surfactant

Abstract

The present invention relates to a surfactant comprising a polycarbonate block polyether of formula I: Z 1 -(PC) P -(PE) Q -Z 2 (I) (wherein, PC represents a carbonate block having P repeating units of the formula 【Chemical Formula 1】 JPEG2026516837000017.jpg3657 (wherein, R e1 , R e2 , R e3 , and R e4 are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, provided that when one of R e1 , R e2 , R e3 , and R e4 is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, the remaining R e1 , R e2 , R e3 , and R e4 are H), PE represents a polyether block having Q repeating units of the formula 【Chemical Formula 2】 JPEG2026516837000018.jpg3641 (wherein, R e1’ , R e2’ , R e3’ , and R e4’ are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, provided that when one of R e1’ , R e2’ , R e3’ , and R e4’ is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, the remaining R e1’ , R e2’ , R e3’ , and R e4’ are H), and Z 1R is R, RO, RC(O)-O, or ROC(O)-O, where R is a linear or branched C1-C that has been optionally substituted. 11 It is an alkyl group, Z 2 (where is H, R, R-(O)C or RO-(O)C, and the value of P is greater than the value of Q).

Description

[Technical Field]

[0001] This invention relates to surfactants, catalysts and processes for producing them, and specific applications. [Background technology]

[0002] Nonionic surfactants are typically manufactured using monoall starters that have a large hydrophobic block. An example is palm oil alcohol, which provides the hydrophobic block. The use of palm oil has led to deforestation of other plant species and a corresponding reduction in the natural habitats of numerous endangered species. As a result, palm oil alcohol, etc. (C 12 ~C 20 The search for alternatives to alcohol is underway.

[0003] Surfactants combining polyethers and polycarbonate blocks are well known in the field of oil extraction. International Publication No. 2010 / 062703 and International Publication No. 2015 / 031348 describe polymer compositions and supercritical CO2 solutions of such polymers, potentially a wide range, for aiding oil extraction. Such solutions form emulsion wastewater with water to aid oil extraction. The solubility or use of such water-soluble polymers in water is not shown. The polymer compositions are designed for applications where they dissolve in liquid or supercritical CO2. International Publication No. 2010 / 062703 mentions examples having polyether blocks and polycarbonate blocks, but such examples are not illustrated, and the blocks are neither fully characterized nor tested. International Publication No. 2015 / 031348 describes the following types of polycarbonate blocks: YO-APC-OC x H y (In the formula, APC is polycarbonate, C x H y(These are saturated or unsaturated hydrocarbons.) The terminal group Y can be H or several other groups such as a polyether chain, the latter of which are not exemplified or further specified.

[0004] U.S. Patent Application Publication No. 2021309801A1 discloses degradable ethylene oxide copolymers produced by boron-activated copolymerization of ethylene oxide monomer and carbon dioxide, and their use as surfactants. Certain triblock amphiphilic compounds are reported.

[0005] The UK Patent Application Publication No. 2612195A discloses a method for producing a surfactant, comprising (i) reacting carbon dioxide with an epoxide in the presence of a carbonate catalyst (e.g., a bimetallic phenolate complex) and a monofunctional starter to form a polycarbonate compound, and (ii) reacting the formed polycarbonate compound with an epoxide and an ether catalyst (e.g., a DMC catalyst) to produce a surfactant. The use of the surfactant as an agrochemical adjuvant for the preparation of foams, coatings, paints, adhesives, and sealants, and for improving crude oil recovery rates is also disclosed.

[0006] U.S. Patent Application Publication No. 2019 / 0382528A1 discloses a method for preparing high molecular weight polyether carbonates by reacting epoxides with carbon dioxide in the presence of a bimetallic complex catalyst and a double metal cyanide (DMC) catalyst.

[0007] U.S. Patent No. 4,415,502A discloses a polycarbonate-type nonionic surfactant composition comprising a monohydroxy alcohol capped with polycarbonate groups. More specifically, the surfactant composition comprises an aliphatic, non-aromatic alicyclic, or aromatic alcohol capped with block polycarbonate groups formed by the reaction of an alcohol with ethylene carbonate in the presence of an alkali metal salt catalyst.

[0008] Current aqueous nonionic surfactants that use a highly hydrocarbyl alcohol derivative as the hydrophobic moiety from either a fossil fuel or a plant-based source (such as palm oil) are more expensive and less readily available and would benefit from being replaced with a lower hydrocarbyl source potentially produced from a bio-source such as bioethanol or butanol.

[0009] Surprisingly, the inventors have found that by varying the relative structure of the polycarbonate block polyether backbone, a hydrophobic group can be formed using a lower hydrocarbyl alcohol together with the polycarbonate section, providing an aqueous surfactant without the need for a higher hydrocarbyl alcohol derivative. SUMMARY OF THE INVENTION

[0010] According to a first aspect of the present invention, there is provided a surfactant comprising a polycarbonate block polyether of formula I, Z 1 -(PC) P -(PE) Q -Z 2 (I) wherein PC represents a carbonate block having P repeating units of the formula

Chemical formula

[0011] Preferably, Z 1 is RC(O)-O or ROC(O)-O. Preferably, Z 1 These are short-chain (e.g., C2-C5 or C2-C4) carbonate or ester groups.

