RU2793322C2 - Method for obtaining simple polyethercarbonates - Google Patents

Abstract

FIELD: medicine.

SUBSTANCE: invention encompasses a group of inventions: a method for producing a high molecular weight polyether carbonate, a polymerization system for the copolymerization of carbon dioxide and epoxide, a high molecular weight simple polyester carbonate. This method involves the reaction of carbon dioxide and epoxide in the presence of a double-metal cyanide catalyst (DMC catalyst) and a catalyst with formula (I), where the catalyst with formula (I) has the following structure:

The polymerization system contains a catalyst with formula (I) and a DMC catalyst. The high molecular weight polyether carbonate has the following formula:

EFFECT: development of a catalytic system for changing the amount of ether and carbonate bonds at lower pressures (< 20 bar) in order to control the properties of the resulting polymer and obtain a range of different products for different markets.

30 cl, 1 tbl, 8 ex

Description

Description

Technical field

The present invention relates to a process for producing a high molecular weight polyether carbonate by the reaction of epoxide and carbon dioxide in the presence of a catalyst of formula (I) and a bimetallic cyanide catalyst (double metal cyanide, DMC).

State of the art

It is known in the art that epoxides can homopolymerize to form polyethers. Polyethers are polymers having –C–O–C– bonds in their backbones. Typical examples of polyethers are polyethylene oxide (PEO) and polypropylene oxide (PPO).

Epoxides also copolymerize with carbon dioxide to form alternating aliphatic polycarbonates. Polycarbonates are polymers containing –O–C(=O)O– bonds in their backbones. Typical examples of aliphatic polycarbonates derived from epoxides and CO ₂ are polypropylene carbonate (PPC), polycyclohexene carbonate (PCHC) and polyethylene carbonate (PEC).

Polyethers are used in a variety of products including elastomers, adhesives, sealants and epoxy plasticizers. Polyethers are also used as hydraulic fluids and lubricants, as additives in cosmetics, and as binders in ceramic and metal powders. Polyethers generally have very low glass transition temperatures (typically _Tg well below 0°C) and therefore cannot be used as engineering plastics. In addition, polyethers generally have poor UV stability and are prone to oxidative degradation, resulting in severe fading.

Aliphatic polycarbonates such as PPC can be used as sacrificial binders and adhesives because they have relatively low heat resistance and usually decompose very cleanly. However, the low temperature resistance of polycarbonates may limit their applicability in some applications. For example, polycarbonates may be unstable under typical processing conditions required to produce packaging materials. Generally, aliphatic polycarbonates have better UV resistance and better mechanical properties than polyethers. In addition, polycarbonates have higher glass transition temperatures (T _g ) than polyethers. PCHC polycarbonate has a high glass transition temperature (~110°C) but limited industrial use as a thermoplastic because it is very brittle.

Polyether carbonates contain both ether bonds (hereinafter referred to as ether bonds) and carbonate bonds in their main chains and can be obtained by the reaction of epoxides with CO ₂ using catalysts capable of catalyzing both homo- and copolymerization reactions. The formation of polyethers is generally faster than the formation of polycarbonates, so catalysts that allow both reactions tend to form polyether carbonates that contain predominantly ether bonds, that is, polyether carbonates with less than 50% carbonate bonds. Harsh conditions (e.g. high pressures) are usually required to achieve carbonate bond levels in the 50–100% range.

The ability to control the amount of ester and carbonate linkages in the polymer backbone, ranging from polyethers to polycarbonates, allows the physical and mechanical properties of the resulting polymer to be tailored to the desired end use. It is desirable to have both carbonate and ether linkages in the same polymer backbone, since mixtures of polyethers and polycarbonates may not be compatible. In addition, mixtures of polyethers and polycarbonates can delaminate. It is also desirable to form mixed ether and carbonate bonds in a random polymerization rather than a block polymerization in order to actually achieve intermediate properties.

As noted above, polycarbonates can be brittle, especially CO ₂ based polycarbonates, and the addition of ester linkages can improve flexibility and elongation at break. On the other hand, carbonate bonds can increase the strength of polyethers, which can be soft. Thus, it is desirable to be able to create polyether carbonate products having a specific balance of flexibility and strength by adjusting the relative amounts of ether and carbonate linkages.

The heat resistance of aliphatic polycarbonates can be improved by adding ether bonds, and the UV resistance of polyethers can be improved by adding carbonate bonds. Aliphatic polycarbonates may be unstable under alkaline conditions, while polyethers are usually stable under such conditions. Therefore, it is desirable to be able to obtain polyester carbonate products having a particular degree of stability for a particular application.

Thus, it would be advantageous to develop a catalyst system for changing the amount of ester and carbonate bonds in order to properly control the properties of the resulting polymer and obtain a range of different products for different markets. It would also be preferable if the catalyst system could do this under mild conditions, eg at lower pressures (<20 bar).

Bimetallic cyanide catalyst (DMC catalyst) can be used to produce polyethers by ring-opening polymerization of epoxides. The term "DMC catalyst" is widely used in documents and published patents to refer to catalysts containing at least two metal centers and a cyanide ligand. There are many patents relating to methods for producing DMC catalysts and methods for producing polyethers using a DMC catalyst [for example, US 2008/0167502 (BASF), US 2003/0158449 (Bayer), US 2003/0069389 (Shell), US 2004 /0220430 (Repsol Quimica), US 5536883 (Arco); US 2005/0065383 (Dow) and US 3427256 (The General Tire and Rubber Company)].

DMC catalysts are also capable of producing polyether carbonates. To obtain polymers of these types, the reaction is usually carried out at high pressures of carbon dioxide (eg 40 bar). It is very difficult to introduce more than 50% carbonate bonds into the backbone of a polyether carbonate using only a DMC catalyst, even at this pressure.

As a rule, it turns out that in order to introduce more than 50% carbon dioxide in the case of DMC catalysts, the reaction must be carried out at pressures above 40 bar. This may be undesirable, since industrial equipment for the production of polyether carbonates is usually limited to pressures up to 10 bar. For example, US 2013/0072602 provides examples of the polymerization of propylene oxide in the presence of a starting compound and an additive at a CO ₂ pressure of 50 bar.

Many other catalysts are known in the art for use in the preparation of polyether carbonates. For example, WO 2012/121508 relates to a process for the preparation of polyether carbonates which are ultimately intended for use as resins and soft plastics. The method described in WO 2012/121508 requires the copolymerization of epoxide and carbon dioxide in the presence of a DMC catalyst and a metal salt catalyst having the following formula:

All examples were carried out at 16 bar CO ₂ or higher. The polyether carbonates obtained contain varying amounts of ether and carbonate bonds, with the highest carbonate content achieved in WO 2012/121508 being 67% at 28 bar. WO 2012/121508 lacks examples of polyether carbonates containing more than 70% carbonate bonds in the polymer backbone.

Wang et al . ( J. Polymer. Sci., Part A: Polymer Chemistry , 2012 , 50, 362–370) describe a method for producing high molecular weight polyether carbonates by copolymerization of epoxide and carbon dioxide using a two-catalyst system in the presence of a starting compound. The dual catalyst system described by Wang contains a DMC catalyst and a ternary rare earth (RET) catalyst. Polyether carbonates formed using Wang's two-catalyst system at 40 bar CO ₂ have a molecular weight of about 100,000 daltons and contain about 70-80% carbonate bonds in the polymer backbone.

To prepare high molecular weight polyethers or polyester carbonates using only a DMC catalyst, it is usually necessary to use a starting compound to start the reaction. A starter compound (or initiator) is a compound that can react with the first base molecule to start (or initiate) the polymerization reaction. For example, Wang (see above) used a starter compound to initiate the polymerization reaction.

Even when an initiator compound is present, it is difficult to obtain polyethers or polyester carbonates having an appreciable molecular weight (eg, 50,000 daltons or higher) using a DMC catalyst alone. For example, Varghese et al. reported that in the reaction using a DMC catalyst it was possible to obtain poly[PC-co-PO] diols having a molecular weight of up to about 46,000 daltons (see J. Polymer. Sci., Part A: Polymer Chemistry , 2013 , 51, 4811-4818). In addition, it should be noted that Varghese et al . managed to reach the level of carbonate bonds in the obtained polymers only up to about 60%.

Thus, it is desirable to be able to produce polyether carbonates at the pressures used in typical industrial equipment. It is also desirable to achieve a perceptible introduction of carbon dioxide (eg, ≥20 wt.% carbon dioxide, which requires a share of carbonate bonds of ~0.5 in the main polymer chain at low pressures).

It is also desirable to develop a process for the production of high molecular weight polyether carbonates. High molecular weight polymers (ie, polymers with longer chains) generally have better mechanical properties than their lower molecular weight counterparts. For example, high molecular weight polymers generally have better abrasion resistance, chemical resistance, fracture toughness, and friction behavior. In the context of the present invention, high molecular weight polymers means polymers having a molecular weight of at least about 25,000 Daltons, for example, at least about 40,000 Daltons, for example, at least about 50,000 Daltons, or at least about 100,000 Daltons, for example, from about 50,000 Daltons up to about 1,000,000 daltons. The high molecular weight polymers formed by the process of the present invention typically have molecular weights above about 50,000 daltons. Unless otherwise indicated, the term "molecular weight" refers to the number average molecular weight.

Surprisingly, it has been found that a combination of a catalyst of formula (I) and a DMC catalyst can be used to produce high molecular weight polyether carbonates without the need for an initiator.

The essence of the invention

The invention relates to a process for the production of polyether carbonate by the reaction of epoxide and carbon dioxide in the presence of a catalyst of formula (I) and a bimetallic cyanide catalyst (DMC catalyst). In addition, the present invention relates to high molecular weight polyester carbonates obtained by this method.

The catalyst of formula (I) has the following structure:

Where:

M ₁ and M ₂ 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 ;

R ₁ and R ₂ are independently selected from hydrogen, a halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or from (possibly substituted ) an alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R ₃ is independently selected from (possibly substituted) alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group ;

R ₅ is independently selected from H, or a (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl group;

E ₁ means C, E ₂ means O, S or NH, or E ₁ means N, and E ₂ means O;

означает

, а когда E₃, E₄, E₅ или E₆ представляет собой NR₄, O или S, то

означает

; R₄ независимо выбран из H, или (возможно замещенной) алифатической, гетероалифатической, алициклической, гетероалициклической, арильной, гетероарильной, алкилгетероарильной группы, –алкил–C(O)OR₁₉ или –алкилC≡N или алкиларила;E ₃ , E ₄ , E ₅ and E ₆ are selected from N, NR ₄ , O and S, and when E ₃ , E ₄ , E ₅ or E ₆ is N, Io

means

, and when E ₃ , E ₄ , E ₅ or E ₆ is NR ₄ , O or S, then

means

; R ₄ is independently selected from H, or (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkyl-C(O)OR ₁₉ or -alkylC≡N, or alkylaryl;

X is independently selected from OC(O)R ^x , OSO ₂ R ^x , OSOR ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or a (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, where all X may be the same or different, and where X may form a bridge between M ₁ and M ₂ ;

R _x is independently hydrogen, or a (possibly substituted) aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl group; And

G is absent or is independently selected from a neutral or anionic Lewis acid donor ligand.

The DMC catalyst contains at least two metal centers and cyanide ligands. The DMC catalyst may further contain at least one of the following: one or more complexing agents, water, metal salt, and/or acid (eg, in non-stoichiometric amounts).

For example, a DMC catalyst may contain:

M' _d [M" _e (CN) _f ] _g

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),

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

d, e, f and g are integers and are chosen so that the DMC catalyst is electrically neutral.

The method can be carried out at a pressure of carbon dioxide from about 1 bar to about 60 bar, from about 1 bar to about 30 bar, from about 1 bar to about 20 bar, from about 1 bar to about 15 bar, or from about 1 bar to about 10 bar. It should also be understood that the reaction may be carried out at a pressure of about 5 bar or less.

The method can be carried out at temperatures from about 0°C to about 250°C, for example, from about 40°C to about 140°C, for example, from about 50°C to about 110°C, such as from about 60 °C to about 100°C, for example, from about 70°C to about 100°C, for example, from about 55°C to about 80°C.

The invention also provides a polymerization system for the copolymerization of carbon dioxide and epoxide, comprising:

a. a catalyst of formula (I) as defined herein, and

b. DMC catalyst as defined herein.

The invention makes it possible to obtain high molecular weight polyether carbonates that have n ether bonds and m carbonate bonds, where n and m are integers, and where the ratio m/(n+m) is greater than zero but less than 1.

High molecular weight polyether carbonates can be used as thermoplastic polymers, for example in molding and extrusion processes.

Definitions

For the purposes of the present invention, an aliphatic group means a hydrocarbon component which may be linear (ie, unbranched), branched or cyclic, and may be fully saturated or contain one or more unsaturated units, but which is not aromatic. The term "unsaturated" means a component that has one or more double and/or triple bonds. Thus, the term "aliphatic" embraces alkyl, cycloalkyl, alkenylcycloalkenyl, alkynyl, or cycloalkenyl groups, and combinations thereof.

The aliphatic group is preferably a C _1-30 aliphatic group, i.e. an aliphatic group with 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. Preferably, the aliphatic group is C _1-15 aliphatic, more preferably C _1-12 aliphatic, more preferably C _1-10 aliphatic, even more preferably C _1-8 aliphatic, eg C _1-6 aliphatic. Suitable aliphatic groups include straight or branched alkyl, alkenyl and alkynyl, as well as mixtures thereof, such as (cycloalkyl)alkyl groups, (cycloalkenyl)alkyl groups and (cycloalkyl)alkenyl groups.

Used in the context of the invention, the term "alkyl" refers to saturated, linear or branched hydrocarbon radicals obtained by removing one hydrogen atom from an aliphatic component. The alkyl group is preferably a C _1-20 alkyl group, that is, an alkyl group having a straight or branched chain with 1-20 carbon atoms. Thus, an alkyl group contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Preferably, the alkyl group is C _1-15 alkyl, preferably C _1-12 alkyl, more preferably C _1-10 alkyl, even more preferably C _1-8 alkyl, even more preferably C _1-6 alkyl. Specific examples of the C _1-20 alkyl group 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 group, 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, 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, etc. P.

