Surface-active agent

Abstract

The present invention relates to surfactants comprising polycarbonate block polyethers of formula (I): Z1-(PC) P-(PE) Q-Z2 (I) wherein PC represents a carbonate block having P repeating units of formula (I) wherein Re1, Re2, Re3 and Re4 are independently selected from H, methyl, ethyl, propyl, butyl or ether, ester or carbonate groups, with the proviso that when one of Re1, Re2, Re3 and Re4 is methyl, ethyl, propyl, butyl or ether, ester or carbonate groups, R1 represents a methyl group, ethyl group, propyl group, butyl or ether, ester or carbonate group, and R2 represents a methyl group, ethyl group, propyl group, butyl or ether, ester or carbonate group. The remaining Re1, Re2, Re3 and Re4 are H; pE represents a polyether block having Q repeating units of formula (II) wherein Re1 ', Re2', Re 3 'and Re4' are independently selected from H, methyl, ethyl, propyl, butyl or ether, ester or carbonate groups, with the proviso that when one of Re1 ', Re2', Re 3 'and Re4' is methyl, ethyl, propyl, butyl or ether, ester or carbonate group, the remaining Re1 ', Re2', Re 3 'and Re4' is H; z1 is R, R-O, R-C (O)-O-or R-O-C (O)-O; r is an optionally substituted straight chain or branched chain C1-C11 alkyl group; z2 is H, R, R-(O) C or R-O-(O) C; and wherein the value of P is greater than the value of Q. (I) (II)

Description

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202480028160.9 (22) Application Date 2024.04.23 (30) Priority Data 2306045.2 2023.04.25 GB (85) PCT International Application Entering National Phase Date 2025.10.24 (86) PCT International Application Application Data PCT / EP2024 / 061012 2024.04.23 (87) PCT International Application Publication Data WO2024 / 223521 EN 2024.10.31 (71) Applicant: Econik Technology Ltd. Address: Cheshire, UK (72) Inventors: Michael Kemper, Ancia Blackburn, Charlotte Williams (74) Patent Agency: Beijing Gaowo Law Firm 11569 Patent Attorney Zhao Xiaolin (51) Int.Cl. C08G 64 / 02 (2006.01) C08G 64 / 18 (2006.01) C08G 64 / 34 (2006.01) (54) Invention Title Surfactant (57) Abstract This invention relates to a surfactant comprising a polycarbonate block polyether of formula (I): Z1-(PC)P-(PE)Q-Z2 (I), wherein PC represents a carbonate block having P repeating units of formula (I), wherein Re1, Re2, Re3 and Re4 are independently selected from H, methyl, ethyl, propyl, butyl or ether, ester or carbonate, provided that Re1, Re2, Re3 and Re4 When one of them is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining Re1, Re2, Re3, and Re4 are H; PE represents a polyether block having Q repeating units of formula (II), wherein Re1', Re2', Re3', and Re4' are independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, provided that when one of Re1', Re2', Re3', and Re4' is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining Re1', Re2', Re3', and Re4' are H; Z1 is R, R-O, R-C(O)-O-, or R-O-C(O)-O; R is an optionally substituted straight-chain or branched C1-C11 alkyl group; Z2 is H, R, R-(O)C, or R-O-(O)C; and wherein the value of P is greater than the value of Q. (I) (II) Claims 2 pages Description 13 pages CN 121013876 A 2025.11.25 CN 1 21 01 38 76 A 1. Surfactant comprising polycarbonate block polyether of formula I: Z1-(PC)P-(PE)Q-Z 2 (I)Wherein, PC represents a carbonate block having P repeating units of the following formula: , wherein Re1, Re2, Re3, and Re4 are independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, provided that when one of Re1, Re2, Re3, and Re4 is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining Re1, Re2, Re3, and Re4 are H; PE represents a polyether block having Q repeating units of the following formula: , wherein Re1', Re2', Re3', and Re4' are independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, provided that when one of Re1', Re2', Re3', and Re4' is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining Re1', Re2', Re3', and Re4' are H; Z1 is R, R-O, R-C(O)-O-, or R-O-C(O)-O; R is an optionally substituted straight-chain or branched C1 to C11 alkyl group; Z2 is H, R, R-(O)C, or R-O-(O)C; and wherein the value of P is greater than the value of Q. 2. The surfactant according to claim 1, wherein R is a C2 to C11 alkyl group. 3. The surfactant according to any one of the preceding claims, wherein R is a straight-chain alkyl group. 4. The surfactant according to any one of claims 1 to 3, wherein R is a C2 to C6 alkyl group, typically a C2 to C5 alkyl group or a C2 to C4 alkyl group. 5. The surfactant according to any one of claims 2 to 4, wherein Re1, Re2, Re3, Re4, Re1', Re2', Re3', and Re4' are independently selected from H, methyl, or ethyl, preferably wherein Re1, Re2, Re3, Re4, Re1', Re2', Re3', and Re4' are each H. 6. The surfactant according to any one of the preceding claims, wherein Z1 is R-C(O)-O or R-O-C(O)-O, preferably a short-chain (e.g., C2 to C5 or C2 to C4) carbonate or ester R-O. 7. The surfactant according to any one of the preceding claims, wherein Z2 is H or methyl. 8. The surfactant according to any one of the preceding claims, wherein the total surfactant has a CO2 incorporation of greater than 10 wt%, more typically greater than 15 wt%, 20 wt%, or 21 wt%. 9. The surfactant according to any one of the preceding claims, wherein the total surfactant has a CO2 incorporation of 10 wt% to 40 wt%, typically 15 wt% to 40 wt%, more typically 20 wt% to 40 wt%.10. The surfactant according to any one of the preceding claims, wherein the difference between the value of P and the value of Q is about 1 to about 10, or about 1 to about 5, or about 1 to about 3. 11. The surfactant according to any one of the preceding claims, wherein the ratio of P to Q is not greater than about 1.3:1, not greater than about 1.25:1, not greater than about 1.2:1, more preferably not greater than about 1.15:1, even more preferably not greater than about 1.125:1, and most preferably not greater than about 1.1:1. 12. The surfactant according to any one of the preceding claims, wherein the polyether block has less than 40% carbonate bonds, preferably less than 30%, less than 20%, less than 10%, less than 5%, less than 2%, or less than 1%. 13. The surfactant according to any one of the preceding claims, wherein the polyether block has 0% carbonate bonds. 14. The surfactant according to any one of the preceding claims, wherein the surfactant is water-soluble. 15. The surfactant according to any one of the preceding claims, wherein the surfactant has water solubility of at least about 0.01 g / mL, at least about 0.05 g / mL, or at least about 0.1 g / mL at room temperature and pressure. 16. The surfactant according to any one of the preceding claims, wherein the surfactant is water solubility at a concentration of 0.01 g / mL, at a concentration of 0.05 g / mL, and / or at a concentration of 0.1 g / mL at room temperature and pressure. 17. A method for preparing the surfactant according to any one of claims 1 to 16, wherein the method comprises the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional starting compound to form a polycarbonate compound, and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to prepare the surfactant according to any one of claims 1 to 16. 18. A method for preparing the surfactant of any one of claims 1 to 16 in a multi-reactor system; said system comprising 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 monofunctional starting compound and optionally a solvent to prepare a polycarbonate compound, and the second reaction is a semi-batch or continuous reaction of an ether catalyst with said polycarbonate compound and epoxide of the first reaction to prepare the surfactant of any one of claims 1 to 16. 19. The method of claim 17 or claim 18, wherein the carbonate catalyst is a bimetallic phenolic complex. 20. The method of any one of claims 17 to 19, wherein the ether catalyst is a DMC catalyst.21. A method for preparing a surfactant according to any one of claims 1 to 16, wherein a monohydroxy functional polyether is reacted (i) with a carbonate catalyst, an epoxide, and CO2, and (ii) with a capping group (such as an anhydride) to prepare a surfactant according to any one of claims 1 to 20. 22. The surfactant according to any one of claims 1 to 16 is used for: as an agricultural chemical adjuvant; for the preparation of foams, coatings, paints, adhesives, and sealants in the construction industry; for use in the automotive industry; for use in the preparation of textiles; and for enhancing oil recovery. Claims 2 / 2 pages 3 CN 121013876 A Surfactant Technology Field

