Narrow polydispersity alkoxylation with alternative catalyst

Abstract

Methods for generating alcohol alkoxylates may include a first reaction of a C6 to C18 alcohol with a first alkylene oxide of C3 or more in the presence of a first catalyst to produce a first alkoxylated product; and a second reaction of the first alkoxylated product with a second alkylene oxide of C2 or more in the presence of a second catalyst to produce a second alkoxylated product; wherein the first catalyst is a modified dual metal cyanide or a Lewis acid catalyst, and the second catalyst is a modified dual metal cyanide, a Lewis acid catalyst, or an alkaline metal hydroxide.

Description

[0001] NARROW POLYDISPERSITY ALKOXYLATION WITH ALTERNATIVE CATALYST FIELD Embodiments relate to narrow polydispersity index alcohol alkoxylates, and processes and catalyst compositions for synthesizing the same. BACKGROUND Alcohol alkoxylates are widely used in various industrial applications, including as surfactants, emulsifiers, and detergents. Traditional methods of producing alcohol alkoxylates often involve the use of alkali hydroxide catalyst to achieve the desired block structure on an appropriate initiator / starting alcohol. The efficiency and properties of alkoxylates can be significantly influenced by the structure of the constituent alkoxylate chains, which may be varied in composition to modify solubility, hydrophilic lipophilic balance, and other properties. Alcohol alkoxylates may be generated by multi-step reactions in which blocks are produced using monomers of differing carbon number that are added at successive intervals. However, the varying reactivity of various monomers (e.g., ethylene oxide as opposed to propylene oxide) can generate reaction products having a broad molecular weight distribution (e.g., polydispersity of 1.3 or greater) and other byproducts, which can affect performance of the materials in various applications. Isolation and purification of intermediates and final products can improve performance, but additional processing steps can increase time and material costs, and increase waste generation. Summary In an aspect, embodiments disclosed herein are directed to methods for generating alcohol alkoxylates including a first reaction of a C6 to C18 alcohol with a first alkylene oxide of C3 or more in the presence of a first catalyst to produce a first alkoxylated product; and a second reaction of the first alkoxylated product with a second alkylene oxide of C2 or more in the presence of a second catalyst to produce a second alkoxylated product; wherein the first catalyst is a modified dual metal cyanide or a Lewis acid catalyst, and the second catalyst is a modified dual metal cyanide, a Lewis acid catalyst, or an alkaline metal hydroxide; wherein each modified dual metal cyanide catalyst, if present, independently has the general formula: M1b[M2(CN)r(X1)t]c[M3(X2)6]d∙nM4xA1y∙pM5wA2z∙qM6gA3h wherein M1and M4each represent a metal ion independently selected from Zn2+, Fe2+, Co2+, Ni2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+, and Cr3+; M2and M3each represent a metal ion independently selected from Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+, and Pt2+; M5represents one or more of gallium, hafnium, manganese, titanium and indium; M6represents one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5; X1represents a group other than cyanide that coordinates with the M2ion; X2represents a group other than cyanide that coordinates with the M3ion; A1represents a halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate, an arylenesulfonate, trifluoromethanesulfonate, or a C1-4 carboxylate; A2and A3each represents least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, halide or hydrocarbon anion; b, c and d are each numbers that reflect an electrostatically neutral complex, provided that b and c each are greater than zero; x and y are integers that balance the charges in the metal salt M4xA1y; r is an integer from 4 to 6; t is an integer from 0 to 2; n is a number from 0 and 20; p is a number from 0.001 to 10; q is a number from 0.002 to 10; p+q = 0.025 to 1.5; w and z are numbers that balance the charges in the metal salt M5wA2z, provided that w is from 1 to 4; and g and h are numbers that balance the charges in the metal salt Μ6gΑ3h, provided that w is from 1 to 4; and wherein the M5wA2zpromoter complex includes a mixture of a zinc hexacyanocobaltate catalyst having a particulate M5metal oxide, wherein M5is selected from one or more of gallium, hafnium, manganese, titanium or indium and a particulate M6metal or semi-metal oxide; wherein M6is selected from one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5, wherein the M5metal oxide is present in an amount that provides 0.001 to 10 moles of M5metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst and the M6metal or semi-metal oxide is present in an amount that provides 0.002 to 10 moles of M6metal or semi-metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst, and the mole ratio of M5metal to M6metal or semi-metal is 0.025 to 1.5; and wherein each Lewis acid catalyst, if present, independently the has the general formula: M(R1)1(R2)1(R3)1(R4)0 or 1, where M is boron, aluminum, indium, bismuth or erbium, R1, R2, R3, and R4are each independent, R1includes a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R2includes a second fluoro / chloro or fluoroalkyl-substituted phenyl group, R3includes a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, optional R4is a second functional group or functional polymer group. In another aspect, embodiments disclosed herein are directed to alcohol alkoxylates generated by a first reaction of a C6 to C18 alcohol with a first alkylene oxide of C3 or more in the presence of a first catalyst to produce a first alkoxylated product; and a second reaction of the first alkoxylated product with a second alkylene oxide of C2 or more in the presence of a second catalyst to produce a second alkoxylated product; wherein the first catalyst is a modified dual metal cyanide or a Lewis acid catalyst, and the second catalyst is a modified dual metal cyanide, a Lewis acid catalyst, or an alkaline metal hydroxide; the alcohol alkoxylates having the formula: wherein AO is an alkylene EO is ethylene oxide m is 1 to 20; n is 1 to 20; R is C6 to