Surface active agent

Abstract

To provide an aqueous surfactant using a lower hydrocarbyl raw material which is more inexpensive and easily available and may be produced from a biological source such as bioethanol or butanol, and not using a higher hydrocarbyl alcohol derivative.SOLUTION: A surfactant comprising a polycarbonate block polyether of formula (I). Z1 - (PC) P - (PE) Q - Z2 (I). Wherein PC represents a carbonate block having repeating units of P, PE represents a polyether block having repeating units of Q, and Z1 is R, R-O, R-C (O) - O - or R-O-C (O) - O -; R is an optionally substituted straight or branched C1-C11 alkyl group; Z2 is H, R, R - (O) C or R - O - (O) C. Here, the value of P does not exceed the value of Q.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to surfactants, catalysts and processes for making them, as well as specific applications. [Background technology]

[0002] Nonionic surfactants are typically produced using mono-all-starters with large hydrophobic blocks. Examples include palm oil alcohol, which provides the hydrophobic block. The use of palm oil leads to the deforestation of other plant species, which in turn leads to the reduction of the natural habitats of many endangered species. As a result, palm oil alcohol (C 12 ~C 20 There is a demand for alternatives to alcohol.

[0003] Surfactants combining polyether and polycarbonate blocks are known in the field of oil extraction. International Publications WO 2010 / 062703 and WO 2015 / 031348 describe polymer compositions and potentially a wide range of such polymers in supercritical CO solutions to aid in oil extraction. Such solutions form a waste emulsion with water, aiding in oil extraction. Neither water solubility nor the use of such water-soluble polymers is demonstrated. The polymer compositions are designed to dissolve in liquid or supercritical CO applications. While WO 2010 / 062703 mentions examples using polyether and polycarbonate blocks, they are not exemplified, and the blocks are not fully characterized or tested. WO 2015 / 031348 describes the following types of polycarbonate blocks: YO-APC-OC x H y where APC is polycarbonate and C x H yis a saturated or unsaturated hydrocarbon. The terminal group Y can be H or some other group such as a polyether chain, although the polyether chain is not exemplified or further specified.

[0004] US Patent No. 2021309801 (A1) discloses degradable ethylene oxide-based copolymers prepared by boron-activated copolymerization of ethylene oxide monomers with carbon dioxide and their use as surfactants. Certain triblock amphiphilic compounds are reported.

[0005] It would be beneficial to replace current aqueous nonionic surfactants that use high hydrocarbyl alcohol derivatives as the hydrophobic moiety and form fossil fuel or plant-derived sources (such as palm oil) with lower hydrocarbyl feedstocks that are cheaper, more readily available, and potentially produced from biological sources such as bioethanol or butanol.

[0006] Surprisingly, the inventors have discovered that by varying the relative structure of the polycarbonate block polyether backbone, lower hydrocarbyl alcohols can be utilized in conjunction with the polycarbonate moieties to form the hydrophobic groups, thereby providing aqueous surfactants without the need for higher hydrocarbyl alcohol derivatives. Summary of the Invention

[0007] According to a first aspect of the present invention, there is provided a surfactant comprising a polycarbonate block polyether of formula I: Z 1 -(PC) P -(PE) Q -Z 2 (I) Here, the PC [ka] represents a carbonate block having repeating units of P of the formula: e1 , R e2 , R e3, and R e4 are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, with the proviso that R e1 , R e2 , R e3 , and R e4 If one of R is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, the remaining R e1 , R e2 , R e3 , and R e4 is conditioned on H; Here, PE is [ka] represents a polyether block having repeating units of Q of the formula: e1’ , R e2’ , R e3’ , and R e4’ are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, with the proviso that R e1 , R e2 , R e3 , and R e4 If one of R is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, the remaining R e1’ , R e2’ , R e3’ , and R e4’ is conditioned on H; Z 1 is R, RO, RC(O)-O or ROC(O)-O; R is an optionally substituted straight or branched chain C1-C 11 is an alkyl group; Z 2 is H, R, R—(O)C, or R—O—(O)C; Here, the value of P does not exceed the value of Q.

[0008] Preferably, Z 1is RC(O)-O or ROC(O)-O. Preferably, Z 1 is a short chain (eg, C2-C5 or C2-C4) carbonate or ester group.

[0009] Preferably, Z 2 is H or methyl, and most preferably Z 2 is H.