[0012] Preferably, Z 2 It is either H or methyl.

[0013] In the present invention, the polycarbonate block acts as a hydrophobic material, and the polyether block acts as a hydrophilic material. As a result, when producing a surfactant according to the first aspect of the present invention, the starter molecule does not need to be a large hydrocarbon chain as found in palm oil alcohol and other long-chain alcohols, but may instead be a short-chain alcohol or other starter, which is used to initiate the synthesis of the polycarbonate block using a carbonate catalyst before synthesizing the polyether block using an ether catalyst. Lower alcohol starters are also less expensive and more likely to be environmentally sustainable.

[0014] Alternatively, production can be carried out via a monohydroxyl-functionalized polyether, which can be used as an initiator for synthesizing polycarbonate blocks using a carbonate catalyst, thereby producing polycarbonate block polyethers via an alternative route without requiring long-chain or short-chain alcohol starters. When this method is used in production, it is preferable to end-cap the polycarbonate blocks, for example, by reaction with an anhydride, to provide stability under basic conditions and prevent degradation of the polycarbonate blocks. Surprisingly, the use of appropriately balanced hydrophobic and hydrophilic polyether blocks has been shown to provide alternative surfactants with far greater design flexibility, independent of environmentally harmful higher alcohols. This makes it possible to produce surfactants with smaller terminal hydrocarbyl groups.

[0015] Furthermore, a process for producing a surfactant according to a first aspect of the present invention is also provided, comprising: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound; and (ii) reacting the polycarbonate compound from step (i) with an epoxide and an ether catalyst to produce a surfactant according to a first aspect of the present invention.

[0016] The present invention also provides a process for producing a surfactant according to a first aspect of the present invention in a multi-reactor system, wherein the system comprises first and second reactors, the first reaction occurring in the first reactor, the second reaction occurring in the second reactor, the first reaction being the reaction of a carbonate catalyst with CO2 and an epoxide in the presence of a monofunctional starter compound and optionally a solvent for producing a polycarbonate compound, and the second reaction being a semi-batch or continuous reaction of the polycarbonate compound and epoxide from the first reaction with an ether catalyst for producing a surfactant according to a first aspect of the present invention.

[0017] Furthermore, the present invention also provides the use of the aforementioned surfactants as pesticide adjuvants, for the preparation of foams, coatings, paints, adhesives and sealants for the building and construction industry, in the automotive industry, in textile manufacturing, and for increasing crude oil recovery rates. [Modes for carrying out the invention]

[0018] Preferably, the surfactant has more than 10% by weight of CO2 uptake, more typically more than 15, 20, or 21% by weight. Preferably, the surfactant has 10–40% by weight of CO2 uptake, typically 15–40% by weight, more typically 20–40% by weight. (Wt% CO2 uptake can be analytically established by 1H NMR spectroscopy, for example, as described in U.S. Patent No. 20140323670.)

[0019] The epoxides of both the polycarbonate and polyether portions are independently selected from ethylene oxide (EO), propylene oxide (PO), butylene oxide, pentylene oxide, hexylene oxide, glycidyl ether, glycidyl ester, or glycidyl carbonate, or mixtures of two or more thereof. Preferably, in the polycarbonate block, the epoxide is ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide. Preferably, in the polyether block, the epoxide is ethylene oxide or propylene oxide, or a mixture thereof, preferably ethylene oxide or propylene oxide, typically ethylene oxide.

[0020] When epoxide mixtures are used, it will also be understood that the epoxides are typically statistically distributed along the polymer backbone.

[0021] In other words, when epoxide mixtures are used, polycarbonate and polyether blocks can be referred to as random copolymers or statistical copolymers, respectively.

[0022] R e1 , R e2 , R e3 , R e4 , R e1’ , R e2’ , R e3’ , and R e4’ The identity depends on the properties of the epoxide used to prepare the polycarbonate or polyether. However, R e1 ~R e4 one of or R e1’ ~R e2’ If one of the groups is a methyl, ethyl, propyl, butyl, or ether, ester, or carbonate group, the remaining three groups are H. Preferably, R e1 , R e2 , R e3 , R e4 , R e1’ , Re2’ , R e3’ , and R e4’ H is H.

[0023] When an epoxide mixture 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’ The presence of each of the elements does not have to be the same; for example, if a mixture of ethylene oxide and propylene oxide is used in the PC block, R e1 (or R e3 ) may independently be hydrogen or methyl, R e2 (or R e4 It will also be understood that ) may independently be hydrogen or methyl.

[0024] Those skilled in the art will understand that, when an epoxide is asymmetric, adjacent epoxide monomer units in the skeleton may be head-to-tail, head-to-head, or tail-to-tail.

[0025] 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 8,000 Da, and most preferably in the range of about 500 to 6,000 Da.

[0026] The polycarbonate block of the surfactant preferably has a molecular weight (Mn) in the range of about 200 to 4000 Da, more preferably in the range of about 200 to 2000 Da, most preferably in the range of about 200 to 1000 Da, and particularly in the range of about 400 to 800 Da.

[0027] The polyether 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, and most preferably about 200 to 5,000 Da.