C18 alkyl, wherein the polydispersity index of the alkoxylate is 1.13 or less, wherein the fraction of terminal OH group on ethylene oxide is more than 90.0 percent by mole, and wherein the composition comprises no more than 0.5 percent by weight of residual alcohol. Detailed Description Embodiments relate to methods and catalyst compositions for generating alcohol alkoxylates having low polydispersity. Alcohol ethoxylates may be generated by methods that include multi-stage alkoxylations that utilize dual metal cyanide (DMC) catalysts and / or Lewis acid catalysts. Alcohol alkoxylates produced by the methods disclosed herein may have a polydispersity index (PDI) of 1.15 or lower. Methods of alkoxylation disclosed herein may include the polyaddition of alkylene oxides (alkoxylation) onto a starter compound (e.g., alcohol, amine, ester) in the presence of one or more catalysts. Methods disclosed herein may also utilize modified DMC catalysts and / or Lewis acid catalysts in various catalyst combinations to control overall molecular weight, alkoxylate unit number and type, which decreases polydispersity and minimizes byproduct formation. In some embodiments, methods may be used to generate alcohol alkoxylates, in which the alkoxylate component may be generated from multiple types of alkylene oxide. Methods disclosed herein may include production of alkoxylates by two or more steps (or stages in which a step may be repeated multiple times before proceeding). Alkoxylation reactions can be carried out in batch or continuous methods, and methods may optionally include steps for isolation and purification of intermediates and final products to improve performance and reduce byproducts. In the first step, a starter compound is reacted under alkoxylation conditions in the presence of a first catalyst and an alkylene oxide of C3 or more (e.g., propylene oxide, butylene oxide, etc.). The alcohol and alkylene oxide are then reacted to generate an alkoxylated product. The number of alkylene repeats generated in the first step may range from 1 to 20, and may be modified by the concentration of monomer, catalyst, and / or reaction time. In the second step, the alkoxylated product of the first step is modified or “capped” with a second alkylene oxide of C2 or more (e.g., ethylene oxide) in the presence of a second catalyst to generate the alcohol alkoxylate product. The number of alkylene repeats generated in the second step may range from 1 to 20, and may be modified by the concentration of monomer, catalyst, and / or reaction time. The catalyst used in the second step may be the same as the catalyst used in the first step, or it may be different. In some embodiments, at least part of the catalyst used in the second step may include residual catalyst from the first step. During alkoxylation one or more catalysts may be used for each alkoxylation step to generate a low PDI alcohol alkoxylate. In a first example, the first catalyst and the second catalyst may be a modified DMC. In another example, the first catalyst is the Lewis acid catalyst and the second catalyst is potassium hydroxide. In another example, the first catalyst is the modified DMC catalyst and the second catalyst is the Lewis acid catalyst. In yet another example, the first catalyst is the Lewis acid catalyst and the second catalyst is the modified DMC catalyst. Reaction conditions may vary with the particular catalyst(s) used, and temperatures may range from 50oC to 200oC, Catalysts employed in alkoxylation reactions of the present disclosure may include one or more modified DMC catalysts. Modified DMC catalysts may be differentiated from traditional DMC catalyst in the use of an additional promoter complex that reduces cycle time of alkoxylation processes and improve reactant selectivity and reduce polydispersity. Modified DMC catalysts disclosed herein may have the general formula: M1b[M2(CN)r(X1)t]c[M3(X2)6]d∙nM4xA1y∙pM5wA2z∙qM6gA3h where M1and M4each represent a metal ion independently selected from Zn2+, Fe2+, Co2+, Ni2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+, and Cr3+; M2and M3each represent a metal ion independently selected from Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+, and Pt2+; M5represents one or more of gallium, hafnium, manganese, titanium and indium; M6represents one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5; X1represents a group other than cyanide that coordinates with the M2ion; X2represents a group other than cyanide that coordinates with the M3ion; A1represents a halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate, an arylenesulfonate, trifluoromethanesulfonate, or a C1 to C4 carboxylate; A2and A3each represents least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, halide or hydrocarbon anion; b, c and d are each numbers that reflect an electrostatically neutral complex, provided that b and c each are greater than zero; x and y are integers that balance the charges in the metal salt M4xA1y; r is an integer from 4 to 6; t is an integer from 0 to 2; n is a number from 0 and 20; p is a number from 0.001 to 10; q is a number from 0.002 to 10; p+q = 0.025 to 1.5; w and z are numbers that balance the charges in the metal salt M5wA2z, provided that w is from 1 to 4; and g and h are numbers that balance the charges in the metal salt Μ6gΑ3h, provided that w is from 1 to 4. In some cases, the promoter complex (i.e., M5wA2z) is a mixture of a zinc hexacyanocobaltate catalyst, a particulate M5metal oxide where M5is selected from one or more of gallium, hafnium, manganese, titanium or indium and a particulate M6metal or semi-metal oxide, where M6is selected from one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5, where the M5metal oxide is present in an amount that provides 0.001 to 10 moles of M5metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst and the M6metal or semi- metal oxide is present in an amount that provides 0.002 to 10 moles of M6metal or semi-metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst, and the mole ratio ofM5metal to M6metal or semi-metal is 0.025 to 1.5. Modified DMC catalysts may be added to an alkoxylation reaction to provide an concentration ranging up to 400 ppm based on the weight of the product, such as in a range of 10 ppm to 200 ppm, 25 ppm to 100 ppm, or 25 ppm to 50 ppm. In some