ⁿ _i ⁿ _{i d} ⁿ _{e y a} ⁿ _{i A} ^h _t ⁿ _i m m ^m _n ^{m T} _{A E} ^e _i ^{m o D} _a ^{i A A} r _{3 3 4} i _A D _{( t} N N N _t ^c _a ^e _{r e 1} ^l _{p e} ^{l m} _{b a} ^{a x} _{T E 1 2 3 4 1} ¹ _{0 8 1 6 4} ¹ ₄ ² ₄ ⁹ ₃ ⁹ _{3 6} ⁵ ₉ ⁷ _{0 5 0 2 2} ¹ ₂ ⁶ ₂ ⁷ _{2 5} ¹ _{3 8 2} ² ₂ ⁹ _{0 1 -} ³ ₂ ³ ₉ ^. _{2 3 8 7 3} ^{. . . .} _{6 4 6 3 4} ¹ ₀ ³ ₂ ⁰ ₀ ^{0 3} _{8 0 0 0 1} ³ ₁ ⁸ ₆ ⁴ ₆ ⁵ ₇ 7_{3 A B A} C _B 5_{3 1} ^{5 5 . .} ₃ ^. _{9 1 1 1 1} ^{. . / / /} ₀ ^/ _{1 2 2 2 2} ^/ _{2 l} ^y _{l l} l dⁱ - ^y c ^e _d - ^y _d ^{- y -} - y_{l r} g_i ^e _n ⁱ h ^a _c ^{e y} _{l r} ^e _n ^{i a} _{c e} y_{l r} ⁿ _d ⁱ a _{c e} y_{l r} t _t ^{u l} _o ^{i g} _{i h} ^t _t ^{u l} _o ^{i g} _i ^e _h ^{t x} _e ^l _o ^{i g} _i ^e _h ^t _I ⁿ _{e a} ^{- t} o _a ^{e n} _n ^a D ^x _e ^s _i ⁱ _{a t} ^{u l} _o D _{e B d} D _{e B d} D _e H _d D _e H H _d ^y _{c B} ⁱ _d - ^e e ⁾ _n ^{e e )} _n ^{e )} e ⁿ _{e l} ^y _e ⁿ _{l e} n _{e i} ^{y n} i ^l _y ⁿ _{i e h} ^t _h ^t _i h ^{m n} _{i e} m _e m m A ^A _{t 4 T} ^e _a ^a m ^{A a} _r ^{a t} _t ^{n A a} _r ^{a t} _t ⁿ N ^{E i} _{r T} ^T _rt ^A ( ^e _{t 4 P} N ^E _{e T} ^T _{e P (} ^p - ^E _{e T} ^T _{e (} ^p - ^E _{S F} ^S _A ^B _{5 6 7 8 9 5} ³ _{0 0 5 4 4} ⁴ ₄ ² ₄ ⁷ ₄ ³ _{4 8} ⁵ ₅ ⁵ ₈ ⁵ ₂ ⁴ _{0 2 2 2 2} ⁵ _{2 7} ⁴ ₅ ³ _{0 9 2 2} ² _{2 -} ² ₂ ³ ₃ ^. _{3 0 0 1 4} ^{. . . .} _{6 4 5 4 4} ¹ ₀ ³ ₂ ⁰ ₁ ⁰ ₂ ⁰ ₄ ⁰ ₆ ^{0 3} ₁ ³ ₁ ² ₁ ¹ _{7 1} ⁰ ₁ 8_{3 A A B} C _{B 3} ^. ₄ ^. _{2 9 2 1 1} ^. ₁ ^{. . / / /} ₀ ^/ _{1 2 2 2 2} ^/ _{2 l} ^y _l l d - ^y _d ^y _{d l l} i ^{e y} _d - ^{y i} _c ^{e i} _{c c} ) _{n l} ^{i e} _d ^{i y} _{l r n i} ^{a y} _{l r} ^y _{l r} ^e _l ^o _{c c} ^y _{l r n c} ^y _{l r} g ^e _{h t} ^{l g e} _h ^g _i ^e _h ^y _h ^{y g e} _{h I} ^a _t ^{l g e} _h D ^t _e ^u _{o B} ⁱ _{d i} D ^t _e ^D ₍ ^t _e ^t _{l E} G _i D ^t E ^D _T ^u _{o B} ⁱ _{d i} D ^t _e e_n ^{e e} _l ⁾ _n y _e ^e _l ⁾ _{e h} ^{) t n} _i ^y _h A _e ^{t n} _i -^e _e ⁿ - ^{) e} _e ⁿ - ^{) e} _e ⁿ P ^a m r ^a _e m^a -^{a t} _t ^{A a} _{r t n i} - m ^a _{t n i} - _i m ^a _{t n} m E _e ⁿ _{e P} ^t _{t A e} ⁿ _e H ^{n e} _l ^a _A ^{n e} _l ^a _A ^{n e} _l ^a T ^T ₍ ^p - ^E _T ^T ₍ ^p - ^E _e ^y _{h x} H P ^P ₍ ^t _e ^e _h ^E _e ^y _{h x} H _e ^y _{h x P} ^P ₍ ^t _e ^e _h ^E P ^P ₍ ^t _e ^e _h ^E _{S F} ^S _{A 0} ^{B 1 1} ₁ ² ₁ ³ ₁ ⁴ ₁ BASF SE 230163 Examples 6 and 9 were additionally propoxylated with 1,5mmol PO/g polymer to yield Examples 19 and 20 Example 19 A 1 L stainless steel reactor with stirrer was charged with 250 g of the polymer example 6, followed by 250 g water. The reactor was evacuated (60 mbar) and purged with nitrogen 3 times while increasing the temperature to 100°C. The reactor was pressurized to 2 bar and 21,8 of propylene oxide (PO) were added within 5 minutes. While stirring at 150rpm over a period of 3,5 hours, the temperature was raised to and kept at 115°C. Then the reactor was cooled to 60°C and depressurized. Finally, the reactor was treated for 10 minutes at 100 mbar and purged with nitrogen.520 g of a slightly yellowish liquid was obtained. Example 20 The procedure of example 19 was repeated with 250g polymer, example 9. In addition, the amine sorbents were supported on silica and the CO2 absorption was investigated before and after a storage at 90°C for 14 days under air. Determining the equilibrium loading with CO₂ The equilibrium loading is determined in a bubble column reactor as described in BRECHTEL, K. Einfluss der Molekülstruktur auf die -Abtrennung mit wässrigen Aminlösungen aus Rauchgasen fossil befeuerter Kraftwerke. Dissertation/PhD, Universität Stuttgart, 2011; A. Schäffer, Amine und Aminmischungen zur -Absorption aus Kraftwerksrauchgasen und ihr Energiebedarf zur Regeneration Dissertation/PhD, Universität Stuttgart, 2013. Therein, 0.15 kg of the sample is diluted with 0,15kg water to yield a 50% aqueous solution. The sample is heated in a water bath on an adjustable heating plate and exposed to a stream of 2l /min of synthetic flue gas with the composition 15% by volume CO2, 5% O2 and 80% N2. The flue gas is