[0001] The present invention relates to surfactants, catalysts, methods for their preparation, and some applications. Background Art

[0002] Nonionic surfactants are typically prepared using monohydric alcohol starting materials having large hydrophobic blocks. Examples include palm oil alcohol having hydrophobic blocks. The use of palm oil has led to the deforestation of other plant species and correspondingly reduced the natural habitats of many endangered species. Therefore, alternatives to palm oil alcohol and its analogues (C12-C20 alcohols) are being sought.

[0003] Surfactants combining polyether and polycarbonate blocks are known in the field of oil extraction. WO2010 / 062703 and WO2015 / 031348 describe polymer compositions and supercritical CO2 solutions of various such polymers to facilitate oil extraction. This solution forms an emulsion waste with water to facilitate oil extraction. No mention is made of the water solubility and uses of such water-soluble polymers. The polymer compositions are designed to dissolve in liquid or supercritical CO2 applications. WO2010 / 062703 mentions examples having polyether and polycarbonate blocks, but this is not illustrative, and the blocks are not characterized or tested at all. WO2015 / 031348 describes polycarbonate blocks having the following type:

[0004] Y-O-APC-O-CxHy

[0005] where APC is polycarbonate and CxHy is a saturated or unsaturated hydrocarbon. The terminal group Y can be H or several other groups such as a polyether chain, but the latter is not exemplified or further defined.

[0006] US2021309801A1 discloses biodegradable ethylene oxide copolymers prepared by boron-activated copolymerization of ethylene oxide monomers and carbon dioxide, and their use as surfactants. Some triblock amphiphilic compounds are reported.

[0007] GB2612195A discloses a method for preparing a surfactant, comprising (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst (such as a bimetallic phenolic complex) and a monofunctional initiator to form a polycarbonate compound, and (ii) reacting the formed polycarbonate compound with an epoxide and an ether catalyst (such as a DMC catalyst) to produce a surfactant.Surfactants. Surfactants are also disclosed as agricultural chemical adjuvants; for the preparation of foams, coatings, paints, adhesives, sealants, and for enhancing oil recovery.

[0008] US2019 / 0382528A1 discloses a method for preparing high molecular weight polyether carbonates by reacting an epoxide with carbon dioxide in the presence of a bimetallic complex catalyst and a bimetallic cyanide (DMC) catalyst.

[0009] US4415502A discloses a polycarbonate-type nonionic surfactant composition comprising a monohydroxy alcohol terminated with a polycarbonate group. More specifically, the surfactant composition comprises an aliphatic, non-aromatic alicyclic, or aromatic alcohol terminated with a block polycarbonate group, formed by reacting said alcohol with ethylene carbonate in the presence of an alkali metal salt catalyst.

[0010] It would be beneficial to replace existing aqueous nonionic surfactants with lower hydrocarbon sources (derived from fossil fuels or plant sources such as palm oil) as the hydrophobic moiety, which are less costly, more readily available, and can be prepared from biological sources (such as bioethanol or butanol).

[0011] Surprisingly, the inventors have discovered that by changing the relative structure of the polycarbonate block polyether backbone, lower hydrocarbon alcohols can be used to form hydrophobic groups together with the polycarbonate moiety to provide aqueous surfactants without the need for higher hydrocarbon alcohol derivatives. Specification 1 / 13 Page 4 CN 121013876 A Summary of the Invention

[0012] According to a first aspect of the invention, a surfactant comprising a polycarbonate block polyether of formula I is provided:

[0013] Z1-(PC)P-(PE)Q-Z2 (I)

[0014] wherein PC represents a carbonate block having P repeating units of the following formula:

[0015]

[0016] wherein Re1, Re2, Re3 and Re4 are independently selected from H, methyl, ethyl, propyl, butyl or ether, ester or carbonate, provided that when one of Re1, Re2, Re3 and Re4 is methyl, ethyl, propyl, butyl or ether, ester or carbonate, the remaining Re1, Re2, Re3 and Re4 are H;

[0017] PE represents a polyether block having Q repeating units of the following formula:

[0018]

[0019] Wherein Re1', Re2', Re3', and Re4' are independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate groups, provided that when one of Re1', Re2', Re3', and Re4' is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining Re1', Re2', Re3', and Re4' are H;

[0020] Z1 is R, R-O, R-C(O)-O, or R-O-C(O)-O;

[0021] R is an optionally substituted straight-chain or branched C1-C11 alkyl group;

[0022] Z2 is H, R, R-(O)C, or R-O-(O)C; and

[0023] wherein the value of P is greater than the value of Q.

[0024] Preferably, Z1 is R-C(O)-O or R-O-C(O)-O. Preferably, Z1 is a short-chain (e.g., C2-C5 or C2-C4) carbonate group or ester group.

[0025] Preferably, Z2 is H or methyl.

