surfactants

Abstract

発明は、式(I)のポリカーボネートまたはポリ(カーボネートエーテル)を含むイオン性表面活性剤に関し:A-((PC)P-(PE)Q-Z)X(I)式中:Aは官能性スターター化合物から誘導され;PCは式(II)のP個の繰り返し単位を有するカーボネートブロックを表し:【化1】TIFF2026506349000032.tif42159式中:Re1、Re2、Re3、およびRe4は全てHであり;またはRe1、Re2、Re3、およびRe4の1つはメチル、エチル、プロピル、ブチル、またはエーテル、エステルもしくはカーボネート基であり、Re1、Re2、Re3、およびRe4の残りの3つは全てHであり;PEは式(III)のQ個の繰り返し単位を有するポリエーテルブロックを表し:【化2】TIFF2026506349000033.tif34159式中:Re1’、Re2’、Re3’、およびRe4’は全てHであり;またはRe1’、Re2’、Re3’、およびRe4’の1つはメチル、エチル、プロピル、ブチル、またはエーテル、エステルもしくはカーボネート基であり、Re1’、Re2’、Re3’、およびRe4’の残りの3つは全てHであり;少なくとも1つのZはイオン性構成要素であり;そのまたは各Pの値は独立して1~50であり;そのまたは各Qの値は独立して0~50であり;ならびにXは1以上である。

Description

[Technical Field]

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

[0002] Ionic surfactants are typically produced from petrochemical feedstocks, including ammonium and sodium lauryl and lauryl ether sulfates, methyl ester sulfonates, ammonium and imidazolium salts, and phospholipids, all of which may emit significant amounts of CO2 during their manufacture or may otherwise lack environmental sustainability.

[0003] Surfactants combining 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. WO2010 / 062703A1 mentions examples having polyether and polycarbonate blocks, but these are not exemplified, and the blocks are not fully characterized or tested. WO2015 / 031348A1 also describes YO-APC-OC x H y Describes 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.

[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 are 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] US2020 / 0085059A1 describes antimicrobial cationic polycarbonates and polyurethanes containing one or more pendant guanidinium and / or isothiouronium groups.

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

[0008] WO2014 / 042924 describes an antibacterial composition comprising an anionic drug and an amine polymer, which is a primary amine-containing polycarbonate prepared by ring-opening polymerization with an organic catalyst.

[0009] Our co-pending application WO 2023 / 072843 A1 discloses surfactants containing polycarbonate block polyethers, 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 or each polycarbonate chain or block polyether. Our co-pending application GB 2301055.6 discloses surfactants containing polycarbonate block polyethers, which can be similarly prepared from polyfunctional starter compounds. These disclosures relate only to nonionic surfactants.

[0010] It would be beneficial to replace current entirely petrochemical and otherwise environmentally undesirable ionic 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. The incorporation of CO2 into these copolymers provides the surfactants with novel and beneficial properties, such as the opportunity for enhanced biodegradation. The incorporation of CO2-containing chains or blocks, even at longer chain lengths, can enhance the biodegradability of such surfactants.

[0011] It would also be beneficial to provide ionic surfactants with a high degree of flexibility in terms of chain length, chain hydrophobicity, 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 heretofore been achievable. 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: A-((PC) P -(PE) Q -Z) X (I) During the ceremony: A is derived from a functional 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 , 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: [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; at least one Z is an ionic component; the or each P value is independently 1 to 50; the or each Q value is independently 0 to 50; and X is 1 or greater.

[0013] The surfactant may comprise a block copolymer comprising individual PC and PE blocks; or it may comprise a random or statistical copolymer comprising only PC blocks (which may incorporate ether (PE) linkages). For the avoidance of doubt, the PC blocks of the block copolymer may (or may not) also comprise ether (PE) linkages, and the PE blocks of the block copolymer (if present) may (or may not) comprise carbonate (PC) linkages.

[0014] At least one Z may be anionic; in that case, the surface-active agent is an anionic surfactant.

