Method for the manufacture of new amines from alcohols

Abstract

The present invention relates to a process for the manufacture of diamines useful in the preparation of polyurethane materials and useful in a system for removing carbon dioxide gas from gaseous streams.

Description

TITLE OF THE INVENTION:METHOD FOR THE MANUFACTURE OF NEW AMINES FROM ALCOHOLSFIELD OF THE INVENTION

[0001] The field of invention concerns a method to manufacture amines useful in the preparation of polyurethane materials and useful in a system for removing carbon dioxide gas from gaseous streams.BACKGROUND OF THE INVENTION

[0002] The invention is a new process and compositions for the manufacture of amines that are useful in various applications including their use in polyurethane and useful in systems for carbon dioxide removal from gaseous streams. In one embodiment, the scope of the amines prepared according to the new method comprise amines of formula 1 :Formula 1 where R1and R2are independently aliphatic groups or R1and R2are cycloaliphatic or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (O) and where A is an aliphatic group or a cycloaliphatic ring, R3is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and R4is a hydrogen atom, methyl group or R3. In another embodiment, the scope of the amines prepared according to the new method comprise amines of formula 2: R5-O-(CH2)n-NH2, wherein R5is a C1-12 linear or branched alkyl group and n = 2-3.

[0003] US11745137 discloses several methods for the synthesis of amines which is defined according to the general Formula I:R^JN-L’-NH^R3wherein R1and R2independently is aliphatic, cycloaliphatic, or R1and R2together with the nitrogen to which they are attached, form a heterocyclic ring. L1is aliphatic, cycloaliphatic, or L1and R1together with the nitrogen to which they are attached form a heterocyclyl ring and R3is aliphatic, cycloaliphatic, cycloalkylalkyl, or alkoxyalkyl.

[0004] According to US11745137, compound of Formula I can be made in different ways. One such way involves a two step reaction. The first reaction can be summarized according to the general scheme A:in which R1and R2independently is aliphatic, cycloaliphatic, or R1and R2together with the nitrogen to which they are attached, form a heterocyclic ring. L is aliphatic, cycloaliphatic, or L and R1together with the nitrogen to which they are attached form a heterocyclyl ring and R3is aliphatic, cycloaliphatic, cycloalkylalkyl, or alkoxyalkyl such that R4and the carbon to which it is attached together form R3as defined above for formula I. The acid reactant denoted as 1 above could be activated for reaction in the presence of a suitable solvent and reacted with amine 2 to form amide 3. The recommended activating agents might be any reagent able to facilitate acid coupling with an amine. Among the activating agents mentioned include boric acid, a carbodiimide reagent like DCC (N, N’-dicyclohexylcarbodimide optionally used in combination with hydroxybenzotriazole, bis-(2-oxo-3-oxazolidinyl)phosphinic chloride, thionyl chloride, mesyl chloride, tosyl chloride or their combination. Non-limiting examples of solvents include aprotic solvents such as toluene, chlorinated solvents such as chloroform, dichloromethane, dimethylformamide (DMF), tetrahydrofuran (THF) or their combinations. In some embodiments the reaction might be carried out with the removal of water such as by using a drying agent or azeotropic water removal. The second step is shown according to the general scheme B:where amine 3 is reacted with reducing agent 4 to form the diamine 5. A variety of reducing agents can be used such as lithium aluminum hydride, borane dimethyl sulfide, borane-THF or lithium borohydride. The reduction can be carried out in a suitable solvent such as THF, methanol, ether, or a combination thereof. The temperature of the reaction can range from room temperature to the refluxing temperature of the solvent.

[0005] Example 1 in US11745137 disclosed a preparation procedure according to general scheme A and B shown above to make specifically N-(2-ethoxyethyl)-3- morpholinopropan-1-amine. The experimental procedure consists of contacting 2-ethoxy acetic acid (200 mmol), 3-morpholinopropane-1-amine (200 mmol) and 0.5% boric acid and heat the mixture to reflux in toluene with azeotropic removal of water until no more water is produced. The reaction was cooled down to room temperature washed with aqueous base, dried and evaporated to yield the corresponding amine which was then reduced with lithium aluminum hydride (200 mmol) in refluxing THF to give N-(2- ethoxyethyl)-3-morpholinopropan-1-amine after purification. This is illustrated in the following reaction sequence:

[0006] Thus, this method requires the formation of an amide that needs the constant removal of water from the reaction media by virtue of an azeotropic distillation using toluene. The amide produced in this way requires full reduction with lithium aluminum hydride which is known to react violently even with small amounts of water causing the risk of a potential explosion particularly if the water produced in the first step is not fully removed. In addition, plant storage of large scale quantities of UAIH4 is not an option because in addition to its strong reactivity, the material is also shock sensitive and could explode during its handling. Finally, the mehod also requires solid contaminated waste containing lithium / aluminum salts that need to be treated and disposed. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large scale tonne production.

[0007] Another way involves a reaction that can be summarized according to the general scheme C:wherein R5is hydrogen or alkyl such as C1-6 alkyl, C1-4 alkyl, ethyl or methyl. The carbonyl compound 6 is reacted with amine 2 and a reducing agent to form amine 7. Examples of reducing agents that can be used include borohydrides such as sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride or lithum borohydride or by catalytic reduction such as by hydrogen with palladium, nickel, ruthenium and platinum on carbon. The reaction can be performed in one step such as by reductive alkylation or in two sequential steps where the amine is allowed to react with the carbonyl compound to form an imine before being contacted with a reducing agent. Suitable solvents include alcohols such as methanol, ethanol, or isopropanol, toluene, THF, acetonitrile or a combination thereof.Example 2 in US11745137 disclosed a preparation procedure according to general scheme A and B shown above to make N-isobutyl-3-morpholinopropan-1-amine. The experimental procedure consists of contacting 3-aminopropylmorpholine (53.5 g, 370 mmol) with isobutylaldehyde (31.6 g, 438 mmol) in 300 ml of methanol until the reaction was completed. Upon cooling to about 0°C sodium borohydride (15.44g, 408 mmol) was added in small portions and when the addition was completed the reactions was warmed up to room temperature. The mixture was placed under rotary evaporation to remove methanol and the white slurry dissolved in 100 ml of aqueous 10M KOH and the aqueous layer extracted with methylene chloride. The organic layer was further washed with 10M solution of KOH followed by a wash with distilled water and then dried over magnesium sulfate, filtered and evaporated. Distillation of the desired product under reduced pressure gave a yield of about 53 %. This is illustrated in the following reaction sequence:M OH lM

[0009] Thus, this method requires the formation of an imine that requires reduction with sodium borohydride which is known to release flammable gases which might ignite spontaneously especially because water is produced during the condensation of 3- aminopropylmorpholine with isobutylaldehyde. In addition, plant storage of large scale quantities of NaBH4 is not a viable option because in addition to its strong reactivity, the material could ignite causing a fire and explosion if exposed to adventitious moisture. Finally, this mehod also requires solid contaminated waste containing lithium / boron salts that need to be treated and disposed. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large scale tonne production.

[0010] Another way involves a reaction that can be summarized according to the general scheme D:

[0011] Amine 2 is treated with compound 8 to form compound 4. Typically, amine 2 is provided in excess, such as two times, three times, four ties or five times or more excess with respect to compound 8 to facilitate the formation of compound 4 to drive the reaction to completion and to limit the formation of tertiary amine. X in scheme D is a suitable leaving group such as halogen (chloro or bromo) methylate or tosylate. The reaction might be performed neat without any solvent or alternatively using a solvent in the presence (or absence) of additional base. Examples of solvents include chlorinated solvents such as chloroform or dichloromethane, toluene, acetonitrile, DMF, THF, pyridine or a combination thereof. Suitable bases include any base that can facilitate the reaction such as trialkylamines, pyrdine or inorganic bases such as potassium carbonate. The reaction mixture might optionally be contacted with aqueous base to remove excess of amine and / or neutralize any salt of the product that might have formed. The reaction might be performed at a suitable temperature to drive the reaction such as from 20°C to 120°C or more or to a reflux temperature of the solvent(s).

[0012] Example 3 in US11745137 disclosed a preparation procedure according to general scheme D shown above to make N-(2-ethoxyethyl)-3-morpholinopropan-1- amine. The experimental procedure consists of contacting 3-aminopropylmorpholine (307 g, 2.13 mol) that was heated to a temperature of about 80°C with 2-bromo-ethylether (116 g, 0.739 mol) that was added dropwise to the neat amine. The reaction temperature increased to about 110°C and it was maintained until complete addition. After stirring overnight, the excess amine was distilled under reduced pressure. The residue was poured on 250 ml chloroform chilled on ice and washed with 10M KOH aqueous solution followed by distilled water. The organic layer was separated and the aqueous layer washed with chloroform followed by combining all the chloroform fractions which were dried with Na2SO4, filtered and evaporated. The amine was distilled under reduced pressure with a yield of 55 %.

[0013] Thus, this method requires the reaction of 3-aminopropylmorpholine with 2- bromoethyl ether a flammable substance that requires storage at low temperatures to prevent its exposure to sources of ignition. Furthermore, the procedure of isolation using chloroform is not suitable in large scale due to the challenges that involve the toxicity associated with chloroform including the risk of cancer of the bladder and gastrointestinal track due to accidental release or exposure. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large scale tonne production.

[0014] Thus, there is a need for new methods and proceses to make amines of Formula 1 and Formula 2 using chemicals and raw materials that are amenable to large scale processes as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions caused by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using UAIH4 or NaBH4), d) exposure to highly toxic material carrying risk of cancer and death due to accidental release; e) fire and explosion due to highly flammable materials that require storage under cold temperature to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge.

[0015] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.BRIEF SUMMARY OF THE INVENTION

[0016] The present invention relates to a new process for the manufacture of amines that are useful in various applications including their use in polyurethane applications as well as the preparation of liquid systems for carbon dioxide removal from gaseous streams. In one embodiment, the scope of the amines prepared according to the new method comprise amines of formula 1 :Equation 1 -- - R1R1Amine Alcohol Formula 1 where R1and R2are independently aliphatic groups, or R1and R2are cycloaliphatic, or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (O) and where A is an aliphatic group or a cycloaliphatic ring, R3is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and R4is hydrogen atom, methyl group or R3.

[0017] In another embodiment, the scope of the amines prepared according to the new method comprise amines of formula 2:Equation 2. HVCatalystR5— O - (CH2)n- NH2 +HO - R3- ► R5— O - (CH2)n- NHR3-NH3Amine Alcohol Formula 2 wherein R5is a C1-12 linear or branched alkyl group and n = 2-3, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group.

[0018] Amines of Formula 1 made according to the new process are useful in making liquid systems comprising compounds of Formula 1. In some cases, one or more or the following conditions may apply: a) at least one of R1and R2is branched alkyl or cycloalkyl; b) R1forms a heterocyclyc with A; c) R1and R2together with the nitrogen towhich they are attached, forms a heterocyclic ring; d) al least one of R1and R2is not linear alkyl; v) R3is alkoxyalkyl or tertiary aminoalkyl; vi) R4is hydrogen atom, methyl group or R3. Amines of Formula 2 made according to the new process are also useful in making liquid systems comprising compounds of Formula 2.

[0019] In some embodiments, the amine compositions comprising amines of Formula 1 and the amine compositions comprising amines of Formula 2 can be used as solvents in carbon dioxide capture from various gaseous streams comprising gaseous streams from flue gas (exhaust gas or stack gas from combustion plants), form natural gas streams where carbon dioxide is removed from natural gas or any gaseous stream that requires the removal of acid gases such as carbon dioxide or other acid gases from sulfur (SO2 for example) or nitrogen (NOXfor example). The amine composition comprising compounds of Formula 1 and the amine composition comprising compounds of Formula 2 are used preferably as solvents for the removal of carbon dioxide but other acid gases are not necessarily excluded.

[0020] In some embodiments, the amine solvent made according to the new process does not contain an additional solvent, such as any added solvent, including water.

[0021] In some embodiments, the solvent comprises less than 10 wt. % water, the amine solvent typically absorbing such water from a carbon dioxide-rich gas stream such as an exhaust gas, while absorbing carbon dioxide. Each of R1and R2independently may be C1-6 alkyl but in certain embodiments, R1and R2together with the nitrogen to which they are attached form a heterocyclyl ring. In some embodiments, A is C2-4 alkyl, but in other examples, A and R1together with the nitrogen to which they are attached form a heterocyclyl ring. In some embodiments, R3is branched C3-6 alkyl or alkoxyalkyl. The solvent may have a low vapor pressure of less than 1 mm Hg at 40°C and with a water content of less than 0.1 wt % and / or a viscosity of less than 75 CP at a carbon dioxide loading of 40 mol % and at a temperature of 40°C. Contacting the gas stream with carbon dioxide-poor solvent may comprise contacting the gas stream at a first temperature of from 30°C to 80°C to facilitate carbon dioxide capture and heating the carbon dioxide-rich solvent may comprise heating the carbon dioxide-rich solvent to a second temperature of from 80°C to 160°C or more such as from 100°C to 160°C to facilitate carbon dioxide desorption. Heating the carbon dioxide-rich solvent may be performed at a pressure of from 1 atmosphere (atm) to 6 atms or more, such as from greater than 1 atm to 3 atms, or from 1.5 atms to 2 atms. In some embodiments, themethod further comprises cooling the regenerated carbon dioxide-poor solvent to a temperature of from 30°C to 60°C.