injected into the sample using a mass flow controller via a glass frit (pore size 1), so that good mixing and a large mass transfer area are achieved. The exiting(surplus) low-CO₂ gas flow is fed to an infrared gas analyzer via a return flow and sample gas cooler. The reflux cooler BASF SE 230163 condenses the evaporated water or solvent and feeds it back into the sample. The gas composition is continuously measured with the infrared gas analyzer and recorded via a computer interface. The sample of mass [kg] is then in equilibrium with the CO2 concentration in the flue gas or with the prevailing CO₂ partial pressure. The CO₂ volume absorbed by the solvent [m] results from integral formation over time [min]. The entering flue gas volume flow [l /min] is constant. The equilibrium loading] is then calculated in terms of weight % CO2 with respect to the mass of the 50% sample solutions. For this purpose, the equilibrium loadings are determined at a temperature of 50 °C. Table 2 Example Nitrogen-containing CO2 uptake using an polymer from Example No aqueous solution of the N-containing polymer (50% by weight) Wt% Comparative Example 5 Comparative Example 1 6.75 Comparative Example 6 Comparative Example 2 7.1 Comparative Example 7 Comparative Example 3 7.25 Comparative Example 8 Comparative Example 4 6.4 Example 21 Example 1 5.8 Example 22 Example 2 6.5 Example 23 Example 3 6.1 Example 24 Example 4 7.9 Example 25 Example 5 7.7 Example 26 Example 6 8.1 Example 27 Example 7 7.8 Example 28 Example 8 7.2 Example 29 Example 9 8.20 Example 30 Example 10 8.55 Example 31 Example 11 7.0 Example 32 Example 12 7.95 BASF SE 230163 Example 33 Example 13 7.8 Example 34 Example 14 8.70 Example 35 Example 15 6.9 Example 36 Example 16 7.4 Example 37 Example 17 7.1 Example 38 Example 18 7.25 Example 39 Example 19 7.4 Example 40 Example 20 7.25 For the determination of the resistance vs evaporation, the amines of examples 1-20 and the comparative examples were absorbed on a silica compound (we take the silica as described in the patent from University of California- this is Sipernat 50S2, Evonik Resource Efficiency GmbH) The silica supported examples were obtained by treating a 50% aqueous solution of examples 1-20 and the comparative examples with Sipernat 50S2 with a ratio of 1/1. After evaporation of the solvent (90°C, 100mbar) 100 g of the sorbent were stored at 90°C under an atmosphere that contains 95% CO₂ and 5% O₂ for 14 days. Every 48hours, the sorbent was evacuated at 40 mbar and a desorption temperature of 105°C for 90 minutes before the sorbent was again stored under a CO2/O2 atmosphere, which corresponds to 10 cycles after 20 days. Table 3 CO2 uptake of 50% amine sorbent on silica before and after storage at 90°C, 20 days and 10 adsorption-desorption cycles Example Nitrogen- CO2 uptake before CO2 uptake after containing storage (50% by storage (50% by polymer from weight) weight) Example No Wt% Wt% Comparative Comparative 6.9 3.4 Example 9 Example 1 Comparative Comparative 7.4 3.0 Example 10 Example 2 BASF SE 230163 Comparative Comparative 7.6 2.4 Example 11 Example 3 Comparative Comparative 6.8 2.95 Example 12 Example 4 Example 41 Example 1 6.0 4.8 Example 42 Example 2 6.3 5.4 Example 43 Example 3 6.45 6.0 Example 44 Example 4 7.75 6.9 Example 45 Example 5 7.5 7.1 Example 46 Example 6 8.2 7.0 Example 47 Example 7 7.65 6.9 Example 48 Example 8 7.1 6.4 Example 49 Example 9 8.0 7.0 Example 50 Example 10 8.3 7.2 Example 51 Example 11 7.1 5.9 Example 52 Example 12 8.1 7.25 Example 53 Example 13 7.6 6.8 Example 54 Example 14 8.35 7.4 Example 55 Example 15 6.6 6.3 Example 56 Example 16 7.5 6.8 Example 57 Example 17 7.2 6.5 Example 58 Example 18 7.5 7.0 Example 59 Example 19 7.35 6.75 Example 60 Example 20 7.6 7.05

Claims