[0010] In the present invention, the polycarbonate block acts as a hydrophobic material, and the polyether block acts as a hydrophilic material. As a result, when producing surfactants according to the first aspect of the present invention, the starter molecule does not need to be a large hydrocarbon chain, such as found in palm oil alcohol and other long-chain alcohols. Instead, a short-chain alcohol or other starter can be used to initiate the synthesis of the polycarbonate block using a carbonate catalyst before synthesizing the polyether block using an ether catalyst. Low-alcohol starters are less expensive and more likely to be environmentally sustainable. Alternatively, a unique combination of polyether blocks with the same or greater number of repeating units as the polycarbonate block can be used and solubilized in an aqueous surfactant composition, thereby enabling production via a monohydroxyl-functional polyether that can be used as an initiator for the synthesis of the polycarbonate block using a carbonate catalyst, producing polycarbonate block polyethers via an alternative route without the need for a long- or short-chain alcohol starter. When this method is used for production, it is preferable to end-cap the polycarbonate block, for example, by reaction with an anhydride, to provide stability to basic conditions and prevent decomposition of the polycarbonate block. Surprisingly, it has been found that the use of a properly balanced hydrophobic polycarbonate and hydrophilic polyether block provides an alternative surfactant with much greater design flexibility that does not rely on environmentally harmful fatty alcohols. This allows the production of surfactants with smaller terminal hydrocarbyl groups.

[0011] There is also provided a process for producing a surfactant according to the first aspect of the invention, the method comprising the steps of (i) reacting carbon dioxide with an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound, and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to produce a surfactant according to the first aspect of the invention.

[0012] There is also provided a process for producing a surfactant according to the first aspect of the invention in a multiple reactor system; the system comprising first and second reactors, wherein a first reaction occurs in the first reactor and a second reaction occurs in the second reactor; the first reaction is a reaction of a carbonate catalyst with CO and an epoxide in the presence of a monofunctional starter compound and optionally a solvent, thereby producing a polycarbonate compound, and the second reaction is a semi-batch or continuous reaction of an ether catalyst with the polycarbonate compound and epoxide from the first reaction, thereby producing a surfactant according to the first aspect of the invention.

[0013] The present invention also provides the use of the above surfactants as pesticide adjuvants; for preparing foams, coatings, paints, adhesives and sealants in the building and construction industry; in the automotive industry; in the manufacture of fibers; and for enhanced crude oil recovery. DETAILED DESCRIPTION OF THE INVENTION

[0014] Preferably, the surfactant has a CO2 uptake of greater than 10 wt%, more typically greater than 15 wt%, 20 wt% or 21 wt%. Preferably, the surfactant has a CO2 uptake of 10-40 wt%, typically 15-40 wt%, more typically 20-40 wt%.

[0015] The epoxides in both the polycarbonate and polyether portions are independently selected from ethylene oxide (EO), propylene oxide (PO), butylene oxide, pentylene oxide, hexylene oxide, glycidyl ethers, glycidyl esters, or glycidyl carbonates, or mixtures of two or more thereof. Preferably, in the polycarbonate block, the epoxide is ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide. Preferably, in the polyether block, the epoxide is ethylene oxide or propylene oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0016] It will also be understood that when a mixture of epoxides is used, the epoxides will typically be statistically distributed along the polymer backbone.

[0017] Thus, when a mixture of epoxides is used, the polycarbonate and polyether blocks may be referred to as random or statistical copolymers, respectively.

[0018] R e1 , R e2 , R e3 , R e4 , R e1’ , R e2’ , R e3’ , and R e4’ The identity of R depends on the nature of the epoxide used to prepare the polycarbonate or polyether. e1 ~R e4 or R e1’ ~R e2’ When one of R is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, the remaining three groups are H. Preferably, R e1 , R e2 , R e3 , R e4 , Re1’ , R e2’ , R e3’ , and R e4’ is H.

[0019] If a mixture of epoxides is used, R e1 and / or R e2 (or R e3 and / or R e4 , R e1’ and / or R e2’ and R e3’ and / or R e4’ It will be understood that each occurrence of R ) need not be the same. For example, if a mixture of ethylene oxide and propylene oxide is used in the PC block, then R e1 (or R e3 ) may independently be hydrogen or methyl, and R e2 (or R e4 ) may independently be hydrogen or methyl.

[0020] Those skilled in the art will appreciate that when the epoxide is asymmetric, adjacent epoxide monomer units in the backbone can be linked head-to-tail, head-to-head, or tail-to-tail.

[0021] Preferably, the surfactant has a molecular weight (Mn) in the range of about 300 to 20,000 Da, more preferably in the range of about 400 to 8000 Da, and most preferably about 500 to 6000 Da.

