Polyol block copolymers, compositions, and methods thereof

Abstract

A process is described for producing a polyol block copolymer in a multi-reactor system comprising a first reactor and a second reactor wherein a first reaction takes place in the first reactor and a second reaction takes place in the second reactor. The first reaction is a reaction of a carbonate catalyst with CO2 and an epoxide in the presence of a starter and / or a solvent to produce a polycarbonate polyol copolymer, and the second reaction is a reaction of a DMC catalyst with the polycarbonate polyol compound and the epoxide of the first reaction to produce a polyol block copolymer. The product of the first reaction is fed as a crude reaction mixture to the second reaction, the epoxide and the polycarbonate polyol compound of the first reaction are fed in a continuous or semi-intermittent manner, and / or the product of the first reaction has a neutral or alkaline pH when added to the second reaction. The invention further relates to copolymers and products comprising such copolymers.

Description

[0001] Related Applications

[0002] This application is a divisional of patent application number 2020800476613, filed on May 01, 2020, entitled “Polyol Block Copolymers, Compositions, and Methods Thereof”. TECHNICAL FIELD

[0003] The present invention relates to a process for producing polyol block copolymers from a two-step process performed in two separate reactors, as well as products and compositions comprising such copolymers. BACKGROUND

[0004] WO 2015059068 and US2015 / 0259475 from Covestro (EP2888309 equivalent) disclose the use of DMC catalysts for producing polyether carbonate polyols from CO2 and alkylene oxides in the presence of a starter compound. A number of H-functional starter compounds are listed, including polyether carbonate polyols, polycarbonate polyols, and polycarbonates.

[0005] However, the DMC catalyst alone limits the amount of carbon dioxide that can be incorporated into the polyether carbonate polyol, requiring high pressures (typically over 40 bar) to achieve a maximum of about 50% possible CO2 incorporation. Furthermore, the DMC catalyst typically requires a pre-activation step in the absence of CO2, which initially produces a polyether. CO2 is then added and incorporated into the polymer structure. This means that the DMC catalyst alone cannot produce low molecular weight polyols (e.g., <1000 Mn) with a high CO2 content, and the CO2 content of the polyol is limited even at higher weights such as 2000 Mn. Polyether carbonate polyols produced by DMC alone typically have a structure that is rich in ether linkages at the center of the polymer chain and more rich in carbonate groups near the hydroxyl end groups. This is not advantageous because ether groups are significantly more stable to heat and basic conditions than carbonate linkages.

[0006] WO 2010062703 discloses the production of block copolymers having polycarbonate blocks and hydrophilic blocks (e.g., polyether). A two pot production is described, producing alternating polycarbonate blocks in the first reaction using a carbonate catalyst, followed by quenching the reaction, separating the polyol from the solvent and unreacted monomers, and then performing a second batch reaction (in the absence of CO2) with a DMC catalyst to incorporate a hydrophilic oligomer such as a poly(alkylene oxide). This process can be used to produce B-A-B polymers, where A is a polycarbonate and B is a hydrophilic block such as a polyether. These polymers can be used to enhance oil recovery.

[0007] The present invention allows the production of polycarbonate block polyether polyols containing a significantly increased CO2 content at mild pressure by using a low molecular weight polycarbonate polyol containing CO2 (produced in a first reaction by a carbonate catalyst) as a starter for the reaction between a DMC catalyst and an epoxide. Unlike polycarbonate polyether polyols produced by a DMC catalyst alone, the polycarbonate block polyether polyols produced by the present invention can produce low molecular weight polyols (e.g., < 1000 Mn) with a high CO2 content (e.g., > 7 wt%).

[0008] Advantageously, the low molecular weight polycarbonate polyol does not need to be isolated, but can be prepared in one reactor and transferred directly to the second reactor without removing any catalyst or solvent.

[0009] WO 2017037441 describes a process in which a polycarbonate polyether polyol is produced in one reactor using a carbonate catalyst and a DMC catalyst. The reaction conditions must be balanced to meet the requirements of the two different catalysts.

[0010] Advantageously, the present invention allows the conditions to be optimized for the use of two different types of catalysts (a carbonate catalyst and a DMC catalyst), thus enabling the conditions for each catalyst to be optimized individually rather than compromising to fit the whole system. It is also possible to add the high carbonate content polyol directly to a pre-activated DMC catalyst, which is more desirable as it reduces cycle time and increases process safety by limiting the content of unreacted epoxide in the reactor.

[0011] Furthermore, the present invention can be used to produce polycarbonate block polyether polyol block copolymers containing a core of high carbonate content chains with terminal blocks of polyether chains. Polyurethanes made from such polyols benefit from the advantages of high carbonate linkages (e.g., increased strength, increased chemical resistance, resistance to both hydrolysis and oil, etc.) while still retaining the higher thermal stability provided by the ether end blocks. The polyols can advantageously be made in two reactions using the same or similar epoxide reactants. SUMMARY

[0012] According to a first aspect of the application, there is also provided a process for producing a polyol block copolymer in a multiple reactor system; the system comprising a first reactor and a second reactor, wherein a first reaction occurs in the first reactor and a second reaction occurs in the second reactor; wherein the first reaction is a carbonate catalyst reacting with CO2 and an epoxide in the presence of a starter and / or solvent to produce a polycarbonate polyol copolymer and the second reaction is a DMC catalyst reacting with the polycarbonate polyol compound of the first reaction and an epoxide to produce a polyol block copolymer, wherein the product of the first reaction is fed to the second reactor as a crude reaction mixture, (ii) the epoxide and the polycarbonate polyol compound of the first reaction are fed to the second reactor in a continuous or semi-batch manner, and / or (iii) the product of the first reaction has a neutral or basic pH when added to the second reaction.

[0013] According to a second aspect of the application, there is also provided a process for producing a polyol block copolymer in a multiple reactor system; the system comprising a first reactor and a second reactor, wherein a first reaction occurs in the first reactor and a second reaction occurs in the second reactor; wherein the first reaction is a carbonate catalyst reacting with CO2 and an epoxide in the presence of a multi-functional starter and optionally a solvent to produce a polycarbonate polyol, and the second reaction is a DMC catalyst reacting with the polycarbonate polyol compound of the first reaction and an epoxide in a semi-batch or continuous reaction to produce a polyol block copolymer.

[0014] The addition of components in separate reactions and reactors can usefully increase the activity of the catalysts and can result in a more efficient process compared to processes where all materials are provided at the start of one reaction. The presence of large amounts of some components throughout the entire reaction can decrease the efficiency of the catalysts. Reacting such materials in separate reactors can prevent such decreased catalyst efficiency and / or can optimise catalyst activity. The reaction conditions of each reactor can be adjusted to optimise the reaction of each catalyst.

[0015] Additionally, not loading the total amount of each component at the start of the reaction and having the catalyst of the first reaction in a separate reactor to the catalyst of the second reaction can result in uniform catalysis and a more uniform polymer product. This in turn can result in a polymer with a narrower molecular weight distribution, a desired ratio and distribution of chains along the ether to carbonate linkages and / or increased polyol stability.

[0016] It can also be useful to separate the reactions with the two different catalysts and mix only certain components in the first reaction and add the remainder in the second reaction, as the DMC catalyst can be pre-activated. This pre-activation can be achieved by mixing one or both of the catalysts with the epoxide (and optionally other components). Pre-activation of the DMC catalyst is useful as it enables safe control of the reaction (preventing uncontrolled increases in unreacted monomer content) and removes the unpredictable activation period.

[0017] It will be appreciated that the present invention relates to a reaction that adds carbonate and / or ether linkages to a growing polymer chain. Having separate reactions allows the first reaction to proceed before the second stage in the reaction. Mixing the epoxide, carbonate catalyst, starting compounds and carbon dioxide can allow a polymer with a high number of carbonate linkages to grow. Subsequently, adding the product to a DMC catalyst in the absence of CO2 allows the reaction to proceed by adding ether linkages to the growing polymer chain. Ether linkages are more thermally stable than carbonate linkages and are less susceptible to degradation by bases such as amine catalysts used in PU formation. Thus, these applications benefit from the high carbonate linkage introduced by block A (such as strength, increased resistance to chemicals, increased resistance to both oil and hydrolysis etc.) while still retaining the stability of the polyol through the ether linkages from block B at the end of the polymer chain.

[0018] In general, the aim of the present invention is to control the polymerisation reaction through a two reactor system to increase the CO2 content of the polyol at low pressure (making a more cost effective process and equipment design possible) and to make a product with a high CO2 content but with good stability and application performance. The method herein can allow the product made by such a method to be tailored to the requirements necessary.

[0019] The polyol block copolymer of the present invention can be made from: for the first reaction, a suitable epoxide and carbon dioxide in the presence of a starting compound and a carbonate catalyst; and then in the second reaction, a suitable epoxide in the presence of a double metal cyanide (DMC) catalyst.

[0020] While typically any residual CO2 from the first reaction can be removed from the crude reaction product of the first reaction before the second reaction is started, such that the second reaction is run in the absence of CO2, it will be appreciated that a small amount of CO2 can be present in the second reaction mixture as un-used reagent from the first reaction.

[0021] Typically, the first reaction mixture contains less than 5% by weight, preferably less than 2.5%, such as less than 1.0%, less than 0.5%, or less than 0.1% CO2before being added to the second reaction. Typically, the second reaction is carried out without the independent addition of CO2. The polyether blocks produced in the second reaction can have less than 1% carbonate linkages, preferably less than 0.5% carbonate linkages, more preferably less than 0.1% carbonate linkages. Preferably, the polyether blocks produced in the second reaction are substantially free of carbonate linkages.

[0022] Typically, therefore, the second reaction is carried out in the substantial absence of CO2.

[0023] By substantial absence of CO2, it is meant that the second reaction is carried out in the presence of less than 4% by weight, preferably less than 2% by weight, such as less than 1.0%, less than 0.5%, or less than 0.1% CO2of the total reactants, catalyst, and products in the second reaction.

[0024] By crude reaction mixture, it is meant that the products of the reaction are typically not isolated before the reaction mixture is added to the second reaction. Preferably, the reaction mixture does not undergo additional processing steps before it is added to the second reaction.

[0025] The carbonate catalyst of the present invention can be a catalyst that produces a polycarbonate polyol having greater than 76% carbonate linkages, preferably greater than 80% carbonate linkages, more preferably greater than 85% carbonate linkages, most preferably greater than 90% carbonate linkages that can be present in block A.

[0026] If the epoxide used is asymmetric (e.g., propylene oxide), the catalyst can produce a polycarbonate polyol having a high proportion of head to tail linkages, such as greater than 70%, greater than 80%, or greater than 90% head to tail linkages. Alternatively, the catalyst can produce a polycarbonate polyol without stereoselectivity, resulting in a polyol having about 50% head to tail linkages.

[0027] The carbonate catalyst can be heterogeneous or homogeneous.

[0028] The carbonate catalyst can be a single metal, double metal, or multiple metal homogeneous complex.

[0029] The carbonate catalyst can comprise a phenolic or phenoxide ligand.

[0030] Typically, the carbonate catalyst can be a double metal complex comprising a phenolic or phenoxide ligand. The two metals can be the same or different.

[0031] The carbonate catalyst can be a catalyst of formula (IV):

[0032]

[0033] wherein:

[0034] M is a metal cation represented by M-(L) v x is an integer from 1 to 4, preferably x is 1 or 2;

[0035] x is an integer from 1 to 4, preferably x is 1 or 2;

[0036] is a polydentate ligand or a plurality of polydentate ligands;

[0037] L is a coordinating ligand, for example, L can be a neutral ligand or an anionic ligand capable of ring opening an epoxide;

[0038] v is an integer that independently satisfies the valence of each M and / or the preferred coordination geometry of each M, or is an integer such that the complex represented by the above formula (IV) has an overall neutral charge. For example, each v can independently be 0, 1, 2, or 3, for example v can be 1 or 2. When v > 1, each L can be different.

[0039] The term polydentate ligand includes bidentate, tridentate, tetradentate, or higher dentate ligands. Each polydentate ligand can be a macrocyclic ligand or an open ring ligand.

[0040] Such catalysts include those in WO 2010022388 (metal salen and derivatives, metal porphyrin, corrole and derivatives, metal tetraazacycloalkane and derivatives), WO 2010028362 (metal salen and derivatives, metal porphyrin, corrole and derivatives, metal tetraazacycloalkane and derivatives), WO 2008136591 (metal salen), WO 2011105846 (metal salen), WO 2014148825 (metal salen), WO 2013012895 (metal salen), EP 2258745A1 (metal porphyrin and derivatives), JP 2008081518A (metal porphyrin and derivatives), CN 101412809 (metal salen and derivatives), WO 2019126221 (metal aminotriol complex), US 9018318 (metal beta-diiminate complex), US 6133402A (metal beta-diiminate complex), and US 8278239 (metal salen and derivatives), the entire contents of which, especially insofar as they relate to suitable carbonate catalysts (for the reaction of CO2 with an epoxide in the presence of a starter and optionally a solvent to produce a polycarbonate polyol copolymer as defined herein), are incorporated herein by reference.

[0041] Such catalysts also include those in WO 2009 / 130470, WO 2013 / 034750, WO 2016 / 012786, WO 2016 / 012785, WO 2012037282 and WO 2019048878A1 (all bimetallic phenolate complexes), the entire contents of which, especially insofar as they relate to suitable carbonate catalysts (for the reaction of CO2 with an epoxide in the presence of a starter and optionally a solvent to produce a polycarbonate polyol copolymer as defined herein), are incorporated herein by reference.

