surfactants

Abstract

The invention relates to a surfactant comprising a polycarbonate block polyether of formula (I): A-((PC) P -(PE) Q -Z) X (I) During the ceremony: A is derived from a polyfunctional starter compound; PC represents a carbonate block having P repeating units of formula (II): [C12] JPEG2026504673000019.jpg32159In formula: R e1 , R e2 , R e3 , and R e4 are all H; or R e1 , R e2 , R e3 , and R e4 is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; e1 , R e2 , R e3 , and R e4 The remaining three are all H; PE represents a polyether block having Q repeating units of formula (III): [C13] JPEG2026504673000020.jpg36159In formula: R e1’ , R e2’ , R e3’ , and R e4’ are all H; or R e1’ , R e2’ , R e3’ , and R e4’ is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; e1’ , R e2’ , R e3’ , and R e4’ The remaining three are all H; Z is OH, OR, OC(O)-R or OC(O)-OR; each R is independently an optionally substituted (e.g., with a heteroatom) straight or branched chain or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl, or aralkenyl group; each value of P and each value of Q are each independently 1 to 50; and X is 2 or greater.

Description

[Technical Field]

[0001] The present invention relates to surfactants, processes for making same, and certain applications. [Background technology]

[0002] Nonionic surfactants are typically produced from petrochemical feedstocks. Examples include propylene and ethylene oxide, both of which emit significant amounts of CO2 during their production. As a result, more environmentally friendly alternatives to these feedstocks are sought. Epoxide-based nonionic surfactants, especially those containing propylene oxide and those with higher molecular weights, do not readily biodegrade, contrary to global legislation.

[0003] Surfactants incorporating polyether and polycarbonate blocks are known in the field of oil extraction. WO2010 / 062703A1 and WO2015 / 031348A1 describe polymer compositions and potentially a wide range of such polymers in supercritical CO2 solutions to aid in oil extraction. Such solutions form emulsion waste with water to aid in oil extraction. No mention is made of the solubility in water or the use of such water-soluble polymers. The polymer compositions are designed to dissolve in liquid or supercritical CO2 applications.

[0004] WO 2010 / 062703 A1 mentions examples having polyether blocks and polycarbonate blocks, but such are not exemplified, and the blocks have not been fully characterized and tested. In the general structure provided for the polymer composition, L is used as a linker moiety or covalent bond between the hydrophobic moiety and the hydrophilic oligomer (B).

[0005] WO2015 / 031348A1 is YO-APC-OC x H yDescribes a polycarbonate block of the type, where APC is polycarbonate and C x H y is a saturated or unsaturated hydrocarbon. The terminal group Y can be H or some other group, such as a polyether chain, although the latter is not exemplified or further identified.

[0006] EP 0338396 A1 describes a polyether polycarbonate surfactant comprising: a hydrophilic portion containing a polymer selected from the group consisting of polyoxyalkylene polyethers, saccharides, saccharide polyoxyalkylenates, polycarbonates having a carbon dioxide content of about 1 to 15 mole percent, and mixtures thereof; and a hydrophobic portion containing alternating or randomly arranged alkylene and carbonate units to form a poly(alkylene carbonate) having a total carbon dioxide content of about 25 to 50 mole percent and a total molecular weight of 300 to 10,000. The hydrophobic portion is bonded to the hydrophilic portion on both sides of the reactive hydrogen. The surfactant is prepared by polymerizing the hydrophilic portion with the hydrophobic portion in a weight ratio of about 10:90 to 90:10.

[0007] US 2021 / 309801 A1 discloses degradable ethylene oxide-based copolymers prepared via boron-activated copolymerization of ethylene oxide monomers with carbon dioxide and their use as surfactants. Certain triblock amphiphilic compounds are reported.

[0008] WO2022 / 096889A1, WO2020 / 222019A1, WO2020 / 222018A1, WO2021 / 176211A1 and WO2021 / 176212A1 disclose polyol block copolymer compositions and processes for producing the same.

[0009] US 4382014A describes a process for producing a polyether carbonate surface-active material having a hydrocarbon residue at its terminal end, in which an active hydrogen-containing compound has a hydrocarbon residue containing four or more carbon atoms, and a five-membered ring carbonate ester is telomerized in the presence of an ate complex of a metal from Group II, III, or IV of the periodic table having at least two alkoxy groups.

[0010] US 4,488,982 A describes surfactants prepared by reacting a monofunctional initiator with an alkylene carbonate or alkylene oxide and carbon dioxide to form a polyether polycarbonate material.

[0011] US2019 / 0382528A1 describes a method for preparing high molecular weight polyether carbonates by reacting epoxides and carbon dioxide in the presence of a bimetallic complex catalyst and a double metal cyanide (DMC) catalyst.

[0012] Our co-pending application WO2023072843A1 discloses a compound of formula Z 1 -(PC) P -(PE) Q -Z 2 discloses a surfactant comprising a polycarbonate block polyether of the formula (I), which can be prepared by reacting carbon dioxide with an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound, and then reacting the polycarbonate compound with an epoxide and an ether catalyst to produce the polycarbonate block polyether.