[0022] The polycarbonate blocks of the surfactant preferably have a molecular weight (Mn) in the range of about 200 to 4000 Da, more preferably in the range of about 200 to 2000 Da, most preferably about 200 to 1000 Da, especially about 400 to 800 Da.

[0023] The polyether blocks of the surfactant preferably have a molecular weight (Mn) in the range of about 100 to 20,000 Da, more preferably about 200 to 10,000 Da, and most preferably about 200 to 5000 Da.

[0024] The Mn and therefore PDI of the polymers produced by the process of the present invention can be measured using gel permeation chromatography (GPC). For example, GPC can be performed using an Agilent 1260 Infinity GPC machine with two Agilent PLgel μm Mixed-D columns connected in series. Samples can be measured at room temperature (293 K) in THF at a flow rate of 1 mL / min against narrow polystyrene standards (e.g., polystyrene low EasiVials with an Mn range of 405 to 49,450 g / mol, provided by Agilent Technologies). Optionally, samples can be measured against poly(ethylene glycol) standards, such as polyethylene glycol EasiVials, provided by Agilent Technologies.

[0025] The polycarbonate blocks of the surfactant may have at least 50% carbonate linkages, preferably at least 60% carbonate linkages, preferably at least 70% carbonate linkages, preferably at least 76% carbonate linkages, preferably at least 80% carbonate linkages, more preferably at least 85% carbonate linkages, at least 90% carbonate linkages, or at least 95% carbonate linkages.

[0026] The polycarbonate blocks of the surfactant may comprise ether linkages. The polycarbonate blocks may have less than 50% ether linkages, preferably less than 40% ether linkages, preferably less than 30% ether linkages, preferably less than 24% ether linkages, preferably less than 20% ether linkages, more preferably less than 15% ether linkages, less than 10% ether linkages, less than 5% ether linkages, less than 3% ether linkages, or less than 1% ether linkages.

[0027] For the avoidance of doubt, when the polycarbonate blocks contain ether linkages, the polycarbonate blocks may be [ka] The PC block does not contain only repeat units of P, i.e., only carbonate linkages, but instead contains a mixture of both carbonate linkages as shown and ether linkages as shown for the PE block. P is the sum of the carbonate and ether linkages in the PC block. Each carbonate or ether linkage may be a repeat unit that can be derived from an alkylene oxide moiety, i.e., [ka] Thus, when ether linkages are present, P can be considered as the number of repeats of alkylene oxide-derived moieties in the PC block.

[0028] Optionally, the polycarbonate blocks may be approximately alternating polycarbonate residues. When the epoxide is asymmetric, the polycarbonate may have 0-100% head-to-tail linkages, preferably 40-100% head-to-tail linkages, and more preferably 50-100% head-to-tail linkages. The polycarbonate may have a statistical distribution of head-to-head, tail-to-tail, and head-to-tail linkages in a 1:2:1 order, indicating non-stereoselective ring-opening of the epoxide, or may preferentially form greater than 50%, optionally greater than 60%, greater than 70%, greater than 80%, or greater than 90% head-to-tail linkages.

[0029] Optionally, the polyether blocks contain only ether linkages. Typically, the polyether blocks are at least 90%, typically at least 95%, more typically at least 99%, and most typically 100% epoxide derived.

[0030] Typically, the polyether blocks have less than 40% carbonate linkages, typically less than 30% carbonate linkages, typically less than 20% carbonate linkages, more typically less than 10% carbonate linkages, and most typically less than 5%, 2% or 1% carbonate linkages. The polyether blocks may have 0% carbonate linkages.

[0031] For the avoidance of doubt, when the polyether block contains carbonate linkages, the polyether block has the formula: [ka] The polyether block does not contain only Q repeat units, i.e., only ether linkages, but instead contains a mixture of both ether linkages as shown and carbonate linkages as shown for the PC block. Q is the sum of the ether and carbonate linkages in the PE block. Each ether or carbonate linkage is a repeat unit that can be derived from an alkylene oxide moiety, i.e., [ka] Thus, when carbonate linkages are present in the PE block, Q can be considered as the number of repeating alkylene oxide-derived moieties in the PE block.