[0042] The carbonate catalyst can have the following structure:

[0043]

[0044] wherein:

[0045] M1and M2are 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, Y(III)-X, Sc(III)-X or Ti(IV)-(X)2;

[0046] R1and R2are independently selected from hydrogen, halide, nitro, nitrile, imine, amine, ether, silyl, silyl ether group, sulfoxide group, sulfonyl, sulfinate group or acetylene compound group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

[0047] R3is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene can optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic group;

[0048] R5is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl group;

[0049] E1is C and E2is O, S or NH, or E1is N and E2is O;

[0050] E3, E4, E5, and E6 are selected from N, NR4, O, and S, wherein when E3, E4, E5, or E6 is N, is =, and wherein when E3, E4, E5, or E6 is NR4, O, or S, is -;

[0051] R4is independently selected from H or an optionally substituted aliphatic, heteroaliphatic, alicyclo, heteroalicyclo, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 or -alkylC≡N or alkylaryl;

[0052] X is independently selected from OC(O)R x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinates, phosphates, halides, nitrates, hydroxyls, carbonates, amines, nitro groups, amide groups, or optionally substituted aliphatic, heteroaliphatic, alicyclo, heteroalicyclo, aryl, or heteroaryl groups, wherein each X can be the same or different and wherein X can form a bridge between M1and M2;

[0053] R x is independently hydrogen, or an optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclo, heteroalicyclo, aryl, alkylaryl, or heteroaryl group; and

[0054] G is absent or independently selected from neutral or anionic donor ligands that are Lewis bases.

[0055] Each occurrence of groups R1and R2may be the same or different, and R1and R2may be the same or different.

[0056] The DMC catalyst is a complex compound that includes at least two metal centers and a cyanide ligand. The DMC catalyst can additionally include at least one of the following: one or more complexing agents, water, metal salts, and / or acids (e.g., non-stoichiometric amounts).

[0057] The first two of the at least two metal centers can be represented by M’ and M”.

[0058] 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), optionally M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), optionally M' is Zn(II).

[0059] M" is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V), optionally M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), optionally M" is selected from Co(II) and Co(III).

[0060] It will be appreciated that the above optional definitions of M' and M" can be combined. For example, optionally M' can be selected from Zn(II), Fe(II), Co(II), and Ni(II), and M" can be optionally selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II). For example, M' can be optionally Zn(II), and M" can be optionally selected from Co(II) and Co(III).

[0061] If one or more additional metal centres are present, the additional metal can further be selected from the definitions of M' or M".

[0062] Examples of DMC catalysts that can be used in the process of the present application include those described in US 3,427,256, US 5,536,883, US 6,291,388, US 6,486,361, US 6,608,231, US 7,008,900, US 5,482,908, US 5,780,584, US 5,783,513, US 5,158,922, US 5,693,584, US 7,811,958, US 6,835,687, US 6,699,961, US 6,716,788, US 6,977,236, US 7,968,754, US 7,034,103, US 4,826,953, US 4,500 704, US 7,977,501, US 9,315,622, EP-A-1568414, EP-A-1529566 and WO 2015 / 022290, the entire contents of which, to the extent that they relate to a DMC catalyst for producing a block copolymer as defined herein or a reaction as defined herein, are incorporated herein by reference.

[0063] It will be appreciated that the DMC catalyst can comprise:

[0064] M’ [M” e (CN)f]g

[0065] wherein M’ and M” are as defined above, d, e, f and g are integers and are selected such that the DMC catalyst is electrically neutral. Optionally, d is 3. Optionally, e is 1. Optionally, f is 6. Optionally, g is 2. Optionally, M’ is selected from Zn(II), Fe(II), Co(II) and Ni(II), optionally M’ is Zn(II). Optionally, M” is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), optionally M” is Co(II) or Co(III).

[0066] It will be appreciated that any of these optional 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).

[0067] Suitable DMC catalysts having the above formula can include zinc(III) hexacyanocobaltate, zinc(III) hexacyanoferrate, nickel(II) hexacyanoferrate and cobalt(III) hexacyanocobaltate.

[0068] There have been many developments in the field of DMC catalysts, and the skilled person will appreciate that in addition to the above formula, DMC catalysts can comprise additional additives to improve the activity of the catalyst. Thus, while the above formula can form the "core" of a DMC catalyst, the DMC catalyst can additionally comprise stoichiometric or non-stoichiometric amounts of one or more additional components, such as at least one complexing agent, an acid, a metal salt, and / or water.

[0069] For example, the DMC catalyst can have the following formula:

[0070] M'd[M” e (CN)f]g-hM”’X”i-jR c -kH2O-lH r X”

[0071] where M', M", X", d, e, f, and g are as defined above. M'" can be M' and / or M". X" is an anion selected from the group consisting of a halide ion, an oxide ion, a hydroxide, a sulfate, a carbonate, a cyanide, an oxalate, a thiocyanate, an isocyanate, an isothiocyanate, a carboxylate, and a nitrate, optionally X" is a halide ion. i is an integer of 1 or greater, and the charge on the anion X" multiplied by i satisfies the valence of M'". r is an integer corresponding to the charge on the counterion X". For example, when X" is CI - , r is 1. I is 0 or a number between 0.1 and 5. Optionally, I is between 0.15 and 1.5.

[0072] R c is a complexing agent or a combination of one or more complexing agents. For example, R c may be a (poly)ether, a polyether carbonate, a polycarbonate, a poly(tetramethylene ether glycol), a ketone, an ester, an amide, an alcohol (e.g., a C 1-8 alcohol), a urea, or the like, such as propylene glycol, polypropylene glycol, methoxyethanediol or ethoxyethanediol, dimethoxyethane, t-butanol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof, for example, R c may be t-butanol, dimethoxyethane, or polypropylene glycol.

[0073] As indicated above, more than one complexing agent can be present in the DMC catalyst used in the present invention. Optionally, one of the complexing agents of R c may be a polymeric complexing agent. Optionally, R cmay be a combination of a polymeric complexing agent and a non-polymeric complexing agent. Optionally, a combination of the complexing agents t-butyl alcohol and polypropylene glycol can be present.

[0074] It is understood that h, j, k, and / or 1 are zero if water, complexing agent, acid, and / or metal salt are not present in the DMC catalyst. If water, complexing agent, acid, and / or metal salt are present, h, j, k, and / or 1 are positive numbers and can be, for example, between 0 and 20. For example, h can be between 0.1 and 4. j can be between 0.1 and 6. k can be between 0 and 20, for example, between 0.1 and 10, such as between 0.1 and 5. 1 can be between 0.1 and 5, such as between 0.15 and 1.5.

[0075] The polymeric complexing agent is optionally selected from polyethers, polycarbonate ethers, and polycarbonates. The polymeric complexing agent can be present in an amount of from about 5% to about 80% by weight of the DMC catalyst, optionally from about 10% to about 70% by weight of the DMC catalyst, optionally from about 20% to about 50% by weight of the DMC catalyst.

[0076] In addition to the at least two metal centers and the cyanide ligand, the DMC catalyst can comprise, optionally in non-stoichiometric amounts, at least one of the following: one or more complexing agents, water, metal salt, and / or acid.

[0077] An exemplary DMC catalyst has the formula Zn3[Co(CN)6]2· hZnCl2· kH2O· j[(CH3)3COH], where h, k, and j are as defined above. For example, h can be from 0 to 4 (e.g., from 0.1 to 4), k can be from 0 to 20 (e.g., from 0.1 to 10), and j can be from 0 to 6 (e.g., from 0.1 to 6). As noted above, the DMC catalyst is a complex structure and thus the above formula including additional components is not intended to be limiting. Rather, the skilled artisan will understand that this definition is non-exhaustive of DMC catalysts that can be used in the present invention.

[0078] The DMC catalyst can be pre-activated. This pre-activation can be achieved by mixing one or both of the catalysts with the alkylene oxide (and optionally other components). Pre-activation of the DMC catalyst is useful because it enables safe control of the reaction (preventing uncontrolled increases in unreacted monomer content) and removes unpredictable activation periods. Optionally, the DMC catalyst can be pre-activated in reactor 2 or separately. Optionally, the DMC catalyst can be pre-activated with the starting compounds or with the reaction products of the first reaction or the second reaction. When the DMC catalyst is pre-activated with the reaction products of the first reaction, it can be pre-activated with some or all of the reaction products of the first reaction. The DMC catalyst can be pre-activated with the polyol block copolymer product, which can be added to the reactor, or can be the remaining product from the previous reaction (the so-called ‘reaction heel’).

[0079] The starting compounds that can be used in the process for forming the polycarbonate polyols of the application comprise at least one group, preferably at least two groups, selected from a hydroxyl group (-OH), a thiol group (-SH), an amine group having at least one N-H bond (-NHR’), a group having at least one P-OH bond (for example, -PR’(O)OH, PR’(O)(OH)2or -P(O)(OR’)(OH)), or a carboxylic acid group (-C(O)OH).

[0080] -PR’(O)OH, PR’(O)(OH)2or -P(O)(OR’)(OH)), or a carboxylic acid group (-C(O)OH).

[0081] In the case where the starting material is a polyfunctional starting compound, the starting compound comprises at least two groups selected from a hydroxyl group (-OH), a thiol group (-SH), an amine group having at least one N-H bond (-NHR’), a group having at least one P-OH bond (for example, -PR’(O)OH, PR’(O)(OH)2or -P(O)(OR’)(OH)), or a carboxylic acid group (-C(O)OH).

[0082] Thus, the starting compounds that can be used in the process for forming the polycarbonate ether polyols can have the formula (III):

[0083]

[0084] Z can be a group that can have 1 or more -R Z groups attached thereto, preferably 2 or more -R zAny of the groups. Thus, Z can be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be a combination of any of these groups, for example, Z can be alkylarylene, heteroalkylarylene, heteroalkylheteroarylene, or alkylheteroarylene. Optionally, Z is alkylene, heteroalkylene, arylene, or heteroarylene.

[0085] a is an integer of at least 1, preferably at least 2, optionally a is in the range of 1 to 8, optionally a is in the range of 2 to 6.

[0086] each R Z may be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH)2, or -PR'(O)OH, optionally R Z is selected from -OH, -NHR', or -C(O)OH, optionally each R z is -OH, -C(O)OH, or a combination thereof (e.g., each R z is -OH).

[0087] R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, optionally R' is H or optionally substituted alkyl.

[0088] Z' corresponds to R z , except that a bond replaces the labile hydrogen atom. Thus, the identity of each Z' depends on the definition of R Z in the starting compound. Thus, it is understood that each Z' can be -O-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -PR'(O)(O-)2, or -PR'(O)O- (where R' can be H or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, preferably R' is H or optionally substituted alkyl), preferably Z' can be -C(O)O-, -NR'-, or -O-, more preferably each Z' can be -O-, -C(O)O-, or a combination thereof, more preferably each Z' can be -O-.

[0089] More than one starting compound can be present in each reaction. The starting compounds of the first reaction and the second reaction can be the same or different. In the case of two different starting compounds, there can be two starting compounds in the second reaction, where the starting compound in the first reaction is a first starting compound, and where the second reaction includes adding the first crude reaction mixture to a second reactor including a second starting compound and a double metal cyanide (DMC) catalyst, and optionally a solvent and / or an epoxide. The second reaction of the present invention can be conducted at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, optionally at least about 5 hours, after the first reaction. It is understood that in a continuous reaction, these time periods are the average time periods from the addition of monomer in the first reactor to the transfer of monomer residue to the second reactor.

[0090] If a polymer, the starting compound can have a molecular weight of at least about 200 Da or at most about 1000 Da.

[0091] For example, a molecular weight of about 200 to 1000 Da, optionally about 300 to 700 Da, optionally about 400 Da.

[0092] The starting compound or each starting compound typically has one or more R z groups, optionally two or more, optionally three or more, optionally four or more, optionally five or more, optionally six or more, optionally seven or more, optionally eight or more R z groups, in particular, where R z is a hydroxyl group.

[0093] It is understood that any of the above features can be combined. For example, a can be between 1 and 8, each R Z may be -OH, -C(0)OH, or a combination thereof, and Z can be selected from an alkylene, heteroalkylene, arylene, or heteroarylene.

[0094] Exemplary starting compounds of either reaction include monofunctional starting materials such as alcohols, phenols, amines, thiols, and carboxylic acids; for example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, 1-butanol and 2-butanol; linear or branched C3-C 20- monoalcohols such as tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine; monoethers or monoesters of ethylene, propylene, polyethylene; polypropylene glycols such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; phenols such as linear or branched C3-C 20 alkyl-substituted phenols, e.g., nonyl-phenol or octylphenol; monofunctional carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid; fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and acrylic acid; and monofunctional thiols such as ethanethiol, propan-1-thiol, propan-2-thiol, butan-1-thiol, 3-methylbutan-1-thiol, 2-buten-1-thiol, and benzenethiol; or amines such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine; and / or selected from diols such as 1,2-ethanediol (ethylene glycol), 1-2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-hydroquinone, 1,3-hydroquinone, 1,4-hydroquinone, neopentyl glycol, pyrocatechol, cyclohexene diol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or polyethylene glycol (PEG) having an Mn of up to about 1500 g / mol such as PPG 425, PPG 725, PPG 1000, and the like; triols such as glycerol, hydroquinone, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methylol)propane, tris(methylol)ethane, tris(methylol)nitropropane, trimethylolpropane, poly(ethylene oxide) triol, poly(propylene oxide) triol, and polyester triol; tetraols such as calix[4]arene, 2,2-bis(methylol)-1,3-propanediol, erythritol, pentaerythritol, or polyalkylene glycol (PEG or PPG) having 4 -OH groups; polyols such as sorbitol or polyalkylene glycol (PEG or PPG) having 5 or more -OH groups; or compounds having mixed functionality including ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine.

[0095] For example, the starting compound can be a monofunctional alcohol such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol; a phenol such as nonyl-phenol or octyl phenol; or a monofunctional carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid; a fatty acid such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.

[0096] For example, the starting compound can be a diol such as 1,2-ethanediol (ethyleneglycol), 1-2-propanediol, 1,3-propanediol (propyleneglycol), 1,2-butanediol, 1-3- butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-hydroquinone, 1,3- hydroquinone, 1,4-hydroquinone, neopentyl glycol, pyrocatechol, cyclohexene diol, 1,4- cyclohexanedimethanol, poly(caprolactone) diol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or polyethylene glycol (PEG) having a Mn of up to about 1500 g / mol (such as PPG 425, PPG 725, PPG 1000, etc.). It is understood that the starting compound can be 1,6-hexanediol, 1,4- cyclohexanedimethanol, 1,12-dodecanediol, poly(caprolactone) diol, PPG 425, PPG 725, or PPG 1000. Preferably, the starting compound can be a diol such as 1,2-ethanediol (ethyleneglycol), 1,3-propanediol (propyleneglycol), 1,2-butanediol, 1-3- butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-hydroquinone, 1,3- hydroquinone, 1,4-hydroquinone, neopentyl glycol, pyrocatechol, cyclohexene diol, 1,4- cyclohexanedimethanol, poly(caprolactone) diol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or polyethylene glycol (PEG) having a Mn of up to about 1500 g / mol (such as PPG 425, PPG 725, PPG 1000, etc.). It is understood that the starting compound can be 1,6-hexanediol, 1,4- cyclohexanedimethanol, 1,12-dodecanediol, poly(caprolactone) diol, PPG 425, PPG 725, or PPG 1000.

