Polyol Block Copolymer

Abstract

The present invention relates to (poly)ol block copolymers of the general structure BA-(B)n, where block A is a polycarbonate block or a polyester block, where n=t-1 and t=the number of reactive end residues on block A, and block B is a polyether carbonate block, and where greater than 70% of the copolymer chain ends are terminated with primary hydroxyl groups. The present invention also relates to processes for making such copolymers and to products incorporating such copolymers.

Description

[Technical Field]

[0001] The present invention relates to (poly)ol block copolymers comprising polycarbonate (A) and polyether carbonate blocks (B) of the general structure BA(B)n and having greater than 70% primary hydroxyl end groups, a process for producing such (poly)ol block copolymers by a two-step process generally carried out in two separate reactions, and products and compositions incorporating such copolymers or their residues. [Background technology]

[0002] It is generally desirable for polyols used in polyurethane applications to have primary hydroxyl end groups because of their high reactivity with isocyanates (compared to less reactive secondary hydroxyls). Polyether polyols are typically produced by basic catalysis using sodium hydroxide or potassium hydroxide, or by using so-called double metal cyanide (DMC) catalysts. Hydroxide catalysts are advantageously capable of reacting with both ethylene oxide (EO) and propylene oxide (PO), allowing PO-based polyols to be end-capped with EO to obtain polyols with all primary hydroxyl end groups. Unfortunately, the hydroxide-catalyzed process involves tedious purification steps, including neutralization, filtration, and drying. Furthermore, alkaline catalysts promote the formation of unsaturated, non-hydroxyl end groups at higher molecular weights, reducing the functionality of the polyol and reducing the quality of the polyurethane. DMC catalysts produce polyols with very low amounts of unsaturated end groups, even at higher molecular weights, and do not require any purification. However, DMC catalysts are less reactive with EO than with PO, and cannot effectively produce PO polyols end-capped with EO and having 100% primary hydroxyl end groups. Instead, most of the EO reacts to long polyethylene oxide chains, leaving behind high molecular weight components (which reduce the quality of polyurethane products) and PO polyols with mostly less reactive secondary hydroxyl end groups.

[0003] To produce polyols with low unsaturation, desirable functionality, and a high proportion of primary hydroxyl end groups and molecular weights higher than about 2000, it has been necessary to produce PO-based polyols using DMC catalysts, which are then end-capped with EO using hydroxide catalysts, which entails a complex purification process, which is inefficient and expensive.

[0004] Various methods have been proposed for increasing the primary hydroxyl end groups using DMC catalysts, such as those disclosed in U.S. Patent Nos. 5,629,999 and 5,749,333. This generally involves starting with a primarily PO feed and increasing the proportion of EO in the feed as the reaction continues. This method has demonstrated primary hydroxyl contents of about 40-60%.

[0005] It is also known to use DMC catalysts with epoxides and carbon dioxide to produce so-called "polyether carbonate" polyols. Various methods are known, including those disclosed in U.S. Patent Nos. 5,629,999, 5,729,965, 5,829,975, and 5,929,975. These processes typically require high pressures to allow for some CO content in the polyol. These polyols are primarily made with PO and therefore have very low (less than 5%) primary hydroxyl content.

[0006] Patent Document 6 discloses a method for preparing polyether carbonate polyols using DMC, in which a polyol is first prepared using CO and PO in a solvent (cyclic propylene carbonate or ethylene carbonate) using DMC, and then end-capped with an increasing EO / PO ratio. In this method, the maximum primary hydroxyl content is said to be 65%.

[0007] Patent Documents 7 and 8 from Covestro disclose the use of a DMC catalyst to produce polyether carbonate polyols from CO and alkylene oxides in the presence of a starter compound. Many H-functional initiator compounds are listed, including polyether carbonate polyols, polycarbonate polyols, and polycarbonates.

[0008] Polyethercarbonate polyols made solely from DMC generally have a structure with more ether linkages in the middle of the polymer chain and more carbonate groups toward the hydroxyl end groups, which is not advantageous because ether groups are substantially more stable to heat and basic conditions than carbonate linkages.

[0009] U.S. Patent No. 5,949,693 discloses the preparation of block copolymers having polycarbonate blocks and hydrophilic blocks (e.g., polyethers). Various structures are described, each having a polyether block flanked by a polycarbonate block. Some examples include polycarbonate blocks with polyether end blocks. A two-pot process is described, in which alternating polycarbonate blocks are prepared in a first reaction using a carbonate catalyst, followed by quenching and isolation of the polyol from solvent and unreacted monomers, and then a second batch reaction incorporating a hydrophilic oligomer, such as a poly(alkylene oxide), using a DMC catalyst (in the absence of CO). Some examples use ethylene oxide as the ether block, but the ratio of primary to secondary hydroxyl end groups is not quantified. These polymers have applications in enhanced oil recovery. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] International Publication No. 2001 / 044347 [Patent Document 2] International Publication No. 2004 / 111107 [Patent Document 3] International Publication No. 2008 / 058913 [Patent Document 4] International Publication No. 2008 / 013731 [Patent Document 5] U.S. Patent No. 6,762,278 [Patent Document 6] U.S. Patent No. 10,174,151 [Patent Document 7] International Publication No. 2015 / 059068 [Patent Document 8] US Patent Application Publication No. 2015 / 0259475 [Patent Document 9] International Publication No. 2010 / 062703 Summary of the Invention [Means for solving the problem]

[0011] Advantageously, it has been found that by using a polycarbonate initiator and a DMC catalyst together with an epoxide and CO, it is possible to produce (poly)ols with very high primary hydroxyl content (greater than 70% or even 80% primary hydroxyl end groups). The use of a carbonate initiator (either directly from the first reaction mixture or by using purified initiator material) is advantageous in facilitating end-capping in the presence of CO with a DMC catalyst.

[0012] (Poly)ols with various CO2 contents, low levels of unsaturation, and high primary hydroxyl content can be produced without the need for purification processes as used with hydroxide catalysts. Therefore, the process has advantages over metal hydroxide catalysts and DMC catalysts (alone), and allows the use of CO2 to produce (poly)ols with a low carbon footprint.

[0013] Advantageously, the low molecular weight polycarbonate (poly)ol initiator does not need to be isolated but can be made in one reactor and transferred directly into a second reactor without removing any catalyst, unreacted monomers, or solvent. DETAILED DESCRIPTION OF THE INVENTION

[0014] In a first aspect of the present invention, (poly)ol block copolymers of the general structure BA-(B)n are provided, where block A is a polycarbonate or polyester block, where n=t-1, and t=the number of reactive end residues on block A, and where block B is a polyether carbonate block, and where greater than 70% of the copolymer chain ends are terminated with primary hydroxyl groups.

[0015] Preferably, greater than 75%, more preferably greater than 80%, of the copolymer chain ends are terminated with primary hydroxyl groups. Preferably, the polymer chains are evenly end-capped, meaning that, on average, more than 75% of the polymer chains are end-capped with EO residues, more typically, more than 85% of the polymer chains are end-capped with EO residues, and most typically, at least 90% of the polymer chains are end-capped with EO residues.

[0016] The A blocks typically have greater than 70% carbonate linkages and the B blocks typically have less than 50% carbonate linkages. The polycarbonate of block A can also be prepared from alkylene oxide and CO2 by any suitable method in addition to the process defined in the embodiments herein. For example, polycarbonate diols can be prepared by reacting phosgene with a dihydrocarbyl carbonate, such as dimethyl carbonate, diethyl carbonate, or diphenyl carbonate. Examples of polycarbonates can be found, for example, in EP-A-1 359 177.

[0017] Typically, block A is a polyalkylene carbonate block, more typically derived from alkylene oxide and CO, and most typically alkylene oxide and CO represent at least 90% of the residues in the block, particularly at least 95%, more particularly at least 99%, and most particularly about 100% of the residues in the block, and are residues of alkylene oxide and CO. Most typically, block A comprises ethylene oxide and / or propylene oxide residues, but optionally also other alkylene oxide residues, such as butylene oxide, glycidyl ethers, glycidyl esters, and glycidyl carbonate. Typically, at least 50% of the alkylene oxide residues in block A are ethylene oxide or propylene oxide residues, more typically, at least 70% of the alkylene oxide residues in block A are ethylene oxide or propylene oxide residues, and most typically, at least 90% of the alkylene oxide residues in block A are ethylene oxide or propylene oxide residues, particularly at this level, ethylene oxide.

[0018] Typically, the carbonate of block A is derived from CO2, i.e., the carbonate contains CO2 residues. Block A typically has between 70 and 100%, more typically between 80 and 100%, and most typically between 90 and 100% carbonate linkages. The polycarbonate block A of the (poly)ol block copolymer may have at least 76% carbonate linkages, preferably at least 80% carbonate linkages, and more preferably at least 85% carbonate linkages. Block A may have less than 98% carbonate linkages, preferably less than 97% carbonate linkages, and more preferably less than 95% carbonate linkages. Optionally, block A has between 75% and 99% carbonate linkages, preferably between 77% and 95% carbonate linkages, and more preferably between 80% and 90% carbonate linkages.

[0019] Surprisingly, it has been found that the block A of the present invention facilitates the incorporation of more primary hydroxyl ends into the B blocks. Thus, the block A attached to each B block is surprisingly adapted to react with alkylene oxide, so that the (poly)ol block copolymer has more than 70% primary hydroxyl ends, typically more than 75%, and more preferably more than 80% primary hydroxyl ends.

[0020] Typically, block B comprises ethylene oxide and, optionally, other alkylene oxide residues. Typically, the alkylene oxide residues provide at least 90% non-carbonate functional residues in the block, particularly at least 95% non-carbonate functional residues in the block, more particularly at least 99% non-carbonate functional residues in the block, and most particularly about 100% non-carbonate functional residues in the block, alkylene oxide residues. Typically, the ethylene oxide residues form 5 to 100% of the alkylene oxide residues in block B, more typically 10 to 100%, and most typically 10 to 50% of the alkylene oxide residues. Typically, block B is a mixture of at least ethylene oxide and propylene oxide residues. Typically, at least 50% of the alkylene oxide residues in block B are ethylene oxide or propylene oxide residues, more typically at least 70% of the alkylene oxide residues in block B are ethylene oxide or propylene oxide residues, and most typically at least 90% of the alkylene oxide residues in block B are ethylene oxide or propylene oxide residues, especially at this level, ethylene oxide. Generally, to form a primary hydroxyl terminus, at least the terminal alkylene oxide residue is an ethylene oxide residue. Typically, at least 70% of the terminal alkylene oxide residues are ethylene oxide residues, more typically at least 75%, and most typically at least 80% of the terminal alkylene oxide residues are ethylene oxide residues. Although it is also possible for a small proportion of other alkylene oxides to form primary hydroxyl termini, such primary hydroxyl placement is unusual due to ring-opening preference at unhindered methylene carbons.

