Method for forming polycarbonate ether polyols and high molecular weight polyether carbonates

Abstract

A method for preparing polycarbonate ether polyols or high molecular weight polyether carbonates using controlled addition of materials during polymerization includes the steps of: 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 starter compound and / or carbon dioxide; or mixing a DMC catalyst and optionally a starter compound, carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent; or mixing an epoxide, a catalyst of formula (I), a starter compound and carbon dioxide and optionally a solvent; or mixing a catalyst of formula (I), a DMC catalyst, and optionally a starter compound, an epoxide, carbon dioxide and / or a solvent, in each case to form a mixture (α); and adding one or more of a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a DMC catalyst, and / or a solvent to the mixture (α) to form a mixture (β) containing a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a DMC catalyst, and optionally a solvent.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing polycarbonate ether polyols and high molecular weight polyether carbonates. More specifically, the present invention relates to a method having improved control through controlled addition of materials during polymerization, although not necessarily limited thereto. [Background technology]

[0002] Polycarbonate ether polyols are useful as starting materials for polyurethane synthesis. Polyurethane is a polymer prepared by reacting a diisocyanate or polyisocyanate with a polyol. Polyurethane is used in many different products and applications, including insulating panels, high-performance adhesives, highly resilient foam seats, seals and gaskets, wheels and tires, and synthetic fibers.

[0003] Polyether carbonate polyols can be produced by catalytic addition of epoxides and carbon dioxide to a starter (a compound having H functional groups). One method for preparing polyether carbonate polyols involves the use of a double metal cyanide (DMC) catalyst. Such methods are described in U.S. Patent No. 4,500,704, U.S. Patent No. 6,762,278, International Publication No. 2006 / 103213, and International Publication No. 2015 / 022290.

[0004] The term "DMC" catalyst is commonly used in literature and published patents to refer to catalysts having at least two metal centers and cyanide ligands. Numerous patents disclose methods for preparing DMC catalysts and methods for preparing polyethers using DMC catalysts [e.g., U.S. Patent Publication No. 2008 / 0167502 (BASF); U.S. Patent Publication No. 2003 / 0158449 (Bayer); U.S. Patent Publication No. 2003 / 0069389 (Shell); U.S. Patent Publication No. 2004 / 0220430 (Repsol Quimica); U.S. Patent No. 5,536,883 (Arco); U.S. Patent Publication No. 2005 / 0065383 (Dow); and U.S. Patent No. 3,427,256 (General Tyre and Rubber Company)].

[0005] Polyether carbonate polyols formed by DMC catalysts generally have a low carbon dioxide content (less than 20% CO2 by weight), requiring high pressures such as 40 or 50 bar to incorporate such CO2 levels. International Publication No. 2006 / 103213 discloses a semi-batch process for producing polyether oligomers by pre-activating the catalyst in the reactor in the presence of a starter by adding an initial amount of epoxide (such as propylene oxide). Subsequently, the remaining epoxide and carbon dioxide are slowly weighed into the reaction to control the highly exothermic reaction and ensure safe operation. This process has the disadvantage that, if the first segment of the chain contains only polyether bonds, the initial activation step in the absence of carbon dioxide essentially reduces the carbon dioxide content of the polyol. This method is also limited to high equivalent starters (such as polypropylene glycol 460) because low equivalent starters (such as propylene glycol, PG, molecular weight 76 g / mol) inhibit catalyst activation. Therefore, this method only produces a moderate CO2 content at high molecular weight and cannot be used to incorporate large amounts of CO2 into low molecular weight polyols (Mn less than 1500).

[0006] International Publication No. 2008 / 092767 discloses a semi-batch process using a DMC catalyst, in which a higher equivalent initial starter (e.g., PPG-460) is introduced into the reactor along with the DMC catalyst for the activation step. During the reaction, even lower equivalent starters, such as PG, are weighed into the reactor along with the epoxide. These do not hinder the reactivity after initiation, thus allowing the use of lower molecular weight starters; however, the catalyst still needs to be activated, and some polyols still contain activated polyether products. The overall CO2 content remains moderate even under high pressure. Operation under high pressure significantly increases the cost and complexity of the design, making it unsuitable for industrial-scale production.

[0007] International Publication No. 2017 / 037441 discloses a batch method for the production of polyether carbonate polyols using a composite catalyst system that enables operation at low pressure (e.g., 5-10 bar CO2) and allows for the production of polyether carbonate polyols with a significantly increased CO2 content (over 30 wt% CO2). Such a batch operation, in which all epoxides are added to the reactor at the start of the reaction, would likely not be industrially applicable due to the possibility of a highly exothermic reaction between the DMC catalyst and the epoxides.

[0008] Surprisingly, it has been found that such composite catalyst systems can be handled in a semi-continuous or continuous form, enabling the safe operation of this process by weighing one or more components into the reactor during the reaction. This is particularly surprising, as homogeneous polycarbonate catalysts are generally demonstrated in batch form (as described in International Publication No. 2013 / 034750, International Publication No. 2016 / 012786, or International Publication No. 2016 / 012785). Furthermore, since the semi-continuous or continuous process can be carried out without the need to pre-activate the DMC, CO2 can be incorporated from the beginning of the reaction, increasing the potential CO2 content of the polyol. This process can be carried out using only low equivalent starters (e.g., 1,6-hexanediol, equivalent 118 g / mol) to produce polyols of a wide range of molecular weights with higher CO2 content.

[0009] It was found that by continuously adding the starter and epoxide to the reactor, it is possible to produce a lower molecular weight material with a high CO2 content. Surprisingly, this process can also be employed in a continuous form in the absence of a starter to produce polyether carbonates (e.g., high molecular weight polyether carbonates).

[0010] The object of the present invention is to prevent or mitigate the problems of existing methods for preparing polycarbonate ether polyols and / or methods for preparing high molecular weight polyether carbonates, and / or to provide improved methods and / or alternative methods. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] U.S. Patent No. 4,500,704 [Patent Document 2] U.S. Patent No. 6,762,278 [Patent Document 3] International Publication No. 2006 / 103213 [Patent Document 4] International Publication No. 2015 / 022290 [Patent Document 5] U.S. Patent Application Publication No. 2008 / 0167502 [Patent Document 6] U.S. Patent Application Publication No. 2003 / 0158449 [Patent Document 7] U.S. Patent Application Publication No. 2003 / 0069389 [Patent Document 8] U.S. Patent Application Publication No. 2004 / 0220430 [Patent Document 9] U.S. Patent No. 5,536,883 [Patent Document 10] U.S. Patent Application Publication No. 2005 / 0065383 [Patent Document 11] U.S. Patent No. 3,427,256 [Patent Document 12] International Publication No. 2008 / 092767 [Patent Document 13] International Publication No. 2017 / 037441 [Patent Document 14] International Publication No. 2013 / 034750 [Patent Document 15] International Publication No. 2016 / 012786 [Patent Document 16] International Publication No. 2016 / 012785 [Overview of the Initiative]

[0012] According to the present invention, a method for preparing a polycarbonate ether polyol is provided, and the method is as follows: (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst and optionally a starter 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) A step of mixing an epoxide, a catalyst of formula (I), a starter compound, carbon dioxide, and optionally a solvent to form a mixture (α), or (d) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a starter compound, an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) Adding one or more of the following to mixture (α): a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and / or a solvent, to form a mixture (β) containing the starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and optionally a solvent. The catalyst of formula (I) includes the following structure:

[0013] [ka] It has, In the formula, 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, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R3 is independently and optionally selected from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and if E3, E4, E5 or E6 is N,

[0014] [ka] teeth,

[0015] [ka] And if E3, E4, E5 or E6 is NR4, O or S,

[0016] [ka] teeth,

[0017] [ka] And, R4 is independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)Rx , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amide or selected from optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl or heteroaryl, each X can be the same or different, X can form a bridge between M1 and M2, R x is independently hydrogen or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl or heteroaryl, G is absent or independently selected from neutral or anionic donor ligands that are Lewis bases.

[0018] A method for preparing high molecular weight polyether carbonate is also provided, the method comprising (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 carbon dioxide to form a mixture (α), or (b) mixing a double metal cyanide (DMC) catalyst and optionally 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) and carbon dioxide and optionally a solvent to form a mixture (α), or (d) mixing a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) adding one or more of 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 an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally a solvent comprising, the catalyst of formula (I) has the following structure:

[0019] [Chemical formula] having, 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 hydrogen, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group or 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, and alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be sandwiched by aryl, heteroaryl, aliphatic ring or heteroaliphatic ring; R5 is independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and when E3, E4, E5 or E6 is N,

[0020] [Chemical formula] is,

[0021] [Chemical formula] when E3, E4, E5 or E6 is NR4, O or S,

[0022] [Chemical formula] is,

[0023] [Chemical formula] and R4 is independently selected from H or an optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 , or -alkylC≡N, or alkylaryl, X is independently OC(O)R x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amide or is selected from an optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl or heteroaryl, each X can be the same or different, and X can form a bridge between M1 and M2, R x is independently hydrogen or an optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl or heteroaryl, G is either absent or independently selected from neutral or anionic donor ligands that are Lewis bases.

[0024] Products obtained by the methods described herein are also provided. definition For the purposes of the present invention, an aliphatic group is a hydrocarbon moiety that can be linear (i.e., unbranched), branched, or cyclic, and can be fully saturated or contain one or more unsaturated units, but is not aromatic. The term “unsaturated” means a moiety having one or more double and / or triple bonds. Accordingly, the term “aliphatic” is intended to include alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or cycloalkenyl groups and combinations thereof.

[0025] The aliphatic group is optionally C 1~30 An aliphatic group is an aliphatic group 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. Optionally, the aliphatic group is, optionally, C 1~12 Aliphatic group, optionally C 1~10 Aliphatic group, optionally C 1~8 Aliphatic groups, for example, C 1~6 It is an aliphatic group. Suitable aliphatic groups include linear or branched alkyl, alkenyl and alkynyl groups and mixtures thereof, such as (cycloalkyl)alkyl groups, (cycloalkenyl)alkyl groups and (cycloalkyl)alkenyl groups.

[0026] The term "alkyl," as used herein, refers to a saturated, linear, or branched hydrocarbon group derived from the removal of a single hydrogen atom from an aliphatic moiety. An alkyl group is optionally a linear or branched alkyl group having 1 to 20 carbon atoms. 1~20 It is an "alkyl group". Therefore, an alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, an alkyl group may have C 1~15 Alkyl, optionally C 1~12Alkyl, optionally C 1~10 Alkyl, optionally C 1~8 Alkyl, optionally C 1~6 It is an alkyl group. Specifically, "C 1~20 Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, sec-pentyl, isopentyl, n-pentyl group, neopentyl, n-hexyl group, sec-hexyl, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, This includes 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, 3-methylpentyl group, and the like.

[0027] The term "alkenyl," as used herein, refers to a group derived from the removal of a single hydrogen atom from a linear or branched 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 a single hydrogen atom from a linear or branched aliphatic moiety having at least one carbon-carbon triple bond. The alkenyl and alkynyl groups are optionally defined as "C" groups, respectively. 2~20 "Alkenil" and "C 2~20 "Alkinyl", optionally "C 2~15 "Alkenil" and "C 2~15 "Alkinyl", optionally "C 2~12 "Alkenil" and "C 2~12 "Alkinyl", optionally "C 2~10 "Alkenil" and "C 2~10"Alkinyl", optionally "C 2~8 "Alkenil" and "C 2~8 "Alkinyl", optionally "C 2~6 "Alkenil" and "C 2~6 The "alkynyl" group. 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 ethinyl, 2-propynyl (propargyl), and 1-propynyl.

[0028] The terms “alicyclic,” “carbocyclic,” or “carbocyclic” refer, as used herein, to saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including condensation, bridging, and spiro-condensation) ring systems having 3 to 20 carbon atoms, which are 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, alicyclic groups have 3 to 15, optionally 3 to 12, optionally 3 to 10, optionally 3 to 8, or optionally 3 to 6 carbon atoms. The terms “alicyclic,” “carbocyclic,” or “carbocyclic” also include aliphatic rings condensed to one or more aromatic or non-aromatic rings, such as a tetrahydronaphthyl ring, where the attachment site is on the aliphatic ring. Carbocyclic groups can be polycyclic, such as bicyclic or tricyclic. Alicyclic groups may include alicyclic rings supporting one or more linked or unlinked alkyl substituents, such as -CH2-cyclohexyl. Specifically, examples of carbocyclic groups include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4.5]decane, cycloheptane, adamantane, and cyclooctane.

[0029] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl, and heteroalkynyl) are aliphatic groups as described above that further contain one or more heteroatoms. Thus, heteroaliphatic groups optionally contain 2 to 21 atoms, optionally 2 to 16 atoms, optionally 2 to 13 atoms, optionally 2 to 11 atoms, optionally 2 to 9 atoms, optionally 2 to 7 atoms, where at least one atom is a carbon atom. Optional heteroatoms are selected from O, S, N, P, and Si. When a heteroaliphatic group has two or more heteroatoms, the heteroatoms can be the same or different. Heteroaliphatic groups can be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.

[0030] An alicyclic group is a saturated or partially unsaturated cyclic aliphatic 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, optionally 3 to 6 carbon atoms. The term "alicyclic" includes cycloalkyl, cycloalkenyl, and cycloalkynyl groups. It will be understood that alicyclic groups can include alicyclic rings having one or more linked or unlinked alkyl substituents such as -CH2-cyclohexyl. Specifically, C 3~20 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0031] A heteroalicyclic group is an alicyclic group as defined above, having one or more ring heteroatoms, in addition to a carbon atom, optionally selected from O, S, N, P, and Si. A heteroalicyclic group optionally contains 1 to 4 heteroatoms, which may be the same or different. A heteroalicyclic group optionally contains 5 to 20 atoms, optionally 5 to 14 atoms, or optionally 5 to 12 atoms.

[0032] An aryl group or aryl ring is a monocyclic or polycyclic ring system having 5 to 20 carbon atoms, where at least one ring in the system is aromatic, and each ring in the system contains 3 to 12 ring members. The term "aryl" can be used alone or as part of a larger group, as in "aralkyl," "aralkoxy," or "aryloxyalkyl." The aryl group can optionally be "C 6~12 An aryl group is an aryl group composed of 6, 7, 8, 9, 10, 11, or 12 carbon atoms, and includes fused ring groups, such as monocyclic or bicyclic ring groups. Specifically, "C 6~10 Examples of "aryl groups" include phenyl, biphenyl, indenyl, anthrasyl, naphthyl, or azulenyl groups. It should be noted that fused rings, such as indan, benzofuran, phthalimide, phenanthridine, and tetrahydronaphthalene, are also included in the category of aryl groups.

[0033] The term "heteroaryl" is used alone or as part of another term (e.g., "heteroaryl" or "heteroarylcoxy") to refer to a group having 5 to 14 ring atoms, optionally 5, 6, or 9 ring atoms, and 6, 10, or 14 π electrons shared in a cyclic arrangement, and having 1 to 5 heteroatoms in addition to 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 the heteroaryl ring is fused to one or more aryl rings, alicyclic rings, or heterocyclyl rings, where the group or attachment site is on a heteroaromatic ring. Examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, sinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolidinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazine-3(4H)-one. Thus, heteroaryl groups can be monocyclic or polycyclic.

[0034] The term "heteroaralkyl" refers to an alkyl group that is substituted with a heteroaryl group, where the alkyl and heteroaryl portions are independently and selectively substituted. As used herein, the terms “heterocyclic,” “heterocyclyl,” “heterocyclic group,” and “heterocyclic ring” are interchangeable and refer to stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclic heterocyclic parts that are saturated, partially unsaturated, or aromatic and have one or more, optionally 1 to 4 heteroatoms in addition to carbon atoms, as defined above. When used in relation to the ring atoms of a heterocyclic ring, the term “nitrogen” includes substituted nitrogen.

[0035] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithian, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indidine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazole, and This includes xathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazolin, pyrazolidine, pyridazine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolidine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiadin, thiazole, thiamorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithian.

[0036] The terms “halide,” “halo,” and “halogen” are used interchangeably and, as used herein, mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., optionally a fluorine atom, a bromine atom, or a chlorine atom, and optionally a fluorine atom.

[0037] Haloalkyl groups can be optionally selected as "C 1~20 "Haloalkyl group", optionally "C 1~15 "Haloalkyl group", optionally "C 1~12 "Haloalkyl group", optionally "C 1~10 "Haloalkyl group", optionally "C 1~8 "Haloalkyl group", optionally "C 1~6 A haloalkyl group, where each is substituted with at least one halogen atom, optionally one, two, or three halogen atoms, as described 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 alkyl group. The term "haloalkyl" includes fluorinated or chlorinated groups, including perfluorinated compounds. Specifically, "C 1~20 Examples of "haloalkyl groups" include fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, chloromethyl, bromomethyl, and iodomethyl groups.

[0038] As used herein, the term "acyl" refers to a group having the formula -C(O)R, where R is a hydrogen atom or an optionally substituted aliphatic, aryl, or heterocyclic group.

[0039] The alkoxy group can be optionally selected as "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 These are "alkoxy groups," and each is defined as C as previously defined. 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. Specifically, "C 1~20Examples of "alkoxy groups" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, n-hexyloxy group, isohexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, and n-hexadecyl This includes oxy groups, n-heptadecyloxy groups, n-octadecyloxy groups, n-nonadecyloxy groups, n-eicosyloxy groups, 1,1-dimethylpropoxy groups, 1,2-dimethylpropoxy groups, 2,2-dimethylpropoxy groups, 2-methylbutoxy groups, 1-ethyl-2-methylpropoxy groups, 1,1,2-trimethylpropoxy groups, 1,1-dimethylbutoxy groups, 1,2-dimethylbutoxy groups, 2,2-dimethylbutoxy groups, 2,3-dimethylbutoxy groups, 1,3-dimethylbutoxy groups, 2-ethylbutoxy groups, 2-methylpentyloxy groups, 3-methylpentyloxy groups, and the like.

[0040] The aryloxy group can optionally be "C 5~20 "Aryloxy group", optionally "C 6~12 "Aryloxy group", optionally "C 6~10 These are "aryloxy groups," and each is defined as C as previously defined. 5~20 Ariel, C 6~12 Aryl or C 6~10 It is an oxy group bonded to an aryl group.

[0041] The alkylthio group can be optionally selected as "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 This is an alkylthio group, which is defined as C 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 a thio (-S-) group respectively bonded to an alkyl group.

[0042] The arylthio group is optionally a "C 5~20 Arylthio group", optionally "C 6~12 Arylthio group", optionally "C 6~10 Arylthio group", which is C 5~20 Aryl, C 6~12 Aryl or C 6~10 It is a thio (-S-) group respectively bonded to an aryl group.

[0043] [[ID=三十一]]The alkylaryl group is optionally a "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 bonded at any position to an alkyl group as defined above. The attachment point of the alkylaryl group to the molecule can be via the alkyl portion, and thus, optionally, the alkylaryl group is -CH2-Ph or -CH2CH2-Ph. The alkylaryl group can also be referred to as "aralkyl".

[0044] The silyl group is optionally a group -Si(R s )3, where each R s is independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. Optionally, each R s is independently an unsubstituted aliphatic, alicyclic or aryl. Optionally, each R s is an alkyl group selected from methyl, ethyl or propyl. [[ID=五十七]]

[0045] The silyl ether group may optionally be the group OSi(R6)3, where each R6 is independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. Each R6 may independently be an unsubstituted aliphatic, aliphatic ring, or aryl group. Optionally, each R6 is an optionally substituted phenyl or an optionally substituted alkyl group selected from methyl, ethyl, propyl, or butyl (e.g., 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).

[0046] The nitrile group (also called the cyano group) is a CN group. The imine group is a -CRNR, optionally -CHNR7 group, where R7 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. R7 can be an unsubstituted aliphatic, aliphatic ring, or aryl group. Optionally, R7 is an alkyl group selected from methyl, ethyl, or propyl.

[0047] The acetylide group contains a triple bond -C≡C-R9, and optionally R9 may be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. For the purposes of the present invention, if R9 is alkyl, the triple bond may be located at any position along the alkyl chain. R9 may be an unsubstituted aliphatic, aliphatic ring, or aryl group. Optionally, R9 may be methyl, ethyl, propyl, or phenyl.

[0048] The amino group can be optionally -NH2 or -NHR. 10 or -N(R 10 )2, R 10 The amino group may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, silyl, aryl, or heteroaryl group as defined above. 10 If )2, then each R10 It will be understood that the bases may be the same or different. Each R 10 R can be independently an unsubstituted aliphatic, aliphatic ring, silyl, or aryl. Optionally, 10 These are methyl, ethyl, propyl, SiMe3, or phenyl.

[0049] The amide group can optionally be -NR 11 C(O)- or -C(O)-NR 11 - and R 11 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 11 R can be an unsubstituted aliphatic, aliphatic ring, or aryl. Optionally, R 11 The group may be hydrogen, methyl, ethyl, propyl, or phenyl. The terminus of the amide group may be hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl.

[0050] The ester group can be optionally -OC(O)R 12 - or -C(O)OR 12 - and in the formula, R 12 R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 12 R may be unsubstituted aliphatic, alicyclic, or aryl. Optionally, 12 The ester group is methyl, ethyl, propyl, or phenyl. The ester group can be terminated by an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. 12 If it is hydrogen, then -OC(O)R 12 - or -C(O)OR 12 Please note that the group defined by - is a carboxylic acid group.

[0051] Sulfoxides can be optionally -S(O)R 13 The sulfonyl group is optionally -S(O)2R 13 And R 13R can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 13 R can be an unsubstituted aliphatic, aliphatic ring, or aryl. Optionally, R 13 These are methyl, ethyl, propyl, or phenyl.

[0052] The carboxylic acid group can be optionally -OC(O)R 14 And in the formula, R 14 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 14 R may be unsubstituted aliphatic, alicyclic, or aryl. Optionally, 14 These are 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] Acetamide is optionally MeC(O)N(R) 15 )2, R 15 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 15 R can be an unsubstituted aliphatic, aliphatic ring, or aryl. Optionally, R 15 These are hydrogen, methyl, ethyl, propyl, or phenyl.