[0028] The manganese (Mn), or PDI (polydispersity index), of polymers produced by the method of the present invention can be measured using gel permeation chromatography (GPC). For example, GPC can be measured using an Agilent 1260 Infinity GPC instrument equipped with two Agilent PLgel μ-m mixed D columns in series. The sample can be measured at room temperature (293 K) in THF at a flow rate of 1 mL / min against a narrow polystyrene standard (e.g., polystyrene low EasiVials supplied by Agilent Technologies with a Mn range of 405–49,450 g / mol). Optionally, the sample can be measured against a poly(ethylene glycol) standard, e.g., polyethylene glycol EasiVials supplied by Agilent Technologies.

[0029] 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.

[0030] The surfactant polycarbonate block 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. (The % ether and carbonate bonds can be analytically established by 1H NMR spectroscopy, for example, as described in U.S. Patent No. 20140323670.)

[0031] To avoid any doubt, if the polycarbonate block contains ether bonds, the polycarbonate block is defined by the formula [ka] The P repeating units, i.e., not simply containing carbonate bonds alone, but instead containing a mixture of both carbonate bonds as shown and ether bonds as shown for the PE block, where P is the total number of carbonate and ether bonds in the PC block. Each carbonate or ether bond is an alkylene oxide moiety, i.e. [ka] It contains repeating units that may originate from it. Therefore, if an ether bond is present, P can be considered as the number of parts derived from the repeating alkylene oxide in the PC block.

[0032] Selectively, the polycarbonate block may consist of substantially alternating polycarbonate residues. If the epoxide is asymmetric, the polycarbonate may have 0-100% head-tail bonds, preferably 40-100% head-tail bonds, and more preferably 50-100% head-tail bonds. The polycarbonate may have a statistical distribution of head-head, tail-tail, and head-tail bonds on the order of 1:2:1, exhibiting non-stereoselective ring-opening of the epoxide, or preferentially forming head-tail bonds on the order of greater than 50%, selectively greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0033] Optionally, polyether blocks contain only ether bonds. Typically, polyether blocks are derived from epoxides by at least 90%, typically at least 95%, more typically at least 99%, and most typically 100%.

[0034] Typically, polyether blocks have less than 40% carbonate bonds, typically less than 30% carbonate bonds, typically less than 20% carbonate bonds, more typically less than 10% carbonate bonds, most typically less than 5%, less than 2%, or less than 1% carbonate bonds. Polyether blocks may have 0% carbonate bonds.

[0035] To avoid any doubt, if the polyether block contains carbonate bonds, the polyether block is defined by the formula [ka] The Q repeating units, i.e., not consist solely of ether bonds, but rather contain a mixture of both ether bonds as shown and carbonate bonds as shown for the PC block. Q is the total number of ether and carbonate bonds in the PE block. Each ether or carbonate bond is an alkylene oxide moiety, i.e. [ka] It contains repeating units that may originate from it. Therefore, if carbonate bonds are present in the PE block, Q can be considered as the number of parts derived from the repeating alkylene oxide in the PE block.

[0036] Typically, polycarbonate blocks are derived from epoxides and CO2, and more typically, epoxides and CO2 constitute at least 70%, particularly at least 80%, more particularly at least 90%, and most typically at least 95% of the residues in the block. Most typically, polycarbonate blocks contain ethylene oxide and / or propylene oxide residues, as well as optionally butylene oxide. At least 30% of the epoxide residues in a polycarbonate block may be ethylene oxide or propylene oxide residues, and typically, at least 50% of the epoxide residues in a polycarbonate block are ethylene oxide or propylene oxide residues, more typically, at least 75% of the epoxide residues in a polycarbonate block are ethylene oxide or propylene oxide residues, and most typically, at least 90% of the epoxide residues in a polycarbonate block are ethylene oxide or propylene oxide residues.

[0037] Typically, polycarbonate blocks are derived from CO2, meaning the carbonate incorporates CO2 residues. Typically, polycarbonate blocks have 70–100%, more typically 80–100%, and most typically 90–100% carbonate bonds.

[0038] In equation I, the value of P is greater than the value of Q. The difference between the value of P and the value of Q can be in the range of approximately 1 to approximately 10, for example, approximately 1 to approximately 5, or approximately 1 to approximately 3.

[0039] Preferably, the ratio of P to Q is about 1.3:1 or less, more preferably about 1.25:1 or less, more preferably about 1.2:1 or less, more preferably about 1.15:1 or less, even more preferably about 1.125:1 or less, and most preferably about 1.1:1 or less. For example, the ratio of P to Q may be in the range of 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.

[0040] The value of P is typically about 3 to about 100, preferably about 3 to about 50 or about 3 to about 20. The value of Q is typically 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 may be about 15 to about 100. The value of Q may be about 15 to about 100 (where P is greater than Q).

[0041] Preferably, the value of Q is about 12 to about 19, and more preferably about 15 to about 18.

[0042] The surfactant may have water solubility of at least approximately 0.01 g / ml, at least approximately 0.05 g / ml, or at least approximately 0.1 g / ml at room temperature and pressure (NTP).

[0043] The surfactant may be water-soluble at concentrations of 0.01 g / ml, 0.05 g / ml, and / or 0.1 g / ml at room temperature and pressure (NTP).