[0032] Typically, the polycarbonate blocks are derived from epoxide and CO, more typically, epoxide and CO provide at least 70% of the residues in the block, particularly at least 80% of the residues in the block, even more particularly at least 90% of the residues in the block, and most particularly, in polycarbonate blocks, at least 95% of the residues in the block are epoxide and CO residues. Most typically, the polycarbonate blocks contain ethylene oxide and / or propylene oxide residues, and optionally butylene oxide. At least 30% of the epoxide residues in the polycarbonate blocks can be ethylene oxide or propylene oxide residues, typically at least 50% of the epoxide residues in the polycarbonate blocks are ethylene oxide or propylene oxide residues, more typically at least 75% of the epoxide residues in the polycarbonate blocks are ethylene oxide or propylene oxide residues, and most typically at least 90% of the epoxide residues in the polycarbonate blocks are ethylene oxide or propylene oxide residues.

[0033] Typically, the polycarbonate blocks are derived from CO2, i.e., the carbonate captures residual CO2. Typically, the polycarbonate blocks have 70-100%, more typically 80-100%, and most typically 90-100% carbonate linkages.

[0034] The value of P in Formula I does not exceed the value of Q. Preferably, the ratio of Q to P is 5:1 to 1:1, preferably 2:1 to 1:1. Having P less than or equal to Q improves the solubility of the surfactant in water. Preferably, when the PC block is derived from ethylene oxide, the P:Q ratio is such that the carbonate block accounts for at least about 50% w / w of the composition, preferably at least about 60% w / w. In this case, the weight contribution of PC is most preferably about 50% w / w to about 66-67% w / w of the composition. Preferably, when the PC block is derived from propylene oxide, the P:Q ratio is such that the carbonate block accounts for at least about 25% w / w of the composition, preferably at least about 40% w / w. In this case, the weight contribution of PC is most preferably about 50% w / w to about 70% w / w of the composition. Controlling the w / w carbonate content allows for control of water solubility, renewable carbon content, and amphiphilicity, which in turn relates to surfactant performance. More preferred surfactants according to the present invention are found to contain 50-70 wt. % carbonate blocks, and even more preferred are 55-70 wt. %.

[0035] The value of P is typically 3 to 100, preferably 3 to 50, 3 to 20, or 3 to 15. The value of Q is typically 3 to 200, preferably 3 to 100, 3 to 50, 5 to 20, or 5 to 15. The value of P can be 20 to 100. The value of Q can be 20 to 200.

[0036] Z 1 is R, RO, RC(O)—O— or ROC(O)—O. Preferably, Z 1 is RC(O)-O or ROC(O)-O. Preferably, Z 1 is a short chain (eg, C2-C5 or C2-C4) carbonate or ester group.

[0037] R is C1~C 11 R is a linear or branched C1-C alkyl group. 11 It may be an alkyl group. Preferably, R is a C2 to C11 Preferably, R is a linear alkyl group, preferably a linear C2-C6 or C2-C5 alkyl group, typically a C2-C4 alkyl group. 11 Preferably, R is a C1 to C 11 Preferably, R is derived from a linear C1-C 11 The alcohol is preferably a linear C2-C6 or C2-C5 alcohol, typically a linear C2-C4 alcohol or a linear C2-C4 alcohol. Preferably, the alcohol is a C1-C 11 The alcohol is derived from a renewable feedstock, for example, the alcohol may be bioethanol, etc.

[0038] Z 2 is H, R, R—(O)C or R—O—(O)C, preferably Z 2 is H or methyl, and most preferably Z 2 is H.

[0039] In certain embodiments, R e1 , R e2 , R e3 , and R e4 may be independently selected from H, methyl, or ethyl; R e1’ , R e2’ , R e3’ , and R e4’ may be independently selected from H, methyl, or ethyl; Z 2 can be methyl or H, and the polyether blocks can have less than 2% carbonate linkages.

[0040] According to a second aspect of the present invention, there is also provided a process for producing a surfactant according to the first aspect of the present invention, the process comprising the steps of (i) reacting carbon dioxide with an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound, and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to produce a surfactant according to the first aspect of the present invention.

[0041] Monofunctional starters are C1 to C 11 Alcohol or C1-C 11 Typically, the monofunctional starter is a C1-C carboxylic acid. 11 Alcohols, preferably C2-C 11 Alcohol, typically C 2~6 Alcohol or C 2~4 It's alcohol.

[0042] The epoxide is selected from ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, glycidyl ether, glycidyl ester or glycidyl carbonate, or a mixture of two or more thereof. Typically, the epoxide is selected from ethylene oxide, propylene oxide, or a mixture thereof, preferably ethylene oxide.

[0043] The carbonate catalyst may be heterogeneous or homogeneous.

[0044] The carbonate catalyst may be a monometallic, bimetallic, or polymetallic homogeneous complex, or may be a non-metallic Lewis acid-base pair (e.g., based on a combination of borane and an ammonium salt, as disclosed in WO2016203408, WO2020121262, WO2021005470).

