Method for preparing surfactants by copolymerization of epoxides with CO2 using a mixture of macrocyclic bimetallic and double metal cyanide catalysts

Abstract

The present invention relates to a catalytic process for preparing surfactant molecules, the surfactant molecules obtained by the process, compositions comprising the surfactant molecules, and the use of the surfactant molecules so prepared in cleaning products. The process comprises reacting carbon dioxide with an epoxide in the presence of a double metal cyanide (DMC) catalyst, a catalyst of formula (I), and a monofunctional initiator compound. JPEG2024531955000022.jpg56170

Description

[Technical field]

[0001] The present invention relates to surfactant molecules, catalytic methods for preparing surfactant molecules, and uses of the surfactant molecules so prepared. The present invention more particularly, but not necessarily exclusively, relates to methods having improved specificity through the controlled addition of materials during polymerization. [Background technology]

[0002] Surfactants are compounds that typically reduce the tension between two liquid phases. Typically, surfactants used in aqueous systems contain a hydrophobic group and a hydrophilic group and are described as amphiphilic.

[0003] Traditionally, the hydrophobic portion of nonionic surfactants contains hydrocarbon chains derived from either petroleum or natural oils such as palm oil, and polyether chains, which are also derived from petroleum. It is therefore desirable to form surfactants from alternative feedstocks, especially more sustainable feedstocks.

[0004] It would be advantageous to produce water-soluble surfactant molecules for use in cleaning systems that use carbon dioxide as a renewable feedstock but under moderate pressures that can operate with existing manufacturing facilities. It would also be advantageous to produce them in a one-pot reaction without multiple reaction steps.

[0005] It is an object of the present invention to provide a method for producing CO2-containing surfactant molecules at moderate pressures using a two catalyst system. Summary of the Invention

[0006] According to the present invention, there is provided a method for preparing a surfactant molecule, comprising reacting carbon dioxide with an epoxide in the presence of a double metal cyanide (DMC) catalyst, a catalyst of formula (I), and a monofunctional initiator compound, wherein the catalyst of formula (I) has the following structure:

[0007] [ka]

[0008] wherein M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2, or Ti(IV)-(X)2; R1 and R2 are independently selected from hydrogen, a halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, where the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene are optionally interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic; R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; E1 is C and E2 is O, S, or NH, or E1 is N and E2 is O; E3, E4, E5, and E6 are selected from N, NR4, O, and S, where if E3, E4, E5, or E6 is N,

[0009] [ka]

[0010] teeth

[0011] [ka]

[0012] and E3, E4, E5, or E6 is NR4, O, or S;

[0013] [ka]

[0014] teeth

[0015] [ka]

[0016] and; R4 is H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 or -alkylC≡N, or alkylaryl; X is O.C.O.R. x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl, where each X may be the same or different, and X may form a bridge between M1 and M2; R xis independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl; G is independently selected from neutral or anionic donor ligands that are absent or Lewis bases.

[0017] The method may include forming a mixture including a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent, followed by increasing the temperature by at least 10°C.

[0018] This method involves the following steps: (I)(a) mixing a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent, with an epoxide and optionally a monofunctional initiator compound and / or carbon dioxide to form a mixture (α); or (b) mixing a double metal cyanide (DMC) catalyst and optionally a monofunctional initiator compound, carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α); or (c) mixing an epoxide, a catalyst of formula (I), a monofunctional initiator compound, and carbon dioxide, and optionally a solvent, to form a mixture (α); or (d) mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a monofunctional initiator compound, an epoxide, carbon dioxide, and / or a solvent to form a mixture (α); and (II) adding one or more of a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent to the mixture (α) to form a mixture (β) comprising a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent, and / or increasing the temperature by 10° C. may include.

[0019] Also provided are surfactant molecules obtainable by the methods described herein, uses of said surfactant molecules in cleaning products, and compositions comprising said surfactant molecules, said compositions being surfactant formulations for cleaning products.

[0020] The surfactant molecules of the present invention can also be used as functional additives in agricultural chemicals, enhanced oil recovery, building materials in foam properties, coatings, paints, adhesives, automotive applications, and textile manufacturing. Compositions suitable for use in such applications can be formulated comprising the surfactant molecules of the present invention.

[0021] definition For purposes of the present invention, an aliphatic group is a hydrocarbon moiety that may be straight-chained (i.e., unbranched), branched, or cyclic, and may be fully saturated or may contain one or more units of unsaturation, but is not aromatic. The term "unsaturated" refers to a moiety having one or more double and / or triple bonds. Thus, the term "aliphatic" is intended to include alkyl, cycloalkyl, alkenyl cycloalkenyl, alkynyl, or cycloalkenyl groups, and combinations thereof.

[0022] The aliphatic group is optionally C 1~30 Aliphatic groups, i.e., aliphatic groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms. 1~6 Aliphatic groups, such as C 1~15 Aliphatic, optionally C 1~12 Aliphatic, optionally C 1~10 Aliphatic, optionally C 1~8 Aliphatic. Suitable aliphatic groups include straight-chain or branched alkyl, alkenyl, and alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, and (cycloalkyl)alkenyl groups.

[0023] The term "alkyl" as used herein refers to a saturated, straight or branched chain hydrocarbon radical derived from an aliphatic moiety by removing one hydrogen atom. An alkyl group is defined as "C 1~20 The alkyl group may be a "alkyl group," which is an alkyl group that is straight or branched chain having 1 to 20 carbons. Thus, the alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alkyl group is 1~15 Alkyl, optionally C 1~12 Alkyl, optionally C 1~10 Alkyl, optionally C 1~8 Alkyl, optionally C 1~6 It is an alkyl group. 1~20 Examples of the "alkyl group" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, an isopentyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a sec-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, and an n-nonadecyl group. , n-eicosyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, and 3-methylpentyl group.

[0024] The term "alkenyl" as used herein denotes a group derived from the removal of a single hydrogen atom from a straight or branched chain aliphatic moiety having at least one carbon-carbon double bond. The term "alkynyl" as used herein refers to a group derived from the removal of one hydrogen atom from a straight or branched chain aliphatic moiety having at least one carbon-carbon triple bond. Alkenyl and alkynyl groups each optionally include the moiety "C 2~20 alkenyl" and "C 2~20 alkynyl", optionally with "C 2~15 alkenyl" and "C 2~15 alkynyl", optionally with "C 2~12 alkenyl" and "C 2~12 alkynyl", optionally with "C 2~10 alkenyl" and "C 2~10 alkynyl", optionally with "C 2~8 alkenyl" and "C 2~8 alkynyl", optionally with "C 2~6 alkenyl" and "C 2~6 Examples of alkenyl groups include ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, 1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, and allenyl. Examples of alkynyl groups include ethynyl, 2-propynyl (propargyl), and 1-propynyl.

[0025] The terms "cycloaliphatic", "carbocycle", or "carbocyclic" as used herein refer to saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring systems having 3 to 20 carbon atoms, i.e., alicyclic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alicyclic group has 3 to 15, optionally 3 to 12, optionally 3 to 10, optionally 3 to 8 carbon atoms, optionally 3 to 6 carbon atoms. The terms "cycloaliphatic", "carbocycle", or "carbocyclic" also include an aliphatic ring fused to one or more aromatic or non-aromatic rings, such as a tetrahydronaphthyl ring, where the point of attachment is on the aliphatic ring. A carbocyclic group may be polycyclic, for example bicyclic or tricyclic. It will be understood that an alicyclic group may include an alicyclic ring having one or more linked or unlinked alkyl substituents, such as -CH2-cyclohexyl. Specifically, examples of carbocyclic rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4.5]decane, cycloheptane, adamantane, and cyclooctane.

[0026] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl, and heteroalkynyl) are aliphatic groups as described above further containing one or more heteroatoms. Thus, heteroaliphatic groups optionally contain 2-21 atoms, optionally 2-16 atoms, optionally 2-13 atoms, optionally 2-11 atoms, optionally 2-9 atoms, and optionally 2-7 atoms, with at least one atom being a carbon atom. The optional heteroatoms are selected from O, S, N, P, and Si. When a heteroaliphatic group has more than one heteroatom, the heteroatoms may be the same or different. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and may contain saturated, unsaturated, or partially unsaturated groups.

[0027] An alicyclic group refers to a saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring system having 3 to 20 carbon atoms, i.e., an alicyclic group having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alicyclic group has 3 to 15, optionally 3 to 12, optionally 3 to 10, optionally 3 to 8 carbon atoms, optionally 3 to 6 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl, and cycloalkynyl groups. It will be understood that an alicyclic group may include an alicyclic ring having one or more linked or unlinked alkyl substituents, such as -CH2-cyclohexyl. C 3~20 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0028] Heteroalicyclic groups are alicyclic groups as defined above having, in addition to carbon atoms, one or more ring heteroatoms optionally selected from O, S, N, P, and Si. Heteroalicyclic groups optionally contain 1 to 4 heteroatoms which may be the same or different. Heteroalicyclic groups optionally contain 5 to 20 atoms, optionally 5 to 14 atoms, optionally 5 to 12 atoms.

[0029] An aryl group or ring is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms, at least one ring in the system is aromatic, and each ring in the system contains from 3 to 12 ring members. The term "aryl" can be used alone or as part of a larger moiety, such as in "aralkyl," "aralkoxy," or "aryloxyalkyl." An aryl group is optionally followed by "C 6~12 "C" may be an aryl group, which is an aryl group consisting of 6, 7, 8, 9, 10, 11, or 12 carbon atoms, including monocyclic or fused ring groups such as bicyclic ring groups. 6~10Specific examples of the "aryl group" include a phenyl group, a biphenyl group, an indenyl group, an anthracyl group, a naphthyl group, and an azulenyl group. Note that fused rings such as indane, benzofuran, phthalimide, phenanthridine, and tetrahydronaphthalene are also included in the aryl group.