BASF SE 230163 Claims 1. Use of an optionally alkoxylated nitrogen containing polymer in carbon dioxide capturing, the optionally alkoxylated nitrogen containing polymer being obtainable by a process comprising the following steps: a) reaction of (i) a di- or oligoamine (A) with (ii) a bridging compound (BC), the bridging compound (BC) (I) being phosgene; or (II) comprising at least two amine reactive groups (ARG), wherein the bridging compound (BC) is capable of bonding to amine groups of at least two di- or oligoamine (A) molecules, to provide the nitrogen containing polymer (NP), wherein the nitrogen-containing polymer (NP) comprises bridging compound (BC) molecular components that are bonded to at least two molecular components of di- or oligoamine (A), and wherein the proportion of bridging compound (BC) molecules bonded to at least two di- or oligoamine (A) molecules is the nitrogen-containing polymer (NP) bridging factor (BF), wherein the bridging factor (BF) is greater than 50%, wherein the sum of the primary amine groups and the secondary amine groups of the nitrogen-containing polymer (NP) is at least 600 mg KOH/g, and wherein the number average molecular weight (Mn) of the nitrogen-containing polymer (NP) is greater than 600 g/mol and b) optionally reaction of the nitrogen containing polymer (NP) with an alkylene oxide (AO), preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is no more than 0.25, BASF SE 230163 in order to obtain alkylene oxide side chains (AB) linked to nitrogen atoms of the nitrogen containing polymer (NP) thus providing the alkoxylated nitrogen containing polymer (ANP). 2. The use according to claim 1, wherein the bridging compound (BC) is (1) a reaction product formed by reacting (i) a di-or polyol with (ii) epichlorohydrin; or (2) a compound comprising at least two amine reactive groups (ARG) selected from a compound comprising at least two glycidyl ether groups or a compound comprising at least two isocyanate groups; or (3) phosgene. 3. The use according to claim 1 or claim 2, wherein the bridging compound (BC) is a compound comprising at least two glycidyl ether groups is a compound that (i) comprises at least two times a structure according to formula (I) wherein the dotted line indicates bond to the remaining part of the compound comprising at least two glycidyl ether groups, preferably the compound comprising at least two glycidyl ether groups possesses the structure according to formula (I) two times; and/or (ii) is selected from the group consisting of 1,4-butandiol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether, diglycidyl ether, 1,3-neopentylglycol bisglycidyl ether, 1,4-cyclohexanedimethanol bisglycidyl ether, ethylene glycol bisglycidyl ether, glycerine triglycidyl ether and trimethylolpropane triglycidyl ether. 4. The use according to claim 2, wherein the di- or polyol is selected from the group consisting of 1,4-butandiol, 1,6-hexanediol, 1,3-neopentylglycol, 1,4- cyclohexanedimethanol, glycerine and trimethylolpropane. 5. The use according to any of claims 1 to 4, wherein the at least one di- or oligoamine (A) BASF SE 230163 (i) has at least 2 amino groups, suitably 2 to 12 amino groups, preferably 2 to 8 amino groups, more preferably 3, 4, 5, 6, 7 or 8 amino groups; (ii) has at least one carbon atom per nitrogen atom, preferably 1 to 5 carbon atoms per nitrogen atom, more preferably 1 to 3 carbon atoms per nitrogen atom; (iii) comprises at least two primary and/or secondary amino groups, preferably at least two primary amino groups; (iv) has a molecular weight (Mw) that lies in the range of 50 to 500 g/mol, preferably in the range of 60 to 300 g/mol, more preferably 80 to 250 g/mol, more preferably still from 120 to 250 g/mol, especially preferably from 150 to 250 g/mol; and/or (v) is selected from the group consisting of ethylenediamine, hexamethylenediamine, methylcyclohexane diamine (MCDA), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), dipropylene-triamine (DPTA), tripropylene-tetramine (TPTA), tris(2-aminoethyl)amine (TAEA), tetrapropylenpentamin (TPPA), N,N'-Bis-(3-aminopropyl)-ethylenediamine (N4-amine), 3-(2-aminoethylamino)propylamine (N3-amine), spermine, spermidine, triamino nonane, diethylentriamin (DETA), triethylentetramine (TETA), tetraethylenpentamine (TEPA), pentaethylenhexamine (PEHA) and a compounds according to Formulas (II) to (X), BASF SE 230163 6. The use according to any of claims 1 to 5, wherein the molar ratio of bridging compound (BC) to di- or oligoamine is from 0.35 to 0.85, preferably 0.4 to 0.8, more preferably 0.45 to 0.75. 