[0044] When water solubility is given at a specific concentration, this indicates that the surfactant is water-soluble at that concentration, but it will be understood that the surfactant is soluble over a range of concentrations (not just at a specific concentration).

[0045] Here, "normal temperature and pressure (NTP)" refers to the generally accepted meaning of 20°C and 1 atmosphere of pressure. 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 or not it dissolves.

[0046] Z 1 is R, RO, RC(O)-O, or ROC(O)-O. Preferably, Z 1 is RC(O)-O or ROC(O)-O. Preferably, Z 1 These are short-chain (e.g., C2-C5 or C2-C4) carbonate or ester groups.

[0047] R is C1 - C 11 an alkyl group. R can be a linear or branched C1 - C 11 alkyl group. Preferably, R is a C2 - C 11 alkyl group, more preferably a C2 - C6 or C2 - C5 alkyl group, typically a C2 - C4 alkyl group. Preferably, R is a linear alkyl group, preferably a linear C2 - C 11 alkyl group. Preferably, R is derived from a C1 - C 11 alcohol, preferably a C2 - C6 alcohol, typically a C2 - C5 alcohol or a C2 - C4 alcohol. Preferably, R is derived from a linear C1 - C 11 alcohol, preferably a linear C2 - C6 or C2 - C5 alcohol, typically a linear C2 - C4 alcohol or a linear C2 - C4 alcohol. Preferably, the C1 - C 11 alcohol is derived from a renewable feedstock. For example, the alcohol can be bioethanol or the like.

[0048] Z 2 is H, R, R-(O)C or R-O-(O)C, and preferably, Z 2 is H or methyl.

[0049] In certain embodiments, R e1 , R e2 , R e3 and R e4 can each independently be selected from H, methyl, or ethyl. R e1’ , R e2’ , R e3’ and R e4’ can each independently be selected from H, methyl, or ethyl, Z 2 can be methyl or H, and the polyether block can have less than 2% carbonate linkages.

[0050] According to a second aspect of the present invention, there is provided a process for producing a surfactant according to the first aspect of the present invention, the process comprising: (i) reacting carbon dioxide and an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound; and (ii) reacting the polycarbonate compound of step (i) with an epoxide and an ether catalyst to produce a surfactant according to the first aspect of the present invention.

[0051] The monofunctional starter may be a C1-C 11 alcohol or a C1-C 11 carboxylic acid. Typically, the monofunctional starter is a C1-C 11 alcohol, preferably a C2-C 11 alcohol, typically a C 2-6 alcohol or a C 2-4 alcohol.

[0052] The epoxide is selected from ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, glycidyl ether, glycidyl ester or glycidyl carbonate or a mixture of two or more thereof. Typically, the epoxide is selected from ethylene oxide, propylene oxide or a mixture thereof, preferably ethylene oxide.

[0053] The carbonate catalyst may be heterogeneous or homogeneous.

[0054] The carbonate catalyst may be a homogeneous complex of a single metal, bimetal, or polymetal, or a non-metal Lewis acid-base pair (e.g., based on a combination of borane and ammonium salts as disclosed in WO 2016 / 203408, WO 2020 / 121262, WO 2021 / 005470).

[0055] The carbonate catalyst may contain a phenol or phenolate ligand.

[0056] Typically, a carbonate catalyst can be a bimetallic complex containing a phenol or phenolate ligand. The two metals may be the same or different.

[0057] A carbonate catalyst may be a catalyst of formula (IV): [ka] During the ceremony, M is M-(L) v It is a metal cation represented by, x is an integer from 1 to 4, preferably 1 or 2. [ka] is a polydentate ligand or a group of polydentate ligands, L is a coordinating ligand; for example, L can be a neutral ligand or an anionic ligand that can open the ring of the epoxide. v is an integer that independently satisfies the valence of each M and / or the preferred coordination structure of each M, or such that the complex represented by formula (IV) above has an overall neutral charge. For example, each v can independently be 0, 1, 2, or 3, for example, v can be 1 or 2. If v > 1, each L may be different.

[0058] The term polydentate ligand includes bidentate, tridentate, tetradentate, and higher-order ligands. Each polydentate ligand can be a macrocyclic ligand or an open ligand.

[0059] Such catalysts include International Publication No. 2010 / 022388 (metallic salens and derivatives, metallic porphyrins, colorols and derivatives, metallic tetraazaanurenes and derivatives), International Publication No. 2010 / 028362 (metallic salens and derivatives, metallic porphyrins, colorols and derivatives, metallic tetraazaanurenes and derivatives), International Publication No. 2008 / 136591 (metallic salen), International Publication No. 2011 / 105846 (metallic salen), International Publication No. 2014 / 148825 (metallic salen), International Publication No. 2013 / 012895 (metallic salen), and European Patent No. 2258745A1 (metallic porphyrins and Examples include those described in Japanese Patent Application Publication No. 2008081518 (Metallic Porphyrins and Derivatives), Chinese Patent No. 101412809 (Metallic Salen and Derivatives), International Publication No. 2019 / 126221 (Metallic Aminotriphenol Complexes), U.S. Patent No. 9018318 (Metallic Beta-Diimic Acid Complexes), U.S. Patent No. 6133402A (Metallic Beta-Diimic Acid Complexes), and U.S. Patent No. 8278239 (Metallic Salen and Derivatives), the entire contents of which, in particular with respect to carbonate catalysts suitable for the reaction of CO2 with epoxides in the presence of starters and optionally solvents as defined herein, are incorporated herein by reference.