Used in the context of the invention, the term "alkenyl" means a group resulting from the removal of one hydrogen atom from a linear or branched aliphatic component containing at least one carbon-carbon double bond. The term "alkynyl" as used herein refers to a group resulting from the removal of one hydrogen atom from a linear or branched aliphatic component containing at least one carbon-carbon triple bond. The alkenyl and alkynyl groups are preferably "C _2-20 alkenyl" and "C _2-20 alkynyl", more preferably "C _2-15 alkenyl" and "C _2-15 alkynyl", even more preferably "C _2-12 alkenyl" and "C _2-12 alkynyl", even more preferably "C _2-10 alkenyl" and "C _2-10 alkynyl", even more preferably "C _2-8 alkenyl" and "C _2-8 alkynyl", most preferably " C _2-6 alkenyl" and "C _2-6 alkynyl", respectively. Examples of alkenyl groups include ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, 1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, and allenyl. Examples of alkynyl groups include ethynyl, 2-propynyl (propargyl), and 1-propynyl.

Used in the context of the invention, the terms "cycloaliphatic", "carbocycle" or "carbocyclic" refer to a saturated or partially unsaturated, cyclic aliphatic monocyclic or polycyclic ring system (including fused, bridged and spiro-fused) containing from 3 to 20 carbon atoms, which is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, the alicyclic group contains 3 to 15, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 6 carbon atoms. The terms "cycloaliphatic", "carbocycle", or "carbocyclic" also encompass aliphatic rings which are fused to one or more aromatic or non-aromatic rings, such as tetrahydronaphthyl rings, with the point of attachment being on the aliphatic ring. The carbocyclic group may be polycyclic, eg bicyclic or tricyclic. It should be understood that an alicyclic group may contain an alicyclic ring bearing one or more bonding or non-bonding alkyl substituents such as -CH ₂ -cyclohexyl. Specific examples of carbocycles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4,5]decane, cycloheptane, adamantane and cyclooctane.

A heteroaliphatic group (including heteroalkyl, heteroalkenyl, and heteroalkynyl) is an aliphatic group as described above that further contains one or more heteroatoms. Thus, heteroaliphatic groups preferably contain 2 to 21 atoms, preferably 2 to 16 atoms, more preferably 2 to 13 atoms, more preferably 2 to 11 atoms, more preferably 2 to 9 atoms, even more preferably 2 to 7 atoms, with at least one atom being a carbon atom. Particularly preferred heteroatoms are selected from O, S, N, P and Si. When heteroaliphatic groups contain two or more heteroatoms, the heteroatoms may be the same or different. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.

An alicyclic group is a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system (including fused, bridged and spiro-fused) containing from 3 to 20 carbon atoms, which is an alicyclic group with 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, the alicyclic group contains 3 to 15, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 6 carbon atoms. The term "alicyclic" embraces cycloalkyl, cycloalkenyl and cycloalkynyl groups. It should be understood that an alicyclic group may contain an alicyclic ring bearing one or more bonding or non-bonding alkyl substituents such as -CH ₂ -cyclohexyl. Specific examples of the C _3-20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

A heteroalicyclic group is an alicyclic group as defined above which, in addition to carbon atoms, contains one or more ring heteroatoms which are preferably selected from O, S, N, P and Si. Heteroalicyclic groups preferably contain from one to four heteroatoms, which may be the same or different. Heteroalicyclic groups preferably contain 5 to 20 atoms, more preferably 5 to 14 atoms, even more preferably 5 to 12 atoms.

An aryl group or aryl ring is a monocyclic or polycyclic ring system containing from 5 to 20 carbon atoms, where at least one ring in the system is aromatic, and where each ring in the system contains from three to twelve members. The term "aryl" may be used alone or as part of a broader component such as "aralkyl", "aralkoxy", or "aryloxyalkyl". The aryl group is preferably a "C _6-12 aryl group" and is an aryl group consisting of 6, 7, 8, 9, 10, 11, or 12 carbon atoms and containing fused ring groups such as a monocyclic ring group or a bicyclic ring group etc. Specific examples of the "C _6-10 aryl group" include a phenyl group, a biphenyl group, an indenyl group, an anthracyl group, a naphthyl group, or an azulenyl group, and the like. It should be noted that fused rings such as indan, benzofuran, phthalimide, phenanthridine and tetrahydronaphthalene are also included in the aryl group.

The term "heteroaryl", whether used alone or as part of another term (such as "heteroaralkyl" or "heteroaralkoxy"), refers to groups containing 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms containing 6, 10 , or 14 π-electrons common in the cyclic system, and containing, in addition to carbon atoms, from one to five heteroatoms. The term "heteroatom" refers to nitrogen, oxygen or sulfur and includes any oxidized form of nitrogen or sulfur and any quaternized form of nitrogen. The term "heteroaryl" also includes groups in which a heteroaryl ring is fused to one or more aryl, cycloaliphatic, or heterocyclic rings, wherein the radical or point of attachment is on the heteroaromatic ring. Примеры включают индолил, изоиндолил, бензотиенил, бензофуранил, дибензофуранил, индазолил, бензимидазолил, бензотиазолил, хинолил, изохинолил, циннолинил, фталазинил, хиназолинил, хиноксалинил, 4H–хинолизинил, карбазолил, акридинил, феназинил, фенотиазинил, феноксазинил, тетрагидрохинолинил, тетрагидроизохинолинил и пиридо[ 2,3-b]-1,4-oxazin-3(4Η)-one. Thus, a heteroaryl group may be mono- or polycyclic.

The term "heteroaralkyl" refers to an alkyl group substituted with a heteroaryl, wherein the alkyl and heteroaryl moieties may be independently substituted.

In the context of the invention, the terms "heterocycle", "heterocyclyl", "heterocyclic radical" and "heterocyclic ring" are used interchangeably and refer to a stable 5-7 unit monocyclic or 7-14 unit bicyclic moiety that is saturated, partially unsaturated or aromatic. and contains, in addition to carbon atoms, one or more, preferably one to four, heteroatoms as defined above. The term "nitrogen" when used in connection with a heterocycle ring atom includes a substituted nitrogen.

Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groups include, without limitation, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithian, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazole, oxathiazol, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolysine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, tianaphthalene, thiopyran, triazine, triazole and tritian.

The terms "halide", "halo" and "halogen" are used interchangeably and in the context of the invention mean fluorine atom, chlorine atom, bromine atom, iodine atom and the like, preferably fluorine atom, bromine atom or chlorine atom, more preferably fluorine atom .

The haloalkyl group is preferably "C _1-20 haloalkyl group", more preferably "C _1-15 haloalkyl group", more preferably "C _1-12 haloalkyl group", more preferably "C _1-10 haloalkyl group", even more preferably " C _1-8 haloalkyl group", even more preferably "C _1-6 haloalkyl group" and is C _1-20 alkyl, C _1-15 alkyl, C _1-12 alkyl, C _1-10 alkyl, C _{1- 8} alkyl or C _1-6 alkyl, respectively, substituted with at least one halogen atom, preferably 1, 2 or 3 halogen atoms. The term "haloalkyl" embraces fluorinated or chlorinated groups, including perfluorinated compounds. Specific examples of the "C _1-20 haloalkyl group" include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, and the like.

The term "acyl" as used herein refers to a group of the formula -C(O)R, where R is hydrogen or an (optionally substituted) aliphatic, aryl, or heterocyclic group.

The alkoxy group is preferably "C _1-20 alkoxy", more preferably "C _1-15 alkoxy", more preferably "C _1-12 alkoxy", more preferably "C _1-10 alkoxy" , even more preferably "C _1-8 alkoxy", even more preferably "C _1-6 alkoxy" and is an oxy group that is connected to the above-defined C _1-20 alkyl, C _1-15 alkyl, C _1-12 alkyl, C _1-10 alkyl, C _1-8 alkyl or C _1-6 alkyl, respectively. Specific examples of "C _1-20 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, n-hexadecyloxy-group, n-heptadecyloxy-group, n-octadecyloxy group, n-nanodecyloxy group, n-eicosyloxy group, 1,1-dimethylpropoxy-group, 1,2-dimethylpropoxy-group, 2,2-dimethylpropoxy-group, 2-methylbutoxy-group, 1- ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy-group, 1,1-dimethylbutoxy-group, 1,2-dimethylbutoxy-group, 2,2-dimethylbutoxy-group, 2,3-dimethylbutoxy-group, 1,3-dimethylbutoxy group, 2-ethylbutoxy-group, 2-methylpentyloxy-group, 3-methylpentyloxy-group, etc.

The aryloxy group is preferably a "C _5-20 aryloxy group", more preferably a "C _6-12 aryloxy group", even more preferably a "C _6-10 aryloxy group" and is an oxy group which is connected to the above-defined C _5–20 aryl, C _6–12 aryl, or C _6–10 aryl, respectively.

The alkylthio group is preferably "C _1-20 alkylthio", more preferably "C _1-15 alkylthio", more preferably "C _1-12 alkylthio", more preferably "C _1-10 alkylthio", even more preferably "C _1-8 alkylthio-group", even more preferably "C _1-6 alkylthio-group" and is a thio-group (-S-), which is connected to the above-defined C _1-20 alkyl, C _{1 –15} alkyl, C _1–12 alkyl, C _1–10 alkyl, C _1–8 alkyl, or C _1–6 alkyl, respectively.

The arylthio group is preferably "C _5-20 arylthio-group", more preferably "C _6-12 arylthio-group", even more preferably "C _6-10 arylthio-group", and is a thio-group (–S–), which is connected to C _5-20 aryl, C _6-12 aryl, or C _6-10 aryl as defined above, respectively.

The alkylaryl group is preferably a "C _6-12 aryl-C _1-20 alkyl" group, more preferably a "C _6-12 aryl-C _1-16 alkyl" group, even more preferably a "C _6-12 aryl-C _{1 –6} alkyl" and is an aryl group as defined above linked at any position to an alkyl group as defined above. The alkylaryl group can be attached to the molecule via an alkyl site, and thus, preferably, the alkylaryl group is -CH ₂ -Ph or -CH ₂ CH ₂ -Ph. An alkylaryl group may also be referred to as "aralkyl".

The silyl group is preferably a -Si(R _s ) ₃ group in which each R _s can independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, each R _s is independently an unsubstituted aliphatic, alicyclic, or aryl group. Preferably, each R _s is an alkyl group selected from methyl, ethyl or propyl.

Silyl ether groups are preferably an OSi(R ₆ ) ₃ group in which each R ₆ may independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, each R ₆ may independently represent an unsubstituted aliphatic, alicyclic or aryl group. Preferably, each R ₆ is (optionally substituted) phenyl or (optionally substituted) alkyl selected from methyl, ethyl, propyl, or butyl (such as n-butyl (nBu) or tert-butyl (tBu)). Examples of 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).

The nitrile group (also called the cyano group) refers to the CN group.

The imino group is a -CRNR group, preferably a -CHNR ₇ group, where R ₇ is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₇ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₇ is an alkyl group selected from methyl, ethyl or propyl.

The acetylide group contains a –C≡C–R ₉ triple bond, in which R ₉ may preferably be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. For the purposes of the invention, when R ₉ is alkyl, the triple bond may be present at any position along the alkyl chain. In some embodiments, R ₉ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₉ is methyl, ethyl, propyl or phenyl.

The amino group is preferably -NH ₂ , -NHR ₁₀ or -N(R ₁₀ ) ₂ where R ₁₀ may be aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, silyl, aryl or heteroaryl as defined above. It should be understood that when the amino group is N(R ₁₀ ) ₂ , all R ₁₀ groups may be the same or different. In some embodiments, each R ₁₀ is independently an unsubstituted aliphatic, alicyclic, silyl, or aryl group. Preferably R ₁₀ is methyl, ethyl, propyl, SiMe ₃ or phenyl.

The amido group is preferably —NR ₁₁ C(O)— or —C(O)—NR ₁₁ —, where R ₁₁ may be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₁ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₁ is hydrogen, methyl, ethyl, propyl or phenyl. The amido group may end with a hydrogen atom, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.

The ester group is preferably -OC(O)R ₁₂ - or -C(O)OR ₁₂ - where R ₁₂ may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₂ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₂ is methyl, ethyl, propyl or phenyl. The ester group may end with an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. It should be understood that if R ₁₂ is a hydrogen atom, then the group corresponding to the formula -OC(O)R ₁₂ - or -C(O)OR ₁₂ - will be a carboxyl group.

The sulfoxide is preferably -S(O)R ₁₃ and the sulfonyl group is preferably -S(O) ₂ R ₁₃ where R ₁₃ may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₃ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₃ is methyl, ethyl, propyl or phenyl.

The carboxylate group is preferably —OC(O)R ₁₄ where R ₁₄ may be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₄ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₄ is hydrogen, methyl, ethyl, propyl, butyl (e.g. n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl , tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

The acetamide is preferably MeC(O)N(R ₁₅ ) ₂ where R ₁₅ may be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₅ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₅ is hydrogen, methyl, ethyl, propyl or phenyl.

The phosphinate group is preferably -OP(O)(R ₁₆ ) ₂ or -P(O)(OR ₁₆ )(R ₁₆ ), where each R ₁₆ is independently selected from hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or a heteroaryl group as defined above. In some embodiments, R ₁₆ is an aliphatic, alicyclic, or aryl group that is optionally substituted with an aliphatic, alicyclic, aryl, or C _1-6 alkoxy group. Preferably, R ₁₆ is (optionally substituted) aryl or C _1-20 alkyl, more preferably phenyl, (optionally substituted) C _1-6 alkoxy (preferably methoxy), or unsubstituted C _1-20 alkyl (such as hexyl, octyl, decyl , dodecyl, tetradecyl, hexadecyl, stearyl). The phosphonate group is preferably a -P(O)(OR ₁₆ ) ₂ group in which R ₁₆ is defined above. It should be understood that when either or both of the R ₁₆ groups are hydrogen in the –P(O)(OR ₁₆ ) ₂ group, then the group given as –P(O)(OR ₁₆ ) ₂ will be a phosphonic acid group.

The sulfinate group is preferably -S(O)OR ₁₇ or -OS(O)R ₁₇ where R ₁₇ can be hydrogen, aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₇ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₇ is hydrogen, methyl, ethyl, propyl or phenyl. It should be understood that if R ₁₇ is a hydrogen atom, then the group given as -S(O)OR ₁₇ will be a sulfonic acid group.

The carbonate group is preferably —OC(O)OR ₁₈ where R ₁₈ may be hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl as defined above. In some embodiments, R ₁₈ is a (possibly substituted) aliphatic, alicyclic, or aryl group. Preferably, R ₁₈ is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or t-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl , pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. It should be understood that if R ₁₇ is a hydrogen atom, then the group given as -OC(O)OR ₁₈ will be a carboxyl group.