[0054] The phosphinate group can be optionally -OP(O)(R 16 )2 or -P(O)(OR 16 )(R 16 ) and each R 16 R is independently selected from hydrogen or the aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl groups defined above. 16These can be aliphatic, aliphatic ring, or aryl, and these are aliphatic, aliphatic ring, aryl, or C 1~6 It is optionally substituted by an alkoxy. Optionally, R 16 This is an aryl or C that is optionally substituted. 1~20 Alkyl, optionally C 1~6 Alkoxy (optionally methoxy) or unsubstituted C 1~20 These are phenyl compounds that are optionally substituted with alkyl groups (hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, etc.). The phosphonate group is optionally substituted with -P(O)(OR 16 )2, R 16 This is as defined above. -P(O)(OR 16 ) 2 R units 16 If either or both are hydrogen, then -P(O)(OR 16 It will be understood that the group defined in 2 is a phosphonic acid group.

[0055] The sulfinate group can be optionally -S(O)OR 17 Or -OS(O)R 17 And R 17 R can be a hydrogen, aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 17 R can be an unsubstituted aliphatic, aliphatic ring, or aryl. Optionally, R 17 R is hydrogen, methyl, ethyl, propyl, or phenyl. 17 If it is hydrogen, then -S(O)OR 17 It will be understood that the group defined by this is a sulfonic acid group.

[0056] The carbonate group can be optionally -OC(O)OR 18 And in the formula, R 18 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 18 R may be an aliphatic, alicyclic, or aryl compound that is optionally substituted. 18R is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. 17 If it is hydrogen, then -OC(O)OR 18 Please note that the group defined by is a carbonate group.

[0057] -alkylC(O)OR 19 or -alkyl C(O)R 19 In the base, R 19 R can be a hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 19 R can be an unsubstituted aliphatic, aliphatic ring, or aryl. Optionally, R 19 These are 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.

[0058] If any of the above groups are present on a Lewis base G, it will be understood that one or more additional R groups may be present as needed to complete the valence. For example, with respect to an amino group, RNHR 10 An additional R group may be present to give the result, where R is hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group, which can be optionally substituted as defined above. Optionally, R is hydrogen or an aliphatic, aliphatic ring, or aryl group.

[0059] As used herein, the term “optionally substituted” means that one or more hydrogen atoms at the optionally substituted site are substituted with appropriate substituents. Unless otherwise indicated, an “optionally substituted” group may have appropriate substituents at each substitutedable position of the group, and if two or more positions in any given structure can be substituted with two or more substituents selected from a particular group, the substituents may be the same or different at all positions. The substituent combinations envisioned by the present invention optionally form stable compounds. As used herein, “stable” means a compound that is chemically feasible and can exist at room temperature (i.e., 16–25°C) for a sufficiently long time to be usable in detection, isolation and / or chemical synthesis.

[0060] Optional substituents for use in the present invention include, but are not limited to, halogens, hydroxy, nitro, carboxylates, carbonates, alkoxys, aryloxys, alkylthios, arylthios, heteroaryloxys, alkylaryls, aminos, amides, imines, nitriles, silyls, silyl ethers, esters, sulfoxides, sulfonyls, acetylides, phosphinates, sulfonates, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl groups (for example, optionally substituted with halogens, hydroxy, nitros, carbonates, alkoxys, aryloxys, alkylthios, arylthios, aminos, imines, nitriles, silyls, sulfoxides, sulfonyls, phosphinates, sulfonates, or acetylides).

[0061] In formula (I), groups X and G are shown as being involved in a single M1 or M2 metal center, but it will be understood that one or more X and G groups can form bridges between M1 and M2 metal centers.

[0062] For the purposes of the present invention, the epoxide substrate is not limited. Therefore, the term epoxide relates to any compound containing an epoxide moiety (i.e., substituted or unsubstituted oxiran compounds). Substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. An epoxide contains a single oxiran moiety. An epoxide contains two or more oxiran moieties.

[0063] 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, and substituted cyclohexene oxides (e.g., limonene oxide, C). 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 22 This includes alkylene oxides (e.g., ethylene oxide and substituted ethylene oxide), unsubstituted or substituted oxiranes (e.g., oxiranes, epichlorohydrins, 2-(2-methoxyethoxy)methyloxiran (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxiran (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxiran (ME3MO), 1,2-epoxybutane, glycidyl ether, 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-dioxa epoxides. Examples of functionalized 3,5-dioxa epoxides are:

[0064] [ka] Includes.

[0065] The epoxide portion may be a glycidyl ether, glycidyl ester, or glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters, and glycidyl carbonates are:

[0066] [ka] Includes.

[0067] As mentioned above, the epoxide substrate may contain multiple epoxide moieties, i.e., these may be bis-epoxide, tris-epoxide, or multi-epoxide-containing moieties. Examples of compounds containing multiple epoxide moieties include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It is understood that reactions carried out in the presence of one or more compounds having multiple epoxide moieties may result in crosslinking in the polymer thus obtained.

[0068] Those skilled in the art will recognize that epoxides can be obtained from "environmentally friendly" or renewable resources. Epoxides can also be obtained from (poly)unsaturated compounds, such as those derived from fatty acids and / or terpenes obtained using standard oxidative chemical reactions.

[0069] The epoxide moiety may contain an -OH moiety or a protected -OH moiety. The -OH moiety may be protected by 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), benzoyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (e.g., trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), tri-isopropylsilyloxomethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

[0070] The epoxides have a purity of at least 98%, and optionally >99%. The term "epoxide" is understood 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, an epoxide substrate may 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.

[0071] Polyether carbonate and polycarbonate ether are used interchangeably herein and both refer to polymers having multiple ether bonds and multiple carbonate bonds. The term polyether carbonate polyol generally refers to a polymer whose respective ends are substantially terminated with -OH, -SH, and / or -NHR' groups (including moieties such as C-OH, P-OH, and -C(O)OH). R' may be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' may be H or optionally substituted alkyl.

[0072] For example, at least about 90%, at least about 95%, at least about 98%, or at least about 99% of the polymer may be terminated with -OH groups at each end. Those skilled in the art will understand that if the polymer is linear, both ends may be capped with -OH groups. If the polymer is branched, each branch may be capped with -OH groups. Such polymers are generally useful for preparing higher-order polymers such as polyurethanes. The chain may contain a mixture of functional groups (e.g., -OH and -SH groups) or may contain the same functional group (e.g., all -OH groups).

[0073] As used herein, the term “continuous” may be defined as the form of material addition, or it may refer to the nature of the reaction method as a whole. Regarding continuous addition methods, the relevant materials are added continuously or constantly during the reaction process. This can be achieved, for example, by adding a flow of materials at either a constant or variable flow rate. In other words, one or more materials are added in an essentially nonstop manner. However, it should be noted that, for practical reasons, it may be necessary to temporarily interrupt the nonstop addition of materials, for example, to refill or replace the material containers for adding these materials.

[0074] Regarding the continuous nature of the reaction as a whole, the reaction can take place over a long period of time, such as several days, weeks, or months. In such continuous reactions, reactants may be continuously replenished and / or the reaction products may be removed. Although the catalyst may not be consumed during the reaction, removal can drastically reduce the amount of catalyst present; therefore, in either case, it will be understood that the catalyst may need to be replenished.

[0075] Continuous reactions can utilize the continuous addition of materials. As used herein, the term “discontinuous” means that the addition of materials is carried out in small increments. This can be done, for example, by dropwise adding the materials. Alternatively, the materials may be added to the container in portions (i.e., batch feeding) with time intervals between additions. These time intervals may be regular or may be changed during the course of the reaction. Such time intervals may be as short as a few minutes or as long as several hours. For example, the time intervals may be 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. When materials are added in portions (i.e., batch feeding), the materials as a whole must be added separately at least twice during the course of the reaction.

[0076] Continuous reactions can utilize discontinuous (i.e., batch) addition of materials. [Modes for carrying out the invention]

[0077] The present invention relates to continuous and discontinuous methods for preparing polycarbonate ether polyols by reacting an epoxide with carbon dioxide in the presence of a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and a starter compound.

[0078] The present invention further relates to continuous and discontinuous methods for preparing high molecular weight polyether carbonates by reacting epoxides and carbon dioxide in the presence of a catalyst of formula (I) and a double metal cyanide (DMC) catalyst.

[0079] Therefore, the present invention relates to a method for preparing a polycarbonate ether polyol, the method being: (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst and optionally a starter 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) A step of mixing an epoxide, a catalyst of formula (I), a starter compound, carbon dioxide, and optionally a solvent to form a mixture (α), or (d) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a starter compound, an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) Adding one or more of the following to mixture (α): a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and / or a solvent, to form a mixture (β) containing the starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and optionally a solvent. The catalyst of formula (I) includes the following structure:

[0080] [ka] It has, In the formula, 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, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R3 is independently and optionally selected from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and if E3, E4, E5 or E6 is N,

[0081] [ka] teeth,

[0082] [ka] And if E3, E4, E5 or E6 is NR4, O or S,

[0083] [ka] teeth,

[0084] [ka] And, R4 is independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x , selected from phosphinates, halides, nitrates, hydroxyls, carbonates, aminos, amides, or optionally substituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls, where each X may be the same or different, and X may form a bridge between M1 and M2. R x These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, G is either absent or selected independently from neutral or anionic donor ligands that are Lewis bases.

[0085] The present invention relates to a method for preparing polycarbonate ether polyols and high molecular weight polyether carbonates. This method is carried out in two or more steps. In this method, one or more reactants are added (continuously or discontinuously) as the reaction progresses, after a part of the reaction has started.

[0086] Adding specific components in the second step can be useful in increasing catalyst activity and can make the process more efficient compared to a process where all materials are supplied at the start of the reaction. If certain components are present in large quantities throughout the reaction, the catalyst's efficiency may decrease. Adding materials slowly to the reaction can prevent this decrease in catalyst efficiency and / or optimize catalytic activity.

[0087] Furthermore, not adding the total amount of each component at the start of the reaction can homogenize the catalytic action and result in a more uniform polymer product. This, therefore, can produce polymers with a narrower molecular weight distribution, a desired ether-to-carbonate bond ratio, and / or an improved (i.e., lower) polydispersity index.

[0088] Mixing only specific components in the first step and adding the remainder in the second step can also be useful for pre-activating the catalyst. Such pre-activation can be carried out by mixing one or both catalysts with the epoxide (and optionally other components) in step (I)(a) or (b) above. Pre-activation can be useful in stimulating one or both catalysts, which can then increase the efficiency of the reaction when the remaining components are added in step (II).

[0089] It will be understood that the present invention relates to a reaction in which carbonate and ether bonds are added to a growing polymer chain. Mixing only specific components in the first step and adding the remainder in the second step can be useful in allowing part of the reaction to proceed before the second step of the reaction. For example, by mixing an epoxide, a catalyst of formula (I), a starter compound, carbon dioxide, and optionally a solvent in step (I)(c) above, a polymer having a large number of carbonate bonds can be grown. Subsequently, by adding the remaining components (including the DMC catalyst), the reaction can proceed by adding ether bonds (and continuing to add carbonate bonds) to the growing polymer chain.

[0090] Generally, the objective of the present invention is to control polymerization reactions by adding controlled materials. The methods described herein can be adapted to meet specific requirements for products prepared by such methods.

[0091] The mixture (α) formed by step (I)(a) or (b) may be held at a temperature of about 50–150°C, optionally about 80–130°C, before step (II). The mixture (α) formed by step (I)(c) or (d) may be held at a temperature of about 0 to 120°C, optionally about 40 to 100°C, and optionally about 50 to 90°C before step (II).

[0092] The 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, or optionally at least about 5 hours prior to step (II).

[0093] The mixture (α) formed by step (I)(c) may be held prior to step (II) 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, or optionally at least about 16 hours.

[0094] 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, or optionally about 0% by weight of water. The presence of water in the mixture may cause deactivation of the catalyst or each of the catalysts. Therefore, it is desirable to minimize the water content in the mixture.

[0095] Step (I)(a) may include first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide to form mixture (α'), and then subsequently adding the epoxide and optionally a starter compound and / or carbon dioxide to form mixture (α). Carrying out the method in this manner may be useful for pre-activating one or both catalysts, as described above.

[0096] The mixture (α') may be held at temperatures of approximately 0–250°C, optionally approximately 40–150°C, optionally approximately 50–150°C, optionally approximately 70–140°C, and optionally approximately 80–130°C before the subsequent addition.

[0097] Following step (I)(c), step (II) may include mixing a double metal cyanide (DMC) catalyst, an epoxide, and optionally a starter compound, carbon dioxide and / or a solvent to form a pre-activated mixture, and adding the pre-activated mixture to mixture (α) to form mixture (β).

[0098] The pre-activated mixture can be held at a temperature of approximately 50–110°C, or optionally approximately 60–90°C, before addition. The reaction method as a whole can be carried out in a batch manner. In such a case, the method can use the total amount of each related material used in the reaction (epoxide, starter compound, etc.), and a portion of that total amount can be added at different steps of the reaction.

[0099] The method may use the total amount of epoxide, with approximately 1-95% of the total amount of epoxide being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0100] The method may use the total amount of the starter compound, where approximately 1-95% of the total amount of the starter compound is mixed in step (I) and the remainder is added in step (II), where optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% can be mixed in step (I).

[0101] The method may use the entire amount of catalyst of formula (I), where approximately 1-100% of the total amount of catalyst of formula (I) may be mixed in step (I), and the remainder may be added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0102] The method may use the entire amount of the double metal cyanide (DMC) catalyst, where approximately 1-100% of the total amount of the double metal cyanide (DMC) catalyst is mixed in step (I), and the remainder is added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0103] The method may use the total amount of carbon dioxide, with approximately 1-100% of the total amount of carbon dioxide being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0104] The method may use the entire amount of solvent, with approximately 1-100% of the total amount of solvent being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0105] The total amount of catalyst of formula (I) can be low so that the method of the present invention can be carried out with a low amount of catalyst added. For example, the amount of catalyst of formula (I) can be in the range of about 1:100,000 to 300,000 [total catalyst of formula (I)]:[total epoxide], such as about 1:10,000 to 100,000 [total catalyst of formula (I)]:[total epoxide], for example, in the range of about 1:10,000 to 50,000 [total catalyst of formula (I)]:[total epoxide], for example, in the range of 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 method.

[0106] The method may be continuous, and there is a predetermined molar or weight ratio of epoxide to catalyst of formula (I) in mixture (β), and the method is (III) Adding epoxide to mixture (β) to form mixture (γ). The mixture further comprises the epoxide, which is added in an amount sufficient to make the molar or weight ratio of the epoxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar or weight ratio, and step (III) is optionally repeated.

[0107] The method may be continuous, and there exists a predetermined molar or weight ratio of the starter compound to the catalyst of formula (I) in the mixture (β), and the method is (III) Adding a starter compound to mixture (β) to form mixture (γ). The mixture further comprises the starter compound, which is added in an amount sufficient to make the molar or weight ratio of the starter compound to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar or weight ratio, and step (III) is optionally repeated.

[0108] The method may be continuous, and there is a predetermined molar or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (β), and the method is (III) Adding carbon dioxide to mixture (β) to form mixture (γ) The mixture further comprises carbon dioxide, which is added in an amount sufficient to make the molar or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar or weight ratio, and step (III) is optionally repeated.

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

[0110] Step (III) may be carried out such that the molar or weight ratio of the epoxide, starter compound, carbon dioxide, and solvent to the catalyst of formula (I) in mixture (γ) is not less than approximately 75% of the predetermined molar or weight ratio.

[0111] The method can be continuous, and a predetermined amount of the catalyst of formula (I) is present in the mixture (β), and the method is (III) Adding the catalyst of formula (I) to mixture (β) to form mixture (γ). The mixture further includes the catalyst of formula (I) added in an amount sufficient to make the amount of the catalyst of formula (I) in the mixture (γ) about 50-550% of the predetermined amount, and step (III) is optionally repeated.

[0112] Step (III) may be carried out such that the amount of catalyst of formula (I) in mixture (γ) is not less than approximately 50% of the predetermined amount. The method may be continuous, and a predetermined amount of the bimetallic cyanide (DMC) catalyst is present in the mixture (β), and the method is (III) Adding a double metal cyanide (DMC) catalyst to mixture (β) to form mixture (γ). The mixture further comprises the double metal cyanide (DMC) catalyst, which is added in an amount sufficient to bring the amount of the double metal cyanide (DMC) catalyst in the mixture (γ) to about 50-550% of the predetermined amount, and step (III) is optionally repeated.

[0113] Step (III) may be carried out such that the amount of the double metal cyanide (DMC) catalyst in mixture (γ) is not less than approximately 50% of the predetermined amount. The rate at which the material is added can be chosen such that the temperature of the (exothermic) reaction does not exceed a selected temperature (i.e., the material is added slowly enough to dissipate excess heat and keep the remaining temperature nearly constant).

[0114] If the addition of materials (i.e., by step III) is repeated, the addition may be repeated 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more. In mixture (α), the amounts of the catalyst of formula (I) and the amounts of the double metal cyanide (DMC) catalyst may be in predetermined weight ratios of about 300:1 to about 1:100, about 120:1 to about 1:75 such as about 40:1 to about 1:50, about 30:1 to about 1:30 such as about 20:1 to about 1:1, for example, about 10:1 to about 2:1, for example, about 5:1 to about 1:5.

[0115] In step (I), the double metal cyanide (DMC) catalyst can be dry-mixed with other components. In step (I), the double metal cyanide (DMC) catalyst may be mixed as a slurry, the slurry comprising the double metal cyanide (DMC) catalyst and a starter compound and / or solvent.

[0116] In step (I), the catalyst of formula (I) can be dry-mixed with other components. In step (I), the catalyst of formula (I) may be mixed as a solution, the solution comprising the catalyst of formula (I) and one or more starter compounds, epoxides and / or solvents.

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

[0118] The starter compound may be added in step (II). Both the epoxide and the starter compound may be added in step (II). Epoxides, catalysts of formula (I), double metal cyanide (DMC) catalysts, and / or starter compounds may be added independently and sequentially in step (II).

[0119] Epoxides, catalysts of formula (I), double metal cyanide (DMC) catalysts, and / or starter compounds may be added independently and discontinuously in step (II). Carbon dioxide can be supplied continuously.

[0120] The method can be carried out at carbon dioxide pressures of approximately 1 bar to 60 bar, optionally 1 bar to 40 bar, optionally 1 bar to 20 bar, optionally 1 bar to 15 bar, optionally 1 bar to 10 bar, and optionally 1 bar to 5 bar.

[0121] The reaction temperature may rise during the process. Starter compounds that can be used in methods for forming polycarbonate ether polyols include at least two groups selected from a hydroxyl group (-OH), a thiol (-SH), an amine (-NHR') having at least one NH bond, a group having at least one P-OH bond (e.g., -PR'(O)OH, PR'(O)(OH)2 or -P(O)(OR')(OH)), or a carboxylic acid group (-C(O)OH).

[0122] Therefore, the starter compound that can be used in a method for forming a polycarbonate ether polyol is formula (III):

[0123] [ka] Z can be any base, and two or more -Rs can be linked to it. ZIt can be any group that may have a group. Therefore, Z can be optionally substituted from alkylene, alkenylene, alkylylene, heteroalkylene, heteroalkenylene, heteroalkylynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be any combination of these groups, for example, Z can be an alkylarylene, heteroalkylarylene, heteroalkylhetearene, or alkylhetearene group. Optionally, Z is alkylene, heteroalkylene, arylene, or heteroarylene.

[0124] It will be understood that a is an integer at least 2, and that a is optionally in the range of 2 to 8, and optionally in the range of 2 to 6. Each R Z R can be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH)2, or -PR'(O)OH, and R can be selected at will. Z The R is selected from -OH, -NHR', or -C(O)OH, and each R is selected at will. Z These are -OH, -C(O)OH, or combinations thereof (for example, each R Z (is -OH).

[0125] R' may be H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' may be H or optionally substituted alkyl.

[0126] Two starter compounds may be present in mixture (β), the starter compound in step (I) is the first starter compound, and step (II) is, (A) Adding one or more of the following to mixture (α): a first starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent, (B) Adding a second starter 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) containing the first starter compound, the second starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally a solvent. Includes.

[0127] Step (B) may be performed 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, or optionally at least about 5 hours.

[0128] The first starter compound may have a molecular weight of at least about 200 Da, and the second starter compound may have a molecular weight of up to about 200 Da. The second starter compound may be polypropylene glycol having a molecular weight of about 200 to 1000 Da, optionally about 300 to 700 Da, and optionally about 400 Da.

[0129] The starter compound, or each starter compound, has two or more hydroxyl groups, optionally three or more, optionally four or more, optionally five or more, optionally six or more, optionally seven or more, or optionally eight or more hydroxyl groups.

[0130] It will be understood that any of the above features can be combined. For example, a can be 2 to 8, and each R Z Z can be -OH, -C(O)OH, or a combination thereof, and Z can be selected from alkylene, heteroalkylene, arylene, or heteroarylene.

[0131] Examples of starter compounds include polyethylene glycol with a maximum Mn of approximately 1500 g / mol, such as 1,2-ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexendiol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or PPG425, PPG725, PPG1000, etc. Examples include diols such as PEG; triols such as glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, triols such as tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, polypropylene oxidetriol and polyestertriol; tetraols such as calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, erythritol, pentaerythritol or polyalkylene glycol (PEG or PPG) having four -OH groups; polyols such as sorbitol or polyalkylene glycol (PEG or PPG) having five or more -OH groups; or compounds having mixed functional groups such as ethanolamine, diethanolamine, methyldiethanolamine and phenyldiethanolamine.

[0132] For example, starter compounds include 1,2-ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, and 1,4-diphenol. The starter compound may be a diol such as phenol, neopentyl glycol, catechol, cyclohexendiol, 1,4-cyclohexanedimethanol, poly(caprolactone)diol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, or polypropylene glycol (PPG) or polyethylene glycol (PEG) (PPG425, PPG725, PPG1000, etc.) having up to approximately 1500 g / mol of Mn. It will be understood that the starter compound may be 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, poly(caprolactone)diol, PPG425, PPG725, or PPG1000.