[0045] The carbonate catalyst may include a phenol or phenolate ligand.

[0046] Typically, the carbonate catalyst may be a bimetallic complex containing a phenol or phenolato ligand, where the two metals may be the same or different. The carbonate catalyst may be a catalyst of formula (IV): [ka] During the ceremony: M is M-(L) v is a metal cation represented by the formula: x is an integer of 1 to 4, preferably, x is 1 or 2; [ka] is a polydentate ligand or ligands,

[0047] L is a coordinating ligand, for example, L can be a neutral ligand or an anionic ligand capable of ring-opening an epoxide.

[0048] v is an integer that independently satisfies the valence of each M and / or the preferred coordination geometry of each M, or an integer such that the complex represented by formula (IV) above has an overall neutral charge. For example, each v may independently be 0, 1, 2, or 3, e.g., v may be 1 or 2. When v>1, each L may be different.

[0049] The term multidentate ligand includes bidentate, tridentate, tetradentate and higher dentate ligands. Each multidentate ligand may be a macrocyclic or open-ring ligand.

[0050] Examples of such catalysts include those described in International Publication No. 2010022388 (metalsalens and derivatives, metalloporphyrins, corroles and derivatives, metaltetraazaannulenes and derivatives), International Publication No. 2010028362 (metalsalens and derivatives, metalloporphyrins, corroles and derivatives, metaltetraazaannulenes and derivatives), International Publication No. 2008136591 (metalsalens), International Publication No. 2011105846 (metalsalens), International Publication No. 2014148825 (metalsalens), International Publication No. 2013012895 (metalsalens), European Patent No. 2258745(A1) (metalloporphyrins and derivatives), and Japanese Patent Application Laid-Open No. 2013012895 (metalsalens). No. 08081518A (metalloporphyrins and derivatives), Chinese Patent No. 101412809 (metalsalens and derivatives), WO 2019126221 (metal aminotriphenol complexes), U.S. Pat. No. 9018318 (metal beta-diiminate complexes), U.S. Pat. No. 6133402A (metal beta-diiminate complexes), and U.S. Pat. No. 8278239 (metalsalens and derivatives), the entire contents of which are incorporated herein by reference, particularly insofar as they relate to carbonate catalysts suitable for the reaction of CO with epoxides in the presence of a starter as defined herein and optionally a solvent.

[0051] Preferably, the carbonate catalyst is a bimetallic phenolate catalyst. Suitable bimetallic phenolate complexes are those described in WO 2009 / 130470, WO 2013 / 034750, WO 2016 / 012786, WO 2016 / 012785, WO 2012037282, and WO 2019048878(A1), the entire contents of which are incorporated herein by reference, in particular as far as they relate to carbonate catalysts suitable for the reaction of CO with epoxides in the presence of a starter and, optionally, a solvent as defined herein.

[0052] The ether catalyst can be any catalyst suitable for polymerizing epoxides to form polyethers. Suitable ether catalysts include DMC catalysts, metal alkoxides, boron-based catalysts such as BF or BH, anionic catalysts such as KOH, cationic, acidic or superacid catalysts (e.g., HSbF, CFSOH), PF, activated monomer catalysts, organic catalysts such as imidazole or phosphazene reagents, and metallosalenate catalysts. Preferably, the ether catalyst is a DMC catalyst. Examples of DMC catalysts that can be used in the process of the present invention include those described in U.S. Pat. Nos. 3,427,256, 5,536,883, 6,291,388, 6,486,361, 6,608,231, 7,008,900, 5,482,908, 5,780,584, 5,783,513, 5,158,922, 5,693,584, 7,811,958, 6,835,687, 6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500, 704, U.S. Pat. No. 7,977,501, U.S. Pat. No. 9,315,622, EP-A-1568414, EP-A-1529566, and WO 2015 / 022290, the entire contents of which are incorporated by reference.

[0053] The ratio of carbonate catalyst to ether catalyst can be within the range of about 300:1 to about 1:100, for example, about 120:1 to about 1:75, for example, about 40:1 to about 1:50, for example, about 30:1 to about 1:30, for example, about 20:1 to about 1:1, for example, about 10:1 to about 2:1, for example, about 5:1 to about 1:5. These ratios are by mass.

[0054] The process may be carried out in a one-pot reactor or may be a dual reactor process.