In the -alkylC(O)OR ₁₉ or -alkylC(O)R ₁₉ group, R ₁₉ may be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In some embodiments, R ₁₉ is an unsubstituted aliphatic, alicyclic, or aryl group. Preferably R ₁₉ is hydrogen, methyl, ethyl, propyl, butyl (e.g. n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

It should be understood that when any of the above groups is present in the Lewis acid G, one or more additional R groups may also be present, if desired, to complete the valency. For example, in connection with the amino group, an additional R group may be present to summarize RNHR ₁₀ where R is hydrogen, an (optionally substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. Preferably R is hydrogen or an aliphatic, alicyclic or aryl group.

As used herein, the term "possibly substituted" means that one or more hydrogen atoms in a possibly substituted component has been replaced with a suitable substituent. Unless otherwise indicated, a "possibly substituted" group may have a suitable substituent at any position suitable for substitution, and if in a given structure more than one position may be substituted by more than one substituent selected from a given group, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably combinations that lead to the formation of stable compounds. The term "stable", as used here, refers to compounds that are chemically tolerant and that can exist for a sufficiently long time at room temperature (i.e., 16–25°C) to be detected, isolated and/or use in chemical synthesis.

Preferred possible substituents for use in the present invention include, without limitation, halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester , sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate, or (optionally substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl groups (e.g., optionally substituted with halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate or acetylide).

It should be understood that although in formula (I) the X and G groups are shown as being associated with a single M ₁ or M ₂ metal center, one or more of the X and G groups may form a bridge between the M ₁ and M ₂ metal centers.

For the purposes of the present invention, the epoxy base is not limiting. Thus, the term "epoxide" refers to any compound containing an epoxy unit (ie, a substituted or unsubstituted oxirane compound). Substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. In some embodiments, the epoxides contain a single oxirane component. In some embodiments, the epoxides contain two or more oxirane components.

Examples of epoxides that can be used in the present invention include, without limitation, cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C ₁₀ H ₁₆ O, or 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, C ₁₁ H ₂₂ O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2- methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, vinylcyclohexene oxide, 3-phenyl-1,2 -epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indenoxide and functionalized 3,5-dioxaepoxides Examples of functionalized 3,5-dioxaepoxides include:

The epoxy unit may be a glycidyl ether, a glycidyl ester, or a glycidyl carbonate. Examples of glycidyl ethers, glycidyl ethers and glycidyl carbonates include:

As noted above, an epoxy base may contain more than one epoxy component, i.e., it may be a component containing a bis-epoxy, tris-epoxy or multi-epoxy compound. Examples of compounds containing more than one epoxy component include bisphenol-A diglycidide ester and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. It should be understood that reactions carried out in the presence of one or more compounds containing more than one epoxy unit can lead to crosslinking of the resulting polymer.

It will be appreciated by those skilled in the art that epoxide can be obtained from "green" or renewable sources. The epoxide can be obtained from a (poly)unsaturated compound, a fatty acid derivative and/or a terpene obtained using standard oxidation chemistry.

The epoxy component may contain an -OH group or a protected -OH group. The -OH groups may be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl group, benzyl, allyl, t-butyl, tetrahydropyranl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzyl (C(O)Ph), dimethoxytrityl (DMT) , methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), triisopropylsilyloxymethyl (TOM) and triisopropylsilyl (TIPS)), ( 4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

The epoxide is preferably at least 98% pure, more preferably >99%.

It should be understood that the term "epoxide" is used to refer to one or more epoxides. In other words, the term "epoxide" refers to a single epoxide or a mixture of two or more different epoxides. For example, the epoxy base 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.

Detailed description

The present invention provides a process for preparing a polyether carbonate by reacting an epoxide with carbon dioxide in the presence of a catalyst of formula (I) and a bimetallic cyanide catalyst (DMC catalyst), as well as high molecular weight polyether carbonates obtained by this method.

Catalysts of formula (I)

The catalyst of formula (I) has the following structure:

Where:

M ₁ and M ₂ 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 ;

R ₁ and R ₂ are independently selected from hydrogen, a halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or from (possibly substituted ) an alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R ₃ is independently selected from (possibly substituted) alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be interrupted by an aryl, heteroaryl, alicyclic, or heteroalicyclic group ;

R ₅ is independently selected from H or a (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl group;

E ₁ means C, E ₂ means O, S or NH, or E ₁ means N, and E ₂ means O;

означает

, а когда E₃, E₄, E₅ или E₆ означают NR₄, O или S,

означает

; R₄ независимо выбран из H или (возможно замещенной) алифатической, гетероалифатической, алициклической, гетероалициклической, арильной, гетероарильной, алкилгетероарильной группы, –алкил–C(O)OR₁₉ или –алкилC≡N или алкиларила;E ₃ , E ₄ , E ₅ and E ₆ are selected from N, NR ₄ , O and S, and when E ₃ , E ₄ , E ₅ or E ₆ is N,

means

, and when E ₃ , E ₄ , E ₅ or E ₆ means NR ₄ , O or S,

means

; R ₄ is independently selected from H or (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkyl-C(O)OR ₁₉ or -alkylC≡N, or alkylaryl;

X is independently selected from OC(O)R ^x , OSO ₂ R ^x , OSOR ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or a (possibly substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, where all X may be the same or different, and where X may form a bridge between M ₁ and M ₂ ;

R _x is independently hydrogen or an (optionally substituted) aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl group; And

the G group is absent or is independently selected from a neutral or an anion donor ligand that is a Lewis acid.

All members of the groups R ₁ and R ₂ may be the same or different, and R ₁ and R ₂ may be the same or different.

Preferably, R ₁ and R ₂ 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. Preferably, all R ₂ members are the same. Preferably, all R ₂ members are the same and are hydrogen.

Both R ₁ members may be the same and may 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, both R ₁ members may be the same and may be selected from hydrogen, halide, sulfoxide, and (optionally substituted) alkyl, heteroaryl, silyl, alkylthio, or alkoxy. Examples of possible representatives of R ₁ (which may be the same) include hydrogen, methyl, tert-butyl, methoxy, ethoxy, alkylthio, trialkylsilyl such as trimethylsilyl or triethylsilyl, bromide, methanesulfonyl or piperidinyl, for example, both R ₁ options can be the same and may be selected from methyl, tert-butyl or trialkylsilyl.

Preferably each R ₂ is hydrogen and each R ₁ is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate and (optionally substituted) alkyl, alkenyl, aryl, heteroaryl, silyl, silyl ether, alkoxy, aryloxy , alkylthio, arylthio, for example, is hydrogen, C _1-6 -alkyl (for example, haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, tBu, iPr, Me, OMe, H, nitro , SO ₂ Me, SiEt ₃ , SiMe ₃ , SMe, halogen or phenyl.

It should be understood that all R ¹ may be the same, and all R ₂ may be the same, but R ₁ may be different from R ₂ .

It should be understood that the R ₃ group may be a disubstituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or heteroalkynyl group, which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or may be a disubstituted aryl or cycloalkyl group which acts as a bridging group between two nitrogen centers in the catalyst of formula (I). Thus, when R ₃ is an alkylene group such as dimethylpropylene, the R ₃ group may have the structure -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -. Thus, the above definitions of alkyl, aryl, cycloalkyl and other groups also refer respectively to the divalent alkylene, arylene, cycloalkylene and other groups described for R ₃ and may optionally be substituted. Examples of options for R ₃ include ethyleneyl, 2,2-fluoropropylenyl, 2,2-dimethylpropylenyl, propylene, butylenyl, phenylenyl, cyclohexylenyl, or biphenylenyl. When R ₃ is cyclohexylenyl, it may be in racemic, RR– or SS– form.

R ₃ can be independently selected from substituted or unsubstituted alkylene and substituted or unsubstituted arylene, preferably substituted or unsubstituted propylene, such as propylene and 2,2-dimethylpropylene, and substituted or unsubstituted phenylenyl or biphenylenyl. Preferably, both R ₃ representatives are the same. Still more preferably, R ₃ is a substituted propylene, such as 2,2-di(alkyl)propylenyl, in particular 2,2-di(methyl)propylenyl.

R ₃ may be independently selected from substituted or unsubstituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene, arylene or cycloalkylene. Preferably, R ₃ is selected from substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene. More preferably, R ₃ is selected from 2,2-dimethylpropylenyl, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -, -CH ₂ C(CH ₂ C ₆ H ₅ ) ₂ CH ₂ - , phenylene, –CH ₂ CH ₂ –, –CH ₂ CH ₂ CH ₂ CH ₂ –, –CH ₂ CH ₂ N(CH ₃ )CH ₂ CH ₂ –, 1,4-cyclohexanediide or –CH ₂ CH ₂ CH( C ₂ H ₅ )–. Even more preferably, R ₃ is selected from 2,2-dimethylpropylenyl, -CH ₂ CH ₂ CH _2- , -CH ₂ CH(CH ₃ )CH ₂ -, -CH ₂ C(CH ₂ C ₆ H ₅ ) ₂ CH ₂ –, –CH ₂ CH ₂ CH (C ₂ H ₅ )–, –CH ₂ CH ₂ CH ₂ CH ₂ –. Even more preferably R ₃ is selected from 2,2-dimethylpropylene, -CH ₂ C(CH ₂ C ₆ H ₅ ) ₂ CH ₂ -, CH ₂ CH(CH ₃ )CH ₂ and -CH ₂ C(C ₂ H ₅ ) ₂ CH ₂ –.

Most preferably R ₃ is a substituted propylene such as 2,2-di(alkyl)propylenyl, more preferably 2,2-dimethylpropylenyl _.

означает

, а если какой–то из E₃, E₄, E₅ или E₆ является NR₄, O или S, то

означает

. Предпочтительно, все E₃, E₄, E₅ и E₆ независимо выбраны из NR₄, O и S.As stated above, E ₃ , E ₄ , E ₅ , and E ₆ are independently selected from N, NR ₄ , O, and S. The skilled artisan will appreciate that if any of E ₃ , E ₄ , E ₅ , or E ₆ is N, then

means

, and if any of E ₃ , E ₄ , E ₅ or E ₆ is NR ₄ , O or S, then

means

. Preferably, E ₃ , E ₄ , E ₅ and E ₆ are all independently selected from NR ₄ , O and S.

Preferably, each R ₄ is independently selected from hydrogen and (possibly substituted) alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(O)OR ₁₉ or -alkylC≡N. All R ₄ may be the same or different. Preferably, R ₄ is selected from hydrogen and (possibly substituted) alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl. Examples of options for R ₄ include H, Me, Et, Bn, iPr, tBu or Ph and -CH ₂ -(pyridine). Preferably each R ₄ is hydrogen or alkyl.

Preferably, each R ₅ is independently selected from hydrogen and an (optionally substituted) aliphatic or aryl group. More preferably, each R ₅ is independently selected from hydrogen and (optionally substituted) alkyl or aryl. Even more preferably, all R ₅ are the same and are selected from hydrogen and (possibly substituted) alkyl or aryl. Examples of R ₅ groups include hydrogen, methyl, ethyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. Even more preferably, all R ₅ are hydrogen.

Preferably both E ₁ are C and both E ₂ are the same and are selected from O, S or NH. Even more preferably, both E ₁ are C and both E ₂ are O.

The person skilled in the art will appreciate that the macrocyclic ligand of the catalyst of formula (I) may be symmetrical or may be asymmetric.

When the macrocyclic ligand is symmetrical, it should be understood that all members of E ₃ , E ₄ , E ₅ and E ₆ must be the same. For example, all representatives of E ₃ , E ₄ , E ₅ and E ₆ can mean NR ₄ (and all R ₄ can be the same). It should be understood that E ₃ , E ₄ , E ₅ and E ₆ may be the same and may be NH. In other words, the catalyst of formula (I) may have the following structure:

It should be understood that when the macrocyclic ligand is symmetrical, all R ₁ members may be the same, all R ₂ members may be the same, all R ₃ members may be the same, all R ₅ members may be the same, all E ₁ members may be the same, and all members of E ₂ may be the same (although R ₁ , R ₂ , R ₃ and R ₅ need not be identical to each other), and E ₃ , E ₄ , E ₅ and E ₆ are the same.

For example, each of R ₂ and R ₅ may be hydrogen, each of E ₃ , E ₄ , E ₅ and E ₆ is NR ₄ and each R ₄ is hydrogen or alkyl, each of R ₃ may be substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene, each of R ¹ may be selected from hydrogen, halogen, sulfoxide or substituted or unsubstituted alkyl, heteroaryl, silyl, alkylthio or alkoxy, both E ₁ may be C, and both E ₂ can be O.

It should be understood that in the case of an asymmetric ligand in the catalyst of formula (I), at least one of the members of the group R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , E ₁ or E ₂ may differ from other members of the same group, or at least one of the members of E ₃ , E ₄ , E ₅ and E ₆ is different from the other members of E ₃ , E ₄ , E ₅ and E ₆ . For example, all members of R ₃ may be different, or all members of R ₁ may be different.

It should also be understood that E ₃ and E ₅ may be the same, and E ₄ and E ₆ may be the same, but E ₃ and E ₅ are different from E ₄ and E ₆ . It should also be understood that E ₃ and E ₄ may be the same, and E ₅ and E ₆ may be the same, but E ₃ and E ₄ are different from E ₅ and E ₆ . Alternatively, one representative of E ₃ , E ₄ , E ₅ and E ₆ is different from the rest of the representatives of E ₃ , E ₄ , E ₅ and E ₆ (and the other three representatives are the same).

For example, E ₃ , E ₄ and E ₅ may be -NR ₄ where R ₄ is H, and R ₆ may be NR ₄ where R ₄ is alkyl. In addition, E ₃ and E ₅ may be NR ₄ where R ₄ is H, and E ₄ and E ₆ may be NR ₄ where R ₄ is alkyl, or E ₃ and E ₄ may be NR ₄ , where R ₄ means H, and E ₅ and E ₆ may represent NR ₄ where R ₄ means alkyl. Thus, it should be understood that each E ₃ , E ₄ , E ₅ and E ₆ preferably represent NR ₄ in which at least one of the representatives of R ₄ is different from the remaining representatives of R ₄ .

For the catalysts of formula (I) (symmetrical and asymmetric), each X is independently selected from OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , phosphinate, halide, nitro, hydroxyl, carbonate, amino, nitrate, amido and (possibly substituted) aliphatic, heteroaliphatic (eg silyl), alicyclic, heteroalicyclic, aryl or heteroaryl group. Preferably, each X is independently OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (eg branched alkyl), heteroalkyl (eg silyl), aryl or heteroaryl. Even more preferably, each X is independently OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate, or OSO ₂ R ^x . Preferred optional substituents when X is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group include halogen, hydroxyl, nitro, cyano, amino, or a substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. All X's may be the same or different, preferably all X's are the same. It should also be understood that X may form a bridge between two metal centers.