[0030] The term "heteroaryl," used alone or as part of another term (such as "heteroaralkyl" or "heteroaralkoxy"), refers to a group having 5 to 14 ring atoms, optionally 5, 6, or 9 ring atoms; having 6, 10, or 14 pi electrons shared in a cyclic arrangement; and having 1 to 5 heteroatoms in addition to the carbon atoms. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of nitrogen. The term "heteroaryl" also includes groups in which a heteroaryl ring is fused to one or more aryl, alicyclic, or heterocyclic rings, where the radical or point of attachment is on the heteroaromatic ring. Examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. Thus, heteroaryl groups can be monocyclic or polycyclic.

[0031] The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, where the alkyl and heteroaryl portions independently are optionally substituted. As used herein, the terms "heterocycle," "heterocyclic," "heterocyclic group," and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclic heterocyclic moiety that is saturated, partially unsaturated, or aromatic, as defined above, having, in addition to carbon atoms, one or more, optionally 1-4 heteroatoms. The term "nitrogen" when used in reference to a ring atom of a heterocycle also includes substituted nitrogen.

[0032] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxine, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazo Examples of suitable aryls include aryl, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.

[0033] The terms "halide", "halo" and "halogen" are used interchangeably and as used herein refer to fluorine, chlorine, bromine, iodine atoms and the like, optionally referring to fluorine, bromine or chlorine atoms, optionally referring to fluorine atoms.

[0034] The haloalkyl group is optionally represented by "C 1~20 Haloalkyl group", optionally with "C 1~15 Haloalkyl group", optionally with "C 1~12 Haloalkyl group", optionally with "C 1~10 Haloalkyl group", optionally with "C 1~8 Haloalkyl group", optionally with "C 1~6 haloalkyl groups, each of which is a C group as described above, optionally substituted with at least one halogen atom, optionally 1, 2, or 3 halogen atoms. 1~20 Alkyl, C 1~15 Alkyl, C 1~12 Alkyl, C 1~10 Alkyl, C 1~8 Alkyl, or C 1~6 The term "haloalkyl" includes fluorinated or chlorinated groups, such as perfluorinated compounds. 1~20 Examples of the "haloalkyl group" include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, and the like.

[0035] The alkoxy group is optionally represented by "C 1~20 Alkoxy group", optionally "C 1~15 Alkoxy group", optionally "C 1~12 Alkoxy group", optionally "C 1~10 Alkoxy group", optionally "C 1~8 Alkoxy group", optionally "C 1~6 "alkoxy group" as defined above, 1~20 Alkyl, C 1~15 Alkyl, C 1~12 Alkyl, C 1~10 Alkyl, C 1~8 Alkyl, or C 1~6 It is an oxy group bonded to an alkyl group. 1~20Examples of the "alkoxy group" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, an isohexyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, an n-hexadecyoxy group, an Examples of the aryloxy group include aryloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 2-methylbutoxy, 1-ethyl-2-methylpropoxy, 1,1,2-trimethylpropoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 1,3-dimethylbutoxy, 2-ethylbutoxy, 2-methylpentyloxy, and 3-methylpentyloxy groups.

[0036] The aryloxy group is optionally represented by "C 5~20 aryloxy group", optionally "C 6~12 aryloxy group", optionally "C 6~10 aryloxy group" as defined above, 5~20 Aryl, C 6~12 Aryl, or C 6~10 It is an oxy group attached to an aryl group.

[0037] The alkylthio group is optionally represented by "C 1~20 alkylthio group", optionally "C 1~15 alkylthio group", optionally "C 1~12 alkylthio group", optionally "C 1~10 alkylthio group", optionally "C 1~8 alkylthio group", optionally "C 1~6 "alkylthio group" as defined above, 1~20Alkyl, C 1~15 Alkyl, C 1~12 Alkyl, C 1~10 Alkyl, C 1~8 Alkyl, or C 1~6 It is a thio (-S-) group attached to an alkyl group.

[0038] The arylthio group is optionally represented by "C 5~20 arylthio group", optionally "C 6~12 arylthio group", optionally "C 6~10 arylthio group" as defined above, 5~20 Aryl, C 6~12 Aryl, or C 6~10 It is a thio (-S-) group attached to an aryl group.

[0039] The alkylaryl group is optionally represented by "C 6~12 Aryl C 1~20 Alkyl group", optionally "C 6~12 Aryl C 1~16 Alkyl group", optionally "C 6~12 Aryl C 1~6 "alkyl group", which is an aryl group as defined above attached at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to the molecule may be through the alkyl portion, thus optionally the alkylaryl group is -CH2-Ph or -CH2CH2-Ph. The alkylaryl group may also be referred to as an "aralkyl".

[0040] The silyl group is optionally represented by -Si(R s )3, and R s is independently an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. s is independently unsubstituted aliphatic, alicyclic, or aryl. s is an alkyl group selected from methyl, ethyl, or propyl.

[0041] The silyl ether group is optionally an OSi(R6)3 group, where each R6 can be independently an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. Each R6 can be independently an unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, each R6 is an alkyl group selected from an optionally substituted phenyl or an optionally substituted methyl, ethyl, propyl, or butyl, such as n-butyl (nBu) or tert-butyl (tBu). Exemplary silyl ether groups include OSi(Me)3, OSi(Et)3, OSi(Ph)3, OSi(Me)2(tBu), OSi(tBu)3, and OSi(Ph)2(tBu).

[0042] The nitrile group (also called the cyano group) is the group CN. The imine group is a -CRNR group, optionally -CHNR7, where R7 is an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. R7 can be unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, R7 is an alkyl group selected from methyl, ethyl, or propyl.

[0043] The acetylide group has a triple bond -C≡C-R9, where optionally R9 can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. For the purposes of the present invention, when R9 is an alkyl group, the triple bond can be at any position of the alkyl chain. R9 can be an unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, R9 is methyl, ethyl, propyl, or phenyl.

[0044] The amino group is optionally -NH2, -NHR 10 , or -N(R 10 )2, and R 10can be an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, silyl, aryl, or heteroaryl group as defined above. 10 )2, then each R 10 It will be understood that the groups may be the same or different. 10 can be independently unsubstituted aliphatic, alicyclic, silyl, or aryl. 10 is methyl, ethyl, propyl, SiMe3, or phenyl.

[0045] The amide group is optionally represented by -NR 11 C(O)- or -C(O)-NR 11 - and R 11 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 11 can be unsubstituted aliphatic, alicyclic, or aryl. 11 is hydrogen, methyl, ethyl, propyl, or phenyl. The amide group may have a terminal hydrogen, an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group.

[0046] The ester group is optionally -OC(O)R 12 -OR-C(O)OR 12 - and R 12 R can be an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. 12 can be unsubstituted aliphatic, alicyclic, or aryl. 12 R is methyl, ethyl, propyl, or phenyl. The ester group can have a terminal aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group. 12 If is hydrogen, -OC(O)R 12 -OR-C(O)OR 12It will be understood that a group defined with - will be a carboxylic acid group.

[0047] The sulfoxide is optionally represented by -S(O)R 13 and the sulfonyl group is optionally -S(O)R 13 and R 13 R can be an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. 13 can be unsubstituted aliphatic, alicyclic, or aryl. 13 is methyl, ethyl, propyl, or phenyl.

[0048] The carboxylate group is optionally represented by -OC(O)R 14 and R 14 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 14 can be unsubstituted aliphatic, alicyclic, or aryl. 14 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, or adamantyl.

[0049] The phosphinate group is optionally represented by -OP(O)(R 16 )2 or -P(O)(OR 16 )(R 16 ) and each R 16 R is independently selected from hydrogen or an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. 16 can be aliphatic, alicyclic, or aryl, which is aliphatic, alicyclic, aryl, or C 1~6Optionally, R is substituted with alkoxy. 16 is optionally substituted aryl or C 1~20 Alkyl, optionally C 1~6 Phenyl optionally substituted with alkoxy (optionally methoxy) or unsubstituted C 1~20 The phosphonate group is optionally -P(O)(OR 16 )2, and R 16 is as defined above. -P(O)(OR 16 ) 2 R 16 If one or both are hydrogen, -P(O)(OR 16 It will be understood that the group defined as 2) will be a phosphonic acid group.

[0050] The sulfinate group is optionally -S(O)OR 17 or -OS(O)R 17 and R 17 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a haloaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 17 can be unsubstituted aliphatic, alicyclic, or aryl. 17 is hydrogen, methyl, ethyl, propyl, or phenyl. 17 If is hydrogen, -S(O)OR 17 It will be understood that a group defined as: is a sulfonic acid group.

[0051] The carbonate group is optionally -OC(O)OR 18 and R 18 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 18 can be optionally substituted aliphatic, alicyclic, or aryl. 18is 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. R 17 It will be appreciated that when is hydrogen, the group defined as -OC(O)OR18 becomes a carbonate group.

[0052] -AlkylC(O)OR 19 or -alkylC(O)R 19 In the group, R 19 R is hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 19 can be unsubstituted aliphatic, alicyclic, or aryl. 19 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, or adamantyl.