[0021] Generally, when two or more alkylene oxides are used, more than 50% of the ethylene oxide residues in block B are incorporated into the copolymer chain closer to the terminus of the copolymer than to the terminus of the A block, more typically more than 60%, and most typically at least 70% of the ethylene oxide residues are so incorporated.

[0022] Optionally, block B incorporates a CO residue in its carbonate group. Typically, the polyether carbonate block B of the (poly)ol block copolymer may have less than 40% carbonate linkages, preferably less than 35% carbonate linkages, more preferably less than 30% carbonate linkages. Block B may have at least 5% carbonate linkages, preferably at least 10% carbonate linkages, more preferably at least 15% carbonate linkages. Optionally, block B may have between 1% and 50% carbonate linkages, preferably between 5% and 45% carbonate linkages, more preferably between 10% and 40% carbonate linkages.

[0023] The polyether carbonate block B of the (poly)ol block copolymer may have at least 60% ether linkages, preferably at least 65% ether linkages, and more preferably at least 70% ether linkages. The polyether carbonate block B of the (poly)ol block copolymer may have less than 95% ether linkages, preferably less than 90% ether linkages, and more preferably less than 85% ether linkages. Optionally, block B may have between 50% and 99% ether linkages, preferably between 55% and 95% ether linkages, and more preferably between 60% and 90% ether linkages.

[0024] The polycarbonate block A of the (poly)ol block copolymer may further comprise ether linkages. Block A may have less than 24% ether linkages, preferably less than 20% ether linkages, more preferably less than 15% ether linkages, such as less than 10%, for example less than 5% ether linkages. Block A may have at least 1% ether linkages, such as at least 2% ether linkages, or even at least 5% ether linkages. Optionally, block A may have between 0% and 25% ether linkages, preferably between 1% and 20% ether linkages, more preferably between 1% and 15% ether linkages.

[0025] Optionally, block A of the present invention may generally be alternating polycarbonate (poly)ol residues. If the alkylene oxide is asymmetric, the polycarbonate may have between 0 and 100% head-to-tail linkages, preferably between 40 and 100%, and more preferably between 50 and 100% head-to-tail linkages. The polycarbonate may have a statistical distribution of head-to-head, tail-to-tail, and head-to-tail linkages on the order of 1:2:1, suggesting non-stereoselective ring opening of the alkylene oxide, or it may have a preferential head-to-tail linkage distribution on the order of greater than 50%, optionally greater than 60%, 70%, 80%, or 90%.

[0026] Typically, in the (poly)ol block copolymers of the present invention, ethylene oxide residues form 0 to 100% of the alkylene oxide residues in the (poly)ol block copolymer, typically 5 to 70%, more typically 10 to 60%, and most typically 10 to 40% of the alkylene oxide residues in the (poly)ol block copolymer, and / or at least 5%, 10%, 15%, 20%, 25%, or 30% of the alkylene oxide residues in the (poly)ol block copolymer are ethylene oxide residues.

[0027] The A block of the present invention, which comprises an initiator, can be defined as follows: -A'-Z'-Z-(Z'-A') n - Thus, the polyblock structure of the copolymer can be defined as follows: B-A'-Z'-Z-(Z'-A'-B) n wherein n=t-1 and t=the number of residues of terminal OH groups on block A; and each A' is independently a polycarbonate chain having at least 70% carbonate linkages, and each B is independently a polyethercarbonate chain having 50-99% ether linkages and at least 1% carbonate linkages, and Z'-Z-(Z') n is the initiator residue. The (poly)ol has at least 70% primary hydroxyl end groups.

[0028] For the avoidance of doubt, when t=1, n=0 and the polyblock structure is: -B-A'-Z'-Z The claimed "% of copolymer chain ends terminated with primary hydroxyl groups" refers to the percentage of OH-functional chain ends that are terminated.

[0029] The polycarbonate block includes -A'-, which may have the following structure:

[0030] [ka]

[0031] wherein the ratio of (p:q) is at least (7:3); and R e1 and R e2 depends on the identity of the alkylene oxide used to prepare block A].

[0032] The polyether carbonate block B may have the following structure:

[0033] [ka]

[0034] wherein the ratio of w:v is 1:1 or greater; and R e3 and R e4 depends on the identity of the alkylene oxide used to prepare block B].

[0035] Each R e1 , R e2 , R e3 , or R e4 are independently H, halogen, hydroxyl, or optionally substituted alkyl (e.g., methyl, ethyl, propyl, butyl, -CH2Cl, -CH2-OR 20 , -CH2-OC(O)R 12 , or -CH2-OC(O)OR 18 ), alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl; preferably, H, or optionally substituted alkyl.

[0036] R e1 and R e2 , or R e3 and R e4 may combine to form a ring which is saturated, partially unsaturated or unsaturated and which contains carbon and hydrogen atoms and, optionally, one or more heteroatoms.

[0037] As mentioned above, R e1 , R e2 , R e3 , and R e4 The identity of R will depend on the alkylene oxide used in the reaction. For example, if the alkylene oxide is cyclohexene oxide (CHO), then Re1 and R e2 (or R e3 and R e4 ) may combine to form a six-membered alkyl ring (e.g., a cyclohexyl ring). If the alkylene oxide is ethylene oxide, then R e1 and R e2 (or R e3 and R e4 ) will be H. If the alkylene oxide is propylene oxide, then R e1 (or R e3 ) is H and R e2 (or R e4 ) would be methyl (or R e1 (or R e3 ) will be methyl, and R e2 (or R e4 ) will be H, depending on how the alkylene oxide is incorporated into the polymer backbone. If the alkylene oxide is butylene oxide, then R e1 (or R e3 ) will be H, and R e2 (or R e4 ) will be ethyl (and vice versa). If the alkylene oxide is styrene oxide, then R e1 (or R e3 ) will be hydrogen, and R e2 (or R e4 ) may be phenyl (and vice versa). When the alkylene oxide is a glycidyl ether, R e1 (or R e3 ) is an ether group (-CH2-OR 20 ) and R e2 (or R e4 ) will be H (and vice versa). If the alkylene oxide is a glycidyl ester, then R e1 (or R e3 ) is an ester group (-CH2-OC(O)R 12 ) and R e2 (or Re4 ) will be H (and vice versa). If the alkylene oxide is glycidyl carbonate, then R e1 (or R e3 ) is a carbonate group (CH2-OC(O)OR 18 ) and R e2 (or R e4 ) will be H (and vice versa).

[0038] When a mixture of alkylene oxides is used, R e1 and / or R e2 (or R e3 and / or R e4 ) may not be identical in each occurrence; 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 It will also be understood that ) can independently be hydrogen or methyl.

[0039] Therefore, R e1 and R e2 (or R e3 and R e4 ) can be independently selected from hydrogen, alkyl, or aryl, or R e1 and R e2 (or R e3 and R e4 ) can be taken together to form a cyclohexyl ring, preferably R e1 and R e2 (or R e3 and R e4 ) can be independently selected from hydrogen, methyl, ethyl, or phenyl, or R e1 and R e2 (or R e3 and R e4 ) can be taken together to form a cyclohexyl ring.

[0040] The identities of Z and Z' will vary depending on the nature of the initiator compound. The initiator compound has the formula (III):

[0041] [ka]

[0042] The present invention can be applied to a semiconductor device having a semiconductor substrate. Z may have one or more, typically two or more, -R Z

[0023] Z can be any group capable of carrying a group. Thus, Z can be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z can be any combination of these groups, for example, Z can be an alkylarylene group, a heteroalkylarylene group, a heteroalkylheteroarylene group, or an alkylheteroarylene group. Optionally, Z is alkylene, heteroalkylene, arylene, or heteroarylene.

[0043] It will be understood that a is an integer of at least 1, typically at least 2, optionally a is 1 or an integer in the range of 2 to 8, and optionally a is an integer in the range of 2 to 6.

[0044] R Z can each be —OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), —PR′(O)(OH), or —PR′(O)OH, and optionally, R Z is selected from —OH, —NHR′, or —C(O)OH, and optionally, R z are each —OH, —C(O)OH, or a combination thereof (e.g., R z are -OH).

[0045] R' can be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' is H or an optionally substituted alkyl.

[0046] Z' is R except that the highly reactive hydrogen atom is replaced by a bond. z Therefore, the identity of each Z' is determined by the R Z It will therefore be understood that each Z' can be -O-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -PR'(O)(O-), or -PR'(O)O- (where R' can be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, preferably R' is H or an 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-.

[0047] Preferably, the molecular weight (Mn) of the (poly)ol block copolymer is in the range of about 300 to 20,000 Da, more preferably in the range of about 400 to 8000 Da, and most preferably in the range of about 500 to 6000 Da.

[0048] The molecular weight (Mn) of the polycarbonate block A of the (poly)ol block copolymer is preferably in the range of about 200 to 4000 Da, more preferably in the range of about 200 to 2000 Da, most preferably in the range of about 200 to 1000 Da, and particularly in the range of about 400 to 800 Da.

[0049] The molecular weight (Mn) of the polyether carbonate block B of the (poly)ol block copolymer is preferably in the range of about 100 to 20,000 Da, more preferably in the range of about 200 to 10,000 Da, and most preferably in the range of about 200 to 5000 Da.

[0050] Alternatively, the polyether carbonate block B, and therefore the (poly)ol block copolymer, can have a high molecular weight. The molecular weight (Mn) of the polyether carbonate block B can be at least about 25,000 daltons, e.g., at least about 40,000 daltons, e.g., at least about 50,000 daltons, or at least about 100,000 daltons. The high molecular weight (poly)ol block copolymers of the present invention can have a molecular weight greater than about 100,000 daltons.

[0051] The Mn, and therefore the PDI, of a polymer can be measured using gel permeation chromatography (GPC). For example, GPC can be performed using an Agilent 1260 Infinity GPC system with two Agilent PLgel μm mixed-D columns connected in series. Samples can be measured at room temperature (293 K) in THF at a flow rate of 1 mL / min against narrow molecular weight polystyrene standards (e.g., polystyrene low molecular weight (low) EasiVials, with Mn in the range of 405 to 49,450 g / mol, available from Agilent Technologies). Optionally, samples can be measured against poly(ethylene glycol) standards, such as polyethylene glycol EasiVials, available from Agilent Technologies.

[0052] Typically, the mol / mol ratio of block A to block B is in the range of 25:1 to 1:250. Usually, the weight ratio of block A to block B is in the range of 50:1 to 1:100.

[0053] According to a second aspect of the present invention, there is also provided a composition comprising the (poly)ol block copolymer according to the first aspect of the present invention. The composition may also contain one or more additives known in the art. Additives may include, but are not limited to, catalysts, blowing agents, stabilizers, plasticizers, fillers, flame retardants, antifoaming agents, and antioxidants.