[0097] Further exemplary starting compounds can include diacids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, or other compounds with mixed functionality such as lactic acid, glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid.

[0098] The ratio of starting compound, if present, to carbonate catalyst can be in an amount from about 1000: 1 to about 1 : 1, for example from about 750: 1 to about 5: 1, such as from about 500: 1 to about 10: 1, for example from about 250: 1 to about 20: 1, or from about 125: 1 to about 30: 1, or from about 50: 1 to about 20: 1. These ratios are molar ratios. These ratios are the ratio of the total amount of starting material used in these processes to the total amount of carbonate catalyst. These ratios can be maintained during the course of adding materials.

[0099] The DMC catalyst can be pre-activated. Optionally, the DMC catalyst can be pre-activated in reactor 2 or separately. Optionally, the DMC catalyst can be pre-activated with a starting compound or with the reaction product of the first reaction or the second reaction. When the DMC catalyst is pre-activated with the reaction product of the first reaction, it can be pre-activated with some or all of the reaction product of the first reaction. The DMC catalyst can be pre-activated with a polyol block copolymer product, which can be added to the reactor, or can be the remaining product from a previous reaction (a so-called ‘reaction heel’).

[0100] The product of the first reaction can be a low molecular weight polycarbonate polyol. The preferred molecular weight (Mn) of the polycarbonate polyol depends on the preferred overall molecular weight of the polyol block copolymer. The molecular weight (Mn) of the polycarbonate polyol, as measured by gel permeation chromatography, can be in the range from about 200 to about 4000 Da, from about 200 to about 2000 Da, from about 200 to about 1000 Da, or from about 400 to about 800 Da.

[0101] The first reaction can produce a generally alternating polycarbonate polyol product.

[0102] The product of the first reaction can be fed into a separate reactor containing a pre-activated DMC catalyst. The first product can be fed into the separate reactor as a crude reaction mixture.

[0103] The first reaction of the present invention can be conducted at a CO2 pressure of less than 20 bar, preferably at a CO2 pressure of less than 10 bar, more preferably at a CO2 pressure of less than 8 bar. The second reaction of the present invention can be conducted at a CO2 pressure of less than 60 bar, preferably at a CO2 pressure of less than 20 bar, more preferably at a CO2 pressure of less than 10 bar, most preferably at a CO2 pressure of less than 5 bar.

[0104] CO2 can be added continuously in the first reaction, preferably in the presence of a starter.

[0105] The first reaction can be conducted at a carbon dioxide pressure of between about 1 bar and about 60 bar, optionally between about 1 bar and about 40 bar, optionally between about 1 bar and about 20 bar, optionally between about 1 bar and about 15 bar, optionally between about 1 bar and about 10 bar, optionally between about 1 bar and about 5 bar.

[0106] The second reaction can be conducted under reduced pressure or an inert gas such as N2or Ar. Any residual CO2remaining from the first reaction can be stripped by gas stripping of the reaction mixture or by applying a vacuum to the reaction mixture. As discussed above, a residual amount of CO2may be present in the reaction mixture from the first reaction, but the reaction mixture is less than 5% by weight, preferably less than 2.5%, less than 1.0%, less than 0.5%, or less than 0.1% CO2prior to addition to the second reaction. No additional CO2is added during the second reaction. The product of the first reaction can be transferred to the second reaction at the pressure of the unused CO2from the first reaction, but no additional CO2is added in the second reactor.

[0107] The first reaction process conducted at these relatively low CO2pressures and continuous addition of CO2can produce a polyol with a high CO2content at low pressure. CO2can be introduced into the first reactor by standard methods, such as directly into the headspace or directly into the reaction liquid by standard methods such as an inlet tube, sparge ring, or hollow shaft agitator. Mixing can be optimized by using different agitator configurations, such as a single agitator or a multi-stage configuration of agitators.

[0108] The first reaction can be conducted in a batch, semi-batch, or continuous process. In a batch process, all of the carbonate catalyst, epoxide, CO2, starter, and optionally solvent are present at the beginning of the reaction. In a semi-batch or continuous reaction, one or more of the carbonate catalyst, epoxide, CO2, starter, and / or solvent are added to the reactor in a continuous, semi-continuous, or discontinuous manner.

[0109] The second reaction including DMC can be conducted as a continuous process or a semi-batch process. In a semi-batch or continuous process, one or more of the DMC catalyst, epoxide, starter, and / or solvent are added to the reaction in a continuous or discontinuous manner.

[0110] Optionally, the crude reaction mixture fed to the second reactor can contain an amount of unreacted epoxide and / or starter.

[0111] Optionally, the crude reaction mixture feed can contain an amount of carbonate catalyst. Optionally, the carbonate catalyst can be removed prior to addition to the second reactor.

[0112] The polycarbonate product of the first reaction can be referred to as a crude product.

[0113] The polycarbonate product of the first reaction can be fed to the second reaction in a single slug or in a continuous, semi-continuous or discontinuous manner. Preferably, the product of the first reaction is fed to the second reactor in a continuous manner, which optionally contains unreacted epoxide and / or carbonate catalyst. This is advantageous because the continuous addition of the reaction 1 product as a starting material for the DMC catalyst allows the DMC catalyst to operate in a more controlled manner in reactor 2 because the ratio of starting material to DMC catalyst is always decreasing in the reactor. This can prevent the DMC catalyst from deactivating in reactor 2. The polycarbonate of reaction 1 can be fed to the second reactor prior to DMC activation and can be used during DMC activation. The DMC catalyst can also be pre-activated with a polyol block copolymer, which can be added to the reactor or can be the remaining product from the previous reaction (so-called'reaction heel').

[0114] The reaction temperature in the first reactor can be in the range from about 0°C to 250°C, preferably from about 40°C to about 160°C, more preferably from about 50°C to 120°C.

[0115] The reaction temperature in the second reactor can be in the range from about 50°C to about 160°C, preferably in the range from about 70°C to about 140°C, more preferably from about 80°C to about 130°C.

[0116] The two reactors can be placed in series, or the reactors can be nested. Each reactor can individually be a stirred tank reactor, a loop reactor, a tubular reactor or other standard reactor design.

[0117] The first reaction can be carried out continuously with the crude reaction mixture feed to the second reaction and more than one reactor. Preferably, reaction 2 is run in a continuous mode.

[0118] The product of the first reaction can be stored for later use in the second reactor.

[0119] Advantageously, the two reactions can be run independently to obtain optimal conditions for each reaction. If the two reactors are nested, they can effectively provide different reaction conditions to each other at the same time.

[0120] Optionally, the polycarbonate polyol can not be acid stabilized prior to addition to the second reactor.

[0121] If the polycarbonate polyol is acid stabilized prior to addition to the second reactor, the acid can be an inorganic acid or an organic acid. Such acids include, but are not limited to, phosphoric acid derivatives, sulfonic acid derivatives (e.g., methanesulfonic acid, p-toluenesulfonic acid), carboxylic acids (e.g., acetic acid, formic acid, oxalic acid, salicylic acid), inorganic acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid), nitric acid, or carbonic acid. The acid can be part of an acidic resin such as an ion exchange resin. Acidic ion exchange resins can be in the form of a polymeric matrix such as polystyrene or polymethacrylic acid, featuring acidic sites such as strong acid sites (e.g., sulfonic acid sites) or weak acid sites (e.g., carboxylic acid sites). Exemplary ion exchange resins include Amberlyst 15, Dowex Marathon MSC, and Amberlite IRC 748.

[0122] The first reaction and the second reaction of the present invention can be carried out in the presence of a solvent, however, it is also understood that these processes can also be carried out in the absence of a solvent. When a solvent is present, it can be toluene, hexane, t-butyl acetate, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, dichloromethane, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), and the like. The solvent can be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0123] The solvent can be used to dissolve one or more of these materials. However, the solvent can act as a carrier and be used to suspend one or more of these materials in a suspension. The solvent can be needed to aid in the addition of one or more of these materials during the steps of the process of the present invention.

[0124] The process can employ a total amount of solvent, and wherein about 1% to 100% of the total amount of solvent can be mixed in the first reaction, the remainder being added in the second reaction; optionally about 1% to 75%, optionally about 1% to 50%, optionally about 1% to 40%, optionally about 1% to 30%, optionally about 1% to 20%, optionally about 5% to 20% is mixed in the first reaction.

[0125] The total amount of carbonate catalyst can be low, such that the first reaction of the present application can be carried out at a low catalytic loading. For example, the catalytic loading of carbonate catalyst can be in the range of about 1 :500-100,000 [total carbonate catalyst]:[total epoxide], such as about 1 :750-50,000 [total carbonate catalyst]:[total epoxide], for example in the region of about 1 :1,000-20,000 [total carbonate catalyst]:[total epoxide], for example in the region of about 1 :10,000 [total carbonate catalyst]:[total epoxide]. The above ratios are molar ratios. These ratios are the ratio of the total amount of carbonate catalyst used in the first reaction to the total amount of epoxide.

[0126] The method can employ a total amount of epoxide, and about 1% to 100% of the total amount of epoxide can be mixed in the first reaction. The remainder of the epoxide can be added in the second reaction; optionally about 5% to 90%, optionally about 10% to 90%, optionally about 20% to 90%, optionally about 40% to 90%, optionally about 40% to 80%, optionally about 5% to 50% is mixed in the first reaction.

[0127] The epoxide used in the first and second reactions can be any suitable compound containing an epoxide moiety. Exemplary epoxides include oxirane, propylene oxide, butylene oxide, and cyclohexene oxide. The epoxide(s) used in the second reaction can be the same as or different from the epoxide(s) used in the first reaction. Thus, a mixture of epoxide(s) can be present in one or both of the reactions. For example, the first reaction can include propylene oxide and the second reaction can include oxirane, or both reactions can include oxirane, or one or both reactions can use a mixture of epoxides, such as a mixture of oxirane and propylene oxide.

[0128] The epoxide can be purified (e.g., by distillation, such as distillation over calcium hydride) prior to reaction with carbon dioxide. For example, the epoxide can be distilled prior to addition.

[0129] Examples of epoxides that can be used in the present application include, but are not limited to, cyclohexene oxide, styrene oxide, oxirane, 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 22O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (such as ethylene oxide, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1,2- butylene oxide, glycidyl ether, glycidyl ester, glycidyl carbonate, vinyl-oxycyclohexene, 3-phenyl-1,2-epoxypropane, 2,3-epoxybutane, isobutylene oxide, oxycyclopentene, 2,3- epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxirane. Examples of functionalized 3,5-dioxiranes include:

[0130]

[0131] The epoxide moiety can be a glycidyl ether, a glycidyl ester, or a glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters, glycidyl carbonates include:

[0132]

[0133] As noted above, the epoxide substrate can contain more than one epoxide moiety, i.e., it can be a bis-epoxide, a tris-epoxide, or a poly-epoxide containing moiety. Examples of compounds containing more than one epoxide moiety include bis-epoxybutane, bis-epoxyoctane, bis-epoxydecane, bisphenol A diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3',4'- epoxycyclohexane carboxylate. It will be appreciated that reactions conducted in the presence of one or more compounds having more than one epoxide moiety can result in crosslinking of the resulting polymer.

[0134] Optionally, between 0.1% and 20% of the total epoxide in the first reaction can be an epoxide substrate containing more than one epoxide moiety. Preferably, the poly-epoxide substrate is a bis-epoxide.

[0135] The skilled person will appreciate that epoxides can be obtained from “green” or renewable resources. Epoxides can be obtained from (poly)unsaturated compounds obtained using standard oxidation chemistry, such as those derived from fatty acids and / or terpenes.

[0136] The epoxide portion can contain an -OH portion or a protected -OH portion. The -OH portion can be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, t- butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzoyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl groups such as trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), triisopropylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

[0137] The epoxide optionally has a purity of at least 98%, optionally >99%.

[0138] The rate at which the material is added can be selected so that the temperature of the (exothermic) reaction does not exceed a selected temperature (i.e., the material is added slowly enough to allow any excess heat to dissipate so that the temperature remains approximately constant). The rate at which the material is added can be selected so that the epoxide concentration does not exceed a selected epoxide concentration.

[0139] The method can produce a polyol having a polydispersity between 1.0 and 2.0, preferably between 1.0 and 1.8, more preferably between 1.0 and 1.5, most preferably between 1.0 and 1.3.

[0140] The method can include mixing a double metal cyanide (DMC) catalyst, an epoxide, a starter, and optionally a solvent to form a pre-activation mixture, and adding the pre-activation mixture to the second reactor before or after the crude reaction mixture of the first reaction to form a second reaction mixture. However, this can occur continuously so that the pre-activation mixture is added simultaneously with the crude reaction mixture. The pre-activation mixture can also be formed in the second reactor by mixing the DMC catalyst, the epoxide, the starter, and optionally the solvent. The pre-activation can occur at a temperature of about 50°C to 160°C, preferably between about 70°C to 140°C, more preferably about 90°C to 140°C. The pre-activation mixture can be mixed at a temperature of between about 50°C to 160°C, optionally between about 70°C to 140°C, before being contacted with the crude reaction mixture.