[0133] Further exemplary starter compounds include diacids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid; or other compounds having mixed functional groups such as lactic acid, glycolic acid, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, and 5-hydroxypentanoic acid.

[0134] The ratio of the starter compound (if present) to the catalyst of formula (I) can be about 750:1 to about 5:1, such as about 1000:1 to about 1:1, 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 starter to the total amount of catalyst of formula (I) used in the method. These ratios can be maintained throughout the process of adding the materials.

[0135] The starter can be pre-dried (e.g., with a molecular sieve) to remove moisture. It will be understood that any combination of the above reaction conditions described may be used. For example, the reaction may be carried out at temperatures in the range of about 10°C to about 150°C, such as about 20°C to about 90°C, at temperatures of about 5°C to 200°C, such as about 15°C to about 100°C, and optionally at temperatures of about 60 bar or less, such as about 30 bar or less, and optionally at 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.

[0136] The methods of the present invention can, for example, prepare polycarbonate ether polyols that can be used to prepare polyurethanes. In particular, the continuous and discontinuous methods of the present invention can provide polycarbonate ether polyols having a low polydispersity index (PDI).

[0137] The method of the present invention can produce polycarbonate ether polyols in which the amounts of ether bonds and carbonate bonds can be controlled. Thus, the present invention can provide polycarbonate ether polyols having 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. Therefore, it will be understood that n≧1 and m≧1.

[0138] For example, the method of the present invention can prepare polycarbonate ether polyols 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 created 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.

[0139] As shown above, the method of the present invention can prepare polycarbonate ether polyols in which m / (n+m) is about 0.7 to about 0.95, for example, about 0.75 to about 0.95.

[0140] Therefore, the method of the present invention makes it possible to prepare polycarbonate ether polyols having a high ratio of carbonate bonds, for example, m / (n+m) can be greater than about 0.50, such as greater than about 0.55 and less than about 0.95, for example, about 0.65 to about 0.90, for example, about 0.75 to about 0.90, etc.

[0141] For example, a polycarbonate ether polyol produced by the method of the present invention may have the following formula (IV).

[0142] [ka] The identification of Z and Z' depends on the properties of the starter compound, and R e1 and R e2 It will be understood that the identification depends on the properties of the epoxide used to prepare the polycarbonate ether polyol. m and n define the amounts of carbonate and ether bonds in the polycarbonate ether polyol.

[0143] Those skilled in the art will understand that in the polymer of formula (IV), adjacent epoxide monomer units in the main chain may be head-to-tail, head-to-head, or tail-to-tail linked. It will also be understood that equation (IV) does not require the carbonate bond and ether bond to be in two separate "blocks" of each part defined by "a", and that the repeating units of carbonate and ether may be statistically distributed along the polymer backbone, or that the carbonate bond and ether bond may be arranged so as not to be in two separate blocks.

[0144] Therefore, polycarbonate ether polyols (e.g., polymers of formula (IV)) prepared by the method of the present invention may be called random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers.

[0145] Those skilled in the art will understand that the weight percentage of carbon dioxide incorporated into a polymer cannot be definitively used to determine the amount of carbonate bonds in the polymer backbone. For example, two polymers incorporating the same weight percentage of carbon dioxide may have significantly different carbonate-to-ether bond ratios. This is because the "weight percentage" of carbon dioxide does not take into account the length and properties of the starter compound. For example, if one polymer (Mn 2000 g / mol) is prepared using a 100 g / mol molar starter and another polymer (also Mn 2000 g / mol) is prepared using a 500 g / mol molar starter, and both resulting polymers have the same m / n ratio, then the weight percentage of carbon dioxide in the polymers will differ because the mass ratio of the starter to the total molecular weight (Mn) of the polymers will be different. For example, if m / (m+n) is 0.5, the carbon dioxide content of the two polyols mentioned above would be 26.1% and 20.6% respectively.

[0146] As emphasized above, the method of the present invention can prepare polyols having a wide range of carbonate-to-ether bond ratios (e.g., m / (n+m) can be greater than zero and less than 1), which corresponds to up to about 43 wt% carbon dioxide incorporation when using propylene oxide. This is remarkable because previously reported DMC catalysts can typically only prepare polyols with a carbonate-to-ether bond ratio of up to 0.75, and these amounts can usually only be achieved at high pressures of carbon dioxide, such as 30 bar, and more commonly 40 bar or higher.

[0147] Furthermore, catalysts used to prepare polycarbonate polyols can typically incorporate high wt% carbon dioxide, as they can achieve a carbonate bond-to-ether bond ratio of approximately 0.95 or higher (usually approximately 0.98 or higher). However, these catalysts cannot prepare polyols with a carbonate bond-to-ether bond ratio of less than 0.95. The wt% of carbon dioxide can be controlled by changing the mass of the starter, and the resulting polyol will contain blocks of polycarbonate. Polycarbonates produced from epoxides and carbon dioxide are less thermally stable than polyethers, and block copolymers can have properties very different from random or statistical copolymers, which is undesirable in many applications.

[0148] All other conditions being equal, polyethers have a higher decomposition temperature than polycarbonates produced from epoxides and carbon dioxide. Therefore, polyols with a statistical or random distribution of ether and carbonate bonds will have a higher decomposition temperature than polycarbonate polyols or polyols with a block of carbonate bonds. The thermal decomposition temperature can be measured using thermogravimetric analysis (TGA).

[0149] As described above, the method of the present invention prepares random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers. Thus, the carbonate bonds are not located within a single block, thereby providing polymers with improved properties, such as improved thermal decomposition, compared to polycarbonate polyols. The polymers prepared by the method of the present invention may be random copolymers or statistical copolymers.

[0150] The polycarbonate ether polyol prepared by the method of the present invention may be of formula (IV), where n and m are integers of 1 or more, the sum of all m and n groups is between 4 and 200, and m / (m+n) is in the range greater than 0 and less than 1.00. As described above, m / (n+m) may 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 created from these specific values. For example, m / (n+m) can be approximately 0.05 to 0.95, 0.10 to 0.90, 0.15 to 0.85, 0.20 to 0.80, or 0.25 to 0.75, etc.

[0151] Those skilled in the art will also understand that a polyol must contain at least one carbonate bond and at least one ether bond. Therefore, it will be understood that the number of ether and carbonate bonds in a polyol (n+m) is ≥ a. The sum of n+m must be greater than or equal to "a".

[0152] Each R e1 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. e1 This can be selected from H or an optionally substituted alkyl group.

[0153] 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 This can be selected from H or an optionally substituted alkyl group.

[0154] R e1 and R e2 It will also be understood that these can together form saturated, partially saturated, or unsaturated rings containing carbon and hydrogen atoms, and optionally containing one or more heteroatoms (e.g., O, N, or S). For example, R e1 and R e2 These can together form a ring with 5 or 6 members.

[0155] As explained above, R e1 and R e2 The properties depend on the epoxide used in the reaction. If the epoxide is cyclohexene oxide (CHO), e1 and R e2 They form a 6-membered alkyl ring (e.g., a cyclohexyl ring) together. When the epoxide is ethylene oxide, R e1 and R e2 Both are H. When the epoxide is propylene oxide, R e1 H is R e2 It is methyl (or R by the method of adding the epoxide to the polymer backbone). e1 is methyl, R e2 (where H is). If the epoxide is butylene oxide, R e1 H is R e2 is ethyl (and vice versa). If the epoxide is styrene oxide, R e1 It can be hydrogen, R e2 It can be phenyl (and vice versa).

[0156] When an epoxide mixture is used, R e1 and / or R e2 Each of the elements does not have to be the same; for example, if a mixture of ethylene oxide and propylene oxide is used, R e1 R can be independently hydrogen or methyl, e2 It will also be understood that these can independently be hydrogen or methyl.

[0157] Therefore, R e1 and R e2 This can be independently selected from hydrogen, alkyl, or aryl, or R e1 and R e2 They can form a cyclohexyl ring together, R e1 and R e2 This can be independently selected from hydrogen, methyl, ethyl, or phenyl, or R e1 and R e2 These can form a cyclohexyl ring together.

[0158] Except for the bond replacing an unstable hydrogen atom, Z' is R z This corresponds to the R in the starter compound. Therefore, the identification of each Z' is determined by the R in the starter compound. Z It depends on the definition. Therefore, it will be understood that each Z' can be -O-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -PR'(O)(O-)2 or -PR'(O)O- (wherein R' can be H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, and optionally R' is H or optionally substituted alkyl), optionally Z' can be -C(O)O-, -NR'- or -O-, each Z' can be -O-, -C(O)O- or a combination thereof, and optionally each Z' can be -O-.

[0159] Z also depends on the properties of the starter compound. Therefore, Z can be selected from alkylene, alkenylene, alkylylene, heteroalkylene, heteroalkenylene, heteroalkylynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be any combination of these groups, for example, Z can be an alkylarylene, heteroalkylarylene, heteroalkylhetearene, or alkylhetearene group. Optionally, Z is alkylene, heteroalkylene, arylene, or heteroarylene, for example, alkylene or heteroalkylene. It will be understood that each of the above groups can be optionally substituted with, for example, alkyl.

[0160] The variable a also depends on the properties of the starter compound. Those skilled in the art will recognize that the value of a in formula (IV) is the same as that of a in formula (III). Therefore, in formula (IV), a is at least an integer of 2, and optionally a is in the range of 2 to 8, and optionally a is in the range of 2 to 6.

[0161] Those skilled in the art will understand that the value of a also affects the shape of the polyol prepared by the method of the present invention. For example, when a is 2, the polyol of formula (IV) has the following structure:

[0162] [ka] It may have, in the formula Z, Z', m, n, R e1 and R e2 As stated above, equation (IV) is correct.

[0163] For example, if a is 3, the polyol of formula (IV) is given by the following formula:

[0164] [ka] It may have, in the formula Z, Z', m, n, R e1 and R e2 As stated above, equation (IV) is correct.

[0165] Those skilled in the art will understand that each of the above features can be combined. For example, R e1 and R e2 This can be independently selected from hydrogen, alkyl, or aryl, or R e1 and R e2 The elements can form a cyclohexyl ring together, each Z' can be -O-, -C(O)O-, or a combination thereof (optionally, each Z' can be -O-), Z can be optionally substituted alkylene, heteroalkylene, arylene, or heteroarylene, for example alkylene or heteroalkylene, and a can be 2 to 8.

[0166] The polyols produced by the method of the present invention are optionally low molecular weight polyols. It will be understood that the properties of the epoxide used to prepare the polycarbonate ether polyols affect the molecular weight of the resulting product. Therefore, the upper limit of n+m is used herein to define the “low molecular weight” polymers of the present invention.

[0167] The method of the present invention can advantageously prepare polycarbonate ether polyols having a narrow molecular weight distribution. In other words, polycarbonate ether polyols may have a low polydispersity index (PDI). The PDI of a polymer is related to the weight-average molecular weight (M) of the polymer. w ) number average molecular weight (M n This is determined by dividing by ), which reveals the chain length distribution in the polymer product. The rate of variation in polymer chain length is greater in short-chain polymers compared to long-chain polymers, even if both polymers have the same PDI, so it can be seen that PDI becomes more important as the molecular weight of the polymer decreases.

[0168] Optionally, polymers produced by the method of the present invention have a PDI of about 1 to less than 1.75, such as about 1 to less than 2, optionally about 1 to less than 1.5, about 1 to less than 1.3, about 1 to less than 1.2, and about 1 to less than 1.1.

[0169] M of polymer produced by the method of the present invention n and M w Furthermore, the resulting 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. The sample can be measured at room temperature (293K) in THF at a flow rate of 1 mL / min against a narrow polystyrene standard (e.g., polystyrene low EasiVials with various Mn values ​​from 405 to 49,450 g / mol, supplied by Agilent Technologies). Optionally, the sample may be measured against a poly(ethylene glycol) standard, such as polyethylene glycol easivials supplied by Agilent Technologies.

[0170] Optionally, the polyether carbonate polyol produced by the method of the present invention may have a molecular weight in the range of about 500 to about 6,000 Da, optionally, about 700 to about 5,000 Da, or about 500 to about 3,000 Da.

[0171] The present invention also relates to a method for preparing high molecular weight polyether carbonates, the method being: (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst and optionally carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α), or (c) A step of mixing an epoxide, a catalyst of formula (I), carbon dioxide, and a solvent to form a mixture (α), or (d) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) Adding one or more of the following to mixture (α): epoxide, carbon dioxide, catalyst of formula (I), bimetallic cyanide (DMC) catalyst and / or solvent, to form a mixture (β) containing epoxide, carbon dioxide, catalyst of formula (I), bimetallic cyanide (DMC) catalyst and optionally a solvent. The catalyst of formula (I) includes the following structure:

[0172] [ka] It has, In the formula, 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, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R3 is independently and optionally selected from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and if E3, E4, E5 or E6 is N,

[0173] [ka] teeth,

[0174] [ka] And if E3, E4, E5 or E6 is NR4, O or S,

[0175] [ka] teeth,

[0176] [ka] And, R4 is independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)R xOSO2R x OSOR x OSO(R x )2, S(O)R x , OR x , selected from phosphinates, halides, nitrates, hydroxyls, carbonates, aminos, amides, or optionally substituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls, where each X may be the same or different, and X may form a bridge between M1 and M2. R x These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, G is either absent or selected independently from neutral or anionic donor ligands that are Lewis bases.

[0177] The advantages described above regarding methods for preparing polycarbonate ether polyols, such as controlling the polymerization reaction through controlled addition of materials, are equally applicable to methods for preparing high molecular weight polyether carbonates.

[0178] It will be understood that the method of the present invention can advantageously prepare high molecular weight polyether carbonates having a large molecular weight distribution. In other words, polyether carbonates can have a relatively high polydispersity index (PDI).

[0179] The mixture (α) formed by step (I)(a) or (b) may be held at a temperature of about 50–110°C, optionally about 60–90°C, before step (II). The mixture (α) formed by step (I)(c) or (d) may be held at a temperature of about 0 to 120°C, optionally about 40 to 100°C, and optionally about 50 to 90°C before step (II).

[0180] The 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, or optionally at least about 5 hours prior to step (II).

[0181] The mixture (α) formed by step (I)(c) may be held prior to step (II) for 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, or optionally at least about 16 hours.

[0182] 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, or optionally about 0% by weight of water. The presence of water in the mixture may cause deactivation of the catalyst or each of the catalysts. Therefore, it is desirable to minimize the water content in the mixture.

[0183] Step (I)(a) may include first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide to form mixture (α'), and then subsequently adding the epoxide and optionally carbon dioxide to form mixture (α). Carrying out the method in this manner may be useful for pre-activating one or both catalysts, as described above.

[0184] The mixture (α') may be held at temperatures of approximately 0–250°C, optionally approximately 40–150°C, optionally approximately 50–150°C, optionally approximately 70–140°C, and optionally approximately 80–130°C before the subsequent addition.

[0185] Following step (I)(c), step (II) may include mixing a double metal cyanide (DMC) catalyst, an epoxide, and optionally carbon dioxide and / or a solvent to form a pre-activated mixture, and adding the pre-activated mixture to mixture (α) to form mixture (β).

[0186] The pre-activated mixture can be held at a temperature of approximately 50–110°C, or optionally approximately 60–90°C, before addition. The reaction method as a whole can be carried out in a batch manner. In such a case, the method can use the total amount of each related material used in the reaction (epoxide, starter compound, etc.), and a portion of that total amount can be added at different steps of the reaction.

[0187] The method may use the total amount of epoxide, with approximately 1-95% of the total amount of epoxide being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0188] The method may use the entire amount of catalyst of formula (I), where approximately 1-100% of the total amount of catalyst of formula (I) may be mixed in step (I), and the remainder may be added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0189] The method may use the entire amount of the double metal cyanide (DMC) catalyst, where approximately 1-100% of the total amount of the double metal cyanide (DMC) catalyst is mixed in step (I), and the remainder is added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0190] The method may use the total amount of carbon dioxide, with approximately 1-100% of the total amount of carbon dioxide being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0191] The method may use the entire amount of solvent, with approximately 1-100% of the total amount of solvent being mixed in step (I) and the remainder being added in step (II), with optional amounts of approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% being mixed in step (I).

[0192] The total amount of catalyst of formula (I) can be low so that the method of the present invention can be carried out with a low amount of catalyst added. For example, the amount of catalyst of formula (I) can be in the range of about 1:100,000 to 300,000 [total catalyst of formula (I)]:[total epoxide], such as about 1:10,000 to 100,000 [total catalyst of formula (I)]:[total epoxide], for example, in the range of about 1:10,000 to 50,000 [total catalyst of formula (I)]:[total epoxide], for example, in the range of 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 method.

[0193] The method may be continuous, and there is a predetermined molar or weight ratio of epoxide to catalyst of formula (I) in mixture (β), and the method is (III) Adding epoxide to mixture (β) to form mixture (γ). The mixture further comprises the epoxide, which is added in an amount sufficient to make the molar or weight ratio of the epoxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated.

[0194] The method may be continuous, and there is a predetermined molar or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (β), and the method is (III) Adding carbon dioxide to mixture (β) to form mixture (γ) The mixture further comprises the carbon dioxide, which is added in an amount sufficient to make the molar ratio or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated.

[0195] The method may be continuous, and there exists a predetermined molar or weight ratio of solvent to catalyst of formula (I) in mixture (β), and the method is (III) Adding a solvent to mixture (β) to form mixture (γ) The mixture further comprises the solvent, which is added in an amount sufficient to make the molar ratio or weight ratio of the solvent to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated.

[0196] Step (III) may be carried out such that the molar ratio or weight ratio of the epoxide, carbon dioxide and / or solvent to the catalyst of formula (I) in mixture (γ) is not less than approximately 75% of the predetermined molar ratio or weight ratio.

[0197] Step (III) may be carried out such that the molar ratio or weight ratio of the epoxide, carbon dioxide, and solvent to the catalyst of formula (I) in mixture (γ) is not less than approximately 75% of the predetermined molar ratio.

[0198] The method can be continuous, and a predetermined amount of the catalyst of formula (I) is present in the mixture (β), and the method is (III) Adding the catalyst of formula (I) to mixture (β) to form mixture (γ). The mixture further includes the catalyst of formula (I) added in an amount sufficient to make the amount of the catalyst of formula (I) in the mixture (γ) about 50-550% of the predetermined amount, and step (III) is optionally repeated.

[0199] Step (III) may be carried out such that the amount of catalyst of formula (I) in mixture (γ) is not less than approximately 50% of the predetermined amount. The method may be continuous, and a predetermined amount of the bimetallic cyanide (DMC) catalyst is present in the mixture (β), and the method is (III) Adding a double metal cyanide (DMC) catalyst to mixture (β) to form mixture (γ). The mixture further comprises the double metal cyanide (DMC) catalyst, which is added in an amount sufficient to bring the amount of the double metal cyanide (DMC) catalyst in the mixture (γ) to about 50-550% of the predetermined amount, and step (III) is optionally repeated.

[0200] Step (III) may be carried out such that the amount of the double metal cyanide (DMC) catalyst in mixture (γ) is not less than approximately 50% of the predetermined amount. The rate at which the material is added can be chosen so that the temperature of the (exothermic) reaction does not exceed a selected temperature (i.e., the material is added slowly enough to dissipate excess heat and keep the remaining temperature nearly constant).

[0201] If the addition of materials (i.e., by step III) is repeated, the addition may be repeated 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more. In mixture (α), the amounts of the catalyst of formula (I) and the amounts of the double metal cyanide (DMC) catalyst may be in predetermined weight ratios of about 300:1 to about 1:100, about 120:1 to about 1:75 such as about 40:1 to about 1:50, about 30:1 to about 1:30 such as about 20:1 to about 1:1, for example, about 10:1 to about 2:1, for example, about 5:1 to about 1:5.

[0202] In step (I), the double metal cyanide (DMC) catalyst can be dry-mixed with other components. In step (I), the double metal cyanide (DMC) catalyst may be mixed as a slurry, the slurry comprising the double metal cyanide (DMC) catalyst and a solvent.

[0203] In step (I), the catalyst of formula (I) can be dry-mixed with other components. In step (I), the catalyst of formula (I) may be mixed as a solution, the solution comprising the catalyst of formula (I) and one or more epoxides and / or solvents.

[0204] The epoxide may be added in step (II). The catalyst of formula (I) may be added in step (II). A double metal cyanide (DMC) catalyst may be added in step (II).

[0205] Epoxides, catalysts of formula (I), and / or bimetallic cyanide (DMC) catalysts may be added independently and sequentially in step (II). Epoxides, catalysts of formula (I), and / or double metal cyanide (DMC) catalysts may be added independently and discontinuously in step (II).

[0206] Carbon dioxide can be supplied continuously. The method can be carried out at carbon dioxide pressures of approximately 1 bar to 60 bar, optionally 1 bar to 40 bar, optionally 1 bar to 20 bar, optionally 1 bar to 15 bar, optionally 1 bar to 10 bar, and optionally 1 bar to 5 bar.

[0207] The reaction temperature may rise during the process. The method of the present invention can prepare polyether carbonates. The method of the present invention makes it possible to produce polyether carbonates in which the amount of ether bonds and carbonate bonds can be controlled. Accordingly, the present invention provides a polycarbonate ether polyol having 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.

[0208] For example, the method of the present invention can prepare polyether carbonates 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 created 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.

[0209] Therefore, the method of the present invention makes it possible to prepare polyether carbonates having a high ratio of carbonate bonds, for example, m / (n+m) can be greater than about 0.50, such as greater than about 0.55 and less than about 0.95, for example, about 0.65 to about 0.90, for example, about 0.75 to about 0.90, etc. The method of the present invention makes it possible to prepare polymers having a high m / (n+m) ratio under mild conditions, such as under pressures of 20 bar or less, such as 10 bar or less.

[0210] For example, the polyether carbonate produced by the method of the present invention may have the following formula (IV).