7. The use according to any of claims 1 to 6, wherein the molar ratio of the epoxide groups of the bridging compound (BC) to the NH function of the di- or oligoamine is less than 0.5, preferably up to 0.45 and more preferably from 0.15 to 0.4. 8. The use according to any of claims 1 to 7, wherein the optionally alkoxylated nitrogen containing polymer is an alkoxylated nitrogen-containing polymer (ANP) and the molar ratio of alkylene oxide (AO) to NH functionality is from 0.05 to 0.25, more preferably from 0.05 to 0.2. 9. The use according to any of claims 1 to 8, wherein the alkoxylated nitrogen containing polymer (ANP) comprises a structural element according to Formula (XI) wherein the dotted lines indicate bonds to the remaining parts of the alkoxylated nitrogen containing polymer; and AB represent one alkylene oxide side chain. BASF SE 230163 10. The use according to any of claims 1 to 9, wherein optionally alkoxylated nitrogen-containing polymer has a weight average molecular weight (MW) at least 70% greater than the weight average molecular weight (M_W) of the di- or oligoamine (A). 11. The use according to any of claims 1 to 10, wherein the optionally alkoxylated nitrogen-containing polymer has a number average molecular weight (Mn) which lies in the range of 600 to 150,000 g/mol, more desirably in the range of 600 to 75,000 g/mol, more desirably in the range of 600 to 50,000 g/mol, for example from 600 to 20,000 g/mol, preferably from 600 to 10,000 g/mol, more preferably from 800 to 5000 g/mol, more preferably from 600 to 2500 g/mol, more preferably still from 1000 to 2500 g/mol. 12. The use according to any one of claims 1 to 11, wherein the optionally alkoxylated nitrogen containing polymer is (i) soluble in water; and/or (ii) a branched polymer. 13. The use according to any one of claims 1 to 12, wherein less than 10%, preferably less than 5%, of the nitrogen atoms present in the optionally alkoxylated nitrogen containing polymer are quaternized. 14. The use according to any of claims 1 to 13, wherein optionally alkoxylated nitrogen containing polymer is alkoxylated and the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is from 0.05 to 0.25 and preferably from 0.05 to 0.2, and wherein more than 50 mol% of the alkylene oxide is based on ethylene oxide, propylene oxide and/or butylene oxide, preferably propylene oxide or butylene oxide. 15. The use according to any of claims 1 to 14, wherein (1) in step a) the di- or oligoamine (A) is TPTA or PEHA and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and BASF SE 230163 in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (2) in step a) the di- or oligoamine (A) is 3-(2-aminoethylamino)propylamine (N3- amine) and the compound comprising at least two glycidyl ether groups is 1,4- butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (3) in step a) the di- or oligoamine (A) is N,N'-Bis-(3-aminopropyl)- ethylenediamine (N4-amine) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or 1,6-hexanediol bisglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (4) in step a) the di- or oligoamine (A) is triethylentetramine (TETA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (5) in step a) the di- or oligoamine (A) is tris(2-aminoethyl)amine (TAEA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (6) in step a) the di- or oligoamine (A) is diethylentriamin (DETA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether, 1,3- neopentylglycol bisglycidyl ether or 1,4-cyclohexanedimethanol bisglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (7) in step a) the di- or oligoamine (A) is triamino nonane