[0141] The predetermined weight ratio of the amount of the carbonate catalyst to the amount of the double metal cyanide (DMC) catalyst to each other throughout the reaction can be from about 300: 1 to about 1 : 100, for example from about 120: 1 to about 1 : 75, such as from about 40: 1 to about 1 : 50, for example from about 30: 1 to about 1 : 30, such as from about 20: 1 to about 1 : 1, for example from about 10: 1 to about 2: 1, for example from about 5: 1 to about 1 : 5. The method of the present application can be carried out at any scale. The method can be carried out at an industrial scale. As will be appreciated by the skilled person, catalytic reactions are generally exothermic. Heat production during small scale reactions is unlikely to be problematic as any temperature increase can be controlled relatively easily, for example by the use of an ice bath. In the case of larger scale reactions, and in particular industrial scale reactions, heat production during the reaction can be problematic and potentially dangerous. Thus, gradual addition of materials can allow the rate of the catalytic reaction to be controlled and can minimise the build-up of excess heat. The rate of reaction can be controlled, for example, by adjusting the flow rate of the materials during addition. Thus, the method of the present application has particular advantages if applied to large industrial scale catalytic reactions.

[0142] The temperature can increase or decrease during the course of the method of the present application.

[0143] The amount of the carbonate catalyst to the amount of the double metal cyanide (DMC) catalyst will vary depending on the carbonate catalyst and DMC catalyst used.

[0144] The product of the method of the first aspect of the present application is a polyol block copolymer. According to a third aspect of the present application, there is provided a polyol block copolymer comprising polycarbonate blocks A (-A’-Z’-Z-(Z’-A’) n -) and polyether blocks B, wherein the polyol block copolymer has a multi-block structure:

[0145] B-A’-Z’-Z-(Z’-A’-B) n

[0146] wherein n = t - 1 and wherein t = the number of terminal OH group residues on the block A; and wherein each A’ is independently a polycarbonate chain having at least 70% carbonate linkages, and wherein each B is independently a polyether chain and wherein Z’-Z-(Z’ n is a starter residue.

[0147] In the method according to the first aspect, the starter can be a monofunctional starter. In this case, for the avoidance of doubt, the multi-block structure is:

[0148] B-A’-Z’-Z

[0149] The polycarbonate block comprises -A' - which can have the structure:

[0150]

[0151] wherein the ratio of p:q is at least 7:3; and

[0152] R e1 and R e2 depend on the nature of the epoxide used to make block A.

[0153] The polyether block B can have the structure:

[0154]

[0155] wherein

[0156] R e3 and R e4 depend on the nature of the epoxide used to make block B.

[0157] R e1 , R e2 , R e3 or R e4 may each independently be selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl, preferably from H or optionally substituted alkyl.

[0158] R e1 and R e2 or R e3 and R e4 may together form a saturated, partially unsaturated, or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms.

[0159] As noted above, the nature of R e1 , R e2 , R e3 and R e4 will depend on the epoxide used in the reaction. For example, if the epoxide is cyclohexene oxide (CHO), R e1 and R e2 (or R e3 and R e4 ) will together form a six-membered alkyl ring (e.g., a cyclohexyl ring). If the epoxide is ethylene oxide, R e1 and R e2 (or R e3 and R e4 ) will be H. If the epoxide is propylene oxide, R e1 (or R e3 ) will be H and R e2 (or Re4 ) will be methyl (or R e1 (Or R e3 ) will be methyl and R e2 (Or R e4 ) will be H, depending on the way the epoxide is added to the polymer backbone). If the epoxide is butylene oxide, R e1 (Or R e3 ) will be H and R e2 (Or R e4 ) will be ethyl (or vice versa). If the epoxide is styrene oxide, R e1 (Or R e3 ) can be hydrogen and R e2 (Or R e4 ) can be phenyl (or vice versa). If the epoxide is glycidyl ether, R e1 (Or R e3 ) will be an ether group (-CH2-OR 20 ) and R e2 (Or R e4 ) will be H (or vice versa). If the epoxide is glycidyl ester, R e1 (Or R e3 ) will be an ester group (-CH2-OC(O)R 12 ) and R e2 (Or R e4 ) will be H (or vice versa). If the epoxide is glycidyl carbonate, R e1 (Or R e3 ) will be a carbonate group (CH2-OC(O)OR 18 ) and R e2 (Or R e4 ) will be H (or vice versa).

[0160] It will also be appreciated that if a mixture of epoxides is used, each occurrence of R e1 and / or R e2 (Or R e3 and / or R e4 ) can be different, for example if a mixture of ethylene oxide and propylene oxide is used, R e1 (Or R e3 ) can independently be hydrogen or methyl and R e2 (Or R e4 ) can independently be hydrogen or methyl.

[0161] Thus, R e1 and R e2 (Or R e3 and R e4 ) can independently be selected from hydrogen, alkyl or aryl, or Re1 and R e2 (or R e3 and R e4 ) can together form a cyclohexyl ring, preferably R e1 and R e2 (or R e3 and R e4 ) can independently be selected from hydrogen, methyl, ethyl or phenyl, or R e1 and R e2 (or R e3 and R e4 ) can together form a cyclohexyl ring.

[0162] The nature of Z and Z’ will depend on the nature of the starting compound.

[0163] The starting compound can have formula (III) as described above.

[0164] Preferably, the polyol block copolymer has a molecular weight (Mn) in the range from about 300 to 20,000 Da, more preferably in the range from about 400 to 8000 Da, most preferably from about 500-6000 Da.

[0165] The polycarbonate block A of the polyol block copolymer preferably has a molecular weight (Mn) in the range from about 200 to 4000 Da, more preferably in the range from about 200 to 2000 Da, most preferably from about 200 to 1000 Da, especially from about 400 to 800 Da.

[0166] The polyether block B of the polyol block copolymer preferably has a molecular weight (Mn) in the range from about 100 to 20,000 Da, more preferably from about 200 to 10,000 Da, most preferably from about 200 to 5000 Da.

[0167] Alternatively, the polyether block B and thus also the polyol block copolymer can have a high molecular weight. The polyether block B can have a molecular weight of at least about 25,000 Daltons, such as at least about 40,000 Daltons, for example at least about 50,000 Daltons or at least about 100,000 Daltons. The high molecular weight polyol block copolymer formed by the process of the present application can have a molecular weight higher than about 100,000 Daltons.

[0168] The Mn and thus PDI of the polymers produced by the methods of the present application can be measured using gel permeation chromatography (GPC). For example, GPC can be measured using an Agilent 1260 Infinity GPC machine with two Agilent PLgel μ-m Mixed-D columns in series. Samples can be measured against narrow polystyrene standards (e.g., polystyrene low EasiVial with a range of Mn from 405 to 49,450 g / mol provided by Agilent Technologies) in THF at room temperature (293 K) at a flow rate of 1 mL / min. Optionally, samples can be measured against poly(ethylene glycol) standards such as polyethylene glycol easivial provided by Agilent Technologies.

[0169] The polycarbonate block A of the polyol block copolymer can have at least 76% carbonate linkages, preferably at least 80% carbonate linkages, more preferably at least 85% carbonate linkages. The block A can have less than 98% carbonate linkages, preferably less than 97% carbonate linkages, more preferably less than 95% carbonate linkages. Optionally, the block A has between 75% and 99% carbonate linkages, preferably between 77% and 95% carbonate linkages, more preferably between 80% and 90% carbonate linkages.

[0170] The polycarbonate block A of the polyol block copolymer can also include ether linkages. The block A can have less than 24% ether linkages, preferably less than 20% ether linkages, more preferably less than 15% ether linkages. The block A can have at least 1% ether linkages, preferably at least 3% ether linkages, more preferably at least 5% ether linkages. Optionally, the block A can have between 1% and 25% ether linkages, preferably between 5% and 20% ether linkages, more preferably between 10% and 15% ether linkages.

[0171] Optionally, the block A can be generally alternating polycarbonate polyol residues. If the epoxide is asymmetric, the polycarbonate can have between 0-100% head-to- tail linkages, preferably between 40-100% head-to-tail linkages, more preferably between 50-100% head-to-tail linkages. The polycarbonate can have a statistical distribution of head-to-head, tail-to-tail, and head-to-tail linkages of approximately 1 :2: 1, which indicates a non-stereoselective ring opening of the epoxide, or it can preferentially have head-to-tail linkages approximately greater than 50%, optionally greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0172] Optionally, block B comprises only ether linkages. Typically, at least 90% of block B is derived from, typically at least 95% is derived from, more typically at least 99%, most typically 100% is derived from an epoxide, and wherein optionally the epoxide is selected from the group consisting of cyclohexene oxide, styrene oxide, oxirane, oxetane, butylene oxide, substituted cyclohexene oxide (such as limonene oxide C10H16O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane C11H22O), alkylene oxide (such as oxirane and substituted oxirane), unsubstituted or substituted oxirane (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1,2-epoxybutane, glycidyl ether, vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide and functionalized 3,5-dioxepane.

[0173] Typically, block B has less than 10% carbonate linkages, typically less than 5% carbonate linkages, more typically less than 1% carbonate linkages, most typically 0% carbonate linkages.

[0174] Typically, block B has less than 10% carbonate linkages, typically less than 5% carbonate linkages, more typically less than 1% carbonate linkages, most typically 0% carbonate linkages.

[0175] Block A can have a high carbonate content and block B can have a low carbonate content, for example block A can have more than 70% carbonate linkages and / or for example block B can have less than 10% carbonate linkages, typically less than 5% carbonate linkages, more typically less than 1% carbonate linkages, most typically 0% carbonate linkages.

[0176] Optionally, block A of the present application can be a typically alternating polycarbonate polyol residue.

[0177] Typically, the mol / mol ratio of block A to block B is in the range of 25:1 to 1:250. Typically, the weight ratio of block A to block B is in the range of 50:1 to 1:100.

[0178] Typically, block A (the polycarbonate block) is derived from an epoxide and CO2, more typically the epoxide and CO2 provide at least 90% of the residues in the block, especially at least 95% of the residues in the block, more especially at least 99% of the residues in the block, most especially about 100% of the residues in the block are residues of the epoxide and CO2. Most typically, block A comprises ethylene oxide and / or propylene oxide residues and optionally other epoxide residues such as cyclohexylene oxide, butylene oxide, glycidyl ether, glycidyl ester and glycidyl carbonate. At least 30% of the epoxide residues of block A can be ethylene oxide or propylene oxide residues, typically at least 50% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, more typically at least 75% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, most typically at least 90% of the epoxide residues of block A are ethylene oxide or propylene oxide residues.

[0179] Typically, the carbonate of block A is derived from CO2, i.e. the carbonate comprises CO2 residues. Typically, block A has between 70-100% carbonate linkages, more typically between 80-100% carbonate linkages, most typically between 90-100% carbonate linkages.

[0180] Typically, block B (the polyether carbonate block) is derived from an epoxide and CO2. Typically, the epoxide and CO2provide at least 90% of the residues in the block, in particular at least 95% of the residues in the block, more particularly at least 99% of the residues in the block, most particularly about 100% of the residues in the block are residues of the epoxide and CO2. Most typically, block B comprises ethylene oxide and / or propylene oxide residues and optionally other epoxide residues such as e.g. cyclohexene oxide, butylene oxide, glycidyl ether, glycidyl ester and glycidyl carbonate. At least 30% of the epoxide residues of block B can be ethylene oxide or propylene oxide residues, typically at least 50% of the epoxide residues of block B are ethylene oxide or propylene oxide residues, more typically at least 75% of the epoxide residues of block B are ethylene oxide or propylene oxide residues, most typically at least 90% of the epoxide residues of block B are ethylene oxide or propylene oxide residues. According to the fourth aspect of the application, there is also provided a polyurethane resulting from the reaction of the polyol block copolymer product of the process of the first aspect of the application with a (poly)isocyanate. The polyurethane can also result from the reaction of a composition comprising the product of the first aspect of the application with a (poly)isocyanate. The polyurethane can be in the form of a soft foam, a flexible foam, an integral skin foam, a high resilience foam, a viscoelastic or memory foam, a semi-rigid foam, a rigid foam (such as a polyurethane (PUR) foam, a polyisocyanurate (PIR) foam and / or a spray foam), an elastomer (such as a cast elastomer, a thermoplastic elastomer (TPU) or a microcellular elastomer), an adhesive (such as a hot melt adhesive, a pressure sensitive adhesive or a reactive adhesive), a sealant or a coating (such as a waterborne or solvent dispersion (PUD), a two-component coating, a one-component coating, a solventless coating). The polyurethane can be formed by a process comprising extrusion, moulding, injection moulding, spraying, foaming, casting and / or curing. The polyurethane can be formed by a 'one-pot' or 'prepolymer' process.

[0181] Typically, the (poly)isocyanate comprises two or more isocyanate groups per molecule. Preferably, the (poly)isocyanate is a diisocyanate. However, the (poly)isocyanate can be a higher (poly)isocyanate such as a triisocyanate, a tetraisocyanate, an isocyanate polymer or oligomer etc. The (poly)isocyanate can be an aliphatic (poly)isocyanate or a derivative or oligomer of an aliphatic (poly)isocyanate or can be an aromatic (poly)isocyanate or a derivative or oligomer of an aromatic (poly)isocyanate. Typically, the (poly)isocyanate component has a functionality of 2 or more. In some embodiments, the (poly)isocyanate component comprises a mixture of diisocyanates and higher isocyanates, the mixture being formulated to achieve a particular number of functionalities for a given application.

[0182] In some embodiments, the (poly)isocyanate employed has a functionality greater than 2. In some embodiments, such (poly)isocyanates have a functionality between 2 and 5, more typically 2-4, most typically 2-3.

[0183] Suitable (poly)isocyanates that can be used include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Such polyisocyanates can be selected from the group consisting of 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane (H6-XDI), 1,4-cyclohexyl diisocyanate, 1,2-cyclohexyl diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI), 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 2,6-toluene diisocyanate (TDI), 4,4' methylene-bis(cyclohexyl isocyanate) (H12MDI), naphthalene-1,5-diisocyanate, diphenylmethane-2,4'-diisocyanate (MDI), diphenylmethane-4,4'-diisocyanate (MDI), triphenylmethane-4,4',4"-triisocyanate, isocyanatomethyl-1,8-octane diisocyanate (TIN), meta-tetramethylxylylene diisocyanate (TMXDI), para-tetramethylxylylene diisocyanate (TMXDI), tris(p-isocyanatomesityl) thiophosphate, trimethylhexane diisocyanate, lysine diisocyanate, meta-xylylene diisocyanate (XDI), para-xylylene diisocyanate (XDI), 1,3,5-hexamethyl-mesitylene triisocyanate, 1-methoxyphenyl-2,4-diisocyanate, toluene-2,4,6-triisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, and mixtures of any two or more of these. In addition, the (poly)isocyanate can be selected from polymeric versions of any of these isocyanates, which can have high or low functionality. Preferred polymeric isocyanates can be selected from MDI, TDI, and polymeric MDI.