[0053] It will be understood that when any of the above groups are present in the Lewis base G, one or more additional R groups may optionally be present to satisfy valences. For example, an additional R group associated with an amino group is RNHR. 10 where R is hydrogen, an optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. Optionally, R is hydrogen or an aliphatic, cycloaliphatic, or aryl.

[0054] As used herein, the term "optionally substituted" means that one or more of the hydrogen atoms of the optionally substituted moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when more than one position of any given structure can be substituted with more than one substituent selected from a particular group, the substituents can be the same or different at every position. Combinations of substituents contemplated by the present invention are optionally those that result in the formation of stable compounds. As used herein, the term "stable" refers to a compound that is chemically feasible and can exist at room temperature, i.e. (16-25°C), for a sufficient period of time to allow its detection, isolation, and / or use in chemical synthesis.

[0055] Optional substituents for use in the present invention include, but are not limited to, halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate, or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group (e.g., optionally substituted with halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate, or acetylide).

[0056] Although in formula (I) the X and G groups are illustrated as being attached to one M1 or M2 metal center, it will be understood that one or more of the X and G groups may form a bridge between the M1 and M2 metal centers.

[0057] For the purposes of the present invention, the epoxide substrate is not limited. Thus, the term epoxide refers to any compound containing an epoxide moiety (i.e., a substituted or unsubstituted oxirane compound). Substituted oxiranes include mono-, di-, tri-, and tetra-substituted oxiranes. An epoxide can contain a single oxirane moiety. An epoxide can contain two or more oxirane moieties.

[0058] Examples of epoxides that can be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (limonene oxide, C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 22 O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO)), 1,2-epoxybutane, glycidyl ethers, vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy 1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides. Examples of functionalized 3,5-dioxaepoxides include:

[0059] [ka]

[0060] Examples include: The epoxide moiety may be a glycidyl ether, a glycidyl ester, or a glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters, and glycidyl carbonates include:

[0061] [ka]

[0062] Examples include: As described above, the epoxide substrate can contain more than one epoxide moiety. That is, it can be a bis-epoxide, tris-epoxide, or multi-epoxide-containing moiety. Examples of compounds containing more than one epoxide moiety include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds with more than one epoxide moiety can result in crosslinking in the resulting polymer.

[0063] Those skilled in the art will appreciate that epoxides can be obtained from "green" or renewable resources. Epoxides can be obtained from (poly)unsaturated compounds such as those derived from fatty acids and / or terpenes obtained using standard oxidation chemistry.

[0064] The epoxide moiety can include an -OH moiety or a protected -OH moiety. The -OH moiety can be protected with any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), triisopropylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP). The purity of the epoxide is optionally at least 98%, and optionally >99%. It will be understood that the term "epoxide" is intended to encompass one or more epoxides. In other words, the term "epoxide" refers to a single epoxide or a mixture of two or more different epoxides. For example, the epoxide substrate can be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide, and cyclohexene oxide.

[0065] Polyether carbonate and polycarbonate ether are used interchangeably herein and both refer to polymers having at least one ether linkage, preferably multiple ether linkages, and at least one carbonate linkage, preferably multiple carbonate linkages.

[0066] As used herein, the term "continuous" can be defined as the manner in which materials are added, or it can refer to the nature of the reaction process as a whole. In the sense of continuous addition, the corresponding material is added continuously or constantly throughout the reaction. This can be achieved, for example, by adding a stream of material at a constant flow rate or at a varying flow rate. In other words, one or more materials are added essentially without interruption. However, it should be noted that, due to practical considerations, even when adding a material without interruption, it may be necessary to interrupt it for a short period of time, for example, to refill the original container from which the material is added or to replace the container.

[0067] In the sense that the overall reaction is continuous, the reaction may be carried out over an extended period of time, e.g., days, weeks, months, etc. In such a continuous reaction, reaction materials may be continuously added and / or reaction products may be withdrawn. It will be understood that the catalyst may not be consumed during the reaction, but may be replenished as the amount of catalyst present may be depleted when withdrawals are made.

[0068] In a continuous reaction, continuous addition of materials can be performed. The term "discontinuous" as used herein means that the addition of material is made in portions. This can be accomplished, for example, by dropwise addition of the material. Alternatively, the material may be added in portions to the vessel (i.e., batch-fed) with time intervals between additions. These time intervals may be regular or may vary over the course of the reaction. Such time intervals may be only a few minutes or may be several hours. For example, the time intervals may be from 1 minute to 12 hours; 5 minutes to 6 hours; 10 minutes to 4 hours; 15 minutes to 3 hours; 20 minutes to 2 hours; or 30 minutes to 1 hour. If the material is added in portions (i.e., batch-fed), there must be at least two separate additions of the material during the course of the reaction as a whole.

[0069] A continuous reaction can also involve discontinuous (ie, batchwise) addition of materials. A surfactant molecule refers to a molecule that reduces the surface and / or interfacial tension of the medium it is dissolved in. In the context of an aqueous phase, a surfactant typically contains a hydrophobic portion and a hydrophilic portion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0070] The present invention relates to continuous and discontinuous processes for the preparation of surfactant molecules by reacting epoxides with carbon dioxide in the presence of a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and a monofunctional initiator compound.

[0071] Accordingly, the present invention provides a method for preparing a surfactant molecule, comprising reacting carbon dioxide with an epoxide in the presence of a double metal cyanide (DMC) catalyst, a catalyst of formula (I), and a monofunctional initiator compound, wherein the catalyst of formula (I) has the following structure:

[0072] [ka]

[0073] (M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2, or Ti(IV)-(X)2; R1 and R2 are independently selected from hydrogen, a halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, where the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene are optionally interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic; R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; E1 is C and E2 is O, S, or NH, or E1 is N and E2 is O; E3, E4, E5, and E6 are selected from N, NR4, O, and S, where if E3, E4, E5, or E6 is N,

[0074] [ka]

[0075] teeth

[0076] [ka]

[0077] and E3, E4, E5, or E6 is NR4, O, or S;

[0078] [ka]

[0079] teeth

[0080] [ka]

[0081] and; R4 is H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 or -alkylC≡N, or alkylaryl; X is O.C.O.R. x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl, where each X may be the same or different, and X may form a bridge between M1 and M2; R x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl; G is independently selected from neutral or anionic donor ligands that are absent or Lewis bases. has.

[0082] The method may include forming a mixture including a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent, followed by increasing the temperature by at least 10°C.

[0083] This method involves the following steps: (I)(a) mixing a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent, with an epoxide and optionally a monofunctional initiator compound and / or carbon dioxide to form a mixture (α); or (b) mixing a double metal cyanide (DMC) catalyst and optionally a monofunctional initiator compound, carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α); or (c) mixing an epoxide, a catalyst of formula (I), a monofunctional initiator compound, and carbon dioxide, and optionally a solvent, to form a mixture (α); or (d) mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a monofunctional initiator compound, an epoxide, carbon dioxide, and / or a solvent to form a mixture (α); and (II) adding one or more of a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent to the mixture (α) to form a mixture (β) comprising a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent, and optionally increasing the temperature by at least 10° C. may include.

[0084] The present invention relates to a method for preparing surfactant molecules, which is preferably carried out in two or more stages, such that one part of the reaction is initiated, and then one or more of the reaction ingredients are further added (either in a continuous or discontinuous manner) and / or the temperature of the reaction is increased in a second stage as the reaction continues.

[0085] Preferably, the reaction occurs in a single reactor, ie, step (I) and step (II) occur in the same reactor. It may be useful to add certain components in the second step to increase the activity of the catalyst, which may result in a more efficient process compared to a process in which all of the materials are provided at the beginning of the reaction. Large amounts of some components present throughout the reaction may reduce the efficiency of the catalyst. By slowly adding materials to the reaction, this reduced efficiency of the catalyst can be prevented and / or the catalyst activity can be optimized.

[0086] Furthermore, not adding the entire amount of each component at the beginning of the reaction can result in uniform catalysis and a more homogeneous polymer product, which in turn can result in a narrower molecular weight distribution, a desired ratio of ether to carbonate linkages, and / or an improved (i.e., lower) polydispersity index.

[0087] Mixing only certain components in a first step and adding the rest in a second step can also be useful to preactivate the catalysts. Such preactivation can be achieved by mixing one or both catalysts with the epoxide (and optionally other components) per step (I)(a) or (b) above. Preactivation can be useful to prepare one or both catalysts so that upon addition of the remaining components in step (II), the efficiency of the reaction can be increased.

[0088] It will be understood that the present invention is directed to reactions that add carbonate and ether linkages to growing polymer chains. It may be useful to mix only certain components in a first step and add the rest in a second step to allow part of the reaction to proceed before the second stage of the reaction.

[0089] Generally speaking, it is an object of the present invention to control the polymerization reaction by controlled addition of materials. The methods herein can allow the products prepared by such methods to be tailored to requirements.

[0090] The mixture (α) formed by step (I)(b) may be held at a temperature of about 50-150° C., optionally about 80-130° C., prior to step (II). Mixture (α) formed by step (I)(a), (c), or (d) may be held at a temperature of about 0-120° C., optionally about 40-100° C., optionally about 50-90° C., about 50-80° C., about 55-80° C., or about 60-80° C. prior to step (II).

[0091] In step (II), the temperature can be increased to 60-150° C., optionally 65-150° C., optionally 80-130° C. Optionally, additional epoxide is also added.

[0092] Mixture (α) may be held for at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, optionally at least about 5 hours prior to step (II).