[0026] In this invention, the polycarbonate block acts as a hydrophobic group, and the polyether block acts as a hydrophilic group. Therefore, when preparing a surfactant according to the first aspect of the invention, the starting molecule need not be a large molecular hydrocarbon chain (e.g., found in palmitole alcohol and other long-chain alcohols), but can be a short-chain alcohol or other starting material used to initiate the synthesis of the polycarbonate block using a carbonate catalyst, followed by the synthesis of the polyether block using an ether catalyst. Lower alcohol starting materials are not only less expensive but also more environmentally sustainable.

[0027] Alternatively, it can be prepared by a monohydroxy functionalized polyether, which can be used as an initiator for synthesizing polycarbonate blocks using a carbonate catalyst, to generate polycarbonate block polyethers via an alternative pathway without the need for long-chain or short-chain alcohol starting materials. If this method is used for preparation, it is preferable to end-cap the polycarbonate blocks (e.g., by reaction with acid anhydrides) to enhance their stability under alkaline conditions and prevent polycarbonate block degradation. Surprisingly, it has been found that using a properly balanced combination of hydrophobic polycarbonate and hydrophilic polyether blocks provides an alternative surfactant with greater design flexibility, which is no longer dependent on environmentally harmful higher alcohols. This makes it possible to prepare surfactants with smaller end-hydroxyl groups (see specification 2 / 13 pages, 5 CN 121013876 A).

[0028] A method for preparing a surfactant according to the first aspect of the invention is also provided, the method comprising the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional starting compound to form a polycarbonate compound, and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to prepare a surfactant according to the first aspect of the invention.

[0029] A method for preparing a surfactant according to the first aspect of the invention is also provided in a multi-reactor system; the system comprising 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 to react a carbonate catalyst with CO2 and an epoxide in the presence of a monofunctional starting compound and an optional solvent to prepare a polycarbonate compound, and the second reaction is to react an ether catalyst with the polycarbonate compound and the epoxide of the first reaction in a semi-batch or continuous manner to prepare a surfactant according to the first aspect of the invention.

[0030] According to the invention, the use of the above-described surfactant is also provided: as an agricultural chemical adjuvant; for use in the preparation of building materials.Industrial foams, coatings, paints, adhesives, and sealants; used in the automotive industry; used in the preparation of textiles; used to enhance oil recovery. Detailed Description

[0031] Preferably, the CO2 incorporation of the surfactant is greater than 10 wt%, more typically, greater than 15 wt%, 20 wt%, or 21 wt%. Preferably, the CO2 incorporation of the surfactant is from 10 wt% to 40 wt%, typically from 15 wt% to 40 wt%, more typically from 20 wt% to 40 wt%. (The CO2 incorporation in wt% can be determined by 1H NMR spectroscopy as described, for example, in US20140323670).

[0032] The epoxides in the polycarbonate blocks and polyether blocks are independently selected from ethylene oxide (EO), propylene oxide (PO), butane oxide, pentane oxide, hexane oxide, glycidyl ether, glycidyl ester, or glycidyl carbonate, or mixtures of two or more thereof. Preferably, in the polycarbonate blocks, the epoxide is ethylene oxide, propylene oxide, butane oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide. Preferably, in the polyether blocks, the epoxide is ethylene oxide or propylene oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0033] It should also be understood that when a mixture of epoxides is used, the epoxides are typically statistically distributed along the polymer backbone.

[0034] Therefore, when a mixture of epoxides is used, the polycarbonate blocks and polyether blocks can be referred to as random copolymers or statistical copolymers, respectively.

[0035] The groups of Re1, Re2, Re3, Re4, Re1', Re2', Re3', and Re4' will depend on the nature of the epoxide used to prepare the polycarbonate or polyether. However, when one of Re1 to Re4 or one of Re1' to Re2' is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining three groups are H. Preferably, Re1, Re2, Re3, Re4, Re1', Re2', Re3', and Re4' are H.

[0036] It should also be understood that if a mixture of epoxides is used, the Re1 and / or Re2 (or Re3 and / or Re4, Re1' and / or Re2' and Re3' and / or Re4') may be different each time they appear. For example, if a mixture of ethylene oxide and propylene oxide is used in the PC block, Re1 (or Re3) may be independently hydrogen or methyl, while Re2 (or Re4) may be independently hydrogen or methyl.

[0037] Those skilled in the art will understand that when the epoxide is asymmetric, adjacent epoxide monomer units in the main chain can be head-to-tail, head-to-head, or tail-to-tail connected.

[0038] Preferably, the molecular weight (Mn) of the surfactant is from about 300 Da to 20,000 Da, more preferably about 400 Da.The molecular weight (Mn) of the polycarbonate block of the surfactant is preferably about 200 Da to 4000 Da, more preferably about 200 Da to 2000 Da, and most preferably about 200 Da to 1000 Da, especially about 400 Da to 800 Da.

[0040] The molecular weight (Mn) of the polyether block of the surfactant is preferably about 100 Da to 20000 Da, more preferably about 200 Da to 10000 Da, and most preferably about 200 Da to 5000 Da.

[0041] The Mn and therefore the PDI (polydispersity index) of the polymer prepared by the method of the present invention can be measured by gel permeation chromatography (GPC). For example, GPC can be performed using an Agilent 1260 Infinity GPC instrument with two tandem Agilent PLgel μ-m mixed-D columns. Samples can be measured at room temperature (293 K) with THF as the mobile phase and a flow rate of 1 mL / min, using a narrow-distribution polystyrene standard (e.g., low EasiVials polystyrene standards with Mn ranging from 405 g / mol to 49450 g / mol provided by Agilent Technologies) as a reference. Optionally, polyethylene glycol standards (e.g., polyethylene glycol EasiVials standards provided by Agilent Technologies) can be used as a reference for sample measurement.

[0042] The polycarbonate block of the surfactant may have at least 50% carbonate bonds, preferably at least 60% carbonate bonds, preferably at least 70% carbonate bonds, preferably at least 76% carbonate bonds, preferably at least 80% carbonate bonds, more preferably at least 85% carbonate bonds, at least 90% carbonate bonds, or at least 95% carbonate bonds.

[0043] The polycarbonate block of the surfactant may also contain ether bonds. The polycarbonate block may have less than 50% ether bonds, preferably less than 40% ether bonds, preferably less than 30% ether bonds, preferably less than 24% ether bonds, preferably less than 20% ether bonds, more preferably less than 15% ether bonds, less than 10% ether bonds, less than 5% ether bonds, less than 3% ether bonds, or less than 1% ether bonds.

[0044] (%Ether bonds and carbonate bonds can be determined by 1H NMR spectroscopy as described, for example, in US20140323670.)