[0022] Amines made according to the new process comprising compounds of Formula 1 and amines made according to the new process comprising compounds of Formula 2 are also useful in a method comprising contacting a gas stream comprising a first amount of carbon dioxide with a solvent comprising a compound according to Formula 1 or Formula 2 to form a treated gas stream comprising a second amount of carbon dioxide that is less than the first amount. Then, heating the carbon dioxide-rich solvent stream to form a carbon dioxide stream and regenerate the solvent, thereby forming a carbon dioxide-poor solvent stream with the solvent having a viscosity of less than 75 CP at a carbon dioxide loading of 40 mol % and at a temperature of 40°C. In some embodiments, the solvent comprising amines of Formula 1 or Formula 2 does not comprise an additional solvent and in some embodiments, the solvent has a vapor pressure of less than 1 mm Hg at 40°C. when measured with a water content of less than 0.1 wt %.

[0023] Compounds according to the new process comprising amines of Formula 1 or Formula 2 are useful in building a system comprising an absorption unit comprising a gas entry, a first solvent entry and a first solvent egress, a regeneration unit comprising a second solvent entry fluidly coupled to the first solvent egress, and a second solvent egress fluidly coupled to the first solvent entry, and a solvent comprising a compound comprising amines according to Formula 1 or Formula 2. The sysem may further comprise a heat exchange unit coupled to the regeneration unit and the absorption unit such that the heat exchange unit facilitates transfer of heat energy from the solvent stream leaving the regeneration unit and to the solvent stream entering the regeneration unit.

[0024] The instant invention also solve some problems associated with conventional proceses to make amines comprising compounds of Formula 1 or Formula 2. The instant invention provides processes and methods using chemicals and raw materials that are amenable to large scale production as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions caused by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using LiAIF or NaBF ), d) exposure to highly toxic material carrying risk of cancer and death due toaccidental release; e) fire and explosion due to highly flammable materials that require storage under cold to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge.

[0025] The processes and methods to make amines comprising Formula 1 provided by the invention allow the scale production of these products to be used in multiple applications. The processes and methods to make amines comprising Formula 2 provided by the invention also allow the scale production of these products to be used in multiple applications.

[0026] In addition, the amines provided by the new process comprising amines of Formula 1 and the amines provided by the new process comprising amines of Formula 2 are useful in polyurethane foam applications which are typically prepared by reacting an isocyanate and a premix which consists of isocyanate-reactive components such as a polyol. The premix optionally also contains other components such as water, flame retardants, blowing agents, foam-stabilizing surfactants, and catalysts to promote the reactions of isocyanate with polyol to make urethane, with water to make CO2 and urea, and with excess isocyanate to make isocyanurate (trimer). The blowing agent in the premix is usually a liquid or gas with a boiling point sufficiently low to be vaporized by the heat released during the polymerization reaction. Examples of blowing agents useful in the production of insulating polyurethane foam include but are not limited to hydrofluorocarbons, hydrofluoroolefins, hydrofluorochloroolefins, hydrochlorofluorocarbons, formates, ketones such as acetone and hydrocabons. Unlike simple hydrocarbons, such as pentane, halogen containing molecules such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are far less flammable and safer to use in foam production. However, they either harm the ozone layer or contribute to global warming in other ways. In contrast, HFOs are very efficient and environmentally friendly blowing agents with a much lower global warming potential (GWP). However, decomposition of HFO can happen in a polyol premix formulation having an amine catalyst. Nevertheless, compounds according to the new process comprising Formula 1 or Formula 2 can be successfully used with HFO- blowing agents present in polyurethane formulations.

[0027] In one exemplary embodiment, the present invention provides new chemical compositions comprising amines of Formula 1 useful in the capture of carbon dioxide from gaseous streams.

[0028] In one exemplary embodiment, the present invention provides new chemical compositions comprising amines of Formula 2 useful in the capture of carbon dioxide from gaseous streams.

[0029] In one exemplary embodiment, the present invention provides methods and procedures to make amine compounds comprising Formula 1 useful in the capture of carbon dioxide from gaseous streams.

[0030] In one exemplary embodiment, the present invention provides methods and procedures to make amine compounds comprising Formula 2 useful in the capture of carbon dioxide from gaseous streams.

[0031] In another exemplary embodiment, the invention provides composition and methods to make a polyurethane formulation that includes at least one catalyst component comprising compounds of Formula 1.

[0032] In another exemplary embodiment, the invention provides composition and methods to make a polyurethane formulation that includes at least one catalyst component comprising compounds of Formula 2.

[0033] In another exemplary embodiment, the invention provides a polyurethane catalyst component comprising compounds of the Formula 1 of the new composition and / or a tertiary amine catalyst comprising compounds of formula 1 containing an isocyanate reactive group which causes no amine emissions in finished products.

[0034] In another exemplary embodiment, the invention provides a polyurethane catalyst component comprising compounds of the Formula 2 of the new composition and / or a tertiary amine catalyst comprising compounds of formula 2 containing an isocyanate reactive group which causes no amine emissions in finished products.

[0035] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1 is a schematic diagram of a carbon capture process for removing at least a portion of the carbon dioxide from a gas stream.

[0037] FIG 2 is a schematic diagram illustrating an alternative carbon capture process option pathway comprising a heat exchanger.DEFINITIONS

[0038] The following definitions are provided in order to aid those skilled in the art in understanding the detailed description of the present invention.PUR - Polyurethane.Isocyanate Index - The actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. Also known as (Eq NCO / Eq of active hydrogen)x100. pphp - parts by weight per hundred weight parts polyol.Polycat®-5 - A commercial catalysts supplied by Evonik Corporation with a chemical name pentamethyldiethylenetriaminePolycat®-8 - A commercial catalysts supplied by Evonik Corporation with a chemical name dimethylaminocyclohexaneDETAILED DESCRIPTION OF THE INVENTION

[0039] The invention is a new process for the manufacture of amines that are useful in various applications including their use in polyurethane applications and use in the preparation of systems for carbon dioxide removal from gaseous streams. In one embodiment, the scope of the amines prepared according to the new method comprise amines of formula 1 :Formula 1 where R1and R2are independently aliphatic groups or R1and R2are cycloaliphatic, or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (O), and where A is an aliphatic group, or a cycloaliphatic ring, R3is aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl, and R4is a hydrogen atom, methyl group or R3.

[0040] In another embodiment, the scope of the amines prepared according to the new method comprise amines of formula 2:R5-O-(CH2)n-NHR3Formula 2wherein R5is a C1-12 linear or branched alkyl group and n = 2-3, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group.

[0041] The present invention provides new methods and proceses to make new amines compositions comprising amines of Formula 1 or Formula 2 using chemicals and raw materials that are amenable to large scale processes as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions caused by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using LiAIF or NaBF ), d) exposure to highly toxic material carrying risk of cancer and death due to accidental release; e) fire and explosion due to highly flammable materials that require storage under cold temperature to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge.

[0042] These processes and methods consist of contacting an amine with an alcohol in the presence of a metal catalyst under hydrogen pressure. In one embodiment, the amine is contacted with an alcohol in the presence of a metal catalyst under hydrogen pressure as shown in the following equation for compounds comprising amines of Formula 1 :Equation 1Amine Alcohol Formula 1 where R1and R2are independently aliphatic groups, or R1and R2are cycloaliphatic, or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (O), and where A is an aliphatic group or a cycloaliphatic ring, R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group and R4is a hydrogen atom, methyl group or R3.

[0043] In another embodiment, the amine is contacted with an alcohol in the presence of a metal catalyst under hydrogen pressure as shown in the following equation for compounds comprising amines of Formula 2:Equation 2Amine Alcohol Formula 2 wherein R5is a C1-12 linear or branched alkyl group and n = 2-3, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group.

[0044] In one embodiment, the conversion of alcohol to amine can be carried out in a reactor with a suitable configuration which may be any of a variety of types and sizes as soon as there can be good contact between the vaporized feeds and catalyst. Typically, the reactions may be most simply carried out in a fixed bed, single tube, adiabatic reactor but other configurations that may be used include fixed bed reactors containing multiple tubes, with or without cooling, and fluidized bed systems.

[0045] Alcohols and amines according to the invention may be fed to the reactor by any of various means known in the art including for example a metering pump from two separate feeds. Alternatively, the amine-alcohol may be combined prior to introduction into the reactor. Hydrogen is co-fed to the reactor via a flow controller or other metering device to maintain the catalyst in an active reduced state. These reactants, either separately or combined, must be preferably vaporized and / or heated to a sufficient temperature to ensure that they are preferably in the vapor phase prior to contacting the catalyst. The products of the reaction are then condensed by cooling and may then be separated via distillation or other techniques known in the chemical engineering art.

[0046] The metal catalysts utilized for the conversion of the alcohol to amine are any of a broad class of Cu / Zn materials. Typically, the catalyst will be reduced prior to performing the conversion of the alcohol to the amine. Such reduction may be by any chemical means. Most the reduction may be performed by contacting the catalyst with hydrogen at an elevated temperature. The hydrogen may be most typically introduced as H2 gas, or it may be formed by interaction of the catalyst with an organic compound, for example isopropyl alcohol. Typically the reducing agent is used to pre-treat the catalyst prior to use, and typically its introduction into the reactor is continued on either an intermittent or continuous basis during the amination reaction, to keep the catalyst in an active state. Catalysts suitable for use accordingly comprise a copper salt and / or oxideand a zinc salt and / or oxide. The weight ratio of Cu / Zn (as the metals) may be 0.3 to 6, preferably 0.4 to 3, more preferably 0.45 to 2.75. The copper and zinc salts or oxides may include as nonlimiting examples as carbonates, hydroxides, and / or salts of carboxylic acids. In one exemplary embodiment, the catalyst comprises 20 to 70 wt % of CuO and 20 to 65 wt % of ZnO. In another exemplary embodiment, the catalyst comprises CuO, ZnO, AI2O3, and SiO2. The content of SiO2 in the catalyst may range from 0 to 40% by weight, preferably 0 to 10%. The content of AI2O3 in the catalyst may range from 0 to 40% by weight, preferably 0 to 20%. Other materials may be present in the catalyst as well. In some cases the catalyst has a Cu / Zn ratio of about 0.8. Also, since the vapor phase processing requires a lower reactor pressure and operates in a continuous mode, reactor construction and operation may be simplified. Copper leaching from the catalyst is essentially eliminated in vapor processing, resulting in longer catalyst life, minimal copper contaminants in the product, and alleviating the need for equipment cleaning to remove deposited copper. The presence of one or more promoters chosen from the Group 1 or 2 elements or early lanthanides, to the base Cu / Zn catalysts, can result in improvements in catalyst selectivity for the desired reaction vs. side reactions. Suitable promoters may be chosen from the alkali metals (Group 1 of the periodic table), alkaline earth metals (Group 2 of the periodic table), or early lanthanides (Group 3 of the periodic table, particularly those elements ranging from atomic number 57, lanthanum, to atomic number 65 terbium, with the exception of element number 61 , promethium. Examples of suitable promoters include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and terbium. More preferred promoters include sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, and samarium. Most preferred promoters are potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, and praseodymium. Promoters may be present in the catalyst at levels of 0.05 to 5 wt %, preferably 0.2 to 2 wt %, most preferably, 0.3 to 1.5 wt %.The reaction conditions can be carried out at temperatures in the range of 120° to 300°C and pressures in the range of 0 to 500 psig (101 to 3549 kPa). We have found that the process operates quite effectively in the range of 180° to 220°C. and 0 to 100 psig (101 to -700 kPa), although not restricted to these ranges. The pressure ranges typically from 40 to 80 psig (377 to 653 kPa). The amine and the alcohol can be co-fed to the reactor over a broad range of ratios. The molar ratio of alcohol to amine can be from 8 to 0.3, preferably from 4 to 1. Ifhydrogen is fed to the reactor, it is typically fed at a molar ratio of 1 to 8, preferably 2 to 5, relative to alcohol amine ratio. Rates of addition of alcohol and amine to the reactor vary according to a variety of factors, including the exact composition of these materials, the exact catalyst used, the temperature of the reactor, the pressure, and other variables. Determination of optimum conditions for any particular combination of these parameters is well within the ability of the skilled artisan.

[0047] One aspect of the invention relates to a process for the manufacture of diamines comprising the steps of (a) contacting an amine compound having the formulaC R2- NHR4with an alcohol compound having the formula HO - R3jn the presence of a metal catalyst under hydrogen pressure, wherein wherein R1and R2are independently aliphatic groups, or R1and R2are cycloaliphatic, or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom of oxygen, and A is an aliphatic group, or a cycloaliphatic ring, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group and R4is a hydrogen atom, a methyl group or R3.

[0048] Preferred examples of amines that can be used in the process comprise N-(3- aminopropyl)-morpholine, N-(2-aminoethyl)-morpholine, and the like.

[0049] In one preferred embodiment, the amine is N-(3-aminopropyl)-morpholine.

[0050] Preferred examples of alcohols that can be used in the process comprise 2- ethoxyethyl-1-ol, 2-(n-propoxy)ethyl-1-ol, 2-(isopropoxy)ethyl-1-ol, 2-(n-butoxy)ethyl-1-ol, 2-(iso-butoxy)ethyl-1-ol, 2-(sec-butoxy)ethyl-1-ol, 2-(t-butoxy)ethyl-1-ol, 2-(n- pentoxy)ethyl-1-ol, 2-(n-isopentoxy)ethyl-1-ol, 2-(tert-pentoxy)ethyl-1-ol, 2-(neo- pentoxy)ethyl-1-ol, 2-(n-isopentoxy)ethyl-1-ol, 2-(sec-isopentoxy)ethyl-1-ol, 2-(3- pentoxy)ethyl-1-ol, 2-(n-hexoxy)ethyl-1-ol, 2-(2-hexoxy)ethyl-1-ol, 2-(3-hexoxy)ethyl-1-ol, 2-(iso-hexoxy)ethyl-1-ol, 2-(4-methylpent-1-yloxy)ethyl-1-ol, 2-(4-methylpent-2- yloxy)ethyl-1-ol, 2-(2-methylpent-1-yloxy)ethyl-1-ol, 2-(3,3-dimethylbut-1-yloxy)ethyl-1-ol, 2-(3,3-dimethylbut-2-yloxy)ethyl-1-ol, 2-(2,2-dimethylbut-1-yloxy)ethyl-1-ol, 2- heptoxyethyl-1-ol, 2-octoxyethyl-1-ol, 2-(2-ethylhexyloxy)-1-ol, 3-ethoxypropyl-1-ol, 3-propoxypropyl-1-ol, 3-butoxypropyl-1-ol, 3-pentoxypropyl-1-ol, 3-hexoxypropyl-1-ol, 3- heptoxypropyl-1-ol, 3-octoxypropyl-1-ol, 3-(2-ethylhexyloxy)propyl-1-ol, and the like.