[0013] It would be beneficial to replace current entirely petrochemical nonionic surfactants with more sustainable alternatives that incorporate abundant and cheaper captured CO2 moieties and can be produced from a single epoxide supply (which can also be sustainably produced), such as ethylene oxide. Incorporating CO2 into these copolymers provides novel, beneficial properties to the surfactants, including the opportunity to enhance biodegradation. The incorporation of CO2-containing blocks, even at longer chain lengths, can enhance the biodegradability of such surfactants.

[0014] It would also be beneficial to provide amphiphilic surfactants that have a high degree of flexibility with respect to hydrophobicity versus hydrophilicity, and the ultimate ability to target specific end-use applications by providing a range of properties, as well as a higher degree of control over macromolecular symmetry than has been previously achievable. Summary of the Invention

[0015] According to a first aspect of the present invention, there is provided a surfactant comprising a polycarbonate block polyether of formula I: A-((PC) P -(PE) Q -Z) X (I) During the ceremony: A is derived from a polyfunctional starter compound; PC represents a carbonate block having P repeating units of the formula: [ka] During the ceremony: R e1 , R e2 , R e3 , and R e4 are all H; or R e1 , R e2 , R e3 , and R e4 is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; e1 , Re2 , R e3 , and R e4 The remaining three are all H; PE represents a polyether block having Q repeating units of the formula: [ka] During the ceremony: R e1’ , R e2’ , R e3’ , and R e4’ are all H; or R e1’ , R e2’ , R e3’ , and R e4’ is a methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; e1’ , R e2’ , R e3’ , and R e4’ The remaining three are all H; Z is OH, OR, OC(O)-R or OC(O)-OR; each R is independently an optionally substituted (e.g., with a heteroatom) straight or branched chain or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl, or aralkenyl group; each value of P and each value of Q are each independently 1 to 50; and X is 2 or greater.

[0016] Preferably, Z is OH or OMe, most preferably OH.

[0017] Preferably, the value of each P and the value of each Q are each independently 1-15.

[0018] In the present invention, the polycarbonate block acts as a hydrophobizing agent and the polyether block acts as a hydrophilizing agent. The use of a multifunctional starter compound results in multiple (at least two) amphiphilic chains pendant from the root portion of the starter compound.

[0019] It will be clear that if a difunctional starter (e.g., a diol) is selected, then X will be 2. Selection of a trifunctional starter (e.g., a triol) will result in X being 3, and so on.

[0020] Preferably, X is 2.

[0021] 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 and an epoxide in the presence of a carbonate catalyst and a polyfunctional 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.

[0022] 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, a first reaction occurring in the first reactor and a second reaction occurring in the second reactor; the first reaction being a carbonate-catalyzed reaction of CO and an epoxide in the presence of a polyfunctional starter compound, and optionally a solvent, to produce a polycarbonate compound, and the second reaction being an ether-catalyzed semi-batch or continuous reaction of the polycarbonate compound from the first reaction and an epoxide to produce a surfactant according to the first aspect of the invention.

[0023] In PC chains containing multiple Re groups, the individual Re groups may be different in different blocks of the chain. In PE chains containing multiple Re' groups, the individual Re' groups may be different in different blocks of the chain.

[0024] For example, if a mixture of propylene and ethylene oxide is used as the epoxide in the first reaction in the process according to the invention, then in some blocks of the PC chain, each Re is H (ethylene oxide is the reagent that generates such PC blocks), while in other blocks of the PC chain, one of the Re groups is methyl (propylene oxide is the reagent that generates such PC blocks). The same applies mutatis mutandis to the PE chain.

[0025] According to the invention there is also provided the use of said surfactants as adjuvants in pesticides, cosmetics or pharmaceuticals; for the preparation of low foaming detergents / cleaners, institutional cleaning & hygiene products, industrial cleaning products, personal care products, adhesives, metal working fluids, paints & coatings, textiles, water treatment coatings and in food & beverage processing. DETAILED DESCRIPTION OF THE INVENTION

[0026] Preferably, the surfactant has a CO2 incorporation of greater than 5 wt%, greater than 10 wt%, more typically greater than 15 wt%, greater than 20 wt%, or greater than 21 wt%. Preferably, the surfactant has a CO2 incorporation of 5-40 wt%, a CO2 incorporation of 10-40 wt%, a CO2 incorporation of 15-40 wt%, a CO2 incorporation of 20-40 wt%, typically a CO2 incorporation of 10-35 wt%, more typically a CO2 incorporation of 15-30 wt%.

[0027] It will be appreciated that the carbonate block of the copolymer is hydrophobic and the ether block is hydrophilic. Adjusting the relative ratio of the two blocks alters the properties of the copolymer to provide a surfactant suitable for use in water-in-oil and oil-in-water applications.

[0028] In accordance with the present invention, there is provided a surfactant comprising a polycarbonate block polyether of Formula I having a P:Q ratio tailored to provide a surfactant with amphiphilic properties suitable for oil-in-water applications.

[0029] The present invention also provides surfactants comprising polycarbonate block polyethers of Formula I having a P:Q ratio tailored to provide surfactants with amphiphilic properties suitable for water-in-oil applications.

[0030] The epoxides used in producing both the polycarbonate and polyether sections 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 producing the polycarbonate blocks, the epoxide is ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, preferably ethylene oxide or propylene oxide. Preferably, in producing the polyether blocks, the epoxide is ethylene oxide or propylene oxide, or mixtures thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0031] It will also be appreciated that when a mixture of epoxides is used, the epoxides will typically be statistically distributed along the polymer backbone.