[0045] To avoid ambiguity, in the case where the polycarbonate block contains ether bonds, the polycarbonate block does not contain only P repeating units of the following formula (i.e., only carbonate bonds):

[0046] ,

[0047] Instead, it contains a mixture of the carbonate bonds shown and the ether bonds shown in the PE block. P is the sum of the carbonate bonds and ether bonds in the PC block. Each carbonate or ether bond contains repeating units that may be derived from the olefin oxide moiety, i.e.,

[0048] .

[0049] Therefore, in the presence of ether bonds, P can be considered as the total number of repeating units derived from the olefin oxide in the PC block.

[0050] Optionally, the polycarbonate block can be a substantially alternating arrangement of polycarbonate residues. If the epoxide is asymmetric, then the polycarbonate can have 0 to 100% head-to-tail linkages, preferably 40% to 100% head-to-tail linkages, more preferably 50% to 100%. The polycarbonate can have a statistical distribution of head-to-head linkages, tail-to-tail linkages, and head-to-tail linkages on the order of 1:2:1, indicating that the epoxide has undergone non-stereoselective ring opening, or can preferably form head-to-tail linkages on the order of greater than 50%, optionally greater than 60%, greater than 70%, greater than 80%, or greater than 90%. Specification 4 / 13 page 7 CN 121013876 A

[0051] Optionally, the polyether block contains only ether bonds. Typically, the polyether block is at least 90%, typically at least 95%, more typically at least 99%, and most typically, 100% derived from epoxides.

[0052] Typically, the polyether block has less than 40% carbonate bonds, typically less than 30% carbonate bonds, typically less than 20% carbonate bonds, more typically less than 10% carbonate bonds, and most typically less than 5%, less than 2%, or less than 1% carbonate bonds. The polyether block may have 0% carbonate bonds.

[0053] To avoid ambiguity, in the case where the polyether block contains carbonate bonds, the polyether block does not contain only Q repeating units of the following formula (i.e., only ether bonds):

[0054] ,

[0055] but rather a mixture of the ether bonds shown and the carbonate bonds shown in the PC block. Q is the sum of the ether bonds and carbonate bonds in the PE block. Each ether bond or carbonate bond contains repeating units that may be derived from the olefin oxide moiety, i.e.:

[0056] .

[0057] Therefore, in the case where carbonate bonds are present in the PE block, Q can be considered as the total number of repeating units derived from the olefin oxide in the PE block.

[0058] Typically, the polycarbonate block is derived from epoxide and CO2, more typically, the epoxide and CO2 provide at least 70% of the residues in the block, especially at least 80% of the residues in the block, more particularly, at least 90% of the residues in the block, and most particularly, at least 95% of the residues in the polycarbonate block are epoxide and CO2 residues. Most typically, the polycarbonate block comprises ethylene oxide and / or propylene oxide residues and optionally butylene oxide. At least 30% of the epoxide residues of the polycarbonate block may be ethylene oxide or propylene oxide residues, typically, at least 50% of the epoxide residues of the polycarbonate block are ethylene oxide or propylene oxide residues.Ethylene oxide or propylene oxide residues, more typically, at least 75% of the epoxide residues of the polycarbonate block are ethylene oxide or propylene oxide residues, most typically, at least 90% of the epoxide residues of the polycarbonate block are ethylene oxide or propylene oxide residues.

[0059] Typically, the polycarbonate block is derived from CO2, i.e., the carbonate is incorporated with CO2 residues. Typically, the polycarbonate block has 70% to 100% carbonate bonds, more typically, 80% to 100%, most typically, 90% to 100%.

[0060] The value of P in Formula I is greater than the value of Q. The difference between the value of P and the value of Q can be from about 1 to about 10, for example, from about 1 to about 5, or from about 1 to about 3.

[0061] Preferably, the ratio of P to Q is not greater than about 1.3:1, more preferably not greater than about 1.25:1, more preferably not greater than about 1.2:1, more preferably not greater than about 1.15:1, even more preferably not greater than about 1.125:1, and most preferably not greater than about 1.1:1. For example, the ratio of P to Q can be greater than 1:1 to about 1.3:1, greater than 1:1 to about 1.25:1, greater than 1:1 to about 1.2:1, greater than 1:1 to about 1.15:1, greater than 1:1 to about 1.125:1, or greater than 1:1 to about 1.1:1.

[0062] The value of P is generally about 3 to about 100, preferably about 3 to about 50 or about 3 to about 20. The value of Q is generally about 3 to about 100, preferably about 3 to about 50, about 5 to about 20 or about 5 to about 15. The value of P can be from about 15 to about 100. The value of Q can be from about 15 to about 100 (all conditions being that P is greater than Q).

[0063] Preferably, the value of Q is from about 12 to about 19, more preferably from about 15 to about 18.

[0064] The water solubility of the surfactant at room temperature and pressure (NTP) can be at least about 0.01 g / mL, at least about 0.05 g / mL, or at least about 0.1 g / mL.

[0065] The surfactant can be water-soluble at room temperature and pressure (NTP) at a concentration of 0.01 g / mL, at a concentration of 0.05 g / mL, and / or at a concentration of 0.1 g / mL.

[0066] When water solubility is shown in a specific concentration, it indicates that the surfactant is water-soluble at that concentration, but it should be understood that the surfactant is soluble in a certain concentration range (not only at a specific concentration).

[0067] In this document, "normal temperature and pressure" has a generally accepted meaning, namely a temperature of 20°C and a pressure of 1 atm. The water solubility of a surfactant can be determined by adding the surfactant to water at a specific concentration, stirring the mixture, and visually observing whether it dissolves.

[0068] Z1 is R, R-O, R-C(O)-O, or R-O-C(O)-O. Preferably, Z1 is R-C(O)-O or R-O-C(O)-O. Preferably, Z1 is a short-chain (e.g., C2-C5 or C2-C4) carbonate or ester group.

[0069] R is a C1 to C11 alkyl group. R can be a straight-chain or branched C1 to C11 alkyl group. Preferably, R is a C2 to C11 alkyl group, more preferably a C2 to C6 or C2 to C5 alkyl group, and typically a C2 to C4 alkyl group. Preferably, R is a straight-chain alkyl group, preferably a straight-chain C2 to C11 alkyl group. Preferably, R is derived from a C1 to C11 alcohol, preferably a C2 to C6 alcohol, typically a C2 to C5 alcohol or a C2 to C4 alcohol. Preferably, R is derived from a straight-chain C1 to C11 alcohol, more preferably a straight-chain C2 to C6 or C2 to C5 alcohol, typically a straight-chain C2 to C4 alcohol or a straight-chain C2 to C4 alcohol. Preferably, the C1 to C11 alcohol is derived from a renewable feedstock. For example, the alcohol can be bioethanol, etc.