[0055] Thus, according to a third aspect of the present invention, there is also provided a process for producing a surfactant according to the first aspect of the present invention in a multiple reactor system; the system comprising first and second reactors, a first reaction occurring in the first reactor and a second reaction occurring in the second reactor; the first reaction being a reaction of a carbonate catalyst with CO and an epoxide in the presence of a monofunctional starter compound and optionally a solvent, thereby producing a polycarbonate compound, and the second reaction being a semi-batch or continuous reaction of an ether catalyst with the polycarbonate compound and epoxide of the first reaction, thereby producing a surfactant according to the first aspect of the present invention.

[0056] Typically, the reaction mixture from the first step contains less than 5%, preferably less than 2.5%, for example less than 1.0%, less than 0.5%, or less than 0.1% CO2 by weight of the reaction mixture before the second step. Typically, the second step is carried out without the independent addition of CO2, but can also be carried out under CO2 pressure. The polyether blocks produced in the second step can have less than 40% carbonate linkages, preferably less than 30% carbonate linkages, or less than 20% carbonate linkages, more preferably less than 10%, less than 5%, less than 2%, or less than 1% carbonate linkages. Preferably, the polyether blocks produced in the second step are substantially free of carbonate linkages.

[0057] Thus, the second step is typically carried out substantially in the absence of CO2.

[0058] Thus, substantially in the absence of CO means that the second step is carried out in the presence of less than 4 wt. %, preferably less than 2 wt. %, for example less than 1.0 wt. %, less than 0.5 wt. %, or less than 0.1 wt. % CO, based on the weight of all reactants, catalyst, and products in the second step.

[0059] Adding components in separate steps can be useful for increasing catalyst activity and can lead to a more efficient process compared to providing all of the materials at the beginning of the process. The presence of large amounts of some components throughout the process can reduce the efficiency of the catalyst. Reacting this material in a separate step can prevent a reduction in catalyst efficiency and / or optimize catalyst activity. The reaction conditions for each step can be adjusted to optimize the reaction of each catalyst.

[0060] The ether catalyst can be pre-activated before being added in the second step. Such pre-activation can be achieved by mixing one or both catalysts with the epoxide (and optionally other ingredients). Pre-activation of the ether catalyst allows for safe control of the reaction (to prevent uncontrolled growth of unreacted monomer content) and is useful for eliminating unpredictable activation periods.

[0061] Typically, any residual CO from the first step will be removed from the crude reaction product of the first step before the start of the second step so that the second step is carried out without CO, although it will be appreciated that small amounts of CO may be present in the reaction mixture of the second step as unused reagent from the first step. Alternatively, both steps may be carried out under a pressure of CO.

[0062] The reactions of the present invention can be carried out in the presence of a solvent; however, it will be understood that these processes can also be carried out in the absence of a solvent. When a solvent is present, the solvent can be toluene, hexane, t-butyl acetate, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), and the like. The solvent can be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0063] Adding components to separate reactions and reactors can be useful for increasing catalyst activity and can lead to a more efficient process compared to providing all of the materials at the beginning of a single reaction. The presence of large amounts of some components throughout the reaction can reduce the efficiency of the catalyst. Reacting this material in a separate reactor can prevent a reduction in catalyst efficiency and / or optimize catalyst activity. The reaction conditions for each reactor can be adjusted to optimize the reaction of each catalyst.

[0064] Furthermore, by not charging the entire amount of each component at the beginning of the reaction, and by charging the catalyst for the first reaction in a separate reactor from the catalyst for the second reaction, uniform catalysis can be achieved, resulting in a more uniform polymer product, which can lead to polymers with narrower molecular weight distributions, desirable ratios, and distributions along the ether-carbonate linkage, and / or improved stability.

[0065] It may also be useful to react separately with two different catalysts, mixing only certain components in the first reaction and adding the rest in the second reaction, for example, by adding a pre-activated ether catalyst or by adding the reaction mixture to a pre-activated ether catalyst.

[0066] The preferred ether catalyst and carbonate catalyst are the same as those in the second aspect of the present invention.

[0067] The first reaction may be carried out in two or more reactors, with the crude reaction mixture being continuously fed to the second reaction vessel. Preferably, the second reaction is carried out in a continuous mode.

[0068] The product of the first reaction may be stored in a second reactor for later use.

[0069] The two reactors may be arranged in series or nested, and each reactor individually may be a stirred tank reactor, loop reactor, tubular reactor, or other standard reactor design.

