Surfactants

Abstract

The present invention relates to an ionic surfactant comprising a polycarbonate or a poly (carbonate ether) of formula (I): A-((PC) P-(PE) Q-Z) X (I) wherein: A is derived from a functional starter compound; pC represents a carbonate block having P repeating units of formula (II): wherein: Re1, Re2, Re3 and Re4 are all H; or one of Re1, Re2, Re3 and Re4 is a methyl group, an ethyl group, a propyl group, a butyl group, or an ether, ester or carbonate group, and the remaining three of Re1, Re2, Re3 and Re4 are H; pE represents a polyether block having Q repeating units of the following formula (III): wherein: Re1, Re2, Re3 and Re4 are all H; or one of Re1, Re2, Re3 and Re4 is a methyl group, an ethyl group, a propyl group, a butyl group, or an ether, ester or carbonate group, and the remaining three of Re1, Re2, Re3 and Re4 are H; at least one Z is an ionic component; wherein the value of the or each P is independently from 1 to 50; wherein the value of the or each Q is independently from 0 to 50; and X is 1 or more.

Description

Technical Field

[0001] This invention relates to ionic surfactants, to processes for making them, and to certain uses. Background Art

[0002] Ionic surfactants are often made from petrochemical raw materials. Examples include ammonium and sodium lauryl sulfate, ammonium and sodium lauryl ether sulfate, methyl ester sulfonates, ammonium and imidazolium salts, and phospholipids. Their manufacturing processes generate significant CO2 emissions or lack environmental sustainability.

[0003] Surfactants combining polyether and polycarbonate blocks are known in the art of oil extraction. WO2010 / 062703A1 and WO2015 / 031348A1 describe polymer compositions and supercritical CO2 solutions of a potentially wide range of such polymers that aid in oil extraction. Such solutions form emulsion waste products with water to aid in oil extraction. There is no indication of any solubility in water or use of such water-soluble polymers. The polymer compositions are designed to dissolve in liquid or supercritical CO2 applications. WO2010 / 062703A1 mentions examples with polyether blocks and polycarbonate blocks, but no examples are given and these blocks have not been fully characterized or tested. WO2015 / 031348A1 describes YO-APC-OC x H y Type of polycarbonate block, wherein APC is polycarbonate, C x H y The terminal group Y can be H or several other groups, such as a polyether chain, but the latter is not exemplified or further clarified.

[0004] 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 have also been reported.

[0005] WO2022 / 096889A1, WO2020 / 222019A1, WO2020 / 222018A1, WO2021 / 176211A1 and WO2021 / 176212A1 disclose polyol block copolymer compositions and processes for producing the same.

[0006] US 2020 / 0085059 A1 describes antimicrobial cationic polycarbonates and polyurethanes comprising one or more pendant guanidine groups and / or isothiourea groups.

[0007] US2011 / 0151566A1 describes a biodegradable cationic polymer comprising a first repeating unit derived from a first cyclic carbonyl monomer by ring-opening polymerization, wherein more than 0% of the first repeating units comprise a side chain moiety comprising a quaternary amine group; a subunit derived from a monomeric diol initiator for the ring-opening polymerization; and an optional end-capping group.

[0008] WO2014 / 042924 describes an antimicrobial composition comprising an anionic drug and an amine polymer, wherein the amine polymer is a primary amine-containing polycarbonate prepared by organocatalytic ring-opening polymerization.

[0009] Our co-pending application WO2023 / 072843A1 discloses a surfactant comprising a polycarbonate block polyether, which can be prepared by reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional initiator compound to form a polycarbonate compound, followed by reacting the polycarbonate compound with an epoxide and an ether catalyst to form the or each polycarbonate chain or block polyether. Our co-pending application GB2301055.6 discloses a surfactant comprising a polycarbonate block polyether, which can be prepared in a similar manner from a multifunctional initiator compound. These disclosures relate only to nonionic surfactants.

[0010] It would be beneficial to replace current ionic surfactants that are entirely petrochemical-based or otherwise environmentally unfriendly with more sustainable alternatives that incorporate a portion of abundant and cheaper captured CO₂ and can be made from a single epoxide feedstock, such as ethylene oxide, which is also sustainably produced. The incorporation of CO₂ into these copolymers can bring new beneficial properties to the surfactants, including enhanced biodegradation opportunities. The incorporation of CO₂-containing chains or blocks can enhance the biodegradability of such surfactants, even at longer chain lengths.

[0011] Providing highly adaptable ionic surfactants would also be beneficial due to the ability to influence chain length, chain hydrophobicity, and therefore target specific end-use applications by providing a range of properties, and to control macromolecular symmetry to a greater extent than has been possible to date. Summary of the Invention

[0012] According to a first aspect of the present invention, there is provided an ionic surfactant comprising a polycarbonate or poly(carbonate ether) of formula I:

[0013] A-((PC) P -(PE) Q -Z) X (I)

[0014] in:

[0015] A is derived from a functional initiator compound;

[0016] PC represents a carbonate block having P repeating units of the formula:

[0017]

[0018] in:

[0019] R e1 、R e2 、R e3 and R e4 All are H; or

[0020] R e1 、R e2 、R e3 and R e4 One of the groups is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, and R e1 、R e2 、R e3 and R e4 The other three are H;

[0021] PE represents a polyether block having Q repeating units of the following formula:

[0022]

[0023] in:

[0024] R e1’ 、R e2’ 、R e3’ and R e4’ All are H; or

[0025] R e1’ 、R e2’ 、R e3’ and R e4’ One of the groups is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, and R e1’ 、R e2’ 、R e3’ and R e4’ The other three are H;

[0026] At least one Z is an ionic constituent;

[0027] wherein the or each P value is independently 1 to 50;

[0028] wherein the or each Q value is independently from 0 to 50; and

[0029] X is 1 or greater.

[0030] The surfactant may include block copolymers comprising individual PC and PE blocks; random or statistical copolymers containing only PC blocks which may incorporate ether (PE) linkages. For the avoidance of doubt, the PC blocks of the block copolymers may (or may not) also contain ether (PE) linkages, and the PE blocks of the block copolymers (when present) may (or may not) contain carbonate (PC) linkages.

[0031] At least one Z may be anionic; in this case, the surfactant is an anionic surfactant.

[0032] Examples of anions Z include O-[ion], OC(O)-[ion] and OC(O)-O-[ion], wherein [ion] is selected from sulfate, sulfonate, phosphate, hydrogen phosphate and dihydrogen phosphate, phosphite, hypophosphite, carboxylate, gluconate and suitable combinations of two or more thereof.

[0033] At least one Z may be cationic; in this case, the surfactant is a cationic surfactant.