[0184] The polyurethane of the fourth aspect can also comprise one or more chain extenders, which are typically low molecular polyols, polyamines or compounds having both amine and hydroxyl functionality known in the art. Such chain extenders include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, trimethylolpropane (TMP), diethylene glycol, dipropylene glycol, diamines such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N-methylpropylene-1,3-diamine, 2,4-toluene diamine, 2,6-toluene diamine and diethanolamine.

[0185] The composition comprising the product of the first aspect of the application can also comprise one or more additives from those known in the art. These additives can include, but are not limited to, catalysts, blowing agents, stabilizers, plasticizers, fillers, flame retardants, antifoams and antioxidants.

[0186] The filler can be selected from mineral fillers or polymeric fillers, for example styrene-acrylonitrile (SAN) dispersion fillers.

[0187] The blowing agent can be selected from chemical blowing agents or physical blowing agents. Chemical blowing agents typically react with the (poly)isocyanate and release a volatile compound such as CO2. Physical blowing agents typically evaporate during foam formation due to their low boiling point. Suitable blowing agents are known to the person skilled in the art and the amount of blowing agent added can be a matter of routine experimentation. One or more physical blowing agents can be used or one or more chemical blowing agents can be used, furthermore one or more physical blowing agents can be used in combination with one or more chemical blowing agents.

[0188] Chemical blowing agents include water and formic acid. Both react with a portion of the (poly)isocyanate, thereby generating carbon dioxide which can act as a blowing agent. Alternatively, carbon dioxide can be used directly as a blowing agent, which has the advantage of avoiding side reactions and reducing the formation of urea crosslinks, if desired, water can be used in combination with other blowing agents or alone.

[0189] Typically, the physical blowing agents for use in the present application can be selected from the group consisting of acetone, carbon dioxide, optionally substituted hydrocarbons and chloro / fluoro-carbons. Chloro / fluoro-carbons include hydrochlorofluorocarbons, chlorofluorocarbons, fluorocarbons and chlorocarbons. Fluorocarbon blowing agents are typically selected from the group consisting of difluoromethane, trifluoromethane, fluoroethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, tetrafluoroethane, difluorochloroethane, dichloromonofluoromethane, 1,1-dichloro-1-fluoroethane, 1,1-difluoro-1,2,2-trichloroethane, chloropentafluoroethane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane.

[0190] Olefinic blowing agents, i.e., trans-1-chloro-3,3,3-trifluoropropene (LBA), trans-1,3,3,3-tetrafluoro-prop-1-ene (HFO-1234ze), 2,3,3,3-tetrafluoro-propene (HFO-1234yf), cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) can be included.

[0191] Typically, the non-halogenated hydrocarbon used as a physical blowing agent can be selected from butanes, isobutanes, 2,3-dimethylbutanes, n- and iso-pentane isomers, hexane isomers, heptane isomers, and cycloalkanes including cyclopentane, cyclohexane, and cycloheptane. More typically, the non-halogenated hydrocarbon used as a physical blowing agent can be selected from cyclopentane, isopentane, and n-pentane.

[0192] Typically, the one or more blowing agents are used in amounts from about 0 to about 10 parts, more typically 2-6 parts, of the total formulation. Where water is used in conjunction with another blowing agent, the ratio of the two blowing agents can vary widely, for example, from 1 to 99 parts by weight of water in the total blowing agent, preferably 25 to 99+ parts by weight of water.

[0193] Preferably, the blowing agent is selected from cyclopentane, isopentane, n-pentane. More preferably, the blowing agent is n-pentane.

[0194] Typical plasticizers can be selected from succinates, adipates, phthalates, diisooctyl phthalate (DIOP), benzoates, and N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES).

[0195] Typical flame retardants are known to those skilled in the art and can be selected from phosphinamidates, 9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide (DOPO), chlorinated phosphate esters, tris(2-chloroisopropyl)phosphate (TCPP), triethyl phosphate (TEP), tris(chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, 2,2-bis(chloromethyl)-1,3- propylenebis(di(2-chloroethyl)phosphate), tris(1,3-dichloropropyl)phosphate, tetra(2- chloroethyl)ethylene diphosphate, cresyl phosphate, cresyl diphenyl phosphate, diammonium hydrogen phosphate, melamine, melamine pyrophosphate, urea phosphate, aluminum oxide, boric acid, various halogenated compounds, antimony oxide, chlorendic acid derivatives, phosphorus-containing polyols, bromine-containing polyols, nitrogen-containing polyols, and chlorinated waxes. The flame retardant can be present in amounts from 0-60 parts of the total mixture.

[0196] According to a fifth aspect of the present application, there is also provided a polyurethane comprising block copolymer residues having a polycarbonate block A(-A'-Z'-Z-(Z'-A' n) and polyether block B, wherein A' is a polycarbonate chain having at least 70% carbonate linkages, wherein the residue has a multi-block structure B-A'-Z'-Z-(Z'-A'-B) n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z' n is the starting residue.

[0197] The block copolymer residue of the polyurethane of the fifth aspect can include any one or more of the features as defined above in relation to the product of the third aspect of the application.

[0198] According to a sixth aspect of the application, there is also provided an isocyanate-terminated polyurethane prepolymer comprising the reaction product of the polyol block copolymer product according to the method of the first aspect of the application with an excess of (poly)isocyanate, such as at least >1 mole of isocyanate groups per mole of OH groups.

[0199] According to a seventh aspect of the application, there is provided an isocyanate-terminated polyurethane prepolymer comprising a block copolymer residue having a polycarbonate block A(-A'-Z'-Z-(Z'-A' n ) and polyether block B, wherein A' is a polycarbonate chain having at least 70% carbonate linkages, wherein the residue has a multi-block structure B-A'-Z'-Z-(Z'-A'-B) n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z' n is the starting residue.

[0200] The isocyanate-terminated polyurethane prepolymer of the seventh aspect can include any one or more of the features as defined above in relation to the product of the third aspect of the application.

[0201] The catalyst that can be added to the polyol block copolymer product of the method of the first aspect of the application can be a catalyst for the reaction of (poly)isocyanate with polyol. These catalysts include suitable urethane catalysts, such as tertiary amine compounds and / or organometallic compounds.

[0202] Optionally, a trimerisation catalyst can be used. There can be an excess of (poly)isocyanate, or more preferably an excess of polymeric isocyanate, relative to the polyol, such that a polyisocyanurate ring can form in the presence of the trimerisation catalyst. Any of these catalysts can be used in combination with one or more other trimerisation catalysts.

[0203] According to an eighth aspect of the application, there is provided a composition comprising the polyol block copolymer according to the third aspect and one or more additives selected from the group consisting of catalysts, blowing agents, stabilizers, plasticizers, fillers, flame retardants and antioxidants.

[0204] The composition can further comprise a (poly)isocyanate.

[0205] Typically, the catalyst for the reaction of the (poly)isocyanate and the polyol block copolymer comprises a suitable urethane catalyst such as a tertiary amine compound and / or an organometallic compound. Typically, a trimerization catalyst is present.

[0206] There can be an excess of (poly)isocyanate, more typically polymeric isocyanate, relative to the polyol, such that polyisocyanurate rings can form in the presence of the trimerization catalyst.

[0207] According to a ninth aspect of the application, there is provided a lubricant composition comprising the polyol block copolymer according to the third aspect of the application.

[0208] According to a tenth aspect of the application, there is provided a surfactant composition comprising the polyol block copolymer according to the third aspect of the application.

[0209] Definitions

[0210] For the purposes of the present application, an aliphatic group is a hydrocarbon moiety which can be straight chain (i.e. unbranched), branched or cyclic, and can be fully saturated, or contain one or more unsaturated units, but not aromatic. The term "unsaturated" means a moiety having one or more double and / or triple bonds. The term "aliphatic" is therefore intended to encompass alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl or cycloalkynyl groups, and combinations thereof.

[0211] An aliphatic group is optionally a C 1-30 An aliphatic group which is an aliphatic group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms. Optionally, the aliphatic group is a C 1-15 An aliphatic, optionally a C 1-12 An aliphatic, optionally a C 1-10 An aliphatic, optionally a C 1-8 An aliphatic, such as a C 1-6 An aliphatic group. Suitable aliphatic groups include straight chain or branched chain alkyl, alkenyl and alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl and (cycloalkyl)alkenyl groups.

[0212] As used herein, the term "alkyl" refers to a saturated straight-chain or branched hydrocarbon group derived by removing a single hydrogen atom from the aliphatic moiety. Alkyl is optionally "C 1-20 "Alkyl" refers to a straight-chain or branched alkyl group having 1 to 20 carbon atoms. Alkyl groups thus have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alkyl group is C10. 1-15 Alkyl, optionally C 1-12 Alkyl, optionally C 1-10 Alkyl, optionally C 1-8 Alkyl, optionally C 1-6 Alkyl group. Specifically, "C 1-20 Examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, isopentyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, 1,1-dimethylpropyl, 1,2-Dimethylpropyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1-Ethyl-2-methylpropyl, 1,1,2-Trimethylpropyl, 1-Ethylbutyl, 1-Methylbutyl, 2-Methylbutyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 2,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,3-Dimethylbutyl, 2-Ethylbutyl, 2-Methylpentyl, 3-Methylpentyl, etc.

[0213] As used herein, the term "alkenyl" refers to a group derived from a straight-chain or branched aliphatic moiety having at least one carbon-carbon double bond by removing a single hydrogen atom. As used herein, the term "alkynyl" refers to a group derived from a straight-chain or branched aliphatic moiety having at least one carbon-carbon triple bond by removing a single hydrogen atom. Alkenyl and alkynyl groups are optionally "C" and "H" respectively. 2-20 "Alkenyl" and "C" 2-20 "Alkyne", optionally "C" 2-15 "Alkenyl" and "C" 2-15 "Alkyne", optionally "C" 2-12 "Alkenyl" and "C" 2-12 "Alkyne", optionally "C" 2-10 "Alkenyl" and "C" 2-10 "Alkyne", optionally "C" 2-8 "Alkenyl" and "C" 2-8 "Alkyne", optionally "C" 2-6 "Alkenyl" and "C" 2-6"Alkenyl". Examples of alkenyl groups include ethylenyl, propylenyl, allyl, 1,3- butadienyl, butenylyl, 1 -methyl-2-buten- 1 -yl, allyl, 1,3-butadienyl, and propadienyl. Examples of alkynyl groups include ethynyl, 2-propynyl (propargyl), and 1 -propynyl.

[0214] As used herein, the term "cycloaliphatic", "carbocycle", or "carbocyclic" refers to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring system having from 3 to 20 carbon atoms, i.e., a cycloaliphatic group having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the cycloaliphatic group has from 3 to 15, optionally from 3 to 12, optionally from 3 to 10, optionally from 3 to 8, optionally from 3 to 6 carbon atoms. The term "cycloaliphatic", "carbocycle", or "carbocyclic" also includes aliphatic rings fused to one or more aromatic or non-aromatic rings, such as a tetrahydronaphthyl ring, where the point of attachment is on the aliphatic ring. The carbocyclic group can be polycyclic, e.g., bicyclic or tricyclic. It is understood that the cycloaliphatic group can include a cycloaliphatic ring bearing one or more attached or unattached alkyl substituents, such as -CH2-cyclohexyl. Specifically, examples of carbocyclic include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4.5]decane, cycloheptane, adamantane, and cyclooctane.

[0215] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl, and heteroalkynyl) are aliphatic groups as described above, which additionally contain one or more heteroatoms. Heteroaliphatic groups thus optionally contain from 2 to 21 atoms, optionally from 2 to 16 atoms, optionally from 2 to 13 atoms, optionally from 2 to 11 atoms, optionally from 2 to 9 atoms, optionally from 2 to 7 atoms, where at least one atom is a carbon atom. The optional heteroatoms are selected from O, S, N, P, and Si. When the heteroaliphatic group has two or more heteroatoms, the heteroatoms can be the same or different. Heteroaliphatic groups can be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.

[0216] Cycloaliphatic groups are saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring systems having from 3 to 20 carbon atoms, i.e., cycloaliphatic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, cycloaliphatic groups have from 3 to 15, optionally from 3 to 12, optionally from 3 to 10, optionally from 3 to 8, optionally from 3 to 6 carbon atoms. The term “cycloaliphatic” encompasses cycloalkyl, cycloalkenyl, and cycloalkynyl groups. It is understood that cycloaliphatic groups can include cycloaliphatic rings bearing one or more attached or unattached alkyl substituents, such as -CH2-cyclohexyl. In particular, C 3-20 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0217] Heterocycloaliphatic groups are cycloaliphatic groups as defined above, which, in addition to carbon atoms, also have one or more ring heteroatoms, which are optionally selected from O, S, N, P, and Si. Heterocycloaliphatic groups optionally contain from one to four heteroatoms, which can be the same or different. Heterocycloaliphatic groups optionally contain from 5 to 20 atoms, optionally from 5 to 14 atoms, optionally from 5 to 12 atoms.

[0218] Aryl or aryl ring is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms, wherein at least one ring in the system is aromatic, and wherein each ring in the system contains from three to twelve ring members. The term “aryl” can be used alone or as part of a larger moiety as in “aralkyl,” “aralkoxy,” or “aryloxyalkyl.” Aryl is optionally “C 6-12 Aryl” and is an aryl group composed of 6, 7, 8, 9, 10, 11, or 12 carbon atoms, and includes fused ring groups such as monocyclic ring groups or bicyclic ring groups, and the like. In particular, “C 6-10 Examples of “C Aryl” include phenyl, biphenyl, indenyl, anthryl, naphthyl, or azulenyl, and the like. It is noted that fused rings such as indane, benzofuran, phthalimide, phenanthridine, and tetrahydronaphthalene are also included in aryl.