[0070] Alternatively, the surfactant of the first aspect can be formed by reacting a monofunctional polyether starter compound with an epoxide and carbon dioxide in the presence of a carbonate catalyst. Thus, according to a further aspect of the present invention, there is provided a method for producing a surfactant according to the first aspect of the present invention, wherein a monohydroxy-functional polyether is reacted (i) with a carbonate catalyst, an epoxide, and CO2, and (ii) with an end-capping group, such as an anhydride, to produce the surfactant of the present invention. Typically, the resulting polycarbonate block is end-capped with any suitable functional group. End-capping of the polycarbonate block stabilizes the surfactant. Typically, the polycarbonate block is end-capped with a suitable anhydride, typically an alkyl anhydride. The monofunctional polyether starter compound may be any suitable monofunctional polyether starter compound, typically a monofunctional PEG compound.

[0071] definition The term "alkyl," as used herein, unless otherwise defined, refers to a saturated, straight- or branched-chain hydrocarbon radical derived by removing one hydrogen atom from an aliphatic moiety. An alkyl group is defined as "C 1-20 The alkyl group may be an alkyl group that is a straight or branched chain having 1 to 20 carbon atoms. Thus, the alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Preferably, the alkyl group is a C 1-15 Alkyl, preferably C 1-12 Alkyl, more preferably C 1-10 Alkyl, even more preferably C 1-8 Alkyl, even more preferably C 1-6 It is an alkyl group.

[0072] Unless otherwise defined herein, ester groups are optionally represented by the formula -OC(O)R 1 -or-C(O)OR 1 -, wherein R1 R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 1 may be unsubstituted aliphatic, alicyclic, or aryl. 1 is methyl, ethyl, propyl, or phenyl. The ester group may terminate in an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. R 1 If is hydrogen, -OC(O)R 1 -or-C(O)OR 1 It will be understood that a group defined by - will be a carboxylic acid group.

[0073] The carbonate group is optionally -OC(O)OR 2 where R 2 R can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 2 may be optionally substituted aliphatic, alicyclic or aryl. 2 is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. 2 is methyl, ethyl, propyl, or phenyl. 2 If is hydrogen, -OC(O)OR 2 It will be understood that a group defined by:

[0074] The carbonate functional group is —OC(O)O— and can be derived from a suitable source. Generally, it is derived from CO.

[0075] The ether group is optionally -OR 3 where R3 R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 3 may be unsubstituted aliphatic, alicyclic, or aryl. 3 is methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl. 3 is methyl, ethyl, propyl, or phenyl.

[0076] As used herein, the term "optionally substituted" means that one or more of the hydrogen atoms in the optionally substituted moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when multiple positions in any given structure may be substituted with multiple substituents selected from a specified group, the substituents may be the same or different at all positions. Combinations of substituents envisioned by the present invention are preferably those that result in the formation of stable compounds. As used herein, the term "stable" refers to compounds that are chemically feasible and can exist long enough at room temperature (i.e., 16-25°C) to allow for detection, isolation, and / or use in chemical synthesis.

[0077] Substituents may be depicted as attached to bonds that cross bonds within a depicted molecule's ring. This convention indicates that one or more of the substituents may be attached to the ring at any available position (usually in place of a hydrogen atom in the structure). If a ring atom has two substitutable positions, then two groups (the same or different) may be present on that atom.

[0078] Preferred optional substituents for use in the present invention include, but are not limited to, halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate, optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl groups (e.g., optionally substituted with halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate, or acetylide).

[0079] Particularly preferred optional substituents for use in the present invention are nitro, C 1-12 Alkoxy (e.g., OMe, OEt, O i Pr, O n Bu, O t Bu), C 6-18 Aryl, C 2-14 Heteroaryl, C 2-14 Heteroalicyclic, C 1-6 Alkyl, C 1-6 haloalkyl, F, Cl, Br, I, and OH, wherein C 1-12 Alkoxy, C 6-18 Aryl, C 2-14 Heteroaryl, C 2-14 Heteroalicyclic, C 1-6 Alkyl groups and C 1-6 Each haloalkyl group may be optionally substituted with any of the substituents defined herein.

[0080] The term "continuous" as used herein can be defined as the mode of addition of materials or can refer to the nature of the reaction process as a whole.

[0081] With regard to the continuous addition method, the relevant materials are added continuously or constantly during the course of the reaction. This can be achieved, for example, by adding a stream of materials at a constant or variable rate. In other words, one or more materials are added essentially nonstop. However, it should be noted that practical considerations, such as the need to temporarily interrupt the nonstop addition of materials to refill or replace the containers into which these materials are added, may necessitate.