[0034] Examples of cations Z include [ion], O-[ion], OC(O)-[ion] and OC(O)-O-[ion], wherein [ion] is selected from nitrogen-containing moieties such as secondary, tertiary or quaternary ammonium, pyridinium, pyrrolinium, pyrrolidinium, imidazolium, guanidinium, piperazinium, piperidinium, selected from phosphonium or sulfonium, and suitable combinations thereof of two or more.

[0035] At least one Z may be a zwitterion; in this case, the surfactant is a zwitterionic surfactant.

[0036] Examples of zwitterions Z include any suitable combination of the above-mentioned examples of anions and cations. In other words, Z may include O-[anion]-[cation], OC(O)-[anion]-[cation], and OC(O)-O-[anion]-[cation], and may include [cation]-[anion], O-[cation]-[anion], OC(O)-[cation]-[anion], and OC(O)-O-[cation]-[anion], wherein [anion] is selected from any suitable example of [ion] given above for anionic surfactants, and wherein [cation] is selected from any suitable example of [ion] given above for cationic surfactants.

[0037] When the surfactant is anionic, a cationic counterion is typically provided in association with it. For example, the counterion can be selected from alkali metal or alkaline earth metal cations, or nitrogen-containing cations such as primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, or quaternary ammonium ions, and suitable combinations of two or more thereof.

[0038] When the surfactant is cationic, an anionic counterion is typically provided in association with it. For example, the counterion can be selected from halides, carboxylates, sulfates, nitrates, hydroxides, and suitable combinations of two or more thereof. In some cases, other types of anions can be used, such as fluorinated anions [PF6] - 、[BF4] - wait.

[0039] When the surfactant is zwitterionic, a counterion may not be required.

[0040] The or each P value may independently be 1 to 50, 1 to 45, 1 to 40, 1 to 35, 1 to 30, 1 to 25, 1 to 20 or 1 to 15. Preferably, the or each P value is independently 1 to 15.

[0041] The or each value of Q may independently be from 0 to 50, 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, 0 to 20 or 0 to 15. Preferably, the or each value of Q is independently from 0 to 15.

[0042] In the present invention, the polymer chain A-((PC) P -(PE) Q ) X Acts as a hydrophobic group and Z acts as a hydrophilic group. However, the hydrophobicity of the polymer chain can be adjusted by selecting the P:Q ratio (polycarbonate is more hydrophobic than polyether), thereby controlling the hydrophobicity of the chain to tailor it to the end use.

[0043] Obviously, when a monofunctional initiator is chosen (e.g. a monoalcohol or a polyalkylene glycol monoethyl ether), X is 1. Choosing a difunctional initiator (e.g. a diol) will result in X being 2, and so on.

[0044] Preferably, X is 1, 2 or 3.

[0045] The monofunctional initiator compound (from which A can be derived) can be selected from C1 to C 30 Alcohols, C1 to C 30 Carboxylic acids or monofunctional polyethers, such as polyalkylene glycol monomethyl ether. In all cases, the hydrocarbon chain may be linear, branched, cyclic, aromatic, and / or contain heteroatoms, or may be substituted. Typically, when the monofunctional initiator is an alcohol or carboxylic acid, it is preferably C1 to C 11 Alcohol or carboxylic acid, more preferably C2 to C11 Alcohol or carboxylic acid, usually C 2-6 or C 2-4 Typically, when the monofunctional initiator compound is a polyalkylene glycol monoethyl ether, PEG or PPG monomethyl ether is preferred.

[0046] The polyfunctional initiator compound (from which A can be derived) can be selected from the following compounds:

[0047] Y(R Y ) a

[0048] Y can be connected with 2 or more R Y Thus, Y can be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or a combination of any of these groups, for example, Y can be an alkylenearyl, heteroalkylenearyl, heteroalkyleneheteroaryl or alkyleneheteroaryl group. Optionally, Y is an alkylene, heteroalkylene, arylene or heteroarylene.

[0049] It will be understood that in this case, a is an integer of at least 2. Optionally, a is in the range of 2 to 8 or 2 to 4.

[0050] Each R Y It can be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH)2 or -PR'(O)OH, optionally, R Y Selected from -OH, -NHR' or -C(O)OH, optionally, each R Y is -OH, -C(O)OH, or a combination thereof (e.g., each R Y is -OH).

[0051] R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, optionally, R' is H or optionally substituted alkyl.

[0052] A is typically derived from a starter compound by removal of one or more hydrogen atoms therefrom, followed by polymerization from one or more deprotonated derivatives.

[0053] Also provided is a method for producing a surfactant according to the first aspect of the present invention, the method comprising the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a functional initiator compound to form a polycarbonate compound, (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to form a poly(carbonate ether), and (iii) modifying at least one end group of the poly(carbonate ether) to produce the surfactant according to the first aspect of the present invention.

[0054] Also provided is a method for producing a surfactant according to the first aspect of the present invention in a multi-reactor system; the system comprises at least a first reactor and a second reactor, wherein a first reaction occurs in the first reactor and a second reaction occurs in the second reactor; wherein the first reaction is a reaction of a carbonate catalyst with CO2 and an epoxide in the presence of a functional initiator compound and an optional solvent to produce a polycarbonate compound, and the second reaction is a semi-batch or continuous reaction of an ether catalyst with the first-reacted polycarbonate compound and the epoxide to produce a poly(carbonate ether), the method further comprising a third reaction which may occur in a third reactor, the third reaction comprising modifying at least one end group of the poly(carbonate ether) product to produce a surfactant according to the first aspect of the present invention.

[0055] Alternatively, certain surfactants of the first aspect (derived from a monofunctional starter compound) can be formed by the following steps: (i) reacting a monohydroxy-functional polyether with a carbonate catalyst, an epoxide and CO2 to produce a poly(carbonate ether); and (iii) modifying at least one end group of the poly(carbonate ether) to produce a surfactant according to the first aspect of the invention.

[0056] One or more end groups of the poly(carbonate ether) are selected from OH, OR, OC(O)-R and / or OC(O)-OR; wherein each R is independently an optionally substituted (including heteroatoms) linear or branched or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl or aralkenyl group; preferably, the or each end group of the poly(carbonate ether) is OH or OMe, more preferably OH.

[0057] The step of modifying the compound in step (iii) preferably introduces at least one ionic component into one or more end groups of the polymer compound. This step preferably comprises removing H or R from one or more end groups of the poly(carbonate ether) and replacing them with the ionic component. Furthermore, it is contemplated that the ionic component may be introduced in successive steps, such as chlorination followed by amination.

[0058] When the polycarbonate or poly(carbonate) ether to be modified contains multiple modifiable end groups (e.g., when the polycarbonate or poly(carbonate) ether is a polycarbonate or poly(carbonate) ether polyol), for the purposes of the present invention, it is sufficient to convert only one of the modifiable end groups into an ionic substituent. However, it may also be desirable to convert more than one or all of such modifiable end groups to be modified into ionic components.