and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or BASF SE 230163 (8) in step a) the di- or oligoamine (A) is tetraethylenpentamine (TEPA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or diglycidyl ether ether or ethylene glycol diglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP); or (9) in step a) the di- or oligoamine (A) is pentaethylenhexamine (PEHA) and the compound comprising at least two glycidyl ether groups is 1,4-butandiol bisglycidyl ether or ethylene glycol bisglycidyl ether; and in step b) less than 0.25 mol of propylene oxide or butylene oxide is employed per mol of NH-functionality of nitrogen containing polymer (NP). 16. The use according to any of claims 1 to 15, wherein the optionally alkoxylated nitrogen containing polymer is employed for capturing carbon dioxide from a mixture of gases. 17. The use according to any of claims 1 to 16, wherein the optionally alkoxylated nitrogen containing polymer is incorporated into a formulation for direct capturing of carbon dioxide, preferably the formulation comprises (i) the alkoxylated nitrogen containing polymer on a solid support; or (ii) the optionally alkoxylated nitrogen containing polymer in a liquid composition, for instance as in aqueous solution. 18. The use according to claim 16 or claim 17, wherein the gas mixture is either atmospheric air or exhaust fumes. 19. The use according to any of claims 1 to 18, wherein the optionally alkoxylated nitrogen containing polymer is supported on a solid inorganic support (SIS), suitably the solid inorganic support (SIS) being particulate or a macroscopic support, preferably the solid inorganic support (SIS) being particulate, suitably as a powder or granular. 20. The use according to claim 19, wherein the solid inorganic support (SIS) is selected from silica or alumina supports. BASF SE 230163 21. The use according to any of claims 1 to 20, wherein the optionally alkoxylated nitrogen containing polymer is employed in direct air capture (DAC). 22. A method of capturing carbon dioxide, comprising contacting a mixture of gases comprising carbon dioxide by an optionally alkoxylated nitrogen containing polymer in carbon dioxide capturing, the optionally alkoxylated nitrogen containing polymer being obtainable by a process comprising the following steps: a) reaction of (i) a di- or oligoamine (A) with (ii) a bridging compound (BC), the bridging compound (BC) (I) being phosgene; or (II) comprising at least two amine reactive groups (ARG), wherein the bridging compound (BC) is capable of bonding to amine groups of at least two di- or oligoamine (A) molecules, to provide the nitrogen containing polymer (NP), wherein the nitrogen-containing polymer (NP) comprises bridging compound (BC) molecular components that are bonded to at least two molecular components of di- or oligoamine (A), and wherein the proportion of bridging compound (BC) molecules bonded to at least two di- or oligoamine (A) molecules is the nitrogen-containing polymer (NP) bridging factor (BF), wherein the bridging factor (BF) is greater than 50%, wherein the sum of the primary amine groups and the secondary amine groups of the nitrogen-containing polymer (NP) is at least 600 mg KOH/g, and wherein the number average molecular weight (Mn) of the nitrogen-containing polymer (NP) is greater than 600 g/mol and b) optionally reaction of the nitrogen containing polymer (NP) with an alkylene oxide (AO), preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to NH functionality of the nitrogen-containing polymer (NP) is no BASF SE 230163 more than 0.25, in order to obtain alkylene oxide side chains (AB) linked to nitrogen atoms of the nitrogen containing polymer (NP) thus providing the alkoxylated nitrogen containing polymer (ANP), contacting the optionally alkoxylated nitrogen-containing polymer (NP) with carbon dioxide. 23. The method according to claim 22, wherein the optionally alkoxylated nitrogen-containing polymer (NP) comprises any of the features of claims 2 to 21.