R ^x is independently hydrogen, or an (optionally substituted) aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl group. Preferably R ^x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Preferred optional substituents for ^Rx include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio, or a substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group (eg, optionally substituted alkyl, aryl, or heteroaryl).

Examples of options for X include OAc, OC(O)CF ₃ , halogen, OSO(CH ₃ ) ₂ , Et, Me, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr) ₂ or N( SiMe ₃ ) _2, OPh, OBn, salicylate, dioctylphosphinate, etc.

Preferably, all X are the same and are selected from OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate, or OSO ₂ R ^x , where R ^x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl. More preferably, all X are the same and represent OC(O)R ^x , OR ^x , halide, alkyl, aryl, heteroaryl, phosphinate or OSO ₂ R ^x . Even more preferably, all X are the same and mean OC(O)R ^x . Even more preferably, all X are the same and are selected from OAc, O ₂ CCF ₃ or O ₂ C(CH ₂ ) ₃ Cy. Most preferably, all X's are the same and are OAc.

Preferably, all R ^x are the same and are selected from (possibly substituted) alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. More preferably, all R ^x are the same and represent (possibly substituted) alkyl, alkenyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Even more preferably, all R ^x are the same and represent alkyl, alkenyl, heteroalkyl, optionally substituted, or cycloalkyl. Even more preferably, R ^x is (possibly substituted) alkyl, heteroalkyl or cycloalkyl. Most preferably R ^x is alkyl, optionally substituted.

It should be understood that preferred definitions for X and preferred definitions for R ^x can be combined. For example, each X can independently represent OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (e.g., branched alkyl), heteroalkyl, (e.g., silyl), aryl, or heteroaryl, for example, each can independently be OC(O)R ^x , OR ^x , halide, carbonate, amino , nitro, alkyl, aryl, heteroaryl, phosphinate, or OSO ₂ R ^x , and R ^x may be (possibly substituted) alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl.

As detailed above, M ₁ and M ₂ are independently selected from any of the following: 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 .

Preferably, at least one of M ₁ and M ₂ is selected from Zn(II), Cr(III)-X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II) and Fe(III)-X, more preferably at least one M ₁ and M ₂ is selected from Mg(II), Zn(II) and Ni(II), e.g. at least one of M ₁ and M ₂ is Ni (II).

It should be understood that M ₁ and M ₂ may be the same or different. For example, M ₁ and/or M ₂ may be selected from Zn(II), Cr(III)–X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II) and Fe(III)-X, more preferably M ₁ and/or M ₂ is selected from Mg(II), Zn(II) and Ni(II), eg M ₁ and/or M ₂ are Ni(II).

Examples of combinations of M ₁ and M ₂ 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).

It should be understood that when one of M ₁ or M ₂ is Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Al(III), Ti(III) or V (III), the catalyst of formula (I) will contain an additional X group coordinated to a metal center, the X group being as defined above. It should also be understood that when one of M ₁ or M ₂ is Ge(IV) or Ti(IV), the catalyst of formula (III) will contain two additional X groups coordinated to the metal center, the X group being as defined above. . In some embodiments, when one of M ₁ or M ₂ is Ge(IV)-(X) ₂ or Ti(IV)-(X) ₂ , both G groups may be absent.

If the G group is present, it is a group capable of donating one pair of electrons (ie, a Lewis acid). In some embodiments, G is a nitric Lewis acid. Each G group can be neutral or negatively charged. If G is negatively charged, then one or more positive counterions are required to balance the charge of the complex. Suitable positive counterions include group 1 metal ions (Na ⁺ , K ⁺ etc.), group 2 metal ions (Mg ²⁺ , Ca ²⁺ etc.), positively charged imidazolium ions (possibly substituted) heteroaryl, heteroaliphatic or heteroalicyclic group, ammonium ions (i.e., N(R ¹² ) ₄ ⁺ ), iminium ions (i.e., (R ¹² ) ₂ C=N(R ¹² ) ₂ ⁺ , such as ions bis(triphenylphosphine)iminium) or phosphonium ions (P(R ¹² ) ₄ ⁺ ), each R ¹² being independently selected from hydrogen or an (optionally substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. Examples of counterions include [H-B] ⁺ where B is selected from triethylamine, 1,8-biazabicyclo[5.4.0]undec-7-ene and 7-methyl-1,5,7-triazabicyclo[4,4, 0]Dec–5–ene.

The G groups are preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, halide, hydroxide, hydride, carboxylate, and water. More preferably, the G group is independently selected from water, alcohol (eg methanol), substituted or unsubstituted heteroaryl (imidazole, methylimidazole (eg N-methylimidazole), pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc.), simple ether (dimethyl ether, diethyl ether, cyclic ethers, etc.), thioether, carbene, phosphine, phosphine oxide, substituted or unsubstituted heteroalicyclic compound (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc.), amine, alkylamine, trimethylamine , triethylamine, etc., acetonitrile, ester (ethyl acetate, etc.), acetamide (dimethylacetamide, etc.), sulfoxide (dimethyl sulfoxide, etc.), carboxylate, hydroxide, hydride, halide, nitrate, sulfonate, etc. In some embodiments, one or both G groups are independently selected from a possibly substituted heteroaryl, a possibly substituted heteroaliphatic, a possibly substituted heteroalicyclic, halide, hydroxide, hydride, ether, thioether, carbene, phosphine, phosphine oxide, amine, alkylamine, acetonitrile, ester, acetamide, sulfoxide, carboxylate, nitrate or sulfonate. In some embodiments, G may be a halide, hydroxide, hydride, water, heteroaryl, heteroalicyclic, or carboxylate group, which is optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro, or nitrile. In preferred embodiments, the G group is independently selected from halide, water, heteroaryl optionally substituted with alkyl (eg, methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (preferably methoxy), halo, hydroxyl, nitro, or nitrile. In some embodiments, one or both of the G groups are negatively charged (eg, halide). In the following embodiments, one or both of the G groups are heteroaryl, optionally substituted. Examples of G groups include chloride, bromide, pyridine, methylimidazole (eg N-methylimidazole) and dimethylaminopyridine (eg 4-methylaminopyridine).

It should be understood that when a G group is present, it may be associated with a single metal center M, as shown in formula (I), or a G group may be associated with both metal centers and form a bridge between the two metal centers, as shown in the formula below (IIa):

where R₁, R₂, R₃, R₄, R₅, M₁, M₂, G, X, E₁ and E₂ are as defined for formula (I) and formula (II).

One skilled in the art will appreciate that, in the solid state, the catalysts of the first aspect (i.e., the catalysts of formulas (I), (II), or any subset thereof) may be associated with solvent molecules such as water or an alcohol (e.g., methanol or ethanol). It should be understood that the solvent molecules may be present in a ratio of less than 1:1 to the catalyst molecules (i.e., in a ratio of 0.2:1, 0.25:1, 0.5:1), in a ratio of 1:1 to catalyst molecules according to the first aspect or in a ratio greater than 1:1 to the catalyst molecules according to the first aspect.

The person skilled in the art will appreciate that in the solid state the catalysts of the first aspect may form aggregates. For example, the catalyst of the first aspect may be a dimer, trimer, tetramer, pentamer, or higher aggregate.

Typical catalysts of formula (I) are as follows:

where M ₁ , M ₂ , G and X are as defined above for formula (I), and it should be understood that one or both of the G groups may be absent.

For example, at least one of M ₁ and M ₂ can 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 M ₁ and M ₂ can be selected from Mg(II), Zn(II) and Ni(II), for example, at least one of M ₁ and M ₂ may be Ni(II).

As stated above, M ₁ and M ₂ may be the same or different. For example, M ₁ and/or M ₂ can be selected from Zn(II), Cr(III)–X, Co(II), Mn(II), Mg(II), Ni(II), Fe(II) and Fe(III)-X, preferably M ₁ and/or M ₂ is selected from Mg(II), Zn(II) and Ni(II), eg M ₁ and/or M ₂ is Ni(II). Examples of combinations of M ₁ and M ₂ include Mg(II)/Mg(II), Zn(II)/Zn(II), Ni(II)/Ni(II), Mg(II)/Zn(II), Mg( II)/Ni(II), Zn(II)/Ni(II).

For example, each X can independently represent OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (eg, branched alkyl), heteroalkyl (eg, silyl), aryl, or heteroaryl, for example, each can independently be OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO ₂ R ^x . For example, R ^x can be alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or alkylaryl.

For example, if any G group is present, it may be independently selected from halide, water, heteroaryl optionally substituted with alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile, for example one or both of G (if present) may be chloride, bromide, pyridine, methylimidazole (eg N-methylimidazole) and dimethylaminopyridine (eg 4-methylaminopyridine).

One skilled in the art will appreciate that the above definitions may be combined. For example, in the above catalysts, M ₁ and M ₂ may be the same or different and 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 can independently be OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate, amino , nitro, amido, alkyl (eg, branched alkyl), heteroalkyl (eg, silyl), aryl, or heteroaryl, for example, each can independently represent OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl , aryl, heteroaryl, phosphinate or OSO ₂ R ^x ; R ^x may be alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl; The G group may be absent or, if present, it may be independently selected from halide, water, heteroaryl, optionally substituted with alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl , nitro or nitrile.

Thus, the specialist should understand that the above examples of catalysts of formula (I) cover, but are not limited to, the following catalysts:

[L ¹ Ni ₂ (OAc) ₂ ], [L ¹ Mg ₂ (OAc) ₂ ], [L ¹ Zn ₂ (OAc) ₂ ], [L ¹ MgZn(OAc) ₂ ], [L ¹ MgNi(OAc) ₂ ],

[L ¹ Ni ₂ (CO ₂ CF ₃ ) ₂ ], [L ¹ Mg ₂ CO ₂ CF ₃ ) ₂ ], [L ¹ Zn ₂ (CO ₂ CF ₃ ) ₂ ], [L ¹ MgZn(CO ₂ CF ₃ ) ₂ ], [L ¹ MgNi(CO ₂ CF ₃ ) ₂ ],

[L ¹ Ni ₂ (CO ₂ ^t Bu) ₂ ], [L ¹ Mg ₂ (CO ₂ ^t Bu) ₂ ], [L ¹ Zn ₂ (CO ₂ ^t Bu) ₂ ], [L ¹ MgZn (CO ₂ ^t Bu) ₂ ], [L ¹ MgNi(CO ₂ ^t Bu) ₂ ], [L ¹ Ni ₂ (OPh) ₂ ], [L ¹ Mg ₂ (OPh) ₂ ], [L ¹ Zn ₂ (OPh) ₂ ] , [L ¹ MgZn(OPh) ₂ ], [L ¹ MgNi(OPh) ₂ ],

[L ¹ Ni ₂ (Ph) ₂ ], [L ¹ Mg ₂ (Ph) ₂ ], [L ¹ Zn ₂ (Ph) ₂ ], [L ¹ MgZn(Ph) ₂ ], [L ¹ MgNi(Ph) ₂ ],

[L ¹ Ni ₂ (O ⁱ Pr) ₂ ], [L ¹ Mg ₂ (O ⁱ Pr) ₂ ], [L ¹ Zn ₂ (O ⁱ Pr) ₂ ], [L ¹ MgZn(O ⁱ Pr) ₂ ] , [L ¹ MgNi(O ⁱ Pr) ₂ ],

[L ¹ Ni ₂ (C ₆ F ₅ ) ₂ ], [L ¹ Mg ₂ (C ₆ F ₅ ) ₂ ], [L ¹ Zn ₂ (C ₆ F ₅ ) ₂ ], [L ¹ MgZn(C ₆ F ₅ ) ₂ ], [L ¹ MgNi(C ₆ F ₅ ) ₂ ],

[L ¹ Ni ₂ Cl ₂ ], [L ¹ Mg ₂ Cl ₂ ], [L ¹ Zn ₂ Cl ₂ ], [L ¹ MgZnCl ₂ ], [L ¹ MgNiCl ₂ ],

[L ¹ Ni ₂ Br ₂ ], [L ¹ Mg ₂ Br ₂ ], [L ¹ Zn ₂ Br ₂ ], [L ¹ MgZnBr ₂ ], [L ¹ MgNiBr ₂ ],

[L ¹ Ni ₂ I ₂ ], [L ¹ Mg ₂ I ₂ ], [L ¹ Zn ₂ I ₂ ], [L ¹ MgZnI ₂ ], [L ¹ MgNiI ₂ ],

[L ¹ Ni ₂ (OC(O)(CH ₂ ) ₄ CH ₃ ) ₂ ], [L ¹ Mg ₂ (OC(O)(CH ₂ ) ₄ CH ₃ ) ₂ ], [L ¹ Zn ₂ (OC( O)(CH ₂ ) ₄ CH ₃ ) ₂ ], [L ¹ MgZn(OC(O)(CH ₂ ) ₄ CH ₃ ) ₂ ], [L ¹ MgNi(OC(O)(CH ₂ ) ₄ CH ₃ ) ₂ ],

[L ¹ Ni ₂ (OC(O)(CH ₂ ) ₆ CH ₃ ) ₂ ], [L ¹ Mg ₂ (OC(O)(CH ₂ ) ₆ CH ₃ ) ₂ ], [L ¹ Zn ₂ (OC( O)(CH ₂ ) ₆ CH ₃ ) ₂ ], [L ¹ MgZn(OC(O)(CH ₂ ) ₆ CH ₃ ) ₂ ], [L ¹ MgNi(OC(O)(CH ₂ ) ₆ CH ₃ ) ₂ ],

[L ¹ Ni ₂ (OC(O)(CH ₂ ) ₁₀ CH ₃ ) ₂ ], [L ¹ Mg ₂ (OC(O)(CH ₂ ) ₁₀ CH ₃ ) ₂ ], [L ¹ Zn ₂ (OC( O)(CH ₂ ) ₁₀ CH ₃ ) ₂ ], [L ¹ MgZn(OC(O)(CH ₂ ) ₁₀ CH ₃ ) ₂ ], [L ¹ MgNi(OC(O)(CH ₂ ) ₁₀ CH ₃ ) ₂ ],

[L ¹ Ni ₂ (OC(O)C ₆ F ₅ ) ₂ ], [L ¹ Mg ₂ (OC(O)C ₆ F ₅ ) ₂ ], [L ¹ Zn ₂ (OC(O)C ₆ F ₅ ) ₂ ], [L ¹ MgZn(OC(O)C ₆ F ₅ ) ₂ ], [L ¹ MgNi(OC(O)C ₆ F ₅ ) ₂ ],