[0059] If not all modifiable end groups are so modified, then in the presently claimed compounds, Z comprises the ionic substituent for each such modified substituent and any remaining Z comprises an unmodified end group of the polycarbonate or poly(carbonate ether) (as described above).

[0060] Furthermore, regardless of whether the surfactant of the present invention is derived from a monofunctional or polyfunctional initiator, it is apparent that it is not necessary to provide ionic substituents on all available end groups of the poly(carbonate) ether. As long as at least a portion of the available end groups are functionalized by the introduction of ionic components, the conditions of the present invention are met.

[0061] In a PC chain comprising multiple Re groups, the individual Re groups may be different in different segments and blocks of the chain.In a PE chain comprising multiple Re' groups, the individual Re' groups may be different in different segments or blocks of the chain.

[0062] For example, if, in the above-described process according to the invention, a mixture of propylene oxide and ethylene oxide is used as the epoxide in the first reaction, then in some blocks of the PC chain, each Re will be H (ethylene oxide is the reagent that generates such PC blocks); while in other blocks of the PC chain, one of the Re groups will be methyl (propylene oxide is the reagent that generates such PC segments or blocks). The same applies to PE chains.

[0063] The present invention also provides uses of the above-mentioned surfactants: as agricultural chemicals, cosmetics or pharmaceutical adjuvants, excipients or auxiliary agents; for preparing or functionalizing low-foaming detergents / cleaners, institutional cleaning and hygiene products, industrial cleaning products, personal care products, adhesives, metalworking fluids, paints and coatings; as adjuvants or other agents or excipients in the construction, mining and oilfield industries; as preparative or functional ingredients in microcapsules, batteries, crystal growth modifiers, biocontrol agents, demulsifiers, foam flotation systems, textiles, water treatment coatings, and in the processing of food and beverages. DETAILED DESCRIPTION

[0064] Preferably, the surfactant has a CO2 incorporation of greater than 5 wt%, a CO2 incorporation of greater than 10 wt%, more typically a CO2 incorporation of greater than 15 wt%, a CO2 incorporation of greater than 20 wt%, or a CO2 incorporation of greater than 21 wt%. Preferably, the surfactant has a CO2 incorporation of 5 to 40 wt%, a CO2 incorporation of 10 to 40 wt%, a CO2 incorporation of 15 to 40 wt%, a CO2 incorporation of 20 to 40 wt%, typically a CO2 incorporation of 10 to 35 wt%, more typically a CO2 incorporation of 15 to 30 wt%.

[0065] It should be understood that when the surfactant is a block copolymer (i.e., Q is not zero), the carbonate blocks of the block copolymer are hydrophobic, while the ether blocks are hydrophilic. Tailoring the relative proportions of the two blocks will change the properties of the copolymer, thereby obtaining a surfactant suitable for the end use.

[0066] It will also be appreciated that whether or not the surfactant of the present invention is a block copolymer, the hydrophobicity of the polymer chain can be adjusted by incorporating ether linkages into the PC blocks and / or by incorporating carbonate linkages into the PE blocks (when present).

[0067] The epoxides used in the production of both the polycarbonate portion and the polyether portion are independently selected from ethylene oxide (EO), propylene oxide (PO), butylene oxide, pentyl oxide, hexyl oxide, glycidyl ether, glycidyl ester or glycidyl carbonate or a mixture thereof. Preferably, in the production of the polycarbonate component, the epoxide is ethylene oxide, propylene oxide, butylene oxide or a mixture thereof, preferably ethylene oxide or propylene oxide. Preferably, in the production of the polyether component, the epoxide is ethylene oxide or propylene oxide or a mixture thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0068] It will also be understood that when a mixture of epoxides is used, the epoxides are generally statistically distributed along the polymer backbone.

[0069] Thus, when a mixture of epoxides is used, the polycarbonate chains and polyether chains can be referred to as random copolymers or statistical copolymers, respectively.

[0070] R e1 、R e2 、R e3 、R e4 、R e1’ 、R e2’ 、R e3’ and R e4’ The properties of will depend on the nature of the epoxide used to prepare the polycarbonate or polyether. However, when R e1 to R e4 One or Re1’ to R e2’ When one of the groups is a methyl, ethyl, propyl, butyl, or 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’ It’s H.

[0071] It will also be understood that if a mixture of epoxides is used, each occurrence of 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 component, then R e1 (or R e3 ) may independently be hydrogen or methyl, and R e2 (or R e4 ) may independently be hydrogen or methyl.

[0072] The skilled artisan will understand that when the epoxide is asymmetric, adjacent epoxide monomer units in the backbone may be linked head-to-tail, head-to-head, or tail-to-tail.

[0073] 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.

[0074] In the block copolymer, the or each polycarbonate chain or block of the surfactant preferably has 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.

[0075] When present, the or each polyether chain or block of the surfactant preferably has a molecular weight (Mn) in the range of about 100 to 20,000 Da, more preferably about 200 to 10,000 Da, most preferably about 200 to 6000 Da.

[0076] The Mn and hence the PDI of the polymers produced by the process of the present invention can be measured using gel permeation chromatography (GPC). For example, one can use a gel permeation chromatography (GPC) with two Agilent TM Agilent PLgel μ-m mixed D column TM GPC can be measured using an Agilent 1260 Infinity GPC machine. 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., TM Technologies, with Mn ranging from 405 to 49,450 g / mol). Optionally, samples can be compared to poly(ethylene glycol) standards (such as those supplied by Agilent Technologies). TM Measurements were performed using polyethylene glycol EasiVials supplied by Technologies.

[0077] 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.

[0078] The polycarbonate blocks of the surfactant may also include 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.

[0079] For the avoidance of doubt, when the polycarbonate block comprises ether linkages, the polycarbonate block will not only comprise P groups of the formula The repeating units are not just carbonate bonds, i.e., but rather comprise a mixture of carbonate bonds as shown and ether bonds as shown for the PE block. In this case, P is the sum of carbonate bonds and ether bonds in the PC block. Each carbonate or ether bond comprises a repeating unit that may be derived from an alkylene oxide moiety, i.e., Therefore, when ether linkages are present, P can be considered as the number of repeating alkylene oxide-derived moieties in the PC block.

[0080] Notably, when Q is zero, the surfactants of the present invention include ionic polycarbonates that may (or may not) incorporate ether linkages into the polycarbonate chain as random or statistical linkages.

[0081] Optionally, the polycarbonate blocks may be generally alternating polycarbonate residues. If the epoxide is asymmetric, the polycarbonate may have between 0-100% head-to-tail linkages, preferably between 40-100% head-to-tail linkages, and more preferably between 50-100%. The polycarbonate may have a statistical distribution of head-to-head, tail-to-tail, and head-to-tail linkages in the order 1:2:1, indicating non-stereoselective ring opening of the epoxide, or it may preferentially have head-to-tail linkages at greater than approximately 50%, optionally greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0082] Optionally, the polyether blocks comprise only ether linkages. Typically, the or each polyether chain or block is at least 90% derived from, typically at least 95% derived from, more typically at least 99% derived from, most typically 100% derived from, epoxides.