cases, reactions incorporating a modified DMC catalyst may conducted a temperatures up to 200oC, such as in a range from 120oC to 180oC, or 140oC to 160oC. Catalysts employed in alkoxylation reactions of the present disclosure may include one or more Lewis acid catalysts. In some cases, the use of Lewis acid catalysts may include the proportion of primary and secondary hydroxyls and associated performance properties (e.g., solubility) in the resulting alkoxylate product. Lewis acid catalysts disclosed herein may be an arylborane catalyst that has at least one fluoro / chloro or fluoroalkyl-substituted phenyl group. In some cases, the Lewis acid catalyst may have the general formula: M(R1)1(R2)1(R3)1(R4)0 or 1where M is boron, aluminum, indium, bismuth or erbium, R1includes a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R2includes a second fluoro / chloro or fluoroalkyl- substituted phenyl group, R3includes a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, and optional R4is a second functional group or functional polymer group. As used herein, by fluoro / chloro or fluoroalkyl-substituted phenyl group is a fluoro / chloro substituted phenyl group or fluoroalkyl-substituted phenyl group. As used herein, a fluoroalkyl-substituted phenyl group is a phenyl group that includes a least one hydrogen atom replaced with a fluoroalkyl group. As used herein, a fluoro-substituted phenyl group is a phenyl group that includes at least one hydrogen atom replaced with a fluorine atom. As used herein, a chloro-substituted phenyl group is a phenyl group that includes at least one hydrogen atom replaced with a chlorine atom. As used herein, a fluoro / chloro substituted phenyl group is a phenyl group that includes at least one hydrogen atom replaced with a fluorine or chlorine atom, where the phenyl group can include a combination of fluorine and chlorine atom substituents. R1, R2, and R3may each independently contain a fluoro / chloro or fluoroalkyl- substituted phenyl group. The M in the general formula may exist as a metal salt ion or as an integrally bonded part of the formula. With respect to R3and optional R4, the functional group or functional polymer group may be a Lewis base that forms a complex with the Lewis acid catalyst (e.g., a boron based Lewis acid catalyst) and / or a molecule or moiety that contains at least one electron pair that is available to form a dative bond with a Lewis acid. The Lewis base may be a polymeric Lewis base. By functional group or functional polymer group it is meant a molecule that contains at least one of the following: water, an alcohol, an alkoxy (examples include a linear or branched ether and a cyclic ether), a ketone, an ester, an organosiloxane, an amine, a phosphine, an oxime, and substituted analogs thereof. Each of the alcohol, linear or branched ether, cyclic ether, ketone, ester, alkoxy, organosiloxane, and oxime may include from 2-20 carbon atoms, from 2-12 carbon atoms, from 2-8 carbon atoms, and / or from 3-6 carbon atoms. For example, the functional group or functional polymer group may have the formula (OYH)n, whereas O is O oxygen, H is hydrogen, Y is H or an alkyl group, and n is an integer (e.g., an integer from 1 to 100). However, other known functional polymer groups combinable with a Lewis acid catalyst such as a boron based Lewis acid catalyst may be used. Exemplary cyclic ethers include tetrahydrofuran and tetrahydropyran. Lewis acid catalysts may be added to an alkoxylation reaction to provide an concentration ranging up to 500 ppm based on the weight of the product, such as in a range of 10 ppm to 200 ppm, 25 ppm to 100 ppm, or 25 ppm to 50 ppm. In some cases, reactions incorporating a Lewis acid catalyst may conducted a temperatures up to 150oC, such as in a range from 50oC to 120oC, or 40oC to 120oC. Starter compounds may include saturated or unsaturated C6 to C18 alcohols, such as hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 2-ethylhexanol, 2- propylheptanol, 2-butyloctanol, and the like. Catalysts and methods disclosed herein may also be applied to other alkoxylations reactions such as alkoxylation of starter compounds containing active hydrogen (e.g. amines), polyesters, and the like. Alcohol alkoxylates disclosed herein may have the general formula: wherein AO is an alkylene EO is ethylene oxide m is 1 to 20; n is 1 to 20; R is C6 to C18 alkyl, the polydispersity index of the alkoxylates is 1.13 or less, the fraction of terminal OH group on ethylene oxide as percent by mole is more than 90.0 mol%, and the composition includes residual alcohol at a percent by weight (wt%) of 0.5 wt% or less. Alcohol alkoxylates may have a number average molecular weight of 400 Da or more, 450 Da or more, or 500 Da or more, such as in a range of 400 Da to 2,500 Da, or 400 Da to 2,000 Da. Alcohol alkoxylates may have an ethylene oxide content at a percent by weight (wt%) of 40 wt% or more, or 45 wt% or more. Alcohol alkoxylates disclosed herein may be “capped” with ethylene oxide with high efficiency (e.g., >94%). Alcohol alkoxylates can have a narrow range of molecular weights, measured by the ratio of weight average to number average molecular weights (Mw / Mn) using gel permeation chromatography. This ratio, or PDI, can be 1.15 or lower, 1.13 or lower, or 1.1 or lower for some alkoxylates, such as between 0.9 and 1.15, or 1 and 1.13. Alcohol alkoxylates may have a residual alcohol as a percent by weight (wt%) of 5 wt% or less, 2 wt% or less, or 1 wt% or less. While formulation components and properties have been disclosed individually, it is envisioned that component elements may be included, excluded, or combined in any manner or subcombination utilizing any of the above concentration ranges and nested subranges therein. Further, that the recited formulation properties may be similarly achieved through various combinations of the recited components within the recited ranges. Examples The following examples are provided to illustrate the embodiments of the invention, but are not intended to limit the scope thereof. Catalysts used in the examples are shown in Table 1. An overview of the synthesis methodology for each sample generated is shown in Table 2. Table 1: Catalysts used in the examples. Catalyst Description Table 2: Overview of samples generated in the examples. Sample Description