[0070] Z2 is H, R, R-(O)C or R-O-(O)C, preferably Z2 is H or methyl.

[0071] In some embodiments, Re1, Re2, Re3 and Re4 can be independently selected from H, methyl or ethyl; Re1', Re2', Re3' and Re4' can be independently selected from H, methyl or ethyl, Z2 can be methyl or H, and the polyether block can have less than 2% carbonate bonds.

[0072] According to a second aspect of the invention, a method for preparing a surfactant according to the first aspect of the invention is also provided, the method comprising the steps of: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional starting compound to form a polycarbonate compound, and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to prepare a surfactant according to the first aspect of the invention.

[0073] The monofunctional starting material may be a C1 to C11 alcohol or a C1 to C11 carboxylic acid. Typically, the monofunctional starting material is a C1 to C11 alcohol, preferably a C2 to C11 alcohol, typically a C2-6 alcohol or a C2-4 alcohol.

[0074] The epoxide is selected from ethylene oxide, propylene oxide, butane oxide, pentane oxide, hexane 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.

[0075] The carbonate catalyst can be heterogeneous or homogeneous.

[0076] The carbonate catalyst can be a monometallic, bimetallic, or multimetallic homogeneous complex, or it can be a nonmetallic Lewis acid-base pair (e.g., based on a combination of borane and ammonium salt, as disclosed in patents WO2016 / 203408, WO2020 / 121262, WO2021 / 005470).

[0077] The carbonate catalyst can contain phenol or phenolate ligands.

[0078] Typically, the carbonate catalyst can be a bimetallic complex containing phenol or phenolate ligands. These two metals can be the same or different, as specified in the specification 6 / 13 pages 9 CN 121013876 A.

[0079] The carbonate catalyst can be a catalyst of formula (IV):

[0080] (IV)

[0081] Wherein:

[0082] M is a metal cation represented by M-(L)v;

[0083] X is an integer from 1 to 4, preferably x is 1 or 2;

[0084] is a polydentate ligand or multiple polydentate ligands;

[0085] L is a coordinating ligand, for example, L can be a neutral ligand or an anionic ligand capable of opening the ring of an epoxide;

[0086] v is an integer that independently satisfies the following conditions: the valence of each M and / or the preferred coordination geometry of each M, or such that the complex represented by the above formula (IV) is electrically neutral as a whole. For example, each v can be independently 0, 1, 2, or 3; for example, v can be 1 or 2. When v > 1, each L can be different.

[0087] The term multidentate ligand includes ligands with a number of teeth of two, three, four, and higher. Each multidentate ligand can be a macrocyclic ligand or an open ligand.

[0088] Such catalysts include those disclosed in the following patents: WO2010 / 022388 (metal salon and its derivatives, metal porphyrin, corrole and its derivatives, metal tetrazonium and its derivatives), WO2010 / 028362 (metal salon and its derivatives, metal porphyrin, corrole and its derivatives, metal tetrazonium and its derivatives), WO2008 / 136591 (metal salon), WO2011 / 105846 (metal salon), WO2014 / 148825 (metal salon), WO2013 / 012895 (metal salon), EP2258745A1 (metal porphyrin and its derivatives), JP2008081518A (metal porphyrin and its derivatives). CN101412809 (metal salten and its derivatives), WO2019 / 126221 (metal aminopyrogallol complex), US9018318 (metal β-diimine complex), US6133402A (metal β-diimine complex), and US8278239 (metal salten and its derivatives). The entire contents of the foregoing documents—especially the relevant descriptions relating to suitable carbonate catalysts for the CO2 and epoxide reactions in the presence of starting materials and optional solvents as defined herein—are incorporated herein by reference.

[0089] Preferably, the carbonate catalyst is a bimetallic phenolate catalyst. Suitable bimetallic phenolate complexes are those in the following...The following patents are disclosed: WO2009 / 130470, WO2013 / 034750, WO2016 / 012786, WO2016 / 012785, WO2012 / 037282, and WO2019 / 048878A1. The entire contents of the foregoing documents—especially the relevant descriptions relating to suitable carbonate catalysts for the reaction of CO2 and epoxides in the presence of starting materials and optional solvents as defined herein—are incorporated herein by reference.

[0090] The ether catalyst can be any catalyst suitable for polymerizing epoxides to form polyethers. Suitable ether catalysts include DMC catalysts, metal alkoxides, boron-based catalysts (such as BF3 or BH3), anionic catalysts such as (KOH), cationic catalysts, acidic or superacidic catalysts (such as HSbF6, CF3SO3H), PF5, active monomer catalysts, organic catalysts (such as imidazole or phosphazene reagents), and metal Schiff base catalysts. Preferably, the ether catalyst is a DMC catalyst. Examples of DMC catalysts that can be used in the method of the present invention include those disclosed in the following patents: 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 US Patents 4,826,953, 4,500,704, 7,977,501, 9,315,622, EP-A-1568414, EP-A-1529566, and WO 2015 / 022290. The entire contents of these patents are incorporated herein by reference on page 7 / 13 of the specification, CN 121013876 A.

[0091] The ratio of carbonate catalyst to ether catalyst can be from about 300:1 to about 1:100, for example from about 120:1 to about 1:75, for example from about 40:1 to about 1:50, for example from about 30:1 to about 1:30, for example from about 20:1 to about 1:1, for example from about 10:1 to about 2:1, for example from about 5:1 to about 1:5. These ratios are by mass.

[0092] The method can be carried out in a single-reactor reactor, or the method can be a two-reactor method.

[0093] Therefore, according to a third aspect of the invention, a method for preparing the product according to the invention in a multi-reactor system is also provided.A method for a surfactant according to a first aspect; the system comprises 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 to react a carbonate catalyst with CO2 and an epoxide in the presence of a monofunctional starting compound and optionally a solvent to prepare a polycarbonate compound, and the second reaction is to react an ether catalyst with the polycarbonate compound and the epoxide of the first reaction in a semi-batch or continuous manner to prepare a surfactant according to the first aspect of the invention.

[0094] Typically, the CO2 content in the reaction mixture from the first step is less than 5% by weight of the reaction mixture before the second step reaction is carried out; preferably less than 2.5% by weight, for example less than 1.0% by weight, less than 0.5% by weight or less than 0.1% by weight. Typically, the second step is carried out without the addition of additional CO2, but can be carried out under CO2 pressure. The polyether block prepared in the second step may 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 polyether block prepared in the second step is substantially free of carbonate bonds.