[0060] Preferably, the carbonate catalyst is a bimetallic phenolate catalyst. Suitable bimetallic phenolate complexes are described in International Publication Nos. 2009 / 130470, 2013 / 034750, 2016 / 012786, 2016 / 012785, 2012 / 037282, and 2019 / 048878A1, and their entire contents, in particular with respect to carbonate catalysts suitable for the reaction of CO2 with epoxides in the presence of starters and optionally solvents as defined herein, are incorporated herein by reference.

[0061] 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, cations, acidic or superacidic catalysts (e.g., HSbF6, CF3SO3H), PF5, activated monomer catalysts, organocatalysts such as imidazole or phosphazene reagents, and metallosalenate catalysts. Preferably, the ether catalyst is a DMC catalyst. Examples of DMC catalysts that can be used in the process of the present invention include U.S. Patent Nos. 3,427,256, 5,536,883, 6,291,388, 6,486,361, 6,608,231, 7,008,900, 5,482,908, 5,780,584, 5,783,513, 5,158,922, 5,693,584, 7,811,958, and 6,835,687. This includes the documents, U.S. Patent Nos. 6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500,704, 7,977,501, 9,315,622, European Patent Application Publication No. 1568414, European Patent Application Publication No. 1529566, and the contents of International Publication No. 2015 / 022290, all of which are incorporated by reference.

[0062] The ratio of carbonate catalyst to ether catalyst can range from approximately 300:1 to approximately 1:100, for example, approximately 120:1 to approximately 1:75, for example, approximately 40:1 to approximately 1:50, for example, approximately 30:1 to approximately 1:30, for example, approximately 20:1 to approximately 1:1, for example, approximately 10:1 to approximately 2:1, for example, approximately 5:1 to approximately 1:5. These ratios are mass ratios.

[0063] This process may be carried out in a one-pot reactor or it may be a double-reactor process.

[0064] Accordingly, according to a third aspect of the present invention, a process for producing a surfactant according to the first aspect of the present invention in a multi-reactor system is also provided, the system comprising first and second reactors, wherein the first reaction occurs in the first reactor and the second reaction occurs in the second reactor, the first reaction being the reaction of a carbonate catalyst with CO2 and an epoxide in the presence of a monofunctional starter compound and optionally a solvent for producing a polycarbonate compound, and the second reaction being a semi-batch or continuous reaction of the polycarbonate compound and epoxide from the first reaction with an ether catalyst for producing a surfactant according to the first aspect of the present invention.

[0065] Typically, the reaction mixture from the first step contains less than 5% by weight, preferably less than 2.5%, for example less than 1.0%, less than 0.5%, or less than 0.1% CO2, before the second step. Typically, the second step is carried out without the independent addition of CO2, but can be carried out under CO2 pressure. The polyether block produced in the second step may have less than 40% carbonate bonds, preferably less than 30% 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 produced in the second step is substantially free of carbonate bonds.

[0066] Therefore, typically, the second step is carried out in virtually the absence of CO2.

[0067] Therefore, substantially the absence of CO2 means that the second step is carried out in the presence of less than 4%, preferably less than 2%, for example less than 1.0%, less than 0.5%, or less than 0.1%, by weight, of CO2 in the total reactants, catalyst, and products in the second step.

[0068] Adding components in separate steps can be useful in enhancing catalytic activity and may result in a more efficient process compared to a process where all materials are provided at the start of the process. A significant portion of some components present throughout the entire process can reduce catalytic efficiency. Reacting these materials in separate steps can prevent this reduction in catalytic efficiency and / or optimize catalytic activity. The reaction conditions at each step can be adjusted to optimize the reaction of each catalyst.

[0069] The ether catalyst can be pre-activated before its addition in the second step. Such pre-activation can be achieved by mixing one or both catalysts with the epoxide (and optionally other components). Pre-activation of the ether catalyst is useful for enabling safe control of the reaction (preventing an uncontrolled increase in unreacted monomer content) and eliminating unpredictable activation periods.

[0070] Typically, residual CO2 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 can be carried out without CO2. However, it will be understood that a small amount of CO2 may be present in the reaction mixture of the second step as unused reagent from the first step. Alternatively, both steps may be carried out under CO2 pressure.

[0071] The reaction of the present invention may be carried out in the presence of a solvent; however, it will be understood that the method may also be carried out in the absence of a solvent. If 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), etc. The solvents may be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0072] Adding components to separate reactions and reactors can be useful in enhancing catalytic activity and may result in a more efficient process compared to a process where all materials are provided at the start of a single reaction. If some components present throughout the reaction are present in large quantities, the catalytic efficiency may decrease. Reacting these materials in separate reactors can prevent this decrease in catalytic efficiency and / or optimize catalytic activity. The reaction conditions in each reactor can be adjusted to optimize the reaction of each catalyst.