h CE4 Monopropylene glycol (MPG) initiated PO-EO block copolymer with 33mol PO and 5 mol EO. Product was made with modified DMC catalyst for both PO nd EO bl k ct In this example, a standard alkoxylation was performed under alkaline conditions in the presence of potassium hydroxide. A 15 L conical reaction vessel, equipped with magnetically coupled stirrerhead and temperature control, was charged with 249.2 g of 2-ethylhexanol and 5.20 g of 45% potassium hydroxide aqueous solution. This solution was stirred and heated up to a temperature of 105 °C. Vacuum was applied to keep the solution at 30 mbar in order to remove the water. Residual water was measured by Karl Fischer titration to be 363 ppm after two hours. The solution was cooled to 100 °C and nitrogen was introduced in the reactor to release vacuum. The alkoxylation reaction was carried out in two steps. In the first step, 554.9 g of 1,2- propylene oxide were fed to the solution in 240 min at 140 °C with stirring. The reaction was then allowed to progress for 3 h at 140°C to digest all the oxide present. In the second step, 757.8g of ethylene oxide were fed in 420 min at 140°C. In both steps, pressure in the reaction vessel was closely monitored and oxide feed constraints were in place to not exceed a pressure of 3.5 bar. After all the oxide was fed, the reaction was allowed to progress for a period of 4h at 140°C to digest all the oxide present. The solution was then cooled to 80°C and 3.7g of acetic acid 70% solution in water were added. The solution was stirred for 1h, and product was then discharged from the reactor. Synthesis of IE1 In this example, a two-stage alkoxylation was performed in the presence of the modified DMC catalyst. A solution containing 310.58g of 2-ethylhexanol and 199.5mg of the modified DMC catalyst was dried in a rotavapor for 3h. The water bath of the rotavapor was set to 105 °C and vacuum was applied at 65mbar until water content was below 100ppm. This solution was transferred to a 15L conical reaction vessel, equipped with magnetically coupled stirrerhead and temperature control. In total, 304.6 g of 2-ethylhexanol and 194.4 mg of modified DMC catalyst were charged to the reactor and heated to 160°C. The alkoxylation reaction was carried out in two steps. In the first step, 680.42g of 1,2- propylene oxide were fed to the solution at 160°C with stirring. The first 55g of PO (approximately progress until pressure returned to the pre activation value. Subsequently, the remaining PO amount was fed to the reactor at 2 g / min feed rate. Reaction continued for 1h at 160°C to digest the remaining oxide present. In the second step, 926.35g of ethylene oxide was fed at feed rate of 2g / min at 160°C. Reaction was continued for 2 h at 160°C to digest the remaining oxide present. In both the two steps, pressure in the reaction vessel of the oxide feed did not exceed 3.5 bar. Following reaction, the product solution was then cooled to 80°C and discharged from the reactor. Synthesis of IE2 The 2-ethylhexanol was heated to 70 °C and degassed with nitrogen. Residual water was measured by Karl Fischer titration equipment to be 220 ppm after six hours. A solution containing 656.6 g of dried 2-ethylhexanol and 326.1 mg of Lewis Acid Catalyst 1 was prepared in a glovebox in an inert atmosphere, and transferred to a 15L conical reaction vessel equipped with a stirrerhead and temperature control. The alkoxylation reaction was carried out in two steps. In the first step, 1462.8 g of 1,2- propylene oxide were fed to the solution at a feed rate of 20 g / min at 80°C while stirring. After all the oxide was fed, the reaction was allowed to progress for a period of 3 h at 80 °C to digest the remaining oxide. Volatiles were then stripped by applying vacuum to 10mBar and raising temperature to 140 °C over a period of 5 hours. Reactor was then cooled down to 80°C and the reaction product (2-EH+5PO) was partially discharged from the reactor.905.7g of this product were kept in the reactor and re-catalyzed with 5.91g of KOH 45% aqueous solution. This solution was stirred at 200rpm and heated to 105°C. Vacuum was applied to keep the solution at 30 mBar to remove the water. Residual water was measured by Karl Fischer titration equipment to be 52 ppm after two hours. The solution was cooled to 100°C and nitrogen was introduced to release vacuum. In the second alkoxylation step, 865.16 g of ethylene oxide were fed at feed rate of 2 g / min at 140 °C. After all the oxide was fed, the reaction proceeded for 3 h at 140 °C to digest the remaining oxide. During alkoxylation, pressure of the oxide feed did not exceed 3.5 bar. The solution was then cooled to 80 °C and 4.18 g of 70% acetic acid were added. The solution was stirred at rate of 350 rpm for 1 h after that product was discharged from the reactor. Synthesis of IE3 A solution containing 1254.08 g of 2-ethylhexanol and 405.50 mg of modified DMC catalyst was dried in a rotavapor for 3 h. The water bath of the rotavapor was set to 105 °C and vacuum was applied at 65 mbar. After this process water was measured to be below 100 ppm. This solution was transferred to a 15 L conical reaction vessel, equipped with magnetically coupled stirrerhead and temperature control. In total 1183.64 g of 2-ethylhexanol and 379.98 mg of modified DMC catalyst were charged to the reactor and heated to 160 °C. The alkoxylation reaction was carried out in two steps. In the first step, 2636.8 g of 1,2- propylene oxide were fed to the reaction at 160 °C while stirring at 320rpm. The first 211 g of PO (~8% of total amount) were fed at 30 g / min rate to activate the catalyst. Reaction was allowed to progress until pressure returned to the pre-activation value. Subsequently, the remaining PO amount was fed to the reactor at 7 g / min feed rate. After all the oxide was fed, the reaction proceeded for 1 h at 160 °C to digest all remaining oxide. The reaction product (2-EH+5PO) was discharged from the reactor and degassed with nitrogen. The product was then transferred to an inert atmosphere. A solution containing 158.31 g of 2-EH+5PO product and 0.38 g of Lewis Acid Catalyst 2 was added. In the second step, 149.62 g of ethylene oxide were fed at feed rate of 3 g / min at 80 °C. After all the oxide was fed, the reaction progressed for 3 h at 80°C to digest all remaining