[0211] [ka] The identification of X depends on the properties of X in the compound of formula (I), and R e1 and R e2 It will be understood that the identification depends on the properties of the epoxide used to prepare the polyether carbonate. "m" and "n" define the amounts of carbonate and ether bonds in the polyether carbonate. It will be understood that n ≤ 1 and m ≤ 1.

[0212] It will be understood that X does not necessarily have to be a group containing -OH. Those skilled in the art will understand that in the polymer of formula (IV), adjacent epoxide monomer units in the main chain may be head-to-tail, head-to-head, or tail-to-tail linked.

[0213] It will also be understood that equation (IV) does not require the carbonate and ether bonds to be in two separate "blocks" of parts defined by "m" and "n", and that the repeating units of carbonate and ether may be statistically distributed along the polymer backbone, or that the carbonate and ether bonds may be arranged so as not to be in two separate blocks.

[0214] Therefore, the polyether carbonates prepared by the method of the present invention (e.g., polymers of formula (IV)) may be called random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers.

[0215] Those skilled in the art will understand that the weight percentage of carbon dioxide incorporated into a polymer is directly proportional to the number of carbonate bonds in the polymer backbone. All other conditions being equal, polyethers have a higher decomposition temperature than polycarbonates produced from epoxides and carbon dioxide. Therefore, polyether carbonates with a statistical or random distribution of ether and carbonate bonds will have a higher decomposition temperature than polycarbonates or polyether carbonates with a block of carbonate bonds. The thermal decomposition temperature can be measured using thermogravimetric analysis (TGA).

[0216] As described above, the method of the present invention prepares random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers. Thus, the carbonate bonds are not located within a single block, thereby providing polymers with improved properties, such as improved thermal decomposition, compared to polycarbonates. Optionally, the polyether carbonates prepared by the method of the present invention may be random copolymers or statistical copolymers.

[0217] The polyether carbonate prepared by the method of the present invention may be of formula (IV), where n and m are integers of 1 or more, the sum of all m and n groups is between 4 and 200, and m / (m+n) is in the range greater than 0 and less than 1.00. As described above, m / (n+m) may 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 created from these specific values. For example, m / (n+m) can be approximately 0.05 to 0.95, 0.10 to 0.90, 0.15 to 0.85, 0.20 to 0.80, or 0.25 to 0.75, etc.

[0218] Those skilled in the art will understand that a polyether carbonate must contain at least one carbonate bond and at least one ether bond, for example, n≧1 and ≧1. Therefore, it will be understood that the number of ether bonds and carbonate bonds (n+m) in the polyether carbonate determines the molecular weight of the polymer. For example, optionally, n≧5 and m≧5, or n≧10 and m≧10, or n≧20 and m≧20, or n≧50 and m≧50.

[0219] The conditions are arbitrarily set as follows: m+n≧10, or m+n≧20, or m+n≧100, or m+n≧200, or m+n≧500, or m+n≧1,000. Each R e1 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. Optionally, R e1 This can be selected from H or an optionally substituted alkyl group.

[0220] Each Re2 R can be independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. Optionally, R e2 This can be selected from H or an optionally substituted alkyl group.

[0221] R e1 and R e2 It will also be understood that these can together form saturated, partially saturated, or unsaturated rings containing carbon and hydrogen atoms, and optionally containing one or more heteroatoms (e.g., O, N, or S). For example, R e1 and R e2 These can together form a ring with 5 or 6 members.

[0222] As explained above, R e1 and R e2 The properties depend on the epoxide used in the reaction. If the epoxide is cyclohexene oxide (CHO), e1 and R e2 They form a 6-membered alkyl ring (e.g., a cyclohexyl ring) together. When the epoxide is ethylene oxide, R e1 and R e2 Both are H. When the epoxide is propylene oxide, R e1 H is R e2 is methyl (or R by the method of addition to the polymer backbone of the epoxide, e1 is methyl, R e2 (where H is). If the epoxide is butylene oxide, R e1 H is R e2 is ethyl (and vice versa). If the epoxide is styrene oxide, then R e1 It can be hydrogen, R e2 It can be phenyl (and vice versa).

[0223] When an epoxide mixture is used, R e1 and / or Re2 Each of the elements does not have to be the same; for example, if a mixture of ethylene oxide and propylene oxide is used, R e1 R can be independently hydrogen or methyl, e2 It will also be understood that these can independently be hydrogen or methyl.

[0224] Therefore, R e1 and R e2 This can be independently selected from hydrogen, alkyl, or aryl, or R e1 and R e2 They can form a cyclohexyl ring together, and optionally, R e1 and R e2 This can be independently selected from hydrogen, methyl, ethyl, or phenyl, or R e1 and R e2 These can form a cyclohexyl ring together.

[0225] X depends on the properties of the group X used in the compound of formula (I). Therefore, X is O(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amide or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl or heteroaryl, R x These are independently aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl elements that are optionally substituted with hydrogen.

[0226] Optionally, each X independently becomes OCR x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR xThese are halide, nitrate, hydroxyl, carbonate, amino, nitro, amide, alkyl (e.g., branched alkyl), heteroalkyl (e.g., silyl), aryl, or heteroaryl. Optionally, each X is independently OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x The optional substituents when X is an aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, or heteroaryl include halogens, hydroxyl, nitro, cyano, amino, or substituted or unsubstituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, or heteroaryl.

[0227] Examples of X include OAc, OC(O)CF3, halogens, OSO(CH3)2, Et, Me, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr)2 or N(SiMe3)2, OPh, OBn, salicylate, and dioctyl phosphinate.

[0228] When two or more X groups are present, for example in a compound of formula (IV-A) shown below, each X may be the same or different, and optionally, each X may be the same. Optionally, R x R is an alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. x Examples of optional substituents include halogens, hydroxyls, cyanos, nitros, aminos, alkoxys, alkylthios, or substituted or unsubstituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls (for example, optionally substituted alkyls, aryls, or heteroaryls).

[0229] OC(O)R x , OR x, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x Selected from, R x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, or alkylaryl. Optionally, each X is the same, and OC(O)R x , OR x , halide, alkyl, aryl, heteroaryl, phosphinate or OSO2R x Therefore, each X is the same, and O(O)R x Furthermore, each X is the same and selected from OAc, O2CCF3, or O2C(CH2)3Cy. Each X is the same and is OAc.

[0230] Selectively, each R x The same, and optionally substituted from alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. Optionally, each R x The same, and optionally substituted alkyl, alkenyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. Optionally, each R x The same, and is an alkyl, alkenyl, heteroalkyl, or cycloalkyl that is optionally substituted. Furthermore, optionally, R x R is an alkyl, heteroalkyl, or cycloalkyl that is optionally substituted. x This is an alkyl group that can be optionally substituted.

[0231] Definition of X's options and R x It will be understood that the definition of the options can be combined. For example, each X is independently O(O)R x OSO2R x OS(O)R x OSO(R x )2, S(O)R x , OR xThese can be halides, nitrates, hydroxyls, carbonates, aminos, nitros, amides, alkyls (e.g., branched alkyls), heteroalkyls (e.g., silyls), aryls, or heteroaryls, each independently of the other, for example, O(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x It could be, R x This can be an optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl.

[0232] Those skilled in the art will understand that each of the above features can be combined. For example, R e1 and R e2 This can be independently selected from hydrogen, alkyl, or aryl, or R e1 and R e2 X may form a cyclohexyl ring together, and X may be an aliphatic or heteroaliphatic, such as an alkylene or heteroalkylene, which can be optionally substituted.

[0233] The polyether carbonates produced by the method of the present invention are optionally high molecular weight polyether carbonates. It will be understood that the properties of the epoxide used to prepare the polyether carbonate will affect the molecular weight of the resulting product. Therefore, the lower limit of n+m is used herein to define the “high molecular weight” polymer of the present invention.

[0234] Optionally, the polyether carbonate produced by the method of the present invention may have a molecular weight of at least about 25,000 daltons, such as at least about 40,000 daltons, or at least about 100,000 daltons, such as at least about 50,000 daltons or about 50,000 to 1,000,000 daltons. The high molecular weight polymer formed by the method of the present invention typically has a molecular weight of at least about 500,000 daltons, and optionally at least about 100,000 daltons, such as at least about 1,000,000 daltons.

[0235] The method of the present invention can advantageously prepare polyether carbonates having a large molecular weight distribution. In other words, polyether carbonates can have a relatively large polydispersity index (PDI). The PDI of a polymer is the weight-average molecular weight (M) of the polymer. w ) number average molecular weight (M n It is determined by dividing by ), which shows the chain length distribution in the polymer product. In high molecular weight polymers, a high PDI may be desirable because the shorter chains act as plasticizers for the longer chains, thereby preventing the polymer from becoming too brittle.

[0236] Optionally, polymers produced by the method of the present invention have a PDI greater than about 1, optionally greater than about 2, and optionally greater than about 3. M of polymer produced by the method of the present invention n and M wFurthermore, the resulting PDI can be measured using gel permeation chromatography (GPC). For example, GPC can be performed using an Agilent 1260 Infinity GPC instrument equipped with two Agilent PLgel μ-m mixed-E columns in series. The sample can be measured at room temperature (293K) in THF at a flow rate of 1 mL / min against a narrow polystyrene standard (e.g., polystyrene low easivials with various Mn values ​​from 405 to 49,450 g / mol, supplied by Agilent Technologies). Optionally, the sample may be measured against a poly(ethylene glycol) standard such as polyethylene glycol EasiVials supplied by Agilent Technologies.

[0237] The following are characteristics common to both the method for preparing polycarbonate ether polyols and the method for preparing high molecular weight polyether carbonates. Although the method of the present invention can be carried out in the presence of a solvent, it will also be understood that the method can be carried out in the absence of a solvent. If a solvent is present, it may be toluene, hexane, t-butyl acetate, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), etc. The solvents may be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0238] A solvent can function to dissolve one or more materials. However, a solvent can also function as a carrier and can be used to suspend one or more materials in a suspension. A solvent may be required to facilitate the addition of one or more materials during the steps of the method of the present invention.

[0239] The epoxide used in the method may be any suitable compound containing an epoxide moiety. Exemplary epoxides include ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide.

[0240] Epoxides can be purified (for example, by distillation over calcium hydride) before reacting with carbon dioxide. For example, epoxides can be distilled before being added. The method of the present invention can be carried out on any scale. The method can be carried out on 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). Since the rise in temperature can be controlled relatively easily, for example by using an ice bath, the generation of heat in small-scale reactions is unlikely to be a problem. In larger-scale reactions, especially industrial-scale reactions, the generation of heat during the reaction can be a problem and potentially dangerous. Therefore, the rate of the catalytic reaction can be controlled by gradually adding materials in any of the forms described herein, thereby minimizing the accumulation of excess heat. The reaction rate can be controlled, for example, by adjusting the flow rate of materials during addition. Thus, the method of the present invention has particular advantages when applied to large-scale industrial-scale catalytic reactions.

[0241] The temperature may rise during the process of the method of the present invention. For example, the method may be started at a low temperature (e.g., a temperature of about 50°C to 80°C or lower), and the temperature of the reaction mixture may rise during the process of the method. For example, the temperature of the reaction mixture may rise during the process of the method of the present invention from about 50°C at the start of the reaction to about 80°C at the end of the reaction. This temperature rise may be gradual or rapid. This temperature rise may be obtained by using an external heat source or by an exothermic reaction as described above.

[0242] The temperature of the reaction mixture may decrease during the process of the method of the present invention. For example, the method may be started at a high temperature (e.g., about 90 to 150°C), and the reaction mixture may be cooled during the process (e.g., to a temperature of about 50 to 80°C or lower). This decrease in temperature may be gradual or rapid. This decrease in temperature may be the result of using an external cooling source as described above.

[0243] The present invention also relates to products obtained by the method described above. The catalyst of formula (I) has the following structure:

[0244] [ka] It has, In the formula, 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, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R3 is independently and optionally selected from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and if E3, E4, E5 or E6 is N,

[0245] [ka] teeth,

[0246] [ka] And if E3, E4, E5 or E6 is NR4, O or S,

[0247] [ka] teeth,

[0248] [ka] And, R4 is independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x, selected from phosphinates, halides, nitrates, hydroxyls, carbonates, aminos, amides, or optionally substituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls, where each X may be the same or different, and X may form a bridge between M1 and M2. R x These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, G is either absent or selected independently from neutral or anionic donor ligands that are Lewis bases.

[0249] The existence of bases R1 and R2 may be the same or different, and R1 and R2 may be the same or different. Optionally, R1 and R2 are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, and optionally substituted alkyl, alkenyl, aryl, heteroaryl, silyl, silyl ether, alkoxy, aryloxy, or alkylthio. Optionally, each R2 is identical. Optionally, each R2 is identical and is hydrogen.

[0250] The presence of both R1s can be the same and can be selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, or alkylthio. For example, the presence of both R1s can be the same and can be selected from hydrogen, halide, sulfoxide and optionally substituted alkyl, heteroaryl, silyl, alkylthio, or alkoxy. Exemplary choices for R1 (both can be the same) include hydrogen, methyl, t-butyl, methoxy, ethoxy, alkylthio, trialkylsilyl (e.g., trimethylsilyl or triethylsilyl), bromide, methanesulfonyl, or piperidinyl, for example, the presence of both R1s can be the same and can be selected from methyl, t-butyl, or trialkylsilyl.

[0251] Selectively, each R2 is hydrogen, and each R1 is independently hydrogen, C 1~6 Selected from alkyl (e.g., haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, such as tBu, iPr, Me, OMe, H, nitro, SO2Me, SiEt3, SiMe3, SMe, halogen or phenyl, hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate and optionally substituted alkyl, alkenyl, aryl, heteroaryl, silyl, silyl ether, alkoxy, aryloxy, alkylthio, and arylthio.

[0252] R 1 It will be understood that each existence of R1 can be the same, each existence of R2 can be the same, and R1 can be different from R2. Group R3 can be a disubstituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, or heteroalkynyl group, which may optionally be flanked by an aryl, heteroaryl, alicyclic, or heteroalicyclic group, or it may be a disubstituted aryl or cycloalkyl group that functions as a bridging group between two nitrogen centers in the catalyst of formula (I). Thus, if R3 is an alkylene group such as dimethylpropyrenyl, the R3 group has the structure -CH2-C(CH3)2-CH2-. Therefore, the definitions of alkyl, aryl, cycloalkyl, etc., shown above also relate to the divalent alkylene, arylene, cycloalkylene, etc., shown for R3, which may optionally be substituted. R3 may be an optionally substituted alkylene group, and optionally, R3 is an optionally substituted C2 or C3 alkylene group. Exemplary choices for R3 include ethilenyl, 2,2-fluoropropyrenyl, 2,2-dimethylpropyrenyl, propyrenyl, butyrenyl, phenylenyl, cyclohexylenyl, or biphenylenyl. If R3 is cyclohexylenyl, it may be racemic, RR-, or SS-isomer.

[0253] R3 can be independently selected from substituted or unsubstituted alkylenes and substituted or unsubstituted arylenes, optionally substituted or unsubstituted propyrenyls (such as propyrenyl and 2,2-dimethylpropyrenyl), and substituted or unsubstituted phenylenyl or biphenylenyl. Optionally, the presence of both R3s is equivalent. Optionally, R3 is a substituted propyrenyl such as 2,2-di(alkyl)propyrenyl, particularly 2,2-di(methyl)propyrenyl.

[0254] R3 can be independently selected from substituted or unsubstituted alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene or heteroalkylene, arylene or cycloalkylene. Optionally, R3 can be selected from substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene. Optionally, R3 can be selected from 2,2-dimethylpropyrenyl, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH2C6H5)2CH2-, phenylene, -CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2N(CH3)CH2CH2-, 1,4-cyclohexanediyl or -CH2CH2CH(C2H5)-. Optionally, R3 can be selected from 2,2-dimethylpropyrenyl, -CH2CH2CH 2- R3 is selected from -CH2CH(CH3)CH2-, -CH2C(CH2C6H5)2CH2-, -CH2CH2CH(C2H5)-, and -CH2CH2CH2CH2-. Optionally, R3 is selected from 2,2-dimethylpropyrenyl, -CH2C(CH2C6H5)2CH2-, CH2CH(CH3)CH2, and -CH2C(C2H5)2CH2-.

[0255] Optionally, R3 is a substituted propyrenyl such as 2,2-di(alkyl)propyrenyl or, optionally, 2,2-dimethylpropyrenyl. As explained above, E3, E4, E5, and E6 are each independently selected from N, NR4, O, and S. A person skilled in the art will know that if any of E3, E4, E5, or E6 is N,

[0256] [ka] teeth,

[0257] [ka] And if any of E3, E4, E5, or E6 is NR4, O, or S,

[0258] [ka] teeth,

[0259] [ka] You will understand that E3, E4, E5, and E6 are selected independently from NR4, O, and S, respectively.

[0260] Optionally, each R4 is independently substituted with hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(O)OR 19 Or selected from alkyl C≡N. Each R4 may be the same or different. Optionally, R4 is selected from hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl. Exemplary choices for R4 include H, Me, Et, Bn, iPr, tBu, or Ph and -CH2-(pyridine). Optionally, each R4 is hydrogen or alkyl.

[0261] Optionally, each R5 is independently selected from hydrogen and optionally substituted aliphatic or aryl groups. Optionally, each R5 is independently selected from hydrogen and optionally substituted alkyl or aryl groups. Optionally, each R5 is the same and selected from hydrogen and optionally substituted alkyl or aryl groups. Exemplary R5 groups include hydrogen, methyl, ethyl, phenyl, and trifluoromethyl, and optionally hydrogen, methyl, or trifluoromethyl. Optionally, each R5 is hydrogen. R5 can be H, in which case R2 is H.

[0262] By choice, the existence of both E1 is C, and the existence of both E2 is the same, chosen from O, S, or NH. By choice, the existence of both E1 is C, and the existence of both E2 is O. Alternatively, if E2 is O, then E1 can be C.

[0263] Those skilled in the art will understand that the macrocyclic ligand of the catalyst of formula (I) can be symmetric or asymmetric. If the macrocyclic ligand is symmetric, it will be understood that the existences of E3, E4, E5, and E6 are the same. For example, the existences of E3, E4, E5, and E6 can be NR4 (and each R4 can be the same). It will be understood that E3, E4, E5, and E6 can be the same and can be NH. In other words, the catalyst of formula (I) can have the following structure.

[0264] [ka] If the macrocyclic ligand is symmetric, then each existence of R1 can be the same, each existence of R2 can be the same, each existence of R3 can be the same, each existence of R5 can be the same, each existence of E1 can be the same, each existence of E2 can be the same (however R1, R2, R3 and R5 do not necessarily have to be the same as each other), and E3, E4, E5 and E6 can be the same.

[0265] E3, E4, E5, and E6 can independently be NR4, and the presence of at least one of E3, E4, E5, and E6 differs from the presence of the remaining E3, E4, E5, and E6 in that R4 is optionally H or alkyl.

[0266] E3, E4, E5, and E6 can independently be NR4, where each R4 is independently H or optionally substituted aliphatic, and optionally each R4 is H or alkyl. For example, the presence of R2 and R5 can be hydrogen, the presence of E3, E4, E5 and E6 can be NR4, each R4 is hydrogen or alkyl, and the presence of R3 can be substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene, R 1 Each element can be selected from hydrogen, halogen, sulfoxide, or substituted or unsubstituted alkyl, heteroaryl, silyl, alkylthio, or alkoxy, and the presence of both E1 elements may be C, and the presence of both E2 elements may be O.

[0267] If the ligand of the catalyst of formula (I) is asymmetric, it will be understood that the presence of at least one of the groups R1, R2, R3, R4, R5, E1, or E2 may differ from the remaining presences of the same group, or that the presence of at least one of E3, E4, E5, and E6 may differ from the remaining presences of E3, E4, E5, and E6. For example, each presence of R3 may differ, or each presence of R1 may differ.

[0268] E3 and E5 may be the same, and E4 and E6 may be the same, but it will also be understood that E3 and E5 are different from E4 and E6. E3 and E4 may be the same, and E5 and E6 may be the same, but it will also be understood that E3 and E4 are different from E5 and E6. Instead, one existence of E3, E4, E5, and E6 is different from the remaining existences of E3, E4, E5, and E6 (the remaining three existences are the same).

[0269] For example, E3, E4, and E5 may be -NR4 (where R4 is H), and R6 may be NR4 (where R4 is alkyl). Furthermore, E3 and E5 may be NR4 (where R4 is H) and E4 and E6 may be NR4 (where R4 is alkyl), or E3 and E4 may be NR4 (where R4 is H) and E5 and E6 may be NR4 (where R4 is alkyl). Thus, each of E3, E4, E5, and E6 is optionally NR4, and it will be understood that the presence of at least one R4 is different from the presence of the rest of R4.

[0270] With respect to the catalysts (symmetric and asymmetric) of formula (I), each X independently corresponds to O(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x , selected from phosphinates, halides, nitros, hydroxyls, carbonates, aminos, nitrates, amides and optionally substituted aliphatic, heteroaliphatic (e.g., silyl), aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls. Optionally, each X is independently OC(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x These are halide, nitrate, hydroxyl, carbonate, amino, nitro, amide, alkyl (e.g., branched alkyl), heteroalkyl (e.g., silyl), aryl, or heteroaryl. Optionally, each X is independently OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x The optional substituents when X is an aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, or heteroaryl include halogens, hydroxyls, nitros, cyanos, aminos, or substituted or unsubstituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, or heteroaryl elements. Each X may be the same or different, and optionally, each X is the same. It will also be understood that X may form a bridge between two metal centers.

[0271] R x R is independently an aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl element that is optionally substituted with hydrogen. xR is an alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. x Examples of optional substituents include halogens, hydroxyls, cyanos, nitros, aminos, alkoxys, alkylthios, or substituted or unsubstituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls (for example, optionally substituted alkyls, aryls, or heteroaryls).

[0272] Examples of X include OAc, OC(O)CF3, halogens, OSO(CH3)2, Et, Me, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr)2 or N(SiMe3)2, OPh, OBn, salicylate, and dioctyl phosphinate.