[0015] Examples of anionic Z include O-[ION], OC(O)-[ION] and OC(O)-O-[ION], wherein [ION] is selected from sulfate, sulfonate, phosphate, hydrogen and dihydrogen phosphate, phosphorous acid, hypophosphorous acid, carboxylic acid, gluconate and suitable combinations of two or more thereof.

[0016] At least one Z may be cationic; in that case, the surface-active agent is a cationic surfactant.

[0017] Examples of cationic Z include [ION], O-[ION], OC(O)-[ION] and OC(O)-O-[ION], where [ION] is selected from nitrogen-containing moieties such as secondary, tertiary or quaternary ammonium, pyridinium, pyrrolinium, pyrrolidinium, imidazolium, guanidinium, piperazinium, piperidinium, phosphonium or sulfonium, and suitable combinations of two or more thereof.

[0018] At least one Z may be zwitterionic; in that case, the surface-active agent is a zwitterionic surfactant.

[0019] Examples of zwitterionic Z include any suitable combination of the anionic and cationic examples above. In other words, Z may include O-[ANION]-[CATION], OC(O)-[ANION]-[CATION], and OC(O)-O-[ANION]-[CATION], including [CATION]-[ANION], O-[CATION]-[ANION], OC(O)-[CATION]-[ANION], and OC(O)-O-[CATION]-[ANION], where [ANION] is selected from any suitable example of [ION] provided above for anionic surfactants, and where [CATION] is selected from any suitable example of [ION] provided above for cationic surfactants.

[0020] When the surfactant is anionic, a cationic counterion is typically provided in association therewith, which can be selected, for example, from alkali metal or alkaline earth metal cations, or from nitrogen-containing cations such as primary, secondary, tertiary, or quaternary ammonium ions, and suitable combinations of two or more thereof.

[0021] When the surfactant is cationic, an anionic counterion is typically provided in association therewith. This can be selected from, for example, halides, carboxylates, sulfates, nitrates, hydroxides, and suitable combinations of two or more thereof. In some circumstances, other types of anions, such as fluorine-containing anions [PF6], are also used. - , [BF4] - etc. may also be used.

[0022] If the surfactant is zwitterionic, a counterion may not be necessary.

[0023] The or each P may independently have a value of 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 independently has a value of 1 to 15.

[0024] The or each Q may independently have a value of 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 Q is independently 0 to 15.

[0025] In the present invention, the polymer chain A-((PC) P -(PE) Q ) X acts as a hydrophobizing agent and Z acts as a hydrophilizing agent. However, the hydrophobicity of the polymer chain can be adjusted by choosing the P:Q ratio (polycarbonates are more hydrophobic than polyethers), and thus the hydrophobicity of the chain can be controlled for suitability for the end use.

[0026] It will be apparent that if a monofunctional starter (e.g., a monool or polyalkylene glycol monoethyl ether) is selected, then X will be 1. By selecting a difunctional starter (e.g., a diol), X will be 2, and so on.

[0027] Preferably, X is 1, 2 or 3.

[0028] The monofunctional starter compound (from which A can be derived) is C1-C 30 Alcohols, C1-C 30 The monofunctional starter may be selected from 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 starter is an alcohol or carboxylic acid, it is preferably C1-C 11 , more preferably C2 to C 11 Alcohols or carboxylic acids, typically C 2-6 or C 2-4Typically, when the monofunctional starter compound is a polyalkylene glycol monoethyl ether, it is preferably a PEG or PPG monomethyl ether.

[0029] The polyfunctional starter compound (from which A can be derived) may be selected from compounds of the formula: Y(R Y ) a Y has two or more -R attached to it. Y Y 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, 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.

[0030] It will be appreciated that in this case a is an integer and is at least 2. Optionally, a ranges from 2 to 8, or from 2 to 4.

[0031] 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).

[0032] 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.

[0033] A is typically derived from a starter compound by removal of one or more hydrogen atoms and subsequent polymerization from the deprotonated derivative(s).