[L ¹ Ni ₂ Cl ₂ (methylimidazole)], [L ¹ Mg ₂ Cl ₂ (methylimidazole)], [L ¹ Zn ₂ Cl ₂ (methylimidazole)], [L ¹ MgZnCl ₂ (methylimidazole)], [L ¹ MgNiCl ₂ (methylimidazole)],

[L ¹ Ni ₂ Cl ₂ (pyridine)], [L ¹ Mg ₂ Cl ₂ (pyridine)], [L ¹ Zn ₂ Cl ₂ (pyridine)], [L ¹ MgZnCl ₂ (pyridine)], [L ¹ MgNiCl ₂ (pyridine)],

[L ¹ Ni ₂ Cl ₂ (dimethylaminopyridine)], [L ¹ Mg ₂ Cl ₂ (dimethylaminopyridine)], [L ¹ Zn ₂ Cl ₂ (dimethylaminopyridine)], [L ¹ MgZnCl ₂ (dimethylaminopyridine)], L ¹ MgNiCl ₂ (dimethylaminopyridine)], [L ¹ Ni ₂ Br ₂ (dimethylaminopyridine)], [L ¹ Mg ₂ Br ₂ (dimethylaminopyridine)], [L ¹ Zn ₂ Br ₂ (dimethylaminopyridine)], [L ¹ MgZnBr ₂ (dimethylaminopyridine)] , [L ¹ MgNiBr ₂ (dimethylaminopyridine)],

[L ¹ Ni ₂ (bis(4-methoxy)phenylphosphinate) ₂ ], [L ¹ Mg ₂ (bis(4-methoxy)phenylphosphinate) ₂ ], [L ¹ Zn ₂ (bis(4-methoxy)phenylphosphinate) ₂ ] , [L ¹ MgZn(bis(4-methoxy)phenylphosphinate) ₂ ], [L ¹ MgNi(bis(4-methoxy)phenylphosphinate) ₂ ],

[L ¹ Ni ₂ (adamantyl carbonate) ₂ ], [L ¹ Mg ₂ (adamantyl carbonate) ₂ ], [L ¹ Zn ₂ (adamantyl carbonate) ₂ ], [L ¹ MgZn (adamantyl carbonate) ₂ ], [L ¹ MgNi (adamantyl carbonate) ₂ ],

[L ¹ Ni ₂ (diphenylphosphinate) ₂ ], [L ¹ Mg ₂ (diphenylphosphinate) ₂ ], [L ¹ Zn ₂ (diphenylphosphinate) ₂ ], [L ¹ MgZn (diphenylphosphinate) ₂ ], [L ¹ MgNi (diphenylphosphinate) ₂ ],

[L ² Ni ₂ (OAc) ₂ ], [L ² Mg ₂ (OAc) ₂ ], [L ² Zn ₂ (OAc) ₂ ], [L ² MgZn(OAc) ₂ ], [L ² MgNi(OAc) ₂ ],

[L ³ Ni ₂ (OAc) ₂ ], [L ³ Mg ₂ (OAc) ₂ ], [L ³ Zn ₂ (OAc) ₂ ], [L ³ MgZn(OAc) ₂ ], [L ³ MgNi(OAc) ₂ ],

[L ⁴ Ni ₂ (OAc) ₂ ], [L ⁴ Mg ₂ (OAc) ₂ ], [L ⁴ Zn ₂ (OAc) ₂ ], [L ⁴ MgZn(OAc) ₂ ], [L ⁴ MgNi(OAc) ₂ ],

[L ⁵ Ni ₂ (OAc) ₂ ], [L ⁵ Mg ₂ (OAc) ₂ ], [L ⁵ Zn ₂ (OAc) ₂ ], [L ⁵ MgZn(OAc) ₂ ], [L ⁵ MgNi(OAc) ₂ ],

[L ⁶ Ni ₂ (OAc) ₂ ], [L ⁶ Mg ₂ (OAc) ₂ ], [L ⁶ Zn ₂ (OAc) ₂ ], [L ⁶ MgZn(OAc) ₂ ], [L ⁶ MgNi(OAc) ₂ ],

[L ⁷ Ni ₂ (OAc) ₂ ], [L ⁷ Mg ₂ (OAc) ₂ ], [L ⁷ Zn ₂ (OAc) ₂ ], [L ⁷ MgZn(OAc) ₂ ], [L ⁷ MgNi(OAc) ₂ ],

[L ⁸ Ni ₂ (OAc) ₂ ], [L ⁸ Mg ₂ (OAc) ₂ ], [L ⁸ Zn ₂ (OAc) ₂ ], [L ⁸ MgZn(OAc) ₂ ], [L ⁸ MgNi(OAc) ₂ ],

[L ⁹ Ni ₂ (OAc) ₂ ], [L ⁹ Mg ₂ (OAc) ₂ ], [L ⁹ Zn ₂ (OAc) ₂ ], [L ⁹ MgZn(OAc) ₂ ], [L ⁹ MgNi(OAc) ₂ ],

[L ¹⁰ Ni ₂ (OAc) ₂ ], [L ¹⁰ Mg ₂ (OAc) ₂ ], [L ¹⁰ Zn ₂ (OAc) ₂ ], [L ¹⁰ MgZn(OAc) ₂ ], [L ¹⁰ MgNi(OAc) ₂ ],

[L ¹¹ Ni ₂ (OAc) ₂ ], [L ¹¹ Mg ₂ (OAc) ₂ ], [L ¹¹ Zn ₂ (OAc) ₂ ], [L ¹¹ MgZn(OAc) ₂ ], [L ¹¹ MgNi(OAc) ₂ ],

[L ¹² Ni ₂ (OAc) ₂ ], [L ¹² Mg ₂ (OAc) ₂ ], [L ¹² Zn ₂ (OAc) ₂ ], [L ¹² MgZn(OAc) ₂ ], [L ¹² MgNi(OAc) ₂ ],

[L ¹³ Ni ₂ (OAc) ₂ ], [L ¹³ Mg ₂ (OAc) ₂ ], [L ¹³ Zn ₂ (OAc) ₂ ], [L ¹³ MgZn(OAc) ₂ ], [L ¹³ MgNi(OAc) ₂ ],

[L ¹⁴ Ni ₂ (OAc) ₂ ], [L ¹⁴ Mg ₂ (OAc) ₂ ], [L ¹⁴ Zn ₂ (OAc) ₂ ], [L ¹⁴ MgZn(OAc) ₂ ], [L ¹⁴ MgNi(OAc) ₂ ],

[L ¹⁵ Ni ₂ (OAc) ₂ ], [L ¹⁵ Mg ₂ (OAc) ₂ ], [L ¹⁵ Zn ₂ (OAc) ₂ ], [L ¹⁵ MgZn(OAc) ₂ ], [L ¹⁵ MgNi(OAc) ₂ ],

[L ¹⁶ Ni ₂ (OAc) ₂ ], [L ¹⁶ Mg ₂ (OAc) ₂ ], [L ¹⁶ Zn ₂ (OAc) ₂ ], [L ¹⁶ MgZn(OAc) ₂ ], [L ¹⁶ MgNi(OAc) ₂ ],

[L ¹⁷ Ni ₂ (OAc) ₂ ], [L ¹⁷ Mg ₂ (OAc) ₂ ], [L ¹⁷ Zn ₂ (OAc) ₂ ], [L ¹⁷ MgZn(OAc) ₂ ], [L ¹⁷ MgNi(OAc) ₂ ],

[L ¹⁸ Ni ₂ (OAc) ₂ ], [L ¹⁸ Mg ₂ (OAc) ₂ ], [L ¹⁸ Zn ₂ (OAc) ₂ ], [L ¹⁸ MgZn(OAc) ₂ ], [L ¹⁸ MgNi(OAc) ₂ ],

[L ¹⁹ Ni ₂ (OAc) ₂ ], [L ¹⁹ Mg ₂ (OAc) ₂ ], [L ¹⁹ Zn ₂ (OAc) ₂ ], [L ¹⁹ MgZn(OAc) ₂ ], [L ¹⁹ MgNi(OAc) ₂ ],

[L ²⁰ Ni ₂ (OAc) ₂ ], [L ²⁰ Mg ₂ (OAc) ₂ ], [L ²⁰ Zn ₂ (OAc) ₂ ], [L ²⁰ MgZn(OAc) ₂ ], [L ²⁰ MgNi(OAc) ₂ ],

[L ²¹ Ni ₂ (OAc) ₂ ], [L ²¹ Mg ₂ (OAc) ₂ ], [L ²¹ Zn ₂ (OAc) ₂ ], [L ²¹ MgZn(OAc) ₂ ], [L ²¹ MgNi(OAc) ₂ ],

[L ²² Ni ₂ (OAc) ₂ ], [L ²² Mg ₂ (OAc) ₂ ], [L ²² Zn ₂ (OAc) ₂ ], [L ²² MgZn(OAc) ₂ ], [L ²² MgNi(OAc) ₂ ],

[L ²³ Ni ₂ (OAc) ₂ ], [L ²³ Mg ₂ (OAc) ₂ ], [L ²³ Zn ₂ (OAc) ₂ ], [L ²³ MgZn(OAc) ₂ ], [L ²³ MgNi(OAc) ₂ ],

[L ¹ Co ₂ (OAc) ₃ ], [L ¹ ZnCoI ₂ ], [L ¹ ZnFe(OAc) ₂ ], [L ¹ ZnFeBr ₂ ], [L ¹ ZnFeCl ₂ ], [L ¹ ZnFeI ₂ ], [ L ¹ ZnCo(OAc) ₂ ], [L ¹ ZnCoCl ₂ ], [L ¹ ZnCoBr ₂ ], [L ¹ Fe ₂ Cl ₄ ], [L ¹ Co ₂ Cl ₂ (methylimidazole)], [L ¹ Co ₂ Cl ₂ (pyridine)], [L ¹ Co ₂ Cl ₃ ] ^– [H–DBU] ⁺ and [L ¹ Co ₂ Cl ₃ ] ^– [H–MTBD] ⁺ .

One skilled in the art will appreciate that in any of the above complexes, any ligand designated "L" may be replaced by another ligand designated a different "L". For example, in complexes containing a ligand designated L ¹ , that ligand may be replaced by any of the ligands designated L ² - L ²² .

Bimetallic cyanide catalyst (DMC catalyst)

DMC catalysts are complex compounds that contain at least two metal centers and cyanide ligands. The DMC catalyst may further contain at least one of the following: one or more complexing agents, water, metal salt, and/or acid (eg, in non-stoichiometric amounts).

The first two of at least two metal centers can be represented as M' and M".

M' can be selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II) , Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II) and Cr(III), preferably M' is selected from Zn(II), Fe(II), Co(II) and Ni(II), even more preferably M' is Zn(II).

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), preferably M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr (III), Ir(III) and Ni(II), more preferably M" is selected from Co(II) and Co(III).

It should be understood that the above preferred definitions for M' and M" can be combined. For example, M' can be preferably selected from Zn(II), Fe(II), Co(II) and Ni(II), and M" is be preferably selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). For example, M' may preferably be Zn(II), and M" may preferably be selected from Co(II) and Co(III).

If an additional metal center or centers is present, this additional metal center may also be selected from the definitions for M' or M".

Examples of DMC catalysts suitable for use in the process of the invention include those described in US 3427256, US 5536883, US 6291388, US 6486361, US 6608231, US 7008900, US 5482908, US 5780584, US 5783513, US 5158922 , US 7811958, US 6835687, US 6699961, US 6716788, US 6977236, US 7968754, US 7034103, US 4826953, US 4500704, US 7977501, US 9315622, EP–A–1568414, EP–A–1529566 и WO 2015/022290 , the full content of which is introduced by reference.

DMC catalysts suitable for the invention can be prepared by treating a solution (such as an aqueous solution) of a metal salt with a solution (such as an aqueous solution) of a metal cyanide salt in the presence of one or more complexing agents, water and/or acid. Suitable metal salts include compounds 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), and M' is preferably selected from Zn(II), Fe(II), Co(II) and Ni(II), even more preferably M' means Zn(II). X' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X' is halide. p is an integer greater than or equal to 1, and the charge of the anion multiplied by p corresponds to the valency of M'. Examples of suitable metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel formate( II), nickel(II) nitrate and mixtures thereof.

Suitable metal cyanide salts include compounds of formula (Y)q[M"(CN) _b (A) _c ], 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), preferably M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), more preferably M" is selected from Co(II) and Co(III). Y is a proton (H ⁺ ), or an alkali metal ion, or an alkaline earth metal ion (such as K ⁺ ), 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, preferably b is 4 or 6. c may be zero or an integer greater than or equal to 1. The sum of the charges of Y, CN, and A ions times q, b, and c, respectively ( e.g., Y x q+CN x b+A xc), corresponds to the valence M". Examples of suitable metal cyanide salts include potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), hexacyanocobaltate (III) lithium and mixtures thereof.

Suitable complexing agents include polyethers, polyether carbonates, polycarbonates, polytetramethylene etherdiols, ketones, esters, amides, alcohols, ureas, and the like, and combinations thereof. Examples of complexing agents include propylene glycol, polypropylene glycol (PPG), methoxy and ethoxyethylene glycol, dimethoxyethane, t-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, etc., as well as their combinations. It should be understood that the alcohol may be saturated or may contain an unsaturated component (eg, a double or triple bond). Several (ie, more than one different type) complexing agents may be present in the DMC catalysts used in the present invention.

The DMC catalyst may contain a complexing agent which is a polyether, polyether carbonate or polycarbonate.

Polyethers suitable for use in the DMC catalyst of the present invention include polyesters obtained by ring-opening polymerization of cyclic ethers and include epoxy polymers, oxetane polymers, tetrahydrofuran polymers, and the like. To obtain polyethers, you can use any method of catalysis. Polyethers may have any desired end group, including, for example, hydroxyl, amine, ester, ether, or the like. The polyethers preferred for use in the DMC catalyst of the present invention are polyether polyols containing 2 to 8 hydroxyl groups. It is also preferred that the polyethers for use in the DMC catalyst of the present invention have a molecular weight of from about 1000 Daltons to about 10000 Daltons, more preferably from about 1000 Daltons to about 5000 Daltons. Suitable polyether polyols for use in the DMC catalyst of the present invention include PPG polyols, ethylene oxide terminated PPG polyols, mixed ethylene oxide-propylene oxide polyols, butylene oxide polymers, copolymers of butylene oxide with ethylene oxide and/or propylene oxide, polytetramethylene ether glycols, etc. P. Preferred polyethers include PPGs such as PPG polyols, in particular diols and triols, said PPGs having a molecular weight of from about 250 Daltons to about 8000 Daltons, more preferably from about 400 Daltons to about 4000 Daltons.