oxide. After the digestion step, volatiles were stripped by vacuum at 10mBar and heating 140 °C over 5 hours. In both the two steps, pressure in the reaction vessel of oxide feed did not exceed 3.5 bar. The solution was then cooled to 80 °C and discharged from the reactor. Synthesis of IE4 The same intermediate product (2-EH+5PO) of IE2 was used.120.7 mg of modified DMC catalyst was added to 622.47 g of the intermediate product. This solution was dried in a rotavapor at 105 °C under 65 mbar. Residual water was measured by Karl Fischer titration to be 57 ppm after 2 h. This solution was transferred to a 15 L conical reaction vessel, equipped with stirrerhead and temperature control. In total, 613.54 g of intermediate 2-EH+5PO and 118.13 mg of modified DMC catalyst were charged to the reactor. The ethoxylation step was carried out by feeding 578.48 g of ethylene oxide at feed rate of 2.3 g / min at 160 °C. After all the oxide was fed, the reaction progressed for 3 h at 160 °C to the remaining oxide. Pressure in the reaction vessel for the oxide feed did not exceed 3.5 bar. The solution was then cooled to 80 °C and discharged from the reactor. Synthesis of CE1 The intermediate product 2-EH+5PO of IE2 was used for this synthesis. The intermediate product (2-EH+5PO) was degassed by nitrogen . The product was then transferred to an inert atmosphere. A solution containing 224.2 g of 2-EH+5PO product and 0.36 g of Lewis acid catalyst 1 was prepared. In the second step, 211.8 g of ethylene oxide were fed at 3 g / min at 80 °C. After all the oxide was fed, the reaction progressed for 3 h at 80 °C to digest the remaining. After digestion, volatiles were stripped by vacuum to 10 mBar and raising the temperature to 140 °C over 5 hours. In both steps, pressure in the reaction vessel of the oxide feed did not exceed 3.5 bar. The solution was then cooled to 80 °C and discharged from the reactor. Synthesis of CE2 The intermediate product (2-EH+5PO) of IE2 was degassed with nitrogen. The product was then transferred to an inert atmosphere and a solution containing 195.2g of 2-EH+5PO product and 1.0g of Lewis Acid Catalyst 2 was prepared. In the second step, 187.2g of ethylene oxide were fed at feed rate of 2.5 g / min at 80 °C. After all the oxide was fed, the reaction proceeded for 3 h at 80 °C to digest the remaining oxide. After the digestion step, volatiles were stripped by vacuum at 10mBar and raising the temperature to 140 °C over 5 hours. In both steps, pressure in the reaction vessel did not exceed an oxide feed of 3.5 bar. The solution was then cooled to 80°C and discharged from the reactor. Synthesis of CE3 The intermediate (2-EH+5PO) was used as from IE3. The intermediate product (2- EH+5PO) was degassed by nitrogen. The product was then transferred to an inert atmosphere. A solution containing 204.52 g of 2-EH+5PO product and 0.20 g of Lewis Acid Catalyst 1 catalyst was prepared and transferred to the reactor. In the second step, 193.10 g of ethylene oxide was fed at feed rate of 2.5 g / min at 80 °C. Catalyst activity was noted and EO feed was stopped after 108.7 g were fed to the reactor. The reaction progressed for 2 h at 80 °C to digest all remaining oxide, with no change in pressure or perceived catalyst activity. After digestion, volatiles were stripped by vacuum at 10 mbar and heating to 140 °C over 5 hours. In both steps, pressure in the reaction vessel for the oxide feed did not exceed 3.5 bar. The solution was then cooled to 80 °C and discharged from the reactor. Synthesis of CE4 In this example, a two-stage alkoxylation was performed on a comparative alcohol monopropoylene glycol, where both stages occur in the presence of the modified DMC catalyst. A 15L conical reaction vessel, equipped with magnetically coupled stirrerhead and temperature control, was charged with 295.3 g of polypropylene glycol having a weight average molecular weight of 431.5 Da and 138.1 mg of modified DMC catalyst. This solution was heated up to a temperature of 105°C with stirring. Vacuum was applied to 30 mbar to remove water. Residual water was measured, by means of Karl Fischer titration equipment, to be 25ppm after two hours at the above-mentioned conditions. The solution was cooled to 100°C and nitrogen was introduced in the reactor to release vacuum. The alkoxylation reaction was carried out in two steps. In the first step, 993.2 g of 1,2- propylene oxide was at 160 °C while stirring. The first 79 g of PO (approximately 8% of total amount) was fed at 30 g / min rate to activate the catalyst. Reaction was then allowed to progress until pressure returned to the pre-activation value. Subsequently, the remaining PO amount was then fed to the reactor at 4 g / min feed rate. After all the oxide was fed, the reaction was allowed to progress for a period of 1 h at 160 °C to digest the remaining oxide present. In the second step, 143.14 g of ethylene oxide was fed at feed rate of 1g / min at 160 °C. After all the oxide was fed, the reaction was allowed to progress for a period of 2 h at 160 °C. In both the two steps, pressure in the reaction vessel was closely monitored and oxide feed constraints were in place to not exceed a pressure of 3.5 bar. The solution was then cooled to 80°C and discharged from the reactor. Synthesis of CE5 In this example, a two-stage alkoxylation was performed on a comparative alcohol monopropoylene glycol under conditions substantially similar to CE4, but using potassium hydroxide as the catalyst in both stages. Synthesis of CE6 In this example, a two-stage alkoxylation was performed substantially as described above with respect to IE1, but using a standard DMC catalyst as the catalyst in both stages. Example 1: Characterization of alcohol ethoxylate samples In this example, prepared samples were analyzed for various physical properties between comparative and inventive samples produced under varied catalytic conditions. Water was measured using ASTM E203. Kinematic viscosities at 40 °C and 100 °C were measured using ASTM D445. Viscosity index was calculated using ASTM D2270. Cloud point of surfactants was measured according to ASTM D2024 under conditions specifid. Hydroxyl number as KOH was measured using ASTM D4274D, and pH was determined according to ASTM E70-90 for a 1% sample solubilized in water. Results are shown in Tables 3 to 4.