[0219] The term "heteroaryl" used alone or as part of another term such as "heteroaralkyl" or "heteroaralkoxy" refers to a group having 5 to 14 ring atoms, optionally 5, 6, or 9 ring atoms; having 6, 10, or 14 π electrons shared in a cyclic array; and having, 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 a nitrogen. The term "heteroaryl" also includes heteroaryl rings fused to one or more aryl, alicyclic, or heterocyclyl rings, where the attachment of the heteroaryl ring or the attachment point is through a carbon of the heteroaromatic ring. Examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one. Thus, a heteroaryl group can be a monocyclic or a polycyclic ring.

[0220] The term "heteroaralkyl" refers to an alkyl group substituted with a heteroaryl group, wherein the alkyl and heteroaryl portions are independently optionally substituted.

[0221] As used herein, the terms "heterocycle," "heterocyclyl," "heterocyclic group," and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclic ring ring portion which is saturated, partially unsaturated, or aromatic, and which has, in addition to carbon atoms, from one to four heteroatoms which can be the same or different, as the ring atoms. Use of the term "nitrogen" in reference to the ring atoms of a heterocycle includes substituted and unsubstituted nitrogen.

[0222] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzthiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenoxazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiazine, thiazole, thiazolidine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.

[0223] The terms "halide," "halo," and "halogen" are used interchangeably and as used herein mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, optionally a fluorine atom, a bromine atom, or a chlorine atom, and optionally a fluorine atom.

[0224] Haloalkyl is optionally "C 1-20 Haloalkyl," optionally "C 1-15 Haloalkyl," optionally "C 1-12 Haloalkyl," optionally "C 1-10 Haloalkyl," optionally "C 1-8 Haloalkyl," optionally "C 1-6 Haloalkyl," and is a C 1-20 Haloalkyl," optionally "C 1-15 Haloalkyl," optionally "C 1-12 Haloalkyl," optionally "C 1-10 Haloalkyl," optionally "C 1-8 Haloalkyl," or C 1-6 Haloalkyl." The term "haloalkyl" encompasses fluorinated or chlorinated groups, including perfluorinated compounds. Specifically, "C 1-20 Haloalkyl" includes fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, chloromethyl, bromomethyl, iodomethyl, and the like.

[0225] As used herein, the term "acyl" refers to a group of the formula -C(O)R, wherein R is hydrogen or an optionally substituted aliphatic group, aryl, or heterocyclyl group.

[0226] Alkoxy is optionally "C 1-20 Alkoxy," optionally "C 1-15 Alkoxy," optionally "C 1-12 Alkoxy," optionally "C 1-10 Alkoxy," optionally "C 1-8 Alkoxy," optionally "C 1-6 Alkoxy," and is an oxy group bonded to a previously defined C 1-20 Alkoxy," optionally "C 1-15 Alkoxy," optionally "C 1-12 Alkoxy," optionally "C 1-10 Alkoxy," optionally "C 1-8 Alkoxy," or C 1-6 Alkoxy." Specifically, "C 1-20Examples of "alkoxy groups" include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, t-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, n-hexyloxy, isohexyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-icosyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 2,2-dimethylpropyloxy, 2-methylbutyloxy, 1-ethyl-2-methylpropyloxy, 1,1,2-trimethylpropyloxy, 1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2-ethylbutyloxy, 2-methylpentyloxy, 3-methylpentyloxy, and the like.

[0227] Aryloxy is an optionally "C 5-20 Aryloxy", optionally "C 6-12 Aryloxy", optionally "C 6-10 Aryloxy", and is an oxy group bonded to a previously defined C 5-20 Aryl group, C 6-12 Aryl group, or C 6-10 Aryl group, respectively.

[0228] Alkylthio is an optionally "C 1-20 Alkylthio", optionally "C 1-15 Alkylthio", optionally "C 1-12 Alkylthio", optionally "C 1-10 Alkylthio", optionally "C 1-8 Alkylthio", optionally "C 1-6 Alkylthio", and is a thio group (-S-) bonded to a previously defined C 1-20 Alkyl group, C 1-15 Alkyl group, C 1-12 Alkyl group, C 1-10 Alkyl group, C 1-8 Alkyl group, or C 1-6 Alkyl group, respectively.

[0229] Arylthio is an optionally "C 5-20 Arylthio", optionally "C 6-12 Arylthio", optionally "C 6-10 Arylthio", and is a thio group (-S-) bonded to a previously defined C 5-20 Aryl group, C 6-12 Aryl group, or C 6-10 Aryl group, respectively.

[0230] Alkylaryl is optionally "C 6-12 Aryl group C1-20 alkyl", optionally "C 6-12 arylC 1-16 alkyl", optionally "C 6-12 arylC 1-6 alkyl", and is a aryl group as defined above bonded at any position to an alkyl group as defined above. The point of attachment of the alkaryl group to the molecule can be through the alkyl portion, and thus optionally the alkaryl group is -CH2-Ph or -CH2CH2-Ph. The alkaryl group can also be referred to as an "aralkyl" group.

[0231] silyl groups are optionally -Si(R s )3, where each R s may independently be an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. Optionally, each R s is independently an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, each R s is an alkyl group selected from methyl, ethyl, or propyl.

[0232] silyl ether groups are optionally groups OSi(R6)3, where each R6may independently be an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. Each R6may independently be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, each R6is an optionally substituted phenyl group or an optionally substituted alkyl group selected from methyl, ethyl, propyl, or butyl, such as n-butyl (nBu) or t-butyl (tBu). Exemplary silyl ether groups include OSi(Me)3, OSi(Et)3, OSi(Ph)3, OSi(Me)2(tBu), OSi(tBu)3, and OSi(Ph)2(tBu).

[0233] nitrile groups (also referred to as cyano groups) are groups CN.

[0234] imine groups are groups -CRNR, optionally -CHNR7, where R7is an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. R7may be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, R7is an alkyl group selected from methyl, ethyl, or propyl.

[0235] acetylide groups contain a triple bond -C≡C-R9, optionally where R9may be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. For purposes of the present invention, when R9is an alkyl group, the triple bond can exist at any position along the alkyl chain. R9may be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, R9is methyl, ethyl, propyl, or phenyl.

[0236] Amino groups are optionally -NH2, -NHR 10 or -N(R 10 )2, where R 10 may be an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, a silyl group, an aryl group, or a heteroaryl group, as defined above. It is understood that when the amino group is N(R 10 )2, each R 10 group can be the same or different. Each R 10 may independently be an unsubstituted aliphatic, cycloaliphatic, silyl, or aryl group. Optionally, R 10 is methyl, ethyl, propyl, SiMe3, or phenyl.

[0237] Amido groups are optionally -NR 11 C(O)- or -C(O)-NR 11 -, where R 11 may be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, an aryl group, or a heteroaryl group, as defined above. R 11 may be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, R 11 is hydrogen, methyl, ethyl, propyl, or phenyl. Amido groups can be terminated by hydrogen, aliphatic groups, heteroaliphatic groups, cycloaliphatic groups, heterocycloaliphatic groups, aryl groups, or heteroaryl groups.

[0238] Unless otherwise defined herein, ester groups are optionally -OC(O)R 12 - or -C(O)OR 12 -, where R 12 may be an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, an aryl group, or a heteroaryl group, as defined above. R 12 may be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, R 12 is methyl, ethyl, propyl, or phenyl. Ester groups can be terminated by aliphatic groups, heteroaliphatic groups, cycloaliphatic groups, heterocycloaliphatic groups, aryl groups, or heteroaryl groups. It is understood that if R 12 is hydrogen, the group defined by -OC(O)R 12 - or -C(O)OR 12 - will be a carboxylic acid group.

[0239] Sulfoxides are optionally -S(O)R 13 and sulfonyl groups are optionally -S(O)2R 13 , where R 13 may be an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, an aryl group, or a heteroaryl group, as defined above. R 13 may be an unsubstituted aliphatic, cycloaliphatic, or aryl group. Optionally, R 13is methyl, ethyl, propyl, or phenyl.

[0240] The carboxylate group is optionally -OC(O)R 14 , wherein R 14 may be hydrogen, an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group, as defined above. R 14 may be an unsubstituted aliphatic, alicyclic, or aryl group. Optionally, R 14 is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, iso-butyl, or t-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

[0241] The amide group is optionally MeC(O)N(R 15 )2, wherein R 15 may be hydrogen, an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group, as defined above. R 15 may be an unsubstituted aliphatic, alicyclic, or aryl group. Optionally, R 15 is hydrogen, methyl, ethyl, propyl, or phenyl.

[0242] The phosphinylate group is optionally OP(O)(R 16 )2or -P(O)(OR 16 )(R 16 ), wherein each R 16 is independently selected from hydrogen, or an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group, as defined above. R 16 may be an aliphatic, alicyclic, or aryl group, optionally substituted with an aliphatic, alicyclic, aryl, or C 1-6 alkoxy group. Optionally, R 16 is an optionally substituted aryl group or C 1-20 alkyl, optionally phenyl optionally substituted with C 1-6 alkoxy (optionally methoxy), or an unsubstituted C 1-20 alkyl group (such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl). The phosphonate group is optionally -P(O)(OR 16 )2, wherein R 16 is as defined above. It is understood that when either or both R 16 of the group -P(O)(OR 16 )2is hydrogen, then the group defined by -P(O)(OR 16 )2will be a phosphonic acid group.

[0243] Sulfinate groups are optionally -S(O)OR 17 or -OS(O)R 17 where R 17 may be hydrogen, an aliphatic group as defined above, a heteroaliphatic group, a halogenated aliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R 17 may be an unsubstituted aliphatic group, an alicyclic group, or an aryl group. Optionally, R 17 is hydrogen, methyl, ethyl, propyl, or phenyl. It will be understood that if R 17 is hydrogen, the group defined by -S(O)OR 17 will be a sulfonic acid group.

[0244] Carbonate groups are optionally -OC(O)OR 18 where R 18 may be hydrogen, an aliphatic group as defined above, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R 18 may be an optionally substituted aliphatic group, an alicyclic group, or an aryl group. Optionally, R 18 is hydrogen, methyl, ethyl, propyl, butyl (e.g., 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 will be understood that if R 17 is hydrogen, the group defined by -OC(O)OR 18 will be a carbonic acid group.

[0245] Carbonate functional groups are -OC(O)O- and can be derived from a suitable source. Typically, it is derived from CO2.

[0246] In the -alkylC(O)OR 19 or -alkylC(O)R 19 group, R 19 may be hydrogen, an aliphatic group as defined above, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group. R 19 may be an unsubstituted aliphatic group, an alicyclic group, or an aryl group. Optionally, R 19 is hydrogen, methyl, ethyl, propyl, butyl (e.g., 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, or adamantyl.

[0247] Ether groups are optionally -OR20 wherein R 20 may be an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group, as defined above. R 20 may be an unsubstituted aliphatic, alicyclic, or aryl group. Optionally, R 20 is methyl, ethyl, propyl, butyl (e.g., 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, or adamantyl.

[0248] It is understood that where any of the above groups is present in the Lewis base G, one or more additional R groups can be present as appropriate to complete the valence. For example, in the case of an amino group, additional R groups can be present to give RNHR 10 wherein R is hydrogen, an optionally substituted aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group, as defined above. Optionally, R is hydrogen, or an aliphatic, alicyclic, or aryl group.

[0249] As used herein, the term "optionally substituted" means that one or more hydrogen atoms in an optionally substituted moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group can have suitable substituents at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent selected from a specified group, the substituent can be either the same or different at every position. Combinations of substituents envisioned by this application are optionally those that result in the formation of stable compounds. As used herein, the term "stable" refers to compounds that are chemically feasible and can exist long enough to allow for their detection, isolation, and / or use in chemical synthesis at room temperature (i.e., 16 °C to 25 °C).

[0250] Optional substituents for use in the present application include, but are not limited to, halogen, hydroxyl, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinite, sulfonate, or an optionally substituted aliphatic group, heteroaliphatic group, alicyclic group, heteroalicyclic group, aryl group, or heteroaryl group (e.g., optionally substituted with halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinite, sulfonate, or acetylide).

[0251] It should be understood that while in Formula (V), the groups X and G are shown as being associated with a single M1or M2metal center, one or more X and G groups can form a bridge between the M1and M2metal centers.

[0252] For the purposes of the present invention, the epoxide substrate is not limited. The term epoxide thus relates to any compound comprising an epoxide moiety (i.e., a substituted or unsubstituted oxirane compound). Substituted oxiranes include mono-substituted oxiranes, di-substituted oxiranes, tri-substituted oxiranes, and tetra-substituted oxiranes. The epoxide can comprise a single oxirane moiety. The epoxide can comprise two or more oxirane moieties.

[0253] It should be understood that the term "epoxide" is intended to encompass one or more epoxides. In other words, the term "epoxide" refers to a single epoxide, or a mixture of two or more different epoxides. For example, the epoxide substrate can be a mixture of oxirane and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of oxirane and cyclohexene oxide, or a mixture of oxirane, propylene oxide, and cyclohexene oxide.

[0254] The term polyether carbonate block polyether polyol generally refers to a polymer that is capped at each end with substantially -OH, -SH, and / or -NHR' groups (encompassing C-OH, P-OH, -C(O)OH, and the like moieties). R' can be H, or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl group, optionally R' is H or an optionally substituted alkyl group.

[0255] By way of example, at least about 90%, at least about 95%, at least about 98%, or at least about 99% of the polymer can be capped at each end with -OH groups. The skilled person will appreciate that if the polymer is linear, it can be capped at both ends with -OH groups. If the polymer is branched, each branch can be capped with -OH groups. Such polymers are generally useful in the preparation of advanced polymers, such as polyurethanes. The chain can comprise a mixture of functional group (e.g., -OH and -SH) groups, or can contain the same functional group (e.g., all -OH groups).

[0256] The term "continuous" as used herein can be defined as the mode of addition of the materials or can refer to the nature of the reaction process as a whole.

[0257] With respect to continuous addition mode, the relevant materials are added continuously or constantly during the course of the reaction. This can be achieved, for example, by adding a stream of material at a constant flow rate or at a variable flow rate. In other words, the material or materials are added in a substantially uninterrupted manner. It should be noted, however, that the uninterrupted addition of materials can require brief interruptions for practical considerations, for example in order to fill or replace material containers from which the materials are added.