[0034] Also provided is 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 functional starter 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 according to the first aspect of the invention.

[0035] Also provided is a process for producing a surfactant according to the first aspect of the invention in a multiple reactor system; the system comprises at least first and second reactors, a first reaction occurring in the first reactor and a second reaction occurring in the second reactor; the first reaction is a carbonate-catalyzed reaction of CO and an epoxide in the presence of a functional starter compound, and optionally a solvent, to produce a polycarbonate compound; the second reaction is an ether-catalyzed semi-batch or continuous reaction of the polycarbonate compound of the first reaction and the epoxide to produce a poly(carbonate ether); and the process further comprises a third reaction, which may occur in a third reactor, comprising modifying at least one end group of the poly(carbonate ether) product to produce a surfactant according to the first aspect of the invention.

[0036] Alternatively, certain surfactants of the first aspect (derived from monofunctional starter compounds) may be formed by: (i) reacting a monohydroxy-functional polyether with a carbonate catalyst, an epoxide, and CO to form a poly(carbonate ether); and (iii) modifying at least one end group of the poly(carbonate ether) to form a surfactant according to the first aspect of the invention.

[0037] The end group(s) of the poly(carbonate ether) are or are selected from OH, OR, OC(O)—R, and / or OC(O)—OR; each R is independently an optionally substituted (e.g., with a heteroatom) linear, 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.

[0038] The step of modifying the compound in step (iii) preferably introduces at least one ionic moiety onto the end group(s) of the polymeric compound. Preferably, this step involves removing H or R from the end group(s) of the poly(carbonate ether) and replacing it with the ionic moiety. It is also contemplated that sequential steps of introducing the ionic moiety, such as chlorination followed by amination, may be included.

[0039] 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), it is sufficient for purposes of the invention that only one of the modifiable end groups be converted to an ionic substituent. However, it may be desirable for more than one, or even all, of such modifiable end groups to be modified by conversion to an ionic moiety.

[0040] In the unlikely event that fewer than all of the modifiable end groups are so modified, in the compounds of the claimed invention, Z contains an ionic substituent for each such modified substituent, and the remaining Z contains unmodified end groups (as described above) of the polycarbonate or poly(carbonate ether).

[0041] Furthermore, it will be apparent that, regardless of whether the surfactants of the invention are derived from monofunctional or polyfunctional starters, ionic substituents need not be provided on all available termini of the poly(carbonate) ether. The conditions of the invention are met as long as at least some of the available end groups are functionalized with the introduction of ionic moieties.

[0042] In PC chains containing multiple Re groups, the individual Re groups may be different in different sections or blocks of the chain. In PE chains containing multiple Re' groups, the individual Re' groups may be different in different sections or blocks of the chain.

[0043] For example, in the process according to the invention, if a mixture of propylene and ethylene oxide is used as the epoxide in the first reaction, 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 sections or blocks). The same applies mutatis mutandis to the PE chain.

[0044] According to the invention there is also provided uses of said surfactants as adjuvants, excipients or auxiliaries in pesticides, cosmetics or pharmaceuticals; for preparing or functionalizing low foaming detergents / cleaners, institutional cleaning & sanitation products, industrial cleaning products, personal care products, adhesives, metal working fluids, paints & coatings, as auxiliary or other reagents or excipients in the construction, mining and oil field industries, as preparing or functional ingredients in microcapsules, batteries, crystal growth regulators, biocontrol agents, demulsifiers, froth flotation systems, textiles, water treatment coatings and in food & beverage processing. DETAILED DESCRIPTION OF THE INVENTION

[0045] 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%, 10-40 wt%, 15-40 wt%, 20-40 wt%, typically 10-35 wt%, more typically 15-30 wt%.

[0046] It will be appreciated that if the surfactant is a block copolymer (i.e., Q is other than zero), the carbonate block of the block copolymer is hydrophobic and the ether block is hydrophilic. Adjusting the relative ratio of the two blocks will alter the properties of the copolymer, resulting in a surfactant that can be tailored to the end use.