[0032] Thus, when a mixture of epoxides is used, the polycarbonate and polyether blocks may be referred to as random or statistical copolymers, respectively.

[0033] R e1 、 R e2 、 R e3 , R e4 、 R e1’ 、 Re2’ 、 R e3’ , and R e4’ The identity of R will depend on the nature of the epoxide used to prepare the polycarbonate or polyether. e1 ~R e4 One of 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 , R e1’ , R e2’ , R e3’ , and R e4’ is H.

[0034] When 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’ ) may not be the same, for example, if a mixture of ethylene oxide and propylene oxide is used in the PC block, R e1 (or R e3 ) may independently be hydrogen or methyl, and R e2 (or R e4 It will also be appreciated that ) may independently be hydrogen or methyl.

[0035] Those skilled in the art will appreciate that when the epoxide is asymmetric, adjacent epoxide monomer units in the backbone may be head-to-tail, head-to-head, or tail-to-tail bonded.

[0036] 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 12000 Da, and most preferably about 1000-8000 Da.

[0037] The polycarbonate blocks of the surfactant preferably have a molecular weight (Mn) in the range of about 200 to 5000 Da, more preferably in the range of about 200 to 4000 Da, most preferably about 300 to 3000 Da, especially about 500 to 2000 Da.

[0038] 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 6000 Da.

[0039] The Mn and, therefore, the PDI of polymers produced by the process of the 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 using a flow rate of 1 mL / min against narrow polystyrene standards (e.g., polystyrene low EasiVials supplied by Agilent™ Technologies, with an Mn range of 405 to 49,450 g / mol). Optionally, samples can be measured against poly(ethylene glycol) standards, such as polyethylene glycol EasiVials supplied by Agilent™ Technologies.

[0040] The polycarbonate blocks of the surfactant can 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.

[0041] The polycarbonate blocks of the surfactant may also contain 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.

[0042] For the avoidance of doubt, when the polycarbonate block contains an ether linkage, the polycarbonate block has the formula [ka] The P repeat units of the PE block, i.e., do not contain only carbonate linkages, but instead will contain a mixture of both the carbonate linkages shown and the ether linkages shown for the PE block. P would then be 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] Therefore, when ether linkages are present, P can be considered as the number of repeating alkylene oxide-derived moieties in the PC block.

[0043] Optionally, the polycarbonate blocks may generally be alternating polycarbonate residues. When the epoxide is asymmetric, the polycarbonate may have 0-100% head-to-tail bonds, preferably 40-100% head-to-tail bonds, and more preferably 50-100%. The polycarbonate may have a statistical distribution of head-to-head, tail-to-tail, and head-to-tail bonds on the order of 1:2:1, indicating non-stereoselective ring opening of the epoxide, or it may preferentially form head-to-tail bonds on the order of more than 50%, optionally more than 60%, more than 70%, more than 80%, or more than 90%.

[0044] Optionally, the polyether blocks contain only ether linkages. Typically, the polyether blocks are at least 90% derived, typically at least 95% derived, more typically at least 99%, and most typically 100% derived from epoxides.

[0045] 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%, less than 2%, or less than 1% carbonate linkages. The polyether blocks can have 0% carbonate linkages. For example, the polyether blocks can have about 0% to about 40% carbonate linkages, about 0% to about 30% carbonate linkages, about 0% to about 20% carbonate linkages, about 0% to about 10% carbonate linkages, about 0% to about 5% carbonate linkages, about 0% to about 2% carbonate linkages, or about 0% to about 1% carbonate linkages.

[0046] For the avoidance of doubt, when the polyether block contains a carbonate linkage, the polyether block has the formula [ka] The PC block may not contain only Q repeat units of the formula (I), i.e., only ether linkages, but instead may contain a mixture of both the ether linkages shown and the carbonate linkages shown for the PC block. Q is then the sum of the ether and carbonate linkages in the PE block in question. Each ether or carbonate linkage may be 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 in question.

[0047] Typically, the polycarbonate blocks are derived from epoxide and CO2. More typically, epoxide and CO2 provide at least 70% of the residues in each block, particularly at least 80% of the residues in each block, and more particularly at least 90% of the residues in each block. Most particularly, in the polycarbonate blocks, at least 95% of the residues in each block are residues of epoxide and CO2. Most typically, the polycarbonate blocks contain ethylene oxide and / or propylene oxide residues, optionally butylene oxide. At least 30% of the epoxide residues in the polycarbonate blocks may 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.

[0048] Typically, the polycarbonate blocks are derived from CO2, i.e., carbonate incorporates CO2 residues. Typically, the polycarbonate blocks have 70-100%, more typically 80-100%, and most typically 90-100% carbonate linkages.

[0049] The values ​​of P and Q in Formula I may be adapted as needed for the end use. For oil-in-water applications, the ratio of Q to P is preferably greater than 1:1. For example, the ratio of Q to P may be 5:1 to 1:1, or 2:1 to 1:1. Having P equal to or less than Q improves the solubility of the surfactant in water.

[0050] The surfactant may be water-soluble.