[0093] Mixture (a) formed by step (I)(c) may be held for at least about 1 minute, optionally for at least about 5 minutes, optionally for at least about 15 minutes, optionally for at least about 30 minutes, optionally for at least about 1 hour, optionally for at least about 2 hours, optionally for at least about 3 hours, optionally for at least about 4 hours, optionally for at least about 8 hours, optionally for at least about 16 hours prior to step (II).

[0094] The mixture (α) may contain less than about 1% by weight of water, optionally less than about 0.5% by weight of water, optionally less than about 0.1% by weight of water, optionally less than about 0.05% by weight of water, optionally about 0% by weight of water. The presence of water in the mixture may cause the deactivation of the catalyst or catalysts. Therefore, it is desirable to minimize the water content in the mixture.

[0095] Step (I)(a) may comprise first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide to form a mixture (α'), followed by adding an epoxide and optionally a monofunctional initiator compound and / or carbon dioxide to form a mixture (α). Performing the process in this manner may be useful to pre-activate one or both catalysts, as described above.

[0096] The mixture (α') may be held at a temperature of about 0-250° C., optionally about 40-150° C., optionally about 50-150° C., optionally about 70-140° C., optionally about 80-130° C. prior to the subsequent addition.

[0097] The reaction process may be carried out batchwise as a whole. In such a case, the process may use the total amount of each of the relevant materials (epoxide, monofunctional initiator compound, etc.) used in the reaction, and portions of that total amount may be added at different steps of the reaction.

[0098] The method may use a total amount of epoxide, where about 1-95% of the total amount of epoxide is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0099] The method may use a total amount of monofunctional initiator compound, where about 1-95% of the total amount of monofunctional initiator compound is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0100] The method may use a total amount of catalyst of formula (I), where about 1-100% of the total amount of catalyst of formula (I) is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0101] The method may use a total amount of double metal cyanide (DMC) catalyst, where about 1-100% of the total amount of double metal cyanide (DMC) catalyst is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0102] The method may use a total amount of carbon dioxide, where about 1-100% of the total amount of carbon dioxide is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0103] The method may use a total amount of solvent, where about 1-100% of the total amount of solvent is mixed in step (I) and the remainder is added in step (II), optionally about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in step (I).

[0104] The total amount of catalyst of formula (I) may be low so that the process of the present invention can be carried out at low catalyst loading. For example, the catalyst loading of catalyst of formula (I) can be in the range of about 1:100,000-300,000, such as about 1:10,000-100,000 [total catalyst of formula (I)]: [total epoxide], such as about 1:10,000-50,000 [total catalyst of formula (I)]: [total epoxide], such as about 1:10,000 [total catalyst of formula (I)]: [total epoxide]. The above ratios are molar ratios. These ratios are the ratio of the total amount of catalyst of formula (I) to the total amount of epoxide used in the process.

[0105] The process may be continuous, comprising the steps of: providing a mixture (β) of epoxide in a molar or weight ratio to the catalyst of formula (I); and further comprising: (III) adding an epoxide to mixture (β) to form mixture (γ), wherein the epoxide is added in an amount sufficient to bring the molar or weight ratio of epoxide to catalyst of Formula (I) in mixture (γ) to at least about 75% of the predetermined molar or weight ratio, and optionally repeating step (III).

[0106] The process may be continuous, comprising the steps of: in the mixture (β) a molar or weight ratio of a monofunctional initiator compound to a catalyst of formula (I); and the process further comprising: (III) adding a monofunctional initiator compound to mixture (β) to form mixture (γ), wherein the monofunctional initiator compound is added in an amount sufficient to bring the molar or weight ratio of the monofunctional initiator compound to the catalyst of Formula (I) in mixture (γ) to at least about 75% of the predetermined molar or weight ratio, and optionally repeating step (III).

[0107] The process may be continuous, comprising the steps of: providing a mixture (β) containing carbon dioxide in a molar or weight ratio to the catalyst of formula (I); and further comprising: (III) adding carbon dioxide to mixture (β) to form mixture (γ), said carbon dioxide being added in an amount sufficient to bring the molar or weight ratio of carbon dioxide to catalyst of formula (I) in mixture (γ) to at least about 75% of said predetermined molar or weight ratio, and optionally repeating step (III).

[0108] Step (III) may be carried out such that the molar or weight ratio of epoxide, monofunctional initiator compound, carbon dioxide, and / or solvent to catalyst of formula (I) in mixture (γ) is not less than about 75% of said predetermined molar or weight ratio.

[0109] Step (III) may be carried out such that the molar or weight ratio of the epoxide, monofunctional initiator compound, carbon dioxide, and solvent to the catalyst of formula (I) in mixture (γ) is not less than about 75% of said predetermined molar or weight ratio.

[0110] The process may be continuous, wherein a predetermined amount of catalyst of formula (I) is present in mixture (β), and the process further comprises: (III) adding a catalyst of formula (I) to mixture (β) to form mixture (γ), wherein the catalyst of formula (I) is added in an amount sufficient to bring the amount of catalyst of formula (I) in mixture (γ) to about 50-550% of the predetermined amount, and optionally repeating step (III).

[0111] Step (III) may be carried out such that the amount of catalyst of formula (I) in mixture (γ) is not less than about 50% of said predetermined amount. The method may be continuous, wherein a predetermined amount of a double metal cyanide (DMC) catalyst is present in the mixture (β), and the method further comprises: (III) adding a double metal cyanide (DMC) catalyst to mixture (β) to form mixture (γ), the double metal cyanide (DMC) catalyst being added in an amount sufficient to bring the amount of double metal cyanide (DMC) catalyst in mixture (γ) to about 50-550% of the predetermined amount, and optionally repeating step (III).

[0112] Step (III) may be carried out such that the amount of double metal cyanide (DMC) catalyst in mixture (γ) is not less than about 50% of said predetermined amount. The rate at which the materials are added can be selected so that the reaction temperature (exotherm) does not exceed a selected temperature (i.e., the materials are added slowly enough to allow excess heat to dissipate so that the temperature remains approximately constant).

[0113] When the addition of material (i.e., per step III) is repeated, the addition may be repeated 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more times.

[0114] The amount of catalyst of formula (I) and the amount of double metal cyanide (DMC) catalyst may be in a predetermined weight ratio with respect to each other of about 300:1 to about 1:100, such as about 120:1 to about 1:75, such as about 40:1 to about 1:50, such as about 30:1 to about 1:30, such as about 20:1 to about 1:1, such as about 10:1 to about 2:1, such as about 5:1 to about 1:5.

[0115] The double metal cyanide (DMC) catalyst may be dry mixed with the other ingredients. The double metal cyanide (DMC) catalyst may be mixed as a slurry, the slurry including the double metal cyanide (DMC) catalyst and a monofunctional initiator compound and / or a solvent.

[0116] The catalyst of formula (I) may be dry mixed with the other ingredients. The catalyst of formula (I) may be mixed as a solution, the solution comprising the catalyst of formula (I) and one or more of a monofunctional initiator compound, an epoxide, and / or a solvent.

[0117] An epoxide may be added in step (II). In step (II) a catalyst of formula (I) may be added. A double metal cyanide (DMC) catalyst may be added in step (II).

[0118] A monofunctional initiator compound may be added in step (II). Both the epoxide and the monofunctional initiator compound may be added in step (II). The epoxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and / or the monofunctional initiator compound may be added independently and sequentially in step (II).

[0119] The epoxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and / or the monofunctional initiator compound may be added independently and discontinuously in step (II). The carbon dioxide may be supplied continuously.

[0120] The method can be carried out at a pressure of from about 1 bar to about 60 bar of carbon dioxide, optionally from about 1 bar to about 40 bar, optionally from about 1 bar to about 20 bar, optionally from about 1 bar to about 15 bar, optionally from about 1 bar to about 10 bar, optionally from about 1 bar to about 5 bar.

[0121] The temperature of the reaction may increase during the course of the process. The monofunctional initiator compounds used in the method for forming the surfactant molecules may contain a group selected from a hydroxyl group (-OH), a thiol (-SH), an amine having at least one N-H bond (-NHR'), a group having at least one P-OH bond (e.g., -PR'(O)OH, PR'(O)(OH), or -P(O)(OR')(OH)), or a carboxylic acid group (-C(O)OH).

[0122] Thus, the monofunctional initiator compound used in the process for forming the surfactant molecule may be of formula (II): ZR Z (II) Z is bonded to -R Z The group may be any group having a group. Thus, Z may be selected from optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, or Z may be any combination of these groups, for example, Z may be an alkylaryl, heteroalkylaryl, heteroalkylheteroaryl, or alkylheteroaryl group. Optionally, Z is an alkyl, heteroalkyl, aryl, or heteroaryl.

[0123] R Z can be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH), or -PR'(O)OH, and optionally R Z is selected from -OH, -NHR', or -C(O)OH; optionally, R z is selected from -OH or -C(O)OH.

[0124] R' can be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' is H or an optionally substituted alkyl.

[0125] The method may include a plurality of monofunctional initiator compounds. The plurality of monofunctional initiator compounds may be added as a mixture of monofunctional initiator compounds or may be added in different steps. Preferably, there are one or two different monofunctional initiator compounds. When the method includes more than one step, there may be two monofunctional initiator compounds in the mixture (β), the monofunctional initiator compound in step (I) being the first monofunctional initiator compound and step (II) being the second monofunctional initiator compound. (A) adding one or more of a first monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent to mixture (α); (B) adding a second monofunctional initiator compound, and optionally an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent to form a mixture (β) comprising the first monofunctional initiator compound, the second monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent.