[0047] It will also be appreciated that whether or not the surfactants of the invention are block copolymers, the hydrophobicity of the polymer chain can be adjusted by incorporating ether linkages into the PC blocks and / or carbonate linkages into the PE blocks (if present).

[0048] 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 component, the epoxide is ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, preferably ethylene oxide or propylene oxide. Preferably, in producing the polyether component, the epoxide is ethylene oxide or propylene oxide, or mixtures thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0049] It will also be appreciated that when a mixture of epoxides is used, the epoxides will typically be statistically distributed along the polymer backbone.

[0050] Thus, when a mixture of epoxides is used, the polycarbonate and polyether chains may be referred to as random or statistical copolymers, respectively.

[0051] R e1 、 R e2 、 R e3 , R e4 、 R e1’ 、 R e2’ 、 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, Re1 、 R e2 、 R e3 , R e4 、 R e1’ 、 R e2’ 、 R e3’ , and R e4’ is H.

[0052] 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 component, 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.

[0053] 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.

[0054] 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.

[0055] In block copolymers, 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.

[0056] 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.

[0057] 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 Mn ranging from 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.

[0058] 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.

[0059] 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.

[0060] For the avoidance of doubt, when the polycarbonate block contains an ether linkage, the polycarbonate block has the formula [ka] The PC block will not contain only P repeat units, i.e., 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.

[0061] It will be apparent that when Q is zero, the surfactant of the invention comprises an ionic polycarbonate, which may (or may not) incorporate ether linkages as random or statistical bonds in the polycarbonate chain.

[0062] 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%.

[0063] Optionally, the polyether block contains only ether linkages. Typically, the or each polyether chain or block is at least 90% derived from epoxides, typically at least 95% derived, more typically at least 99%, and most typically 100% derived.

[0064] 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.

[0065] 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 or each 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.

[0066] Typically, the polycarbonate blocks are derived from epoxide and CO2. More typically, epoxide 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 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.

[0067] 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.

[0068] The values ​​of P and Q in formula I may be adapted as needed for the end use, with Q being zero in some applications.

[0069] The epoxide used in the process for producing the surfactant of the invention may be selected from ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, glycidyl ether, glycidyl ester or glycidyl carbonate, or a mixture of two or more thereof. Typically, the epoxide is selected from ethylene oxide, propylene oxide or a mixture thereof, preferably ethylene oxide.

[0070] In the process of the invention, the carbonate catalyst may be heterogeneous or homogeneous.

[0071] The carbonate catalyst may be a monometallic, bimetallic, or multimetallic homogeneous complex, or may be a non-metallic Lewis acid-base pair (e.g., based on a combination of borane and an ammonium salt, as disclosed in 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 in WO2021123761.

[0072] The carbonate catalyst may include a phenol or phenolate ligand.

[0073] 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.

[0074] 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.

[0075] The term polydentate ligand includes bidentate, tridentate, tetradentate and higher dentate ligands. Each polydentate ligand may be a macrocyclic or open ligand.

[0076] 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), JP2008081518A No. 6,133,402A (Metal β-Diiminate Complexes) and US8,278,239 (Metal Salesens 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.

[0077] 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.

[0078] 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 BF3 or BH3, anionic catalysts such as KOH, cationic, acidic or superacidic catalysts (e.g., HSbF6, 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 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.

[0079] The ratio of carbonate catalyst to ether catalyst may be in the range of about 300:1 to about 1:100, for example, about 120:1 to about 1:75, for example, about 40:1 to about 1:50, for example, about 30:1 to about 1:30, for example, about 20:1 to about 1:1, for example, about 10:1 to about 2:1, for example, about 5:1 to about 1:5. These ratios are by mass.

[0080] The process may be carried out in a one-pot reactor, or as previously mentioned, may be a dual reactor process (multi-stage reaction system).

[0081] 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 or each polyether chain or block 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 or each polyether chain or block produced in the second step is substantially free of carbonate linkages.