[0051] The surfactant may have a water solubility of at least about 0.25 g / ml at standard temperature and pressure (STP). Water solubility can be determined by adding the surfactant to water at a particular concentration and then visually observing whether the surfactant dissolves.

[0052] For water-in-oil applications, preferably the ratio of P to Q is greater than 1: 1. Having Q less than or equal to P improves the solubility of the surfactant in oil.

[0053] For most applications, a P:Q ratio of 2:1 or less is desirable.

[0054] The surfactant may be oil soluble.

[0055] The surfactant may have an oil solubility of at least about 0.25 g / ml at standard temperature and pressure (STP). Oil solubility can be determined by adding the surfactant to a selected oil at a particular concentration and then visually observing whether the surfactant dissolves.

[0056] For example, the surfactant may have a solubility of at least about 0.25 g / ml in octanol at STP.

[0057] For oil-in-water applications, when the PC block is derived from or primarily derived from ethylene oxide, the P:Q ratio is preferably such that the carbonate block accounts for up to about 60% w / w of the composition, preferably up to about 50% w / w. We have found that in this case, more preferred surfactants according to the invention for oil-in-water applications contain 20-60 wt% carbonate block. Preferably, when the PC block is derived from or primarily derived from propylene oxide, the P:Q ratio is such that the carbonate block accounts for up to about 70% w / w of the composition, preferably up to about 50% w / w. We have found that in this case, more preferred surfactants according to the invention for oil-in-water applications contain 30-70 wt% carbonate block. Controlling the w / w carbonate content allows for control of water solubility, renewable carbon content, and amphiphilicity, which are related to surfactant performance.

[0058] For water-in-oil applications, when the PC block is derived from or primarily derived from ethylene oxide, the P:Q ratio is preferably such that the carbonate block constitutes at least about 40% w / w, preferably at least about 50% w / w, of the composition. We have found that in this case, more preferred surfactants according to the invention for water-in-oil applications contain 40-80 wt% carbonate blocks. Preferably, when the PC block is derived from or primarily derived from propylene oxide, the P:Q ratio is such that the carbonate block constitutes at least about 30% w / w, preferably at least about 50% w / w, of the composition. We have found that in this case, more preferred surfactants according to the invention for water-in-oil applications contain 40-80 wt% carbonate blocks. Controlling the w / w carbonate content allows for control of water solubility, renewable carbon content, and amphiphilicity, which are related to surfactant performance.

[0059] It will be clear to those skilled in the art that when selecting a P:Q ratio to control chain hydrophobicity, the selected ratio may (or may not) be different, for example, between a PC block derived from ethylene oxide on the one hand and a PC block derived from propylene oxide on the other. A PC block derived from propylene oxide will have a higher molecular weight than a PC block derived from ethylene oxide, and therefore, for a given chain length and w / w% carbonate content, will account for fewer blocks in the chain relative to a PC block derived from ethylene oxide that otherwise has the same chain length and w / w% carbonate content. While this in itself tends to reduce the overall hydrophobicity of the chain, there is a trade-off: the hydrophobicity of each PC block derived from propylene oxide will be somewhat higher than that of each PC block derived from ethylene oxide due to the additional methyl groups. Satisfactory control of the P:Q ratio ideally takes these factors into account.

[0060] The independent values ​​of P and Q are typically 1-50, 1-45, 1-40, 1-35, 1-30, 1-25, 1-20, and preferably 1-15.

[0061] A is derived from a polyfunctional starter compound of the formula: Y(R Y ) a Y has two or more -R attached to it YY can be any group capable of carrying a group. Thus, Y can be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, or heteroarylene, or Y can be a combination of any of these groups, for example, Y can be an alkylarylene, heteroalkylarylene, heteroalkylheteroarylene, or alkylheteroarylene group. Optionally, Y is alkylene, heteroalkylene, arylene, or heteroarylene.

[0062] It will be appreciated that a is an integer and is at least 2. Optionally, a ranges from 2 to 8, or from 2 to 6.

[0063] Each R Y may be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH) or -PR'(O)OH, and optionally R Y is selected from -OH, -NHR', or -C(O)OH, and optionally each R Y is —OH, —C(O)OH, or a combination thereof (e.g., each R Y is -OH).

[0064] R' may be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, and optionally R' is H or an optionally substituted alkyl.

[0065] A is typically derived from a starter compound by removal of two or more hydrogen atoms and subsequent polymerization from the deprotonated derivative.

[0066] According to a second aspect of the invention, there is also provided a process for producing a surfactant according to the first aspect of the invention, the process comprising the steps of (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a polyfunctional 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.

[0067] The epoxide may be selected from ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, glycidyl ethers, glycidyl esters or glycidyl carbonates or mixtures of two or more thereof. Typically, the epoxide is selected from ethylene oxide, propylene oxide or mixtures thereof, preferably ethylene oxide.

[0068] The carbonate catalyst may be heterogeneous or homogeneous.

[0069] The carbonate catalyst may be a monometallic, bimetallic, or multimetallic homogeneous complex, or it may be a non-metallic Lewis acid-base pair (e.g., based on a combination of borane and an ammonium salt, as disclosed in patents WO2016203408, WO2020121262, and WO2021005470). The carbonate catalyst may also be a heterogeneous catalyst, such as a metal-organic framework (MOF), which may be derived from a metal, such as scandium or aluminum, as described, for example, in WO2021123761.