Polyether carbonates suitable for use in the DMC catalyst of the present invention can be prepared by the catalytic reaction of alkylene oxides and carbon dioxide in the presence of a suitable starter or initiator compound. Polyether carbonates used as a complexing agent can also be obtained by other methods known to a person skilled in the art, for example, by partial interesterification of polycarbonate polyols with di- or trifunctional hydroxy compounds. The polyether carbonates used as complexing agents in the DMC catalyst of the present invention preferably have an average hydroxyl number of 1 to 6, more preferably 2 to 3, most preferably 2.

Polycarbonates suitable for use in the DMC catalyst of the present invention can be prepared by polycondensation of difunctional hydroxy compounds (usually bis-hydroxy compounds such as alkanediols or bisphenols) with carboxylic acid derivatives such as, for example, phosgene or bis[chlorocarbonyloxy ]–compounds, carboxylic acid diesters (such as diphenyl carbonate or dimethyl carbonate) or urea. Methods for producing polycarbonates are widely known and are described in detail, for example, in "Houben-Weyl, Methoden der organischen Chemie", Volume E20, Makromolekulare Stoffe, ^4th Edition, 1987, p. 1443–1457, "Ullmann's Encyclopaedia of Industrial Chemistry", Volume A21, ^5th Edition, 1992, p. 207–215 and in "Encyclopaedia of Polymer Science and Engineering", Volume 11, ^2nd Edition, 1988, p. 648–718. Aliphatic polycarbonate diols having a molecular weight of from about 500 Daltons to 5000 Daltons, most preferably from 1000 Daltons to 3000 Daltons, are particularly preferred for use in the DMC catalyst of the present invention. They are usually prepared from non-vicinal diols by reaction with diaryl carbonate, dialkyl carbonate, dioxolanones, phosgene, bischloroformic acid esters or urea (see eg EP-A 292772). Suitable non-vicinal diols are, 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 , triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, alkoxylation products of diols with ethylene oxide and/or propylene oxide and/or tetrahydrofuran with molecular weights up to 1000 daltons, preferably from 200 to 700 daltons, and in more rare cases dimeric diols, which can be obtained by reduction of both carboxyl groups of dimeric acids, which, in turn, can be obtained by dimerization of unsaturated vegetable fatty acids. The non-vicinal diols can be used singly or in mixtures. The reactions can be catalyzed by bases or transition metal compounds by methods known to the person skilled in the art.

Other complexing agents suitable for use in the present invention include polytetramethylene etherdiols. Polytetramethylene etherdiols are polyether polyols based on (tetramethylene ether) glycol, also known as polytetrahydrofuran (PTHF) or polyoxybutylene glycol. These polytetramethyleneetherdiols contain two OH groups per molecule. They can be obtained by cationic polymerization of tetrahydrofuran (THF) using catalysts.

The complexing agents described above can be used to increase or decrease the degree of crystallinity of the resulting DMC catalysts.

Suitable acids for use in the DMC catalyst of the present invention may have the formula H _r X‴, where X‴ is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X‴ is a halide. r is an integer corresponding to the charge of the counterion X‴. For example, when X‴ means Cl ⁻ , r is equal to 1, i.e., the acid will be HCl.

If an acid is present, particularly preferred acids for use in the DMC catalyst of the present invention having the formula H _r X‴ include the following: HCl, H ₂ SO ₄ , HNO ₃ , H ₃ PO ₄ , HF, HI, HBr, H ₃ BO ₃ and HClO ₄ . Particularly preferred are HCl, HBr and H ₂ SO ₄ .

It should also be understood that an alkali metal salt (eg, an alkali metal hydroxide such as KOH, an alkali metal oxide, or an alkali metal carbonate) may be added to the reaction mixture during the synthesis of the DMC catalyst. For example, an alkali metal salt can be added to the reaction mixture after the addition of the metal salt (M'(X') _p ) to the metal cyanide salt ((Y)q[M"(CN) _b (A) _c ]).

In one common method of preparation, an aqueous solution of zinc chloride (in excess) is mixed with an aqueous solution of potassium hexacyanocobaltate and a complexing agent (such as dimethoxyethane) is added to the resulting suspension. After filtering and washing the catalyst with an aqueous solution of a complexing agent (for example, an aqueous solution of dimethoxyethane), an active catalyst is obtained.

In an alternative method of preparation, several separate solutions can be prepared and then combined in order. For example, you can prepare the following solutions:

1. metal cyanide solution (for example, potassium hexacyanocobaltate)

2. metal salt solution, such as zinc chloride (in excess)

3. solution of the first complexing agent (for example, PPG-diol)

4. solution of the second complexing agent (for example, tert-butyl alcohol).

In this method, solutions 1 and 2 are combined immediately, then solution 4 is slowly added, preferably with vigorous stirring. Solution 3 can be added immediately after adding solution 4 or shortly thereafter. The catalyst is removed from the reaction mixture by filtration and then washed with a solution of complexing agents.

If water is desired in the DMC catalyst, then the above solutions (eg solutions 1-4) can be aqueous solutions. However, it should be understood that anhydrous DMC catalysts (ie, DMC catalysts containing no water at all) can also be prepared if the solutions in the preparation methods described above are anhydrous solutions. To avoid hydration of the DMC catalyst and thus the introduction of water molecules, any further processing steps (washing, filtration, etc.) can be carried out using anhydrous solvents.

In one conventional preparation method, several separate solutions can be prepared and then combined in order. For example, you can prepare the following solutions:

1. a solution of a metal mole (for example, zinc chloride in excess) and a second complexing agent (for example, tert-butyl alcohol)

2. metal cyanide solution (eg potassium hexacyanocobaltate)

3. a solution of the first and second complexing agents (eg, the first complexing agent may be a polymer (eg, polypropylene glycol diol) and the second complexing agent may be t-butyl alcohol).

In this method, solutions 1 and 2 are slowly combined (eg over 1 hour) at elevated temperature (eg above 25° C., eg at about 50° C.) with stirring (eg at 450 rpm). Upon completion of the addition, the stirring speed is increased by 1 hour (eg to 900 rpm). The stirring speed is then reduced to a lower value (eg 200 rpm) and Solution 3 is added rapidly with slow stirring. The mixture is filtered. The catalyst solids can be resuspended in the second complexing agent solution at high agitation speed (eg, at about 900 rpm) before adding the first complexing agent at low agitation speed (eg, 200 rpm). The mixture is then filtered. This stage can be repeated several times. The obtained catalyst in the form of a cake can be dried in vacuum (by heating, for example, to 60°C).

Alternatively, after the mixture has first been filtered, it can be resuspended at an elevated temperature (e.g. above 25°C, e.g. at about 50°C) in a solution of the first complexing agent (without the second or next complexing agent) and then homogenized by stirring . After this stage, it is filtered. The catalyst solids are then resuspended in a mixture of the first and second complexing agents. For example, the catalyst solids are resuspended in the second complexing agent at an elevated temperature (eg, above 25° C., such as about 50° C.) and then the first complexing agent is added to the mixture homogenized by stirring. The mixture is filtered and the catalyst is dried under vacuum with heating (for example, up to 100°C).

It should be understood that the DMC catalyst may contain

M' _d [M" _e (CN) _f ] _g

where M' and M" are as defined above, d, e, f and g are integers chosen such that the DMC catalyst is electrically neutral. Preferably, d is 3. Preferably, e is 1. Preferably, f is 6. Preferably, g is 2. Preferably M' is selected from Zn(II), Fe(II), Co(II) and Ni(II), more preferably M' is Zn(II). Preferably M" is selected from Co(III), Fe( III), Cr(III) and Ir(III), more preferably M" is Co(III).

It should be understood that all of these preferred features can be combined, for example, d is 3, e is 1, f is 6 and g is 2, M' is Zn(II) and M" is Co(III).

Suitable DMC catalysts of the above formula may include zinc hexacyanocobaltate(III), zinc hexacyanoferrate(III), nickel hexacyanoferrate(II), and cobalt hexacyanocobaltate(III).

There are many developments in the field of DMC catalysts, and one skilled in the art should understand that a DMC catalyst may contain, in addition to the above formula, additional additives to enhance the activity of the catalyst. Thus, while the above formula may form the "core" of the DMC catalyst, the DMC catalyst may additionally contain stoichiometric or non-stoichiometric amounts of one or more additional components such as at least one complexing agent, acid, metal salt, and/or water.

For example, a DMC catalyst might have the following formula:

,

,

in which M', M", X‴, d, e, f and g are as defined above. M"' may be M' and/or M". X" is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, preferably X" is a halide. i is an integer greater than or equal to 1 and the charge of the anion X" times I corresponds to the valence M‴. r is an integer corresponding to the charge of the counterion X‴. For example, when X‴ is Cl ^- , r is 1. l is 0 or a number in the range of 0.1 to 5. Preferably, l is 0.15 to 1.5.

R ^c is a complexing agent and may be as defined above. For example, R ^c may be a polyether, a polyether carbonate, a polycarbonate, a polytetramethylene ether diol, a ketone, an ester, an amide, an alcohol (e.g., a C _1-8 alcohol), urea, and the like, e.g., propylene glycol, polypropylene glycol , methoxy or ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, for example, R ^c can mean tert-butyl alcohol, dimethoxyethane, or polypropylene glycol.

As noted above, more than one complexing agent may be present in the DMC catalysts used in the present invention. A particularly preferred combination of complexing agents is tert-butyl alcohol and polypropylene glycol.

It is understood that if water, complexing agent, acid, and/or metal salt are absent from the DMC catalyst, h, j, k, and/or l will be zero, respectively. If water, a complexing agent, an acid, and/or a metal salt are present, then h, j, k, and/or l are positive numbers and may, for example, be from 0 to 20. For example, h may be from 0.1 to 4, j may be 0.1 to 6, k may be 0 to 20, such as 0.1 to 10, such as 0.1 to 5, l may be 0.1 to 5, such as 0 .15 to 1.5.

As stated above, DMC catalysts are complex structures and thus the above formula including additional components is not limiting. On the contrary, the specialist will understand that this definition is not exhaustive for DMC catalysts that can be used in the invention.

A typical DMC catalyst has the formula Zn ₃ [Co(CN) ₆ ] ₂ ·hZnCl ₂ ·kH ₂ O·j[(CH ₃ ) ₃ COH], where h, k, and l are defined above. For example, h may be 0 to 4 (eg, 0.1 to 4), k may be 0 to 20 (eg, 0.1 to 10), and j may be 0 to 6 (eg, 0.1 to 6).

Reaction conditions

The process of the invention can be carried out at carbon dioxide pressures of from about 1 bar to about 60 bar, for example, from about 1 bar to about 30 bar, for example, from about 1 to about 20 bar, for example, at a carbon dioxide pressure of from about 1 to about about 15 bar.

The process according to the invention makes it possible to produce polyether carbonates at pressures within the limits of existing industrial polyether carbonate production equipment (eg 10 bar or less). Thus, the process of the invention can be carried out at pressures from about 1 bar to about 10 bar, for example, the reaction can be carried out at a carbon dioxide pressure of about 5 bar or less. Under these conditions, the process of the invention is still capable of producing polyether carbonates having a variable amount of carbonate bonds and can produce polyether carbonates with a high content of carbonate bonds.

The process of the invention can be carried out in the presence of a solvent, but it should also be understood that the reaction can be carried out in the absence of a solvent.

When the process of the invention is carried out in the presence of a solvent, preferred solvents may be selected from hexane, toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tert-butyl acetate and tetrahydrofuran (THF ). If a solvent is present, especially preferred solvents for use in the present invention are hexane, toluene, ethyl acetate, acetone and n-butyl acetate.

The epoxide used in the process may be any component containing an epoxy moiety. Representative epoxides include ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide.

The epoxide may be purified prior to reaction with carbon dioxide (eg by distillation such as distillation over calcium hydride). For example, the epoxide may be distilled before being added to the reaction mixture containing the catalysts.

The method can be carried out at a temperature of from about 0°C to about 250°C, for example, from about 40°C to about 140°C, for example, from about 50°C to about 110°C, such as from about 60 °C to about 100°C, for example, from about 70°C to about 100°C, for example, from about 55°C to about 80°C. The duration of the process can be up to about 168 hours, for example, from about 1 minute to about 24 hours, for example, from about 5 minutes to about 12 hours, for example, from about 1 to about 6 hours.

The process according to the invention can be carried out at low catalyst loading. For example, the content of the catalyst of formula (I) may be in the range of about 1:1000-300000 [catalyst of formula (I)]:[epoxide] such as about 1:1000-100000 [catalyst of formula (I)]:[epoxide ], for example, in the range of about 1:10000-50000 [catalyst of formula (I)]:[epoxide], for example, in the range of about 1:10000 [catalyst of formula (I)]:[epoxide]. These relationships are molar relationships.

The ratio of catalyst of formula (I) to DMC catalyst may be from about 300:1 to about 0.1:1, for example, from about 120:1 to about 0.25:1, for example, from about 40:1 to about 0 .5:1, for example, from about 30:1 to about 0.75:1, for example, from about 20:1 to about 1:1, for example, from about 10:1 to about 2:1, for example, from about 5:1 to about 3:1. These relationships are mass relationships.

The process may be a batch reaction, a semi-continuous reaction, or a continuous reaction.

Polyether carbonates

The process according to the invention makes it possible to obtain high molecular weight polyether carbonates.

The method according to the invention makes it possible to obtain polyether carbonates in which the amount of ester and carbonate bonds can be controlled. Thus, the invention provides a polyether carbonate which has n ether bonds and m carbonate bonds, where n and m are integers, and where the ratio m/(n+m) is greater than zero and less than 1.

For example, the process of the invention makes it possible to obtain polyether carbonates with a wide range of m/(n+m) values. It should be understood that 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 within any range derived from these specific values. For example, m/(n+m) may be from about 0.05 to about 0.95, from about 0.10 to about 0.90, from about 0.15 to about 0.85, from about 0.20 to about 0.80, or about 0.25 to about 0.75, etc.

Thus, the method of the invention makes it possible to obtain polyether carbonates with a high proportion of carbonate bonds, for example, the ratio m/(n+m) can be higher than about 0.50, for example, can be from more than about 0.55 to less than about 0.95, for example, from about 0.65 to about 0.90, for example, from about 0.75 to about 0.90. The process of the invention makes it possible to obtain high m/(n+m) polymers under mild conditions, eg at pressures of about 20 bar or less, eg 10 bar or less.

For example, polyether carbonates obtained by the process of the invention may have the following formula (IV):

It should be understood that the specific value of X will depend on the nature of X in the compound of formula (I), and that the specific value of ^Re1 and ^Re2 will depend on the nature of the epoxide used to prepare the polyether carbonate. The "m" and "n" values determine the amount of carbonate and ester bonds in the polyester carbonate. It is clear that n ≤ 1 and m ≤ 1.