[0082] Typically, therefore, the second step is carried out substantially in the absence of CO2.

[0083] 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.

[0084] Adding components in separate steps 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 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.

[0085] 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.

[0086] Typically, 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.

[0087] 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.

[0088] 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 for each reactor can be adjusted to optimize the reaction for each catalyst.

[0089] 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.

[0090] It may also be useful to separate the reactions using two different catalysts, mixing only certain components in the first reaction and adding the rest in the second reaction, for example, by adding a pre-activated ether catalyst or by adding the reaction mixture to a pre-activated ether catalyst.

[0091] The preferred ether catalysts and carbonate catalysts are the same as those in the second aspect of the invention.

[0092] 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.

[0093] The product of the first reaction may be stored for subsequent use in a second reactor.

[0094] 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.

[0095] 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 1-20The 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.

[0096] 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.

[0097] The carbonate group is optional -OC(O)OR 2 and R 2 R can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 2 may be optionally substituted aliphatic, alicyclic, or aryl. 2is 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.

[0098] The carbonate functional group is —OC(O)O— and can be derived from any suitable source. Generally, it is derived from CO2.

[0099] 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.

[0100] 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 their detection, isolation, and / or use in chemical synthesis.

[0101] 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.

[0102] 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).

[0103] 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.

[0104] 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.

[0105] 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 the material stream 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, for example, to refill or replace the containers from which the materials are being added.

[0106] 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 reactants 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.

[0107] A continuous reaction can employ continuous addition of materials.

[0108] A continuous reaction can employ discontinuous (ie, batch or semi-batch) addition of materials.

[0109] 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.

[0110] 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, the conditions in both reactors affect the other.

[0111] Example Example 1 Non-ionic precursors of the compounds according to the invention were prepared from monofunctional starter compounds as follows: 100 mL of mono-all starter was added to a Parr™ high-pressure reactor system. The vessel was heated to 100° C. under vacuum for 60 minutes, then cooled and dried by filling with low-pressure CO. Catalyst (1) prepared according to Example 2 of WO 2017 / 037441 was added.

[0112] To the mixture was added epoxide (propylene oxide [PO] or ethylene oxide [EO]). The mixture was stirred and pressurized to approximately half the target pressure. The mixture was then heated to the target temperature and pressure and maintained at a constant temperature and target pressure.

[0113] At the end of the desired reaction time, the mixture was cooled to <10° C. and discharged through an acid scrubber system. [Table 1]

[0114] Example 2 Response 1: Non-ionic precursors of the compounds according to the invention were prepared from monofunctional starter compounds as follows: 100 mL of mono-all starter was added to a Parr™ high-pressure reactor system. The vessel was heated to 100° C. under vacuum for 60 minutes, then cooled and dried by filling with low-pressure CO. Catalyst (1) prepared according to Example 2 of WO 2017 / 037441 was added.

[0115] To the mixture was added epoxide (propylene oxide [PO] or ethylene oxide [EO]). The mixture was stirred and pressurized to approximately half the target pressure. The mixture was then heated to the target temperature and pressure and maintained at a constant temperature and target pressure.

[0116] At the end of the desired reaction time, the mixture was cooled to <10° C. and discharged through an acid scrubber system.

[0117] Reaction 2: Pre-dried mono-all starter and DMC composed of zinc hexacyanocobaltate and tert-butyl alcohol were added to a 100 mL Parr™ high-pressure reactor system. The vessel was kept under vacuum for approximately 2 minutes, after which it was filled with low-pressure N2, followed by anhydrous ethyl acetate (15 mL).

[0118] The vessel was then heated with stirring to 130° C. and the DMC was activated with two portions of approximately 0.3 g epoxide (EO or PO). After activation (as evidenced by a pressure drop), the external heater was removed, and optionally the reactor could be pressurized with CO, and the mixture was then cooled to the target addition temperature.