[0070] The carbonate catalyst may include a phenol or phenolate ligand.

[0071] Typically, the carbonate catalyst may be a bimetallic complex containing a phenol or phenolate ligand, where the two metals may be the same or different.

[0072] 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: x is an integer of 1 to 4, preferably 1 or 2; [ka] is a polydentate ligand or multiple polydentate ligands; L is a coordinating ligand, e.g., L can be a neutral ligand or an anionic ligand, which can ring-open the epoxide; v is an integer that independently satisfies the valence of each M and / or the preferred coordination configuration of each M, or 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.

[0073] The term polydentate ligand includes bidentate, tridentate, tetradentate and higher dentate ligands. Each polydentate ligand may be a macrocyclic or open ligand.

[0074] Examples of such catalysts include WO2010022388 (metal salens and derivatives, metal porphyrins, corroles and derivatives, metal tetraazaannulenes and derivatives), WO2010028362 (metal salens and derivatives, metal porphyrins, corroles and derivatives, metal tetraazaannulenes and derivatives), WO2008136591 (metal salens), WO2011105846 (metal salens), WO2014148825 (metal salens), WO2013012895 (metal salens), EP2258745A1 (metal porphyrins and derivatives), and JP2008081518A. (Metalloporphyrins and Derivatives), CN101412809 (Metalsalens and Derivatives), WO2019126221 (Metal Aminotriphenol Complexes), US9018318 (Metal β-Diiminate Complexes), US6133402A (Metal β-Diiminate Complexes) and US8278239 (Metalsalens and Derivatives), the entire contents of which are incorporated herein by reference, inter alia, insofar as they relate to suitable carbonate catalysts for the reaction of CO and epoxides in the presence of a starter and, optionally, a solvent as defined herein.

[0075] Preferably, the carbonate catalyst is a bimetallic phenolate catalyst. Suitable bimetallic phenolate complexes are those described in WO2009 / 130470, WO2013 / 034750, WO2016 / 012786, WO2016 / 012785, WO2012037282 and WO2019048878A1, the entire contents of which are incorporated herein by reference, in particular insofar as they relate to suitable carbonate catalysts for the reaction of CO2 and epoxides in the presence of a starter and, optionally, a solvent as defined herein.

[0076] The ether catalyst may 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 superacidic 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 invention include those described in US 3,427,256, US 5,536,883, US 6,291,388, US 6,486,361, US 6,608,231, US 7,008,900, US 5,482,908, US 5,780,584, US 5,783,513, US 5,158,922, US 5,693,584, US 7,811,958, US 6,835,687 Nos. 6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500704, 7,977,501, 9,315,622, EP-A-1568414, EP-A-1529566, and WO2015 / 022290, the entire contents of which are incorporated by reference.

[0077] The ratio of carbonate catalyst to ether catalyst may be in the range of about 300:1 to about 1:100, such as about 120:1 to about 1:75, such as about 40:1 to about 1:50, such as about 30:1 to about 1:30, such as about 20:1 to about 1:1, such as about 10:1 to about 2:1, such as about 5:1 to about 1:5. These ratios are by weight.

[0078] The process may be carried out in a one-pot reactor or may be a dual reactor process.

[0079] Thus, according to a third aspect of the invention, 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, a first reaction occurring in the first reactor and a second reaction occurring in the second reactor; the first reaction being a carbonate-catalyzed reaction of CO and an epoxide, in the presence of a polyfunctional starter compound, and optionally a solvent, to produce a polycarbonate compound, and the second reaction being an ether-catalyzed semi-batch or continuous reaction of the polycarbonate compound of the first reaction and an epoxide to produce a surfactant according to the first aspect of the invention.

[0080] Typically, the reaction mixture from the first step contains less than 5% by weight of CO, preferably less than 2.5% by weight, e.g., less than 1.0% by weight, less than 0.5% by weight, or less than 0.1% by weight, of the reaction mixture prior to the second step. Typically, the second step is carried out without the sole addition of CO; however, it can be carried out under CO 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.

[0081] Typically, therefore, the second step is carried out substantially in the absence of CO2.

[0082] Thus, by substantially CO2-free, it is meant that the second step is carried out in the presence of less than 4 wt% CO2, preferably less than 2 wt%, for example less than 1.0 wt%, less than 0.5 wt% or less than 0.1 wt% of the total reactants, catalyst, and products in the second step.

[0083] Adding components in separate steps can be useful to increase the activity of the catalyst and can lead to a more efficient process compared to a process in which all materials are provided at the beginning of the process. Large amounts of some of the components present throughout the process can reduce the efficiency of the catalyst. Reacting the materials in separate steps can prevent this reduction in catalyst efficiency and / or optimize catalyst activity. The reaction conditions for each step can be adjusted to optimize the reaction for each catalyst.

[0084] The ether catalyst can be preactivated before addition in the second step. Such preactivation can be achieved by mixing one or both catalysts with the epoxide (and, optionally, other components). Preactivation of the ether catalyst is useful because it allows for safe control of the reaction (preventing uncontrolled growth of unreacted monomer content) and eliminates unexpected activation periods.

[0085] Typically, any residual CO from the first step can 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 in the second step as unused reagent from the first step. Alternatively, either step may be carried out under a pressure of CO.