It should be understood that in the preferred embodiment, X is not a group containing -OH.

One skilled in the art will appreciate that in polymers of formula (IV), adjacent epoxy monomer units in the backbone may be head-to-tail, head-to-head, or tail-to-tail linkages.

It should also be understood that formula (IV) does not require that carbonate bonds and ester bonds be present in two different "blocks" in each of the sites given by "m" and "n", on the contrary, carbonate and ether repeating units can be distributed statistically along the main polymer chain or can be arranged so that the carbonate and ether bonds are not in two different blocks.

Thus, a polyether carbonate obtained by the process of the invention (eg, a polymer of formula (IV)) may be referred to as a random copolymer, a random copolymer, an alternating copolymer, or a periodic copolymer.

One skilled in the art will appreciate that the weight percentage of carbon dioxide incorporated into the polymer will be directly proportional to the number of carbonate bonds in the polymer backbone.

Ceteris paribus, polyethers have a higher degradation temperature than polycarbonates derived from epoxides and carbon dioxide. Thus, a polyether carbonate having a random or random distribution of ether and carbonate bonds will have a higher degradation temperature than a polycarbonate or polyether carbonate containing blocks of carbonate bonds. The thermal degradation temperature can be measured using thermogravimetric analysis (TGA).

As stated above, the process of the invention produces a random copolymer, a random copolymer, an alternating copolymer, or a periodic copolymer. Thus, the carbonate bonds are not in a single block, resulting in a polymer with improved properties, such as reduced thermal degradation, compared to polycarbonate. Preferably, the polyether carbonate produced by the process of the invention is a stochastic copolymer or a random copolymer.

The polyether carbonate obtained by the method of the invention may correspond to the formula (IV) in which n and m are integers greater than or equal to 1, the sum of all groups m and n being from 4 to 200, and wherein the ratio m/(m+ n) ranges from greater than zero to less than 1.00. As indicated 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 given by these particular values. For example, m/(n+m) may be from about 0.05 to about 0.95, from about 0.10 to about 0.90, from about 0.15 to about 0.85, from about 0.20 to about 0.80, or about 0.25 to about 0.75, etc.

It will be obvious to the person skilled in the art that the simple polyester carbonate must contain at least one carbonate and at least one ether bond, for example, n ≥ 1 and m ≥ 1. Thus, it should be understood that the number of ether and carbonate bonds (n + m) in a simple the polyester carbonate will determine the molecular weight of the polymer. For example, preferably n ≥ 5 and m ≥ 5, or n ≥ 10 and m ≥ 10, or n ≥ 20 and m ≥ 20, or n ≥ 50 and m ≥ 50.

Preferably, m+n ≥ 10 or m+n ≥ 20 or m+n ≥ 100 or m+n ≥ 200 or m+n ≥ 500 or m+n ≥ 1000.

Each R ^e1 can be independently selected from H, halogen, hydroxyl, or (possibly substituted) alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. Preferably, R ^e1 may be selected from H or (possibly substituted) alkyl.

Each R ^e2 can be independently selected from H, halogen, hydroxyl, or (possibly substituted) alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl. Preferably R ^e2 may be selected from H or (possibly substituted) alkyl.

It should also be understood that R ^e1 and R ^e2 may together form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms and optionally one or more heteroatoms (eg O, N or S). For example, R ^e1 and R ^e2 can together form a five- or six-link cycle.

As described above, the nature of ^Re1 and ^Re2 depends on the epoxide used in the reaction. If the epoxide is cyclohexene oxide (CHO), R ^e1 and R ^e2 will together form a six-member alkyl ring (eg, cyclohexyl ring). If the epoxide is ethylene oxide, then both R ^e1 and R ^e2 will be H. If the epoxide is propylene oxide, then R ^e1 will mean H and R ^e2 will mean methyl (or R ^e1 will mean methyl and R ^e2 will mean H, depending on how the epoxide was added to the polymer backbone). If the epoxide is butylene oxide, then R ^e1 will mean H and R ^e2 will mean ethyl (or vice versa). If the epoxide is styrene oxide, then R ^e1 may be a hydrogen atom and R ^e2 may be phenyl (or vice versa).

It should also be understood that if a mixture of epoxides is used, then R ^e1 and/or R ^e2 may all be different, for example, if a mixture of ethylene oxide and propylene oxide is used, R ^e1 may independently be hydrogen or methyl, and R ^e2 may independently be hydrogen or methyl.

Thus, R ^e1 and R ^e2 may be independently selected from hydrogen, alkyl or aryl, or R ^e1 and R ^e2 may together form a cyclohexyl ring, preferably R ^e1 and R ^e2 may be independently selected from hydrogen, methyl, ethyl or phenyl, or R ^e1 and R ^e2 can together form a cyclohexyl ring.

X depends on the nature of the X group used in the compound of formula (I). Thus, X can be selected from OC(O)R ^x , OSO ₂ R ^x , OSOR ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino , amido or (optionally substituted) aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, where R _x is independently hydrogen or (possibly substituted) aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl group.

Preferably, each X is independently OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (eg branched alkyl), heteroalkyl (eg silyl), aryl or heteroaryl. Even more preferably, each X is independently OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate, or OSO ₂ R ^x . Preferred optional substituents when X is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group include halogen, hydroxyl, nitro, cyano, amino, or a substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group.

Example options for X include OAc, OC(O)CF ₃ , halogen, OSO(CH ₃ ) ₂ , Et, Me, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr) ₂ or N( SiMe ₃ ) ₂ , OPh, OBn, salicylate, dioctylphosphinate, etc.

If more than one X group is present, for example in a compound of formula (IV-A) below, all Xs may be the same or different, and preferably all Xs are the same.

Preferably R ^x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Preferred optional substituents for R ^x include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio, or a substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group (eg, optionally substituted alkyl, aryl, or heteroaryl).

Preferably, all X are the same and are selected from OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate, or OSO ₂ R ^x , R ^x is alkyl, alkenyl, alkynyl, heteroalkyl , aryl, heteroaryl or alkylaryl. More preferably, all X are the same and are OC(O)R ^x , OR ^x , halide, alkyl, aryl, heteroaryl, phosphinate or OSO ₂ R ^x . Even more preferably, all X are the same and mean OC(O)R ^x . Even more preferably, all X are the same and are selected from OAc, O ₂ CCF ₃ or O ₂ C(CH ₂ ) ₃ Cy. Most preferably, all X's are the same and are OAc.

Preferably, all R ^x are the same and are selected from (possibly substituted) alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. More preferably, all R ^x are the same and represent (possibly substituted) alkyl, alkenyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Even more preferably, all R ^x are the same and are (possibly substituted) alkyl, alkenyl, heteroalkyl, or are cycloalkyl. Even more preferably, R ^x is optionally substituted by alkyl, heteroalkyl or cycloalkyl. Most preferably R ^x is alkyl, optionally substituted.

It should be understood that the preferred definitions for X and the preferred definitions for R ^x can be combined. For example, each X can independently be OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, hydroxyl, carbonate , amino, nitro, amido, alkyl (eg, branched alkyl), heteroalkyl, (eg, silyl), aryl, or heteroaryl, for example, each can independently be OC(O)R ^x , OR ^x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO ₂ R ^x , and R ^x may be (possibly substituted) alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl.

The specialist should understand that all of the above features can be combined. For example, R ^e1 and R ^e2 may be independently selected from hydrogen, alkyl, or aryl, or R ^e1 and R ^e2 may together form a cyclohexyl ring, and X may be a (possibly substituted) aliphatic or heteroaliphatic group, such as alkylene or heteroalkylene.

The polyether carbonates obtained by the process of the invention are preferably high molecular weight polyester carbonates. It should be understood that the nature of the epoxide used to form the polyether carbonate will have an effect on the resulting molecular weight of the product. Thus, the lower limit n+m is used here to define "high molecular weight" polymers according to the invention.

The polymers produced by the process of the invention may preferably have a molecular weight of at least about 25,000 Daltons, such as at least about 40,000 Daltons, such as at least about 50,000 Daltons, or at least about 100,000 Daltons, such as from about 50,000 dalton up to 1000000 dalton. High molecular weight polymers obtained by the process of the present invention typically have molecular weights above about 100,000 daltons.

The process according to the invention can advantageously produce polyether carbonates with a broad molecular weight distribution. In other words, the polyether carbonate may have a relatively large polydispersity index (PDI). The PDI of a polymer is obtained by dividing the weight average molecular weight (M _w ) by the number average molecular weight (M _n ) of the polymer, thereby giving an idea of the polymer chain distribution of the polymer product. For high molecular weight polymers, it may be desirable to have a high PDI, since the short chains act as plasticizers for the longer chains, thereby preventing excessive polymer brittleness.

Preferably, the polymers produced by the process of the invention have a PDI greater than about 1, preferably greater than about 2, more preferably greater than about 3.

M _n , M _w and hence the PDI of the polymers obtained by the process of the invention can be measured by gel permeation chromatography (GPC). For example, GPC measurements can be made on an Agilent 1260 Infinity instrument with two Agilent PLgel µ–m mixed–E columns in series. Samples can be measured at room temperature (293K) in THF at a flow rate of 1 ml/min against polystyrene standards with a narrow molecular weight distribution (e.g. Agilent Technologies EasiVial low molecular weight polystyrene standard with a Mn range of 405 to 49450 g/m). mole). Optionally, samples can be measured against polyethylene glycol standards such as EasiVial polyethylene glycol from Agilent Technologies.

The invention also provides a polymerization system for the copolymerization of carbon dioxide and epoxide, comprising:

d. a catalyst of formula (I) as defined herein, and

e. DMC is a catalyst as defined herein.

The catalyst of formula (IIb) is thus described:

in which R₁, R₂, R₃, R₅, G, X, E₁ and E₂ are as defined for formula (I) or formula (II).

Each R ₄ is independently selected from (optionally substituted) alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(O)OR ₁₉ or -alkylC≡N, preferably each R ₄ is independently selected from (optionally substituted) alkyl, aryl, heteroalkyl or heteroaryl. All R ₄ may be the same or different. Preferably, all R ₄ are the same. For example, all R ₄ are the same and are selected from a (possibly substituted) alkyl, aryl, heteroalkyl or heteroaryl group. Examples of R ₄ groups include (possibly substituted) methyl, ethyl, propyl, butyl, cyclohexyl and phenyl.

It should be understood that all of the preferred definitions given for formula (I) and formula (II) may equally apply to formula (IIb).

It should be understood that a compound of formula (IIb) may have the following structure:

where X and G are defined for formula (I) or formula (II).

It should be understood that the catalyst of formula (IIb) can be used in the method according to the present invention.

Examples

Methods

Nuclear magnetic resonance spectroscopy

^1H -NMR spectra were recorded on a Bruker AV-400 instrument using CDCl ₃ solvent.

The polyether and polycarbonate content of the polyester carbonate has been evaluated in several different ways. To calculate the mole content of carbonate and the weight percentage of CO ₂ in polyester carbonate, the method described in the application US 2014/0323670 was used. This method is as follows:

Relevant resonances in ¹ H-NMR spectra were used for integration.

Table A

resonance ¹ H-NMR (ppm) Protons from repeating links number of protons A(1.08-1.18) CH ₃ from polyether 3 B(1.26–1.38) CH ₃ from polycarbonates 3 C(1.45–1.49) CH ₃ from cyclic carbonate 3 D(2.95–2.99) CH ₃ from propylene oxide 1

Resonances A, B and C have been determined previously in the methods described in US2014/0323670 for polyether carbonates having a low proportion of carbonate bonds.

Carbonate/ether ratio (m/n+m) : molar ratio of carbonate and ether bonds:

(equation 1)

CO ₂ wt % in polyol : amount of CO ₂ injected based on total polyol:

(equation 2)

Here, 44 is the mass of CO ₂ in the carbonate unit, 58 is the mass of the polyester unit, and 102 is the mass of the polycarbonate unit.

Also, resonance B can be split into two different resonances. The interval 1.26–1.32 ppm (B ¹ ) corresponds to the CH ₃ of propylene in the polymer unit between the carbonate and ether bonds (polyether carbonate, PEC bond), while the resonance in the range 1.32–1.38 ppm (B ² ) corresponds to the CH ₃ propylene in the polymer unit between two carbonate bonds (polycarbonate, PC bond). The ratio of the bonds PEC, PC and PE gives an idea of the structure of the polymer. A fully interlocked structure will contain very few PEC bonds (only at block boundaries), while a more stochastic structure will include a significant proportion of PEC bonds where both polyester and polycarbonate units are adjacent to each other in the polymer backbone. The relationship between these two links gives an idea of the structure.

Polyether carbonate/polycarbonate bond ratio:

Gel permeation chromatography

GPC measurements were performed against narrow molecular weight polyethylene glycol or polystyrene standards in THF using an Agilent 1260 Infinity instrument equipped with Agilent PLgel Mixed–D columns.

Mass spectroscopy

All mass-spectroscopic measurements were carried out on a MALDI micro MX micromass instrument.

Example 1

Synthesis of the DMC catalyst A

The DMC catalyst used in this example was prepared by the method described in the Journal of Polymer Science; Part A: Polymer Chemistry, 2002, 40, 1142. Briefly, 1.0 g of K ₃ Co(CN) ₆ was dissolved in a solvent mixture consisting of 13 g of distilled water and 2 g of tert-butyl alcohol. 6 g of ZnCl ₂ were dissolved in a solvent mixture of 13 g of water and 4 g of tert-butyl alcohol, and then this mixture was slowly added to the K ₃ Co(CN) ₆ solution for 20 minutes with stirring. The mixture was then stirred for another 40 minutes, after which it was separated by centrifugation to give a white precipitate. The precipitate was dispersed in a solvent mixture of 16 g of water and 16 g of tert-butyl alcohol and stirred for 20 minutes, then the precipitate was separated in a centrifuge. This washing procedure was repeated 3 times. Then the white precipitate was dispersed in 50 g of tert-butyl alcohol, after which it was stirred for 20 minutes and then separated by centrifugation, obtaining a white precipitate. After that, washing with tert-butyl alcohol was repeated once more. Then the solvent was removed under reduced pressure for 8 hours at 60°C. The resulting compound was found to have the formula Zn ₃ [Co(CN) ₆ ] ₂ hZnCl ₂ 0.5H ₂ O 2[(CH ₃ ) ₃ COH].

Example 2

Synthesis of the DMC catalyst B

The synthesis described in Example 1 of US Pat. No. 5,482,908 was carried out, except that the 4000 molecular weight polypropylene glycol diol was replaced by the 2000 molecular weight polypropylene glycol diol.