[0126] Step (B) may be carried out after step (A) for at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, optionally at least about 5 hours.

[0127] The or each monofunctional initiator compound preferably contains a hydroxyl group. Exemplary monofunctional initiator materials include alcohols, phenols, amines, thiols, and carboxylic acids, such as alcohols (e.g., methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, linear or branched C-C 20- monoalcohols (e.g. tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3 1-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine), monoethers or esters of ethylene, propylene, polyethylene, and polypropylene glycols (e.g., ethylene glycol monomethyl ether and propylene glycol monomethyl ether), phenols (e.g., linear or branched C3-C 20 These may include alkyl-substituted phenols (e.g., nonyl-phenol or octylphenol), monofunctional carboxylic acids (e.g., formic acid, acetic acid, propionic acid, and butyric acid), fatty acids (e.g., stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and acrylic acid), and monofunctional thiols (e.g., ethanethiol, propane-1-thiol, propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol), or amines (e.g., butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine).

[0128] Preferably, the monofunctional initiator is a linear or branched C-C aryl alcohol such as 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, cetyl alcohol, or stearyl alcohol. 20More preferably, it is a linear or branched C alcohol such as 1-decanol, 1-dodecanol, 1-tetradecanol, cetyl alcohol, or stearyl alcohol. 10 ~C 20 It's alcohol.

[0129] The monofunctional initiator is C 12 ~ 14 Alcohol, C. 16 ~ 18 Alcohol, or C 18 ~ 20 It may also be a mixture of related compounds such as alcohols. The ratio of the monofunctional initiator compound to the catalyst of formula (I) can be about 1000:1 to about 1:1, for example, about 750:1 to about 5:1, for example, about 500:1 to about 10:1, for example, about 250:1 to about 20:1, or about 125:1 to about 30:1, or about 50:1 to about 20:1. These ratios are molar ratios. These ratios are the ratio of the total amount of monofunctional initiator to the total amount of catalyst of formula (I) used in the process. These ratios can be maintained during the addition of materials.

[0130] The monofunctional initiator may be pre-dried (e.g., with molecular sieves) to remove moisture. It will be understood that any of the above described reaction conditions may be combined. For example, the reaction may be carried out at a temperature ranging from about 5°C to about 200°C, such as from about 10°C to about 150°C, such as from about 15°C to about 100°C, such as from about 20°C to about 90°C, at 60 bar or less, such as from about 30 bar or less, optionally 20 bar or less (e.g., 10 bar or less). The method of the present invention may be carried out at about 45°C to about 90°C.

[0131] The method of the invention is capable of preparing surfactant molecules which can be used in cleaning products, for example detergents. Thus, in further aspects of the invention there is provided the use of surfactant molecules formed by the method of the first aspect of the invention in cleaning products, as well as compositions comprising surfactant molecules formed by the method of the first aspect of the invention, which compositions are surfactant formulations for cleaning products.

[0132] In particular, the continuous and discontinuous processes of the present invention can provide surfactant molecules with low polydispersity index (PDI). The method of the present invention can produce surfactant molecules that can control the amount of ether and carbonate bonds.Thus, the present invention can provide surfactant molecules that have n ether bonds and m carbonate bonds, where n and m are integers, and m / (n+m) is greater than 0 and less than 1.Thus, it is understood that n≧1 and m≧1.

[0133] For example, the method of the present invention can prepare surfactant molecules having a wide range of m / (n+m) values. It will be understood that m / (n+m) can be about 0.05, about 0.10, about 0.15, about 0.20, about 0.25, about 0.25, about 0.30, about 0.35, about 0.40, about 0.45, about 0.50, about 0.55, about 0.60, about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.90, about 0.95, or any range prepared from these specific values. For example, m / (n+m) can be about 0.05 to about 0.95, about 0.10 to about 0.90, about 0.15 to about 0.85, about 0.20 to about 0.80, or about 0.25 to about 0.75, etc.

[0134] As described above, the method of the present invention can prepare surfactant molecules in which m / (n+m) is from about 0.1 to about 0.5, for example, from about 0.1 to about 0.3. Thus, the method of the present invention allows for the preparation of surfactant molecules having a moderate proportion of carbonate bonds, e.g., m / (n+m) can be greater than about 0.1, e.g., greater than about 0.1 to less than about 0.5, e.g., from about 0.15 to about 0.4, e.g., from about 0.2 to about 0.4.

[0135] For example, a surfactant molecule produced by the methods of the present invention may have the following formula (III or IV):

[0136] [ka]

[0137] The identity of Z and Z' depends on the nature of the monofunctional initiator compound, and R e1 , R e2 , R e3 , and R e4 It is understood that the identity of depends on the nature of the epoxide used to prepare the surfactant molecule. m and n define the amount of carbonate and ether linkages in the surfactant molecule.

[0138] One skilled in the art will appreciate that in the polymers of formula (III and IV), the epoxide monomer units adjacent to each other in the backbone can be head-to-tail, head-to-head, or tail-to-tail linked.

[0139] It will also be understood that formulas (III and IV) are not intended to depict the carbonate and ether linkages as being in two separate moieties, but instead are intended to illustrate the ratio of carbonate to ether linkages (m to n). The carbonate and ether repeat units may be randomly distributed along the polymer backbone.

[0140] Thus, the surfactant molecules prepared by the methods of the present invention (eg, polymers of formula (III or IV)) can be referred to as random, statistical, or periodic copolymers.

[0141] Without wishing to be bound by theory, typically the portion of the surfactant molecule derived from the monofunctional initiator (Z) forms the hydrophobic portion of the surfactant molecule, and the polyether carbonate polymer chain forms the hydrophilic portion of the surfactant.

[0142] Those skilled in the art will understand that the weight percent of carbon dioxide incorporated into a polymer cannot be used conclusively to determine the amount of carbonate bonds in the polymer backbone. For example, two polymers incorporating the same weight percent of carbon dioxide may have very different ratios of carbonate bonds to ether bonds. This is because the "weight percent incorporation" of carbon dioxide does not take into account the length and nature of the monofunctional initiator compound. For example, if one polymer (Mn2000g / mol) is prepared using a monofunctional initiator with a molar mass of 100g / mol and another polymer (Mn2000g / mol) is prepared using a monofunctional initiator with a molar mass of 500g / mol, and both resulting polymers have the same m / n ratio, the weight percent of carbon dioxide in the polymer will be different due to the different proportions of the mass of the monofunctional initiator in the total polymer molecular weight (Mn). For example, when m / (m+n) is 0.5, the two polyols described have carbon dioxide contents of 26.1% and 20.6% by weight, respectively.

[0143] As highlighted above, the methods of the present invention can prepare surfactant molecules with a wide range of carbonate to ether linkages (e.g., m / (n+m) can be greater than 0 and less than 1), which corresponds to up to about 50% by weight carbon dioxide incorporation when ethylene oxide is used. This is surprising because previously reported DMC catalysts can generally only prepare surfactant molecules with a carbonate to ether linkage ratio of up to about 0.2 from monofunctional initiators, ethylene oxide, and CO2, and these amounts can usually only be achieved at high pressures of carbon dioxide, such as 50 bar.

[0144] All other things being equal, polyethers have higher decomposition temperatures than polycarbonates made from epoxides and carbon dioxide. Thus, surfactants with a statistical or random distribution of ether and carbonate linkages have higher decomposition temperatures than polycarbonate surfactants, or surfactants with blocks of carbonate linkages. The temperature of thermal decomposition can be measured using thermogravimetric analysis (TGA).

[0145] As mentioned above, the method of the present invention prepares random copolymer, statistical copolymer, or periodic copolymer.Therefore, carbonate bond is not present in a single block, thereby providing a polymer with improved properties (such as improved thermal decomposition) compared with polycarbonate surfactant.The polymer prepared by the method of the present invention can be a random copolymer or a statistical copolymer.

[0146] The surfactant molecules prepared by the methods of the present invention may be of formula (III) or (IV), where n and m are integers equal to or greater than 1, the sum of all m and n groups is between 4 and 200, and m / (m+n) ranges from greater than 0 to less than 1.00. As noted above, m / (n+m) can be about 0.05, about 0.10, about 0.15, about 0.20, about 0.25, about 0.25, about 0.30, about 0.35, about 0.40, about 0.45, about 0.50, about 0.55, about 0.60, about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.90, about 0.95, or any range delineated from these particular values. For example, m / (n+m) may be about 0.1 to about 0.5, about 0.15 to about 0.4, about 0.2 to about 0.0.4, about 0.0.05 to about 0.5, or about 0.05 to about 0.3.

[0147] One skilled in the art will also understand that the surfactant must contain at least one carbonate and at least one ether linkage. Each R e1R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. e1 may be selected from H or optionally substituted alkyl.

[0148] Each R e2 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. e2 may be selected from H or optionally substituted alkyl.

[0149] Each R e3 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. e3 may be selected from H or optionally substituted alkyl.

[0150] Each R e4 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. e4 may be selected from H or optionally substituted alkyl.

[0151] R e1 (or R e2 ) and R e3 (or R e4It will also be understood that R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 e1 and R e3 may be taken together to form a 5- or 6-membered ring.