[0051] In one preferred embodiment, the alcohol is selected from the group consisting of 2-ethoxyethyl-1-ol and 3-ethoxypropyl-1-ol.

[0052] Another aspect of the invention relates to a process for the manufacture of diamines comprising the steps of (a) contacting an amine compound having the formulaR5-O-(CH2)n-NHR3Formula 2 with an alcohol compound having the formula HO - R3jn the presence of a metal catalyst under hydrogen pressure, wherein R5is a C1-12 linear or branched alkyl group and n = 2-3, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group.

[0053] Preferably in said embodiment, the ether amine is selected from the group consisting of 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine,2-butoxyethylamine, 2-pentoxyethylamine, 2-(n-hexoxy)ethylamine,3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-pentoxypropylmine, 3-(n-hexoxy)propylamine and the like. Preferably in said embodiment, the alcohol is selected from the group consisting of 4-(2- hydroxyethyl)morpholine, 4-(4-hydroxy-n-butyl)morpholine, N-(3-hydroxypropyl)- morpholine and the like.

[0054] In one preferred embodiment, the amine is selected from the group consisting of 2-ethoxyethylamine, 3-ethoxypropylamine, 2-methoxyethylamine, and 3- methoxypropylamine.

[0055] In one preferred embodiment, the alcohol is selected from the group consisting of 4-(2-hydroxyethyl)morpholine, 4-(4-hydroxy-n-butyl)morpholine, N-(3-hydroxypropyl)- morpholine and the like.

[0056] Preferred examples of products made according to Equation 1 comprise N-(2- ethoxyethyl)-3-morpholinopropan-1-amine, N-(2-ethoxyethyl)-2-morpholinoethan-1- amine, N-(3-ethoxypropyl)-2-morpholinoethan-1 -amine, N-(2-(n-propoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(isopropoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2- (n-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(iso-butoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(sec-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2- (t-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-morpholinopropan-1-amine, N- (2-(tert-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(neo-pentoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(sec-isopentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-hexoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(2-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(3- hexoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(iso-hexoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-morpholinopropan-1- amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(2- methylpent-1-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3,3-dimethylbut-1- yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-morpholinopropan-1- amine, N-(2-heptoxyethyl)-3-morpholinopropan-1 -amine, N-(2-octoxyethyl)-3- morpholinopropan-1-amine, N-(2-ethylhexyloxy)-3-morpholinopropan-1 -amine, N-(3- ethoxypropyl)-3-morpholinopropan-1-amine, N-(3-propoxypropyl)-3-morpholinopropan-1- amine, N-(3-butoxypropyl)-3-morpholinopropan-1 -amine, N-(3-pentoxypropyl)-3- morpholinopropan-1-amine, N-(3-hexoxypropyl)-3-morpholinopropan-1 -amine, N-(3- heptoxypropyl)-3-morpholinopropan-1 -amine, N-(3-octoxypropyl)-3-morpholinopropan-1- amine, N-(3-(2-ethylhexyloxy)propyl)-3-morpholinopropan-1-amine, and the like.

[0057] In one preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine comprising the steps of (a) contacting N- (3-aminopropyl)-morpholine with 2-ethoxyethyl-1-ol in the presence of CuO / ZnO / AhCh under hydrogen pressure.

[0058] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxypropyl)-3-morpholinopropan-1 -amine comprising the steps of (a) contacting N-(3-aminopropyl)-morpholine with 3-ethoxypropyl-1-ol in the presence of CuO / ZnO / AhCh under hydrogen pressure.

[0059] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine comprising the steps of (a) contacting 2-ethoxyethylamine with N-(3-hydroxypropyl)-morpholine in the presence of CuO / ZnO / AhCh under hydrogen pressure.

[0060] In another preferred embodiment, the process is a process for the manufacture of 3-ethoxy-N-(2-morpholinoethyl)propan-1-amine comprising the steps of (a) contacting3-ethoxypropylamine with N-(2-hydroxyethyl)-morpholine in the presence of CuO / ZnO / AhCh under hydrogen pressure.

[0061] In one exemplary preferred embodiment, the process involves the reaction of an amine with an alcohol in a continuous mode in a zone containing a metal catalyst such as Cu / ZnO, Cu / ZnO / K, Cu / ZnO / Cs, Cu / ZnO / Rb, Cu / Cr, Cu / Ni, Cu / Ni / Cr which can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or &2O3 or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are in the vapor phase.

[0062] In one exemplary preferred embodiment, the process involves the reaction of an amine with an alcohol in a continuous mode in a zone containing a metal catalyst such as Cu / ZnO, Cu / ZnO / K, Cu / ZnO / Cs, Cu / ZnO / Rb, Cu / Cr, Cu / Ni, Cu / Ni / Cr which can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or C^Ch or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are in the liquid phase under mechanical mixing and under hydrogen pressure.

[0063] Other preferred catalysts that can be used according to the invention comprise copper, nickel, chromium, cobalt, manganese, molybdenum, palladium, platinum and rhodium, oxides or carbonates of these metals and their mixtures. Another preferred catalyst is characterized by having a composition calculated in mole percent on an oxidefree basis of 50-90% nickel, 10-40% copper and 1-10% chromium with the preferred proportions being 70-80% nickel, 20-30% copper and 1-10% chromium and more typically the active components consist essentially of about 70-75 mole % nickel, about 20-25 mole % copper and about 1-4 mole % chromium.

[0064] In another preferred embodiment, the process further comprises the addition of at least one promoter selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and terbium. The addition of promoters to the catalyst might be needed to increase the selectivity for the conversion of the alcohol to the amine. More preferred promoters include sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, and samarium. Most preferred promoters are potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, and praseodymium. Promoters may be present in the catalyst at a level of 0.05 to 5 wt %, preferably 0.2 to 2 wt %, most preferably, 0.3 to 1 .5 wt %.

[0065] The vapor phase processing requires lower reactor pressure and operates in a continuous mode, reactor construction and operation may be simplified. Copper leaching from the catalyst is essentially eliminated in vapor processing, resulting in longer catalyst life, minimal copper contaminants in the product, and alleviating need for equipment cleaning to remove deposited copper. Furthermore, addition of one or more promoters chosen from the Group 1 or 2 elements or early lanthanides, to the base catalysts, can result in a substantial improvement in catalyst selectivity for the desired reaction vs. side reactions.

[0066] Alternatively, if the boiling point of the substrate is too high for example > 190°C then it is possible to carry out the process in liquid phase at temperature and pressure as to achieve reasonable kinetics for product production.

[0067] Reactors suitable for use according to the invention may be any of a variety of types and sizes, with the provision that there be good contact between the vaporized feeds and catalyst. While the reactions may be most simply carried out in a fixed bed, single tube, adiabatic reactor, other configurations that may be used include fixed bed reactors containing multiple tubes, with or without cooling, and fluidized bed systems. The glycol or ether alcohol may be fed to the reactor by any of various means known in the art including for example a metering pump. A second means of introduction is arranged for introducing the sterically hindered amine into the reactor, or the sterically hindered amine may be combined with the amino glycol or ether alcohol prior to introduction. Typically, hydrogen is co-fed to the reactor via a flow controller or other metering device to maintain the catalyst in an active state. These reactants, either separately or commingled, must be vaporized and / or heated to a sulficient temperature to ensure that they are in the vapor phase prior to contacting the catalyst. The products of the reaction are then condensed by cooling and may then be separated via distillation or other techniques known in the art.

[0068] Catalysts suitable for use according to this invention are any of a broad class of Cu / Zn materials comprsing Cu / ZnO, Cu / ZnO / K, Cu / ZnO / Cs, Cu / ZnO / Rb as well as other copper containing catalysts such as Cu / Cr, Cu / Ni, Cu / Ni / Cr which can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or C^Ch or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are either in the gas phase or in the liquid phase depending on the physical properties of the ether-alcohol substrate.

[0069] As used herein, the term "catalyst" will refer to the material that is charged to the reactor for the purpose of acting as a catalyst, but it will be understood that the actual catalytic species that are responsible for the conversion of the ether alcohols to sterically hindered ether amines may represent a change in composition from the catalyst as charged. Typically, the catalyst will be treated with a reducing agent prior to performing the conversion of glycol or ether alcohol to sterically hindered amino ether amine. Such reduction may, according to the invention, be by any chemical means. Typically the reduction may be performed by contacting the catalyst with hydrogen at an elevated temperature. The hydrogen may be introduced as H2 gas, or it may be formed by interaction of the catalyst with an organic compound, for example methanol, formaldehyde, isopropanol, etc. Typically the reducing agent is used to pre-treat the catalyst prior to use, and typically its introduction into the reactor is continued on either an intermittent or continuous basis during the amination reaction, to keep the catalyst in an active state.

[0070] Catalysts suitable for use according to the invention comprise a copper salt and / or oxide and a zinc salt and / or oxide optionally supported on silica, alumina, silico- alumina, titania, chromite, etc. The weight ratio of Cu / Zn as metals may vary from 0.3 to 6 and preferably 0.4 to 3 and more preferably 0.45 to 2.5. A typically supported Cu / Zn catalyst has a composition of about 25-50 wt. % CuO, 25-50 ZnO and 10-25 wt. % AI2O3. The copper and zinc salts or oxides may also include as nonlimiting examples carbonates, hydroxides, and / or salts of carboxylic acids. In another exemplary embodiment, the catalyst comprises 20 to 70 wt % of CuO and 20 to 65 wt % of ZnO. In another exemplary embodiment, the catalyst comprises CuO, ZnO, AI2O3, SiO2,TiO2, Cr20s, etc. The content of SiO2 in the catalyst may range from 0 to 40% by weight, preferably 0 to 25%. The content of AI2O3 in the catalyst may range from 0 to 40% by weight, preferably 0 to 25%. Other materials may be present in the catalyst as well. Catalysts comprising CuO, ZnO, and optionally AhOs and SiO2 are commercially available.

[0071] The catalyst may comprise a promoter to enhance the selectivity of the conversion of the glycol or ether alcohol to the desired sterically hindered ether amine. Promoters suitable for use according to the invention may be chosen from the alkali metals, alkaline earth metals, or early lanthanides. Examples of suitable promoters include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium,gadolinium, and terbium. More preferred promoters include sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, and samarium. Most preferred promoters are potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, and praseodymium. Promoters may be present in the catalyst at a level of 0.05 to 5 wt %, preferably 0.2 to 2 wt %, most preferably, 0.3 to 1.5 wt %.

[0072] One exemplary method of adding promoters to catalysts is for example by the addition of nitrate salts of the promoter metal directly to the Cu / Zn catalyst or by adding it during its formation to the final catalyst product.

[0073] The process of the current invention can be carried out at temperatures in the range of 120 to 300°C and pressures in the range of 0 to 500 psig. Typically, the process operates elfectively in the range of 180 to 220 °C and 0 to 100 psig although it is not restricted to these ranges. The amine and the glycol or ether alcohol can be from 0.3 to 8, preferably from 1 to 4. Hydrogen gas is typically supplied at a molar ratio of 1 to 8, preferably 2 to 5 relative to glycol or ether alcohol.

[0074] Rates of addition of amine and glycol or ether alcohol to the reactor vary according to a variety of factors, including the exact composition of these materials, their physical properties, the type of catalyst used, the reactor temperature, pressure and other variables.

[0075] The metal catalysts utilized for the conversion of the alcohol to amine are any of a broad class of Cu / Zn, Cu / Cr. Cu / Ni, Cu / Ni / Cr materials which can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or C^Ch or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are in the vapor phase or under mechanical mixing in the liquid phase.

[0076] Catalysts suitable for use accordingly comprise a copper salt and / or oxide and in some cases a zinc salt and / or a zinc oxide. The weight ratio of Cu / Zn as metals may be 0.3 to 6, preferably 0.4 to 3, more preferably 0.45 to 2.75. The copper and zinc salts or oxides may include as nonlimiting examples carbonates, hydroxides, and / or salts of carboxylic acids.

[0077] Copper leaching from the catalyst is essentially eliminated in vapor processing, resulting in longer catalyst life, minimal copper contaminants in the product, and alleviating need for equipment cleaning to remove deposited copper. Copper leaching inthe liquid phase is essentially eliminated or reduced to a minimum by the proper choice of the support. In particular, copper leaching is essentially eliminated in liquid phase when using chromite as a support. For example, a catalyst having a composition of about 50-70 wt. % CuCr2O4 to 70 wt % of CuO and 20 to 65 wt % of ZnO upon reduction to its acive state results in a catalyst that showed no copper leaching when the chemical reactions are carried out in the liquid state.

[0078] The presence of one or more promoters chosen from the Group 1 or 2 elements or early lanthanides to the base Cu catalysts can result in improvements in catalyst selectivity for the desired reaction. Suitable promoters may be chosen from the alkali metals, alkaline earth metals, or early lanthanides. Examples of suitable promoters include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and terbium. More preferred promoters include sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, and samarium. Most preferred promoters are potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, and praseodymium.