[0083] Typically, the polyether blocks have less than 40% carbonate linkages, typically less than 30% carbonate linkages, often 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 may have 0% carbonate linkages. For example, the polyether blocks may have from about 0% to about 40% carbonate linkages, from about 0% to about 30% carbonate linkages, from about 0% to about 20% carbonate linkages, from about 0% to about 10% carbonate linkages, from about 0% to about 5% carbonate linkages, from about 0% to about 2% carbonate linkages, or from about 0% to about 1% carbonate linkages.

[0084] For the avoidance of doubt, when the polyether block comprises carbonate linkages, the polyether block will not only comprise Q groups of the formula The repeating units are not ether bonds alone, i.e., but rather comprise a mixture of ether bonds as shown and carbonate bonds as shown for the PC blocks. In this case, Q is the sum of the ether bonds and carbonate bonds in the or each PE block mentioned. Each ether or carbonate bond comprises a repeating unit derivable from an alkylene oxide moiety, i.e., Thus, when carbonate linkages are present in the PE block, Q can be considered to be the number of repeating alkylene oxide derived moieties in the PE block in question.

[0085] Typically, the polycarbonate blocks are derived from epoxides and CO2. More typically, epoxides and CO2 provide at least 70% of the residues in each chain or block, particularly at least 80% of the residues in each chain or block, and more particularly at least 90% of the residues in each chain or block. Most particularly, in the polycarbonate blocks, at least 95% of the residues in each chain or block are residues of epoxides and CO2. Most typically, the polycarbonate blocks include ethylene oxide and / or propylene oxide residues, and optionally butylene oxide. At least 30% of the epoxide residues of the polycarbonate blocks can be ethylene oxide or propylene oxide residues, typically, at least 50% of the epoxide residues of the polycarbonate blocks are ethylene oxide or propylene oxide residues, more typically, at least 75% of the epoxide residues of the polycarbonate blocks are ethylene oxide or propylene oxide residues, and most typically, at least 90% of the epoxide residues of the polycarbonate blocks are ethylene oxide or propylene oxide residues.

[0086] Typically, the polycarbonate blocks are derived from CO2, ie, the carbonate has CO2 residues incorporated therein. Typically, the polycarbonate blocks have between 70-100% carbonate linkages, more typically 80-100%, and most typically 90-100%.

[0087] The values ​​of P and Q in Formula I can be adjusted appropriately depending on the end use, and in some applications, Q can be zero.

[0088] The epoxide used in the process of making surfactant of the present invention can be selected from oxyethane, propylene oxide, butylene oxide, pentyl oxide, hexyl oxide, glycidyl ether, glycidyl ester or glycidyl carbonate or a mixture of two or more thereof.Usually, epoxide is selected from oxyethane, propylene oxide or its mixture, preferably oxyethane.

[0089] In the inventive process, the carbonate catalyst may be heterogeneous or homogeneous.

[0090] The carbonate catalyst can be a monometallic, bimetallic or polymetallic homogeneous complex, or it can be a non-metallic Lewis acid-base pair (e.g., based on a combination of borane and an ammonium salt, as disclosed in patents WO 2016203408, WO 2020121262, WO2021005470). The carbonate catalyst can be a heterogeneous catalyst, such as a metal organic framework (MOF), which can be derived from a metal such as scandium or aluminum, such as those described in WO 2021123761.

[0091] The carbonate catalyst may include a phenol or phenoxide ligand.

[0092] Typically, the carbonate catalyst may be a bimetallic complex comprising a phenol or phenoxide ligand. The two metals may be the same or different.

[0093] The carbonate catalyst may be a catalyst of formula (IV):

[0094]

[0095] in:

[0096] M stands for M-(L) v The metal cation represented by

[0097] x is an integer from 1 to 4, preferably x is 1 or 2;

[0098] is a polydentate ligand or multiple polydentate ligands;

[0099] L is a coordinating ligand, for example, L can be a neutral ligand or an anionic ligand capable of ring-opening the epoxide;

[0100] v is an integer that independently satisfies the valence of each M and / or the preferred coordination geometry of each M, or is an integer that allows the complex represented by formula (IV) above to have an overall neutral charge. For example, each v can independently be 0, 1, 2 or 3, for example, v can be 1 or 2. When v>1, each L can be different.

[0101] The term multidentate ligand includes bidentate, tridentate, tetradentate and higher dentate ligands.Each multidentate ligand can be a macrocyclic ligand or an open ligand.

[0102] Such catalysts include WO 2010022388 (metal salen and derivatives, metal porphyrins, corrole and derivatives, metal tetraazaannulene and derivatives), WO 2010028362 (metal salen and derivatives, metal porphyrins, corrole and derivatives, metal tetraazaannulene and derivatives), WO 2008136591 (metal salen), WO 2011105846 (metal salen), WO 2014148825 (metal salen), WO 2013012895 (metal salen), EP2258745A1 (metal porphyrins and derivatives), JP2008081518A (metal porphyrins and derivatives), CN101412809 (metal salen and derivatives), WO2019126221 (metal aminotriphenol complexes), US9018318 (metal β-diimine complexes), US6133402A (metal β-diimine complexes) and US8278239 (metal salen and derivatives), the entire contents of which, in particular insofar as they relate to suitable carbonate catalysts for the reaction of CO2 and epoxides in the presence of a starter as defined herein and optionally a solvent, are incorporated herein by reference.

[0103] Preferably the carbonate catalyst is a bimetallic phenoxide catalyst. Suitable bimetallic phenoxide complexes are those described in WO2009 / 130470, WO2013 / 034750, WO2016 / 012786, WO2016 / 012785, WO 2012037282 and WO2019048878A1, the entire contents of which, in particular to the extent they relate to suitable carbonate catalysts for the reaction of CO2 and epoxides in the presence of a starter as defined herein and optionally a solvent, are incorporated herein by reference.

[0104] The ether catalyst can be any catalyst suitable for the polymerization of 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 (such as HSbF, CF3SO3H), PF5, 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 useful in the process of the present invention include 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, US 6,699,961, US 6,716,788, US 6,977,236, US 7,968,754, US 7,034,103, US 4,826,953, US 4,500 704, US 7,977,501, US 9,315,622, EP-A-1568414, EP-A-1529566, and WO 2015 / 022290, the entire contents of which are incorporated by reference.

[0105] The ratio of carbonate catalyst to ether catalyst can be in the range of about 300:1 to about 1:100, for example, about 120:1 to about 1:75, such as about 40:1 to about 1:50, for example, about 30:1 to about 1:30, such as 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 mass ratios.

[0106] The process can be carried out in a one-pot reactor or can be the aforementioned two-reactor process (multi-reactor system).