[0152] As described above, R e1 , R e2 , R e3 , and R e4 The nature of R depends on the epoxide used in the reaction. When the epoxide is cyclohexene oxide (CHO), R e1 and R e3 taken together form a six-membered alkyl ring (e.g., a cyclohexyl ring). When the epoxide is ethylene oxide, R e1 , R e2 , R e3 , and R e4 are each H. When the epoxide is propylene oxide, R e1 , R e2 , and R e4 is H and R e3 is methyl (or R depending on how the epoxide is added to the polymer backbone). e1 is methyl and R e3 is H). If the epoxide is butylene oxide, R e1 , R e2 , and R e4 is H and R e3 is ethyl (or R e1 is ethyl and R e3 is H). If the epoxide is styrene oxide, R e1 , R e2 , and R e4 may be hydrogen, R e3 may be phenyl (or R e1 is phenyl and R e3 is H).

[0153] When a mixture of epoxides is used, R e1 , R e2 , R e3 , and / or R e4 Each occurrence of R may not be the same, for example, when a mixture of ethylene oxide and propylene oxide is used, e1 , R e2 , R e3 , and R e4 It will also be understood that may be independently hydrogen or methyl.

[0154] Therefore, R e1 , R e2 , R e3 , and R e4 may be independently selected from hydrogen, alkyl, or aryl, or R e1 (or R e2 ) and R e3 (or R e4 ) may be taken together to form a cyclohexyl ring, or R e1 , R e2 , R e3 , and R e4 may be independently selected from hydrogen, methyl, ethyl, or phenyl, or R e1 (or R e2 ) and R e3 (or R e4 ) may be taken together to form a cyclohexyl ring.

[0155] Z' is R except that a highly reactive hydrogen atom is replaced with a bond. z Therefore, Z' corresponds to R ZIt will thus be understood that Z' can be -O-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -PR'(O)(O-)2, or -PR'(O)O-, where R' can be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' is H or an optionally substituted alkyl, and optionally Z' can be -C(O)O-, -NR'-, or -O-, and each Z' can be -O-, -C(O)O-, or a combination thereof, and optionally each Z' can be -O-.

[0156] Z also depends on the nature of the monofunctional initiator compound. Thus, Z can be selected from optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, or Z can be any combination of these groups, for example, Z can be an alkylaryl, heteroalkylaryl, heteroalkylheteroaryl, or alkylheteroaryl group. Optionally, Z is an alkyl, heteroalkyl, aryl, or heteroaryl, such as alkyl or heteroalkyl. It will be understood that each of the above groups can be optionally substituted, for example by alkyl.

[0157] In some applications, specifically Z is -O- and Z is C1-C 25 In the case of alkyl groups, it may be desirable to provide a surfactant molecule with a relatively short hydrophobic portion, in which case when Z' is -O-, Z is preferably a C1-C8 alkyl group.

[0158] In other applications, specifically Z is -O- and Z is C1-C 25 In the case of alkyl groups, it may be desirable to provide a surfactant molecule with a relatively long hydrophobic portion. In this case, when Z' is -O-, Z is preferably a C9-C25 It is an alkyl group.

[0159] Those skilled in the art will appreciate that each of the above features can be combined. For example, e1 , R e2 , R e3 , and R e4 may be independently selected from hydrogen, alkyl, or aryl, or R e1 (or R e2 ) and R e3 (or R e4 ), taken together, can form a cyclohexyl ring, each Z' can be -O-, -C(O)O-, or combinations thereof (optionally, each Z' can be -O-), and Z can be an optionally substituted alkyl, heteroalkyl, aryl, or heteroaryl (e.g., alkyl or heteroalkyl).

[0160] The surfactant produced by the method of the present invention is optionally a low molecular weight oligomer.It will be understood that the nature of the epoxide used to prepare the surfactant molecule will affect the molecular weight of the resulting product.Therefore, an upper limit of n+m is used herein to define the "low molecular weight" polymer of the present invention.

[0161] The method of the present invention can advantageously prepare surfactant molecules having a narrow molecular weight distribution. In other words, the surfactant molecules can have a low polydispersity index (PDI). The PDI of a polymer is determined by the weight average molecular weight (M w ) to the number average molecular weight (M n ), thereby indicating the distribution of chain lengths in the polymer product. It will be appreciated that PDI becomes more important as the molecular weight of the polymer decreases, since the percent variation in polymer chain length is greater for short chain polymers compared to long chain polymers, even if both polymers have the same PDI.

[0162] Optionally, the polymers produced by the methods of the invention have a PDI of from about 1 to less than about 2, optionally from about 1 to less than about 1.75 (e.g., from about 1 to less than about 1.5, from about 1 to less than about 1.3, from about 1 to less than about 1.2, and from about 1 to less than about 1.1).

[0163] The M of the polymer produced by the method of the present invention n and M. w Thus, PDI 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-E columns in series. Samples can be measured at room temperature (293 K) in THF using a flow rate of 1 mL / min against narrow molecular weight distribution polystyrene standards (e.g., polystyrene low molecular weight EasiVials with Mn in the range of 405-49,450 g / mol, provided by Agilent Technologies). Optionally, samples can be measured against poly(ethylene glycol) standards, such as polyethylene glycol easivials, provided by Agilent Technologies.

[0164] Optionally, the surfactant molecules produced by the methods of the present invention may have a molecular weight in the range of about 400 to about 10,000 Da, optionally about 500 to about 3,000 Da, or about 500 to about 2,000 Da.

[0165] The process of the present invention may be carried out in the presence of a solvent, but it will also be understood that the process may be carried out in the absence of a solvent. When a solvent is present, it may be toluene, hexane, t-butyl acetate, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), etc. The solvent may be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0166] A solvent can act to dissolve one or more materials. Alternatively, a solvent can also act as a carrier and is used to suspend one or more materials in suspension. A solvent may also be required to facilitate the addition of one or more materials during the steps of the method of the present invention.

[0167] The epoxide used in the method can be any suitable compound that contains an epoxide moiety.Exemplary epoxides include ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide.Preferably, the epoxide is ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide.More preferably, the epoxide is ethylene oxide.

[0168] The epoxide can be purified (e.g., by distillation, e.g., with calcium hydride) prior to reaction with carbon dioxide. For example, the epoxide can be distilled before being added.

[0169] The method of the present invention can be carried out at any scale. The method can be carried out at an industrial scale. As will be understood by those skilled in the art, catalytic reactions often involve the generation of heat (i.e., catalytic reactions are generally exothermic). The heat generated during small-scale reactions is less of a problem because the temperature rise, if any, can be relatively easily controlled, for example, by using an ice bath. For larger-scale reactions, especially industrial-scale reactions, the heat generated during the reaction can be problematic and potentially dangerous. Therefore, by gradually adding the materials in any of the manners described herein, the rate of the catalytic reaction can be controlled and excess heat accumulation can be minimized. The rate of the reaction can be controlled, for example, by adjusting the flow rate of the materials when they are added. Therefore, the method of the present invention is particularly advantageous when applied to large-scale catalytic reactions on an industrial scale.

[0170] The temperature may increase during the course of the method of the invention. For example, the method may be initiated at a low temperature (e.g., a temperature of about 50°C to 80°C or less) and the reaction mixture may increase in temperature during the course of the method. For example, the temperature of the reaction mixture increases during the course of the method of the invention from about 50°C at the beginning of the reaction to about 80°C at the end of the reaction. This increase in temperature may be gradual or sudden. This increase in temperature may be the result of application of an external heating source or may be achieved via an exothermic reaction as described above.

[0171] The temperature of the reaction mixture may decrease during the course of the method of the invention. For example, the method may be initiated at an elevated temperature (e.g., a temperature of about 90-150° C.) and the reaction mixture may be cooled during the course of the method (e.g., to a temperature of about 50° C. to 80° C. or less). This decrease in temperature may be gradual or sudden. This decrease in temperature may be the result of application of an external cooling source, as described above.

[0172] The present invention also relates to a surfactant molecule obtainable by the above-mentioned process, preferably the surfactant molecule is according to formula (III) or formula (IV) as above. The present invention also relates to the use of the surfactant molecule obtainable by the above-mentioned process in a cleaning product, and to a composition comprising said surfactant molecule, said composition being a surfactant formulation for a cleaning product.

[0173] The catalyst of formula (I) is a dimetal phenolate such as those disclosed in WO 2009 / 130470, WO 2013 / 034750, WO 2016 / 012786, WO 2016 / 012785, WO 2012037282, and WO 2019048878 A1, the contents of which are incorporated herein by reference.

[0174] Each of the R1 and R2 groups in formula (I) may be the same or different at each occurrence, and R1 and R2 may be the same or different. Optionally, each occurrence of R2 is the same and is hydrogen.

[0175] R3 may be an optionally substituted alkylene group, and optionally R3 is an optionally substituted C2 or C3 alkylene group. Exemplary options for R3 include ethylenyl, 2,2-fluoropropylenyl, 2,2-dimethylpropylenyl, propylenyl, butyrenyl, phenylenyl, cyclohexylenyl, or biphenylenyl. Optionally, R3 is 2,2-di(alkyl)propylenyl, optionally substituted propylenyl, such as 2,2-dimethylpropylenyl.

[0176] Optionally, E3, E4, E5, and E6 are each independently selected from NR4, O, and S. Exemplary choices for R4 include H, Me, Et, Bn, iPr, tBu, or Ph, and -CH2- (pyridine).

[0177] Optionally, each R4 is hydrogen or alkyl. Optionally, both occurrences of E1 are C and both occurrences of E2 are O. Alternatively, when E2 is O, E1 can be C. Each X can be the same or different, and optionally each X is the same. It will also be understood that X can form a bridge between two metal centers.