[0054] The filler may be selected from inorganic fillers or polymeric fillers, such as styrene-acrylonitrile (SAN) dispersion filler. The blowing agent can be selected from chemical blowing agents or physical blowing agents. Chemical blowing agents typically react with (poly)isocyanates to liberate volatile compounds such as CO2. Physical blowing agents typically evaporate during foam formation due to their low boiling points. Suitable blowing agents are known to those 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, or one or more physical blowing agents can be used in combination with one or more chemical blowing agents.

[0055] Chemical blowing agents include water and formic acid. Both react with a portion of the (poly)isocyanate to produce carbon dioxide, which can function 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. Water can be used alone or in combination with other blowing agents, if desired.

[0056] Typically, physical blowing agents for use in the present invention can be selected from acetone, carbon dioxide, optionally substituted hydrocarbons, and chloro / fluorocarbons. Chloro / fluorocarbons 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, and pentafluorobutane.

[0057] Olefin blowing agents, namely, 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), may also be included.

[0058] Typically, non-halogenated hydrocarbons for use as physical blowing agents can be selected from butane, isobutane, 2,3-dimethylbutane, n- and i-pentane isomers, hexane isomers, heptane isomers, and cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane. More typically, non-halogenated hydrocarbons for use as physical blowing agents can be selected from cyclopentane, isopentane, and n-pentane.

[0059] Typically, when one or more blowing agents are present, they are used in an amount of from about 0 to about 10 parts, more typically from 2 to 6 parts, of the total formulation. When water is used in combination with other blowing agents, the ratio of the two blowing agents can vary widely, for example, from 1 to 99 parts by weight of water, preferably from 25 to over 99 parts by weight of water, of the total blowing agent.

[0060] Preferably, the blowing agent is selected from cyclopentane, isopentane, n-pentane, and more preferably, n-pentane. Typical plasticizers can be selected from succinates, adipates, phthalates, diisooctyl phthalate (DIOP), benzoates, and N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES).

[0061] Typical flame retardants are known to those skilled in the art and can be selected from phosphonamidates, 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, tetrakis(2-chloroethyl)ethylene diphosphate, tricresyl phosphate, cresyl diphenyl phosphate, diammonium phosphate, melamine, melamine pyrophosphate, urea phosphate, alumina, boric acid, various halogenated compounds, antimony oxide, chlorendic acid derivatives, phosphorus-containing polyols, bromine-containing polyols, nitrogen-containing polyols, and chlorinated paraffins. The flame retardant may be present in an amount of 0 to 60 parts of the total mixture.

[0062] The composition of the present invention may also further comprise a (poly)isocyanate. Typically, a (poly)isocyanate contains two or more isocyanate groups per molecule. Preferably, the (poly)isocyanate is a diisocyanate. However, the (poly)isocyanate can also be a higher functionality (poly)isocyanate), such as a triisocyanate, tetraisocyanate, isocyanate polymer, or oligomer. The (poly)isocyanate can be an aliphatic (poly)isocyanate or a derivative or oligomer of an aliphatic (poly)isocyanate, or an aromatic (poly)isocyanate or a derivative or oligomer of an aromatic (poly)isocyanate. Typically, the functionality of the (poly)isocyanate component is two or more. In some embodiments, the (poly)isocyanate component comprises a mixture of diisocyanates and higher functionality isocyanates formulated to achieve a specific functionality for a given application.

[0063] In some embodiments, the functionality of the (poly)isocyanates used is greater than 2. In some embodiments, the functionality of such (poly)isocyanates is between 2 and 5, more typically between 2 and 4, and most typically between 2 and 3.

[0064] Suitable (poly)isocyanates that can be used include aromatic, aliphatic, and cycloaliphatic polyisocyanates, and combinations thereof. Polyisocyanates of this type include: 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-hexamethylamine diisocyanate (HDI), isophorone ...4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylamine diisocyanate (HDI), isophorone diisocyanate, 1,2-cyclohexyl diisocyanate, 1,4-phenylene diisocyanate, 1,2-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylamine diisocyanate (HDI), isophorone diisocyanate, 1,2-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate isocyanate (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 Isocyanate, isocyanatomethyl-1,8-octane diisocyanate (TIN), m-tetramethylxylylene diisocyanate (TMXDI), p-tetramethylxylylene diisocyanate (TMXDI), tris(p-isocyanatomethyl) thiosulfate, trimethylhexane diisocyanate, lysine diisocyanate, m-xylylene diisocyanate (XDI), p-xylylene diisocyanate (XDI), 1,3,5-hexamethylmesitylene triisocyanate The (poly)isocyanate may be selected from the group consisting of 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 combinations of any two or more thereof. Additionally, the (poly)isocyanate may be selected from polymeric versions of any of these isocyanates, which may be higher or lower in functionality.Preferred polymeric isocyanates can be selected from MDI, TDI, and polymeric MDI.

[0065] According to a third aspect of the present invention, there is also provided a polyurethane produced by reacting the polyol block copolymer of the first aspect of the present invention with a (poly)isocyanate. Polyurethanes can also be produced by reacting the composition according to the second aspect of the present invention with a (poly)isocyanate. The polyurethanes can be in the form of 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), elastomers (such as cast elastomers, thermoplastic elastomers (TPU), or microcellular elastomers), adhesives (such as hot melt adhesives, pressure-sensitive adhesives, reactive adhesives), sealants, or coatings (such as water-based or solvent-based dispersions (PUDs), two-component coatings, one-component coatings, solventless coatings, etc.). Polyurethanes can be formed via processes including extrusion, molding, injection molding, spraying, foaming, casting, and / or curing. Polyurethanes can be formed via a "one-pot" or "prepolymer" method.

[0066] In a fourth aspect of the invention, there is also provided a polyurethane comprising residues of a block copolymer according to the first aspect of the invention. The block copolymer residue of the polyurethane of the fourth aspect may comprise any one or more of the features defined in relation to the first aspect of the invention.

[0067] According to a fifth aspect of the present invention, there is also provided an isocyanate-terminated polyurethane prepolymer comprising the reaction product of a polyol block copolymer according to the first aspect of the present invention or a composition according to the second aspect of the present invention with an excess of a (poly)isocyanate, e.g., one having at least >1 mole of isocyanate groups per mole of OH groups. The isocyanate-terminated prepolymer can be reacted with one or more chain extenders (water, diols, triols, diamines, etc.) and / or further polyisocyanates and / or other additives to form a polyurethane.

[0068] The isocyanate-terminated polyurethane prepolymer of the fifth aspect can have one or more of the various characteristics defined in the first aspect of the invention (except where such characteristics are mutually exclusive).

[0069] The catalyst that can be added to the polyol block copolymer of the first aspect of the present invention and / or the composition of the second aspect of the present invention can be a catalyst for reacting a (poly)isocyanate and a polyol, and examples of such catalysts include suitable urethane catalysts such as tertiary amine compounds and / or organometallic compounds.

[0070] Optionally, a trimerization catalyst can be used. An excess of (poly)isocyanate, or more preferably an excess of polymeric isocyanate, relative to the polyol can be present to allow for the formation of polyisocyanurate rings in the presence of the trimerization catalyst. Any of these catalysts can be used in combination with one or more other trimerization catalysts.

[0071] In a sixth aspect of the present invention, there is provided a lubricant composition comprising a (poly)ol block copolymer according to the first aspect of the present invention. In a seventh aspect of the present invention, there is provided a surfactant composition comprising a (poly)ol block copolymer according to the first aspect of the present invention.

[0072] In an eighth aspect of the present invention, there is also provided a process for producing a (poly)ol block copolymer comprising reacting a DMC catalyst with a polycarbonate or polyester (poly)ol (co)polymer according to Block A of the first aspect, CO, ethylene oxide, and optionally one or more other alkylene oxides to produce a (poly)ol block copolymer according to the first aspect, or a process for producing a (poly)ol block copolymer comprising a first reaction in a first reactor and a second reaction in a second reactor, wherein the first reaction is reacting a carbonate catalyst with CO and an alkylene oxide in the presence of an initiator and optionally a solvent to produce a polycarbonate (poly)ol copolymer according to Block A of the first aspect, and the second reaction is reacting a DMC catalyst with the polycarbonate (poly)ol copolymer of the first reaction, CO, ethylene oxide, and optionally one or more other alkylene oxides to produce a (poly)ol block copolymer according to the first aspect of the present invention.

[0073] The process may further include third or further reactions, including reactions in which the block copolymer of the first aspect of the present invention is reacted with monomers or further polymers to produce higher molecular weight polymers.

[0074] The monomer or further polymer may be a (poly)isocyanate and the reaction product of the third or further reaction may be a polyurethane. In a ninth aspect of the present invention, there is further provided a process for producing a (poly)ol block copolymer in a multiple reactor system, the system including first and second reactors, wherein a first reaction is carried out in the first reactor and a second reaction is carried out in the second reactor, wherein the first reaction is a reaction of a carbonate catalyst with CO and an alkylene oxide in the presence of an initiator and optionally a solvent to produce a polycarbonate (poly)ol copolymer according to Block A of the first aspect, and the second reaction is a reaction of a DMC catalyst with the polycarbonate (poly)ol compound of the first reaction, CO, ethylene oxide, and optionally one or more other alkylene oxides to produce a (poly)ol block copolymer according to the first aspect of the present invention.

[0075] It is also possible to add components in separate reactions and reactors. Advantageously, this can increase the activity of the catalyst, resulting in a more efficient process compared to processes in which all ingredients are added at the beginning of a single reaction. The presence of large amounts of some of the components throughout the reaction can reduce the efficiency of the catalyst. By reacting the ingredients in separate reactors, this can be prevented and / or the catalyst activity can be optimized. The reaction conditions for each reactor can be individually set to optimize the reaction over each catalyst.

[0076] Additionally, by not adding the entire amount of each component at the beginning of the reaction and by adding the catalyst for the first reaction in a separate reactor from the catalyst for the second reaction, more uniform catalysis can be achieved, resulting in a more homogeneous polymer product, with narrower molecular weight distributions, a desirable ratio and distribution of ether chains to carbonate linkages, and / or improved (poly)ol stability.

[0077] The DMC catalysts can also be pre-activated. Such pre-activation can be achieved by mixing one or both catalysts with the alkylene oxide (and optionally other components). Pre-activation of the DMC catalyst is useful because it allows for safe control of the reaction (preventing uncontrolled growth of unreacted monomer content) and eliminates unpredictable activation times.