[0079] Promoters may be present in the catalyst at a level of 0.05 to 5 wt %, preferably 0.2 to 2 wt %, most preferably, 0.3 to 1.5 wt %.The reaction conditions can be carried out at temperatures in the range of 120° to 300°C and pressures in the range of 0 to 500 psig but the process operates quite effectively in the range of 180° to 220°C. and 0 to 100 psig and it is not restricted to these ranges. The pressure ranges typically from 40 to 80 psig (377 to 653 kPa). The amine and the glycol or ether alcohol can be co-fed to the reactor over a broad ratio range. The molar ratio of amine to glycol or ether alcohol can be from 0.3 to 8, preferably from 1 to 4. If hydrogen is fed to the reactor, it is typically fed at a molar ratio of 1 to 8, preferably 2 to 5, relative to amino ether alcohol. Rates of addition of amine and amino glycol or ether alcohol to the reactor vary according to a variety of factors, including the exact composition of these materials, the exact catalyst used, the temperature of the reactor, the pressure, and other variables. Determination of optimum conditions for any particular combination of these parameters is well within the ability of the skilled artisan.

[0080] The ratio of reactant, i.e. the ratio of alcohol to amine used in this process is 1 :1 to about 8:1.

[0081] Preferred examples of optional solvents that can be used include but are not limited to water, ethers such as diethylether, petroleum ether (ligroine), tetrahydrofuran, glycols and any solvent that does not interfere with the reaction shown in Equation 1 or Equation 2 is a suitable solvent. By “does not interfere” it is meant a solvent that does not poison the catalyst, that does not change substantially the composition of the amines provided by the processs comprising Formula 1 or Formula 2 and that it provides an advantage to the overall process relative to the solvent-free process.USE OF THE NEW AMINES IN CARBON CAPTURE

[0082] The processes and methods to make the new amine compositions comprising amines of Formula 1 or Formula 2 provided by the invention allow the scale production of these products to be used in multiple applications. One such application comprises a method of contacting a gas stream comprising a first amount of carbon dioxide with a carbon dioxide-poor solvent comprising an amine composition comprising compounds according to Formula 1 or Formula 2 to form a treated gas stream comprising a second amount of carbon dioxide that is less than the first amount and a carbon dioxide rich solvent stream and heating the carbon dioxide rich solvent stream to regenerate the carbon dioxide poor solvent. Contacting the gas stream with carbon dioxide-poor solvent may comprise contacting the gas stream at a first temperature of from 30°C to 80°C to help the carbon dioxide capture process. Heating the carbon dioxide-rich solvent may comprise heating the carbon dioxide-rich solvent to a second temperature of from 80°C to 160°C or more, such as from 100°C to 160°C to help desorb the carbon dioxide. Heating the carbon dioxide-rich solvent may be performed at a pressure of from 1.0 atmosphere (ambient pressure) to 6 atmosphere or more, such as from greater than 1 atmosphere to 3 atmosphere or from 1.5 atmosphere to 2 atmosphere. In some embodiments, the method further comprises cooling the regenerated carbon dioxidepoor solvent to a temperature of from 30°C to 60°C.

[0083] The amine composition of the new process comprising amines of formula 1 or formula 2 are useful in methods to capture carbon dioxide by contacting a gas stream comprising a first amount of carbon dioxide with a solvent comprising a compound according to Formula 1 or Formula 2 to form a treated gas stream comprising a second amount of carbon dioxide that is less than the first amount, and heating the carbon dioxide-rich solvent stream to form a carbon dioxide stream and regenerate the solvent, thereby forming a carbon dioxide-poor solvent stream, the solvent having a viscosity ofless than 75 CP at a carbon dioxide loading of 40 mol % and at a temperature of 40°C. In some embodiments, the solvent comprising amines of Formula 1 or Formula 2 does not comprise an additional solvent and in some embodiments, the solvent has a vapor pressure of less than 1 mm Hg at 40°C. when measured with a water content of less than 0.1 wt %.

[0084] Also the amine composition of the new process comprising amines of Formula 1 or Formula 2 are useful in building a system comprising: a) an absorption unit comprising a gas entry, a first solvent entry and a first solvent egress; b) a regeneration unit comprising a second solvent entry fluidly coupled to the first solvent egress, c) and a second solvent egress fluidly coupled to the first solvent entry, and d) a solvent comprising a compound according to Formula 1 or Formula 2. The system may further comprise a heat exchange unit fluidly coupled to the regeneration unit and the absorption unit such that the heat exchange unit facilitates transfer of heat energy from the solvent stream leaving the regeneration unit and to the solvent stream entering the regeneration unit.

[0085] Disclosed herein are embodiments of a method and system for removing carbon dioxide from a gas stream using a solvent comprising the amine composition provided by the new process comprising amines of Formula 1 or Formula 2. In some embodiments, the solvent does not include a cosolvent. However combustion typically produces water as well as carbon dioxide and therefore the gas stream may also comprise water that is formed during combustion. Such water may be removed from the gas stream along with the carbon dioxide such that the solvent may comprise less than 10 % water such as from greater than zero to less than 10 wt %, from 2 wt % to 7 wt % or about 5 wt % water. Part of the water might be removed from the solvent during solvent regeneration such that the solvent may have a steady state water content of less than 10 wt %. A person of ordinary skill in the art understands that such water is not added and therefore is not a co-solvent. Also, the water is not present in sufficient quantities to be considered a co-solvent in the solvent system. Typically, when water is used as a co-solvent, the solvent system comprises 25 % -30 % or more water.Therefore, a solvent consisting essentially of one or more of the compounds disclosed herein may include the water that may be removed from a gas stream along with the carbon dioxide, even though it does not include an added co-solvent, such as an aqueous co-solvent. The method may comprise contacting a gas stream comprising carbon dioxide with a carbon dioxide-poor solvent, thereby facilitating capture of at leasta portion of the carbon dioxide from the gas stream and forming a carbon dioxide-rich solvent, and then releasing at least a portion of the captured carbon dioxide from the carbon dioxide-rich solvent and regenerating the carbon dioxide-poor solvent. The carbon dioxide-poor solvent may comprise substantially zero mol % of carbon dioxide to less than 25 mol % carbon dioxide, such as from 1 mol % to less than 25 mol % carbon dioxide, from 5 mol % to less than 25 mol % carbon dioxide, or from 10 mol % to 20 mol % carbon dioxide. Additionally, or alternatively, the carbon dioxide-rich solvent may comprise from 25 mol % to 60 mol % or more carbon dioxide, such as from greater than 25 mol % to 50 mol %, or from 30 mol % to 45 mol % carbon dioxide. As used herein, mol % refers to the number of moles of carbon dioxide / the total number of moles of carbon dioxide and solvent x 100 %. A person of ordinary skill in the art understands that 50 mol % carbon dioxide refers to a 1:1 ratio between the number of moles of solvent molecules and the number of moles of carbon dioxide present in the solvent. In some embodiments, a carbon dioxide mol % difference between a carbon dioxide-rich solvent and a carbon dioxide-poor solvent is from greater than zero to 50 mol % carbon dioxide, or more, such as from 5 mol % to 50 mol %, from 10 mol % to 40 mol %, from 5 mol % to 30 mol %, from 5 mol % to 20 mol %, or from 5 mol % to 15 mol %. In some embodiments , the carbon dioxide capture occurs under a first set of conditions (lower operation temperature) and the carbon dioxide release and solvent regeneration occurs under a second set of conditions (higher temperature).

[0086] FIG 1 provides a schematic diagram of an exemplary process for removing at least a portion of the carbon dioxide from a gas stream. With respect to FIG 1, the solvent flow pathway comprises carbon dioxide-poor solvent stream “i” and carbon dioxide-rich solvent stream “d”. Carbon dioxide-poor solvent stream “i” enters absorption unit ‘n” through entry “k” and contacts carbon dioxide-rich gas stream “a” that enters absorption unit “n” through gas entry ”b”. Absorption unit ‘n” may be a column or tower and may comprise materials and structures suitable to facilitate contact between the solvent and carbon dioxide-rich gas stream “a”, such as by providing an increased contact surface area. Absorption unit “n” may comprise mesh sheets, fibrous material, such as fiberglass, and packing materials, such as beads, balls, rings, saddle- shaped materials, tubes, or combinations thereof. Typically, carbon dioxide-poor solvent stream “i” contacts carbon dioxide-rich gas stream “a” counter currently. Absorption unit “n” operates at a first temperature and a first pressure suitable to facilitate carbon dioxide capture by the solvent. The first temperature may be of from 25° C to 100°C ormore, such as from 30°C to 80°C or from 40°C to 60°C and in some embodiments, carbon dioxide capture proceeds at about 40°C and the first pressure typically is atmospheric pressure, such as 1 atm.

[0087] Carbon dioxide-rich gas stream 12 may comprise from greater than zero to 25 wt % or more, such as from 1 wt % to 20 wt %, from 1 wt % to 15 wt %, from 1 wt % to 10 wt % or from 1 wt % to 5 wt % carbon dioxide. In certain embodiments, including embodiments comprising coal exhaust, such as from a coal-fired power plant, carbon dioxide-rich gas stream “a” may comprise from 1 wt % to 15 wt % or more carbon dioxide, such as from 5 wt % to 15 wt %, or from 10 wt % to 15 wt % carbon dioxide. In other embodiments comprising gas exhaust, such as from a natural gas power plant, carbon dioxide-rich gas stream “a” may comprise from 1 wt % to 10 wt % carbon dioxide, such as from 1 wt % to 5 wt % carbon dioxide and may be about 4 wt % carbon dioxide.

[0088] Carbon dioxide-poor solvent stream ‘i” captures at least a portion of the carbon dioxide present in carbon dioxide-rich gas stream “a”, thereby producing carbon dioxidepoor gas stream ‘m” and carbon dioxide-rich solvent stream “d”. Carbon dioxide-poor gas stream “m” comprises a reduced amount of carbon dioxide compared to carbon dioxide-rich gas stream “a”, and exits absorption unit “n” through gas exit “I”. In some embodiments, carbon dioxide-rich solvent stream “i” removes at least 60 % of the carbon dioxide in the carbon dioxide-rich gas stream “a”, such as at least 70 %, at least 80 % or at least 90 % of the carbon dioxide from the carbon dioxide-rich gas stream. Therefore, carbon dioxide-poor gas stream “m” comprises 40 % or less carbon dioxide than the corresponding carbon dioxide-rich gas stream after contact with solvent stream “I”, such as 30 % or less, 20 % or less, or 10 % or less carbon dioxide.

[0089] Carbon dioxide-rich solvent stream “d” leaves absorption unit “n” through solvent exit “c”. Solvent exit “c” is fluidly coupled to solvent entry “f” in regeneration unit “g”. In regeneration unit “g”, carbon dioxide-rich solvent stream “d” is heated to a second temperature suitable to facilitate release of at least a portion of the captured carbon dioxide, thereby producing carbon dioxide-poor solvent stream “i”. Carbon dioxide release and solvent regeneration typically proceeds at a second temperature greater than the first temperature . The second temperature may be a boiling point of the solvent, and might be from 100° C to 160°C or more such as from 110°C to 140°C or from 120°C to 140°C and in some embodiments release and regeneration proceeds atabout 120°C. Solvent regeneration is performed at a second pressure suitable to facilitate carbon dioxide release and solvent regeneration.

[0090] In some embodiments, the second pressure is from 1 atm to 6 atm or more, such as from greater than 1 atm to 3 atm, or from 1.5 atm to 3 atm. Carbon dioxide that is released from the solvent exits the regeneration unit “g” as carbon dioxide stream “h”. Carbon dioxide-poor solvent stream “I” exits regeneration unit “g” through solvent exit “o” which is fluidly coupled to solvent entry “k” on absorption unit “n”. Typically, as carbon dioxide-poor solvent stream “i” leaves regeneration unit “g” it is at a temperature greater than the first temperature that is used in absorption unit “n”. Therefore, the process may comprise cooling unit “j” that cools carbon dioxide-poor solvent stream “I” such that the solvent stream enters absorption unit “k” at a temperature suitable to facilitate carbon dioxide capture, such as the first temperature. In some embodiments, the process further comprises a heating unit “e” that heats carbon dioxide-rich solvent stream “d” prior to the solvent entering regeneration unit “g”. Heating unit “e” may heat the solvent stream to a third temperature. The third temperature may be substantially the same as the second temperature, or greater, such that carbon dioxide-rich solvent stream “d” enters regeneration unit “g” at substantially the second temperature. Alternatively , the third temperature may be an intermediate temperature between the first and second temperatures, such that the energy required to heat the carbon dioxide-rich solvent stream “d” to the second temperature in regeneration unit “g” is reduced.

[0091] In certain embodiments, cooling unit “j” and heating unit “e” are combined into a heat exchanger unit “p”. FIG 2 provides an exemplary schematic diagram illustrating an alternative exemplary process option pathway comprising a heat exchanger. With respect to FIG 2 heat exchanger “p” facilitates heat exchange between carbon dioxide poor solvent stream “i” and carbon dioxide-rich solvent stream “d”, such that carbon dioxide-poor solvent stream “i” is cooled and carbon dioxide-rich solvent stream “d” is heated. Typically, carbon dioxide-rich solvent stream “d” enters heat exchanger “p” at about the first temperature, and leaves heat exchanger “p” at a temperature greater than the first temperature and that may be at or less than the second temperature. Conversely, carbon dioxide-poor solvent stream “i” enters heat exchanger “p” at a temperature of about the second temperature or less but greater than the first temperature, and leaves at a temperature of from less than the second temperature to the first temperature.