[0178] Optionally, each X is the same and OC(O)R x groups. Optionally, each X is the same and is selected from OAc, O2CCF3, or O2C(CH2)3Cy. Optionally, each X is the same and is OAc. Optionally, at least one of M1 and M2 is selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X, and optionally at least one of M1 and M2 is selected from Mg(II), Zn(II), and Ni(II), e.g., at least one of M1 and M2 is Ni(II).

[0179] DMC catalysts are complex compounds that contain at least two metal centers and cyanide ligands. DMC catalysts can further include at least one of one or more complexing agents, water, metal salts, and / or acids (e.g., in non-stoichiometric amounts).

[0180] The first two of the at least two metal centers can be represented as M' and M''. M' can be selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II), and Cr(III); M' is optionally selected from Zn(II), Fe(II), Co(II), and Ni(II); and optionally M' is Zn(II).

[0181] M″ is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V), optionally M″ is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), optionally M″ is selected from Co(II) and Co(III).

[0182] It will be understood that the above optional definitions of M' and M" can be combined. For example, M' can optionally be selected from Zn(II), Fe(II), Co(II), and Ni(II), and M" can optionally be selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II). For example, M' can optionally be Zn(II), and M" can optionally be selected from Co(II) and Co(III).

[0183] When an additional metal center is present, the additional metal center may be further selected from the definitions of M' or M''. Examples of DMC catalysts that can be used in the process of the present invention include those disclosed in U.S. Pat. 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, 6,835,687, and 6,699,961. Nos. 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500,704, 7,977,501, 9,315,622, EP 1568414(A), EP 1529566(A), and WO 2015 / 022290, the entire contents of which are hereby incorporated by reference, in particular insofar as they relate to DMC catalysis of the reactions defined herein.

[0184] DMC catalysts are: M' d [M'' e (CN) f ] g where M' and M'' are as defined above and d, e, f, and g are integers selected such that the DMC catalyst is electroneutral. Optionally, d is 3. Optionally, e is 1. Optionally, f is 6. Optionally, g is 2. Optionally, M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), and optionally M' is Zn(II). Optionally, M'' is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), and optionally M'' is Co(II) or Co(III).

[0185] It will be understood that any of these optional features may be combined, for example, d is 3, e is 1, f is 6, g is 2, M' is Zn(II) and M'' is Co(III).

[0186] Suitable DMC catalysts having the above formula can include zinc hexacyanocobaltate(III), zinc hexacyanoferrate(III), nickel hexacyanoferrate(II), and cobalt hexacyanocobaltate(III).

[0187] There has been much development in the field of DMC catalysts, and those skilled in the art will understand that DMC catalysts can further comprise additives to enhance the activity of the catalyst in addition to the above formula. Thus, while the above formula forms the "core" of the DMC catalyst, the DMC catalyst can further comprise one or more additional components, such as at least one complexing agent, acid, metal salt, and / or water, in stoichiometric or non-stoichiometric amounts.

[0188] For example, the DMC catalyst has the formula:

[0189] [ka]

[0190] where M', M'', X''', d, e, f, and g are as defined above. M''' may be M' and / or M''. X'' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and optionally X'' is a halide. i is an integer equal to or greater than 1, and the charge of the anion X'' multiplied by i satisfies the valence of M'''. r is an integer corresponding to the charge of the counterion X'''. For example, if X'' is Cl, - then r is 1. l is 0 or a number between 0.1 and 5. Optionally, l is a number between 0.15 and 1.5.

[0191] R c is a complexing agent or a combination of one or more complexing agents. For example, R c can be a (poly)ether, polyether carbonate, polycarbonate, poly(tetramethylene ether diol), ketone, ester, amide, alcohol (e.g., C1-8 alcohol), urea, and the like, such as propylene glycol, polypropylene glycol, (meth)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof, such as, for example, R c can be tert-butyl alcohol, dimethoxyethane, or polypropylene glycol.

[0192] As indicated above, more than one complexing agent may be present in the DMC catalyst used in the present invention. c One of the complexing agents may be a polymeric complexing agent.c can be a combination of polymeric and non-polymeric complexing agents. Optionally, a combination of the complexing agents tert-butyl alcohol and polypropylene glycol can be present.

[0193] It will be understood that when water, complexing agents, acids, and / or metal salts are not present in the DMC catalyst, h, j, k, and / or l are each 0. When water, complexing agents, acids, and / or metal salts are present, h, j, k, and / or l are positive numbers, for example, between 0 and 20. For example, h can be between 0.1 and 4. j can be between 0.1 and 6. k can be between 0 and 20, for example, between 0.1 and 10, for example, between 0.1 and 5. l can be between 0.1 and 5, for example, between 0.15 and 1.5.

[0194] The polymeric complexing agent is optionally selected from polyethers, polycarbonate ethers, and polycarbonates. The polymeric complexing agent can be present in an amount of about 5% to about 80% by weight of the DMC catalyst, optionally in an amount of about 10% to about 70% by weight of the DMC catalyst, and optionally in an amount of about 20% to about 50% by weight of the DMC catalyst.

[0195] In addition to the at least two metal centers and cyanide ligands, the DMC catalyst can also optionally include non-stoichiometric amounts of at least one of one or more complexing agents, water, metal salts, and / or acids.

[0196] An exemplary DMC catalyst is one having the formula Zn3[Co(CN)6]2·hZnCl2·kH2O·j[(CH3)3COH], where h, k, and j are as defined above. For example, h can be 0-4 (e.g., 0.1-4), k can be 0-20 (e.g., 0.1-10), and j can be 0-6 (e.g., 0.1-6). As described above, DMC catalysts have complex structures, and thus the above formula, including additional components, is not intended to be limiting. Rather, one of ordinary skill in the art will understand that this definition is not exhaustive of DMC catalysts that can be used in the present invention.

[0197] The DMC catalyst may be preactivated. Such preactivation can be achieved by mixing one or both catalysts with the alkylene oxide (and optionally other components). Preactivation of the DMC catalyst is useful because it allows safe control of the reaction (preventing uncontrolled growth of the unreacted monomer content) and eliminates unpredictable activation times. EXAMPLES

[0198] method Nuclear magnetic resonance spectroscopy 1 1 H NMR spectra were recorded on a Bruker AV-400 instrument using the solvent CDCl3.

[0199] Gel Permeation Chromatography GPC measurements were performed in THF against narrow polydispersity poly(ethylene glycol) or polystyrene standards using an Agilent 1260 Infinity instrument equipped with an Agilent PLgel Mixed-E column.

[0200] mass spectrometry All mass spectrometry measurements were performed using a MALDI Micro MX Micromass instrument. Catalyst 1: A 100 mL Parr pressure reactor containing 1-decanol (5.2 g, 27.9 mmol) and DMC catalyst (zinc hexacyanocobaltate catalyst containing t-butanol and a polyether coligand) (9.6 mg) was dried for 30 min at about 100° C. It was charged with catalyst 1 (macrocyclic phenolate catalyst containing two Ni centers according to structure (I)) (96 mg) and ethylene oxide EO (17.6 g, 400 mmol).

[0201] The vessel was pressurised to approximately 3 barg with CO2 and heated to approximately 60°C whilst the pressure was adjusted to a constant 7 barg with CO2. The pressure was maintained at 7 bar while the temperature was increased stepwise to 70° C. after 8 hours, to 75° C. after a total of 24 hours, to 80° C. after a total of 32 hours, to 85° C. after 40 hours, and to 95° C. after 50 hours. After a total of 66 hours, the reaction was cooled to below room temperature, evacuated, and analyzed by NMR and GPC to determine the presence of approximately 12.1 wt. % CO2 and C with a mass of 820 g / mol (polydispersity 1.44). 12 -(CO2) 2.3 (EO) 12.6 The surfactant molecule was obtained as follows:

Claims

1. reacting carbon dioxide with an epoxide in the presence of a double metal cyanide (DMC) catalyst, a catalyst of formula (I), and a monofunctional initiator compound; The catalyst of formula (I) has the following structure: 【Chemical 1】 (In the formula, M １ and M ２ are Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III) )-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) ２ , or Ti(IV)-(X) ２ are independently selected from R １ and R ２ are independently selected from hydrogen, halide, nitro, nitrile, imine, amine, ether, silyl, silyl ether, sulfoxide, sulfonyl, sulfinate, or acetylide groups, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic groups; R ３ are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, where the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene are optionally interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic; R ５ are independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; E １ is C and E ２ is O, S, or NH, or E １ is N and E ２ is O; E ３ , E ４ , E ５ , and E ６ is N, NR ４ , O, and S, wherein E ３ , E ４ , E ５ , or E ６ If is N, then 【Chemistry 2】 teeth 【Chemistry 3】 and E ３ , E ４ , E ５ , or E ６ NR ４ , O, or S, 【Chemistry 4】 teeth 【Chemistry 5】 and R ４ is H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １９ or -alkylC≡N, or alkylaryl; X is OC(O)R ｘ , OSO ２ R ｘ , OSOR ｘ , OSO (R ｘ ) ２ , S(O)R ｘ , OR ｘ , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; R ｘ are independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl; G is independently selected from neutral or anionic donor ligands that are absent or Lewis bases.

2. 10. A method for preparing the surfactant molecule of claim 1, comprising forming a mixture comprising a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent, followed by increasing the temperature by at least 10°C.