[0095] Therefore, typically, the second step is carried out in substantially CO2-free conditions.

[0096] Accordingly, substantially CO2-free means that the second step is carried out at a CO2 content of less than 4% by weight, preferably less than 2% by weight, for example less than 1.0% by weight, less than 0.5% by weight, or less than 0.1% by weight of the total weight of the total reactants, catalyst, and products in the second step.

[0097] Compared to a method in which all materials are added at the beginning of the method, adding components in separate steps may help improve the activity of the catalyst, thus forming a more efficient method. If certain components are present in large quantities throughout the method, the efficiency of the catalyst will be reduced. Reacting these materials in separate steps can prevent a reduction in catalyst efficiency and / or can optimize catalyst activity. The reaction conditions at each step can be adjusted to optimize the reaction of each catalyst.

[0098] The ether catalyst can be pre-activated before being added in the second step. Such pre-activation can be achieved by mixing one or two catalysts with an epoxide (and optionally other components). Pre-activation of the ether catalyst is useful because it allows for safe control of the reaction process (preventing an uncontrolled increase in the content of unreacted monomers) and eliminates unpredictable activation periods.

[0099] Although any residual CO2 from the first step is typically removed from the crude reaction product of the first step before the second step begins, so that the second step is carried out in the absence of CO2, it should be understood that a small amount of CO2 may be present in the reaction mixture of the second step as an unused reagent from the first step. Alternatively, both steps may be carried out under CO2 pressure.

[0100] The reaction of the present invention can be carried out in the presence of a solvent; however, it should also be understood that the method can also be carried out in the absence of a solvent.The reaction is carried out under the following conditions. When a solvent is present, the solvent can be toluene, hexane, tert-butyl acetate, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, dichloromethane, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), etc. The solvent can be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0101] Compared to the method of adding all materials at the beginning of a reaction, adding these components in separate reactions and reactors may help to improve the activity of the catalyst, thereby potentially forming a more efficient method. The presence of certain components in large quantities throughout the reaction process can reduce the efficiency of the catalyst. Reacting these materials in separate reactors can prevent the reduction of catalyst efficiency and / or can optimize catalyst activity. The reaction conditions of each reactor can be adjusted to optimize the reaction of each catalyst.

[0102] Furthermore, by not loading the total amount of each component at the start of the reaction and placing the catalyst for the first reaction in a separate reactor from the catalyst for the second reaction, uniform catalysis and a more uniform polymer product can be achieved. This, in turn, can result in a narrower molecular weight distribution, an ideal ratio and distribution of ether bond to carbonate bond chain lengths, and / or improved stability of the polymer.

[0103] It is also useful to separate the reactions using two different catalysts, mixing only certain components in the first reaction and adding the remaining components 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.

[0104] Preferred ether catalysts and carbonate catalysts are the same as those in the second aspect of the invention.

[0105] The first reaction can be carried out in more than one reactor, which continuously feeds the crude reaction mixture into the second reaction and the reactor. Preferably, the second reaction is carried out in a continuous mode.

[0106] The product of the first reaction can be stored in the second reactor for subsequent use.

[0107] The two reactors can be arranged in series or nested. Each reactor can be designed individually as a stirred tank reactor, loop reactor, tubular reactor, or other standard reactor.

[0108] Alternatively, the surfactant of the first aspect can be formed by reacting a monofunctional polyether starting compound with an epoxide and carbon dioxide in the presence of a carbonate catalyst. Therefore, according to other aspects of the invention, a method for preparing a surfactant according to the first aspect of the invention is provided, wherein a monohydroxy functional polyether is reacted (i) with a carbonate catalyst, an epoxide, and CO2, and (ii) with a capping group (such as an anhydride) to prepare the surfactant of the invention. Typically, the resulting polycarbonate block is capped with any suitable functional group. Capping the polycarbonate block can stabilize the surfactant.Typically, polycarbonate blocks are capped with a suitable anhydride (usually an alkyl anhydride). The monofunctional polyether starting compound can be any suitable monofunctional polyether starting compound, typically a monofunctional PEG compound.

[0109] Definitions

[0110] Unless otherwise defined, the term “alkyl” as used herein refers to a saturated straight-chain or branched hydrocarbon group obtained by removing a single hydrogen atom from an aliphatic group. An alkyl group can be “C1-20 alkyl”, i.e., a straight-chain or branched alkyl group having 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 a C1-15 alkyl group, more preferably a C1-12 alkyl group, more preferably a C1-10 alkyl group, even more preferably a C1-8 alkyl group, and even more preferably a C1-6 alkyl group.

[0111] Unless otherwise defined herein, the ester group is optionally -OC(O)R1- or -C(O)OR1-, wherein R1 can be an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R1 can be an unsubstituted aliphatic group, an alicyclic group, or an aryl group. Optionally, R1 is methyl, ethyl, propyl, or phenyl. The ester group can be terminated by an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. It should be understood that if R1 is hydrogen, then the group defined by -OC(O)R1- or -C(O)OR1- will be a carboxylic acid group.

[0112] The carbonate group is optionally -OC(O)OR2, wherein R2 can be hydrogen, an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R2 can optionally be a substituted aliphatic group, an alicyclic group, or an aryl group. Optionally, R2 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, heptadecanyl, octadecyl, nonadecanyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. Optionally, R2 is methyl, ethyl, propyl, or phenyl. It should be understood that if R2 is hydrogen, then the group defined by -OC(O)OR2 will be a carbonate group. Specification 9 / 13 pages 12 CN 121013876 A

[0113] The carbonate functional group is -OC(O)O- and can be derived from a suitable source. Generally, it is derived from CO2.

[0114] The ether group is optionally -OR3, wherein R3 can be an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R3 can be an unsubstituted aliphatic, alicyclic, or aryl group. Optionally, R3 is methyl, ethyl, or ethyl.R3 is methyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, trifluoromethyl, or adamantyl. Optionally, R3 is methyl, ethyl, propyl, or phenyl.

[0115] As used herein, the term “optionally substituted” means that one or more hydrogen atoms in an optional substituted group are substituted by a suitable substituent. Unless otherwise stated, an “optionally substituted” group may have a suitable substituent at each substituted position of the group, and the substituents at each position may be the same or different when more than one position in any given structure can be substituted by more than one substituent selected from a particular group. The combinations of substituents covered by the present invention are preferably those that form stable compounds. The term “stable” as used herein means a chemically viable compound that can exist for a sufficient period of time at room temperature (16°C to 25°C) to enable its detection, separation, and / or application in chemical synthesis.