[0258] Semi-batch addition mode means that at least one of the reagents is not added in one go, but in multiple batches or continuously / discontinuously.

[0259] Neutral or basic pH means that the product has a pH greater than or equal to 7 when dissolved in water.

[0260] Where the entire reaction is continuous, the reaction can be carried out over a long period of time, such as days, weeks, months, etc. In such a continuous reaction, the reaction materials can be continuously replenished and / or the reaction product can be topped-up. It will be appreciated that while the catalyst can not be consumed during the reaction, it can be necessary to replenish the catalyst in any event, as topping-up can consume the amount of catalyst present.

[0261] Continuous reaction can employ continuous addition of materials.

[0262] Continuous reaction can employ discontinuous (i.e. batch or semi-batch) addition of materials.

[0263] The term in series as used herein refers to the situation when two or more reactors are connected such that the crude reaction mixture can flow from a first reactor to a second reactor.

[0264] The term nested as used herein refers to the situation when two or more reactors are configured such that one reactor is located within another reactor. For example in the present application, when a second reactor is located within a first reactor, the conditions of both reactors are allowed to influence the other reactor. BRIEF DESCRIPTION OF DRAWINGS

[0265] Figure 1 Thermal stability of block copolymer polyols produced by dual reaction versus alternating polycarbonate polyols produced by CO2 / epoxide copolymerization DETAILED DESCRIPTION

[0266] Method

[0267] Gel permeation chromatography

[0268] GPC measurements were performed in THF against narrow polydispersity poly(ethylene glycol) or polystyrene standards using an Agilent 1260 Infinity machine equipped with Agilent PLgel Mixed-D columns.

[0269] Examples

[0270] Example 1

[0271]

[0272] Above: Catalyst (1)

[0273] Hexanediol (2.6 g) was placed in a 100 mL reactor and dried under vacuum at 120 °C for 1 hour. A mixture of catalyst (1) (0.15 g) in PO (12.45 g) was injected into the vessel. The vessel was heated to 75 °C and pressurized to 10 bar and stirred for 16 hours after which it was cooled and vented, resulting in a PPC-polyol of approximately 550 g / mol. The contents of the reactor were then transferred to a clean dry Schlenk with PO (3 mL) and EtOAc (9 mL) and kept under N2.

[0274] In a separate 100 mL reactor, 9.2 mg of DMC catalyst according to WO 2017 / 037441 Example 1 and PPG400 (0.88 g) were dried under vacuum at 120 °C for 1 hour. The reactor was cooled to room temperature and ethyl acetate (12 mL) was injected into the vessel under a continuous flow of N2gas. The vessel was heated to the desired temperature (130 °C). 3.75 g of propylene oxide was added in 3 bursts (1.25 g each) with 30 minutes between each addition to confirm the activity of the DMC catalyst.

[0275] The reactor was cooled to 70 °C while pressurized to 1 bar with N2and PO (1.25 g) was added. The Schlenk mixture from above was then added via an HPLC pump added over 1 hour. The reaction was run over 5 hours. The reactor was cooled to below 10 °C and the pressure was released. NMR and GPC were measured immediately.

[0276] Table 1: Experimental results from Example 1

[0277]

[0278] Examples 2-10

[0279] Examples 2-10 were performed according to Example 1 except that they were performed in a 2 L reactor. Reaction 1 was performed using the amounts detailed in Table 2.

[0280] Reaction 2 was performed in a 2 L reactor using the amounts shown in Table 3. The reactor minimum fill requirement was met by adding ethyl acetate (280 mL) or polycarbonate ether polyol from the previous dual reactor reaction. The mixture was stirred and heated to 130 °C. 15 g of propylene oxide was used to activate the DMC catalyst: propylene oxide was added in 3 portions (5 g each) with about 10 minutes between each addition to confirm activity of the DMC catalyst. The PPC / PO mixture from above was then added at 85 °C by HPLC pump over 1-3 hours. After the PPC addition, an additional amount of PO was then added to the mixture by HPLC at 5 mL / min. The reaction was “cooked out” for an additional 1-16 hours before cooling to below 10 °C and releasing any pressure. NMR and GPC were measured immediately.

[0281] Table 2: Reagent amounts and conditions for Reaction 1

[0282]

[0283] Table 3: Reagent amounts and conditions for Reaction 2

[0284]

[0285] These examples demonstrate that low molecular weight polycarbonate polyols that are less stable do not necessarily have to be stored or purified, but can be produced in situ and used to produce more stable polyols with high total CO2 content at low CO2 pressure in reactor 1 that contain mixed carbonate and ether linkages (see Examples 6-10). Furthermore, this method can produce polymers with CO2 content in the core of the polymer and higher ether content at the end of the polyol.

[0286] Examples 7-10 demonstrate that this method can be used to produce polyols with higher functionality when trimethylolpropane ethoxylate (Mn 450, triol) is used as a starting material in Reaction 1.

[0287] Example 6 demonstrates that this method allows for the use of the final polyol product as a ‘starting material’ to activate the DMC catalyst in reactor 2. This method demonstrates that the reaction ‘tail’ from the previous reaction can be left in the reactor to activate the DMC for the next reaction and meet the reactor’s minimum fill. This is particularly useful in manufacturing to eliminate the need for a solvent or a different starting material to pre-activate the DMC.

[0288] The thermal stability of the PPC polyol (Mn 2000) as produced in Reaction 1 was compared to the polyol of the invention produced by Example 5 Figure 1). It can be clearly seen that the block copolymer polyols produced by the double reaction have improved thermal stability compared with the PPC polyols.

Claims

1. A process for producing a polyol block copolymer in a multiple reactor system; the system comprising a first reactor and a second reactor, wherein a first reaction occurs in the first reactor and a second reaction occurs in the second reactor; wherein the first reaction is a carbonate catalyst reacting with CO2 and an epoxide in the presence of a starter and / or solvent to produce a polycarbonate polyol copolymer having greater than 76% carbonate linkages, and the second reaction is a DMC catalyst reacting with the polycarbonate polyol copolymer of the first reaction and an epoxide to produce a polyol block copolymer, wherein (i) the product of the first reaction is fed to the second reactor as a crude reaction mixture, wherein said crude reaction mixture is not subjected to isolation of product prior to addition to said second reactor, and optionally, (ii) the epoxide and the polycarbonate polyol compound of the first reaction are fed to the second reactor in a continuous or semi-batch manner, and / or (iii) the product of the first reaction has a neutral or basic pH when added to the second reaction.

2. The method of claim 1, wherein, The crude reaction mixture is not subjected to additional processing steps prior to addition to the second reactor.

3. The method of claim 1 or 2, wherein, (ii) the epoxide and the polycarbonate polyol compound of the first reaction are fed to the second reactor in a continuous or semi-batch manner, and (iii) the product of the first reaction has a neutral or basic pH when added to the second reaction.

4. The process for producing a polyol block copolymer according to any preceding claim, wherein, The starter has the formula (III): Z can be any of two or more -R elements attached to it. Z The group can be any group selected from optionally substituted alkylene, alkenylene, ynynylene, heteroalkylene, heteroalkenylene, heteroynynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be a combination of any of these groups, for example, Z can be alkylarylene, heteroalkylarylene, heteroalkylheteroarylene, or alkylheteroarylene; a is an integer of at least 2, optionally a is in the range of between 2 and 8, optionally a is in the range of between 2 and 6; wherein each R Z may be -OH, -NHR', -SH, -C(0)OH, -P(0)(OR')(OH), -PR'(0)(OH)2, or -PR'(0)OH, optionally R Z is selected from -OH, -NHR', or -C(0)OH, optionally each R z is -OH, -C(0)OH, or a combination thereof (e.g., each R z is -OH); wherein R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, optionally R' is H or optionally substituted alkyl.

5. The method of any preceding claim, wherein, The DMC catalyst is optionally pre-activated in the second reactor or separately, optionally wherein the DMC is pre-activated with a starter compound or with a reaction product of the first or second reaction or with a polycarbonate polyol copolymer or with a polyol block copolymer product.

6. The method of any preceding claim, wherein, The polycarbonate polyol copolymer is added to the pre-activated DMC catalyst.

7. The method of any preceding claim, wherein, The DMC catalyst is pre-activated with a starter compound or the polycarbonate polyol copolymer, or with the polyol block copolymer product.

8. The method of any preceding claim, wherein, The product of the first reaction is a low molecular weight polycarbonate polyol product having a molecular weight (Mn) in the range of 200 to 4000 Daltons as measured by gel permeation chromatography (GPC).

9. The method of any preceding claim, wherein, The first reaction produces a generally alternating polycarbonate polyol product.

10. The method of any preceding claim, wherein, The epoxide is asymmetric, and wherein the reaction produces a polycarbonate having between 40-100% head-to-tail linkages, a polycarbonate having preferably greater than 70%, greater than 80%, or greater than 90% head-to-tail linkages.

11. The method of any preceding claim, wherein, The product of the first reaction is fed to the second reactor as a crude reaction mixture, wherein said second reactor contains a pre-activated DMC catalyst.

12. The method of any preceding claim, wherein, The polycarbonate polyol copolymer is fed to the reaction as a crude reaction mixture with the DMC catalyst, wherein said reaction contains a pre-activated DMC catalyst.

13. The method of any preceding claim, wherein, The first reaction is carried out at a CO2 pressure of less than 20 bar, more preferably less than 10 bar, most preferably less than 8 bar.

14. The method of any preceding claim, wherein, The second reaction is carried out at a CO2 pressure of less than 60 bar, preferably less than 20 bar, more preferably less than 10 bar, most preferably less than 5 bar.

15. The method of any preceding claim, wherein, The first reaction is carried out at a CO2 pressure of from about 1 bar to about 60 bar, from about 1 bar to about 40 bar, from about 1 bar to about 20 bar, from about 1 bar to about 15 bar, from about 1 bar to about 10 bar, or from about 1 bar to about 5 bar.

16. The method of any preceding claim, wherein, The CO2 is added continuously in the first reaction.

17. The method of any preceding claim, wherein, The first reaction is a batch, semi-batch or continuous process.

18. The method of any preceding claim, wherein, The second reaction is a continuous process or a semi-batch process.

19. The method of any preceding claim, wherein, The crude reaction mixture fed into the second reactor comprises an amount of unreacted epoxide and / or starting material.

20. The method of any preceding claim, wherein, The carbonate catalyst is present in the crude reaction mixture.

21. The method of any preceding claim, wherein, The carbonate catalyst has been removed from the crude reaction mixture prior to addition to the second reactor.

22. The method of any preceding claim, wherein, The reaction temperature in the first reactor is in the range of from about 0°C to 250°C, preferably from about 40°C to about 160°C, more preferably from about 50°C to 120°C.

23. The method of any preceding claim, wherein, The reaction temperature in the second reactor is in the range of from about 50°C to about 160°C, preferably in the range of from about 70°C to about 140°C, more preferably from about 80°C to about 130°C.

24. The method of any preceding claim, wherein, The reactors are placed in series.

25. The method of any one of claims 1-23, wherein, The reactors are nested.

26. The method of any preceding claim, wherein, The first reactor and the second reactor are effectively simultaneously providing different reaction conditions to each other, such as temperature and / or pressure.

27. The method of any preceding claim, wherein, The process employs a total amount of epoxide, and wherein about 1% to 100% of the total amount of epoxide is mixed in the first reaction, any remainder is added in the second reaction; optionally about 5% to 90%, optionally about 10% to 90%, optionally about 20% to 90%, optionally about 40% to 90%, optionally about 40% to 80%, optionally about 5% to 50% is mixed in the first reaction.

28. The method of any preceding claim, wherein, These epoxides are selected from the group consisting of cyclohexene oxide, styrene oxide, oxirane, propylene oxide, butylene oxide, substituted cyclohexene oxide (such as limonene oxide C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane C 11 H 22 O), alkylene oxides (such as ethylene oxide and substituted ethylene oxide), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1,2-epoxybutane, glycidyl ether, glycidyl ester, glycidyl carbonate, vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxepoxide.

29. The method of any preceding claim, wherein, Between 0.1% and 20% of the total epoxide in the first reaction is an epoxide substrate containing more than one epoxide moiety, preferably a bis-epoxide.

30. The method of any preceding claim, wherein, The carbonate catalyst is a metal catalyst comprising a phenol or phenolate ligand.

31. The method of any preceding claim, wherein, The carbonate catalyst is a bimetallic complex comprising a phenol or phenolate ligand.

32. The method of any preceding claim, wherein, The carbonate catalyst is a catalyst of formula (IV): wherein M is a metal cation represented by M-(L) v ; and n is an integer of 1 or more. x is an integer from 1 to 4, is a polydentate ligand or a plurality of polydentate ligands; L is a coordinating ligand; v is an integer satisfying the valence of M and / or the preferred coordination geometry of M, or is an integer such that the complex represented by the above formula (IV) has an overall neutral charge.

33. The method of any preceding claim, wherein, The carbonate catalyst has the following structure: M1and M2are 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; R1and R2are independently selected from hydrogen, halide, nitro, nitrile, imine, amine, ether group, silyl group, silyl ether group, sulfoxide group, sulfonyl group, sulfinate group, or acetylene compound group, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; R3is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene can optionally be interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic group; R5is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl group; E1is C and E2is O, S, or NH, or E1is N and E2is O; E3, E4, E5 and E6 are selected from N, NR4, O and S, wherein when E3, E4, E5 or E6 is N, is and wherein when E3, E4, E5 or E6 is NR4, O or S, is R4is independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclo, heteroaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 or -alkylC≡N or alkylaryl; X is independently selected from OC(O)R x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinates, halides, nitrates, hydroxyls, carbonates, amines, amides or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl or heteroaryl groups, wherein each X can be the same or different and wherein X can form a bridge between M1and M2; R x independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclyl, heteroalicyclyl, aryl, alkylaryl, or heteroaryl; and G is absent or independently selected from neutral or anionic donor ligand, which is a Lewis base.

34. The method of any one of claims 1-32, wherein, The carbonate catalyst is selected from a catalyst of formula (IV) as defined herein, a metal salen catalyst, a metal porphyrin catalyst, a metal tetraazaporphyrin catalyst, and a metal beta-diiminate catalyst.