[0273] OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x Selected from, R x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, or alkylaryl. Optionally, each X is the same, and OC(O)R x , OR x , halide, alkyl, aryl, heteroaryl, phosphinate or OSO2R x Therefore, each X is the same, and O(O)R x Furthermore, each X is the same and selected from OAc, O2CCF3, or O2C(CH2)3Cy. Each X is the same and is OAc.

[0274] Selectively, each R x The same, and optionally substituted from alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. Optionally, each R xThe same, and optionally substituted alkyl, alkenyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl. Optionally, each R x The same, and is an alkyl, alkenyl, heteroalkyl, or cycloalkyl that is optionally substituted. Furthermore, optionally, R x R is an alkyl, heteroalkyl, or cycloalkyl that is optionally substituted. x This is an alkyl group that can be optionally substituted.

[0275] Definition of X's options and R x It will be understood that the definition of the options can be combined. For example, each X is independently O(O)R x OSO2R x OS(O)R x OSO(R x )2, S(O)R x , OR x These can be halides, nitrates, hydroxyls, carbonates, aminos, nitros, amides, alkyls (e.g., branched alkyls), heteroalkyls (e.g., silyls), aryls, or heteroaryls, each independently of the other, for example, O(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x It could be, R x This can be an optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl.

[0276] As detailed above, M1 and M2 are independently selected from Zn(II), Cr(III)-X, Cr(II), Co(III)-X, Co(II), Cu(II), Mn(III)-X, Mn(II), Mg(II), Ni(II), Ni(III)-X, Fe(II), Fe(III)-X, Ca(II), Ge(II), Ti(II), Al(III)-X, Ti(III)-X, V(II), V(III)-X, Ge(IV)-(X)2, or Ti(IV)-(X)2.

[0277] 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 at least one of M1 and M2 is selected from Mg(II), Zn(II), and Ni(II), for example, at least one of M1 and M2 is Ni(II).

[0278] It will be understood that M1 and M2 may be the same or different. For example, M1 and / or M2 may be selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X, and optionally, M1 and / or M2 may be selected from Mg(II), Zn(II), and Ni(II), for example, M1 and / or M2 may be Ni(II).

[0279] Examples of combinations of M1 and M2 include Mg(II) and Mg(II), Zn(II) and Zn(II), Ni(II) and Ni(II), Mg(II) and Zn(II), Mg(II) and Ni(II), Zn(II) and Co(II), Co(II) and Co(III), Fe(III) and Fe(III), Zn(II) and Fe(II), or Zn(II) and Ni(II).

[0280] If one of M1 and M2 is Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Al(III), Ti(III), or V(III), it will be understood that the catalyst of formula (I) contains an additional X group coordinated to the metal center (where X is as defined above). If one of M1 and M2 is Ge(IV) or Ti(IV), it will also be understood that the catalyst of formula (III) contains two additional X groups coordinated to the metal center (where X is as defined above). If one of M1 and M2 is Ge(IV)-(X)2 or Ti(IV)-(X)2, both G groups may be absent.

[0281] If G is absent, it is a group that can donate a lone pair of electrons (i.e., a Lewis base). G can be a nitrogen-containing Lewis base. Each G can be neutral or negatively charged. If G is negatively charged, one or more positive counterions are required to balance the charge of the complex. Suitable positive counterions are Group 1 metal ions (Na). + , K + (etc.), Group 2 metal ions (Mg 2+ Ca 2+ (etc.), imidazolium ions, positively charged optionally substituted heteroaryl, heteroaliphatic or heteroalicyclic groups, ammonium ions (i.e., N(R) 12 )4 + ), iminium ions (i.e., bis(triphenylphosphine)iminium ions, etc. (R 12 )2C=N(R 12 )2 + ) or phosphonium ion (P(R 12 )4 + ) are listed, and each R 12 This is independently selected from hydrogen or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, or heteroaryl. An exemplary counterion is [HB] + Examples include, where B is selected from triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0282] G is optionally and independently selected from optionally substituted heteroaliphatic groups, optionally substituted heteroalicyclic groups, optionally substituted heteroaryl groups, halides, hydroxides, hydrides, carboxylates, and water. Optionally, G is selected from water, alcohols (e.g., methanol), substituted or unsubstituted heteroaryls (imidazole, methylimidazole (e.g., N-methylimidazole), pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc.), ethers (dimethyl ether, diethyl ether, cyclic ether, etc.), thioethers, carbenes, phosphines, phosphine oxides, substituted or unsubstituted heteroaliphatic rings (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc.), amines, alkylamines (trimethylamine, triethylamine, etc.), acetonitrile, esters (e.g., ethyl acetate), acetamides (e.g., dimethylacetamide), sulfoxides (e.g., dimethyl sulfoxide), carboxylates, hydroxides, hydrides, halides, nitrates, sulfonates, etc. Examples of one or both of G can be independently selected from optionally substituted heteroaryls, optionally substituted heteroaliphatics, optionally substituted heteroaliphatic rings, halides, hydroxides, hydrides, ethers, thioethers, carbenes, phosphines, phosphine oxides, amines, alkylamines, acetonitriles, esters, acetamides, sulfoxides, carboxylates, nitrates, or sulfonates. G may be a halide; hydroxide; hydride; water; or a heteroaryl, heteroalicyclic, or carboxylate group that can be optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro, or nitrile. Optionally, G can be independently selected from a halide; water; or a heteroaryl that can be optionally substituted with alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (optionally methoxy), halogen, hydroxyl, nitro, or nitrile. Examples of one or both of G may be negatively charged (e.g., halide). Examples of one or both of G may be optionally substituted heteroaryls.Examples of G groups include chlorides, bromides, pyridines, methylimidazoles (e.g., N-methylimidazole), and dimethylaminopyridines (e.g., 4-methylaminopyridine).

[0283] It will be understood that, in the presence of G groups, the G group may be involved with a single M metal center, as shown in equation (I), or the G group may be involved with both metal centers, forming a bridge between the two metal centers, as shown in equation (IIa) below.

[0284] [ka] In the formulas, R1, R2, R3, R4, R5, M1, M2, G, X, E1, and E2 are as defined in formulas (I) and (II).

[0285] Those skilled in the art will understand that in the solid state, catalysts of formulas (I), (II), or any sub-concept thereof can associate with solvent molecules such as water or alcohol (e.g., methanol or ethanol). It will be understood that the solvent molecules may be present in a ratio less than 1:1 (i.e., 0.2:1, 0.25:1, 0.5:1), a ratio of 1:1, or a ratio greater than 1:1 with respect to the molecules of the catalyst of the first embodiment.

[0286] Those skilled in the art will understand that in a solid state, the catalyst of the first embodiment may form aggregates. For example, the catalyst of the first embodiment may be a dimer, trimer, tetramer, pentamer, or larger aggregate.

[0287] Examples of catalysts for formula (I) are as follows:

[0288] [ka]

[0289] [ka]

[0290] [ka] In the formula, M1, M2, G, and X are as defined above for formula (I), and it will be understood that one or both of the G groups may not be present.

[0291] For example, at least one of M1 and M2 may be selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X. For example, at least one of M1 and M2 may be selected from Mg(II), Zn(II), and Ni(II). For example, at least one of M1 and M2 may be Ni(II).

[0292] As shown above, M1 and M2 may be the same or different. For example, M1 and / or M2 may be selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X, and optionally, M1 and / or M2 may be selected from Mg(II), Zn(II), and Ni(II), for example, M1 and / or M2 may be Ni(II). Exemplary combinations of M1 and M2 include Mg(II) / Mg(II), Zn(II) / Zn(II), Ni(II) / Ni(II), Mg(II) / Zn(II), Mg(II) / Ni(II), and Zn(II) / Ni(II).

[0293] For example, each X independently of OCR x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR xThese can be halides, nitrates, hydroxyls, carbonates, aminos, nitros, amides, alkyls (e.g., branched alkyls), heteroalkyls (e.g., silyls), aryls, or heteroaryls, each independently of the other, for example, O(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x It is possible. For example, R x This can be alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl.

[0294] For example, if either G is present, G may be independently selected from heteroaryls which can be substituted optionally with a halide; water; alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (optionally, methoxy), halogen, hydroxyl, nitro, or nitrile. For example, examples of one or both of G (if present) may be chloride, bromide, pyridine, methylimidazole (e.g., N-methylimidazole) and dimethylaminopyridine (e.g., 4-methylaminopyridine).

[0295] Those skilled in the art will understand that the above definitions can be combined. For example, for the above catalysts, M1 and M2 may be the same or different, and they may be selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X; each X may be independently O(O)R x OSO2R x OSOR x OSO(R x )2, S(O)R x , OR x These can be halides, nitrates, hydroxyls, carbonates, aminos, nitros, amides, alkyls (e.g., branched alkyls), heteroalkyls (e.g., silyls), aryls, or heteroaryls, each independently of the other, for example, O(O)R x , ORx , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2R x It could be; R x can be alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl; G may be absent, and if present, it can be independently selected from halide; water; and heteroaryls which may be optionally substituted with alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (optionally methoxy), halogen, hydroxyl, nitro, or nitrile.

[0296] Therefore, those skilled in the art will understand that the exemplary catalysts above in formula (I) include, but are not limited to, the following catalysts. [L 1 Ni2(OAc)2], [L 1 Mg2(OAc)2], [L 1 [Zn2(OAc)2], [L 1 MgZn(OAc)2], [L 1 MgNi(OAc)2], [L 1 Ni2(CO2CF3)2], [L 1 Mg2CO2CF3)2],[L 1 [Zn2(CO2CF3)2], [L 1 MgZn(CO2CF3)2], [L 1 MgNi(CO2CF3)2], [L 1 Ni2 (CO2) t Bu)2], [L 1 Mg2(CO2 t Bu)2], [L 1 Zn2(CO2 t Bu)2], [L 1 MgZn(CO2 t Bu)2], [L 1 MgNi(CO2 t Bu)2], [L 1 [Human 2(OPh)2], [L 1 Mg2(OPh)2], [L 1 [Zn2(OPh)2], [L 1 MgZn(OPh)2],[L1 [MgNi(OPh)2]、[L 1 Ni2(Ph)2]、[L 1 Mg2(Ph)2]、[L 1 Zn2(Ph)2]、[L 1 [MgZn(Ph)2]、[L 1 [MgNi(Ph)2]、[L 1 Ni2(O i Pr)2]、[L 1 Mg2(O i Pr)2]、[L 1 Zn2(O i Pr)2]、[L 1 MgZn(O i Pr)2]、[L 1 MgNi(O i Pr)2]、[L 1 Ni2(C6F5)2]、[L 1 Mg2(C6F5)2]、[L 1 Zn2(C6F5)2]、[L 1 MgZn(C6F5)2]、[L 1 [MgNi(C6F5)2]、[L 1 Ni2Cl2]、[L 1 [Mg2Cl2]、[L 1 Zn2Cl2]、[L 1 [MgZnCl2]、[L 1 [MgNiCl2]、[L 1 Ni2Br2]、[L 1 [Mg2Br2]、[L 1 Zn2Br2]、[L 1 [MgZnBr2]、[L 1 [MgNiBr2]、[L 1 Ni2I2]、[L 1 [Mg2I2]、[L 1 Zn2I2]、[L 1 [MgZnI2]、[L 1 [MgNiI2]、[L 1 Ni2(OC(O)(CH2)4CH3)2]、[L 1 Mg2(OC(O)(CH2)4CH3)2]、[L 1 Zn2(OC(O)(CH2)4CH3)2]、[L 1 MgZn(OC(O)(CH2)4CH3)2]、[L 1MgNi(OC(O)(CH2)4CH3)2],[L 1 Ni2(OC(O)(CH2)6CH3)2],[L 1 Mg2(OC(O)(CH2)6CH3)2],[L 1 Zn2(OC(O)(CH2)6CH3)2], [L 1 MgZn(OC(O)(CH2)6CH3)2], [L 1 MgNi(OC(O)(CH2)6CH3)2],[L 1 Ni2(OC(O)(CH2) 10 CH3)2], [L 1 Mg2(OC(O)(CH2) 10 CH3)2], [L 1 Zn2(OC(O)(CH2) 10 CH3)2], [L 1 MgZn(OC(O)(CH2) 10 CH3)2], [L 1 MgNi(OC(O)(CH2) 10 CH3)2], [L 1 Ni2(OC(O)C6F5)2], [L 1 Mg2(OC(O)C6F5)2], [L 1 Zn2(OC(O)C6F5)2], [L 1 MgZn(OC(O)C6F5)2], [L 1 MgNi(OC(O)C6F5)2], [L 1 Ni2Cl2 (methylimidazole), [L 1 Mg2Cl2 (methylimidazole), [L 1 [Zn2Cl2 (methylimidazole)], [L 1 MgZnCl2 (methylimidazole), [L 1 MgNiCl2 (methylimidazole), [L 1 Ni2Cl2(pyridine)), [L 1 Mg2Cl2 (pyridine), [L 1 [Zn2Cl2 (pyridine)], [L 1 MgZnCl2 (pyridine), [L 1 MgNiCl2 (pyridine), [L 1 Ni2Cl2 (dimethylaminopyridine), [L 1Mg2Cl2 (dimethylaminopyridine), [L 1 [Zn2Cl2 (dimethylaminopyridine)], [L 1 MgZnCl2 (dimethylaminopyridine), [L 1 MgNiCl2 (dimethylaminopyridine), [L 1 [N2Br2 (dimethylaminopyridine)], [L 1 Mg2Br2 (dimethylaminopyridine), [L 1 [Zn2Br2 (dimethylaminopyridine)], [L 1 MgZnBr2 (dimethylaminopyridine), [L 1 MgNiBr2 (dimethylaminopyridine), [L 1 Ni2(bis(4-methoxy)phenylphosphinate)2], [L 1 Mg2(bis(4-methoxy)phenylphosphine)2], [L 1 Zn2(bis(4-methoxy)phenylphosphinate)2],[L 1 MgZn(bis(4-methoxy)phenylphosphine)2], [L 1 MgNi(bis(4-methoxy)phenylphosphine)2], [L 1 Ni2 (adamantyl carbonate) 2], [L 1 Mg2 (adamantyl carbonate) 2], [L 1 Zn2 (adamantyl carbonate)2], [L 1 MgZn (adamantyl carbonate) 2], [L 1 MgNi (adamantyl carbonate) 2], [L 1 Ni2 (diphenylphosphine) 2], [L 1 Mg2 (diphenylphosphine)2], [L 1 [Zn2(diphenylphosphine)2], [L 1 MgZn (diphenylphosphine) 2], [L 1 MgNi (diphenylphosphine) 2], [L 2 Ni2(OAc)2], [L 2 Mg2(OAc)2], [L 2 [Zn2(OAc)2], [L 2 MgZn(OAc)2], [L2 MgNi(OAc)2]、[L 3 Ni2(OAc)2]、[L 3 Mg2(OAc)2]、[L 3 Zn2(OAc)2]、[L 3 MgZn(OAc)2]、[L 3 MgNi(OAc)2]、[L 4 Ni2(OAc)2]、[L 4 Mg2(OAc)2]、[L 4 Zn2(OAc)2]、[L 4 MgZn(OAc)2]、[L 4 MgNi(OAc)2]、[L 5 Ni2(OAc)2]、[L 5 Mg2(OAc)2]、[L 5 Zn2(OAc)2]、[L 5 MgZn(OAc)2]、[L 5 MgNi(OAc)2]、[L 6 Ni2(OAc)2]、[L 6 Mg2(OAc)2]、[L 6 Zn2(OAc)2]、[L 6 MgZn(OAc)2]、[L 6 MgNi(OAc)2]、[L 7 Ni2(OAc)2]、[L 7 Mg2(OAc)2]、[L 7 Zn2(OAc)2]、[L 7 MgZn(OAc)2]、[L 7 MgNi(OAc)2]、[L 8 Ni2(OAc)2]、[L 8 Mg2(OAc)2]、[L 8 Zn2(OAc)2]、[L 8 MgZn(OAc)2]、[L 8 MgNi(OAc)2]、[L 9 Ni2(OAc)2]、[L 9 Mg2(OAc)2]、[L 9 Zn2(OAc)2 ]、[L 9 MgZn(OAc)2]、[L 9 MgNi(OAc)2]、[L 10 Ni2(OAc)2]、[L 10Mg2(OAc)2]、[L 10 Zn2(OAc)2]、[L 10 MgZn(OAc)2]、[L 10 MgNi(OAc)2]、[L 11 Ni2(OAc)2]、[L 11 Mg2(OAc)2]、[L 11 Zn2(OAc)2]、[L 11 MgZn(OAc)2]、[L 11 MgNi(OAc)2]、[L 12 Ni2(OAc)2]、[L 12 Mg2(OAc)2]、[L 12 Zn2(OAc)2]、[L 12 MgZn(OAc)2]、[L 12 MgNi(OAc)2]、[L 13 Ni2(OAc)2]、[L 13 Mg2(OAc)2]、[L 13 Zn2(OAc)2]、[L 13 MgZn(OAc)2]、[L 13 MgNi(OAc)2]、[L 14 Ni2(OAc)2]、[L 14 Mg2(OAc)2]、[L 14 Zn2(OAc)2]、[L 14 MgZn(OAc)2]、[L 14 MgNi(OAc)2]、[L 15 Ni2(OAc)2]、[L 15 Mg2(OAc)2]、[L 15 Zn2(OAc)2]、[L 15 MgZn(OAc)2]、[L 15 MgNi(OAc)2]、[L 16 Ni2(OAc)2]、[L 16 Mg2(OAc)2]、[L 16 Zn2(OAc)2]、[L 16 MgZn(OAc)2]、[L 16 MgNi(OAc)2]、[L 17 Ni2(OAc)2]、[L 17 Mg2(OAc)2]、[L 17 Zn2(OAc)2]、[L 17 MgZn(OAc)2]、[L 17[MgNi(OAc)2]、[L 18 Ni2(OAc)2]、[L 18 Mg2(OAc)2]、[L 18 Zn2(OAc)2]、[L 18 MgZn(OAc)2]、[L 18 [MgNi(OAc)2]、[L 19 Ni2(OAc)2]、[L 19 Mg2(OAc)2]、[L 19 Zn2(OAc)2]、[L 19 MgZn(OAc)2]、[L 19 [MgNi(OAc)2]、[L 20 Ni2(OAc)2]、[L 20 Mg2(OAc)2]、[L 20 Zn2(OAc)2]、[L 20 MgZn(OAc)2]、[L 20 [MgNi(OAc)2]、[L 21 Ni2(OAc)2]、[L 21 Mg2(OAc)2]、[L 21 Zn2(OAc)2]、[L 21 MgZn(OAc)2]、[L 21 [MgNi(OAc)2]、[L 22 Ni2(OAc)2]、[L 22 Mg2(OAc)2]、[L 22 Zn2(OAc)2]、[L 22 MgZn(OAc)2]、[L 22 [MgNi(OAc)2]、[L 23 Ni2(OAc)2]、[L 23 Mg2(OAc)2]、[L 23 Zn2(OAc)2]、[L 23 MgZn(OAc)2]、[L 23 [MgNi(OAc)2]、[L 1 [Co2(OAc)3]、[L 1 ZnCoI2]、[L 1 ZnFe(OAc)2]、[L 1 ZnFeBr2]、[L 1 ZnFeCl2]、[L 1 ZnFeI2]、[L 1 ZnCo(OAc)2]、[L 1[ZnCoCl2], [L 1 [ZnCoBr2], [L 1 Fe2Cl4, [L 1 [Co2Cl2 (methylimidazole)], [L 1 Co2Cl2 (pyridine), [L 1 [Co2Cl3] - [H-DBU] + and [L 1 [Co2Cl3] - [H-MTBD] + .

[0297] Those skilled in the art will understand that in any of the above complexes, any one ligand defined by "L" can be replaced by another ligand defined by a different "L". For example, L 1 In the complex mentioned above, this ligand is L 2 ~L 22 It can be replaced by any ligand defined in [the specified field].

[0298] A DMC catalyst is a complex compound comprising at least two metal centers and a cyanide ligand. A DMC catalyst may further comprise one or more complexing agents (e.g., in non-stoichiometric amounts), water, a metal salt, and / or at least one of an acid.

[0299] The first two of the two metallic centers can be represented by 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), and M' can be optionally selected from Zn(II), Fe(II), Co(II), and Ni(II), and M' can be optionally Zn(II).

[0300] 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), and optionally M'' is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), and optionally M'' is selected from Co(II) and Co(III).

[0301] It should be noted that the above optional definitions for M' and M'' can be combined. For example, M' can be optionally selected from Zn(II), Fe(II), Co(II), and Ni(II), and M'' can be optionally selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II). For example, M' can be optionally Zn(II), and M'' can be optionally selected from Co(II) and Co(III).

[0302] If further metallic centers exist, these can be further selected from the definitions of M' or M''. Examples of DMC catalysts that can be used in the method of the present invention are those incorporated by reference in their entirety by U.S. Patent Nos. 3,427,256, 5,536,883, 6,291,388, 6,486,361, 6,608,231, 7,008,900, 5,482,908, 5,780,584, 5,783,513, 5,158,922, 5,693,584, and 7,811,958. This includes, as described in U.S. Patent Nos. 6,835,687, 6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500,704, 7,977,501, 9,315,622, European Patent Application Publication A-1568414, European Patent Application Publication A-1529566, and International Publication Brochure 2015 / 022290.

[0303] A DMC catalyst useful in the present invention can be produced by treating a solution of a metal salt (e.g., an aqueous solution) with a solution of a metal cyanide salt (e.g., an aqueous solution) in the presence of one or more complexing agents, water and / or an acid. A suitable metal salt is given by formula M'(X') pThe compound comprises the following, where M' is 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), and M' is optionally selected from Zn(II), Fe(II), Co(II), and Ni(II), and optionally M' is Zn(II). 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. p is an integer greater than or equal to 1, and the charge on the anion multiplied by p satisfies the valency of M'. Examples of suitable metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetone, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate, and mixtures thereof.