[0086] The reaction of the present invention may be carried out in the presence of a solvent; however, it will be recognized that the process may also be carried out without a solvent. When a solvent is present, it may 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 may be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0087] Adding components in separate reactions and reactors can be useful for increasing the activity of the catalyst and can lead to a more efficient process compared to a process in which all materials are provided at the beginning of one reaction. Large amounts of some of the components present throughout the reaction can reduce the efficiency of the catalyst. Reacting the materials in separate reactors can prevent this reduction in catalyst efficiency and / or optimize catalyst activity. The reaction conditions in each reactor can be adjusted to optimize the reaction for each catalyst.

[0088] Additionally, having the catalyst for the first reaction in a separate reactor from the catalyst for the second reaction, rather than loading the total amount of each component at the beginning of the reaction, can lead to uniform catalysis and a more uniform polymer product, which in turn can lead to polymers with narrower molecular weight distributions, desirable ratios and distributions of ether to carbonate linkages along the chain, and / or improved stability.

[0089] It may also be useful to separate the reactions using two different catalysts and combine only certain components in the first reaction and add 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.

[0090] The preferred ether catalysts and carbonate catalysts are the same as those in the second aspect of the invention.

[0091] The first reaction may be carried out in more than one reactor, with the crude reaction mixture being fed to the second reaction and reactors in succession. Preferably, the second reaction is carried out in a continuous mode.

[0092] The product of the first reaction may be stored for subsequent use in a second reactor.

[0093] The two reactors may be arranged in series or the reactors may be nested. Each reactor individually may be a stirred tank reactor, a loop reactor, a tube reactor, or other standard reactor design.

[0094] definition The term "alkyl," as used herein, unless otherwise specified, refers to a saturated, straight- or branched-chain hydrocarbon radical derived by the removal of a single hydrogen atom from an aliphatic moiety. An alkyl group is defined as "C 1-20 The alkyl group may be an "alkyl group," which is a straight or branched chain alkyl group 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 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.

[0095] Unless otherwise specified herein, the ester group is optionally —OC(O)R 1 -or-C(O)OR 1 - and R 1 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 be terminated by 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 appreciated that the group defined by - is a carboxylic acid group.

[0096] The carbonate group is optional -OC(O)OR 2and 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 appreciated that the group defined by is a carbonate group.

[0097] The carbonate functional group is —OC(O)O— and can be derived from any suitable source. Generally, it is derived from CO2.

[0098] The ether group is optional -OR 3 and R 3 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.

[0099] 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 specified, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at all positions. Combinations of substituents envisioned by this invention preferably are those that result in the formation of stable compounds. The term "stable," as used herein, refers to compounds that are chemically viable and can exist at room temperature, i.e., (16-25°C), long enough to allow for their detection, isolation, and / or use in chemical synthesis.

[0100] Substituents may be drawn as attached to bonds that cross bonds within a depicted molecule's ring. This convention indicates that one or more substituents may be attached to the ring at any available position (usually in place of a hydrogen atom in the structure). When a ring atom has two substitutable positions, two groups (the same or different) may be present on that atom.

[0101] 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, or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group (e.g., optionally substituted with halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate, or acetylide).

[0102] 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; 1-12 Alkoxy, C 6-18 Aryl, C 2-14 Heteroaryl, C 2-14 Heteroalicyclic, C 1-6 Alkyl and C 1-6 Each haloalkyl group may be optionally substituted with the optional substituents defined herein.

[0103] 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.

[0104] In terms of continuous addition mode, the relevant materials are added continuously or constantly throughout the course of the reaction. This can be achieved, for example, by adding a stream of material using either a constant flow rate or a variable flow rate. In other words, one or more materials are added in an essentially nonstop manner. However, it should be noted that the nonstop addition of materials may need to be temporarily interrupted due to practical considerations, such as to refill or replace the containers from which the materials are being added.

[0105] In view of the overall reaction being continuous, the reaction may be carried out over an extended period of time, e.g., many days, weeks, months, etc. In such continuous reactions, the reaction materials may be continuously replenished and / or the reaction products may be removed. It will be appreciated that while the catalyst may not be consumed during the reaction, the catalyst may need to be replenished in either case, as removal may deplete the amount of catalyst present.

[0106] A continuous reaction can employ continuous addition of materials.

[0107] A continuous reaction can employ discontinuous (ie, batch or semi-batch) addition of materials.

[0108] 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.

[0109] The term "nested" as used herein refers to when two or more reactors are configured such that one is positioned within the other. For example, in the present invention, when a second reactor is positioned inside a first reactor, conditions in both reactors affect the other.

[0110] Example Compounds according to the invention were prepared by the following sequential reaction scheme: [ka] The examples provided in Example 1 relate to low molecular weight end products, while the examples provided in Example 2 relate to high molecular weight end products.

[0111] Example 1 Reaction 1 The diol starter was added to the cold, dry base of a 100 mL Parr™ high-pressure reactor system. The added vessel was dried by heating under vacuum (approximately 1 mbar) to 100° C. and held for 60 minutes, then cooled and backfilled with low-pressure CO.

[0112] Catalyst (1) (prepared according to Example 2 of WO2017 / 037441) was added to the reactor, which was vacuum purged at room temperature for <5 minutes and then back-filled with low-pressure CO.