[0073] Furthermore, by not loading the total amount of each component at the start of the reaction, and by using the catalyst for the first reaction separately from the catalyst for the second reaction in separate reactors, uniform catalytic activity and a more uniform polymer product can be obtained. This can result in polymers with a narrower molecular weight distribution, desired ratios, distribution along the ether-carbonate bond chains, and / or improved stability.

[0074] Separating reactions with two different catalysts, mixing only specific components in the first reaction and adding the remaining components in the second reaction, can be useful, for example, by adding a pre-activated ether catalyst or by adding the reaction mixture to a pre-activated ether catalyst.

[0075] Preferred ether catalysts and carbonate catalysts are the same as those in the second embodiment of the present invention.

[0076] The first reaction may be carried out continuously in two or more reactors that supply the crude reaction mixture to the second reaction and reactor. Preferably, the second reaction is carried out in continuous mode.

[0077] The product of the first reaction can be stored for subsequent use in the second reactor.

[0078] The two reactors may be arranged in series, or the reactors may be nested inside each other. Each reactor may be a stirred tank reactor, a loop reactor, a tubular reactor, or other standard reactor design.

[0079] Alternatively, the surfactant of the first embodiment may be formed by reacting a monofunctional polyether starter compound with an epoxide and carbon dioxide in the presence of a carbonate catalyst. Therefore, according to a further embodiment of the present invention, a method for producing a surfactant according to the first embodiment of the present invention is provided, comprising (i) reacting a monohydroxy-functional polyether with a carbonate catalyst, an epoxide and CO2, and (ii) reacting it with an end-capping group, such as an anhydride, to produce the surfactant of the present invention. Typically, the resulting polycarbonate block is end-capped with any suitable functional group. End-capping the polycarbonate block stabilizes the surfactant. Typically, the polycarbonate block is end-capped with a suitable anhydride, typically an alkyl anhydride. The monofunctional polyether starter compound may be any suitable monofunctional polyether starter compound, typically a monofunctional PEG compound.

[0080] definition As used herein, the term “alkyl” refers to a saturated linear or branched hydrocarbon radical derived by removing a single hydrogen atom from an aliphatic moiety, unless otherwise defined. 1-20 An alkyl group can be a linear or branched alkyl group having 1 to 20 carbon atoms. Therefore, an alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Preferably, the alkyl group is C 1-15 Alkyl, preferably C 1-12 Alkyl, more preferably C 1-10 Alkyl, and more preferably C 1-8 Alkyl, and more preferably C 1-6 It is an alkyl group.

[0081] Unless otherwise defined herein, the ester group is optionally -OC(O)R 1 - or -C(O)OR 1 - and in the formula, R 1 R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 1 R can be unsubstituted aliphatic, alicyclic, or aryl. Optionally, 1 The ester group is methyl, ethyl, propyl, or phenyl. The ester group can be terminated with an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 1 If it is hydrogen, then -OC(O)R 1 - or -C(O)OR 1 It will be understood that the group defined by - is a carboxylic acid group.

[0082] The carbonate group can be optionally -OC(O)OR 2 And in the formula, R 2 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 2 R may be optionally substituted aliphatic, alicyclic, or aryl. 2 R is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. Optionally, R 2 R is methyl, ethyl, propyl, or phenyl. 2 If it is hydrogen, then -OC(O)OR 2 It will be understood that the group defined by is a carbonate group.

[0083] The carbonate functional group is -OC(O)O- and can originate from a suitable source. Generally, it originates from CO2.

[0084] The ether group is optionally -OR 3 And in the formula, R 3 R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 3 R can be unsubstituted aliphatic, alicyclic, or aryl. Optionally, 3 These are methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl. Optionally, R 3 These are methyl, ethyl, propyl, or phenyl.

[0085] As used herein, the term “optionally substituted” means that one or more hydrogen atoms of the optionally substituted moiety are substituted by a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substituted position of the group, and the substituents may be the same or different at all positions if two or more positions in any given structure can be substituted by two or more substituents selected from a particular group. The substituent combinations envisioned by the present invention preferably result in the formation of a stable compound. As used herein, “stable” means a compound that is chemically feasible and can exist for a sufficiently long time at room temperature, i.e., (16–25°C), to enable their detection, isolation and / or use in chemical synthesis.

[0086] Substituents may also be shown as being attached to bonds that cross bonds within the ring of the molecule being shown. This convention indicates that one or more substituents can be attached to the ring at any available position (usually instead of the hydrogen atoms of the structure). If an atom in the ring has two substitutable positions, two groups (the same or different) can be present on that atom.

[0087] Preferred optional substituents for use in the present invention include, but are not limited to, halogens, hydroxy, nitro, carboxylates, carbonates, alkoxys, aryloxys, alkylthios, arylthios, heteroaryloxys, alkylaryls, aminos, amides, imines, nitriles, silyls, silyl ethers, esters, sulfoxides, sulfonyls, acetylides, phosphinates, sulfonates, or optionally substituted (e.g., optionally substituted with halogens, hydroxy, nitros, carbonates, alkoxys, aryloxys, alkylthios, arylthios, aminos, imines, nitriles, silyls, sulfoxides, sulfonyls, phosphinates, sulfonates, or acetylides) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl groups.