[0107] Typically, the reaction mixture from the first step contains less than 5% CO by weight of the reaction mixture before the second step , preferably less than 2.5%, such as less than 1.0%, less than 0.5% or less than 0.1%. Typically, the second step is carried out without adding CO separately , but it can be carried out under CO pressure. The or each polyether chain or block produced in the second step can have less than 40% carbonate bonds, preferably less than 30% carbonate bonds or less than 20% carbonate bonds, more preferably less than 10%, less than 5%, less than 2% or less than 1% carbonate bonds. Preferably, the or each polyether chain or block produced in the second step is substantially free of carbonate bonds.

[0108] Typically, therefore, the second step is carried out in the substantial absence of CO2.

[0109] Thus, substantially no CO2 means that the second step is carried out in the presence of less than 4% CO2 by weight, preferably less than 2%, such as less than 1.0%, less than 0.5% or less than 0.1% by weight of the total reactants, catalyst and products in the second step.

[0110] Compared to processes where all materials are provided at the beginning of the process, adding components in separate steps can help increase catalyst activity and can result in a more efficient process. The presence of large amounts of certain components throughout the process can reduce catalyst efficiency. Reacting these materials in separate steps can prevent this reduction in catalyst efficiency and / or optimize catalyst activity. The reaction conditions for each step can be customized to optimize the reaction of each catalyst.

[0111] The ether catalyst can be preactivated before addition in the second step. This preactivation can be achieved by mixing one or both catalysts with the epoxide (and optionally other components). Preactivation of the ether catalyst is very useful because it allows for safe reaction control (preventing uncontrolled buildup of unreacted monomer content) and eliminates unpredictable potency periods.

[0112] Although any residual CO2 from the first step can generally be removed from the crude reaction product of the first step before the second step begins, allowing the second step to be carried out in the absence of CO2, it should be understood that small amounts of CO2 may be present in the reaction mixture in the second step as a reagent not used in the first step. Alternatively, both steps can be carried out under CO2 pressure.

[0113] The reaction of the present invention can be carried out in the presence of a solvent; however, it should also be understood that the process can also be carried out in the absence of a solvent. When a solvent is present, it can be toluene, hexane, tert-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.

[0114] Compared to processes where all materials are provided at the start of a reaction, adding components in separate reactions and reactors can help increase the activity of the catalyst and can lead to a more efficient process. The presence of large amounts of certain components in the overall reaction may reduce the efficiency of the catalyst. Reacting the materials in separate reactors can prevent this reduction in catalyst efficiency and / or can optimize catalyst activity. The reaction conditions of each reactor can be customized to optimize the reaction of each catalyst.

[0115] In addition, not loading the total amount of each component at the beginning of the reaction and placing the catalyst for the first reaction in a separate reactor from the catalyst for the second reaction can result in uniform catalysis and a more uniform polymer product. This in turn can result in polymers having a narrower molecular weight distribution, a desired ratio and distribution along the chain of ether to carbonate bonds, and / or improved stability.

[0116] It may also be useful to separate the reactions with two different catalysts and combine only certain components in the first reaction and add the remainder in the second reaction, for example by adding a preactivated ether catalyst or adding the reaction mixture to a preactivated ether catalyst.

[0117] Preferred ether catalysts and carbonate catalysts are those of the second aspect of the present invention.

[0118] The first reaction may be carried out in more than one reactor, which continuously feeds the crude reaction mixture to the second reaction and reactor. Preferably, the second reaction is run in continuous mode.

[0119] The product of the first reaction can be stored for subsequent use in the second reactor.

[0120] The two reactors can be positioned in series, or the reactors can be nested. Each reactor can individually be a stirred tank reactor, a loop reactor, a tubular reactor or other standard reactor design.

[0121] definition

[0122] Unless otherwise defined, the term "alkyl" as used herein refers to a saturated straight or branched chain hydrocarbon radical derived by removing a single hydrogen atom from an aliphatic moiety.1-20 An "alkyl group" is a straight or branched alkyl group having from 1 to 20 carbon atoms. Thus, an 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 Alkyl group.

[0123] Unless otherwise defined herein, an ester group is optionally -OC(O)R 1 -or-C(O)OR 1 -, where R 1 R may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. 1 Can be unsubstituted aliphatic, alicyclic or aryl. Optionally, R 1 is methyl, ethyl, propyl or phenyl. The ester group may be terminated by an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. It will be understood that if R 1 is hydrogen, then -OC(O)R 1 -or-C(O)OR 1 -Defined groups will be carboxylic acid groups.

[0124] The carbonate group is optionally -OC(O)OR 2 , where R 2 R may be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. 2 can be an optionally substituted aliphatic, alicyclic or aryl group. Optionally, R 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. Optionally, R 2 It should be understood that if R 2 is hydrogen, then -OC(O)OR 2 The defined group will be the carbonic acid group.

[0125] The carbonate functionality is -OC(O)O- and can be derived from a suitable source. Typically, it is derived from CO2.

[0126] The ether group is optionally -OR3 , where R 3 R may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. 3 Can be unsubstituted aliphatic, alicyclic or aryl. Optionally, R 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. Optionally, R 3 It is methyl, ethyl, propyl or phenyl.

[0127] The term "optionally substituted" as used herein means that one or more hydrogen atoms in the optionally substituted part are replaced by a suitable substituent. Unless otherwise indicated, the "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted by more than one substituent selected from a specified group, the substituent can be the same or different at each position. The combination of substituents envisioned by the present invention is preferably those that result in the formation of stable compounds. The term "stable" as used herein means that the compound is chemically feasible and can exist at room temperature, i.e. (16-25° C.), for a long enough time to allow their detection, separation and / or use in chemical synthesis.

[0128] Substituents can be described as being attached to bonds that intersect with bonds in the rings of the described molecule. This convention indicates that one or more substituents can be attached to the ring at any available position (usually replacing a hydrogen atom of the structure). In the case where an atom of a ring has two substitutable positions, two groups (the same or different) can be present on that atom.

[0129] 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, alkaryl, amino, amide, imine, nitrile, silanyl, silyl ether, ester, sulfoxide, sulfonyl, ethynyl, 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, silanyl, sulfoxide, sulfonyl, phosphinate, sulfonate, or ethynyl).

[0130] Particularly preferred optional substituents for use in the present invention are selected from nitro, C 1-12 Alkoxy (e.g., OMe, OEt, O i Pr, On 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 the C 1-12 Alkoxy, C 6-18 Aryl, C 2-14 Heteroaryl, C 2-14 Heteroalicyclic, C 1-6 Alkyl and C 1-6 Each of the haloalkyl groups may be optionally substituted with optional substituents as defined herein.

[0131] As used herein, the term "continuously" may be defined as the manner in which materials are added or may refer to the nature of the overall reaction process.