[0113] EO was added to the mixture, the mixture was stirred and pressurized to approximately half the target pressure, and the mixture was then heated to the target temperature and pressure and maintained at a constant temperature and target pressure using a mass flow controller.

[0114] At the end of the desired reaction time, the mixture was cooled to <10° C. and drained through an acid scrubber system. EO and anhydrous ethyl acetate were added to the cold, stirred mixture, which was then transferred into an intermediate holding vessel.

[0115] Reaction 2 Pre-dried mono-all starter and DMC composed of zinc hexacyanocobaltate and tert-butyl alcohol were added to the cold base of a 100 mL Parr™ high-pressure reactor system. The starter was held under vacuum (approximately 1 mbar) for approximately 2 minutes, after which it was charged via syringe with low-pressure N2, followed by anhydrous ethyl acetate (15 mL).

[0116] This DMC / starter / ethyl acetate mixture was then heated with stirring to 130°C and the DMC was activated with two slugs of approximately 0.3g PO (1 mL / min setpoint). After activation (as evidenced by a pressure drop), the external heater was removed, the reactor could be optionally pressurized with CO, and the mixture was then cooled to the target addition temperature while PO was continuously and gradually added (set at 0.1 mL / min) [approximately 1.2g PO total].

[0117] 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, drained, and sampled for analysis by NMR and GPC.

[0118] The results are shown in Tables 1 to 3 below. [Table 1] [Table 2] [Table 3]

[0119] Example 2 Reaction 1 The diol starter is added to the cold, dry base of a 600 mL Parr™ high-pressure reactor system. The added vessel is dried by heating under vacuum (approximately 1 mbar) to 100° C. and held for 60 minutes, then cooled and filled with low-pressure CO.

[0120] Catalyst (1) (prepared according to Example 2 of WO2017 / 037441) is added to the reactor, which is vacuum purged at room temperature for <5 minutes and then back-filled with low-pressure CO.

[0121] The mixture is stirred and pressurized to approximately half the target pressure. The mixture is then heated to the target temperature and pressure and maintained at a constant temperature and target pressure using a mass flow controller. An epoxide (either ethylene oxide [EO] or propylene oxide [PO]) is added to the mixture in either a batch or semi-batch manner.

[0122] At the end of the desired reaction time, the mixture is cooled to <10° C. and discharged through an acid scrubber system.

[0123] Reaction 2 Pre-dried mono-all starter and DMC composed of zinc hexacyanocobaltate and t-butyl alcohol are added to the cold base of a 600 mL Parr™ high-pressure reactor system. The starter + base is kept under vacuum (approximately 1 mbar) for approximately 2 minutes, after which low-pressure N2 is charged, followed by anhydrous ethyl acetate (15 mL) via an HPLC pump.

[0124] This DMC / starter / ethyl acetate mixture is then heated with stirring to 130°C and the DMC is activated with two slugs of approximately 0.3g EO (1 mL / min set point). After activation (as evidenced by a pressure drop), the external heater is removed, the reactor can optionally be pressurized with CO, and the mixture is then cooled to the target addition temperature.

[0125] Once the target temperature is reached, the product from Reaction 1 and EO are added (semi-batch mode) onto the activated DMC system over approximately 60-90 minutes. Once addition of the mixture is complete, the mixture is allowed to "cook out" for several hours, after which it is cooled, discharged, and sampled for analysis by NMR and GPC.

[0126] The results are shown in Tables 4 to 6 below. [Table 4] [Table 5] [Table 6]

[0127] The data presented in the examples demonstrate that the process of the invention can be used to prepare a range of end products with different p:q ratios and both low and high molecular weights depending on the conditions and reagents selected, thus allowing for convenient adaptive tailoring of the manufacturing process with due consideration of the intended application.

Claims

1. 1. A surfactant comprising a polycarbonate block polyether of Formula I: _(()) Ｐ (!) Ｑ ) Ｘ () During the ceremony: A is derived from a polyfunctional starter compound; PC represents a carbonate block having P repeating units of the formula: 【Chemistry 10】 During the ceremony: R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ are all H; or R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ is methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ The remaining three are all H; PE represents a polyether block having Q repeating units of the formula: 【Chemistry 11】 During the ceremony: R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ are all H; or R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ is methyl, ethyl, propyl, butyl, or an ether, ester, or carbonate group; ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ The remaining three are all H; Z is OH, O—R, O—C(O)—R or O—C(O)—O—R; each R is independently an optionally substituted (e.g., with a heteroatom) straight or branched chain or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl, or aralkenyl group; each value of P and each value of Q is independently from 1 to 50; and X is 2 or more.

2. 2. The surfactant of claim 1, wherein Z is OH or O-R, and R is methyl.

3. 3. The surfactant of claim 2, wherein the value of each P and the value of each Q is independently 1 to 45, 1 to 40, 1 to 35, 1 to 30, 1 to 25, 1 to 20, or 1 to 15.

4. R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ is independently selected from methyl or ethyl, and R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ The remaining three are each H, or R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ The surfactant of any one of claims 1 to 3, wherein each of is H.