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 DI water (40 ml) in a second beaker (solution 2). Solution 3 was obtained in the third beaker: a mixture of DI-water (200 ml), tert-butyl alcohol (2 ml) and polyol (2 g of polypropylene glycol diol with a molecular weight of 2000). Solutions 1 and 2 were combined using a mechanical stirrer. Immediately after this, a mixture (50/50 by volume) of tert-butyl alcohol and DI-water (200 ml in total) was added to the mixture of zinc hexacyanocobaltate, and the product was vigorously stirred for 10 minutes. Solution 3 (a mixture of polyol, water, and tert-butyl alcohol) was added to an aqueous suspension of zinc hexacyanocobaltate, and the product was stirred with a magnetic stirrer for 3 min. The mixture was filtered under pressure to isolate the solids. The solid cake was again suspended in tert-butyl alcohol (140 ml), DI water (60 ml) and 2 g of additional polypropylene glycol diol with a molecular weight of 2000. The mixture was then vigorously stirred for 10 min and filtered. The solid cake was resuspended in tert-butyl alcohol (200 ml) and an additional 1 g of 2000 molecular weight polypropylene glycol diol and stirred vigorously for 10 minutes and then filtered. The resulting solid catalyst was dried under vacuum (<1 mbar) at 50° C. to constant weight. The yield of dry powdered catalyst was 8.5 g.

Example 3

Synthesis [L ¹ Ni ₂ (OAC) ₂ ], catalyst 1

Ligand H ₂ L ¹ was synthesized in the manner described previously by Kember et al , Angew. Chem. Int. Ed., 2009, 48, 931–933.

H ₂ L ¹ (2 mmol) was dissolved in MeOH (50 ml), then Ni(OAc) ₂ ,4H ₂ O (0.498 g, 4 mmol) was added portionwise over 15 minutes and the solution stirred overnight. The solvent was removed in vacuo and excess water/AcOH was removed by azeotropic distillation with toluene (3×40 ml).

[L ¹ Ni ₂ (OAc) ₂ ]: IR (ʋ _C=O , cm ^–1 , pure): 1581 and 1413. MALDI–TOF MS: m/z : 727.6 ([M–OAc)] ⁺ , 100%).

Example 4

Synthesis of [L ² Ni ₂ (OAc) ₂ ] - catalyst 2

Catalyst 2 ([L ² Ni ₂ (OAc) ₂ ]) was prepared as Catalyst 1, except that a methylated macrocyclic ligand was used.

Catalyst 2

Example 5

Synthesis of [L ² Ni ₂ (OAc) ₂ ] - catalyst 3

Catalyst3([L³Ni₂(OAC)₂]) received as a catalyst1,except that a monomethylated macrocyclic ligand was used.

Catalyst 3

Example 6

polymerization reaction

7 mg of DMC catalyst A and 165 mg of [L ¹ Ni ₂ (OAc) ₂ ] were introduced into an oven-dried 100 ml reactor. The catalytic composition was dried at 110–120°C in vacuum for 1–2 hours. The reactor was cooled to room temperature and propylene oxide (PO; 15 ml) was injected into the vessel through a syringe under a continuous flow of gaseous CO ₂ . The vessel was heated to 80°C and CO ₂ was added to a pressure of 25 bar. The reaction was continued at 80°C for 3 hours. At the end of the reaction, the reactor was cooled below 10° C. and the pressure was released very slowly. NMR and GPC measurements were taken immediately. The crude reaction mixture was poured (diluted) into CH ₂ Cl ₂ and HCl/MeOH was added.

As a result of the reaction, a polymer with Mn 44000 and a polydispersity of 2.9 was obtained. The polymer contained 53% carbonate bonds.

Example 7

1 mg of DMC catalyst B was introduced into a 100 ml reactor dried in an oven. The catalytic composition was dried at 110–120°C in vacuum for 1–2 hours. The reactor was cooled to room temperature and Catalyst 2 (36 mg) in propylene oxide (PO; 10 ml) was injected into the vessel via a syringe under a continuous flow of CO ₂ gas. Added 5 ml of ethyl acetate. The vessel was heated to 75°C and CO ₂ was added to a pressure of 10 bar. The reaction was continued at 75°C overnight. At the end of the reaction, the reactor was cooled below 10° C. and the pressure was released very slowly. NMR and GPC measurements were taken immediately.

As a result of the reaction, a polymer with Mn 33,000, Mw 248,000 and a polydispersity of 7.35 was obtained. The polymer contained 33% carbonate bonds.

Example 8

The required amount of DMC catalyst was added to an oven-dried reactor with a volume of 100 ml, and the catalyst was dried at 120°C for 1 hour in a vacuum. The reactor was cooled to room temperature and Catalyst 2 or 3 (36 mg) in propylene oxide (PO; 10 ml) was injected via syringe into the propylene oxide solution under a continuous flow of CO ₂ gas. If necessary, anhydrous EtOAc was injected through a syringe under a continuous flow of gaseous CO ₂ . The vessel was heated to the initial reaction temperature with constant stirring at 600 rpm and CO ₂ was added to a pressure of 10 bar. The reaction was continued at this temperature for a predetermined amount of time. The temperature was then raised and the reaction continued for a total of 16 hours. At the end of the reaction, the reactor was cooled below 10° C. and the pressure was released very slowly. NMR and GPC measurements were taken immediately. All reactions resulted in >98% PO conversion.

The results of Example 8 are shown in Table 1 below.

Example 8 demonstrates that a wide range of polycarbonate contents can be obtained with this dual catalysis and that high molecular weight polymers, with Mw up to 400,000, can be obtained at a pressure of only 10 bar. Polymers with high polydispersity are obtained, which is beneficial for many applications of thermoplastics. The carbonate content can be controlled by temperature, catalyst content, pressure, etc.

Table 1

Cat. content
(mol.%) DMC
(G) PO
(ml) EtOAc (ml) T _original °C/h) T _{of course}
(°C/h) selectivity (%) ether carbonate M _n
(kg/mol) M _w
(kg/mol) PDI 3 0.03 0.002 5 10 60(4) 85 (12) 84 51:49 113 275 2.43 3 0.03 0.003 10 5 60 (8) 85(8) 91 70:30 60 286 4.79 3 0.01 0.001 10 10 60 (8) 75(8) 95 57:43 43 240 5.58 3 0.03 0.002 12.5 2.5 65(4) 85 (12) 93 27:73 154 270 1.76 2 0.03 0.003 10 5 60(4) 85 (12) 93 56:44 47 246 5.26 2 0.03 0.003 10 5 60 (8) 85(8) 92 69:31 57 266 4.65 2 0.02 0.002 10 5 60(4) 85 (12) 88 44:56 38 210 5.59 2 0.01 0.001 10 10 60 (8) 75(8) 95 45:55 77 310 4.02 2 0.03 0.002 12.5 2.5 65(4) 85 (12) 97 26:74 301 406 1.35

Claims (69)

1. A method for producing a high molecular weight polyether carbonate, the method comprising the reaction of carbon dioxide and epoxide in the presence of a bimetallic cyanide catalyst (DMC catalyst) and a catalyst of formula (I), wherein the catalyst of formula (I) has the following structure:

where M ₁ and M ₂ 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 ; R ₁ and R ₂ are independently selected from hydrogen, a halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or from an optionally substituted an alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group; R ₃ is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic group; R ₅ is independently selected from H or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl group; E ₁ means C and E ₂ means O; E ₃ , E ₄ , E ₅ and E ₆ are NR ₄ and

means

; R ₄ is independently selected from H or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl group, -alkyl-C(O)OR ₁₉ or -alkylC≡N group, or alkylaryl; X is independently selected from OC(O)R ^x , OSO ₂ R ^x , OSOR ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, wherein the X groups may be the same or different, and where X may form a bridge between M ₁ and M ₂ ; R _x is independently hydrogen or an optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl group; And G is absent or is independently selected from a neutral or anionic Lewis acid donor ligand. 2. The process of claim 1 wherein the reaction is carried out at a carbon dioxide pressure of from about 1 bar to about 60 bar, preferably from about 1 bar to about 30 bar, more preferably from about 1 bar to about 20 bar, more preferably from about 1 bar to about 15 bar, more preferably from about 1 bar to about 10 bar. 3. Process according to claim 1, wherein M ₁ and/or M ₂ are selected from Mg(II), Zn(II) or Ni(II), preferably where M ₁ and M ₂ are selected from Mg(II), Zn( II) or Ni(II). 4. The method of claim 1 wherein X is independently selected from OC(O)R ^x , OSO ₂ R ^x , OS(O)R ^x , OSO(R ^x ) ₂ , S(O)R ^x , OR ^x , halide, nitrate, carbonate, amino, nitro, amido, alkyl, heteroalkyl, aryl or heteroaryl and/or R ^x may be optionally substituted with alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl, wherein the X groups may be the same or different, and while X can form a bridge between M ₁ and M ₂ . 5. The method according to p. 1, in which the catalyst of formula (I) contains a symmetrical macrocyclic ligand. 6. The method of claim 1 wherein the catalyst of formula (I) contains an asymmetric macrocyclic ligand. 7. The method according to p. 6, in which at least one representative of E ₃ , E ₄ , E ₅ and E ₆ is different from the remaining representatives of E ₃ , E ₄ , E ₅ and E ₆ and R ₄ preferably represents H or alkyl. 8. The method of claim 1 wherein E ₃ , E ₄ , E ₅ and E ₆ are NR ₄ and each R ₄ is independently H or an optionally substituted aliphatic radical, preferably each R ₄ is H or alkyl . 9. The method of claim 1 wherein R ₅ is H and R ₂ is H. 10. The method of claim 1 wherein R ₃ is an optionally substituted alkylene group, preferably R ₃ is an optionally substituted C ₂ or C ₃ alkylene group. 11. The method of claim 1 wherein R ₁ 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 all R ₁ are preferably the same. 12. The method according to p. 1, in which the catalyst has the formula:

13. The method of claim. 1, in which the reaction is carried out at a temperature in the range from about 50°C to about 110°C, preferably from about 60°C to about 100°C, more preferably from about 70°C to about 100°C. C, more preferably from about 55°C to about 80°C. 14. The method of claim 1 wherein the reaction does not use a starting compound or initiator. 15. The method of claim 1 wherein the high molecular weight polyether carbonate has a molecular weight of at least about 25,000 Daltons, preferably at least about 40,000 Daltons, more preferably at least about 50,000 Daltons, and most preferably at least about 100,000 Daltons. 16. The method of claim 1 wherein the DMC catalyst contains at least two metal centers and cyanide ligands. 17. The method of claim 16, wherein the DMC catalyst further comprises at least one of the following: one or more complexing agents, water, metal salt, and/or acid, optionally in non-stoichiometric amounts. 18. The process of claim 1 wherein the DMC catalyst is obtained by treating a metal salt solution with a metal cyanide salt solution in the presence of at least one of the following compounds: a complexing agent, water and/or an acid, the metal salt preferably having 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, and the charge of the anion multiplied by p corresponds to the valency of M'; the metal cyanide salt has the formula (Y) _q M"(CN) _b (A) _c wherein M" is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II) , Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), Y is a proton, or an alkali metal ion, or an alkaline earth metal ion (such as K ⁺ ), 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 may be 0 or be an integer greater than or equal to 1; the sum of the products of the charges of the anions Y, CN and A by q, b and c, respectively (for example, (Y x q) + (CN x b) + (A x c)) is equal to the valence M "; at least one complexing agent is selected from a poly(poly)ether, a polyether carbonate, a polycarbonate, a polytetramethylene ether diol, a ketone, an ester, an amide, an alcohol, a urea, or a combination thereof, preferably said at least one complexing agent is selected from propylene glycol, polypropylene glycol, methoxy or ethoxyethylene glycol, dimethoxyethane, t-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol or their combinations, and where the acid, if present, has the formula H _r X‴ where X‴ is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and r means an integer corresponding to the charge on the counterion X‴. 19. The method according to p. 1, in which the DMC catalyst meets the formula M' _d [M" _e (CN) _f ] _g , in which M' and M" are defined in paragraph 18 and d, e, f and g are integers chosen so that the DMC catalyst is electrically neutral, preferably d is 3, e is 1, f is 6 and g is 2 . 20. The method according to claim 18 or 19, wherein M' is selected from Zn(II), Fe(II), Co(II) and Ni(II), preferably M' is Zn(II). 21. The method according to p. 18 or 19, in which M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II) , preferably M" is Co(II) or Co(III). 22. The method according to p. 1, in which a simple polyester carbonate has the formula (IV)

in which X is defined according to item 1 or 3, n and m are integers, and the ratio m / (n + m) is greater than zero, but less than 1, and R ^e1 and R ^e2 depend on the nature of the epoxide used in the process. 23. Polymerization system for copolymerization of carbon dioxide and epoxide, containing: a) a catalyst of formula (I) according to any one of paragraphs. 1, 3-12 and b) DMC catalyst according to any one of paragraphs. 1, 16-19. 24. High molecular weight polyether carbonate having the formula (IV)

in which X is defined as specified in paragraph 1 or 3, n and m are integers and R ^e1 and R ^e2 depend on the nature of the epoxide used to obtain a simple polyester carbonate. 25. The method of claim 22 or the high molecular weight polyether carbonate of claim 24, wherein R ^e1 and R ^e2 are independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl or adjacent R ^e1 and R ^e2 groups can be combined to form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms and optionally one or more heteroatoms (eg O, N or S). 26. The method of claim 22, or the high molecular weight polyether carbonate of claim 24, wherein R ^e1 and R ^e2 are independently selected from H or optionally substituted alkyl, or adjacent R ^e1 and R ^e2 together may form a five- or six-membered alkyl ring. 27. A high molecular weight polyether carbonate according to claim 24, where m+n ≥ 10, or m+n ≥ 20, or m+n ≥ 100, or m+n ≥ 200, or m+n ≥ 500, or m+n ≥ 1000. 28. The high molecular weight polyether carbonate of claim 24, wherein the PDI of the polymer is greater than about 1, preferably greater than about 2, more preferably greater than about 3. 29. High molecular weight simple polyestercarbonate according to claim 24, obtained by the method according to any one of paragraphs. 1-22. 30. A high molecular weight polyether carbonate according to claim 24, containing n ether bonds and m carbonate bonds, with n and m being integers, the ratio m / (n + m) is preferably from more than about 0.50 to about 0.95, or from about 0.55 to about 0.90, or from about 0.65 to about 0.85, or from about 0.70 to about 0.80, or from about 0.75 to about 0.90.