[0132] In a continuous addition approach, the relevant materials are added continuously or continually during the reaction process. This can be achieved, for example, by adding a material stream with a constant flow rate or a variable flow rate. In other words, one or more materials are added in a substantially uninterrupted manner. However, it is worth noting that for practical reasons, the uninterrupted addition of materials may require brief interruptions, such as to refill or replace the material container from which the materials are added.

[0133] To the extent that the entire reaction is continuous, the reaction can be carried out for a long period of time, such as days, weeks, months, etc. In such a continuous reaction, the reaction materials can be continuously replenished and / or the reaction products can be discharged. It should be understood that although the catalyst may not be consumed during the reaction, the catalyst may need to be replenished in any case because the discharge may deplete the amount of catalyst present.

[0134] Continuous reactions can employ continuous addition of materials.

[0135] Continuous reactions may employ discontinuous (ie, batch or semi-batch) addition of materials.

[0136] As used herein, the term series connection refers to when two or more reactors are connected so that the crude reaction mixture can flow from the first reactor to the second reactor.

[0137] The term nested as used herein refers to when two or more reactors are configured so that one reactor is positioned within another reactor. For example, in the present invention, when the second reactor is positioned inside the first reactor, the conditions of both reactors are allowed to affect the other reactor.

[0138] Example

[0139] Example 1

[0140] The nonionic precursors of the compounds according to the invention are prepared from monofunctional starter compounds as follows:

[0141] Add the monohydric alcohol starter to 100 mL of Parr TM High-pressure reactor system. The vessel was dried by heating to 100°C under vacuum for 60 min, then cooled and filled with low-pressure CO2. Catalyst (1) was added, which was prepared according to Example 2 of WO2017 / 037441.

[0142] To the mixture is added an epoxide (propylene oxide [PO] or ethylene oxide [EO]). 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.

[0143] At the end of the desired reaction time, the mixture was cooled to <10°C and vented through an acid scrubber system.

[0144] Table 1; Example 1; Experimental conditions / results

[0145]

[0146] Example 2

[0147] Reaction 1:

[0148] The nonionic precursors of the compounds according to the invention are prepared from monofunctional starter compounds as follows:

[0149] Add the monohydric alcohol starter to 100 mL of Parr TM High-pressure reactor system. The vessel was dried by heating to 100°C under vacuum for 60 min, then cooled and filled with low-pressure CO2. Catalyst (1) was added, which was prepared according to Example 2 of WO2017 / 037441.

[0150] To the mixture is added an epoxide (propylene oxide [PO] or ethylene oxide [EO]). 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.

[0151] At the end of the desired reaction time, the mixture was cooled to <10°C and vented through an acid scrubber system.

[0152] Reaction 2:

[0153] The pre-dried monool initiator and DMC consisting of zinc hexacyanocobaltate and tert-butyl alcohol were added to 100 mL of Parr TMHigh Pressure Reactor System. The vessel was kept under vacuum for approximately 2 min, then filled with low pressure N2, and then filled with anhydrous ethyl acetate (15 mL).

[0154] The vessel is then heated to 130° C. with stirring and the DMC is activated with two portions of approximately 0.3 g of epoxide (EO or PO). After activation (as evidenced by a pressure drop), the external heater is removed, the reactor is optionally pressurized with CO , and the mixture is then cooled to the target addition temperature.

[0155] After reaching the target temperature, the mixture from Reaction 1 and the epoxide (EO or PO) were added to the active DMC system over approximately 60-90 minutes. Once the mixture addition was complete, the mixture was "cooked out" for several hours before being cooled, vented, and sampled for NMR and GPC analysis.

[0156] Table 2; Example 2; Reaction 1; Experimental conditions / results

[0157]

[0158] Table 3; Example 2; Reaction 2; Experimental conditions

[0159]

[0160] Table 4; Example 2; Reaction 2; Results

[0161] entry Mn(GPC) PDI(GPC) <![CDATA[CO2 wt%]]> p q 1 1800 1.23 29 13 9 2 1300 1.1 27 8 8

[0162] Example 3

[0163] The nonionic precursors of the compounds according to the present invention are prepared according to the following sequential reaction scheme:

[0164]

[0165] Reaction 1:

[0166] The diol starter was charged into 100 mL of Parr TM Cold drying of the bottom of the high-pressure reactor system The filled vessel was heated to 100° C. under vacuum (about 1 mbar) and held for 60 min, then cooled and filled with low-pressure CO 2 .

[0167] Catalyst (1) (prepared according to Example 2 of WO2017 / 037441) was added to the reactor. Vacuum purged at room temperature for <5 min, and then backfilled with low-pressure CO2.

[0168] EO was added to the mixture. The mixture was stirred and pressurized to approximately half of the target pressure. 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.

[0169] At the end of the desired reaction time, the mixture was cooled to <10°C and vented through an acid scrubber system.EO and anhydrous ethyl acetate were added to the cold stirred mixture and then transferred to an intermediate holding vessel.

[0170] Reaction 2:

[0171] The pre-dried monohydric alcohol initiator and DMC composed of zinc hexacyanocobaltate and tert-butyl alcohol were added to 100 mL of Parr TM The initiator and the bottom were kept under vacuum (about 1 mbar) for about 2 min in the cold bottom of the high-pressure reactor system, then filled with low pressure N2 and anhydrous ethyl acetate (15 mL) was injected via syringe.

[0172] The DMC / initiator / ethyl acetate mixture was then heated to 130° C. with stirring and the DMC was activated with two small cups of approximately 0.3 g PO (set point 1 mL / min). After activation (confirmed by pressure drop), the external heater was removed and the reactor was optionally pressurized with CO 2 , and the mixture was then cooled to the target addition temperature while continuing to slowly add PO (set to 0.1 mL / min) [approximately 1.2 g PO total].

[0173] After reaching the target temperature, the mixture from Reaction 1 was added to the active DMC system over approximately 60-90 minutes (semi-batch mode). Once the mixture addition was complete, the mixture was "cooked out" for several hours before being cooled, vented, and sampled for NMR and GPC analysis.

[0174] The results are shown in Tables 5 to 7 below.

[0175] Table 5; Example 3; Reaction 1; Experimental conditions / results

[0176]

[0177] Table 6; Example 3; Reaction 2; Experimental conditions

[0178]

[0179] Table 7: Example 3; Reaction 2; Results

[0180] entry Conversion rate / % Mn PDI(GPC) <![CDATA[CO2 wt%]]> p q 1 100 980 1.04 17 4 12 2 100 1100 1.08 20 6 15 3 100 1050 1.08 24 6 10

[0181] Example 4

[0182] The anionic surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0183]

[0184] Remarks (for each of Examples 4 to 10):

[0185] m represents the chain length of the initiator compound

[0186] • Only one polymer chain extending from the starter compound is shown in the illustrated schemes. Obviously, depending on the functionality of the starter, one or more further polymer chains may be present.