5. R ｅ１’ , R ｅ２’ , R ｅ３’ and R ｅ４’ is independently selected from methyl or ethyl, and R ｅ１’ , R ｅ２’ , R ｅ３’ and R ｅ４’ The remaining three are each H, or R ｅ１’ , R ｅ２’ , R ｅ３’ and R ｅ４’ The surfactant of any one of claims 1 to 4, wherein each of

6. The total surfactant contains more than 5 wt% CO ２ Incorporation, optionally more than 10 wt% CO ２ Incorporating, optionally more than 15 wt% CO ２ Incorporating, optionally more than 20 wt% CO ２ Incorporating, optionally more than 21 wt% CO ２ 10. A surfactant according to any preceding claim, comprising:

7. The total surfactant is 5 to 40 wt % CO ２ Incorporating, optionally 10-40 wt% CO ２ Incorporating, optionally 15-40 wt% CO ２ Incorporating, optionally 20-40 wt% CO ２ Incorporating, optionally 10-35 wt% CO ２ Incorporating, optionally 15-30 wt% CO ２ 10. A surfactant according to any preceding claim, comprising:

8. 10. A surfactant according to any preceding claim, having a P:Q ratio adapted to provide said surfactant with amphiphilic properties suitable for oil-in-water applications.

9. 9. The surfactant of claim 8, wherein the ratio of Q to P is greater than 1:

1.

10. 10. A surfactant according to claim 8 or claim 9, wherein the ratio of Q to P is from 5:1 to 1:1, optionally from 2:1 to 1:

1.

11. The surfactant according to any one of claims 8 to 10, which is water-soluble.

12. 12. The surfactant of claim 11, having a water solubility of at least about 0.25 g / ml at STP.

13. 13. A surfactant according to any one of claims 8 to 12, wherein the PC blocks are derived from or predominantly derived from ethylene oxide and the P:Q ratio is such that the carbonate blocks comprise up to about 60% w / w of the composition, optionally up to about 50% w / w.

14. 14. The surfactant of claim 13, comprising 20-60 wt% carbonate blocks.

15. 14. A surfactant according to any one of claims 8 to 13, wherein the PC blocks are derived from or predominantly derived from propylene oxide and the P:Q ratio is such that the carbonate blocks comprise up to about 70% w / w of the composition, optionally up to about 50% w / w.

16. 16. The surfactant of claim 15, comprising 30-70 wt% carbonate blocks.

17. 8. A surfactant according to any one of claims 1 to 7, having a P:Q ratio adapted to provide said surfactant with amphiphilic properties suitable for water-in-oil applications.

18. 18. The surfactant of claim 17, wherein the ratio of P to Q is greater than 1:

1.

19. 19. The surfactant of claim 17 or claim 18, which is oil-soluble.

20. 20. The surfactant of claim 19 having an oil solubility of at least about 0.25 g / ml at STP.

21. 21. The surfactant of claim 19 or 20, having a solubility in octanol at STP of at least about 0.25 g / ml.

22. 22. A surfactant according to any one of claims 17 to 21, wherein the PC blocks are derived from or predominantly derived from ethylene oxide and the P:Q ratio is such that the carbonate blocks represent at least about 40% w / w, optionally at least about 50% w / w of the composition.

23. 22. A surfactant according to any one of claims 17 to 21, wherein the PC blocks are derived from or predominantly derived from propylene oxide and the P:Q ratio is such that the carbonate blocks represent at least about 30% w / w, optionally at least about 50% w / w of the composition.

24. 24. A surfactant according to claim 22 or claim 23, comprising 40-80 wt% carbonate blocks.

25. 10. A surfactant according to any preceding claim, wherein the P:Q ratio is 2:1 or less.

26. 10. The surfactant of any preceding claim, wherein the polyether blocks have less than 40% carbonate linkages, optionally less than 30%, less than 20%, less than 10%, less than 5%, less than 2% or less than 1% carbonate linkages.

27. 27. The surfactant of claim 26, wherein the polyether blocks have 0% carbonate linkages.

28. A method for producing a surfactant according to any one of claims 1 to 27, comprising the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a polyfunctional starter compound to form a polycarbonate compound; and (ii) reacting the polycarbonate compound of step (i) with an epoxide and ether catalyst to produce the surfactant of any one of claims 1 to 27. A method comprising:

29. 28. A method for producing a surfactant according to any one of claims 1 to 27 in a multiple reactor system; the system comprising a first and a second reactor, a first reaction occurring in the first reactor and a second reaction occurring in the second reactor; the first reaction occurring in a carbonate-catalyzed CO ２ and an epoxide in the presence of a polyfunctional starter compound, and optionally a solvent, to produce a polycarbonate compound, and the second reaction is an ether-catalyzed semi-batch or continuous reaction of the polycarbonate compound of the first reaction and an epoxide to produce the surfactant of any of claims 1 to 27.

30. 30. The method of claim 28 or claim 29, wherein the carbonate catalyst is a bimetallic phenolate complex.

31. 31. The method of any one of claims 28 to 30, wherein the ether catalyst is a DMC catalyst.

32. 28. Use of a surfactant according to any one of claims 1 to 27 as an adjuvant in pesticides, cosmetics or pharmaceuticals; for the preparation of low foaming detergents / cleaners, institutional cleaning & hygiene products, industrial cleaning products, personal care products, adhesives, metal working fluids, paints & coatings, textiles, water treatment coatings and in food & beverage processing.

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