[0119] Once the target temperature was reached, the mixture from reaction 1 and the epoxide (EO or PO) were added to the activated DMC system over approximately 60-90 minutes. Once addition of the mixture was complete, the mixture was allowed to "cook-out" for several hours, after which it was cooled, discharged, and sampled for analysis by NMR and GPC. [Table 2] [Table 3] [Table 4]

[0120] Example 3 Non-ionic precursors of compounds according to the invention were prepared by the following sequential reaction scheme: [ka] Response 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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 + base was held under vacuum (approximately 1 mbar) for approximately 2 minutes, then charged via syringe with low-pressure N2, followed by anhydrous ethyl acetate (15 mL).

[0125] This DMC / starter / ethyl acetate mixture was then heated with stirring to 130°C and the DMC was activated with two slugs of approximately 0.3 g 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 1.2 g PO total].

[0126] Once the target temperature was reached, the mixture from Reaction 1 was added (semi-batch mode) onto the activated DMC system over approximately 60-90 minutes. Once the addition of the mixture was complete, the mixture was allowed to "cook out" for several hours, after which it was cooled, discharged, and sampled for analysis by NMR and GPC.

[0127] The results are shown in Tables 5 to 7 below. [Table 5] [Table 6] [Table 7]

[0128] Example 4 Anionic surfactants according to the invention are prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] Notes (for each of Examples 4-10): m represents the chain length of the starter compound In the illustrated scheme, only one polymer chain extending from the starter compound is shown. It will be apparent that one or more additional polymer chains may be present depending on the functionality of the starter. In other embodiments of the invention, q may be zero.

[0129] To the poly(carbonate ether) polymer in anhydrous CHCl (0.5 g / mL) at 0 °C, chlorosulfonic acid (1 equiv.) was added dropwise. The reaction mixture was warmed to RT and stirred overnight. The solvent was concentrated to dryness. To the resulting polymer mixture, 10% NaOH in EtOH (0.5 g / mL) was added and stirred for 1 h. The resulting solid was filtered, washed with MeOH, and then dried under vacuum to give the sodium salt of the sulfonated polymer.

[0130] Sulfation of polymers can also be carried out by those skilled in the art using SO as the sulfiding agent. Typically, an alcohol-terminated polymer is reacted with SO in air at temperature, followed by neutralization with a base such as NaOH or ammonia in a continuous process.

[0131] Phosphorylation of polymers can also be carried out using techniques known to those skilled in the art. Typically, alcohol-terminated polymers are reacted with polyphosphoric acid / phosphorus pentoxide under cold conditions, followed by a period of heating. Phosphates can be obtained by basic treatment, for example, with NaOH or ammonia. [ka]

[0132] Example 5 Cationic surfactants according to the invention are prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] Note: q can be zero.

[0133] To the poly(carbonate ether) polymer, SOCl (0.5 g / mL) is added and the reaction is heated to reflux for 2 hours, after which the mixture is concentrated to dryness and washed with toluene. The resulting polymer is dissolved in THF (0.5 g / mL) and trimethylamine (1 equivalent) and stirred at reflux overnight. The resulting solid is filtered, washed with EtOH, and then dried under vacuum to give the chloride salt of the cationic polymer. [ka]

[0134] Example 6 Cationic surfactants according to the invention are prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] The mono-ol product from Example 1 is dissolved in dichloromethane containing triethylamine (1.3 equivalents) and nicotinic anhydride (1.05 equivalents) and allowed to react at reflux for 16 hours. The end-capped mono-ol is washed with water and brine, dried over sodium sulfate, and concentrated to dryness in vacuo to give the desired precursor product. The ethylene carbonate by-product is removed using a Kugelrohr or short-path evaporator (SPE). The precursor mono-ol is dissolved in acetone (0.05 g / mL) with methyl iodide (3 equivalents) and stirred at reflux for 1 hour. After cooling to room temperature, the resulting salt is collected by filtration and washed with cold acetone to give the cationic mono-ol.