[0187] In other embodiments of the present invention, q may be zero.

[0188] Chlorosulfonic acid (1 equivalent) was added dropwise to a poly(carbonate ether) polymer (0.5 g / mL) in anhydrous CHCl at 0°C. The reaction mixture was warmed to room temperature and stirred overnight. The solvent was concentrated to dryness. 10% NaOH in EtOH (0.5 g / mL) was added to the resulting polymer mixture, which was stirred for 1 hour. The resulting solid was filtered, washed with MeOH, and then dried under vacuum to yield the sodium salt of the sulfonated polymer.

[0189] Those skilled in the art can also use SO3 as a sulfating agent to sulfate the polymer. Typically, the alcohol-terminated polymer is reacted with SO3 in air at a certain temperature and then neutralized with a base such as NaOH or ammonia in a continuous process.

[0190] Phosphorylation of the polymer can also be carried out using techniques known to those skilled in the art. Typically, the alcohol-terminated polymer is reacted with polyphosphoric acid / phosphorus pentoxide under cooling conditions and then heated for a period of time. Phosphates can be obtained by treatment with an alkali, such as NaOH or ammonia.

[0191]

[0192] Example 5

[0193] The cationic surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0194]

[0195] Note: q can be zero.

[0196] SOCl2 (0.5 g / mL) was added to the poly(carbonate ether) polymer, the reaction was heated at reflux for 2 h, and the mixture was then concentrated to dryness and washed with toluene. The resulting polymer was dissolved in THF (0.5 g / mL) and trimethylamine (1 equivalent) and stirred at reflux overnight. The resulting solid was filtered, washed with EtOH, and then dried under vacuum to obtain the chloride salt of the cationic polymer.

[0197]

[0198] Example 6

[0199] The cationic surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0200]

[0201] The monoalcohol product of Example 1 was dissolved in dichloromethane containing triethylamine (1.3 equivalents) and nicotinic anhydride (1.05 equivalents) and reacted at reflux for 16 hours. The blocked monoalcohol was washed with water and brine, dried over sodium sulfate, and concentrated to dryness in vacuo to obtain the desired precursor product. The ethylene carbonate byproduct was removed using a Kugelrohr or short path evaporator (SPE). The precursor monoalcohol was dissolved in acetone (0.05 g / mL) containing iodomethane (3 equivalents) and stirred at reflux for 1 hour. After cooling to RT, the resulting salt was collected by filtration and washed with cold acetone to obtain the cationic monoalcohol.

[0202] Example 7

[0203] The amphoteric surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0204] The procedure of Example 5 was repeated by incorporating β-alanine (instead of trimethylamine) to produce a zwitterionic polymer.

[0205]

[0206] Example 8

[0207] The anionic surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0208]

[0209] To a polycarbonate polymer (0.5 g / mL) in DCM, succinic anhydride (1.1 eq) and Et3N (1.1 eq) were added. The mixture was stirred at 40°C overnight. The mixture was allowed to cool to room temperature and washed with deionized water (2 x 50 mL) and brine (2 x 50 mL). The organic solution was dried over MgSO4 and concentrated by rotary evaporation. To this product was added Na2CO3 or K2CO3, and the mixture was stirred in THF (0.5 g / mL) at room temperature overnight. The reaction mixture was concentrated by rotary evaporation to isolate the sodium or potassium salt.

[0210] Table 8: Example 8; Results

[0211] entry counterions Mn <![CDATA[CO2 wt%]]> m p q Water soluble? 1 <![CDATA[Na + ]]> 940 33 2 7 0 Y 2 K+ 1000 31 2 7 0 Y 3 <![CDATA[Na + ]]> 1450 24 2 8 8 Y

[0212] Example 9

[0213] The cationic surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0214]

[0215] To a polycarbonate polymer (0.5 g / mL) in DCM was added alanine (1.1 equiv) and Et3N (0.65 equiv). The mixture was stirred at 40°C overnight. The mixture was allowed to cool to room temperature and washed with deionized water (2 x 50 mL) and brine (2 x 50 mL). The organic solution was dried over MgSO4 and concentrated by rotary evaporation. To this product was added HCl, and the mixture was stirred in H2O (0.5 g / mL) at room temperature. The reaction mixture was concentrated by rotary evaporation to isolate the chloride salt.

[0216] Table 9: Example 9; Results

[0217] entry counterions Mn <![CDATA[CO2 wt%]]> m p q Water soluble? 1 <![CDATA[Cl - ]]> 830 37 2 7 0 Y 2 <![CDATA[OAc - ]]> 850 36 2 7 0 Y

[0218] Example 10

[0219] The amphoteric surfactant according to the present invention is prepared from the nonionic precursor compounds prepared in Examples 1-3 above according to the following scheme:

[0220]

[0221] To a polycarbonate polymer (0.5 g / mL) in DCM was added succinic anhydride (1.1 eq) and Et3N (1.1 eq). The mixture was stirred at 40°C overnight. The mixture was allowed to cool to room temperature and washed with deionized water (2 x 50 mL) and brine (2 x 50 mL). The organic solution was dried over MgSO4 and concentrated by rotary evaporation.

[0222] To the intermediate product (0.5 g / mL) in DCM was added alanine (1.1 eq) and EtN (0.65 eq). The mixture was stirred at 40 °C overnight. The mixture was allowed to cool to room temperature and washed with deionized water (2 x 50 mL) and brine (2 x 50 mL). The organic solution was dried over MgSO and concentrated by rotary evaporation.

[0223] To this product, Na2CO3, K2CO3, HCl or acetic acid was added and the mixture was stirred in THF (0.5 g / mL) at RT overnight. The reaction mixture was concentrated by rotary evaporation to separate the anions sodium and potassium and the cations chloride and acetate, respectively.

[0224] Table 10: Example 10; Results

[0225]

[0226]

Claims

1. An ionic surfactant comprising a polycarbonate or poly(carbonate ether) of formula I: A-((PC) P -(INSTEAD) Q -Z) X (ON) in: A is derived from a functional initiator compound; PC represents a carbonate block having P repeating units of the formula: in: R e1 、R e2 、R e3 and R e4 All are H; or R e1 、R e2 、R e3 and R e4 One of the groups is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, and R e1 、R e2 、R e3 and R e4 The other three are H; PE represents a polyether block having Q repeating units of the following formula: in: R e1’ 、R e2’ 、R e3’ and R e4’ All are H; or R e1’ 、R e2’ 、R e3’ and R e4’ One of the groups is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, and R e1’ 、R e2’ 、R e3’ and R e4’ The other three are H; At least one Z is an ionic component; wherein the or each P value is independently 1 to 50; wherein the or each Q value is independently from 0 to 50; and X is 1 or greater.

2. The ionic surfactant according to claim 1, wherein One or more polymer chains of the surfactant include a block copolymer containing individual PC and PE blocks.