[0088] Particularly preferred 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 Ariel, C 2-14 Heteroaryl, C 2-14 Hetero-alicyclic, C 1-6 Alkyl, C 1-6 Selected from haloalkyl, F, Cl, Br, I and OH, and the C 1-12 Alkoxy, C 6-18 Ariel, C 2-14 Heteroaryl, C 2-14 Hetero-alicyclic, C 1-6 Alkyl and C 1-6 Each of the haloalkyl groups is optionally substituted with any substituent as defined herein.

[0089] As used herein, the term “continuous” may be defined as the manner in which materials are added, or it may refer to the nature of the entire reaction method.

[0090] Regarding continuous addition methods, the relevant materials are added continuously or at a constant rate during the course of the reaction. This can be achieved, for example, by adding a flow of materials at either a constant or variable flow rate. In other words, one or more materials are added in an essentially non-stop manner. However, it should be noted that non-stop addition of materials may require brief interruptions for practical considerations, such as replenishing or replacing the containers of materials to which these materials are being added.

[0091] From the perspective that the overall reaction is continuous, the reaction can take place over a long period of time, such as several days, weeks, or months. In such continuous reactions, reactants can be continuously added, and / or the reaction products can be removed. While the catalyst may not be consumed during the reaction, it will be understood that the catalyst may need to be added in either case, as removal can deplete the amount of catalyst present.

[0092] In a continuous reaction, a continuous addition of materials could be employed.

[0093] In continuous reactions, discontinuous addition of materials (i.e., batch or semi-batch addition) can be employed.

[0094] As used herein, the term "series" refers to a case where two or more reactors are connected such that a crude reaction mixture can flow from a first reactor to a second reactor.

[0095] As used herein, the term nesting refers to a configuration in which two or more reactors are arranged such that one is located inside the other. For example, in the present invention, when a second reactor is located inside a first reactor, it is possible for the conditions of both reactors to influence the other.

[0096] example General Example 1 - Formation of carbonate blocks on monofunctional polyethers Catalyst (1) was prepared according to Example 2 of International Publication No. 2017 / 037441. 100 mL of polyethylene glycol monomethyl ether was added to a Parr high-pressure reactor. The vessel was dried by heating at 100°C for 60 minutes under vacuum, then cooled and packed with low-pressure CO2. Catalyst (1) was added.

[0097] An epoxide was added to the mixture. The mixture was stirred and pressurized to approximately half of the target pressure. The mixture was then heated to the target temperature (70°C) and the pressure (20 bar) was maintained at a constant temperature.

[0098] At the end of the desired reaction time, the mixture was cooled to <10°C and aerated through an acid scrubber system.

[0099] The monool was dissolved in dichloromethane containing triethylamine (1.3 equivalents) and alkyl anhydride (1.05 equivalents) and reacted under reflux for 16 hours. The end-capped monool was washed with water and brine, dried on sodium sulfate, and concentrated to dryness under vacuum to obtain the desired product. Ethylene carbonate by-products were removed using a Kugelrohr or short-pass evaporator (SPE).

[0100] [Table 1]

[0101] Mn and PDI were measured using gel permeation chromatography (GPC) as outlined above. The weight percentages of CO2 and carbonate were measured using NMR spectroscopy. Surface tension and critical micelle concentration (CMC) were measured using a tensile meter employing standard techniques.

[0102] Water solubility was measured by weighing 0.25 g of the 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.

[0103] [Table 2]

[0104] [Table 3]

[0105] The P:Q ratios for samples 1, 2, and 3 are 1.0625:1, 1.125:1, and 1.25:1, respectively.

[0106] The data demonstrates that the polycarbonate block polyether of the present invention is water-soluble, reduces surface tension, and promotes micelle formation, which provides surfactant behavior.

[0107] An alternative method for producing the surfactant of the present invention is described below.

[0108] General example 2 Reaction 1 Monoall starter was added to a 100 mL Parr high-pressure reactor system. The vessel was dried by heating at 100°C for 60 minutes under vacuum, then cooled and packed with low-pressure CO2. Catalyst (1) (see Example 1) was added.

[0109] EO was added to the mixture. The mixture was stirred and pressurized to approximately half the target pressure. The mixture was then heated to the target temperature and held at a constant temperature and target pressure.

[0110] At the end of the desired reaction time, the mixture was cooled to <10°C and aerated through an acid scrubber system. After adding EO and anhydrous ethyl acetate to the cold-stirred mixture, it was transferred to an intermediate holding container.

[0111] Reaction 2: Pre-dried monoall starter and DMC, consisting of zinc hexacyanocobaltate and tert-butyl alcohol (2), were added to a 100 mL Parr high-pressure reactor system. After holding the vessel under vacuum for approximately 2 minutes, it was packed with low-pressure N2, followed by anhydrous ethyl acetate (15 mL).

[0112] Next, the container was heated to 130°C with stirring, and the DMC was activated with approximately 0.3 g PO twice. After activation (as evidenced by the pressure drop), the external heater was removed, the reactor was optionally pressurized with CO2, and the mixture was then cooled to the target addition temperature.

[0113] Once the target temperature was reached, the mixture from Reaction 1 was added to the activated DMC system over a period of approximately 60–90 minutes. After the addition of the mixture was complete, the mixture was "cooked out" for several hours, then cooled, aerated, and samples were taken for analysis by NMR and GPC.