[0135] Example 7 Zwitterionic surfactants according to the invention are prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: The procedure of Example 5 above is repeated incorporating β-alanine (instead of trimethylamine) to produce a zwitterionic polymer. [ka]

[0136] Example 8 Anionic surfactants according to the invention were prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] To the polycarbonate polymer in DCM (0.5 g / mL) was added succinic anhydride (1.1 equiv.) and EtN (1.1 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 (MgSO) and concentrated by rotary evaporation. To this product, either NaCO or KCO was added, and the mixture was stirred in THF (0.5 g / mL) at RT overnight. The sodium or potassium salt was isolated by concentrating the reaction mixture by rotary evaporation. [Table 8]

[0137] Example 9 Cationic surfactants according to the invention were prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] To the polycarbonate polymer in DCM (0.5 g / mL) was added alanine (1.1 equiv.) and EtN (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 (MgSO) and concentrated by rotary evaporation. To this product was added HCl, and the mixture was stirred in H2O (0.5 g / mL) at RT. The chloride salt was isolated by concentrating the reaction mixture by rotary evaporation. [Table 9]

[0138] Example 10 Zwitterionic surfactants according to the invention are prepared from the nonionic precursor compounds prepared above in Examples 1-3 according to the following scheme: [ka] To polycarbonate polymer in DCM (0.5 g / mL) was added succinic anhydride (1.1 equiv.) and EtN (1.1 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 (MgSO) and concentrated by rotary evaporation.

[0139] To the intermediate product in DCM (0.5 g / mL) was added alanine (1.1 equiv.) and EtN (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 (MgSO) and concentrated by rotary evaporation.

[0140] To this product was added either Na2CO3, K2CO3, HCl, or acetic acid, and the mixture was stirred in THF (0.5 g / mL) at RT overnight. The individual anionic sodium and potassium salts, and the cationic chloride and acetate salts, respectively, were isolated by concentrating the reaction mixture by rotary evaporation. [Table 10]

Claims

1. 1. An ionic surfactant comprising a polycarbonate or poly(carbonate ether) of Formula I: _(()) Ｐ (!) Ｑ ) Ｘ () During the ceremony: A is derived from a functional starter compound; PC represents a carbonate block having P repeating units of the formula: 【Chemistry 1】 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 2】 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; At least one Z is an ionic entity; the or each value of P is independently 1 to 50; the or each value of Q is independently 0 to 50; and X is 1 or greater, an ionic surfactant.

2. 10. The ionic surfactant of claim 1, wherein the polymer chain(s) of the surfactant comprises a block copolymer comprising individual PC and PE blocks.

3. 3. The ionic surfactant of claim 2, wherein the PC block of the block copolymer can include an ether (PE) linkage and the PE block of the block copolymer (if present) can include a carbonate (PC) linkage.

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

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

6. 6. The ionic surfactant of claim 5, wherein the at least one Z is selected from O-[ION], O-C(O)-[ION] and O-C(O)-O-[ION], wherein [ION] is selected from sulfate, sulfonate, phosphoric acid, hydrogen and dihydrogen phosphate, phosphorous acid, hypophosphorous acid, carboxylic acid, gluconic acid, and suitable combinations of two or more thereof.

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

8. 8. The cationic surfactant of claim 7, wherein said at least one Z is selected from [ION], O-[ION], O-C(O)-[ION] and O-C(O)-O-[ION], wherein [ION] is selected from a nitrogen-containing moiety, such as a primary, secondary, tertiary or quaternary ammonium ion, pyridinium, pyrrolinium, pyrrolidinium, imidazolium, guanidinium, piperazinium, piperidinium, from phosphonium or sulfonium, or from any suitable combination of two or more thereof.

9. 5. The ionic surfactant of claim 1, wherein at least one Z is zwitterionic.