3. The ionic surfactant according to claim 2, wherein The PC blocks of the block copolymer may contain ether (PE) linkages, and the PE blocks of the block copolymer (when present) may contain carbonate (PC) linkages.

4. The ionic surfactant according to claim 2 or claim 3, wherein One or more polymer chains of the surfactant comprise a random copolymer containing only PC blocks incorporating ether (PE) linkages.

5. The ionic surfactant according to any one of claims 1 to 4, wherein At least one Z is anionic.

6. The ionic surfactant according to claim 5, wherein The at least one Z is selected from O-[ion], OC(O)-[ion] and OC(O)-O-[ion], wherein [ion] is selected from sulfate, sulfonate, phosphate, hydrogen phosphate and dihydrogen phosphate, phosphite, hypophosphite, carboxylate, gluconate and suitable combinations of two or more thereof.

7. The ionic surfactant according to any one of claims 1 to 4, wherein At least one Z is cationic.

8. The cationic surfactant according to claim 7, wherein The at least one Z is selected from [ion], O-[ion], OC(O)-[ion] and OC(O)-O-[ion], wherein [ion] is selected from nitrogen-containing moieties such as primary, secondary, tertiary or quaternary ammonium ions, pyridinium, pyrrolinium, pyrrolidinium, imidazolium, guanidinium, piperazinium, piperidinium, selected from phosphonium or sulfonium, or selected from suitable combinations of two or more thereof.

9. The ionic surfactant according to any one of claims 1 to 4, wherein At least one Z is zwitterionic.

10. The ionic surfactant according to claim 9, wherein The at least one Z is selected from O-[anion]-[cation], OC(O)-[anion]-[cation]; OC(O)-O-[anion]-[cation], [cation]-[anion], O-[cation]-[anion], OC(O)-[cation]-[anion] and OC(O)-O-[cation]-[anion], wherein [anion] is selected from any suitable [ion] of claim 6, and wherein [cation] is selected from any suitable [ion] of claim 8.

11. A surfactant according to claim 5 or claim 6, provided in association with at least one cationic counterion.

12. The ionic surfactant according to claim 11, wherein The at least one cationic counterion is selected from alkali metal or alkaline earth metal cations, or from primary, secondary, tertiary or quaternary ammonium ions.

13. A cationic surfactant according to claim 7 or claim 8, provided in association with at least one anionic counterion.

14. The cationic surfactant according to claim 13, wherein The at least one anionic counterion is selected from halides and carboxylates.

15. The ionic surfactant according to any one of claims 1 to 14, wherein The or each value of P is independently from 1 to 45, from 1 to 40, from 1 to 35, from 1 to 30, from 1 to 25, from 1 to 20 or from 1 to 15.

16. The ionic surfactant according to any one of claims 1 to 15, wherein The or each value of Q is independently from 0 to 45, 0 to 40, 0 to 35, 0 to 30, 0 to 25, 0 to 20 or 0 to 15.

17. The ionic surfactant according to any one of claims 1 to 16, wherein A is derived from a group consisting of C1 to C 11 Alcohols, C1 to C 11 Monofunctional starter compounds are carboxylic acids or monofunctional polyethers such as polyalkylene glycol monomethyl ether.

18. The ionic surfactant according to any one of claims 1 to 16, wherein A is derived from a polyfunctional initiator compound selected from the group consisting of compounds of the formula: Y(R Y ) a in: Y is selected from the group consisting of -R Y Any group of groups; Each R Y is independently selected from -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH)2 or -PR'(O)OH, optionally, R Y Selected from -OH, -NHR' or -C(O)OH, optionally, each R Y is -OH, -C(O)OH, or a combination thereof (e.g., each R Y is -OH); wherein R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, optionally wherein R' is H or optionally substituted alkyl; and a is an integer of at least 2.

19. The ionic surfactant according to claim 18, wherein Y is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or a combination of any of these groups, for example, Y can be an alkylenearyl, heteroalkylenearyl, heteroalkyleneheteroaryl, or alkyleneheteroaryl group, optionally wherein Y is an alkylene, heteroalkylene, arylene, or heteroarylene group.

20. The ionic surfactant according to claim 18 or claim 19, wherein a is in the range of 2 to 8 or 2 to 6.

21. A method for producing a surfactant according to any one of claims 1 to 20, comprising the steps of: (i) reacting a monohydroxy-functional polyether with a carbonate catalyst, an epoxide and CO2 to produce a poly(carbonate ether); and (iii) modifying at least one end group of the poly(carbonate ether) to produce a surfactant according to the first aspect of the invention.

22. A method for producing the surfactant according to any one of claims 1 to 20, comprising the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a functional initiator compound to form a polycarbonate compound, (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to form a poly(carbonate ether); and (iii) modifying at least one end group of the poly(carbonate ether) to produce a surfactant.

23. A method for producing a surfactant according to any one of claims 1 to 20 in a multi-reactor system; the system comprising at least a first reactor and a second reactor, wherein: A first reaction occurs in the first reactor and a second reaction occurs in the second reactor; wherein the first reaction is a reaction of a carbonate catalyst with CO2 and an epoxide in the presence of a functional initiator compound and an optional solvent to produce a polycarbonate compound, and the second reaction is a semi-batch or continuous reaction of an ether catalyst with the polycarbonate compound and epoxide of the first reaction to produce a poly(carbonate ether), and the method also includes a third reaction that can occur in a third reactor, the third reaction comprising modifying at least one end group of the poly(carbonate ether) product to produce the surfactant.

24. The method according to any one of claims 21 to 23, wherein The one or more end groups of the poly(carbonate ether) are selected from OH, OR, OC(O)-R and / or OC(O)-OR; wherein each R is independently an optionally substituted (including heteroatoms) linear or branched or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl or aralkenyl group, optionally wherein the or each end group of the poly(carbonate ether) is OH or OMe, preferably OH.

25. The method according to any one of claims 21 to 24, wherein The step of modifying at least one end group of the poly(carbonate ether) introduces at least one ionic component to one or more end groups of the polymer compound.

26. The method according to claim 25, wherein The modification step comprises removing H or R from one or more end groups of the poly(carbonate ether) and replacing them with ionic components.

27. Use of a surfactant according to any one of claims 1 to 20 as an agrochemical, cosmetic or pharmaceutical adjuvant, excipient or auxiliary; in the preparation or functionalization of low-foaming detergents / cleaners, institutional cleaning and hygiene products, industrial cleaning products, personal care products, adhesives, metalworking fluids, paints and coatings, as an adjuvant or other agent or excipient in the construction, mining and oilfield industries, as a preparative or functional ingredient in microcapsules, batteries, crystal growth modifiers, biocontrol agents, demulsifiers, froth flotation systems, textiles, water treatment coatings, and in the processing of food and beverages.

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