[0116] A substituent can be described as being attached to a bond that passes through a bond in the molecular ring. This convention indicates that one or more substituents can be attached to any available position on the ring (typically replacing a hydrogen atom in the structure). In the case where an atom on the ring has two substituted sites, two groups can be present on that atom (these two groups can be the same or different).

[0117] Preferred optional substituents used in the present invention include, but are not limited to: halogen, hydroxyl, nitro, carboxylic ester, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amide, imino, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, alkynyl, hypophosphonic acid, sulfonic acid or optionally substituted aliphatic, heteroaliphatic, alicyclic, heterocyclocyclic, aryl or heteroaryl (e.g., optionally substituted with halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imino, nitrile, silyl, sulfoxide, sulfone, hypophosphonic acid, sulfonic acid or alkynyl).

[0118] Particularly preferred optional substituents used in this invention are selected from nitro, C1-12 alkoxy (e.g., OMe, OEt, OiPr, OnBu, OtBu), C6-18 aryl, C2-14 heteroaryl, C2-14 heterocycloalicyclic group, C1-6 alkyl, C1-6 haloalkyl, F, Cl, Br, I, and OH, wherein each of the said C1-12 alkoxy, C6-18 aryl, C2-14 heteroaryl, C2-14 heterocycloalicyclic group, C1-6 alkyl, and C1-6 haloalkyl may optionally be substituted with optional substituents as defined herein.

[0119] The term “continuous” as used herein may be defined as the manner in which materials are added, or may refer to the nature of the entire reaction method.

[0120] In the case of a continuous addition mode, the relevant materials are added continuously or intermittently during the reaction. This can be achieved, for example, by adding the material stream at a constant or variable flow rate. In other words, one or more materials are added in a substantially uninterrupted manner. However, it should be noted that, for practical reasons (e.g., replenishing or replacing the material container that is supplying the material), it may be necessary to briefly interrupt the uninterrupted addition of materials.

[0121] In the case of a continuous reaction, the reaction can continue for a long period of time, such as days, weeks, months, etc. In such continuous reactions, 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, it may be necessary to replenish the catalyst in any case, as the discharge operation may deplete the catalyst stock.

[0122] Continuous reactions can be carried out using a continuous feeding method.

[0123] Continuous reactions can be carried out using a discontinuous (i.e., batch or semi-batch) feeding method.

[0124] The term “tandem” as used herein refers to the connection of two or more reactors so that the crude reaction mixture can flow from the first reactor to the second reactor.

[0125] The term “nested” as used herein refers to the configuration of two or more reactors such that one is located inside another. For example, in this invention, when the second reactor is located inside the first reactor, the conditions of the two reactors can influence each other.

[0126] Examples

[0127] General Example 1 – Formation of Carbonate Blocks on Monofunctional Polyethers

[0128] Catalyst (1) was prepared according to Example 2 of WO2017 / 037441. Polyethylene glycol monomethyl ether was added to a 100 mL Parr high-pressure reactor. The container was dried by heating to 100 °C under vacuum for 60 min, then cooled and filled with low-pressure CO2. Catalyst (1) was added.

[0129] Epoxide was added to the mixture. The mixture was stirred and pressurized to about half of the target pressure. The mixture was then heated to the target temperature (70°C) and maintained at a constant pressure (20 bar).

[0130] At the end of the specified reaction time, the mixture was cooled to <10°C and vented by an acidic washing system.

[0131] The monohydric alcohol was dissolved in a dichloromethane solution containing triethylamine (1.3 eq) and alkyl anhydride (1.05 eq) and refluxed for 16 hours. The end-capped monohydric alcohol was washed with water and brine, dried with sodium sulfate, and concentrated to dryness under vacuum to obtain the desired product. Ethylene carbonate byproducts were removed using a Kugelrohr evaporator or a short-path evaporator (SPE).

[0132] Table 1: Experimental conditions for Example 1

[0133] Mn and PDI were measured by gel permeation chromatography (GPC) using the method described above. NMR spectroscopy was used to measure the content of Mn and PDI in wt%.CO2 and carbonates by weight. Surface tension and critical micelle concentration (CMA) were measured using a tensiometer with standard techniques.

[0134] Water solubility was measured by weighing 0.25 g of surfactant into a vial and adding an appropriate volume of deionized water to achieve a concentration of 0.01 g / mL. The mixture was stirred using a vortex mixer until dissolution was observed.

[0135] Table 2: Results of Example 1, 11 / 13 pages, 14 CN 121013876 A

[0136] Table 3: Surfactant of Example 1

[0137] Me is methyl

[0138] EO is ethylene oxide

[0139] EC is ethylene carbonate

[0140] PC is propylene carbonate

[0141] The P:Q ratios of samples 1, 2, and 3 were 1.0625:1, 1.125:1, and 1.25:1, respectively.

[0142] Data show that the polycarbonate block polyether of the present invention is soluble in water, reduces surface tension and promotes micelle formation, thereby possessing surfactant properties.

[0143] Another method for preparing the surfactant of the present invention is described below.

[0144] General Example 2

[0145] Reaction 1

[0146] A monohydric alcohol starting material was added to a 100 mL Parr high-pressure reactor system. The container was dried by heating to 100 °C under vacuum for 60 min, then cooled and filled with low-pressure CO2. Catalyst (1) was added (see Example 1).

[0147] EO was added to the mixture. The mixture was stirred and pressurized to about half of the target pressure. The mixture was then heated to the target temperature and maintained at a constant temperature and target pressure.

[0148] At the end of the specified reaction time, the mixture was cooled to <10 °C and vented by an acidic scrubbing system. Before transferring to an intermediate storage container, EO and anhydrous ethyl acetate were added to the cold-stirred mixture.

[0149] Reaction 2

[0150] The pre-dried monohydric alcohol starting material and DMC consisting of zinc hexacyanocobalaminate and tert-butanol (2) were added to a 100 mL Parr high-pressure reactor system. The container was kept under vacuum for about 2 minutes, then filled with low-pressure N2, and then filled with anhydrous ethyl acetate (15 mL).

[0151] The container was then heated to 130 °C with stirring and the DMC was activated with two batches of about 0.3 g PO. After activation (marked by a decrease in pressure), the external heater was removed, and optionally, the reactor was pressurized with CO2, and the mixture was then cooled to the target addition temperature.