[0092] In some embodiments, two or more systems disclose herein are combined in series or in parallel. In certain embodiments, two or more systems are combined in parallel, such that a carbon dioxide-rich gas stream is split between each of the disclosed systems to become carbon dioxide-rich gas stream “a” for each system. In embodiments comprising two or more systems in series, carbon dioxide-poo gas stream “m" that is output from a first system forms carbon dioxide-rich gas stream “a” of a second system.USE IN POLYURETHANE APPLICATIONS

[0093] The present invention provides a novel polyurethane catalyst and a polyol premix composition having the following benefits: a) provides a tertiary amine catalysts bearing an amine functionality capable of providing good foam kinetics and cure including surface cure; b) improves the odor qualities as the amine might bind covalently to the polyurethane polymer or it might be retained due to its low vapor pressure without incurring detrimental foam physical properties; c) provides optimum catalytic activity and foam physical properties.

[0094] Also, the present invention provides a method for preparing a polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of a catalyst composition comprising compounds as defined above in Formula 1 or Formula 2 in combination with a metal catalyst and / or a tertiary amine having or not an isocyanate reactive group.

[0095] Additionally, polyurethane foams can be produced with the novel catalyst system and novel compositions of the present invention by several methods known within the art.

[0096] Any amount of catalyst composition as defined in Formula 1 or Formula 2 above can be used in the compositions of the present invention.

[0097] Applicants disclose several types of ranges in the present invention. These include, but are not limited to, a range of temperatures; a range of number of atoms; a range of foam density; a range of Isocyanate Index; and a range of pphp for the blowing agent, water, surfactant, flame retardant, and catalyst composition as defined in Formula I or Formula 2 above.

[0098] When Applicants disclose or claim a range of any type, Applicants’ intent is to disclose or claim individually each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, when the Applicants disclose or claim a chemical moiety having a certain number of carbon atoms, Applicants’ intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein.

[0099] For example, the disclosure that R1and R2are each independently C1-3 alkyl linear or branched, alkenyl linear or branched mean for example that an alkyl group having up to 3 carbon atoms, or in alternative language a C1-3 alkyl group, as used herein, refers to a “R1” or “R2” group that can be selected independently from an alkyl group having 1, 2, or 3 carbon atoms, as well as a range between these two numbers for example, a C2 to C3 alkyl group.

[0100] Similarly, another representative example follows for the parts by weight of the catalyst composition comprising compounds as defined in formula 1 or formula 2 per hundred weight parts of the at least one active hydrogen-containing compound in a composition or a foam formulation. If the at least one active hydrogen-containing compound is an at least one polyol, the parts by weight per hundred weight parts polyol is abbreviated as pphp. Hence, by the disclosure that the catalyst composition as defined in Formula I or Formula 2 is present in an amount from about 0.05 to about 10 pphp, for example, Applicants intend to recite that the pphp can be selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these two examples.

[0101] Applicants reserve the right to proviso out or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, analogs, compounds, ligands, structures, or groups thereof,or any members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application.

[0102] In another aspect of the invention, the catalyst compositions can be used to make rigid foams (foam that is unable to bend or be forced out of shape) having a density of about 0.5 lb / ft3to about 5 lb / ft3, about 1 lb / ft3to about 4 lb / ft3and in some cases about 2 lb / ft3to about 3 lb / ft3. The catalyst compositions can be used to make close cell rigid foam such as those typically used in spray foam insulation and appliances having desirable physical properties including dimensional stability, adhesion, friability, thermal insulation and compressions strengths. In a further aspect, the catalyst compositions can be used to make rigid foams having a density of about 0.5 lb / ft3to about 5 lb / ft3, about 1 lb / ft3to about 4 lb / ft3and in some cases about 2 lb / ft3to about 3 lb / ft3. Density can be measured in accordance with ASTM D3574 Test A.

[0103] In another aspect of the invention, the catalyst compositions can be used to make flexible foam including fexible slabstock foam and flexible molded foam.

[0104] Flexible molded foams of the invention are characterized by excellent physical properties typically have target density (ASTM 3574-A) with range of about 28 to about 80 kg / m3, air flow (ASTM 3574-G) with range of about 40 to about 120L / M, ILDs (indentation load deflection method ASTM 3574-B1) with range of about 150 to about 600 N, support factor (ASTM 3574-B1) with range of about 2.5 to about 3.5, preferably about 3, and resilience (ASTM 3574-H) range of about 40 to about 80%. In one aspect of the invention a desirable foam has a Tensile / HA Tensile / Elongation / HA Elongation = DIN 53571 - Range of about 80 to about 200%, a 50% Compression Set = ASTM D3574-D - Range of about 1 to about 20%, a HA Compression Set = ASTM D3574-J1 and J2 - Range of about 5 to about 15%, and Tear = ASTM D3574-F - Range of about 150 to about 400.

[0105] In one aspect of the invention, the catalyst composition comprising compounds as defined in Formula 1 or Formula 2 comprise at least one member selected from the group consisting of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine, N-(2-ethoxyethyl)-2- morpholinoethan-1-amine, N-(3-ethoxypropyl)-2-morpholinoethan-1 -amine, N-(2-(n- propoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(isopropoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(n-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2- (iso-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(sec-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(t-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n- pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-isopentoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(tert-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2- (neo-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-isopentoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(sec-isopentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-hexoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(2-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(3- hexoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(iso-hexoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-morpholinopropan-1- amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(2- methylpent-1-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3,3-dimethylbut-1- yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-morpholinopropan-1- amine, N-(2-heptoxyethyl)-3-morpholinopropan-1 -amine, N-(2-octoxyethyl)-3- morpholinopropan-1-amine, N-(2-ethylhexyloxy)-3-morpholinopropan-1 -amine, N-(3- ethoxypropyl)-3-morpholinopropan-1-amine, N-(3-propoxypropyl)-3-morpholinopropan-1- amine, N-(3-butoxypropyl)-3-morpholinopropan-1 -amine, N-(3-pentoxypropyl)-3- morpholinopropan-1-amine, N-(3-hexoxypropyl)-3-morpholinopropan-1 -amine, N-(3- heptoxypropyl)-3-morpholinopropan-1 -amine, N-(3-octoxypropyl)-3-morpholinopropan-1- amine, N-(3-(2-ethylhexyloxy)propyl)-3-morpholinopropan-1-amine, and the like. Such compounds can be employed individually or in any combination thereof.

[0106] The catalyst composition comprising compounds as defined in Formula 1 can be used as the sole catalysts or alternatively in combination with at least one tertiary amine catalyst.

[0107] The catalyst composition comprising compounds as defined in Formula 2 can be used as the sole catalysts or alternatively in combination with at least one tertiary amine catalyst.

[0108] The tertiary amine catalyst comprising compounds according to Formula 1 can have at least one isocyante reactive group in which case Equation 1Equation 1requires that R4is hydrogen atom with all the other substituents as defined above.

[0109] The tertiary amine catalyst comprising compounds according to Formula 1 can also have no isocyante reactive group in which case Equation 1 requires that R4is methyl group or R3with R1, R2and A as defined above.

[0110] Tertiary amines comprising compounds of Formula 1 where R4is a methyl group can also be conveniently prepared in two step reactions using formaldehyde and catalysts as follows:

[0111] The alternative tertiary amine catalyst can have at least one isocyanate reactive group or alternatively it can be a conventional tertiary amine catalyst having noisocyanate reactive groups. Examples of isocyanate reactive groups comprise a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group. Examples of tertiary amine catalyst having an isocyanate reactive group include, but are not limited to N, N-bis(3- dimethylaminopropyl)-N-isopropanolamine, N, N-dimethylaminoethyl-N'-methyl ethanolamine, N, N, N'-trimethylaminopropylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethyl-N', N'-2-hydroxy(propyl)-1 ,3- propylenediamine, dimethylaminopropylamine, (N, N-dimethylaminoethoxy) ethanol, methyl-hydroxy-ethyl-piperazine, bis(N, N-dimethyl-3-aminopropyl) amine, N, N- dimethylaminopropyl urea, diethylaminopropyl urea, N, N'-bis(3- dimethylaminopropyl)urea, N, N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2- propanol, 6-dimethylamino-1 -hexanol, N-(3-aminopropyl) imidazole), N-(2-hydroxypropyl) imidazole, and N-(2-hydroxyethyl) imidazole, 2-[N-(dimethylaminoethoxyethyl)-N- methylamino] ethanol, N,N-bis(dimethylaminopropyl)-N-(3-aminopropyl)amine, N,N- bis(dimethylaminopropyl)-N-(3-aminopropyl)amine; N,N-bis(3-dimethylaminopropyl)-N- {3-[bis(2-hydroxypropyl)]propylamine}; N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxyethyl)]propylamine}; N, N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N, N, N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or a combination thereof. The weight ratio of suitable tertiary amines to the inventive catalyst can range from about 0 to about 100, about 0.1 to about 50 and in some cases about 1 to about 10.

[0112] In one embodiment, the tertiary amine catalyst component is highly volatile and is not isocyanate-reactive. For example, in one embodiment, the tertiary amine catalyst component is a volatile gelling catalyst and is or includes diazobicyclooctane (triethylenediamine), 1,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl) amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, or combinations thereof. Additionally or alternatively, in one embodiment, the tertiary amine catalyst component is or includes a volatile blowing catalyst and is or includes bis(dimethylaminoethy)ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions and higher permethylated polyamines. Additonally or alternatively, in another embodiment, the tertiary amine catalyst component is or includes a blowing catalyst having an isocyanate reactive group such as 2-[N-(dimethylaminoethoxyethyl)- N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, amino propyl-bis(amino-ethyl) ether compositions, or combinations thereof.

[0113] The catalyst composition comprising compounds as defined in Formula 1 or Formula 2 can also be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylicacid and the like. An acid blocked catalyst can be obtained by known methods using conventional equipment.

[0114] In one embodiment, the tertiary amine catalyst component is used in conjunction with a transition metal catalyst. For example, in one embodiment, the catalyst composition comprising compounds as defined in Formula 1 is used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof. Examples of transition metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutylin dilaureate, dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octate, other suitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts includes salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0115] The catalyst system or novel compositions of the present invention can further comprise other catalytic materials such as carboxylate salts in any amount. Illustrative examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2- hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.

[0116] The amount of the other catalytic materials and salts can range from about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp and in some cases about 0.5 pphp to about 10 pphp.

[0117] It is also within the scope of the catalyst composition of this invention to include mixtures or combinations of more that one catalyst composition as defined in Formula 1. Additionally, the catalyst system or the novel compositions of the present invention can also further comprise at least one urethane catalyst having no isocyanate reactive groups.

[0118] It is also within the scope of the catalyst composition of this invention to include mixtures or combinations of more that one catalyst composition as defined in Formula 2. Additionally, the catalyst system or the novel compositions of the present invention can also further comprise at least one urethane catalyst having no isocyanate reactive groups.

[0119] The term “contact product” is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions or foam formulations described herein. Combining additional catalyst components can be done by any method known to one of skill in the art. For example, in one aspect of the present invention, catalyst compositions can be prepared by combining or contacting the catalyst composition as defined in Formula 1 or Formula 2 with at least one tertiary amine having or not at least one isocyanate reactive group and optionally with an alkali metal carboxylate salt. This typically occurs in solution form.

[0120] While compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components or steps.POLYISOCYANATES

[0121] Polyisocyanates that are useful in the PIR / PUR foam formation process include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyante, toluene diisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI), hydrated MDI and 1 ,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, andmixtures thereof, can be readily employed in the present invention. Other suitable mixtures of diisocyanates include, but are not limited to, those known in the art as crude MDI, or PAPI, which contain 4,4’-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. In another aspect of this invention, prepolymers of polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyol are suitable. In still another aspect, the polyisocyanate comprises MDI, or consists essentially of MDI or mixtures of MDI’s.

[0122] The catalyst system, compositions, and methods of producing PIR / PUR foam of the present invention can be used to manufacture many types of foam. This catalyst system is useful, for example, in the formation of foam products for rigid and flame retardant applications, which usually require a high Isocyanate Index. As defined previously, Isocyanate Index is the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. For purposes of the present invention, Isocyanate Index is represented by the equation: Isocyanate Index = (Eq NCO / Eq of active hydrogen)x100, wherein Eq NCO is the number of NCO functional groups in the polyisocyanate, and Eq of active hydrogen is the number of equivalent active hydrogen atoms.

[0123] Foam products which are produced with an Isocyanate Index from about 10 to about 800 are within the scope of this invention. In accordance with other aspects of the present invention, the Isocyanate Index ranges from about 20 to about 700, from about 30 to about 650, from about 50 to about 600, or from about 70 to about 500.POLYOLS

[0124] Active hydrogen-containing compounds for use with the foregoing polyisocyanates in forming the polyisocyanurate / polyurethane foams of this invention can be any of those organic compounds having at least two hydroxyl groups such as, for example, polyols. Polyols that are typically used in PIR / PUR foam formation processes include polyalkylene ether and polyester polyols. The polyalkylene ether polyol includes the poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols, These include, but are not limited to, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol,trimethylol propane, cyclohexane diol, and sugars such as sucrose and the like low molecular weight polyols.

[0125] Amine polyether polyols can be used in the present invention. These can be prepared when an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.

[0126] In another aspect of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as mixtures of different multifunctional materials and / or different molecular weight or different chemical composition materials can be used.

[0127] In yet another aspect of the present invention, polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of a diol. Non-limiting examples include adipic acid or phathalic acid or phthalic anhydride reacting with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of a diol, for example, caprolactone reacted with propylene glycol. In a further aspect, active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.

[0128] The polyol can have an OH number of about 5 to about 600, about 100 to about 600 and in some cases about 50 to about 100 and a functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.