[0304] A suitable metal cyanide salt is given by formula (Y)q[M''(CN) b (A) c The compound comprises ], where 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), and optionally M'' is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), and optionally M'' is selected from Co(II) and Co(III). Y is a proton (H + ), or alkali metal ions, or alkaline earth metal ions (for example, K +) where A is an anion selected from halide, oxide, hydroxide, sulfate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. q and b are integers greater than or equal to 1, and optionally b is 4 or 6. c may be 0 or an integer greater than or equal to 1. The sum of the charges on ions Y, CN, and A multiplied by q, b, and c respectively (e.g., Y × q + CN × b + A × c) satisfies the valence of M''. Examples of suitable metal cyanide salts include potassium hexacyanocobalt(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobalt(III), lithium hexacyanocobalt(III), and mixtures thereof.

[0305] Suitable complexing agents include (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols, urea, etc., or combinations thereof. Exemplary complexing agents include propylene glycol, polypropylene glycol (PPG), (methyl)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyceride, 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, etc., or combinations thereof. It should be noted that alcohols may be saturated or may contain unsaturated moieties (e.g., double or triple bonds). Multiple (i.e., multiple different types) complexing agents may be present in the DMC catalyst used in the present invention.

[0306] The DMC catalyst may contain a complexing agent which is a polyether, polyether carbonate, or polycarbonate. Suitable polyethers for use in the DMC catalyst of the present invention include those produced by ring-opening polymerization of cyclic ethers, and include epoxide polymers, oxetane polymers, tetrahydrofuran polymers, and the like. Polyethers can be prepared using any catalytic method. Polyethers can have any desired end groups, including, for example, hydroxyl, amine, ester, and ether. Optionally, polyethers for use in the DMC catalyst of the present invention are polyether polyols having 2 to 8 hydroxyl groups. Polyethers for use in the DMC catalyst of the present invention may also optionally have molecular weights of about 1,000 daltons to about 10,000 daltons, and optionally, about 1,000 daltons to about 5,000 daltons. Useful polyether polyols in the DMC catalyst of the present invention include PPG polyols, EO-capped PPG polyols, mixed EO-PO polyols, butylene oxide polymers, butylene oxide copolymers having ethylene oxide and / or propylene oxide, polytetramethylene ether glycol, and the like. The optional polyethers include PPGs, such as PPG polyols, particularly diols and triols, wherein the PPGs have molecular weights of about 250 daltons to about 8,000 daltons, and optionally about 400 daltons to about 4,000 daltons.

[0307] A suitable polyether carbonate for use in the DMC catalyst of the present invention can also be obtained by a catalytic reaction of alkylene oxide and carbon dioxide in the presence of a suitable starter or initiator compound. The polyether carbonate used as a complexing agent in the DMC catalyst of the present invention can also be produced by other methods known to those skilled in the art, for example, by partial alcohol decomposition of a polycarbonate polyol with a bifunctional or trifunctional hydroxy compound. The polyether carbonate used as a complexing agent optionally has an average of 1 to 6, optionally 2 to 3, or optionally 2 hydroxyl functional groups.

[0308] Suitable polycarbonates for use in the DMC catalyst of the present invention can also be obtained by polycondensation of a bifunctional hydroxy compound (generally a bis-hydroxy compound, e.g., an alkanediol or bisphenol) with a carbonate derivative, e.g., phosgene or a bis[chlorocarbonyloxy] compound, a carbonate diester (e.g., diphenyl carbonate or dimethyl carbonate), or urea. Methods for producing polycarbonates are generally well known, for example, “Houben-Weyl, Methoden der organischen Chemie”, Volume E20, Makromolekulare Stoffe, 4 th Edition,1987,p.1443-1457, “Ullmann's Encyclopaedia of Industrial Chemistry”,Volume A21,5 th Edition, 1992, pp. 207-215 and "Encyclopaedia of Polymer Science and Engineering", Volume 11, 2 ndThis is described in detail in Edition, 1988, pp. 648-718. Aliphatic polycarbonate diols having molecular weights of approximately 500 to 5000 daltons, and optionally 1000 to 3000 daltons, are optionally used in the DMC catalyst of the present invention. These are generally obtained from non-adjacent diols by reaction with diaryl carbonate, dialkyl carbonate, dioxolanone, phosgene, bischloroformate ester, or urea (see, for example, European Patent Application Publication A292772). Suitable non-adjacent diols include, in particular, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, bis-(6-hydroxyhexyl) ether, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-bis-hydroxymethylcyclohexane, diethylene glycol, and triethylene glycol. Dimerized diols can be obtained by reducing the carboxyl groups of both diols and dimers that can be obtained by reducing the carboxyl groups of dimers, which can be obtained by alkoxylation products of diols with ethylene oxide and / or propylene oxide and / or tetrahydrofuran, and, more rarely, by dimerization of unsaturated vegetable fatty acids, having molar masses of up to 1000 daltons, and optionally 200 to 700 daltons. Non-adjacent diols can be used individually or in mixtures. The reaction can be catalyzed with a base or transition metal compound in a manner known to those skilled in the art.

[0309] Other complexing agents that may be useful in the present invention include poly(tetramethylene ether diols). Poly(tetramethylene ether diols) are polyether polyols based on tetramethylene ether glycol, also known as polytetrahydrofuran (PTHF) or polyoxybutylene glycol. These poly(tetramethylene ether diols) contain two OH groups per molecule. They can be produced by cationic polymerization of tetrahydrofuran (THF) using a catalyst.

[0310] The crystallinity of the DMC catalyst thus obtained can be increased or decreased by using a complexing agent as defined above. A suitable acid for use in the DMC catalyst of the present invention is the acid of formula H r X''' may be present in the formula, where X''' is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and optionally X''' is a halide. r is an integer corresponding to the charge on the counterion X'''. For example, if X''' is Cl - In this case, r is 1, which means the acid is HCl.

[0311] If present, formula H r The optional acids for use in the DMC catalyst of the present invention having X''' include the following: HCl, H2SO4, HNO3, H3PO4, HF, HI, HBr, H3BO3, and HClO4. For example, HCl, HBr, and H2SO4.

[0312] It should also be understood that alkali metal salts (e.g., alkali metal hydroxides, e.g., KOH, alkali metal oxides, or alkali metal carbonates) may be added to the reaction mixture. For example, a metal salt (M'(X') p ) to metal cyanide salt ((Y)q[M''(CN) b (A) c The alkali metal salt may be added to the reaction mixture after it has been added to the ]).

[0313] In one general preparation, an aqueous solution of zinc chloride (in excess) is mixed with an aqueous solution of potassium hexacyanocobaltate, and a complexing agent (e.g., dimethoxyethane) is added to the slurry thus obtained. After filtering and washing the catalyst with an aqueous solution of the complexing agent (e.g., an aqueous solution of dimethoxyethane), the activated catalyst is obtained.

[0314] In alternative preparations, several separate solutions may be prepared and then combined in sequence. For example, the following solutions may be prepared. 1. Solution of a metal cyanide (e.g., potassium hexacyanocobaltate) 2. A solution of a metal salt, for example, (zinc chloride (excess amount)) 3. Solution of the first complexing agent (e.g., PPG diol) 4. A solution of a second complexing agent (e.g., tert-butyl alcohol).

[0315] In this method, solutions 1 and 2 are immediately combined, followed by the slow addition of solution 4 while the mixture is optionally and rapidly stirred. Solution 3 may be added after the addition of solution 4 is complete or immediately thereafter. The catalyst is removed from the reaction mixture by filtration and subsequently washed with a solution of the complexing agent.

[0316] If water is desirable in the DMC catalyst, the above solutions (e.g., solutions 1-4) may be aqueous solutions. However, if the solutions described in the above preparations are aqueous solutions, it is understood that anhydrous DMC catalysts (i.e., DMC catalysts without water) can be prepared. Any further processing steps (washing, filtration, etc.) may be performed using an anhydrous solvent to avoid hydrating the DMC catalyst and thereby introducing water molecules.

[0317] In a single general preparation, several separate solutions may be prepared and then combined in sequence. For example, the following solutions may be prepared: 1. A solution of a metal salt (e.g., zinc chloride (in excess)) and a second complexing agent (e.g., tert-butyl alcohol). 2. Solution of a metal cyanide (e.g., potassium hexacyanocobaltate) 3. Solutions of the first and second complexing agents (for example, the first complexing agent may be a polymer (e.g., polypropylene glycol diol), and the second complexing agent may be tert-butyl alcohol). In this method, solutions 1 and 2 are slowly combined (for example, over 1 hour) at an elevated temperature (for example, above 25°C, e.g., about 50°C) while stirring (e.g., at 450 rpm). After the addition is complete, the stirring speed is increased for 1 hour (e.g., up to 900 rpm). Then, the stirring speed is reduced to a low speed (e.g., up to 200 rpm), and solution 3 is rapidly added while gently stirring. The mixture is filtered. The solid catalyst may be re-slurred in the solution of the second complexing agent at a high stirring speed (e.g., about 900 rpm), and then the first complexing agent may be added at a low stirring speed (e.g., 200 rpm). The mixture is then filtered. This step can be repeated two or more times. The catalyst cake thus obtained can be dried under vacuum (e.g., while heating to 60°C).

[0318] Alternatively, the mixture can be first filtered, then reslurried into a solution of the first complexing agent (without the second or further complexing agent) at a raised temperature (e.g., above 25°C, e.g., about 50°C), and then homogenized by stirring. After this step, it is filtered again. The solid catalyst is then reslurried in a mixture of the first and second complexing agents. For example, the solid catalyst is reslurried into the second complexing agent at a raised temperature (e.g., above 25°C, e.g., about 50°C), followed by the addition of the first complexing agent, and the mixture is homogenized by stirring. The mixture is filtered, and the catalyst is dried under vacuum while heating (e.g., to 100°C).

[0319] DMC catalysts are M' d [M'' e (CN) f ] g It should be noted that the formula may include, where M' and M'' are as defined above, and d, e, f and g are integers selected so that the DMC catalyst is electrically neutral. 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).

[0320] It should be noted that any combination of these optional features is possible. For example, d is 3, e is 1, f is 6, g is 2, M' is Zn(II), and M'' is Co(III).

[0321] Suitable DMC catalysts for the above formula may include zinc hexacyanocobalta(III), zinc hexacyanoferrate(III), nickel hexacyanoferrate(II), and cobalt hexacyanocobalta(III).

[0322] Much progress has been made in the field of DMC catalysts, and those skilled in the art will recognize that, in addition to the above formula, DMC catalysts may include further additives that enhance the catalytic activity. Thus, while the above formula can form the "core" of a DMC catalyst, the DMC catalyst may further include one or more additional components in stoichiometric or non-stoichiometric amounts, such as at least one complexing agent, acid, metal salt, and / or water.

[0323] For example, the DMC catalyst is expressed by the following formula: M' d [M'' e (CN) f ] g ·hM'''X'' i · JR c ·kH2O·lH r X''' The formula may have M', M'', X''', d, e, f, and g as defined above. M''' can 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 greater than or equal to 1, and the charge on the anion X'' multiplied by i satisfies the valence of M'''. r is an integer corresponding to the charge on the counterion X'''. For example, if X''' is Cl - When this is the case, r is 1. l is either 0 or a number between 0.1 and 5. Optionally, l is between 0.15 and 1.5.

[0324] R c R is a complexing agent and can be as defined above. For example, R c (Poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols (for example, C 1~8 Alcohols), urea, etc., for example, propylene glycol, polypropylene glycol, (methyl)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyceride, 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-butin-2-ol, 3-methyl-1-pentin-3-ol, for example, R c This may be tert-butyl alcohol, dimethoxyethane, or polypropylene glycol.

[0325] As described above, multiple complexing agents may be present in the DMC catalyst used in the present invention. Optionally, a combination of tert-butyl alcohol and polypropylene glycol as complexing agents may be present.

[0326] It should be noted that when water, complexing agents, acids, and / or metal salts are not present in the DMC catalyst, h, j, k, and / or l are all zero. When water, complexing agents, acids, and / or metal salts are present, h, j, k, and / or l are positive numbers, for example, 0 to 20. For example, h can be 0.1 to 4. j can be 0.1 to 6. k can be 0 to 20, for example, 0.1 to 10, for example, 0.1 to 5. l can be 0.1 to 5, for example, 0.15 to 1.5.

[0327] As shown above, DMC catalysts have complex structures, and thus the above formula, including further components, is not limiting. Rather, those skilled in the art will recognize that this definition is not comprehensive for all DMC catalysts that can be used in the present invention.

[0328] For example, DMC catalysts are M' d [M'' e (CN) f ] g This may include M' and M'' as defined above, and d, e, f, and g are integers selected such that the DMC catalyst is electrically neutral. 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(III), Fe(III), Cr(III), and Ir(III), and optionally, M'' is Co(III).

[0329] It will be understood that any combination of these options is possible. For example, d is 3, e is 1, f is 6, g is 2, M' is Zn(II), and M' is Co(III).

[0330] Suitable DMC catalysts for the above formula include zinc(III) hexacyanocobaltate, zinc(III) hexacyanoferrate, nickel(II) hexacyanoferrate, and cobalt(III) hexacyanocobaltate.

[0331] Much development has been done in the field of DMC catalysts, and those skilled in the art will understand that a DMC catalyst may include additional additives to enhance the catalytic activity in addition to the formula above. Thus, while the formula above can form the "core" of a DMC catalyst, the DMC catalyst may further include stoichiometric or non-stoichiometric amounts of first and second complexing agents, the first complexing agent being a polymer. The DMC catalyst may also include stoichiometric or non-stoichiometric amounts of one or more additional components (such as acids, metal salts, and / or water).

[0332] For example, the DMC catalyst is expressed by the following formula: M' d [M'' e (CN) f ] g ·hM'''X'' i · JR c ·kH2O·lH r X'''·Pol X' is a halide. The formula may have the following characteristics, where M', M'', d, e, f, and g are as defined above. M''' can be M' and / or M''. M'' is an anion selected from halide, hydroxide, oxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and optionally X' is a halide. i is an integer greater than or equal to 1, and multiplying the charge of the anion X'' 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 - In this case, r becomes 1. l is a number between 0.1 and 5. Arbitrarily, l can be between 0.15 and 1.5.

[0333] R c is a second complexing agent and can be as defined above. For example, R cThese include ethers, ketones, esters, amides, and alcohols (for example, C 1~8 This could be alcohol, urea, etc. c Examples include propylene glycol, ethoxy(or methoxy)ethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyceride, 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-butynic-2-ol, and 3-methyl-1-pentin-3-ol, for example, R c This may be tert-butyl alcohol or dimethoxyethane. Optionally, R c It is tert-butyl alcohol.

[0334] j is a positive number and can be between 0.1 and 6. If water, metal salts, and / or acids are not present in the DMC catalyst, it will be understood that h, k, and / or l are each zero. If water, metal salts, and / or acids are present, h, k, and / or l are positive numbers, and can be, for example, 0 to 20. For example, h can be 0.1 to 4, and k can be 0 to 20, for example, 0.1 to 5, and so on, from 0.1 to 10.

[0335] Pol represents the first complexing agent, which is a polymer. Pol is optionally selected from polyethers, polycarbonate ethers, and polycarbonates. The first complexing agent (e.g., "Pol") is present in amounts of approximately 5% to 80% by weight of the DMC catalyst, optionally 10% to 70% by weight of the DMC catalyst, and optionally 20% to 50% by weight of the DMC catalyst.

[0336] In addition to at least two metal centers and cyanide ligands, the DMC catalyst may optionally contain at least one of one of the following in non-stoichiometric amounts: one or more complexing agents, water, a metal salt, and / or an acid.

[0337] An exemplary DMC catalyst is of the formula Zn3[Co(CN)6]2·hZnCl2·kH2O·j[(CH3)3COH], where h, k, and i are as defined above. For example, h can be 0 to 4 (e.g., 0.1 to 4), k can be 0 to 20 (e.g., 0.1 to 10), and j can be 0 to 6 (e.g., 0.1 to 6).

[0338] As shown above, DMC catalysts have complex structures, and therefore the above formula, which includes additional components, is not intended to be limiting. Rather, those skilled in the art will understand that this definition does not encompass all DMC catalysts that can be used in this invention. [Examples]

[0339] method Nuclear magnetic resonance spectroscopy 1 The 1H NMR spectrum was recorded using a Bruker AV-400 instrument with the solvent CDCl3.

[0340] Gel permeation chromatography GPC measurements were performed on narrow, polydisperse poly(ethylene glycol) or polystyrene standards in THF using an Agilent 1260 Infinity instrument equipped with an Agilent PLgel Mixed-E column.

[0341] mass spectrometry All mass spectrometry measurements were performed using the MALDI micro MX micromass instrument.

[0342] Example 1 Synthesis of DMC catalysts The DMC catalyst used in this example was prepared according to the method reported in Journal of Polymer Science; Part A: Polymer Chemistry, 2002, 40, 1142. Briefly, 1.0 g of K3Co(CN)6 was dissolved in a solvent mixture of 13 g of distilled water and 2 g of tert-butyl alcohol. 6 g of ZnCl2 was dissolved in a solvent mixture of 13 g of water and 4 g of tert-butyl alcohol, and this mixture was then slowly added to the K3Co(CN)6 solution over a period of 20 minutes while stirring. The mixture was then stirred for a further 40 minutes, followed by centrifugation to obtain a white precipitate. The precipitate was dispersed in a solvent mixture of 16 g of water and 16 g of tert-butyl alcohol, stirred for 20 minutes, and then separated by centrifugation. This washing procedure was repeated three times. The white precipitate was then dispersed in 50 g of tert-butyl alcohol, stirred for 20 minutes, followed by centrifugation to obtain a white precipitate. Next, washing with tert-butyl alcohol was repeated. Then, the solvent was removed under reduced pressure at 60°C for 8 hours. The resulting compound is understood to have the formula Zn3[Co(CN)6]2·hZnCl2·0.5H2O·2[(CH3)3COH].

[0343] [L 1 Synthesis of Ni2(OAc)2] and catalyst 1 Ligand H2L 1 It was synthesized by the method previously described in Kember et al., Angew. Chem. Int. Ed., 2009, 48, 931-933.

[0344] [ka] H2L 1 (2 mmol) was dissolved in MeOH (50 mL), then Ni(OAc)2,4H2O (0.498 g, 4 mmol) was added gradually over 15 minutes, and the solution was stirred overnight. The solvent was removed under vacuum, and excess water / AcOH was removed by azeotrope with toluene (3 × 40 mL).

[0345] [L 1 Ni2(OAc)2]:IR(ν C=O ,cm -1 , NEET): 1581 and 1413. MALDI-TOF MS: m / z: 727.6 ([M-OAc)] + 100%).

[0346] Example 2 Synthesis of DMC catalyst (catalyst 2) according to Example 1 of U.S. Patent No. 5,482,908 The synthesis followed the method described in Example 1 of U.S. Patent No. 5,482,908, except that a 4,000 molecular weight polypropylene glycol diol was replaced with a 2,000 molecular weight polypropylene glycol diol.

[0347] Potassium hexacyanocobaltate (8.0 g) was dissolved in deionized (DI) water (140 mL) in a beaker (Solution 1). Zinc chloride (25 g) was dissolved in deionized water (40 mL) in a second beaker (Solution 2). A third beaker containing Solution 3 was prepared: a mixture of deionized water (200 mL), tert-butyl alcohol (2 mL), and polyol (2 g of 2000 molecular weight polypropylene glycol diol). Solutions 1 and 2 were mixed together using a mechanical stirrer. Immediately, a 50 / 50 (by volume) mixture of tert-butyl alcohol and deionized water (200 mL in total) was added to the zinc hexacyanocobaltate mixture, and the product was vigorously stirred for 10 minutes. Solution 3 (polyol / water / tert-butyl alcohol mixture) was added to the aqueous slurry of zinc hexacyanocobaltate, and the product was magnetically stirred for 3 minutes. The mixture was filtered under pressure, and the solid was isolated. The solid cake was reslurried with tert-butyl alcohol (140 mL), deionized water (60 mL), and a further 2 g of 2000 molecular weight polypropylene glycol diol. The mixture was then vigorously stirred for 10 minutes and filtered. The solid cake was reslurried with tert-butyl alcohol (200 mL) and a further 1 g of 2000 molecular weight polypropylene glycol diol, vigorously stirred for 10 minutes, and then filtered. The resulting solid catalyst was dried to a constant weight under vacuum (<1 mmbar) at 50°C. The yield of the dried powdered catalyst was 8.5 g.

[0348] Example 3 DMC was synthesized exactly as described by Chen et al. in Polymer, 45 (2004), 6519 (catalyst 3).

[0349] While vigorously stirring, 10 ml of K3[Co(CN)6] solution (0.2 M) was added dropwise to a ZnCl2 solution (8 g of ZnCl2 in a mixture of 30 ml of water and 15 ml of tert-butanol). The resulting white suspension was filtered to isolate the DMC catalyst precipitate, which was then resuspended in a solution of tert-butanol and water (v / vZ1:1) while vigorously stirring. The precipitate was then filtered again. The precipitate was washed several times by gradually increasing the ratio of tert-butanol to water. Finally, the solid was resuspended in tert-butanol, the water was removed, filtered, and vacuum-dried at 50°C for 8 hours.

[0350] When the catalyst was analyzed by ICP-MS, K + The presence of the component was found to be almost nonexistent (XXX ppm). Powder X-ray diffraction analysis showed the absence of peaks at 17.65° (5.07 Å), 23.72° (3.76 Å), 24.80° (3.59 Å), 35.19° (2.54 Å), and 39.82° (2.26 Å), which would indicate the presence of crystalline zinc hexacyanocobaltate. The broad peaks at 18.37° (4.82 Å) and 23.72° (3.76 Å) indicate that the catalyst prepared by this procedure is substantially or completely amorphous.