[0002] Table 3: Analytical results of comparative and experimental samples Measurement Contro IE1 IE2 IE3 IE4 1 6 8 5 4 2 2 6 6 2 Table 4: Analytical results of comparative and experimental samples 6 29 8 0 4 9 2 3 4 6 The results shown in Tables 3-4 indicate that the innovative experimental samples can be produced with the approximately the same properties of the comparative sample. The deviation in molecular weights is due to batch-to-batch variations and not linked to the use of the catalyst. This variation also leads to slightly differences in viscosities, but overall, there is good agreement between innovative experimental sample and comparative sample. Cloud point values are in line with the comparative sample result. Example 2: Gel permeation chromatography characterization of samples In this example, the molecular weight distribution (MWD) of the samples was determined by GPC. Samples were prepared by solubilizing 130 ± 20 mg of sample in 10 mL tetrahydrofuran, and filtering through a 0.45 µm PTFE filter. Testing conditions are shown in Table 5. Table 5: Instrumental conditions for examples GPC Module Parameters Settings y g y . F). The calculation was based on a broad standard method. The calibration parameters of this standard mixture are: Mw = 2572 and Mn = 1732 g / mol. The calculated molecular weights are only an indication of the real molecular weights because an accurate determination can only be carried out if the GPC system is calibrated with certified standards from the same type as the sample. These standards are not commercially available. Results of GPC testing are shown in Tables 6 and 7. Table 6: GPC results of comparative and inventive samples GPC Control IE1 IE2 IE3 IE4 5 GPC CE1 CE2 CE3 CE6 4 The GPC resul s e o s a e a a e e sa p es e bit narrower PDI than the comparative samples. Example 3: NMR characterization of samples Quantitative 13C NMR spectra are obtained, using a 0.25-0.5g / mL concentration in acetone-d6 (containing 0.025M Cr3+ as relaxation agent), on 500MHz spectrometer equipped with a 10 mm dual channel cryoprobe. Additional spectra, used for signal assignment, are obtained from 0.1g / mL concentration in acetone-d6, using a 400 MHz spectrometer equipped with a 5 mm BBFO probe.