[0078] It should be appreciated that the present invention relates to the reaction of adding carbonate and ether linkages to a growing polymer chain. Separate reactions allow the first reaction to proceed before the second stage of the reaction. Mixing an alkylene oxide, a carbonate catalyst, an initiator compound, and carbon dioxide allows for the growth of a polymer with a high number of carbonate linkages. The reaction is then advanced by adding the reaction product to a DMC catalyst, allowing for a higher incidence of ether linkages to be added to the growing polymer chain. Ether linkages are more thermally stable than carbonate linkages and are less susceptible to degradation by bases such as the amine catalysts used in PU formation. Therefore, in applications, the benefits of the carbonate linkages from the A block (e.g., increased strength, chemical resistance, resistance to both oil degradation and hydrolysis, etc.) are additionally realized, while maintaining the stability of the (poly)ol due to the overwhelming majority of ether linkages from the B block at the end of the polymer chain. Added to this benefit is the high occurrence of primary hydroxyl end groups provided by ethylene oxide on the (poly)ol.

[0079] Further benefits of the present invention when implemented in a two reactor system include: control of the polymerization reaction, increasing the CO content of polyether carbonate (poly)ol at lower pressures (allowing for more cost-effective process and plant designs), and producing products with high CO content yet good stability and performance. The process herein allows for tailoring of products to the required requirements.

[0080] The (poly)ol block copolymers of the present invention can be prepared from a suitable alkylene oxide and carbon dioxide in the presence of an initiator compound and a carbonate catalyst for the first reaction, and then ethylene oxide and optionally one or more other alkylene oxides, and carbon dioxide in the presence of a double metal cyanide (DMC) catalyst in the second reaction.

[0081] The carbonate catalyst of the present invention can be a catalyst that produces polycarbonate (poly)ols having more than 76% carbonate linkages, preferably more than 80% carbonate linkages, more preferably more than 85% carbonate linkages, and most preferably more than 90% carbonate linkages, and therefore such ranges of carbonate linkages can be present in block A.

[0082] If one of the alkylene oxides used is asymmetric (e.g., propylene oxide), the polycarbonate (poly)ol may contain a high proportion of alkylene oxides in head-to-tail bonds, e.g., more than 70%, more than 80%, or more than 90%. Alternatively, polycarbonate (poly)ols containing such asymmetric alkylene oxides may not have stereoselectivity and may give polyols with about 50% head-to-tail bonds on such residues.

[0083] The carbonate catalyst may be heterogeneous or homogeneous. The carbonate catalyst can be a mono-metallic, bimetallic, or multi-metallic homogeneous complex.

[0084] The carbonate catalyst may have a phenol or phenolate ligand. Typically, the carbonate catalyst may be a binuclear metal complex containing a phenol or phenolato ligand, where the two metals may be the same or different.

[0085] The carbonate catalyst is represented by formula (IV):

[0086] [ka]

[0087] (In the formula: M is M-(L) v is a metal cation represented by: x is an integer of 1 to 4, preferably 1 or 2;

[0088] [ka]

[0089] is one or more multidentate ligands; L is a coordinating ligand, for example, L may be a neutral or anionic ligand, preferably one that allows for ring opening of the alkylene oxide; where v is an integer that independently satisfies the valence of each M and / or the preferred coordination geometry of each M, or an integer that results in an overall charge neutrality of the complex represented by formula (IV) above. For example, each v may independently be 0, 1, 2, or 3, e.g., v may be 1 or 2. When v>1, each L may be different.

[0090] The term polydentate ligand includes bidentate, tridentate, tetradentate and higher polydentate ligands. Each polydentate ligand may be a macrocyclic or open ligand. Examples of this type of catalyst include those described in International Publication No. 2010022388 (metal salesens and derivatives, metal porphyrins, corroles and derivatives, metal tetraazaannulenes and derivatives), International Publication No. 2010028362 (metal salesens and derivatives, metal porphyrins, corroles and derivatives, metal tetraazaannulenes and derivatives), International Publication No. 2008136591 (metal salesens), International Publication No. 2011105846 (metal salesens), International Publication No. 2014148825 (metal salesens), International Publication No. 2013012895 (metal salesens), European Patent Application Publication No. 2258745(A1) (metal porphyrins and derivatives), and Japanese Patent Application Laid-Open No. 2008-081518(A1). ) (Metalloporphyrins and Derivatives), CN101412809 (Metalsalens and Derivatives), WO2019126221 (Metal Aminotriphenol Complexes), U.S. Pat. No. 9018318 (Metal β-Diiminato Complexes), U.S. Pat. No. 6133402(A) (Metal β-Diiminato Complexes), and U.S. Pat. No. 8278239 (Metalsalens and Derivatives), the entire contents of which are incorporated herein by reference, in particular insofar as they relate to carbonate catalysts suitable for reacting CO and alkylene oxide in the presence of an initiator and an optional solvent to produce polycarbonate polyol copolymers according to Block A.

[0091] Catalysts of this type also include those described in WO 2009 / 130470, WO 2013 / 034750, WO 2016 / 012786, WO 2016 / 012785, WO 2012037282, and WO 2019048878(A1) (all binuclear metal phenolate complexes), the entire contents of which are incorporated herein by reference, in particular as they relate to carbonate catalysts suitable for reacting CO and alkylene oxide in the presence of an initiator and optionally a solvent to produce polycarbonate polyol copolymers according to Block A.

[0092] The carbonate catalyst has the structure shown below:

[0093] [ka]

[0094] (In the formula: M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2, Y(III)-X, Sc(III)-X, or Ti(IV)-(X)2; R1 and R2 are independently selected from hydrogen, halide, nitro, nitrile, imine, amine, ether, silyl, silyl ether, sulfoxide, sulfonyl, sulfinate, or acetylide groups, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic groups; R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene are optionally interrupted by aryls, heteroaryls, aliphatic rings, or heteroaliphatic rings; R5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; E1 is C and E2 is O, S, or NH, or E1 is N and E2 is O; E3, E4, E5, and E6 are selected from N, NR4, O, and S, where when E3, E4, E5, or E6 is N,

[0095] [ka]

[0096] teeth

[0097] [ka]

[0098] and When E3, E4, E5, or E6 is NR4, O, or S,

[0099] [ka]

[0100] teeth

[0101] [ka]

[0102] and R4 is H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19 or -alkylC≡N, or alkylaryl; X is OC(O)R x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, phosphonate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl, where each X may be the same or different, and X may form a bridge between M1 and M2; R x are independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl; G can be absent or have (independently selected from neutral or anionic donor ligands that are Lewis bases).

[0103] Each R1 and R2 group may be the same or different at each occurrence, and R1 and R2 may be the same or different. DMC catalysts are complex compounds containing at least two metal centers and cyanide ligands. DMC catalysts may further include at least one of: one or more complexing agents, water, metal salts, and / or acids (e.g., in non-stoichiometric amounts).

[0104] The first two of the at least two metal centers can be represented as M' and M''. M' can be selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II), and Cr(III), and M' is optionally selected from Zn(II), Fe(II), Co(II), and Ni(II), and optionally M' is Zn(II).

[0105] 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).

[0106] It will be understood that the above optional definitions of M' and M" can be combined. For example, M' can optionally be selected from Zn(II), Fe(II), Co(II), and Ni(II), and M" can optionally be selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II). For example, M' can optionally be Zn(II), and M" can optionally be selected from Co(II) and Co(III).

[0107] When an additional metal center is present, the additional metal center may be further selected from the definitions of M' or M''. Examples of DMC catalysts that can be used in the process of the present invention include those described in U.S. Pat. Nos. 3,427,256, 5,536,883, 6,291,388, 6,486,361, 6,608,231, 7,008,900, 5,482,908, 5,780,584, 5,783,513, 5,158,922, 5,693,584, 7,811,958, 6,835,687, 6,699,961, 6,716,788, Nos. 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500,704, 7,977,501, 9,315,622, EP 1568414(A), EP 1529566(A), and WO 2015 / 022290, the entire contents of which are incorporated herein by reference, in particular insofar as they relate to DMC catalysts for the preparation of block copolymers of the first aspect as defined herein or for the reactions of the eighth or ninth aspects as defined herein.

[0108] DMC catalysts are: M' d [M'' e (CN) f ] g where M' and M" are as defined above, and d, e, f, and g are integers selected such that the DMC catalyst is electroneutral. Optionally, d is 3. Optionally, e is 1. Optionally, f is 6. Optionally, g is 2. Optionally, M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), and optionally, M' is Zn(II). Optionally, M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II), and optionally, M" is Co(II) or Co(III).

[0109] It will be understood that any of these optional features may be combined, for example, d is 3, e is 1, f is 6, g is 2, M' is Zn(II), and M'' is Co(III).

[0110] Suitable DMC catalysts having the above formula can include zinc hexacyanocobaltate(III), zinc hexacyanoferrate(III), nickel hexacyanoferrate(II), and cobalt hexacyanocobaltate(III).

[0111] There has been much development in the field of DMC catalysts, and those skilled in the art will understand that DMC catalysts can further comprise additives to enhance the activity of the catalyst in addition to the formula above. Thus, while the formula above forms the "core" of a DMC catalyst, the DMC catalyst can further comprise one or more additional components, such as at least one complexing agent, acid, metal salt, and / or water, in stoichiometric or non-stoichiometric amounts.

[0112] For example, a DMC catalyst may be represented by the formula: M' d [M'' e (CN) f ] g ·hM'''X'' i jR c kH2O lHr X'' where M', M'', X''', d, e, f, and g are as defined above. M''' may be M' and / or M''. X'' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and optionally, X'' is a halide. i is an integer equal to or greater than 1, and the charge of the anion X'' multiplied by i satisfies the valence of M'''. r is an integer corresponding to the charge of the counter ion X'''. For example, when X''' is Cl, - then r is 1. l is 0 or a number between 0.1 and 5. Optionally, l is a number between 0.15 and 1.5.

[0113] R c is a complexing agent or a combination of one or more complexing agents. For example, R c are (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols (e.g., C 1-8 alcohol), urea, etc., such as propylene glycol, polypropylene glycol, (meth)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof, such as R c can be tert-butyl alcohol, dimethoxyethane, or polypropylene glycol.

[0114] As indicated above, more than one complexing agent can be present in the DMC catalyst used in the present invention. c One of the complexing agents R may be a polymeric complexing agent. c can be a combination of polymeric and non-polymeric complexing agents. Optionally, a combination of the complexing agents tert-butyl alcohol and polypropylene glycol can be present.

[0115] It will be understood that when water, complexing agent, acid, and / or metal salt are not present in the DMC catalyst, h, j, k, and / or l are each 0. When water, complexing agent, acid, and / or metal salt are present, h, j, k, and / or l are positive numbers, for example, between 0 and 20. For example, h can be between 0.1 and 4. j can be between 0.1 and 6. k can be between 0 and 20, for example, between 0.1 and 10, e.g., between 0.1 and 5. l can be between 0.1 and 5, e.g., between 0.15 and 1.5.