[0129] The amount of polyol can range from about 0 pphp to about 100 pphp about 10 pphp to about 90 pphp and in some cases about 20 pphp to about 80 pphp.BLOWING AGENTS

[0130] In accordance with the compositions, foam formulations, and methods of producing PIR / PUR foam within the scope of the present invention, suitable blowing agents that can be used alone or in combination include, but are not limited to, water, methylene chloride, acetone, hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluoroolefins (HFOs), chlorofluoroolefins (CFOs), hydrochloroolefins (HCOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), chloroolefins, formates and hydrocarbons. Examples of HFCs include, but are not limited to, HFC- 245fa, HFC-134a, and HFC-365; illustrative examples of HCFCs include, but are notlimited to, HCFC-141b, HCFC-22, and HCFC-123. Exemplary hydrocarbons include, but are not limited to, n-pentane, iso-pentane, cyclopentane, and the like, or any combination thereof. In one aspect of the present invention, the blowing agent or mixture of blowing agents comprises at least one hydrocarbon. In another aspect, the blowing agent comprises n-pentane. Yet, in another aspect of the present invention, the blowing agent consists essentially of n-pentane or mixtures of n-pentane with one or more blowing agents. Examples of hydrohaloolefin blowing agents are HFO-1234ze (trans- 1 ,3, 3,3- Tetrafluoroprop-1-ene), HFO-1234yf (2,3,3, 3-Tetrafluoropropene) and HFCO-1233zd (1- Propene,1-chloro-3,3,3-trifluoro), among other HFOs.

[0131] In one embodiment ,the blowing agent component comprises a hydrohaloolefin, preferably comprising at least one of trans-HFO-1234ze and HFCO-1233zd, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, aldehyde, ketone, carbon dioxide generating material, or combinations thereof. The hydrohaloolefin preferably comprises at least one halooalkene such as a fluoroalkene or chloroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins non-exclusively include trifluoropropenes, tetrafluoropropenes such as (HFO-1234), pentafluoropropenes such as (HFO-1225), chlorotrifluoropropenes such as (HFO-1233), chlorodifluoro propenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, and combinations of these. Other preferred blowing agents comprise the tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds in which the unsaturated terminal carbon has not more than one fluorine or chlorine substituent. Included are 1,3, 3, 3- tetrafluoropropene (HFO-1234ze); 1 ,1,3,3-tetrafluoropropene; 1, 2, 3,3,3- pentafluoropropene (HFO-1225ye); 1,1,1- trifluoropropene; 1 ,1,1,3,3-pentafluoropropene (HFO 1225zc); 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1 , 2, 3, 3- pentafluoropropene (HFO- 1225yc); 1,1, 1,2, 3- pentafluoropropene (HFO-1225yez); 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd); 1,1, 1.4.4.4- hexafluorobut-2-ene or combinations thereof, and any and all structural isomers, geometric isomers, or stereoisomers of each of these. Preferred optional blowing agents non-exclusively include water, formic acid, organic acids that produce carbon dioxide when they react with an isocyanate, hydrocarbons; ethers, halogenated ethers; pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans-1.2 dichloro-ethylene; methyl formate; 1-chloro-1 , 2,2,2- tetrafluoroethane; 1 ,1 -dichloro- 1 -fluoroethane; 1,1 ,1 ,2-tetrafluoroethane; 1, 1 ,2,2- tetrafluoroethane; 1-chloro-1,1 -difluoroethane; 1,1 , 1,3,3-pentafluorobutane;1.1.1.2.3.3.3-heptafluoropropane; trichlorofluoromethane; dichlorodifluoromethane;1.1.1.3.3.3-hexafluoropropane; 1,1,1 ,2,3,3-hexafluoropropane; difluoromethane; difluoroethane; 1,1 ,1,3,3-pentafluoropropane; 1,1 -difluoroethane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof. The blowing agent component is usually present in the polyol premix composition in an amount of from about 1 wt.% to about 30 wt.%, preferably from about 3 wt.% to about 25 wt.%, and more preferably from about 5 wt.% to about 25 wt.%, by weight of the polyol premix composition. When both a hydrohaloolefin and an optional blowing agent are present, the hydrohaloolefin component is usually present in the blowing agent component in an amount of from about 5 wt.% to about 90 wt.%, preferably from about 7 wt.% to about 80 wt.%, and more preferably from about 10 wt.% to about 70 wt.%, by weight of the blowing agent component; and the optional blowing agent is usually present in the blowing agent component in an amount of from about 95 wt. % to about 10 wt.%, preferably from about 93 wt.% to about 20 wt.%, and more preferably from about 90 wt.% to about 30 wt.%, by weight of the blowing agent component.

[0132] Due to the discovery that chlorofluorocarbons (CFCs) can deplete ozone in the stratosphere, this class of blowing agents is not desirable for use. A chlorofluorocarbon (CFG) is an alkane in which all hydrogen atoms are substituted with chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane.

[0133] The amount of blowing agent used can vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density. In the compositions, foam formulations and methods for preparing a polyisocyanurate / polyurethane foam of the present invention, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. In another aspect, the blowing agent is present in amounts from about 10 to about 60, from about 15 to about 50, or from about 20 to about 40, parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. If the at least one active hydrogen-containing compound is an at least one polyol, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts polyol (pphp), from about 10 to about 60 pphp, from about 15 to about 50 pphp, or from about 20 to about 40 pphp.

[0134] If water is present in the formulation, for use as a blowing agent or otherwise, water is present in amounts up to about 60 parts by weight per hundred weight parts ofthe at least one active hydrogen-containing compound. Likewise, if the at least one active hydrogen-containing compound is an at least one polyol, water can range from 0 to about 15 pphp. In another aspect, water can range from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, or from 0 to about 4 pphp.URETHANE CATALYST

[0135] Conventional urethane catalysts having no isocyanate reactive group can be employed to accelerate the reaction to form polyurethanes, and can be used as a further component of the catalyst systems and compositions of the present invention to produce polyisocyanurate / polyurethane foam. Urethane catalysts suitable for use herein include, but are not limited to, metal salt catalysts, such as organotins, and amine compounds, such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethyl-imidazole, N- methylmorpholine (commercially available as the DABCO® NMM catalyst), N- ethylmorpholine (commercially available as the DABCO® NEM catalyst), triethylamine (commercially available as the DABCO® TETN catalyst), N,N’-dimethylpiperazine, 1 ,3,5- tris(dimethylaminopropyl)hexahydrotriazine (commercially available as the Polycat® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol (commercially available as the DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commercially available as the Polycat® 12 catalyst), pentamethyldipropylene triamine (commercially available as the Polycat® 77 catalyst), N-methyl-N’-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as the Polycat® 5 catalyst), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine (commercially available as the Polycat® 8 catalyst), pentamethyldipropylenetriamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether (commercially available as the DABCO® BL19 catalyst), tris(3-dimethylamino)- propylamine (commercially available as the Polycat® 9 catalyst), 1 ,8-diazabicyclo[5.4.0] undecene (commercially available as the DABCO® DBU catalyst) or its acid blocked derivatives, and the like, as well as any mixture thereof.

[0136] The present invention can be used with tertiary amine catalysts having isocyanate reactive groups. Isocyanate reactive groups present in the alternative tertiary amine gelling co-catalyst consist essentially of primary amine, secondary amine, secondary-hydroxyl group, amide and urea. Examples of gelling catalysts include N,N- bis(3-dimethylamino-propyl)-N-(2-hydroxypropyl) amine; N,N-dimethyl-N’,N’-bis(2- hydroxypropyl)-1 ,3-propylenediamine; dimethylaminopropylamine (DMAPA); N-methyl-N-2-hydroxypropyl-piperazine, bis(dimethylaminopropyl)amine (POLYCAT® 15), dimethylaminopropylurea and N,N’-bis(3-dimethylaminopropyl) urea (DABCO® NE1060, DABCO® NE1070, DABCO® NE1080 and DABCO® NE1082), 1,3-bis(dimethylamino)- 2-propanol, 6-dimethylamino-1 -hexanol, N-(3-aminopropyl)imidazole, N-(2- hydroxypropyl)imidazole, N,N’-bis(2-hydroxypropyl) piperazine, N-(2-hydroxypropyl)- morpholine, N-(2-hydroxyethylimidazole); N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2- hydroxypropyl)]propylamine}; N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2- hydroxyethyl)]propylamine}. Examples of blowing co-catalysts containing isocyanate reactive groups that can be used with the above mentioned gelling catalysts include 2- [N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol (DABCO® NE200), N,N,N’- trimethyl-N’-3-aminopropyl-bis(aminoethyl) ether (DABCO® NE300).

[0137] Suitable urethane catalyst that can be used in combination with the inventive catalyst also include acid blocked tertiary amines with acids including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids include mono-acids, diacids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid and the like. An acid blocked catalyst can be obtained by known methods using conventional equipment.

[0138] Tertiary amine catalyst component can also be used in conjunction with a metal catalyst. For example, in one embodiment, the tertiary amine catalyst component is used with an organotin compound, tin(ll) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof. Examples of metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutylin dilaureate, dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexylmercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octoate, other suitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts includes salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0139] The present invention can further comprise other catalytic materials such as carboxylate salts in any amount. Illustrative examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, tetramethylammonium carboxylates, tetralkylammonium carboxylates such as tetramethylammonium pivalate (supplied by Evonik Corporation as DABCO®TMR7) and the like, or any combination thereof.

[0140] For preparing a polyisocyanurate / polyurethane foam of the present invention, the urethane catalyst can be present in the formulation from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from 0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. In another aspect, the urethane catalyst is present from 0 to about 0.8 pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 to about 0.2 pphp.MISCELLANEOUS ADDITIVES

[0141] Depending upon the requirements during foam manufacturing or for the enduse application of the foam product, various additives can be employed in the PIR / PUR foam formulation to tailor specific properties. These include, but are not limited to, cell stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers,pigments, or any combination thereof. It is understood that other mixtures or materials that are known in the art can be included in the foam formulations and are within the scope of the present invention.

[0142] Cell stabilizers include surfactants such as organopolysiloxanes. Silicon surfactants can be present in the foam formulation in amounts from about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flame retardants include halogenated organophosphorous compounds and nonhalogenated compounds. A non-limiting example of a halogenated flame retardant is trichloropropylphosphate (TCPP). For example, triethylphosphate ester (TEP) and DMMP are non-halogenated flame retardants. Depending on the end-use foam application, flame retardants can be present in the foam formulation in amounts from 0 to about 50 pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 to about 20 pphp. In another aspect, the flame retardant is present from 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders such as ethylene glycol and butane diol can also be employed in the present invention. Ethylene glycol, for instance, can also be present in the formulation as a diluent or solvent for the carboxylate salt catalysts of the present invention.POLYURETHANE FOAM FORMULATION AND PROCESS

[0143] One aspect of the present invention provides for a composition comprising the contact product of at least one active hydrogen-containing compound, at least one blowing agent, and at least one amine catalyst composition comprising compounds as defined in Formula 1 or Formula 2.

[0144] Another aspect provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition as defined above in Formula 1 or Formula 2 used in combination with at least one tertiary amine having at least one isocyanate reactive group.

[0145] Another aspect provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition as defined above in Formula 1 or Formula 2 used in combination with at least one tertiary amine having no isocyanate reactive group.

[0146] The composition can further comprise catalyst composition as defined above in Formula 1 or Formula 2 with at least one urethane catalyst having no isocyanate reactive group and at least one urethane catalyst having an isocyanate reactive group. Likewise, the compositions can further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0147] The present invention provides a method for preparing a polyurethane foam as well as a polyisocyanurate / polyurethane (PIR / PUR) foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound, in the presence of at least one blowing agent and an effective amount of catalyst composition as defined above in formula I or formula 2. In accordance with the method of the present invention, PUR as well as PIR / PUR foams can be produced having a density from about 8 Kg / m3to about 250 Kg / m3(about 0.5 lb / ft3to about 15.5 lb / ft3), or from about 24 Kg / m3to about 60 Kg / m3(about 1 .5 lb / ft3to about 3.75 lb / ft3).

[0148] The instant invention can be used in a wide range of methods for making rigid closed-cell foams, rigid open cell foams, flexible foam including flexible slabstock foam and flexible molded foam as well as semi-flexible foam and microcellular foam.Examples of suitable methods comprise pouring, molding, spraying, among other rigid foam production methods. In one aspect the inventive method relates to a method for making a laminated foam. The inventive foam can be laminated to a wide range of substrates including wood, steel, paper and plastic.

[0149] The method for preparing PUR as well as PIR / PUR foams also can provide lower ammoniacal odor polyol premix when compared to other commercially available catalyst systems.

[0150] The catalyst composition as defined above in Formula 1 or Formula 2 should be present in the foam formulation in a catalytically effective amount. In PUR as well as in PIR / PUR foam formulations of the present invention, the catalyst composition is present in amounts from about 0.05 to about 20 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, excluding the weight contribution of the catalyst system diluent. In another aspect, the catalyst composition is present in amounts from about 0.4 to about 10 parts, or from about 0.8 to about 8 parts, by weight per hundred weight parts of the at least one active hydrogen-containing compound. Ifthe at least one active hydrogen-containing compound is an at least one polyol, the catalyst composition is present in amounts from about 0.05 to about 10 parts by weight per hundred weight parts polyol (pphp). In another aspect, the catalyst composition is present in amounts from about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.

[0151] In accordance with one aspect of the method of the present invention, the components of the foam formulation are contacted substantially contemporaneously. For example, at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent and an effective amount of catalyst composition as defined above in formula I or formula 2, are contacted together. Given the number of components involved in PUR and PIR / PUR formulations, there are many different orders of combining the components, and one of skill in the art would realize that varying the order of addition of the components falls within the scope of the present invention. As well, for each of the different orders of combining the aforementioned components of the foam formulation, the foam formulation of the present invention can further comprise at least one urethane catalyst. In addition, the method of producing PIR / PUR foams can further comprise the presence of at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof. In one aspect of the present invention, all of the components, including optional components, are contacted substantially contemporaneously.