3. (I) (a) mixing a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally a monofunctional initiator compound and / or carbon dioxide to form a mixture (α); or (b) mixing a double metal cyanide (DMC) catalyst and optionally a monofunctional initiator compound, carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α); or (c) mixing an epoxide, a catalyst of formula (I), a monofunctional initiator compound, and carbon dioxide, and optionally a solvent, to form a mixture (α); or (d) mixing the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and optionally a monofunctional initiator compound, an epoxide, carbon dioxide, and / or a solvent to form a mixture (α); and 10. A method for preparing a surfactant molecule according to claim 1, comprising the steps of: (II) adding one or more of a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent to the mixture (α) to form a mixture (β) comprising a monofunctional initiator compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a solvent; and / or increasing the reaction temperature by 10° C. or more.

4. 3. The method of claim 3(a), 3(c), or 3(d), wherein mixture (α) is held at a temperature of about 50-90°C, optionally about 50-80°C, about 55-80°C, or about 60-80°C prior to step (II).

5. 4. The method of claim 3, wherein in step (II), the temperature is increased to about 60-150°C, optionally 65-150°C, or 80-130°C, and optionally additional epoxide is added.

6. 2. The method of claim 1, wherein the epoxide is ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide, preferably the epoxide is ethylene oxide.

7. 4. The method of claim 3, wherein mixture (a) is held for at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, optionally at least about 5 hours prior to step (II).

8. 3(c), wherein mixture (α) is held for at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, optionally at least about 3 hours, optionally at least about 4 hours, optionally at least about 8 hours, optionally at least about 16 hours prior to step (II).

9. Step (I) comprises first mixing a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide to form a mixture (α′), followed by adding an epoxide and optionally a monofunctional initiator compound and / or carbon dioxide to form a mixture (α); 5. The method of claim 4 when dependent on claim 3(a), wherein optionally, mixture (α') is held at a temperature of about 0-250°C, optionally about 40-150°C, optionally about 50-150°C, optionally about 70-140°C, optionally about 80-130°C prior to the addition.

10. The process is continuous, and in the mixture (β) there is a predetermined molar or weight ratio of epoxide to catalyst of formula (I), and the process further comprises (III) adding an epoxide to mixture (β) to form mixture (γ), wherein said epoxide is added in an amount sufficient to bring said molar or weight ratio of epoxide to catalyst of formula (I) in mixture (γ) to at least about 75% of said predetermined molar or weight ratio, optionally repeating step (III); and / or The process is continuous, and in the mixture (β) there is present a predetermined molar or weight ratio of the monofunctional initiator compound to the catalyst of formula (I), and the process further comprises (III) adding a monofunctional initiator compound to mixture (β) to form mixture (γ), wherein said monofunctional initiator compound is added in an amount sufficient to bring the molar or weight ratio of monofunctional initiator compound to catalyst of formula (I) in mixture (γ) to at least about 75% of said predetermined molar or weight ratio, optionally repeating step (III); and / or The process is continuous, and in the mixture (β) there is present a predetermined molar or weight ratio of carbon dioxide to the catalyst of formula (I), and the process further comprises (III) adding carbon dioxide to mixture (β) to form mixture (γ), wherein the carbon dioxide is added in an amount sufficient to bring the molar or weight ratio of carbon dioxide to catalyst of formula (I) in mixture (γ) to at least about 75% of the predetermined molar or weight ratio, and optionally repeating step (III); and / or The process is continuous, and a predetermined amount of double metal cyanide (DMC) catalyst is present in the mixture (β), and the process further comprises 4. The method of claim 3, comprising: (III) adding a double metal cyanide (DMC) catalyst to mixture (β) to form mixture (γ), wherein the double metal cyanide (DMC) catalyst is added in an amount sufficient to bring the amount of double metal cyanide (DMC) catalyst in mixture (γ) to about 50-550% of the predetermined amount, and optionally repeating step (III).

11. the amount of the catalyst of formula (I) and the amount of the double metal cyanide (DMC) catalyst are in a weight ratio of from about 300:1 to about 1:100, such as 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; and / or The double metal cyanide (DMC) catalyst is dry mixed with other ingredients, or the double metal cyanide (DMC) catalyst is mixed as a slurry, the slurry comprising the double metal cyanide (DMC) catalyst and a monofunctional initiator compound and / or a solvent; and / or The catalyst of formula (I) is dry mixed with other ingredients, or 10. The method of claim 1, wherein the catalyst of formula (I) is mixed as a solution, the solution comprising the catalyst of formula (I) and one or more of a monofunctional initiator compound, an epoxide, and / or a solvent.

12. an epoxide is added in step (II), and / or a catalyst of formula (I) is added in step (II), and / or A double metal cyanide (DMC) catalyst is added in step (II), and / or a monofunctional initiator compound is added in step (II), and / or Both an epoxide and a monofunctional initiator compound are added in step (II), and / or 4. The method of claim 3, wherein the epoxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and / or the monofunctional initiator compound are independently added continuously in step (II), or the epoxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and / or the monofunctional initiator compound are independently added discontinuously in step (II).

13. The or each monofunctional initiator compound is represented by formula (II): Z-R Ｚ (II) (wherein Z is —R bonded to Z) Ｚ may be any group that can have a group, Each R Ｚ are independently —OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), —PR′(O)(OH) ２ or —PR′(O)OH; R' is selected from H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl. and / or The or each monofunctional initiator compound may be an alcohol (e.g., methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, linear or branched C ３ ~C ２０ -monoalcohols (for example tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol) , 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine), monoethers or esters of ethylene, propylene, polyethylene, and polypropylene glycol (e.g., ethylene glycol monomethyl ether and propylene glycol monomethyl ether), phenols (e.g., linear or branched C ３ ~C ２０ alkyl-substituted phenols, such as nonyl-phenol or octylphenol), monofunctional carboxylic acids (such as formic acid, acetic acid, propionic acid, and butyric acid), fatty acids (such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and acrylic acid), and monofunctional thiols (such as ethanethiol, propane-1-thiol, propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol), or amines (such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine), optionally the or each monofunctional initiator compound is selected from linear or branched C olefins such as 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, cetyl alcohol, or stearyl alcohol. ８ ~C ２０ alcohols, more preferably linear or branched C alcohols such as 1-decanol, 1-dodecanol, 1-tetradecanol, cetyl alcohol, or stearyl alcohol. １０ ~C ２０ is alcohol, and / or the carbon dioxide is supplied continuously; and / or and / or carried out at a pressure of from about 1 bar to about 60 bar of carbon dioxide, optionally from about 1 bar to about 40 bar, optionally from about 1 bar to about 20 bar, optionally from about 1 bar to about 15 bar, optionally from about 1 bar to about 10 bar, optionally from about 1 bar to about 5 bar; and / or 10. The method of claim 1, wherein the DMC catalyst, in addition to the at least two metal centers and cyanide ligands, also comprises at least one of one or more complexing agents, water, metal salts, and / or acids, optionally in non-stoichiometric amounts.

14. The DMC catalyst is prepared by treating a solution of a metal salt with a solution of a metal cyanide salt in the presence of at least one of a complexing agent, water, and / or an acid, and optionally the metal salt has the formula M'(X'): ｐ (In the formula, M' is Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III) ), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II), and Cr(III); X' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate; p is an integer of 1 or greater, and the charge of the anion multiplied by p satisfies the valence of M'; The metal cyanide salt is represented by the formula (Y): ｑ M” (CN) ｂ (A) ｃ wherein M″ is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V); Y is a proton or an alkali metal ion or alkaline earth metal ion (e.g., K ＋ ) and A is an anion selected from halide, oxide, hydroxide, sulfate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate; q and b are integers of 1 or more, c may be 0 or an integer of 1 or more; the sum of the charges on the anions Y, CN, and A multiplied by q, b, and c, respectively (e.g., Y x q + CN x b + A x c) satisfies the valence of M″); the at least one complexing agent is selected from (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols, ureas, or combinations thereof; Optionally, the at least one complexing agent is selected from propylene glycol, polypropylene glycol, (m)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof; The acid, if present, is of formula H ｒ X''', where X''' is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and r is an integer corresponding to the charge on the counterion X''', and / or The DMC catalyst has the formula: M' ｄ [M'' ｅ (CN) ｆ ] ｇ wherein M′ and M″ are as defined above, and d, e, f, and g are integers selected such that the DMC catalyst is electroneutral; Optionally, d is 3, e is 1, f is 6, and g is 2. The method of claim 1 , comprising:

15. M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), optionally M' is Zn(II), and / or 15. The method of claim 14, wherein M'' is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), optionally M'' is Co(II) or Co(III).

16. the reaction temperature increases during the course of the process, and / or The method according to any one of claims 1 to 15, carried out on an industrial scale.

17. A surfactant molecule obtainable by the method of claim 1, optionally comprising: Formula (III) or (IV): 【Chemistry 6】 (In the formula, each R ｅ１ , R ｅ２ , R ｅ３ , and R ｅ４ are independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl, or R ｅ１ (or R ｅ２ ) and R ｅ３ (or R ｅ４ ) may be taken together to form a saturated, partially unsaturated, or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms; Z is any group that can have a Z' group attached to it Z' is -O-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -PR'(O)(O-) ２ or —PR′(O)O—, where R′ is selected from H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl; n and m are integers of 1 or more. A surfactant molecule having the formula:

18. When Z' is -O-, Z is C １ ~C ２５ alkyl group, and optionally Z is C １ ~C ８ alkyl group or Z is C ９ ~C ２５ 18. The surfactant molecule of claim 17, which is an alkyl group.

19. 19. Use of a surfactant molecule according to claim 17 or 18 in a cleaning product.

20. 19. A composition comprising a surfactant molecule according to claim 17 or 18, the composition being a surfactant formulation for a cleaning product.

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