10. 10. An ionic surfactant according to claim 9, wherein said at least one Z is selected from O-[ANION]-[CATION], O-C(O)-[ANION]-[CATION]; O-C(O)-O-[ANION]-[CATION], [CATION]-[ANION], O-[CATION]-[ANION], O-C(O)-[CATION]-[ANION] and O-C(O)-O-[CATION]-[ANION], wherein [ANION] is selected from any suitable [ION] according to claim 6 and wherein [CATION] is selected from any suitable [ION] according to claim 8.

11. 7. An ionic surfactant according to claim 5 or claim 6 provided in association with at least one cationic counterion.

12. 12. The ionic surfactant of claim 11, wherein said 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. 9. The cationic surfactant of claim 7 or claim 8 provided in association with at least one anionic counterion.

14. 14. The cationic surfactant of claim 13, wherein said at least one anionic counterion is selected from a halide, a carboxylate.

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

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

17. A is C １ ~C １１ Alcohol, or C １ ~C １１ Ionic surfactants according to any one of claims 1 to 16, which are derived from monofunctional starter compounds selected from carboxylic acids or monofunctional polyethers, such as polyalkylene glycol monomethyl ethers.

18. 17. The ionic surfactant according to claim 1, wherein A is derived from a polyfunctional starter compound selected from compounds of the formula: Y(R Ｙ ) ａ During the ceremony: Y has two or more -R Ｙ is selected from any group that can have a group; Each R Ｙ are independently —OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), —PR′(O)(OH) ２ or —PR′(O)OH, 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); R' may be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, optionally R' is H or an optionally substituted alkyl; and a is an integer and is at least 2;

19. 19. The ionic surfactant of claim 18, wherein Y is selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Y can be a combination of any of these groups, e.g., Y can be an alkylarylene, heteroalkylarylene, heteroalkylheteroarylene, or alkylheteroarylene group, and optionally Y is alkylene, heteroalkylene, arylene, or heteroarylene.

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

21. 21. A process for producing the surfactant of any one of claims 1 to 20, comprising: (i) reacting a monohydroxy-functional polyether with a carbonate catalyst, an epoxide, and CO ２ to form a poly(carbonate ether); and (iii) modifying at least one end group of said poly(carbonate ether) to form a surfactant according to the first aspect of the invention.

22. 21. A process for producing the surfactant of 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 starter 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.

23. 21. A process for producing the surfactant of any one of claims 1 to 20 in a multiple reactor system; the system comprising at least 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 functional starter compound, and optionally a solvent, to produce a polycarbonate compound; the second reaction is a semi-batch or continuous reaction of the polycarbonate compound of the first reaction with an ether catalyst and an epoxide to produce a poly(carbonate ether); the process further comprises a third reaction, which may occur in a third reactor, that modifies at least one end group of the product of the poly(carbonate ether) to produce the surfactant.

24. 24. The process of any one of claims 21 to 23, wherein the end group(s) of the poly(carbonate ether) are or are selected from OH, O-R, O-C(O)-R, and / or O-C(O)-O-R; each R is independently an optionally substituted (e.g., with a heteroatom) linear or branched or cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, alkenaryl, or aralkenyl group, and optionally the or each end group of the poly(carbonate ether) is OH or OMe, preferably OH.

25. 25. The process of any one of claims 21 to 24, wherein the step of modifying the at least one end group of the poly(carbonate ether) introduces at least one ionic component onto the end group(s) of the polymeric compound.

26. 26. The process of claim 25, wherein the modifying step comprises removing H or R from the end group(s) of the poly(carbonate ether) and replacing it with an ionic component.

27. 21. Use of a surfactant according to any one of claims 1 to 20 as an adjuvant, excipient or auxiliary in pesticides, cosmetics or pharmaceuticals; for preparing or functionalizing low foaming detergents / cleaners, institutional cleaning & hygiene products, industrial cleaning products, personal care products, adhesives, metalworking fluids, paints & coatings, as an auxiliary or other reagent or excipient in the construction, mining and oilfield industries, as a preparing or functional ingredient in microcapsules, batteries, crystal growth regulators, biocontrol agents, demulsifiers, froth flotation systems, textile and water treatment coatings, and in food & beverage processing.

Images