[0152] In another aspect of the present invention, a premix of ingredients other than the at least one polyisocyanate are contacted first, followed by the addition of the at least one polyisocyanate. For example, the at least one active hydrogen-containing compound, the at least one blowing agent, the at least one cell stabilizer, and the catalyst composition of the present invention are contacted initially to form a premix. The premix is then contacted with the at least one polyisocyanate to produce PUR or PIR / PUR foams in accordance with the method of the present invention. In a further aspect of the present invention, the same method can be employed, wherein the premix further comprises at least one urethane catalyst. Likewise, the premix can further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0153] One aspect of the present invention provides a method for preparing a polyurethane, polyisocyanurate, polyisocyanurate / polyurethane foam comprising:

[0154] (a) forming a premix comprising: i) at least one polyol; ii) about 1 to about 80 parts by weight per hundred weight parts of the polyol (pphp) blowing agent; iii) about 0.5 to about 10 pphp silicon surfactant; iv) zero to about 60 pphp water; v) zero to about 50 pphp flame retardant; vi) zero to about 10 pphp urethane catalyst; and vii) about 0.05 to about 20 pphp of a catalyst composition as defined above in formula I; and(b) contacting the premix with at least one polyisocyanate at an Isocyanate Index from about 10 to about 800.EXAMPLES

[0155] These Examples are provided to demonstrate certain aspects of the invention and shall not limit the scope of the claims appended hereto.

[0156] EXAMPLE 1 : InventiveSynthesis of N-(2-cyanoethyl)-Morpholine and N-(3-aminopropyl)-Morpholine Morpholine (697 g, 8 mol) and water (140 g) were charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor was sealed and purged with nitrogen for three times. The temperature of the reactor was increased to 50°C and acrylonitrile (553 mL, 446 g, 8.4 mol) was then charged into the reactor from a high pressure syringe pump at a speed sufficient to keep the reactor temperature at 50°C or slightly below (~ 4 hours feeding time) while stirring at about 1000 rpm. Upon completion of addition, the reaction temperature was held at 50°C for 2 hours before the heating was shut down. The reactor was then vented after cooling to room temperature. All volatiles were removed on rotary evaporator under vacuum. N- (2-cyanoethyl)-morpholine was collected with an approximate yield of 99 % yield and 100% purity based on GC analysis.

[0157] Morpholine (697 g, 8 mol) and water (140 g) was charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a highpressure syringe pump connected with stainless steel feeding lines. Then the steel reactor was sealed and purged with nitrogen for three times. The temperature of the reactor was increased to 50°C and acrylonitrile (553 mL, 446 g, 8.4 mol) was then charged into the reactor from a high pressure syringe pump at a speed sufficient to keep the reactor temperature at 50°C or slightly below (~ 4 hours feeding time) while stirring at about 1000 rpm. Upon completion of addition, the reaction temperature was held at 50°C for 2 hours before the heating was shut down. The reactor was then vented after cooling to room temperature. All volatiles were removed on rotary evaporator under vacuum. N- (2-cyanoethyl)-morpholine was collected with an approximate yield of 99 % yield and 100% purity based on GC analysis. N-(3-aminopropyl)-morpholine was subsequently made by placing isopropyl alcohol ( -400 ml) and Raney cobalt (16 g) into a stainless- steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high- pressure syringe pump connected with stainless steel feeding lines. The steel reactor was sealed and purged with N2 for three times followed by H2 for three times while stirring. N-(2-cyanoethyl)-morpholine (-800 g) was charged into the high- pressure syringe pump. The reactor was heated to 100°C and the H2 gas pressure adjusted to 800 psi. N-(2-cyanoethyl)-morpholine was dispensed from the pump into the reactor over - 4 h period. After all N-(2-cyanoethyl)-morpholine was added, the reaction was held at 100°C for 1 hour before the heating was shut down. The reactor was vented after cooling to room temperature. All volatiles were removed on rotary evaporator under reduced pressure. The final product N-(3-aminopropyl)-morpholine was collected (-97% yield).

[0158] EXAMPLE 2 (Inventive)Amination of 2-Ethoxyethanol with N-(3-aminopropyl)-morpholine to Produce N-(2- ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) in a Continuous Fixed Bed Reactor

[0159] A fixed bed tubular reactor, equipped with a quartz preheat bed of about 25 cm, was charged with 27 g of the C^CuO CuO / BaCrO MnsO CrOs / graphite catalyst with an approximate composition of 50-70 % Cr2CuO4, 20-30 % CuO, 1-5 % BaCrC>4, 1-5 % MnsOt, 1-5 % CrOs, and 1-5 % graphite. The catalyst particle size was 18-35 mesh with a tapped density of about 1.5-1.9 g / mL. The reactor was inerted with 200 seem of nitrogen at 75 psia, and the reactor was checked for leaks. The reactor pressure was maintained by means of a backpressure controller, and the gas flow was metered via a mass flow controller. The catalyst was dried at 130°C with 200 seem nitrogen for at least 60 minutes. The catalyst was activated by heating with hydrogen flow over at least 18 h. The starting condition was 200 seem 5% hydrogen / 95% nitrogen at 130°C. The flow of gas remained constant while the temperature and hydrogen concentration were gradually increased until 100% hydrogen at 200°C was reached. The reactor temperature and pressure were adjusted to the desired set points once catalyst activation was complete. The reaction temperature was typically 150-190°C, and the pressure was typically 60-180 psia. The hydrogen flow was adjusted to provide the desired molar ratio of Hydrogen / N-(3-Aminopropyl)-morpholine which usually ranged from about 1 / 1 to 8 / 1. N-(3-Aminopropyl)-morpholine (APM) was fed to the reactor under pressure, via a constant flow syringe pump. 2-Ethoxyethanol (EE) was co-fed to the reactor under pressure, via a constant flow syringe pump at the desired EE / APM molar ratio which usually ranged from about 4 / 1 to 1 / 2. The weight hourly space velocity (WHSV, g of feed / g of catalyst / h) ranged from about 0.1 to 0.8. Effluent from the reactor was analyzed by gas chromatography (GC). After several GC samples, the composition of the mixture was unchanged over time. Recovered product samples showed no sign of a blue-green tint, indicating that copper leaching was not observed to any appreciable extent. Analysis of the effluent by GC and GCMS confirmed the formation of N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine (EEMPA). The main remaining products in the mixture were unconverted raw materials (EE and APM) as well as some bis(3-morpholinopropyl)amine (BMPA). Multiple reaction conditions were evaluated, and the GC results were converted to crude mass% to determine conversion, selectivity, and yield. The most preferred, preferred, and least preferred reaction conditions, conversions, selectivities, and yields are described in Table 1-6. These results indicated that EEMPA can be produced with good selectivity and yield via amination of EE with APM in a continuous fixed bed reactor using different reaction conditions.Table 1. Most preferred APM and EE reaction conditionsTable 2. Most preferred conversions, selectivities, and yields for APM and EE reactionsTable 3. Preferred APM and EE reaction conditionsTable 4. Preferred conversions, selectivities, and yields for APM and EE reactionsTable 5. Least preferred APM and EE reaction conditionsTable 6. Least preferred conversions, selectivities, and yields for APM and EE reactions

[0160] EXAMPLE 3 (Inventive)N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine (EEMPA) Sample Generation via Amination in a Continuous Fixed Bed Reactor

[0161] The reaction was carried out under similar conditions as Example 2 where the reaction temperature was about 170°C and the pressure was about 90 psia. The hydrogen flow was adjusted to provide a Hydrogen / N-(3-Aminopropyl)-morpholine molar ratio that ranged from about 1 / 1 to 4 / 1. N-(3-Aminopropyl)-morpholine (APM) was fed to the reactor under pressure, via a constant flow syringe pump. 2-Ethoxyethanol (EE) was cofed to the reactor under pressure, via a constant flow syringe pump at the desired EE / APM molar ratio that ranged from about 4 / 1 to 2 / 1. The weight hourly space velocity (WHSV, g of feed / g of catalyst I h) ranged from about 0.3 to 0.6. Effluent from the reactor was periodically analyzed by gas chromatography (GC) which was collected in a pressure vessel for a run time of about 8 days. A clear product mixture of about 1700 g was collected which was analyzed via ICP-OES. Leaching of metals from the catalyst into the product was not observed to any appreciable extent. Copper, chromium, barium, and manganese content were each less than 0.1 ppm. The major components of the product mixture were EEMPA (35.3 area%), EE (38.2 area%), APM (19.1 area%), and BMPA (4.5 area%) by GC analysis. The crude yield of EEMPA was about 31%.

[0162] EXAMPLE 4 (Inventive)Amination of 2-Ethoxyethanol with N-(3-aminopropyl)-morpholine to Produce N-(2- ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) in a Continuous Fixed Bed Reactor

[0163] A fixed bed tubular reactor, equipped with a quartz preheat bed of about 39 cm, was charged with 13.5 g of the CuO / AhCh / ZrC^ catalyst with an approximate composition of 30-50 % CuO, 30-50 % AI2O3, and 20-30% ZrC>2. The catalyst particle size was 18-35 mesh with a tapped density of about 0.9-1.0 g / mL. The reactor was inerted with 200 seem of nitrogen at 75 psia, and the reactor was checked for leaks. The reactor pressure was maintained by means of a backpressure controller, and the gas flows were metered via a mass flow controller. The catalyst was dried at 130°C with 200 seem nitrogen for at least 60 minutes. The catalyst was activated with heating and hydrogen over at least 18 h. The starting condition was 200 seem 5% hydrogen / 95% nitrogen at 130°C, and the temperature and hydrogen concentration were gradually increased until the final condition was 200 seem hydrogen at 200°C. The reactor temperature and pressure were adjusted to the desired set points once catalyst activation was complete. The reaction temperature was typically 135-175°C, and the pressure was typically 60-180 psia. The hydrogen flow was adjusted to provide the desired molar ratio of Hydrogen / N-(3-Aminopropyl)-morpholine which usually ranged from about 1 / 1 to 8 / 1. N-(3-Aminopropyl)-morpholine (APM) was fed to the reactor under pressure, via a constant flow syringe pump. 2-Ethoxyethanol (EE) was co-fed to the reactor under pressure, via a constant flow syringe pump at the desired EE / APM molar ratio which usually ranged from about 4 / 1 to 1 / 2. The weight hourly space velocity (WHSV, g of feed / g of catalyst / h) ranged from about 0.3 to 0.7. Effluent from the reactor was analyzed by gas chromatography (GC). After several GC samples, the composition of the mixture was unchanged over time. Recovered product samples showed no sign of a blue-green tint, indicating that copper leaching was not observed to any appreciable extent. Analysis of the effluent by GC and GCMS confirmed the formation of N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine (EEMPA). The main remaining products in the mixture were unconverted raw materials (EE and APM) as well as some bis(3-morpholinopropyl)amine (BMPA). Multiple reaction conditions were evaluated, and the GC results were converted to crude mass% to determine conversion, selectivity, and yield. The most preferred and preferred reaction conditions, conversions, selectivities, and yields are described in Table 7-10. These results indicated that EEMPAcan be produced with good selectivity and yield via amination of EE with APM in a continuous fixed bed reactor using different reaction conditions.Table 7. Most preferred APM and EE reaction conditionsTable 8. Most preferred conversions, selectivities, and yields for APM and EE reactionsTable 9. Preferred APM and EE reaction conditionsTable 10. Most preferred conversions, selectivities, and yields for APM and EE reactions

[0164] EXAMPLE 5 (Inventive, prophetic)Synthesis of 2-Ethoxy-N-(2-morpholinoethyl)ethan-1-amine via Amination in a ContinuousFixed Bed Reactor

[0165] 2-Ethoxy-N-(2-morpholinoethyl)ethan-1 -amine is expected to be generated using similar conditions to Example 4 with N-(2-aminoethyl)-morpholine in lieu of N-(3- Aminopropyl)-morpholine (APM).

[0166] EXAMPLE 6 (Inventive)Synthesis of N-(3-methoxypropyl)-3-morpholinopropan-1 -amine via Amination in aContinuous Fixed Bed Reactor

[0167] N-(3-methoxypropyl)-3-morpholinopropan-1 -amine was generated using similar conditions to Example 4 with 3-methoxy-1 -propanol in lieu of 2-ethoxyethanol.

[0168] EXAMPLE 7 (Inventive, prophetic)Synthesis of 3-Methoxy-N-(2-morpholinoethyl)propan-1-amine via Amination in aContinuous Fixed Bed Reactor

[0169] 3-Methoxy-N-(2-morpholinoethyl)propan-1 -amine is expected to be generated using similar conditions to Example 6 with N-(2-aminoethyl)-morpholine in lieu of N-(3-Aminopropyl)-morpholine (APM).