[0114] [Table 4]

[0115] [Table 5]

Claims

1. Polycarbonate block polyether of formula I: Z １ -(PC) Ｐ -(PE) Ｑ -Z ２ (I) (In the formula, PC is the formula) 【Chemistry 1】 (wherein R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ are independently selected from H, methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, provided that when one of R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ is methyl, ethyl, propyl, butyl, or an ether, ester or carbonate group, the remaining R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ are H), represents a carbonate block having P repeating units, PE is, formula 【Chemistry 2】 (In the formula, R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ is 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’ If one of them is a methyl, ethyl, propyl, butyl, or ether, ester, or carbonate group, then the remaining R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ This represents a polyether block having Q repeating units of H, Z １ These are R, R-O, R-C(O)-O, or R-O-C(O)-O. R is a linear or branched C that has been optionally substituted. １ ~C １１ It is an alkyl group, Z ２ is H, R, R-(O)C or R-O-(O)C, and (The value of P is greater than the value of Q.) A surfactant containing a surfactant.

2. R is C ２ -C １１ The surfactant according to claim 1, wherein it is an alkyl group.

3. The surfactant according to claim 1 or 2, wherein R is a linear alkyl group.

4. R is C ２ -C ６ Alkyl alkyl groups, typically C ２ -C ５ Alkyl or C ２ -C ４ A surfactant according to any one of claims 1 to 3, wherein the surfactant is an alkyl group.

5. R ｅ１ , R ｅ２ , R ｅ３ , R ｅ４ , R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ However, it is independently selected from H, methyl, or ethyl, preferably R ｅ１ , R ｅ２ , R ｅ３ , R ｅ４ , R ｅ１’ , R ｅ２’ , R ｅ３’ , and R ｅ４’ The surfactant according to any one of claims 2 to 4, wherein each of them is H.

6. Z １ However, R-C(O)-O or R-O-C(O)-O, preferably short chain (for example, C ２ -C ５ or C ２ -C ４ ) A surfactant according to any one of claims 1 to 5, wherein the surfactant is a carbonate group or an ester group R-O.

7. Z ２ The surfactant according to any one of claims 1 to 6, wherein is H or methyl.

8. All of the above surfactants contain more than 10% by weight of CO ２ Incorporation, more typically more than 15, 20, or 21% by weight of CO2 ２ A surfactant according to any one of claims 1 to 7, which has incorporation properties.

9. All of the above surfactants contain 10 to 40% by weight of CO ２ Incorporation, typically 15–40% by weight of CO ２ Incorporation, more typically 20–40 wt% CO ２ A surfactant according to any one of claims 1 to 8, which has incorporation properties.

10. The surfactant according to any one of claims 1 to 9, wherein the difference between the value of P and the value of Q is in the range of approximately 1 to approximately 10, or approximately 1 to approximately 5, or approximately 1 to approximately 3.

11. The surfactant according to any one of claims 1 to 10, wherein the ratio of P to Q is about 1.3:1 or less, about 1.25:1 or less, about 1.2:1 or less, more preferably about 1.15:1 or less, even more preferably about 1.125:1 or less, and most preferably about 1.1:1 or less.

12. The surfactant according to any one of claims 1 to 11, 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 claims 1 to 12, wherein the polyether block has 0% carbonate bonds.

14. A water-soluble surfactant according to any one of claims 1 to 13.

15. A surfactant according to any one of claims 1 to 14, having 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 atmospheric pressure.

16. The surfactant according to any one of claims 1 to 15, which is water-soluble at concentrations of 0.01 g / ml, 0.05 g / ml, and / or 0.1 g / ml at room temperature and atmospheric pressure.

17. A method for producing a surfactant according to any one of claims 1 to 16, (i) A step of reacting carbon dioxide with an epoxide in the presence of a carbonate catalyst and a monofunctional starter compound to form a polycarbonate compound, (ii) A step of reacting the polycarbonate compound from step (i) with an epoxide and an ether catalyst to produce the surfactant according to any one of claims 1 to 16, A method that includes this.

18. A method for producing a surfactant according to any one of claims 1 to 16 using a multi-reactor system, wherein the system comprises first and second reactors, the first reaction occurring in the first reactor, the second reaction occurring in the second reactor, and the first reaction comprising a monofunctional starter compound and optionally a carbonate catalyst and CO in the presence of a solvent for producing a polycarbonate compound. ２ A method comprising a reaction with an epoxide, wherein the second reaction is a semi-batch or continuous reaction of the polycarbonate compound and epoxide of the first reaction with an ether catalyst for producing 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 phenolate complex.

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

21. Monohydroxy functional polyethers (i) Carbonate catalysts, epoxides and CO ２ , and (ii) Reacting with an end-capping group such as an anhydride to produce the surfactant according to any one of claims 1 to 20. A method for producing a surfactant according to any one of claims 1 to 16.

22. Use of the surfactant according to any one of claims 1 to 16 as an agricultural chemical adjuvant, for the preparation of foams, coatings, paints, adhesives and sealants for the building and construction industry, in the automotive industry, in textile manufacturing, and for increasing crude oil recovery rates.

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