[0116] 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 in an amount of from about 10% to about 70% by weight of the DMC catalyst, and optionally in an amount of from about 20% to about 50% by weight of the DMC catalyst.

[0117] In addition to at least two metal centers and cyanide ligands, the DMC catalyst may also optionally include non-stoichiometric amounts of at least one of one or more complexing agents, water, metal salts, and / or acids.

[0118] 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 0 to 4 (e.g., 0.1 to 4), k can be 0 to 20 (e.g., 0.1 to 10), and j can be 0 to 6 (e.g., 0.1 to 6). As noted above, DMC catalysts have complex structures, and therefore the above formula, including additional components, is not intended to be limiting. Rather, one of ordinary skill in the art will understand that this definition is not intended to be exhaustive of DMC catalysts that can be used in the present invention.

[0119] Initiator compounds that can be used in the process for forming the polycarbonate polyols of the present invention contain at least two groups selected from a hydroxyl group (—OH), a thiol (—SH), an amine with at least one N-H bond (—NHR′), a group with at least one P—OH bond (e.g., —PR′(O)OH, —PR′(O)(OH), or —P(O)(OR′)(OH)), or a carboxylic acid group (—C(O)OH).

[0120] Thus, initiator compounds that can be used in the process for forming polycarbonate block polyether carbonate polyols have formula (III) defined above:

[0121] [ka]

[0122] It can have: The initiator compounds for the first and second reactions may be the same or different. When two different initiator compounds are used, two initiator compounds may be used in the second reaction. In this case, the initiator compound for the first reaction is the first initiator compound, and the second reaction involves adding the first crude reaction mixture to a second reactor containing the second initiator compound and a double metal cyanide (DMC) catalyst, and optionally a solvent and / or alkylene oxide and / or carbon dioxide. The second reaction of the present invention can be carried out for at least about 1 minute, optionally at least about 5 minutes, optionally at least about 15 minutes, optionally at least about 30 minutes, optionally at least about 1 hour, optionally at least about 2 hours, or optionally at least about 5 hours after the first reaction. It will be understood that in continuous reactions, these periods are the average time periods from the addition of monomer to the first reactor to the transfer of the remaining monomer to the second reactor.

[0123] If the initiator compound is polymeric, the molecular weight (Mn) can be at least about 200 Da or up to about 1000 Da. For example, the molecular weight is about 200-1000 Da, optionally about 300-700 Da, optionally about 400 Da.

[0124] The or each initiator compound typically comprises two or more R z groups, optionally 3 or more, optionally 4 or more, optionally 5 or more, optionally 6 or more, optionally 7 or more, optionally 8 or more R z groups, in particular R z is hydroxyl.

[0125] It will be appreciated that any of the above features may be combined, for example, a is 1 or between 2 and 8, and R Z can each be -OH, -C(O)OH, or a combination thereof, and Z can be selected from alkylene, heteroalkylene, arylene, or heteroarylene.

[0126] Examples of initiator compounds for either reaction, and generally in the process for forming the polycarbonate (poly)ols of the present invention, include the following: monofunctional initiator materials such as alcohols, phenols, amines, thiols, and carboxylic acids, such as alcohols, e.g., methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, linear or branched C-C 20 -monoalcohols 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, mono-ethers or esters of ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, such as ethylene glycol mono-methyl ether and propylene glycol mono-methyl ether, phenols, such as linear or branched C3-C6 20Alkyl-substituted phenols such as nonylphenol or octylphenol, monofunctional carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and acrylic acid, and monofunctional thiols such as ethanethiol, propane-1-thiol, propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol, or amines such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine;and / or diols selected from the following, such as 1,2-ethanediol (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-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexenediol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or polyethylene glycol (PEG) with an Mn of up to about 1500 g / mol, such as PPG 425, PPG 725, PPG 100. triols such as glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, polyethylene oxide triol, polypropylene oxide triol, and polyester triols; tetraols such as calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, erythritol, pentaerythritol, or polyalkylene glycols (PEG or PPG) having four OH groups; polyols having five or more —OH groups such as sorbitol or polyalkylene glycols (PEG or PPG), or compounds with mixed functionality such as ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine;

[0127] For example, the initiator 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 nonylphenol or octylphenol, 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, and acrylic acid.

[0128] For example, the initiator compound may be a diol, 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-diphenol, 1,3- Diphenol, 1,4-diphenol, neopentyl glycol, catechol, 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 an Mn of up to about 1500 g / mol, such as PPG 425, PPG 725, PPG 1000, etc. It is to be appreciated that the initiator compound may be 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, poly(caprolactone) diol, PPG 425, PPG 725, or PPG 1000.Preferably, the initiator compound may be a diol, such as 1,2-ethanediol (ethylene glycol), 1,3-propanediol (propylene glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol. Examples of initiator compounds include 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, poly(caprolactone)diol, 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, etc. It is to be appreciated that the initiator compound may be 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, poly(caprolactone)diol, PPG 425, PPG 725, or PPG 1000.

[0129] Further examples of initiator compounds 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-hydroxypropanoic acid, 4-hydroxybutanoic acid, 5-hydroxypentanoic acid.

[0130] When an initiator compound is present, it can be present in an amount to provide a ratio to the carbonate catalyst of about 1000:1 to about 1:1, e.g., about 750:1 to about 5:1, e.g., about 500:1 to about 10:1, e.g., about 250:1 to about 20:1, or about 125:1 to about 30:1, or about 50:1 to about 20:1. These ratios are molar ratios. These ratios are the ratio of the total amount of initiator to the total amount of carbonate catalyst used in the process. These ratios can be maintained during the addition of the materials.

[0131] The DMC catalyst for producing the block copolymer according to the first embodiment defined herein or according to the eighth and ninth embodiments of the present invention may be preactivated. Optionally, the DMC catalyst may be preactivated in reactor 2, in the reactor, or separately. Optionally, the DMC catalyst may be preactivated with an initiator compound, or with a polycarbonate or polyester (poly)ol (co)polymer according to the first embodiment, or with the reaction product of the first or second reaction. When the DMC catalyst is preactivated with the reaction product of the first reaction, it may be preactivated with some or all of the reaction product of the first reaction. The DMC catalyst may be preactivated with the (poly)ol block copolymer of the first embodiment, B-A'-Z'-Z-(Z'-A'-B) n They may be preactivated with , which may be added to the reactor or may be the remaining products from a previous reaction (the so-called "reaction heel").

[0132] The (poly)ol block copolymers in the eighth and ninth aspects may be according to one or more features of the first aspect of the invention. The reaction product of the first reaction may be a low molecular weight polycarbonate (poly)ol. The preferred molecular weight of the polycarbonate (poly)ol depends on the preferred overall molecular weight of the (poly)ol block copolymer. The molecular weight (Mn) of block A of the polycarbonate (poly)ol may be in the range of about 200 to about 4000 Da, about 200 to about 2000 Da, about 200 to about 1000 Da, or about 400 to about 800 Da, as measured by gel permeation chromatography.

[0133] Block A may generally be an alternating polycarbonate (poly)ol. The polycarbonate or polyester (poly)ol (co)polymer according to Block A of the first embodiment or the product of the first reaction may be fed to another reactor containing a preactivated DMC catalyst. The first product may be fed to another reactor as a crude reaction mixture.

[0134] The first reaction of the present invention can be carried out at a CO pressure of less than 20 bar (2 MPa), preferably less than 10 bar (1 MPa), and more preferably less than 8 bar (0.8 MPa). The second reaction of the present invention can be carried out at a CO pressure of less than 60 bar (6 MPa), preferably less than 20 bar (2 MPa), more preferably less than 10 bar (1 MPa), and most preferably less than 5 bar (0.5 MPa).

[0135] CO2 can be added continuously to the first reaction, preferably in the presence of an initiator. Both reactions can be carried out at carbon dioxide pressures of from about 1 bar (0.1 MPa) to about 60 bar (6 MPa), optionally from about 1 bar (0.1 MPa) to about 40 bar (4 MPa), optionally from about 1 bar (0.1 MPa) to about 20 bar (2 MPa), optionally from about 1 bar (0.1 MPa) to about 15 bar (1.5 MPa), optionally from about 1 bar (0.1 MPa) to about 10 bar (1 MPa), optionally from about 1 bar (0.1 MPa) to about 5 bar (0.5 MPa).

[0136] The second reaction can be carried out in CO2 or in a mixture of CO2 and an inert gas such as N2 or Ar. CO can be introduced into either reactor via standard methods, such as directly into the headspace or directly into the reaction liquid via standard methods, such as via an inlet tube, gassing ring, or hollow shaft stirrer. Mixing can be optimized using various stirrer configurations, such as a single stirrer or multi-stage stirrers.

[0137] The first reaction process is carried out at such a relatively low CO2 pressure, and the continuously added CO2 can produce a (poly)ol with a high CO2 content at low pressure. The first reaction can be carried out in a batch, semi-batch, or continuous process. In a batch process, the carbonate catalyst, alkylene oxide, CO, initiator, and optional solvent are all present at the start of the reaction. In a semi-batch or continuous reaction, one or more of the carbonate catalyst, alkylene oxide, CO, initiator, and / or solvent are added continuously or semi-continuously to the reactor.

[0138] The second reaction involving DMC can be carried out in a continuous or semi-batch process, in which one or more of the DMC catalyst, alkylene oxide, CO, initiator, and / or solvent are added continuously or semi-continuously to the reaction.

[0139] The polycarbonate or polyester (poly)ol (co)polymer may be added to the DMC catalyst continuously or semi-continuously. It is preferred to add the polycarbonate or polyester (poly)ol (co)polymer continuously. The term "semi-continuously" means that the polycarbonate or polyester (poly)ol is added in at least two portions, at least one of which is added after the start of the reaction. It is preferred to add the polycarbonate or polyester (poly)ol in several portions.

[0140] Typically, at least one portion of polycarbonate or polyester (poly)ol (co)polymer is added after the reaction has started. Typically, the DMC catalyst is preactivated with an initiator compound or a polycarbonate or polyester (poly)ol (co)polymer, or (poly)ol block copolymer reaction product.

[0141] Optionally, the crude reaction mixture fed to the second reactor can contain any amount of unreacted alkylene oxide and / or CO2 and / or initiator. Optionally, the crude reaction mixture feed may contain any amount of carbonate catalyst, which may optionally be removed prior to addition to the second reactor.