[0003] Table 8: NMR results of comparative and experimental samples NMR Control IE1 IE3 IE4 IE5 0 0 0 . 5 . NMR CE1 CE2 CE3 CE6 0 0 0 . 0 . NMR results show that the end-EO% is higher in the inventive samples than the comparative, samples indicated higher capping efficiency. The combination of end-EO% and PDI results confirms that the use of alternative catalysts allows a more efficient control of the molecular weight buildup and distribution of oxides than KOH. Example 3: Preparation of alkoxylates with diols In this example, modified DMC catalysts are used to generate alkoxylates with a MPG starter compound. As shown in Table 10, modified DMC does not work well with diols compared to KOH. The higher viscosity of CE4 indicates the presence of higher MW species over CE5, and as opposed to the performance of CE1 using an alcohol. Table 10: Analytical results of comparative alkoxylate samples made with diols. Measurement CE4 (modified CE5 (KOH) Example 4: Comparison of Modified DMC catalysis and standard DMC catalyst In this example, alcohol alkoxylate using a modified DMC is compared with a standard DMC. As shown in Table 11, modified DMC activates faster and allows a shorter cycle time. Table 11: Comparison of modified and standard DMC catalyzed samples 6 0 0 While the foregoing is directed to exemplary embodiments, other and further embodiments may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims 1. A method for generating an alcohol alkoxylate, comprising: a first reaction of a C6 to C18 alcohol with a first alkylene oxide of C3 or more in the presence of a first catalyst to produce a first alkoxylated product; and a second reaction of the first alkoxylated product with a second alkylene oxide of C2 or more in the presence of a second catalyst to produce a second alkoxylated product; wherein the first catalyst is a modified dual metal cyanide or a Lewis acid catalyst, and the second catalyst is a modified dual metal cyanide, a Lewis acid catalyst, or an alkaline metal hydroxide; wherein each modified dual metal cyanide catalyst, if present, independently has the general formula: M1b[M2(CN)r(X1)t]c[M3(X2)6]d∙nM4xA1y∙pM5wA2z∙qM6gA3hwherein M1and M4each represent a metal ion independently selected from Zn2+, Fe2+, Co2+, Ni2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+, and Cr3+; M2and M3each represent a metal ion independently selected from Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+, and Pt2+; M5represents one or more of gallium, hafnium, manganese, titanium and indium; M6represents one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5; X1represents a group other than cyanide that coordinates with the M2ion; X2represents a group other than cyanide that coordinates with the M3ion; A1represents a halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate, an arylenesulfonate, trifluoromethanesulfonate, or a C1-4 carboxylate; A2and A3each represents least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, halide or hydrocarbon anion; b, c and d are each numbers that reflect an electrostatically neutral complex, provided that b and c each are greater than zero; x and y are integers that balance the charges in the metal salt M4xA1y; r is an integer from 4 to 6; t is an integer from 0 to 2; n is a number from 0 and 20; p is a number from 0.001 to 10; q is a number from 0.002 to 10; p+q = 0.025 to 1.5; w and z are numbers that balance the charges in the metal salt M5wA2z, providedthat w is from 1 to 4; and g and h are numbers that balance the charges in the metal salt Μ6gΑ3h, provided that w is from 1 to 4; and wherein the M5wA2z promoter complex comprises a mixture of a zinc hexacyanocobaltate catalyst having a particulate M5metal oxide, wherein M5is selected from one or more of gallium, hafnium, manganese, titanium or indium and a particulate M6metal or semi-metal oxide; wherein M6is selected from one or more of aluminum, magnesium, manganese, scandium, molybdenum, cobalt, tungsten, iron, vanadium, tin, titanium, silicon and zinc and is different from M5, wherein the M5metal oxide is present in an amount that provides 0.001 to 10 moles of M5metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst and the M6metal or semi- metal oxide is present in an amount that provides 0.002 to 10 moles of M6metal or semi-metal per mole of cobalt provided by the zinc hexacyanocobaltate catalyst, and the mole ratio of M5metal to M6metal or semi-metal is 0.025 to 1.5; and wherein each Lewis acid catalyst, if present, independently the has the general formula: M(R1)1(R2)1(R3)1(R4)0 or 1, where M is boron, aluminum, indium, bismuth or erbium, R1, R2, R3, and R4are each independent, R1includes a first fluoro / chloro or fluoroalkyl-substituted phenyl group, R2includes a second fluoro / chloro or fluoroalkyl-substituted phenyl group, R3includes a third fluoro / chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, optional R4is a second functional group or functional polymer group.