[0170] EXAMPLE 8 (Inventive)Amination of 2-Ethoxyethylamine with N-(3-hydroxypropyl)-morpholine to Produce N-(2- ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) in a Continuous Fixed Bed Reactor

[0171] A fixed bed tubular reactor, equipped with a quartz preheat bed of about 25 cm, was charged with 27 g of the C^CuO^CuO / BaCrO^MnsO CrCh / graphite catalyst with an approximate composition of 50-70 % Cr2CuO4, 20-30 % CuO, 1-5 % BaCrC>4, 1-5 % MnsOt, 1-5% CrOs, and 1-5% graphite. The catalyst particle size was 18-35 mesh with a density of about 1.5-1.9 g / mL. The reactor was inerted with 200 seem of nitrogen at 75 psia, and the reactor was checked for leaks. The reactor pressure was maintained by means of a backpressure controller, and the gas flows were metered via a mass flow controller. The catalyst was dried at 130°C with 200 seem nitrogen for at least 60 minutes. The catalyst was activated with heating and hydrogen over at least 18 h. The starting condition was 200 seem 5% hydrogen / 95% nitrogen at 130°C, and the temperature and hydrogen concentration were gradually increased until the final condition was 200 seem hydrogen at 200°C. The reactor temperature and pressure were adjusted to the desired set points once catalyst activation was complete. The reaction temperature was typically 150-190°C, and the pressure was typically 60-180 psia. The hydrogen flow was adjusted to provide the desired molar ratio of Hydrogen / 2-Ethoxyethylamine which usually ranged from about 1 / 1 to 8 / 1. 2-Ethoxyethylamine (EEA) was fed to the reactor under pressure, via a constant flow syringe pump. N-(3- Hydroxypropyl)-morpholine (HPM) was co-fed to the reactor under pressure, via a constant flow syringe pump at the desired EEA / HPM molar ratio which usually ranged from about 2 / 1 to 1 / 2. The weight hourly space velocity (WHSV, g of feed / g of catalyst / h) ranged from about 0.15 to 0.4. Effluent from the reactor was analyzed by gas chromatography (GC). After several GC samples, the composition of the mixture was unchanged over time. Recovered product samples showed no sign of a blue-green tint, indicating that copper leaching was not observed to any appreciable extent. Analysis of the effluent by GC and GCMS confirmed the formation of N-(2-ethoxyethyl)-3- morpholinopropan-1-amine (EEMPA). The main remaining products in the mixture were unconverted raw materials (EEA and HPM) as well as some morpholine (MOR) and N-(2-ethoxyethyl)propan-1 -amine (EEPA). Multiple reaction conditions were evaluated, and the GC results were converted to crude mass% to determine conversion, selectivity, and yield. The most preferred, preferred, and least preferred reaction conditions, conversions, selectivities, and yields are described in Table 12-16. These results indicated that EEMPA can be produced with good selectivity and yield via amination of EEA with HPM in a continuous fixed bed reactor using different reaction conditions.Table 11 . Most preferred HPM and EEA reaction conditionsTable 12. Most preferred conversions, selectivities, and yields for HPM and EEA reactionsTable 13. Preferred HPM and EEA reaction conditionsTable 14. Preferred conversions, selectivities, and yields for HPM and EEA reactionsTable 15. Least preferred HPM and EEA reaction conditionsTable 16. Least preferred conversions, selectivities, and yields for HPM and EEA reactions

[0172] EXAMPLE 9 (Inventive, prophetic)Synthesis of N-(3-ethoxypropyl)-3-morpholinopropan-1-amine via Amination in aContinuous Fixed Bed Reactor

[0173] N-(3-ethoxypropyl)-3-morpholinopropan-1 -amine is expected to be generated using similar conditions to Example 8 with 3-ethoxypropylamine in lieu of 2- ethoxyethylamine.

[0174] EXAMPLE 10 (Inventive)Synthesis of 3-ethoxy-N-(2-morpholinoethyl)propan-1 -amine via Amination in aContinuous Fixed Bed Reactor

[0175] A fixed bed tubular reactor, equipped with a quartz preheat bed of about 35 cm, was charged with 10 g of the CuO / AhCh / ZrCh catalyst with an approximate composition of 30-50 % CuO, 30-50 % AI2O3, and 20-30% ZrC>2. The catalyst particle size was 18-35 mesh with a tapped density of about 0.9-1.0 g / mL. The reactor was inerted with 200 seem of nitrogen at 75 psia, and the reactor was checked for leaks. The reactor pressure was maintained by means of a backpressure controller, and the gas flows were metered via a mass flow controller. The catalyst was dried at 130°C with 200 seem nitrogen for at least 60 minutes. The catalyst was activated with heating and hydrogen over at least 18 h. The starting condition was 200 seem 5% hydrogen / 95% nitrogen at 130°C, and the temperature and hydrogen concentration were gradually increased until the final condition was 200 seem hydrogen at 200°C. The reactor temperature and pressure were adjusted to the desired set points once catalyst activation was complete. The reaction temperature was typically 135-175°C, and the pressure was typically 60-180 psia. The hydrogen flow was adjusted to provide the desired molar ratio of Hydrogen / 3- Ethoxypropylamine usually a range of about 1 / 1 to 8 / 1. 3-Ethoxypropylamine (EP) was fed to the reactor under pressure, via a constant flow syringe pump. N-(2-Hydroxyethyl)-Morpholine (HEM) was co-fed to the reactor under pressure, via a constant flow syringe pump at the desired EP / HEM molar ratio usually a range of about 2 / 1 to 1 / 2. The weight hourly space velocity (WHSV, g of feed / g of catalyst / h) varied from about 0.2 to 0.6. Effluent from the reactor was analyzed by gas chromatography (GC). After several GC samples, the composition of the mixture was unchanged over time. Recovered product showed no sign of a blue-green tint, indicating that copper leaching was not observed to any appreciable extent. Analysis of the effluent by GC and GCMS confirmed the formation of 3-ethoxy-N-(2-morpholinoethyl)propan-1-amine. The main remaining products in the mixture were unconverted raw materials (EP and HEM). The preferred reaction conditions, conversions, selectivities, and yields are described in Table 17-18.These results indicated that 3-ethoxy-N-(2-morpholinoethyl)propan-1-amine can be produced with good selectivity and yield via amination of EP with HEM in a continuous fixed bed reactor.Table 17. Preferred HEM and EP reaction conditionsTable 18. Preferred conversions, selectivities, and yields for HEM and EP reactions

Claims

CLAIMS1. A process for the manufacture of diamines comprising the steps of (a) contacting an amine compound with an alcohol compound in the presence of a metal catalyst under hydrogen pressure.

2. The process of claim 1 comprising the steps of (a) contacting an amine compound having the formula C R2A — NHR4with an alcohol compound having the formula HO - R3jn the presence of a metal catalyst under hydrogen pressure, wherein R1and R2are independently aliphatic groups, or R1and R2are cycloaliphatic, or R1and R2together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom of oxygen, and A is an aliphatic group, or a cycloaliphatic ring, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group and R4is a hydrogen atom, a methyl group or R3.

3. The process of claim 2 wherein the amine is selected from the group consisting of N- (3-aminopropyl)-morpholine, N-(2-aminoethyl)-morpholine, and the like.

4. The process of any of the preceding claims wherein the amine is N-(3-aminopropyl)- morpholine.

5. The process of any of the preceding claims wherein the alcohol is selected from the group consisting of 2-ethoxyethyl-1-ol, 2-(n-propoxy)ethyl-1-ol, 2-(isopropoxy)ethyl-1- ol, 2-(n-butoxy)ethyl-1-ol, 2-(iso-butoxy)ethyl-1-ol, 2-(sec-butoxy)ethyl-1-ol, 2-(t- butoxy)ethyl-1-ol, 2-(n-pentoxy)ethyl-1-ol, 2-(n-isopentoxy)ethyl-1-ol, 2-(tert- pentoxy)ethyl-1-ol, 2-(neo-pentoxy)ethyl-1-ol, 2-(n-isopentoxy)ethyl-1-ol, 2-(sec- isopentoxy)ethyl-1-ol, 2-(3-pentoxy)ethyl-1-ol, 2-(n-hexoxy)ethyl-1-ol, 2-(2- hexoxy)ethyl-1-ol, 2-(3-hexoxy)ethyl-1-ol, 2-(iso-hexoxy)ethyl-1-ol, 2-(4-methylpent-1- yloxy)ethyl-1-ol, 2-(4-methylpent-2-yloxy)ethyl-1-ol, 2-(2-methylpent-1-yloxy)ethyl-1- ol, 2-(3,3-dimethylbut-1-yloxy)ethyl-1-ol, 2-(3,3-dimethylbut-2-yloxy)ethyl-1-ol, 2-(2,2-dimethylbut-1-yloxy)ethyl-1-ol, 2-heptoxyethyl-1-ol, 2-octoxyethyl-1-ol, 2-(2- ethylhexyloxy)-1-ol, 3-ethoxypropyl-1-ol, 3-propoxypropyl-1-ol, 3-butoxypropyl-1-ol, 3- pentoxypropyl-1-ol, 3-hexoxypropyl-1-ol, 3-heptoxypropyl-1-ol, 3-octoxypropyl-1-ol, 3- (2-ethylhexyloxy)propyl-1-ol and the like.

6. The process of any of the preceding claims wherein the alcohol is selected from the group consisting of 2-ethoxyethyl-1-ol and 3-ethoxypropyl-1-ol.

7. The process of claim 1 comprising the steps of (a) contacting an amine compound having the formula R5-O-(CH2)n-NH2 with an alcohol compound having the formula HO - R3jn the presence of a metal catalyst under hydrogen pressure, wherein R5is a C1-12 linear or branched alkyl group and n = 2-3, and wherein R3is an aliphatic, cycloaliphatic, cycloalkyl, alkoxyalkyl or tertiary amino alkyl group.

8. The process of claim 7 wherein the amine is selected from the group consisting of 2- methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-butoxyethylamine,2-pentoxyethylamine, 2-(n-hexoxy)ethylamine, 3-methoxypropylamine,3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-pentoxypropylmine, 3-(n-hexoxy)propylamine and the like.

9. The process of any of the preceding claims wherein the alcohol is selected from the group consisting of 4-(2-hydroxyethyl)morpholine, 4-(4-hydroxy-n-butyl)morpholine, N-(3-hydroxypropyl)-morpholine and the like.

10. The process of any of the preceding claims wherein the process involves the reaction of an amine with an alcohol in a continuous mode in a zone containing a metal catalyst such as Cu / ZnO, Cu / ZnO / K, Cu / ZnO / Cs, Cu / ZnO / Rb, Cu / Cr, Cu / Ni, Cu / Ni / Cr which can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or C^Ch or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are in the vapor phase.

11. The process of any of the preceding claims wherein the process involves the reaction of an amine with an alcohol in a continuous mode in a zone containing a metal catalyst such as Cu / ZnO, Cu / ZnO / K, Cu / ZnO / Cs, Cu / ZnO / Rb, Cu / Cr, Cu / Ni, Cu / Ni / Crwhich can be dispersed on a support such as AI2O3 or SiC>2 or TiC>2 or O2O3 or any metal oxide or mixed metal oxide support of the type MxOyat conditions such that the reactants are in the liquid phase under mechanical mixing and under hydrogen pressure.

12. The process of any of the preceding claims wherein the metal catalyst is selected from the group consisting of copper, nickel, chromium, cobalt, manganese, molybdenum, palladium, platinum and rhodium, oxides or carbonates of these metals and their mixtures.

13. The process of claim 2 for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan- 1-amine comprising the steps of (a) contacting N-(3-aminopropyl)-morpholine with 2- ethoxyethyl-1-ol in the presence of CuO / ZnO / AhCh under hydrogen pressure.

14. The process of claim 2 for the manufacture of N-(2-ethoxypropyl)-3- morpholinopropan-1-amine comprising the steps of (a) contacting N-(3-aminopropyl)- morpholine with 3-ethoxypropyl-1-ol in the presence of CuO / ZnO / AhCh under hydrogen pressure.

15. The process of claim 7 for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan- 1-amine comprising the steps of (a) contacting 2-ethoxyethylamine with N-(3- hydroxypropyl)-morpholine in the presence of CuO / ZnO / AhCh under hydrogen pressure.

16. The process of claim 7 for the manufacture of 3-ethoxy-N-(2-morpholinoethyl)propan- 1-amine comprising the steps of (a) contacting 3-ethoxypropylamine with N-(2- hydroxyethyl)-morpholine in the presence of CuO / ZnO / AhCh under hydrogen pressure.

17. The process of any of the preceding claims wherein the process further comprises the addition of at least one promoter selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and terbium.

18. A polyurethane catalyst composition comprising at least one compound selected from the group consisting of N-(2-ethoxyethyl)-3-morpholinopropan-1 -amine, N-(2- ethoxyethyl)-2-morpholinoethan-1-amine, N-(3-ethoxypropyl)-2-morpholinoethan-1- amine, N-(2-(n-propoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(isopropoxy)ethyl)- 3-morpholinopropan-1-amine, N-(2-(n-butoxy)ethyl)-3-morpholinopropan-1 -amine, N- (2-(iso-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(sec-butoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(t-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2- (n-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(n-isopentoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(tert-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(neo-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(sec-isopentoxy)ethyl)- 3-morpholinopropan-1-amine, N-(2-(3-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(2-hexoxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(3-hexoxy)ethyl)-3-morpholinopropan-1-amine, N- (2-(iso-hexoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(4-methylpent-1- yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3- morpholinopropan-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-morpholinopropan-1- amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(3,3- dimethylbut-2-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(2,2-dimethylbut-1- yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-heptoxyethyl)-3-morpholinopropan-1- amine, N-(2-octoxyethyl)-3-morpholinopropan-1-amine, N-(2-ethylhexyloxy)-3- morpholinopropan-1-amine, N-(3-ethoxypropyl)-3-morpholinopropan-1-amine, N-(3- propoxypropyl)-3-morpholinopropan-1-amine, N-(3-butoxypropyl)-3- morpholinopropan-1-amine, N-(3-pentoxypropyl)-3-morpholinopropan-1 -amine, N-(3- hexoxypropyl)-3-morpholinopropan-1 -amine, N-(3-heptoxypropyl)-3- morpholinopropan-1-amine, N-(3-octoxypropyl)-3-morpholinopropan-1-amine, N-(3- (2-ethylhexyloxy)propyl)-3-morpholinopropan-1-amine, and the like.

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