[0142] The polycarbonate product of the first reaction can be referred to as the crude product. The polycarbonate or polyester (poly)ol (co)polymer in Block A of the first embodiment, or the polycarbonate reaction product of the first reaction (optionally containing unreacted alkylene oxide and / or carbonate catalyst) can be fed into the first or second reaction all at once, or continuously or semi-continuously. The reaction product of the first reaction is preferably fed continuously into the second reactor. This is advantageous because the continuous addition of the reaction product of Reaction 1 as an initiator for the DMC catalyst allows the DMC catalyst in Reactor 2 to operate in a more controlled manner. This can prevent deactivation of the DMC catalyst in Reactor 2. The polycarbonate or polyester (poly)ol (co)polymer in Block A of the first embodiment, or the polycarbonate of Reaction 1 can be fed into the second reactor prior to DMC activation and can be used during DMC activation. The DMC catalyst is reacted with the (poly)ol block copolymer of the first embodiment, B-A'-Z'-Z-(Z'-A'-B) n They may be preactivated with either added to the reactor or as reaction products remaining from a previous reaction (the so-called "reaction heel").

[0143] The reaction temperature in the first reactor can be in the range of about 0°C to 250°C, preferably in the range of about 40°C to about 160°C, and more preferably in the range of about 50°C to 120°C. The reaction temperature in the second reactor can be in the range of about 50 to about 160°C, preferably in the range of about 70 to about 140°C, and more preferably in the range of about 70 to about 110°C.

[0144] The two reactors can be arranged in series or the reactors can be nested. Each reactor individually can be a stirred tank reactor, a loop reactor, a tubular reactor, or other standard reactor design.

[0145] The first reaction can be carried out in more than one reactor, with the crude reaction mixture being continuously fed to the second reaction vessel. Preferably, reaction 2 is operated in a continuous manner. The product of the first reaction may be stored for later use in a second reactor.

[0146] Advantageously, the two reactions can be run independently to achieve optimum conditions for each. If the two reactors are nested, they can be effective in simultaneously providing different reaction conditions.

[0147] Optionally, the polycarbonate (poly)ol may be stabilized with an acid before being added to the second reactor. The acid may be inorganic or organic. Examples of 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 may also be part of an acidic resin, such as an ion exchange resin. Acidic ion exchange resins may be in the form of a polymeric matrix (e.g., polystyrene or polymethacrylic acid) characterized by acidic sites, such as strong acid sites (e.g., sulfonic acid sites) or weak acid sites (e.g., carboxylic acid sites). Examples of ion exchange resins include Amberlyst® 15, Dowex Marathon MSC, and Amberlite® IRC 748.

[0148] The first and second reactions of the present invention can be carried out in the presence of a solvent, although it will be understood that the process 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, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, propyl acetate, n-butyl acetate, tetrahydrofuran (THF), etc. The solvent can be toluene, hexane, acetone, ethyl acetate, and n-butyl acetate.

[0149] The solvent can act to dissolve one or more of the ingredients. Alternatively, the solvent can also act as a carrier, used to suspend one or more of the ingredients in suspension. A solvent may also be required to facilitate the addition of one or more of the ingredients when carrying out a step of the process of the present invention.

[0150] The process can use a total amount of solvent, where about 1-100% of the total amount of solvent is mixed in the first reaction and the remainder is added to the second reaction; optionally, about 1-75%, optionally about 1-50%, optionally about 1-40%, optionally about 1-30%, optionally about 1-20%, optionally about 5-20% is mixed in the first reaction.

[0151] The total amount of carbonate catalyst may be low, thereby allowing the first reaction of the present invention to be carried out with a low catalyst loading. For example, the catalyst loading of the carbonate catalyst may be such that the ratio of [total carbonate catalyst]:[total epoxide] is in the range of about 1:500 to 100,000, e.g., about 1:750 to 50,000 [total carbonate catalyst]:[total epoxide], e.g., about 1:1,000 to 20,000 [total carbonate catalyst]:[total epoxide], e.g., 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 to the total amount of epoxide used in the first reaction.

[0152] In the process, the entire amount of carbon dioxide can be employed, with about 1-99% of the total amount of carbon dioxide being incorporated into Block A. The remainder can be in Block B, optionally about 10-95% being incorporated into Block A, optionally about 20-90%, optionally about 30-85% being incorporated into Block A.

[0153] In the process, the entire amount of alkylene oxide can be employed, with about 1-95% of the total amount of alkylene oxide being incorporated into block A. The remaining alkylene oxide is incorporated into block B, optionally about 5-90% being incorporated into block A, optionally about 10-90%, optionally about 20-90%, optionally about 40-90%, optionally about 40-80%, optionally about 5-50% being incorporated into block A.

[0154] In addition to the ethylene oxide in the B block, ethylene oxide may also be present in the A block, although additional alkylene oxides may optionally be present in either the A block or the B block. Examples of additional alkylene oxides in the A block and in the B block in addition to ethylene oxide include propylene oxide, butylene oxide, glycidyl ethers, glycidyl esters, glycidyl carbonate, and cyclohexene oxide. The alkylene oxide used in the B block may be the same as or different from the alkylene oxide used in the A block. Thus, a mixture of one or more alkylene oxides may be present in one or both of the blocks. For example, the A block may contain propylene oxide and the B block may contain ethylene oxide, or both blocks may contain ethylene oxide, or one or both blocks may use a mixture of alkylene oxides, such as a mixture of ethylene oxide and propylene oxide. Preferably, propylene oxide is used in one or both blocks.

[0155] Examples of alkylene oxides that can be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (limonene oxide, C 10 H 16 O, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 22 O, etc.), alkylene oxides (such as ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (e.g., oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, glycidyl esters, 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 modified 3,5-dioxaepoxides.

[0156] Modified 3,5-dioxaepoxides include:

[0157] [ka]

[0158] Examples include: The epoxide moiety can be a glycidyl ether, glycidyl ester, or glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters, and glycidyl carbonates include:

[0159] [ka]

[0160] Examples include: As noted above, the epoxide substrate can contain more than one epoxide moiety. That is, it can be a bis-epoxide, tris-epoxide, or multi-epoxide-containing moiety. Examples of compounds containing more than one epoxide moiety include bis-epoxybutane, bis-epoxyoctane, bis-epoxydecane, bisphenol A diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. It will be appreciated that conducting the reaction in the presence of one or more compounds having more than one epoxide moiety can result in crosslinking in the resulting polymer.

[0161] Optionally, 0.1 to 20% of the total alkylene oxide in the first reaction can be an alkylene oxide substrate containing more than one epoxide moiety. Preferably, the polyepoxide substrate is a bis-epoxide.

[0162] Those skilled in the art will appreciate that alkylene oxides can be obtained from "green" or renewable resources. Alkylene oxides can be obtained from (poly)unsaturated compounds such as those derived from fatty acids and / or terpenes obtained using standard oxidation chemistry.

[0163] The alkylene oxide moiety can include an -OH moiety or a protected -OH moiety. The -OH moiety can be protected with any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzoyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), triisopropylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

[0164] The purity of the alkylene oxide is optionally at least 98%, optionally >99%. The rate at which the materials are added can be selected so that the reaction temperature (exotherm) does not exceed a selected temperature (i.e., the materials are added slowly enough to allow excess heat to dissipate so that the temperature remains approximately constant). The rate at which the materials are added can be selected so that the alkylene oxide concentration does not exceed a selected alkylene oxide concentration.

[0165] This process can produce (poly)ols with polydispersities between 1.0 and 2.0, preferably between 1.0 and 1.8, more preferably between 1.0 and 1.5, and most preferably between 1.0 and 1.3.

[0166] This process can include combining a double metal cyanide (DMC) catalyst, an alkylene oxide, an initiator, and optionally carbon dioxide and / or a solvent to form a preactivated mixture, and adding the preactivated mixture to a second reactor either before or after the crude reaction mixture of the first reaction to form a second reaction mixture. However, this can also be done sequentially, with the preactivated mixture being added simultaneously with the crude reaction mixture. The preactivated mixture can be formed in the second reactor by combining the DMC catalyst, the alkylene oxide, the initiator, and optionally carbon dioxide and / or a solvent. Preactivation can be carried out at a temperature of about 50°C to 160°C, preferably about 70°C to 140°C, and more preferably about 90°C to 140°C. The preactivated mixture can be mixed at a temperature of about 50°C to 160°C, optionally about 70°C to 140°C, before contacting it with the crude reaction 1 mixture.

[0167] In a typical overall reaction process, the amount of the carbonate catalyst and the amount of the double metal cyanide (DMC) catalyst can be in a predetermined weight ratio of about 300:1 to about 1:100, for example, about 120:1 to about 1:75, for example, about 40:1 to about 1:50, for example, about 30:1 to about 1:30, for example, about 20:1 to about 1:1, for example, about 10:1 to about 2:1, or for example, about 5:1 to about 1:5. The process of the present invention can be carried out at any scale. This process can be carried out on an industrial scale. Those skilled in the art will understand that catalytic reactions are typically exothermic. Heat generated during small-scale reactions is less of a problem because temperature increases, if any, can be relatively easily controlled, for example, by using an ice bath. For larger-scale reactions, especially industrial-scale reactions, heat generation during the reaction can be problematic and potentially dangerous. Therefore, gradual addition of materials can control the rate of the catalytic reaction and minimize excess heat buildup. The reaction rate can be controlled, for example, by adjusting the flow rate of the materials added, making the process of the present invention particularly advantageous when applied to large-scale catalytic reactions on an industrial scale.

[0168] The temperature may be increased or decreased during the process of the present invention. The amount of the carbonate catalyst and the amount of the double metal cyanide (DMC) catalyst will vary depending on which carbonate catalyst and DMC catalyst are used.

[0169] method Gel permeation chromatography GPC measurements were carried out in THF against narrow polydispersity poly(ethylene glycol) or polystyrene standards using an Agilent 1260 Infinity instrument equipped with an Agilent PLgel Mixed-D column.

[0170] definition For purposes of this invention, an aliphatic group is a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic, and that may be fully saturated or contain one or more units of unsaturation, but is not aromatic. The term "unsaturated" refers to a moiety that has one or more double and / or triple bonds. Thus, the term "aliphatic" is intended to encompass alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or cycloalkenyl groups, and combinations thereof.

[0171] The aliphatic group is optionally selected from the group consisting of C 1-30 It is an aliphatic group, i.e., an aliphatic group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms. 1-15 Aliphatic, optionally C 1-12 Aliphatic, optionally C 1-10 Aliphatic, optionally C 1-8 Aliphatic, e.g., C 1-6 Aliphatic groups. Suitable aliphatic groups include linear or branched alkyl, alkenyl, and alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl groups, (cycloalkenyl)alkyl groups, and (cycloalkyl)alkenyl groups.