[0082] In terms of the overall reaction being continuous, the reaction may be carried out over an extended period of time, such as days, weeks, or months. In such continuous reactions, reaction materials may be continuously replenished (tapped-up) and / or reaction products may be tapped-off. It will be understood that the catalyst may not be consumed during the reaction, but that the amount of catalyst present may be depleted by tapping, and therefore the catalyst may need to be replenished in either case.

[0083] In a continuous reaction, the materials may be added continuously.

[0084] In a continuous reaction, the materials may be added discontinuously (ie, batchwise or semi-batchwise).

[0085] As used herein, the term series refers to when two or more reactors are connected such that the crude reaction mixture can flow from the first reactor to the second reactor.

[0086] The term "nested" as used herein refers to two or more reactors configured so that one is located inside the other. For example, in the present invention, if a second reactor is located inside a first reactor, the conditions of both reactors can affect the other reactor.

[0087] Example General Example 1 - Formation of Carbonate Blocks in Monofunctional Polyethers Catalyst (1) was prepared according to Example 2 of WO 2017 / 037441. Polyethylene glycol monomethyl ether was added to a 100 mL Parr high-pressure reactor. The vessel was dried by heating to 100°C under vacuum for 60 minutes, then cooled and filled with low-pressure CO2. Catalyst (1) was added.

[0088] The epoxide was added to the mixture. The mixture was stirred and pressurized to approximately half the target pressure. The mixture was then heated to the target temperature (70°C) and the pressure (20 bar) was maintained constant.

[0089] At the end of the desired reaction time, the mixture was cooled to below 10° C. and vented through an acid scrubber system.

[0090] The monol was dissolved in dichloromethane containing triethylamine (1.3 equiv.) and alkyl anhydride (1.05 equiv.) and reacted at reflux for 16 hours. The end-capped monol was washed with water and brine, dried over sodium sulfate, and concentrated to dryness in vacuo to give the desired product. The ethylene carbonate by-product was removed using a Kugelrohr or short-path evaporator (SPE). [Table 1] [Table 2]

[0091] The data show that the polycarbonate block polyether surfactants of the present invention are water soluble, and that water solubility can be preferentially enhanced with respect to the wt % carbonate content; preferred ranges for the wt % carbonate content are set forth above.

[0092] General Example 2 Reaction 1 Monoall starter was added to a 100 mL Parr high-pressure reactor system. The vessel was dried by heating to 100° C. under vacuum for 60 minutes, then cooled and filled with low-pressure CO. Catalyst (1) (see Example 1) was added.

[0093] EO was added to the mixture. The mixture was stirred and pressurized to approximately half the target pressure. The mixture was then heated to the target temperature and the pressure was maintained at a constant temperature and target pressure.

[0094] At the end of the desired reaction time, the mixture was cooled to below 10° C. and vented through an acid scrubber system. EO and anhydrous ethyl acetate were added to the cold, stirred mixture, which was then transferred to an intermediate holding vessel.

[0095] Reaction 2: Pre-dried mono-all starter and DMC, composed of zinc hexacyanocobaltate and tert-butyl alcohol (2), were added to a 100 mL Parr high-pressure reactor system. The vessel was held under vacuum for approximately 2 minutes, then filled with low-pressure N2 and then with anhydrous ethyl acetate (15 mL).

[0096] The vessel was then heated to 130° C. with stirring, and the DMC was activated with two portions of approximately 0.3 g of PO. After activation (as evidenced by a pressure drop), the external heater was removed, the reactor was optionally pressurized with CO, and the mixture was then cooled to the target addition temperature.

[0097] Once the target temperature was reached, the mixture from Reaction 1 was added to the activated DMC system over approximately 60-90 minutes. Once addition was complete, the mixture was allowed to "cook-out" for several hours, after which it was cooled, vented, and sampled for analysis by NMR and GPC. [Table 3]

[0098] [Table 4]

[0099] Table 5

Claims

[Claim 1] A surfactant comprising a polycarbonate block polyether of formula I: Z １ -(PC) Ｐ -(PE) Ｑ -Z ２ (I) Here, the PC is 【Chemistry 1】 represents a carbonate block having repeating units of P of the formula: ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, with the proviso that R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ When one of R is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, the remaining R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ is H; Here, PE is 【Chemistry 2】 represents a polyether block having repeating units Q of the formula: ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, with the proviso that R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ When one of R is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group, the remaining R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ is H; Z １ is R, R—O, R—C(O)—O— or R—O—C(O)—O; R is an optionally substituted straight or branched chain C １ ~C １１ is an alkyl group; Z ２ is H, R, R—(O)C or R—O—(O)C; Here, the value of P does not exceed the value of Q.

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