35. The method of any preceding claim, wherein, In addition to the at least two metal centers and the cyanide ligand, the DMC catalyst comprises an optionally non-stoichiometric amount of at least one of the following: one or more complexing agents, water, metal salts, and / or acids.

36. The method of any preceding claim, wherein, The DMC catalyst is prepared by treating a solution of a metal salt with a solution of a metal cyanide salt in the presence of at least one of: a complexing agent, water and / or an acid, optionally wherein the metal salt is of the formula M'(X') p wherein 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 of 1 or greater, and the charge on the anion multiplied by p satisfies the valence of M'; the metal cyanide salt has the formula (Y) q M" (CN) b (A) c where M" is selected from the group consisting of 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 of 1 or greater; c can be 0 or an integer of 1 or greater; the sum of the charges on the anions Y, CN, and A multiplied by q, b, and c, respectively (e.g., Y x q + CN x b + A x c) satisfies the valence of M”; the at least one complexing agent is selected from (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether glycol), ketones, esters, amides, alcohols, ureas, or combinations thereof, Optionally wherein the at least one complexing agent is selected from propylene glycol, polypropylene glycol, methoxy- or ethoxy-ethanediol, dimethoxyethane, t-butanol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methanol, ethanol, isopropanol, n-, iso- and sec-butanol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof; and wherein the acid, if present, has the formula H r X''', wherein X''' is an anion selected from the group consisting of halogen, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, and r is an integer corresponding to the charge on the counterion X'''.

37. The method of any preceding claim, wherein, The DMC catalyst has the following formula: M'd[M"] e (CN)f]g wherein M' and M" are as defined in claim 36, and d, e, f and g are integers and selected such that the DMC catalyst is electrically neutral, Optionally, d is 3, e is 1, f is 6 and g is 2.

38. The method of any preceding claim, wherein, The DMC catalyst has the following formula: M'd[M"] e (CN)f]g.hM"X"i.jR c .kH2O.lH r X"' wherein M', M", d, e, f and g are as defined in claim 36, M'" is M' and / or M", X" is an anion selected from the group consisting of halogen ions, oxide ions, hydroxide, sulfate, carbonate, cyanide ions, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, i is an integer of 1 or more, and the charge on the anion X" multiplied by i satisfies the valence of M'", h, j, k and 1 are each independently zero or positive, r is an integer corresponding to the charge on the counterion X'", and R c is a complexing agent or a combination of one or more complexing agents.

39. The method of any preceding claim, wherein, The DMC catalyst is based on Zn3[Co(CN)6]2(zinc hexacyanocobaltate).

40. The method of any preceding claim, wherein, The DMC catalyst is zinc hexacyanocobaltate, and the one or more ligands are selected from alcohols and polyols.

41. The method of claim 36, wherein, The one or more complexing agents are selected from dimethoxyethane, t-butanol, polyethylene glycol, polypropylene glycol, polyethercarbonate, poly(tetramethylene glycol), polycarbonate.

42. The method of any preceding claim, wherein, The product of the first reaction is fed into the second reactor in a single slug or in a continuous or discontinuous manner, preferably in a continuous manner.

43. The method of any preceding claim, wherein, The product of the first reaction is used to pre-activate the DMC catalyst in the second reaction prior to the addition of epoxide.

44. The method of any preceding claim, wherein, The same or different epoxides are used in the first or second reaction.

45. The method of any preceding claim, wherein, The epoxide used in the first or second reaction comprises propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide.

46. The method of any preceding claim, wherein, The epoxide used in the second reactor is propylene oxide.

47. The method of any preceding claim, wherein, The second reaction is carried out in the substantial absence of CO2.

48. The method of any preceding claim, wherein, The polyol block copolymer produced in the second reaction is a polycarbonate block polyether polyol block copolymer.

49. A polyol block copolymer comprising polycarbonate blocks A (-A'-Z'-Z- (Z'-A') having greater than 76% carbonate linkages and polyether blocks B, wherein the polyol block copolymer has a multi-block structure: A - A' - Z' - Z - (Z' - A' ) B n ) and polyether blocks B. B-A'-Z'-Z-(Z'-A'-B) n wherein n = t - 1 and wherein t = the number of terminal OH group residues on the block A; and t = at least 2; and wherein each A' is independently a polycarbonate chain having at least 70% carbonate linkages, and wherein each B is independently a polyether chain; and wherein Z'-Z-(Z') n is a starter residue.

50. The polyol block copolymer of claim 49, wherein, -A' - has the following structure: wherein the ratio of p:q is at least 7:3; and block B has the following structure: and R e1 , R e2 , R e3 and R e4 depend on the nature of the epoxide used to prepare blocks A and B.

51. The polyol block copolymer of claim 49 or 50, wherein, each R e1 , R e2 , R e3 or R e4 is independently selected from H, halogen, hydroxyl or optionally substituted alkyl (such as methyl, ethyl, propyl, butyl, -CH2C1, -CH2-OR 20 , -CH2-OC(0)R 12 or -CH2-OC(0)OR 18 ), alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl or heteroalkenyl, preferably from H or optionally substituted alkyl.

52. The polyol block copolymer of any one of claims 49-51, wherein, R e1 and R e2 or R e3 and R e4 together form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms and optionally one or more heteroatoms.

53. The polyol block copolymer of any one of claims 49-52, wherein, The starting residue depends on the nature of the starting compound, and wherein the starting compound has formula (III): wherein Z can be any of the groups that can have 2 or more -R attached thereto Z group, and can be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be a combination of any of these groups, for example Z can be alkylarylene, heteroalkylarylene, heteroalkylheteroarylene, or alkylheteroarylene; a is an integer of at least 2, optionally a is in the range of between 2 and 8, optionally a is in the range of between 2 and 6; wherein each R Z may be -OH, -NHR', -SH, -C(0)OH, -P(0)(OR')(OH), -PR'(0)(OH)2, or -PR'(0)OH, optionally RZis selected from -OH, -NHR', or -C(0)OH, optionally each R z is -OH, -C(0)OH, or a combination thereof (e.g., each R z is -OH); wherein R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, optionally R' is H or optionally substituted alkyl; and wherein R' can be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, optionally R' is H or optionally substituted alkyl; and wherein Z' corresponds to R z except that a bond replaces the labile hydrogen atom.

54. The polyol block copolymer of claim 53, wherein, The starting compound is selected from diols such as ethanediol or ethylene glycol, 1-3- propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2- benzenediol, 1,3-benzenediol, 1,4-benzenediol, neopentyl glycol, pyrocatechol, cyclohexene diol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol such as PPG 425, PPG 725, PPG 1000, and the like, polypropylene glycol (PPG) or polyethylene glycol (PEG) having a Mn of up to about 1500 g / mol; triols such as glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, tri(methylol)propane, tri(methylol)ethane, tri(methylol)nitropropane, trimethylolpropane, polyethylene oxide triol, polypropylene oxide triol, and polyester triol; tetraols such as calix[4]arene, 2,2-bis(methylol)-1,3-propanediol, erythritol, pentaerythritol, or polyalkylene glycol (PEG or PPG) having 4 -OH groups; polyols such as sorbitol or polyalkylene glycol (PEG or PPG) having 5 or more -OH groups; or compounds having mixed functionality including ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine.

55. The polyol block copolymer of any one of claims 49-54, wherein, The polyol molecular weight (Mn) is in the range of 300-20,000 Da and the molecular weight (Mn) of block A is in the range of 200-4000 Da, and wherein the molecular weight (Mn) of block B is in the range of 100-20,000 Da, more typically the molecular weight (Mn) of block A is 200-2000 Da, more typically 200-1000 Da, most typically 400-800 Da, and / or the molecular weight (Mn) of block B is typically 200-10,000 Da, more typically 200-5000 Da.

56. The polyol block copolymer of claim 55, wherein, The molecular weight (Mn) is measured by gel permeation chromatography (GPC).

57. The polyol block copolymer of any one of claims 49-56, wherein, Block A has at least 76%, more typically at least 80%, or most typically at least 85% carbonate linkages.

58. The polyol block copolymer of any one of claims 49-57, wherein, Block A has less than 98% carbonate linkages, more typically less than 97% carbonate linkages, or most typically less than 95% carbonate linkages.

59. The polyol block copolymer of any one of claims 49-58, wherein, Block A has between 75% and 99% carbonate linkages, more typically between 77% and 95% carbonate linkages, most typically between 80% and 90% carbonate linkages.

60. The polyol block copolymer of any one of claims 49-59, wherein, Block B has less than 1% carbonate linkages.

61. The polyol block copolymer of any one of claims 49-60, wherein, Block A further comprises ether linkages.

62. The polyol block copolymer of claim 61, wherein, Block A has less than 24% ether linkages, more typically less than 20% ether linkages, most typically less than 15% ether linkages.

63. The polyol block copolymer of claim 61 or 62, wherein, Block A has at least 1% ether linkages, more typically at least 3% ether linkages, most typically at least 5% ether linkages.

64. The polyol block copolymer of any one of claims 61-63, wherein, Block A has between 1% and 25% ether linkages, typically between 5% and 20% ether linkages, more typically between 10% and 15% ether linkages.

65. The polyol block copolymer of any one of claims 61-64, wherein, The epoxide is asymmetric and the polycarbonate has between 40-100% head-to-tail linkages, preferably greater than 50% head-to-tail linkages.

66. The polyol block copolymer of any one of claims 61-64, wherein, Between 0.1% and 20% of the total epoxide in Block A is an epoxide substrate containing more than one epoxide moiety, preferably a bis-epoxide.

67. The polyol block copolymer of any one of claims 49-66, wherein, Block A is typically alternating polycarbonate polyol residues.

68. The polyol block copolymer of any one of claims 49-67, wherein, The mol / mol ratio of Block A to Block B is in the range of 25:1 to 1:

250.

69. The polyol block copolymer of any one of claims 49-68, wherein, At least 30% of the epoxide residues of Block A are ethylene oxide or propylene oxide residues, typically at least 50% of the epoxide residues of Block A are ethylene oxide or propylene oxide residues, more typically at least 75% of the epoxide residues of Block A are ethylene oxide or propylene oxide residues, most typically at least 90% of the epoxide residues of Block A are ethylene oxide or propylene oxide residues.

70. The polyol block copolymer of any one of claims 49-69, wherein, At least 30% of the epoxide residues of Block B are ethylene oxide or propylene oxide residues, typically at least 50% of the epoxide residues of Block B are ethylene oxide or propylene oxide residues, more typically at least 75% of the epoxide residues of Block B are ethylene oxide or propylene oxide residues, most typically at least 90% of the epoxide residues of Block B are ethylene oxide or propylene oxide residues.

71. The method of any one of claims 1-48, wherein, The polyol block copolymer produced in the second reaction is according to any one of claims 49-70.

72. A polyurethane produced from the reaction of a polyol block copolymer produced according to the method of any one of claims 1 to 48 and a (poly)isocyanate.

73. A polyurethane comprising block copolymer residues having: a polycarbonate block A (-A'-Z'-Z-(Z'-A' with greater than 76% carbonate linkages, and a polyether block B; wherein A' is a polycarbonate chain having at least 70% carbonate linkages, wherein the residue has a multi-block structure B-A'-Z'-Z-(Z'-A'-B) n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z')n is a starter residue. n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z')n is a starter residue.

74. The polyurethane of claim 73, wherein, The residue includes any one or more of the features defined in claims 49-70.

75. An isocyanate-terminated polyurethane prepolymer comprising the reaction product of a block copolymer produced according to the method of any one of claims 1 to 48 and an excess of a (poly)isocyanate.

76. An isocyanate-terminated polyurethane prepolymer comprising a block copolymer residue having: a polycarbonate block A (-A'-Z'-Z-(Z'-A') having greater than 76% carbonate linkages, and a polyether block B; wherein A' is a polycarbonate chain having at least 70% carbonate linkages, each polyether block having up to 50% carbonate linkages and at least 50% ether linkages, wherein the residue has a multi-block structure B-A'-Z'-Z-(Z'-A'-B) n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z')n is a starter residue. n wherein n = t-1 and wherein t = the number of terminal OH group residues on the block A, and wherein Z'-Z-(Z')n is a starter residue.

77. The isocyanate-terminated polyurethane prepolymer of claim 76, wherein, The residue includes any one or more of the features defined in claims 49-70.

78. The polyurethane of any one of claims 72-74, wherein, The polyurethane is in the form of a soft foam, flexible foam, integral skin foam, high resilience foam, viscoelastic or memory foam, semi-rigid foam, rigid foam (such as polyurethane (PUR) foam, polyisocyanurate (PIR) foam and / or spray foam), elastomer (such as cast elastomer, thermoplastic elastomer (TPU) or microcellular elastomer), adhesive (such as hot melt adhesive, pressure sensitive adhesive or reactive adhesive), sealant or coating (such as aqueous or solvent dispersion (PUD), two-component coating, one-component coating, solventless coating).

79. The polyurethane of claim 78, wherein, The polyurethane is formed by a process comprising extrusion, moulding, injection moulding, spraying, foaming, casting and / or curing.

80. The polyurethane of claim 78 or 79, wherein, The polyurethane is formed by a ‘one-pot’ or ‘prepolymer’ process.

81. A composition comprising the polyol block copolymer of any one of claims 49-70 and one or more additives selected from the group consisting of catalysts, blowing agents, stabilizers, plasticizers, fillers, flame retardants, and antioxidants.

82. The composition of claim 81 further comprising a (poly)isocyanate.

83. The composition of claim 81 or 82, wherein, Catalysts for the reaction of the (poly)isocyanate and the polyol block copolymer include suitable urethane catalysts such as tertiary amine compounds and / or organometallic compounds.

84. The composition of claim 81 or 82, wherein, A trimerization catalyst is present.

85. The composition of claim 84, wherein, An excess of (poly)isocyanate, more typically polymeric isocyanate, relative to the polyol is present, such that polyisocyanurate rings can form in the presence of the trimerization catalyst.

86. A lubricant composition comprising the polyol block copolymer of any one of claims 49-70.

87. A surfactant composition comprising the polyol block copolymer of any one of claims 49-70.

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