[0172] As used herein, the term "alkyl" refers to a saturated, straight or branched chain hydrocarbon group derived from an aliphatic moiety by removing a hydrogen atom. An alkyl group may optionally be a "C 1-20 The alkyl group is an "alkyl group," i.e., an alkyl group that is straight or branched chain and has 1 to 20 carbon atoms. Thus, an alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alkyl group is C 1-15 Alkyl, optionally C 1-12 Alkyl, optionally C 1-10 Alkyl, optionally C1-8 Alkyl, optionally C 1-6 It is an alkyl group. 1-20 Examples of the "alkyl group" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, an isopentyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a sec-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-oct ... -eicosyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, and 3-methylpentyl group.

[0173] As used herein, the term "alkenyl" refers to a group derived by removing a hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond. As used herein, the term "alkynyl" refers to a group derived by removing a hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond. Alkenyl and alkynyl groups are each optionally denoted by "C 2-20 alkenyl" and "C 2-20 alkynyl", optionally "C 2-15 alkenyl" and "C 2-15 alkynyl", optionally "C 2-12 alkenyl" and "C 2-12 alkynyl", optionally "C 2-10 alkenyl" and "C 2-10 alkynyl", optionally "C 2-8alkenyl" and "C 2-8 alkynyl", optionally "C 2-6 alkenyl" and "C 2-6 Examples of alkenyl groups include ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, 1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, and allenyl. Examples of alkynyl groups include ethynyl, 2-propynyl (propargyl), and 1-propynyl.

[0174] As used herein, the terms "cycloaliphatic," "carbocycle," or "carbocyclic" refer to saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring systems having from 3 to 20 carbon atoms, i.e., alicyclic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alicyclic group has from 3 to 15, optionally from 3 to 12, optionally from 3 to 10, optionally from 3 to 8, or optionally from 3 to 6 carbon atoms. The terms "cycloaliphatic," "carbocycle," or "carbocyclic" also include an aliphatic ring fused to one or more aromatic or non-aromatic rings, e.g., a tetrahydronaphthyl ring, where the point of attachment is on the aliphatic ring. A carbocyclic group may be polycyclic, e.g., bicyclic or tricyclic. It will be understood that an alicyclic group can include an alicyclic ring having one or more alkyl substituents, with or without a linking point, e.g., -CH2-cyclohexyl. Specific examples of carbocyclic rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4.5]decane, cycloheptane, adamantane, and cyclooctane.

[0175] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl, and heteroalkynyl) are aliphatic groups, as described above, further containing one or more heteroatoms. Thus, heteroaliphatic groups optionally contain 2 to 21 atoms, optionally 2 to 16 atoms, optionally 2 to 13 atoms, optionally 2 to 11 atoms, optionally 2 to 9 atoms, or optionally 2 to 7 atoms, with at least one atom being a carbon atom. The optional heteroatom is selected from O, S, N, P, and Si. When a heteroaliphatic group contains more than one heteroatom, the heteroatoms may be the same or different. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.

[0176] Alicyclic groups are saturated or partially unsaturated cycloaliphatic mono- or polycyclic (including fused, bridged, and spiro-fused) systems having from 3 to 20 carbon atoms, i.e., alicyclic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Optionally, the alicyclic group has from 3 to 15, optionally from 3 to 12, optionally from 3 to 10, optionally from 3 to 8, or optionally from 3 to 6 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl, and cycloalkynyl groups. It will be understood that alicyclic groups can include alicyclic rings having one or more alkyl substituents, with or without a point of attachment, e.g., -CH-cyclohexyl. Specifically, C 3-20 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0177] Heteroalicyclic groups are alicyclic groups as defined above that, in addition to carbon atoms, optionally have one or more ring heteroatoms selected from O, S, N, P, and Si. Heteroalicyclic groups optionally contain 1 to 4 heteroatoms, which may be the same or different. Heteroalicyclic groups optionally contain 5 to 20 atoms, optionally 5 to 14 atoms, and optionally 5 to 12 atoms.

[0178] An aryl group or ring is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms, at least one ring in the system being aromatic, and each ring in the system containing from 3 to 12 ring members. The term "aryl" can be used alone or as part of a larger moiety, as in "aralkyl," "aralkoxy," or "aryloxyalkyl." An aryl group is optionally substituted with "C 6-12 An aryl group is an aryl group consisting of 6, 7, 8, 9, 10, 11, or 12 carbon atoms, including fused ring groups, and may be monocyclic or bicyclic. 6-10 Examples of the "aryl group" include a phenyl group, a biphenyl group, an indenyl group, an anthracyl group, a naphthyl group, an azulenyl group, and the like. It should be noted that fused rings such as indane, benzofuran, phthalimide, phenanthridine, and tetrahydronaphthalene are also included in the aryl group.

[0179] The term "heteroaryl," used alone or as part of another word (e.g., "heteroaralkyl" or "heteroaralkoxy"), refers to a group having 5 to 14 ring atoms, optionally 5, 6, or 9 ring atoms; having 6, 10, or 14 pi electrons shared within the cyclic arrangement; and having 1 to 5 heteroatoms in addition to carbon atoms. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur and any quaternized form of nitrogen. The term "heteroaryl" also includes groups in which a heteroaryl ring is fused to one or more aryl, alicyclic, or heterocyclic rings, and the radical or point of attachment is on the heteroaromatic ring. Examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. Thus, heteroaryl groups are monocyclic or polycyclic.

[0180] The term "heteroaralkyl" refers to an alkyl group substituted with a heteroaryl, where the alkyl and heteroaryl portions independently are optionally substituted. As used herein, the terms "heterocycle," "heterocyclic," "heterocyclic group," and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclic heterocyclic moiety that is saturated, partially unsaturated, or aromatic, and that contains, in addition to carbon atoms, one or more, optionally 1 to 4, heteroatoms, as defined above. The term "nitrogen" when used in reference to a ring atom of a heterocycle also includes a substituted nitrogen.

[0181] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxine, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazoline, and the like. Examples of suitable amines include benzophenone, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.

[0182] The terms "halide," "halo," and "halogen" are used interchangeably and, as used herein, refer to fluorine, chlorine, bromine, iodine, and the like, optionally referring to fluorine, bromine, or chlorine atoms, and optionally referring to fluorine atoms.

[0183] The haloalkyl group is optionally referred to as "C 1-20 haloalkyl group”, optionally “C 1-15 haloalkyl group”, optionally “C 1-12 haloalkyl group”, optionally “C 1-10 haloalkyl group”, optionally “C 1-8 haloalkyl group”, optionally “C 1-6haloalkyl groups, each of which is substituted with at least one halogen atom, optionally 1, 2, or 3 halogen atoms; 1-20 Alkyl, C 1-15 Alkyl, C 1-12 Alkyl, C 1-10 Alkyl, C 1-8 Alkyl or C 1-6 The term "haloalkyl" includes fluorinated and chlorinated groups, such as perfluorinated compounds. 1-20 Examples of the "haloalkyl group" include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, and the like.

[0184] As used herein, the term "acyl" refers to a group having the formula -C(O)R, where R is hydrogen or an optionally substituted aliphatic, aryl, or heterocyclic group.

[0185] The alkoxy group is optionally designated "C 1-20 alkoxy group”, optionally “C 1-15 alkoxy group”, optionally “C 1-12 alkoxy group”, optionally “C 1-10 alkoxy group”, optionally “C 1-8 alkoxy group”, optionally “C 1-6 alkoxy group" as defined above, 1-20 Alkyl, C 1-15 Alkyl, C 1-12 Alkyl, C 1-10 Alkyl, C 1-8 Alkyl or C 1-6 It is an oxy group bonded to an alkyl group. 1-20Examples of the "alkoxy group" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, an isohexyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, an n-hexadecyloxyloxy group, an Examples thereof include an oxy group, an n-heptadecyloxy group, an n-octadecyloxy group, an n-nonadecyloxy group, an n-eicosyloxy group, a 1,1-dimethylpropoxy group, a 1,2-dimethylpropoxy group, a 2,2-dimethylpropoxy group, a 2-methylbutoxy group, a 1-ethyl-2-methylpropoxy group, a 1,1,2-trimethylpropoxy group, a 1,1-dimethylbutoxy group, a 1,2-dimethylbutoxy group, a 2,2-dimethylbutoxy group, a 2,3-dimethylbutoxy group, a 1,3-dimethylbutoxy group, a 2-ethylbutoxy group, a 2-methylpentyloxy group, and a 3-methylpentyloxy group.

[0186] The aryloxy group is optionally represented by "C 5-20 aryloxy group”, optionally “C 6-12 aryloxy group”, optionally “C 6-10 aryloxy group" and each is a C 5-20 Aryl, C 6-12 Aryl, or C 6-10 It is an oxy group attached to an aryl group.

[0187] The alkylthio group is optionally represented by "C 1-20 alkylthio group”, optionally “C 1-15 alkylthio group”, optionally “C 1-12 alkylthio group”, optionally “C 1-10 alkylthio group”, optionally “C 1-8 alkylthio group”, optionally “C 1-6 alkylthio group" and each is C as defined above.1-20 Alkyl, C 1-15 Alkyl, C 1-12 Alkyl, C 1-10 Alkyl, C 1-8 Alkyl or C 1-6 It is a thio (-S-) group attached to an alkyl group.

[0188] The arylthio group is optionally represented by "C 5-20 arylthio group”, optionally “C 6-12 arylthio group”, optionally “C 6-10 arylthio group" and each is C as defined above. 5-20 Aryl, C 6-12 Aryl, or C 6-10 It is a thio (-S-) group attached to an aryl group.

[0189] The alkylaryl group is optionally designated "C 6-12 Aryl C 1-20 alkyl group”, optionally “C 6-12 Aryl C 1-16 alkyl group”, optionally “C 6-12 Aryl C 1-6 An alkylaryl group is an "aryl group" as defined above attached at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to the molecule may be through the alkyl portion; thus, optionally, the alkylaryl group is -CH-Ph or -CHCH-Ph. An alkylaryl group may also be referred to as an "aralkyl."

[0190] The silyl group is optionally represented by —Si(R s )3 and R s is independently an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. s is independently unsubstituted aliphatic, alicyclic, or aryl. Optionally, each R s is an alkyl group selected from methyl, ethyl, or propyl.

[0191] The silyl ether group optionally is an OSi(R) group, where each R can independently be an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. Each R can independently be an unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, each R is an alkyl group selected from optionally substituted phenyl or optionally substituted methyl, ethyl, propyl, or butyl (such as n-butyl (nBu) or tert-butyl (tBu)). Exemplary silyl ether groups include OSi(Me), OSi(Et), OSi(Ph), OSi(Me)(tBu), OSi(tBu), and OSi(Ph)(tBu).

[0192] A nitrile group (also called a cyano group) is a CN group. The imine group is a -CRNR group, optionally -CHNR, where R is an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. R can be unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, R is an alkyl group selected from methyl, ethyl, or propyl.