2. The method of claim 1, wherein the first catalyst and the second catalyst are each the modified dual metal cyanide catalyst.

3. The method of claim 1, wherein the first catalyst is the Lewis acid catalyst and the second catalyst is potassium hydroxide.

4. The method of claim 1, wherein the first catalyst is the modified dual metal cyanide catalyst and the second catalyst is the Lewis acid catalyst.

5. The method of claim 1, wherein the first catalyst is the Lewis acid catalyst and the second catalyst is the modified dual metal cyanide catalyst.

6. The method of any one of claims 1 to 5, wherein the first alkylene oxide is propylene oxide.

7. The method of any one of claims 1 to 6, wherein the second alkylene oxide is ethylene oxide.

8. The method of any one of claims 1, 3, 4, 5, wherein the Lewis acid catalyst(s) comprises M as boron, R4comprises a datively bonded tetrahydrofuran.

9. The method of any one of claims 1, 2, 4, and 5, wherein the modified dual metal cyanide metal catalyst(s) comprises a structure in which M1and M4are zinc and M2is cobalt.

10. An alkoxylate generated by the method of claim 1, the alkoxylate having the formula: wherein AO is anatoms; EO is ethylene oxide m is 1 to 20; n is 1 to 20; R is C6 to C18 alkyl, wherein the polydispersity index of the alkoxylate is 1.13 or less, wherein the fraction of terminal OH group on ethylene oxide is more than 90.0 percent by mole, and wherein the composition comprises no more than 0.5 percent by weight of residual alcohol.

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