[0351] Example 4 The 206 mg of DMC catalyst (3) mentioned above was placed in a 2 L reactor together with 1,6-hexanediol (30.5 g). The catalyst and starter were dried under vacuum at 110-120°C for 1-2 hours. The reactor was cooled to room temperature, and catalyst 1 (2.06 g) was added as an ethyl acetate solution by injecting it into a container from a syringe while continuously flowing CO2 gas. The reactor was pressurized to 2 bar CO2 at room temperature. The container was heated to the set temperature, and the reactor was stabilized at the set reaction pressure. The reaction was started by adding the first 14 wt% of the total PO. The contents of the reactor were stirred for 45 minutes. A further 4 wt% of PO was slowly added over 30 minutes, and then another 30 minutes were allowed to pass through to consumption. The remaining PO (82 wt%) was added continuously from the HPLC pump over 5-6 hours. The reaction temperature and pressure remained constant throughout the reaction. After 16 hours, the reaction was stopped by cooling the reactor to 5°C, and it was slowly evacuated. Crude polyol 1 Analysis was performed using 1H NMR spectroscopy and gel permeation chromatography.

[0352] PEC1 to PEC7 were manufactured according to this process. The CO2 content of the polyol was controlled by changing the temperature and CO2 pressure. PEC8 and PEC9 were produced by changing the temperatures in steps (α) and (β). 20% of the PO was added in step (α) at ​​65°C, and the remaining 80% of the PO was added in step (β) at 80°C. The remaining procedure was as described above.

[0353] [Table 1] Example 5 The aforementioned 10.3 mg of DMC catalyst (2) was placed together with dodecanediol (2.615 g) in a 100 mL oven-dried reactor. The mixture was dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature, and ethyl acetate (15 mL) was injected into a container from a syringe while continuously flowing CO2 gas. The container was heated to the set temperature (130 °C) and filled to the set CO2 pressure (5 bar). 6% of the total propylene oxide (1.49 g) was added in three portions (2% by weight, 0.5 g each) at 30-minute intervals.

[0354] The reactor was cooled to 70°C, and then catalyst (1) (103 mg) was dissolved in SiO2 (5 mL), and 20% by weight of PO2 (4.98 g) was added via HPLC pump. The remaining 74% by weight of PO2 (18.43 g) was added over 3 hours. The reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were immediately performed.

[0355] [Table 2] Example 6 10.3 mg of DMC catalyst (3) was placed in a 100 mL oven-dried reactor together with polytetrahydrofuran 250 (50% of the total starter, 1.6 g). The catalyst and starter were dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature, and catalyst (1) (103 mg) in ethyl acetate (15 mL) was injected into a container from a syringe while continuously flowing CO2 gas.

[0356] The container was heated to the set temperature (70°C) and filled to the set CO2 pressure (5 bar). 14% by weight (3.5 g) of propylene oxide was added, followed by another 3.8% by weight (0.95 g) of propylene oxide 45 minutes later, and then the mixture was allowed to stand for another 45 minutes. Furthermore, 1.63 g of polytetrahydrofuran 250 (50% of the total starter mixture) was mixed with the remaining 82.2% by weight of propylene oxide (20.45 g), and this mixture was added to the reactor via an HPLC pump over 4 hours. After the reaction was complete, the reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were taken immediately.

[0357] [Table 3] Example 7 3.1 mg of DMC catalyst (3) was placed in a 100 mL oven-dried reactor together with dodecanediol (6.2 g). The mixture was dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature, and ethyl acetate (6 mL) was injected into a container from a syringe while continuously flowing CO2 gas. The container was heated to the set temperature (130 °C). 3.75 g of propylene oxide was added in three portions (1.25 g each) at 30-minute intervals. Exothermic reactions and pressure drops, suggestive of activation, occurred.

[0358] The reactor was cooled to 65°C while pressurizing with CO2 to 5 bar. Catalyst (1) (103 mg) and PO (4.98 g), dissolved in SiO (5 mL), were added via an HPLC pump. The remaining PO (18.43 g) was added over 3 hours, after which the temperature was raised to 85°C. After the reaction was carried out "completely" overnight, the reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were taken immediately.

[0359] Example 8 3.1 mg of DMC catalyst (3) was placed in a 100 mL oven-dried reactor together with dodecanediol (6.2 g). The mixture was dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature, and ethyl acetate (6 mL) was injected into a container from a syringe while continuously flowing CO2 gas. The container was heated to the set temperature (130 °C). 2.25 g of propylene oxide was added in three portions (0.75 g each) at 30-minute intervals. Exothermic reactions and pressure drops, suggestive of activation, occurred.

[0360] The reactor was cooled to 65°C while pressurizing with CO2 to 5 bar. Catalyst (1) (103 mg) and PO (4.98 g), dissolved in SiO (5 mL), were added via an HPLC pump. The remaining PO (18.43 g) was added over 3 hours, after which the temperature was raised to 85°C. After the reaction was carried out "completely" overnight, the reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were taken immediately.

[0361] Example 9 3.1 mg of DMC catalyst (3) was placed in a 100 mL oven-dried reactor together with dodecanediol (6.2 g). The mixture was dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature, and ethyl acetate (6 mL) was injected into a container from a syringe while continuously flowing CO2 gas. The container was heated to the set temperature (130 °C). 3.75 g of propylene oxide was added in three portions (1.25 g each) at 30-minute intervals. Exothermic reactions and pressure drops, suggestive of activation, occurred.

[0362] The reactor was cooled to 65°C while pressurizing with CO2 to 5 bar, and PO(1.25g) was slowly supplied over 30 minutes. At the target temperature, PO(2.5g) was added. After this, catalyst (1) (103mg) dissolved in SiO(5mL) was added via an HPLC pump. The remaining PO(17.4g) was added over 2.5 hours, and then the temperature was raised to 85°C. After the reaction was carried out "completely" overnight, the reactor was cooled to below 10°C and the pressure was released. NMR and GPC were measured immediately.

[0363] Example 10 180.0 mg of DMC catalyst (3) was placed in a 2 L reactor together with dodecanediol (52.0 g). The mixture was dried under vacuum at 120°C for 1 hour. The container was isolated under vacuum and heated to 130°C. 225 g of ethyl acetate was added via an HPLC pump. 75 g of propylene oxide was added in three portions (25 g each) at 30-minute intervals.

[0364] The reactor was cooled to 65°C and pressurized to 5 bar with CO2. Catalyst (1) (2.06 g), dissolved in ethyl acetate (100 g), was added via an HPLC pump, followed by the addition of PO (25 g). The remaining PO (398.4 g) was added over 3 hours at 65°C. The reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were immediately performed.

[0365] Example 11 180.0 mg of DMC catalyst (3) was placed in a 2 L reactor together with dodecanediol (52.0 g). The mixture was dried under vacuum at 120°C for 1 hour. The container was heated to 130°C and pressurized with 5 bar CO2. 225 g of ethyl acetate was added via an HPLC pump. The entire 75 g of propylene oxide was added in three portions (25 g each) at 30-minute intervals.

[0366] The reactor was cooled to 73°C while continuously flowing 5 bar of CO2, and PO(25g) was added when the temperature reached 73°C. Catalyst (1) (2.06g), dissolved in SiO(100g), was added via an HPLC pump. The remaining PO(398.4g) was added over 3 hours at 73°C. After the reaction was carried out "completely" overnight, the reactor was cooled to below 10°C and the pressure was released. NMR and GPC measurements were taken immediately.

[0367] [Table 4] These examples demonstrate that various CO2-containing polyols can be produced using process methods in which one or more reagents or catalysts are added sequentially or semi-continuously at different points in the reaction, thereby improving process safety, productivity, and product design. By producing the product using a low molecular weight starter, polyols with high CO2 content can be produced under low CO2 pressure. Note 1 A method for preparing a polycarbonate ether polyol, (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst and optionally a starter 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) A step of mixing an epoxide, a catalyst of formula (I), a starter compound, carbon dioxide, and optionally a solvent to form a mixture (α), or (d) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally a starter compound, an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) Adding one or more of the following to mixture (α): a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and / or a solvent, to form a mixture (β) containing the starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a bimetallic cyanide (DMC) catalyst, and optionally a solvent. The catalyst of formula (I) includes the following structure: JPEG0007866367000047.jpg94170 It has, In the formula, M 1 and M 2 are independently Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(I II)-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 Selected from, R 1 and R 2 These are independently selected from hydrogen, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R 3 These are independently and optionally substituted from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, and alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R 5 These are independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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 N, NR 4 Selected from O and S, E 3 、E 4 、E 5 or E 6 If it is N, JPEG0007866367000048.jpg7170 teeth, JPEG0007866367000049.jpg6170 And E 3 、E 4 、E 5 or E 6 NR 4 If it is O or S, JPEG0007866367000050.jpg7170 teeth, JPEG0007866367000051.jpg6170 And, R 4 These are independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)R x OSO 2 R x OSOR x OSO(R x ) 2 S(O)R x , OR x , selected from phosphinates, halides, nitrates, hydroxyls, carbonates, aminos, amides, or optionally substituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls, where each X may be the same or different, and X is M 1 and M 2 A bridge can be formed between them, R x These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, A method in which G is independently selected from neutral or anionic donor ligands that are either absent or Lewis bases. Note 2 The mixture (α) is held at a temperature of approximately 50–150°C, optionally approximately 80–130°C, prior to step (II), as described in Appendix 1(a) or 1(b). Note 3 The mixture (α) is held at a temperature of approximately 0 to 120°C, optionally approximately 40 to 100°C, and optionally approximately 50 to 90°C prior to step (II), as described in Appendix 1(c) or 1(d). Note 4 The method according to any one of the appendices 1 to 3, wherein the 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, or optionally at least about 5 hours prior to step (II). Note 5 The method according to Appendix 1(c) or 3, wherein the 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, or optionally at least about 16 hours prior to step (II). Note 6 The mixture (α) comprises 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, and optionally about 0% by weight of water, according to any one of the methods described in Appendix 1 to 5. Appendix 7 Step (I) is the method according to any one of the appendices 1 to 6 as dependent on appendice 1(a), comprising first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally carbon dioxide to form a mixture (α'), and then subsequently adding an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α). Note 8 The method according to Appendix 7, wherein the mixture (α') is held at a temperature of approximately 0 to 250°C, optionally approximately 40 to 150°C, optionally approximately 50 to 150°C, optionally approximately 70 to 140°C, and optionally approximately 80 to 130°C before the subsequent addition. Note 9 The method according to any one of the appendices 1 to 8 as dependent on appendice 1(c), comprising step (II) mixing a double metal cyanide (DMC) catalyst, an epoxide, and optionally a starter compound, carbon dioxide and / or a solvent to form a pre-activated mixture, and adding the pre-activated mixture to mixture (α) to form mixture (β). Note 10 The method according to Appendix 9, wherein the pre-activated mixture is held at a temperature of approximately 50-110°C, optionally approximately 60-90°C, before addition. Note 11 The method described above uses the total amount of epoxide, where approximately 1-95% of the total amount of epoxide is mixed in step (I), the remainder is added in step (II), and optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 10. Note 12 The method described above uses the total amount of the starter compound, where approximately 1-95% of the total amount of the starter compound is mixed in step (I), the remainder is added in step (II), and optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 11. Note 13 The method described above uses the entire amount of the catalyst of formula (I), where approximately 1 to 100% of the total amount of the catalyst of formula (I) is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, optionally approximately 1 to 50%, optionally approximately 1 to 40%, optionally approximately 1 to 30%, optionally approximately 1 to 20%, and optionally approximately 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 12. Note 14 The method described above uses the entire amount of a bimetallic cyanide (DMC) catalyst, where approximately 1 to 100% of the total amount of the bimetallic cyanide (DMC) catalyst is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, 1 to 50%, 1 to 40%, 1 to 30%, 1 to 20%, and 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 13. Note 15 The method described above uses the total amount of carbon dioxide, where approximately 1-100% of the total amount of carbon dioxide is mixed in step (I), the remainder is added in step (II), and optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 14. Note 16 The method described above uses the total amount of solvent, where approximately 1 to 100% of the total amount of solvent is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, optionally approximately 1 to 50%, optionally approximately 1 to 40%, optionally approximately 1 to 30%, optionally approximately 1 to 20%, and optionally approximately 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 1 to 15. Note 17 The method is continuous, and there is a predetermined molar or weight ratio of epoxide to the catalyst of formula (I) in the mixture (β), and the method is (III) The method according to any one of the appendices 1 to 10, further comprising adding an epoxide to mixture (β) to form mixture (γ), wherein the epoxide is added in an amount sufficient to make the molar ratio or weight ratio of the epoxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio or weight ratio, and step (III) is optionally repeated. Note 18 The method is continuous, and there is a predetermined molar or weight ratio of the starter compound to the catalyst of formula (I) in the mixture (β), and the method is (III) The method according to any one of the appendices 1 to 10 or 17, further comprising adding a starter compound to mixture (β) to form mixture (γ), wherein the starter compound is added in an amount sufficient to make the molar ratio or weight ratio of the starter compound to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio or weight ratio, and step (III) is optionally repeated. Note 19 The method is continuous, and there is a predetermined molar or weight ratio of carbon dioxide to the catalyst of formula (I) in the mixture (β), and the method is (III) The method according to any one of the appendices 1 to 10, 17 or 18, further comprising adding carbon dioxide to mixture (β) to form mixture (γ), wherein the amount of carbon dioxide added is sufficient to make the molar ratio or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio or weight ratio, and step (III) is optionally repeated. Note 20 Step (III) is carried out such that the molar ratio or weight ratio of the epoxide, starter compound, carbon dioxide and / or solvent to the catalyst of formula (I) in mixture (γ) is not less than approximately 75% of the predetermined molar ratio or weight ratio, according to any one of the appendices 1 to 10 or 17 to 19. Note 21 Step (III) is carried out in such a way that the molar ratio or weight ratio of the epoxide, starter compound, carbon dioxide, and solvent to the catalyst of formula (I) in mixture (γ) does not fall below approximately 75% of the predetermined molar ratio or weight ratio, as described in Appendix 20. Note 22 The method is continuous, and a predetermined amount of the catalyst of formula (I) is present in the mixture (β), and the method is (III) The method according to any one of the appendices 1 to 10 or 17 to 21, further comprising adding a catalyst of formula (I) to mixture (β) to form mixture (γ), wherein the amount of catalyst of formula (I) in mixture (γ) is added in an amount sufficient to make the amount of catalyst of formula (I) in mixture (γ) about 50 to 550% of the predetermined amount, and optionally repeating step (III). Note 23 The method according to Appendix 22, wherein step (III) is carried out such that the amount of catalyst of formula (I) in the mixture (γ) does not fall below approximately 50% of the predetermined amount. Note 24 The method described above is continuous, and a predetermined amount of the double metal cyanide (DMC) catalyst is present in the mixture (β), and the method described above is (III) The method according to any one of the appendices 1 to 10 or 17 to 23, further comprising adding a bimetallic cyanide (DMC) catalyst to mixture (β) to form mixture (γ), wherein the bimetallic cyanide (DMC) catalyst is added in an amount sufficient to make the amount of bimetallic cyanide (DMC) catalyst in mixture (γ) about 50 to 550% of the predetermined amount, and step (III) is optionally repeated. Note 25 The method according to Appendix 24, wherein step (III) is carried out so that the amount of the double metal cyanide (DMC) catalyst in mixture (γ) does not fall below approximately 50% of the predetermined amount. Note 26 Two starter compounds are present in mixture (β), the starter compound in step (I) is the first starter compound, and step (II) is, (A) Adding one or more of the following to mixture (α): a first starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent, (B) The method according to any one of the appendices 1 to 25, comprising adding a second starter 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 a first starter compound, a second starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally a solvent. Note 27 Step (B) is performed 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, or optionally at least about 5 hours, as described in Appendix 26. Note 28 The method according to Appendix 26 or 27, wherein the first starter compound has a molecular weight of at least about 200 Da, and the second starter compound has a molecular weight of up to about 200 Da. Note 29 The method according to any one of the appendices 26 to 28, wherein the second starter compound is a polypropylene glycol having a molecular weight of about 200 to 1000 Da, optionally about 300 to 700 Da, and optionally about 400 Da. Note 30 The method according to any one of the appendices 1 to 29, wherein the starter compound or each starter compound has two or more hydroxyl groups, optionally three or more, optionally four or more, optionally five or more, optionally six or more, optionally seven or more, or optionally eight or more hydroxyl groups. Note 31 The method according to any one of the appendices 1 to 30, wherein in mixture (α), the amount of the catalyst of formula (I) and the amount of the double metal cyanide (DMC) catalyst are in a predetermined weight ratio of about 300:1 to about 1:100, for example about 40:1 to about 1:50, about 120:1 to about 1:75, for example about 20:1 to about 1:1, for example about 10:1 to about 2:1, for example about 5:1 to about 1:5. Note 32 The method according to any one of the appendices 1 to 31, wherein in step (I), the double metal cyanide (DMC) catalyst is dry-mixed with the other components. Note 33 The method according to any one of Appendix 1 to 31, wherein in step (I), the double metal cyanide (DMC) catalyst is mixed as a slurry, and the slurry comprises the double metal cyanide (DMC) catalyst and the starter compound and / or solvent. Note 34 The method according to any one of the appendices 1 to 33, wherein in step (I), the catalyst of formula (I) is dry-mixed with the other components. Note 35 The method according to any one of the appendices 1 to 33, wherein in step (I), the catalyst of formula (I) is mixed as a solution, and the solution comprises the catalyst of formula (I) and one or more of the starter compound, epoxide and / or solvent. Note 36 The epoxide is added in step (II) according to one of the methods described in Appendix 1 to 35. Note 37 The catalyst of formula (I) is added in step (II), according to any one of the methods described in appendices 1 to 36. Note 38 The double metal cyanide (DMC) catalyst is added in step (II) according to one of the methods described in Appendix 1 to 37. Note 39 The starter compound is added in step (II) according to any one of the methods described in Appendix 1 to 38. Note 40 The method according to any one of the appendices 1 to 39, wherein both the epoxide and the starter compound are added in step (II). Note 41 The method according to any one of the appendices 1 to 40, wherein an epoxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a starter compound are added independently and sequentially in step (II). Note 42 The method according to any one of the appendices 1 to 40, wherein an epoxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a starter compound are added independently and discontinuously in step (II). Note 43 The starter compound or each starter compound is defined by formula (III): JPEG0007866367000052.jpg9170 It has, In the formula, Z is any base and is connected to two or more -Rs. Z It can be any group that may have a group, Each R Z These are independently -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), and -PR'(O)(OH). 2 Alternatively, selected from -PR'(O)OH, R' is selected from H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl. a is an integer that is at least 2, as described in any one of the methods in Appendix 1 to 42. Note 44 The starter compound or each starter compound is 1,2-ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexendiol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG), or polyethylene glycol (PEG) having a maximum of approximately 1500 g / mol of Mn, such as PPG425, PPG725, PPG1000; The method according to any one of the appendices 1 to 43, selected from glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, polypropylene oxidetriol, polyestertriol, and other triols, calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, erythritol, pentaerythritol, sorbitol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, lactic acid, glycolic acid, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, 5-hydroxypentanoic acid, ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine. Note 45 The carbon dioxide is supplied continuously according to any one of the methods described in Appendix 1 to 44. Note 46 The method described above is carried out at a carbon dioxide pressure of approximately 1 bar to approximately 60 bar, optionally approximately 1 bar to approximately 40 bar, optionally approximately 1 bar to approximately 20 bar, optionally approximately 1 bar to approximately 15 bar, optionally approximately 1 bar to approximately 10 bar, or optionally approximately 1 bar to approximately 5 bar, and is one of the methods described in Appendix 1 to 45. Note 47 A method for preparing high molecular weight polyether carbonates, (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst and optionally carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α), or (c) A step of mixing an epoxide, a catalyst of formula (I), carbon dioxide, and a solvent to form a mixture (α), or (d) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally an epoxide, carbon dioxide and / or a solvent to form a mixture (α), and (II) Adding one or more of the following to mixture (α): epoxide, carbon dioxide, catalyst of formula (I), bimetallic cyanide (DMC) catalyst and / or solvent, to form a mixture (β) containing epoxide, carbon dioxide, catalyst of formula (I), bimetallic cyanide (DMC) catalyst and optionally a solvent. The catalyst of formula (I) includes the following structure: JPEG0007866367000053.jpg94170 It has, In the formula, M 1 and M 2 are independently Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(I II)-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 Selected from, R 1 and R 2 These are independently selected from hydrogen, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R 3 These are independently and optionally substituted from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, and alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be flanked by aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring. R 5 These are independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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 N, NR 4 Selected from O and S, E 3 、E 4 、E 5 or E 6 If it is N, JPEG0007866367000054.jpg7170 teeth, JPEG0007866367000055.jpg6170 And E 3 、E 4 、E 5 or E 6 NR 4 If it is O or S, JPEG0007866367000056.jpg7170 teeth, JPEG0007866367000057.jpg6170 And, R 4 These are independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 Selected from , -alkylC≡N, or alkylaryl, X is independently O(O)R x OSO 2 R x OSOR x OSO(R x ) 2 S(O)R x , OR x , selected from phosphinates, halides, nitrates, hydroxyls, carbonates, aminos, amides, or optionally substituted aliphatic, heteroaliphatic, aliphatic rings, heteroaliphatic rings, aryls, or heteroaryls, where each X may be the same or different, and X is M1 and M 2 A bridge can be formed between them, R x These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, A method in which G is independently selected from neutral or anionic donor ligands that are either absent or Lewis bases. Note 48 The mixture (α) is held at a temperature of approximately 50–110°C, optionally approximately 60–90°C, prior to step (II), as described in Appendix 47(a) or 47(b). Note 49 The method according to Appendix 47(c) or 47(d), wherein the mixture (α) is held at a temperature of approximately 0 to 120°C, optionally approximately 40 to 100°C, and optionally approximately 50 to 90°C prior to step (II). Note 50 The method according to any one of the appendices 47 to 49, wherein the 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, or optionally at least about 5 hours prior to step (II). Note 51 The method according to Appendix 47(c) or 49, wherein the mixture (α) is held for 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, or optionally at least about 16 hours prior to step (II). Note 52 The method according to any one of the appendices 47 to 51, wherein mixture (α) comprises 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, and optionally about 0% by weight of water. Note 53 Step (I) is the method according to any one of the appendices 47 to 52 as dependent on appendice 48(a), comprising first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally carbon dioxide to form a mixture (α'), and then subsequently adding an epoxide and optionally carbon dioxide to form a mixture (α). Note 54 The method according to Appendix 53, wherein the mixture (α') is held at a temperature of approximately 0 to 250°C, optionally approximately 40 to 150°C, optionally approximately 50 to 150°C, optionally approximately 70 to 140°C, and optionally approximately 80 to 130°C before the subsequent addition. Note 55 Step (II) is the method according to any one of the appendices 47 to 54 as dependent on appendice 47(c), comprising mixing a double metal cyanide (DMC) catalyst, an epoxide, and optionally carbon dioxide and / or a solvent to form a pre-activated mixture, and adding the pre-activated mixture to mixture (α) to form mixture (β). Note 56 The method according to Appendix 55, wherein the pre-activated mixture is held at a temperature of approximately 50-110°C, optionally approximately 60-90°C, before addition. Note 57 The method described above uses the total amount of epoxide, where approximately 1-95% of the total amount of epoxide is mixed in step (I), the remainder is added in step (II), and optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% are mixed in step (I), according to any one of the methods described in Appendix 47-56. Note 58 The method described above uses the entire amount of catalyst of formula (I), wherein approximately 1 to 100% of the total amount of catalyst of formula (I) is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, optionally approximately 1 to 50%, optionally approximately 1 to 40%, optionally approximately 1 to 30%, optionally approximately 1 to 20%, and optionally approximately 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 47 to 57. Note 59 The method described above uses the entire amount of a bimetallic cyanide (DMC) catalyst, where approximately 1 to 100% of the total amount of the bimetallic cyanide (DMC) catalyst is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, optionally approximately 1 to 50%, optionally approximately 1 to 40%, optionally approximately 1 to 30%, optionally approximately 1 to 20%, and optionally approximately 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 47 to 58. Note 60 The method described above uses the total amount of carbon dioxide, where approximately 1-100% of the total amount of carbon dioxide is mixed in step (I), the remainder is added in step (II), and optionally approximately 1-75%, 1-50%, 1-40%, 1-30%, 1-20%, and 5-20% are mixed in step (I), according to any one of the methods described in Appendix 47-59. Note 61 The method described above uses the entire amount of solvent, where approximately 1 to 100% of the total amount of solvent is mixed in step (I), the remainder is added in step (II), and optionally approximately 1 to 75%, optionally approximately 1 to 50%, optionally approximately 1 to 40%, optionally approximately 1 to 30%, optionally approximately 1 to 20%, and optionally approximately 5 to 20% are mixed in step (I), according to any one of the methods described in Appendix 47 to 60. Note 62 The method is continuous, and there is a predetermined molar or weight ratio of epoxide to the catalyst of formula (I) in the mixture (β), and the method is (III) The method according to any one of the appendices 47 to 56, further comprising adding an epoxide to mixture (β) to form mixture (γ), wherein the epoxide is added in an amount sufficient to make the molar ratio or weight ratio of the epoxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated. Note 63 The method is continuous, and there is a predetermined molar or weight ratio of carbon dioxide to the catalyst of formula (I) in the mixture (β), and the method is (III) The method according to any one of the appendices 47 to 56 or 62, further comprising adding carbon dioxide to mixture (β) to form mixture (γ), wherein the amount of carbon dioxide added is sufficient to make the molar ratio or weight ratio of carbon dioxide to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated. Note 64 The method is continuous, and there is a predetermined molar or weight ratio of solvent to catalyst of formula (I) in mixture (β), and the method is (III) The method according to any one of the appendices 47-56, 62, or 63, further comprising adding a solvent to mixture (β) to form mixture (γ), wherein the amount of the solvent is sufficient to make the molar ratio or weight ratio of the solvent to the catalyst of formula (I) in mixture (γ) at least about 75% of the predetermined molar ratio, and step (III) is optionally repeated. Note 65 Step (III) is carried out such that the molar ratio or weight ratio of the epoxide, carbon dioxide and / or solvent to the catalyst of formula (I) in mixture (γ) is not less than approximately 75% of the predetermined molar ratio, according to any one of the methods in Appendix 47-56 or 62-64. Note 66 The method according to Appendix 65, wherein step (III) is carried out such that the molar ratio or weight ratio of the epoxide, carbon dioxide, and solvent to the catalyst of formula (I) in mixture (γ) does not fall below approximately 75% of the predetermined molar ratio. Note 67 The method is continuous, and a predetermined amount of the catalyst of formula (I) is present in the mixture (β), and the method is (III) The method according to any one of the appendices 47-56 or 62-66, further comprising adding a catalyst of formula (I) to mixture (β) to form mixture (γ), wherein the amount of catalyst of formula (I) in mixture (γ) is added in an amount sufficient to make the amount of catalyst of formula (I) in mixture (γ) about 50-550% of the predetermined amount, and step (III) is optionally repeated. Note 68 The method according to Appendix 67, wherein step (III) is carried out such that the amount of catalyst of formula (I) in the mixture (γ) does not fall below approximately 50% of the predetermined amount. Note 69 The method described above is continuous, and a predetermined amount of the double metal cyanide (DMC) catalyst is present in the mixture (β), and the method described above is (III) The method according to any one of the appendices 47-56 or 62-68, further comprising adding a bimetallic cyanide (DMC) catalyst to mixture (β) to form mixture (γ), wherein the bimetallic cyanide (DMC) catalyst is added in an amount sufficient to make the amount of bimetallic cyanide (DMC) catalyst in mixture (γ) about 50-550% of the predetermined amount, and step (III) is optionally repeated. Note 70 The method according to Appendix 69, wherein step (III) is carried out so that the amount of the double metal cyanide (DMC) catalyst in mixture (γ) does not fall below approximately 50% of the predetermined amount. Note 71 The method according to any one of the appendices 47 to 70, wherein in mixture (α), the amount of the catalyst of formula (I) and the amount of the double metal cyanide (DMC) catalyst are in a predetermined weight ratio of about 300:1 to about 1:100, for example about 40:1 to about 1:50, about 120:1 to about 1:75, for example about 20:1 to about 1:1, for example about 10:1 to about 2:1, for example about 5:1 to about 1:5. Note 72 The method according to any one of the appendices 47 to 71, wherein in step (I), the double metal cyanide (DMC) catalyst is dry-mixed with the other components. Note 73 The method according to any one of the appendices 47 to 72, wherein in step (I), the double metal cyanide (DMC) catalyst is mixed as a slurry, and the slurry contains the double metal cyanide (DMC) catalyst and a solvent. Note 74 The method according to any one of the appendices 47 to 73, wherein in step (I), the catalyst of formula (I) is dry-mixed with the other components. Note 75 The method according to any one of the appendices 47 to 74, wherein in step (I), the catalyst of formula (I) is mixed as a solution, and the solution comprises the catalyst of formula (I) and one or more of the epoxide and / or solvent. Note 76 The epoxide is added in step (II) according to one of the methods described in appendices 47 to 75. Note 77 The catalyst of formula (I) is added in step (II), according to any one of the methods described in appendices 47 to 76. Note 78 The double metal cyanide (DMC) catalyst is added in step (II) according to one of the methods described in Appendix 47 to 77. Note 79 The method according to any one of the appendices 47 to 78, wherein an epoxide, a catalyst of formula (I), and / or a double metal cyanide (DMC) catalyst are added independently and sequentially in step (II). Note 80 The method according to any one of the appendices 47 to 79, wherein an epoxide, a catalyst of formula (I), and / or a double metal cyanide (DMC) catalyst are added independently and discontinuously in step (II). Note 81 The carbon dioxide is supplied continuously according to any one of the methods described in Appendix 47 to 80. Note 82 The method described above is carried out at a carbon dioxide pressure of approximately 1 bar to approximately 60 bar, optionally approximately 1 bar to approximately 40 bar, optionally approximately 1 bar to approximately 20 bar, optionally approximately 1 bar to approximately 15 bar, optionally approximately 1 bar to approximately 10 bar, or optionally approximately 1 bar to approximately 5 bar, and is one of the methods described in any one of the appendices 47 to 81. Note 83 M 1 and / or M 2 It is selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II), and Fe(III)-X, and M is selected arbitrarily. 1 and M 2 The method described in any one of the appendices 1 to 82, wherein the material is selected from Mg(II), Zn(II), or Ni(II). Note 84 X is independently O(O)R x OSO 2 R x OS(O)R x OSO(R x ) 2 S(O)R x , OR x Selected from halide, nitrate, carbonate, amino, nitro, amide, alkyl, heteroalkyl, aryl or heteroaryl, and / or R x X may be optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl, where each X may be the same or different, and X is M 1 and M 2 A method according to any one of the appendices 1 to 83, which can form a bridge between the two. Note 85 The catalyst of formula (I) is the method described in any one of the appendices 1 to 84, having a symmetric macrocyclic ligand. Note 86 The catalyst of formula (I) is the method described in any one of the appendices 1 to 84, wherein the catalyst has an asymmetric macrocyclic ligand. Note 87 E 3 、E 4 、E 5 and E 6 is NR 4 And E 3 、E 4 、E 5 and E 6 The existence of at least one of E 3 、E 4 、E 5 and E 6 Unlike the remaining existence of R, which can be selected at will. 4 The method described in Appendix 86, wherein is H or alkyl. Note 88 E 3 、E 4 、E 5 and E 6 is NR 4 And each R 4 These are independently H or optionally substituted aliphatic, and each R is optionally substituted 4 The method described in Appendix 86, wherein is H or alkyl. Note 89 E1 C is E 2 The method described in any one of the appendices 1 to 88 is O. Note 90 R 5 H is R 2 The method described in any one of the appendices 1 to 89 is H. Note 91 R 3 is an alkylene group that is optionally substituted, and optionally R 3 C is optionally substituted. 2 or C 3 The method described in any one of the appendices 1 to 90, which is an alkylene group. Note 92 R 1 R is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate and optionally substituted alkyl, alkenyl, aryl, heteroaryl, silyl, silyl ether, alkoxy, aryloxy or alkylthio, and optionally each R 1 The method is the same as any one of the methods described in Appendix 1 to 91. Note 93 Each R 4 These are independently hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(O)OR 19 Alternatively, selected from alkyl C≡N, each R is optionally selected. 4 R is selected from hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl, and optionally each R 4 R is hydrogen or alkyl, and optionally each R 4 These are H, Me, Et, Bn, iPr, tBu or Ph and -CH 2 -A method selected from (pyridine) as described in any one of the appendices 1 to 92. Note 94 The catalyst of formula (I) above is given by the following formula: JPEG0007866367000058.jpg235163 JPEG0007866367000059.jpg235157 JPEG0007866367000060.jpg235159 The method described in any one of the appendices 1 to 82. Note 95 The method according to any one of the appendices 1 to 94, wherein the DMC catalyst optionally comprises, in addition to at least two metal centers and cyanide ligands, at least one of one of one complexing agents, water, a metal salt, and / or an acid, in a non-stoichiometric amount. Note 96 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, wherein the metal salt is of formula M'(X')p, where M' is 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). X' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. p is an integer greater than or equal to 1, the charge on the anion multiplied by p satisfies the valence of M', and the metal cyanide salt is given by formula (Y) q M''(CN) b (A) c The formula is such that 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 an alkaline earth metal ion (for example, 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 greater than or equal to 1. c can be 0 or an integer greater than or equal to 1. The sum of the charges on the anions Y, CN, and A multiplied by q, b, and c respectively (for example, Y × q + CN × b + A × 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, (me)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyceride, 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-butin-2-ol, 3-methyl-1-pentin-3-ol or a combination thereof. If the aforementioned acid is present, then formula H r The method according to any one of the appendices 1 to 95, wherein the formula has 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'''. Note 97 The aforementioned DMC catalyst is of formula: M' d [M’’ e (CN) f ] g The formula includes, where M' and M'' are as described in Appendix 96, d, e, f, and g are integers, and the DMC catalyst is selected to be electrically neutral. The method described in any one of the appendices 1 to 96, wherein d is 3, e is 1, f is 6, and g is 2, at any discretion. Note 98 The method according to Appendix 96 or 97, wherein M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), and optionally M' is Zn(II). Note 99 The method according to any one of the appendices 96 to 98, wherein 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). Note 100 The method according to any one of the appendices 1 to 99, wherein the reaction temperature rises during the process of the aforementioned method. Note 101 A method described in any one of the appendices 1 to 100, performed on an industrial scale. Note 102 A product formed by any one of the methods described in Appendix 1 to 101. Note 103 A polycarbonate ether polyol or polyether carbonate manufactured by the method described in any one of the appendices 1 to 101. Note 104 A higher-order polymer produced from a polycarbonate ether polyol or polyether carbonate as described in Appendix 103.