[0152] After reaching the target temperature, the mixture from reaction 1 was added to the activated DMC system over about 60 to 90 minutes.Once the mixture has been added, allow it to stand for several hours to “mature,” then cool, depressurize, and sample for NMR and GPC analysis. Table 4: Embodiment 2 Reaction 1 Experimental Conditions / Results Table 5: Embodiment 2 Reaction 2 Experimental Conditions Instructions 13 / 13 Page 16 CN 121013876 A SURFACE-ACTIVE AGENT The invention concerns a surface-active agent comprising a polycarbonate block polyether of the formula (I): Z1 - (PC)P - (PE)Q - Z2 (I), where PC represents a carbonate block with P repeat units of formula wherein Re1, Re2, Re3, and Re4 are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, with the proviso that when one of Re1, Re2, Re3, and Re4 is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, the remaining Re1, Re2, Re3, and Re4 are H.; PE represents a polyether block with Q repeat units of formula (II) wherein Re1' , Re2' , Re3' , and Re4' are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester or carbonate groups, with the proviso that when one of Re1' , Re2' , Re3' , and Re4' is methyl, ethyl, propyl, butyl, or an ether, ester orcarbonate group, the remaining Re1’ , Re2’ , Re3’ , and Re4’ are H; Z1 is R, R-O, R- C(O)-O- or R-O-C(O)-O; R is an optionally substituted straight or branched chain C1 - C11 alkyl group; Z2 is H, R, R-(O)C orR-O-(O)C ; and wherein the value of P is greater than the value of Q. (I) (II) Abstract

Claims

1. Surfactants comprising polycarbonate block polyethers of formula I: WITH 1 -(PC) P -(PE) Q -WITH 2 (AND) in, PC represents a carbonate block having P repeating units of the following formula: ， Where R e1 R e2 R e3 and R e4 Independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate groups, provided that R e1 R e2 R e3 and R e4 When one of them is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining R e1 R e2 R e3 and R e4 For H; PE represents a polyether block having Q repeating units of the following formula: ， Among them, R e1’ R e2’ R e3’ and R e4’ Independently selected from H, methyl, ethyl, propyl, butyl, or ether, ester, or carbonate groups, provided that R e1’ R e2’ R e3’ and R e4’ When one of them is methyl, ethyl, propyl, butyl, or ether, ester, or carbonate, the remaining R e1’ R e2’ R e3’ and R e4’ For H; Z 1 For R, RO, RC(O)-O- or ROC(O)-O; R represents the optionally substituted straight or branched chains C1 to C2. 11 alkyl; Z 2 For H, R, R-(O)C or RO-(O)C; and The value of P is greater than the value of Q.

2. The surfactant according to claim 1, wherein R is C2 to C3. 11 alkyl.

3. The surfactant according to any one of the preceding claims, wherein R is a straight-chain alkyl group.

4. The surfactant according to any one of claims 1 to 3, wherein R is a C2 to C6 alkyl, typically a C2 to C5 alkyl or a C2 to C4 alkyl.

5. The surfactant according to any one of claims 2 to 4, wherein R e1 R e2 R e3 R e4 R e1’ R e2’ R e3’ and R e4’ Independently selected from H, methyl or ethyl, preferably, wherein R e1 R e2 R e3 R e4 R e1’ R e2’ R e3’ and R e4’ Each is represented by H.

6. The surfactant according to any one of the preceding claims, wherein Z 1 It is RC(O)-O or ROC(O)-O, preferably a short-chain (e.g., C2 to C5 or C2 to C4) carbonate or ester group RO.

7. The surfactant according to any one of the preceding claims, wherein Z 2 It is H or methyl.

8. The surfactant according to any one of the preceding claims, wherein the total surfactant contains more than 10 wt% CO2, more typically, more than 15 wt%, 20 wt%, or 21 wt% CO2.

9. The surfactant according to any one of the preceding claims, wherein the total surfactant has a CO2 incorporation of 10 wt% to 40 wt%, typically 15 wt% to 40 wt%, and more typically 20 wt% to 40 wt%.

10. The surfactant according to any one of the preceding claims, wherein the difference between the value of P and the value of Q is about 1 to about 10, or about 1 to about 5, or about 1 to about 3.

11. The surfactant according to any one of the preceding claims, wherein the ratio of P to Q is not greater than about 1.3:1, not greater than about 1.25:1, not greater than about 1.2:1, more preferably not greater than about 1.15:1, even more preferably not greater than about 1.125:1, and most preferably not greater than about 1.1:

1.

12. The surfactant according to any one of the preceding claims, wherein the polyether block has less than 40% carbonate bonds, preferably less than 30%, less than 20%, less than 10%, less than 5%, less than 2% or less than 1% carbonate bonds.

13. The surfactant according to any one of the preceding claims, wherein the polyether block has 0% carbonate bonds.

14. The surfactant according to any one of the preceding claims, wherein the surfactant is water-soluble.

15. The surfactant according to any one of the preceding claims, wherein the surfactant has water solubility of at least about 0.01 g / mL, at least about 0.05 g / mL, or at least about 0.1 g / mL at room temperature and pressure.

16. The surfactant according to any one of the preceding claims, wherein the surfactant is water-soluble at a concentration of 0.01 g / mL, 0.05 g / mL and / or 0.1 g / mL at room temperature and pressure.

17. A method for preparing the surfactant according to any one of claims 1 to 16, wherein the method comprises the following steps: (i) In the presence of a carbonate catalyst and a monofunctional initiating compound, carbon dioxide and an epoxide are reacted to form a polycarbonate compound, and (ii) Reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to prepare the surfactant according to any one of claims 1 to 16.

18. A method for preparing a surfactant according to any one of claims 1 to 16 in a multi-reactor system; said system comprising 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 to react a carbonate catalyst with CO2 and an epoxide in the presence of a monofunctional starting compound and optionally a solvent to prepare a polycarbonate compound, and the second reaction is to react an ether catalyst with the polycarbonate compound and the epoxide of the first reaction in a semi-batch or continuous reaction to prepare the surfactant according to any one of claims 1 to 16.

19. The method according to claim 17 or claim 18, wherein the carbonate catalyst is a bimetallic phenolic complex.

20. The method according to any one of claims 17 to 19, wherein the ether catalyst is a DMC catalyst.

21. A method for preparing a surfactant according to any one of claims 1 to 16, wherein the monohydroxy functionalized polyether is... (i) Reaction with carbonate catalysts, epoxides and CO2, and (ii) Reaction with end-capping groups (such as acid anhydrides) to prepare the surfactant according to any one of claims 1 to 20.

22. The surfactant according to any one of claims 1 to 16 is used as an agricultural chemical adjuvant; for the preparation of foams, coatings, paints, adhesives and sealants in the construction industry; for use in the automotive industry; for use in the preparation of textiles; and for enhancing oil recovery.