Claims

1. A method for preparing a polycarbonate ether polyol, (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst with an optional starter compound, carbon dioxide and / or a solvent with an epoxide and an optional carbon dioxide and / or solvent to form a mixture (α), or (c) A step of mixing an epoxide, a catalyst of formula (I), a starter compound, carbon dioxide, and optionally a solvent to form a mixture (α), and (II) A step of adding one or more of a starter compound, an epoxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and / or a solvent, and optionally carbon dioxide, to a mixture (α) to form a mixture (β) containing a starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally a solvent, The epoxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst and / or starter compound are added independently, continuously or discontinuously, in step (II). The epoxide is added in at least step (II), The catalyst of formula (I) has the following structure: 【Chemistry 1】 It has, In the formula, M １ and M ２ are independently Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(I II)-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 Selected from, R １ and R ２ These are independently selected from hydrogen, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R ３ These are independently selected from optionally substituted alkylenes, alkenylenes, alkynylenes, heteroalkylenes, heteroalkenylenes, heteroalkynylenes, arylenes, heteroarylenes, or cycloalkylenes, wherein alkylenes, alkenylenes, alkynylenes, heteroalkylenes, heteroalkenylenes, and heteroalkynylenes may have aryl, heteroaryl, aliphatic rings, or heteroaliphatic rings sandwiched between them. R ５ These are independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, 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, and E ３ , E ４ , E ５ and E ６ N, NR ４ Selected from O and S, E ３ , E ４ , E ５ or E ６ If it is N, 【change】 teeth, 【change】 E ３ , E ４ , E ５ or E ６ NR ４ If it is O or S, 【change】 teeth, 【change】 And, R ４ These are independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １９ Selected from -alkylC≡N or alkylaryl, X independently, OC(O)R ｘ OSO ２ R ｘ OSOR ｘ OSO(R ｘ ) ２ S(O)R ｘ , OR ｘ , selected from phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amide or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl or heteroaryl, where each X may be the same or different, X is M １ and M ２ A bridge can be formed between them, R ｘ These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, G is either absent or is independently selected from neutral or anionic donor ligands that are Lewis bases. The starter compound or each starter compound is defined by formula (III): 【Chemistry 2】 It has, In the formula, Z is any group and is connected to two or more -R groups. Ｚ It can be any group that may have a group, Each R Ｚ These are independently -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), and -PR'(O)(OH). ２ Or selected from -PR'(O)OH, R' is selected from H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, A method in which a is an integer that is at least 2.

2. The method according to claim 1, wherein step (I) is carried out by (a) or (b), and the mixture (α) is held at a temperature of 50 to 150°C before step (II).

3. The method according to claim 1, wherein step (I) is carried out by (c), and the mixture (α) is held at a temperature of 0 to 120°C before step (II).

4. The method according to claim 1, wherein step (I) is carried out according to (a), and step (I) comprises first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally carbon dioxide to form a mixture (α'), and then subsequently adding an epoxide and optionally a starter compound and / or carbon dioxide to form a mixture (α).

5. The method according to claim 1, wherein step (I) is carried out by (c), and step (II) is to mix a double metal cyanide (DMC) catalyst, an epoxide, and optionally a starter compound, carbon dioxide and / or a solvent to form a pre-activated mixture, and to add the pre-activated mixture to mixture (α) to form mixture (β).

6. The method according to any one of claims 1 to 5, wherein the method uses the entire amount of epoxide, with 1 to 95% of the total amount of epoxide being mixed in step (I) and the remainder being added in step (II).

7. Two starter compounds are present in mixture (β), the starter compound in step (I) is the first starter compound, and step (II) is, (A) Adding one or more of the following to mixture (α): a first starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent, (B) The method according to any one of claims 1 to 6, comprising adding a second starter 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 a first starter compound, a second starter compound, an epoxide, carbon dioxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally a solvent.

8. The starter compound or each starter compound has two or more hydroxyl groups, and / or The starter compound is added in step (II), and / or The method according to any one of claims 1 to 7, wherein both the epoxide and the starter compound are added in step (II).

9. The starter compound or each starter compound is 1,2-ethanediol (ethylene glycol), 1-2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexendiol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, Tetraethylene glycol, polypropylene glycol (PPG), or polyethylene glycol (PEG) having a maximum of 1500 g / mol of Mn; selected from triols, calix[4]arenes, 2,2-bis(methyl alcohol)-1,3-propanediol, erythritol, pentaerythritol, sorbitol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, lactic acid, glycolic acid, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, 5-hydroxypentanoic acid, ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine, and / or The method according to any one of claims 1 to 8, wherein the carbon dioxide is continuously supplied.

10. A method for preparing high molecular weight polyether carbonates, (I) (a) A step of mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst, and optionally carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide to form a mixture (α), or (b) A step of mixing a double metal cyanide (DMC) catalyst with carbon dioxide and / or a solvent with an epoxide and optionally carbon dioxide and / or a solvent to form a mixture (α), or (c) A step of mixing the epoxide, the catalyst of formula (I), carbon dioxide, and optionally a solvent to form a mixture (α), and (II) The process includes adding one or more of the following to a mixture (α): an epoxide, a catalyst of formula (I), a double metal cyanide (DMC) catalyst, and / or a solvent, and optionally carbon dioxide, to form a mixture (β) containing the epoxide, carbon dioxide, the catalyst of formula (I), the double metal cyanide (DMC) catalyst, and optionally a solvent. The epoxide, the catalyst of formula (I), and / or the double metal cyanide (DMC) catalyst are added independently, continuously or discontinuously, in step (II). The epoxide is added in at least step (II), The catalyst of formula (I) has the following structure: 【Transformation 3】 It has, In the formula, M １ and M ２ are independently Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(I II)-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 Selected from, R １ and R ２ These are independently selected from hydrogen, halide, nitro group, nitrile group, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group or acetylide group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic groups. R ３ These are independently selected from optionally substituted alkylenes, alkenylenes, alkynylenes, heteroalkylenes, heteroalkenylenes, heteroalkynylenes, arylenes, heteroarylenes, or cycloalkylenes, wherein alkylenes, alkenylenes, alkynylenes, heteroalkylenes, heteroalkenylenes, and heteroalkynylenes may have aryl, heteroaryl, aliphatic rings, or heteroaliphatic rings sandwiched between them. R ５ These are independently selected from H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, or alkylaryl, E １ is C and E ２ is O, S, NH, or E １ is N and E ２ is O, E ３ , E ４ , E ５ and E ６ N, NR ４ Selected from O and S, E ３ , E ４ , E ５ or E ６ If it is N, 【change】 teeth, 【change】 E ３ , E ４ , E ５ or E ６ NR ４ If it is O or S, 【change】 teeth, 【change】 And, R ４ These are independently H or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １９ Selected from -alkylC≡N or alkylaryl, X independently, OC(O)R ｘ OSO ２ R ｘ OSOR ｘ OSO(R ｘ ) ２ S(O)R ｘ , OR ｘ , selected from phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amide or optionally substituted aliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl or heteroaryl, where each X may be the same or different, X is M １ and M ２ A bridge can be formed between them, R ｘ These are independently hydrogen- or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, aliphatic ring, heteroaliphatic ring, aryl, alkylaryl, or heteroaryl, A method in which G is independently selected from neutral or anionic donor ligands that are either nonexistent or Lewis bases.

11. The method according to any one of claims 1 to 10, wherein the mixture (α) contains less than 1% by weight of water.

12. The method according to claim 10, wherein step (I) is carried out according to (a), and step (I) comprises first mixing the catalyst of formula (I), a double metal cyanide (DMC) catalyst and optionally carbon dioxide to form a mixture (α'), and then subsequently adding an epoxide and optionally carbon dioxide to form a mixture (α).

13. The method according to claim 10, wherein step (I) is carried out by (c), and step (II) is to mix a double metal cyanide (DMC) catalyst, an epoxide, and optionally carbon dioxide and / or a solvent to form a pre-activated mixture, and to add the pre-activated mixture to mixture (α) to form mixture (β).

14. The method according to any one of claims 10 to 13, wherein the method uses the entire amount of epoxide, and 1 to 95% of the total amount of epoxide is mixed in step (I) and the remainder is added in step (II).

15. In mixture (α), the amount of the catalyst of formula (I) and the amount of the double metal cyanide (DMC) catalyst are in a predetermined weight ratio of 300:1 to 1:100, and / or In step (I), the double metal cyanide (DMC) catalyst is dry-mixed with other components and / or, In step (I), the double metal cyanide (DMC) catalyst is mixed as a slurry, and the slurry contains the double metal cyanide (DMC) catalyst and a solvent, and / or In step (I), the catalyst of formula (I) is mixed as a solution, the solution comprising the catalyst of formula (I) and one or more of the epoxide and / or solvent, and / or The epoxide is added in step (II) and / or, The catalyst of formula (I) is added in step (II), and / or, The double metal cyanide (DMC) catalyst is added in step (II), and / or The method according to any one of claims 1 to 14, wherein the carbon dioxide is continuously supplied.

16. 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, wherein the metal salt is of the formula M'(X')p, where M' is 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). X' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. p is an integer greater than or equal to 1, the charge on the anion multiplied by p satisfies the valency of M', and the metal cyanide salt is given by formula (Y) ｑ M'' (CN) ｂ (A) ｃ The formula is such that 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 an alkaline earth metal ion (for example, 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 greater than or equal to 1. c can be 0 or an integer greater than or equal to 1. The sum of the charges on the anions Y, CN, and A multiplied by q, b, and c respectively (for example, Y × q + CN × b + A × 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, urea, or combinations thereof. If the aforementioned acid is present, then formula H ｒ The method according to any one of claims 1 to 15, comprising X'''', wherein 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''''.

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