[0193] An acetylide group has a triple bond -C≡C-R, where optionally R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. For purposes of the present invention, when R is alkyl, the triple bond can be located at any position on the alkyl chain. R can be unsubstituted aliphatic, cycloaliphatic, or aryl. Optionally, R is methyl, ethyl, propyl, or phenyl.

[0194] The amino group is optionally -NH2, -NHR 10 , or -N(R 10 )2 and R 10 can be an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, silyl, aryl, or heteroaryl group as defined above.10 )2, then each R 10 It will be understood that the groups may be the same or different. 10 can be independently unsubstituted aliphatic, alicyclic, silyl, or aryl. 10 is methyl, ethyl, propyl, SiMe3, or phenyl.

[0195] The amide group is optionally represented by -NR 11 C(O)- or -C(O)-NR 11 - and R 11 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 11 can be unsubstituted aliphatic, alicyclic, or aryl. 11 is hydrogen, methyl, ethyl, propyl, or phenyl. The amide group may have a terminal hydrogen, an aliphatic group, a heteroaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group.

[0196] An ester group is optionally represented by -OC(O)R, unless defined elsewhere herein. 12 -or-C(O)OR 12 - and R 12 R can be an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. 12 can be unsubstituted aliphatic, alicyclic, or aryl. 12 is methyl, ethyl, propyl, or phenyl. The ester group can have a terminal aliphatic group, heteroaliphatic group, alicyclic group, heteroalicyclic group, aryl group, or heteroaryl group. R 12 If is hydrogen, -OC(O)R 12 -or-C(O)OR 12 It will be understood that a group defined by - will be a carboxylic acid group.

[0197] The sulfoxide is optionally represented by —S(O)R 13 and the sulfonyl group is optionally —S(O)R 13 and R 13 R can be an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. 13 can be unsubstituted aliphatic, alicyclic, or aryl. 13 is methyl, ethyl, propyl or phenyl.

[0198] The carboxylate group is optionally —OC(O)R 14 and R 14 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 14 can be unsubstituted aliphatic, alicyclic, or aryl. 14 is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

[0199] The acetamide is optionally represented by MeC(O)N(R 15 )2 and R 15 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 15 can be unsubstituted aliphatic, alicyclic, or aryl. 15 is hydrogen, methyl, ethyl, propyl or phenyl.

[0200] The phosphinate group is optionally —OP(O)(R 16 )2 or -P(O)(OR 16 )(R16 ) and each R 16 are independently selected from hydrogen or an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group as defined above. 16 can be aliphatic, alicyclic, or aryl, which can be aliphatic, alicyclic, aryl, or C 1-6 Optionally, R is substituted with alkoxy. 16 is optionally substituted aryl or C 1-20 Alkyl, optionally C 1-6 Phenyl optionally substituted with alkoxy (optionally methoxy), or unsubstituted C 1-20 The phosphonate group is optionally -P(O)(OR 16 )2 and R 16 is as defined above. -P(O)(OR 16 ) 2 R 16 If one or both of the groups are hydrogen, then -P(O)(OR 16 It will be understood that the group defined as )2 will be a phosphonic acid group.

[0201] The sulfinate group is optionally —S(O)OR 17 or -OS(O)R 17 and R 17 R can be hydrogen, an aliphatic group, a heteroaliphatic group, a haloaliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 17 can be unsubstituted aliphatic, alicyclic, or aryl. 17 is hydrogen, methyl, ethyl, propyl, or phenyl. 17 If is hydrogen, -S(O)OR 17 It will be understood that a group defined as: will be a sulfonic acid group.

[0202] The carbonate group is optionally —OC(O)OR 18 and R 18R can be hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 18 can be optionally substituted aliphatic, alicyclic, or aryl. Optionally, R 18 is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl, or adamantyl. 18 If is hydrogen, -OC(O)OR 18 It will be understood that a group defined as: is a carbonate group.

[0203] The carbonate functional group is —OC(O)O— and can be derived from a suitable source. Generally, it is derived from CO.

[0204] -AlkylC(O)OR 19 or -alkylC(O)R 19 In the group, R 19 R is hydrogen, an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 19 can be unsubstituted aliphatic, alicyclic, or aryl. 19 is hydrogen, methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

[0205] The ether group is optionally -OR20 and R 20 R may be an aliphatic group, a heteroaliphatic group, a cycloaliphatic group, a heteroalicyclic group, an aryl group, or a heteroaryl group as defined above. 20 can be unsubstituted aliphatic, alicyclic, or aryl. 20 is methyl, ethyl, propyl, butyl (e.g., n-butyl, isobutyl, or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, or adamantyl.

[0206] It will be understood that when any of the above groups are present in the Lewis base G, one or more additional R groups may be present as needed to satisfy valence. For example, an additional R group associated with an amino group may be RNHR 10 where R is hydrogen, an optionally substituted aliphatic group, heteroaliphatic group, cycloaliphatic group, heteroalicyclic group, aryl group, or heteroaryl group as defined above. Optionally, R is hydrogen or an aliphatic, cycloaliphatic, or aryl group.

[0207] When the suffix "ene" is used with a chemical group, for example, "alkylene," it is intended to mean that the group, as defined herein, has two points of attachment to another group. As used herein, the term "alkylene" by itself or as part of another substituent refers to an alkyl group that is divalent, i.e., has two points of attachment to other groups.

[0208] As used herein, the term "optionally substituted" means that one or more of the hydrogen atoms of the optionally substituted moiety have been replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at every position. Combinations of substituents contemplated by the present invention are those that, optionally, result in the formation of stable compounds. As used herein, the term "stable" refers to a compound that is chemically feasible and can exist at room temperature (i.e., 16-25°C) for a period of time sufficient to allow its detection, isolation, and / or use in chemical synthesis.

[0209] Optional substituents for use in the present invention include, but are not limited to, halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate, or an optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group (e.g., optionally substituted with halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate, or acetylide).

[0210] Although in formula (V) the X and G groups are illustrated as being attached to a single M1 or M2 metal center, it will be understood that one or more X and G groups may form a bridge between the M1 and M2 metal centers.

[0211] For purposes of the present invention, the epoxide substrate is not limited. Thus, the term alkylene oxide refers to any compound containing an epoxide moiety (i.e., a substituted or unsubstituted oxirane compound). Substituted oxiranes include mono-, di-, tri-, and tetra-substituted oxiranes. An alkylene oxide may contain a single oxirane moiety. An alkylene oxide may contain two or more oxirane moieties.

[0212] It will be understood that the term "alkylene oxide" is intended to encompass one or more alkylene oxides. In other words, the term "alkylene oxide" refers to a single type of alkylene oxide or a mixture of two or more different alkylene oxides. For example, the alkylene oxide substrate can be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide, and cyclohexene oxide.

[0213] The term polycarbonate block polyether carbonate (poly)ol generally refers to a polymer having substantially -OH, -SH, and / or -NHR' groups (including C-OH, P-OH, -C(O)OH moieties, etc.) at one or each terminal end. R' can be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, and optionally R' is H or an optionally substituted alkyl.

[0214] As an example, at least about 90%, at least about 95%, at least about 98%, or at least about 99% of the polymer can have an -OH group at each end. Those skilled in the art will understand that if the polymer is linear, both ends can be end-capped with an -OH group. If the polymer is branched, each branch can be end-capped with an -OH group. This type of polymer is generally useful for preparing higher molecular weight polymers, such as polyurethanes. The chains can contain a mixture of functional groups (e.g., -OH and -SH groups) or can contain the same functional groups (e.g., all -OH groups).

[0215] As used herein, the term "continuous" can be defined as the manner in which materials are added, or it can refer to the nature of the reaction process as a whole. In the sense of continuous addition, the corresponding material is added continuously or constantly throughout the reaction. This can be achieved, for example, by adding the material at a constant flow rate or at a variable flow rate. In other words, one or more materials are added essentially without interruption. However, it should be noted that, in practical terms, even when adding materials without interruption, short interruptions may be necessary, for example, to replenish the original container from which the material is added or to replace the container.

[0216] In the sense that the overall reaction is continuous, the reaction may be carried out over an extended period of time, e.g., days, weeks, months, etc. In such a continuous reaction, reaction materials may be continuously added and / or reaction products may be withdrawn. It will be understood that the catalyst may not be consumed during the reaction, but may be replenished as the amount of catalyst present during withdrawal may be depleted.

[0217] In a continuous reaction, continuous addition of materials can be carried out. Continuous reactions can also involve semi-continuous (ie, batch or semi-batch) addition of materials.

[0218] As used herein, the term series refers to when two or more reactors are connected such that the crude reaction mixture can flow from the first reactor to the second reactor. The term "nested" as used herein refers to a configuration in which two or more reactors are configured such that one is located within the other. For example, in the present invention, when a second reactor is located inside a first reactor, the conditions of both reactors affect the other reactor.

[0219] The term "end part of the reaction" means the total reaction time until 50% of all monomers to be incorporated into the polymer chain have been incorporated into the growing polymer chain, preferably until 75% of all have been incorporated into the growing polymer chain, more preferably until 90% of all monomers have been incorporated into the growing polymer chain, and most preferably until 95% of all monomers have been incorporated into the growing polymer chain.

[0220] The term "after initiation of the reaction" refers to the total time since the reaction began. The term "(co)polymer" is used in reference to polycarbonate or polyester (poly)ols. The parentheses are used to indicate that if the compound is a polycarbonate (poly)ol, it would be a copolymer since both carbon dioxide and epoxide residues are present, whereas if the compound is a polyester (poly)ol, it would be a homopolymer if only one monomer was used (e.g., via ring-opening polymerization).

[0221] As used herein, the term "(poly)ol" means polyol or mono-ol, and thus refers to an organic compound, such as a mono-ol, diol, or triol, that contains one or more hydroxyl groups and is typically free of other functional groups. [Example]

[0222] experiment Example 1: Comparison example with only PO in the second container (98% second grade) Hexanediol (2.9 g), catalyst (1) (0.2 g), and EO (30 mL) were added to a 100 mL reactor. The vessel was heated to 75°C, pressurized to 20 bar (2 MPa) with CO, and stirred for 16 hours, after which it was cooled and vented. This yielded approximately 1100 g / mol polyethylene carbonate polyol. The contents of the reactor were transferred to a Schlenk tube, and simultaneously PO (6 mL) and EtOAc (20 mL) were added.

[0223] Into another 100 mL reactor, 9.2 mg of DMC catalyst and 0.4 mL of PPG400 were added. Ethyl acetate (15 mL) was poured into the vessel. The vessel was heated to 130°C. 2 x 0.5 g of PO was added to ensure the activity of the DMC catalyst.

[0224] The reactor was cooled to 85°C (4.5 bar CO pressure). The first reaction mixture was then added via HPLC pump. The addition took 1 hour. The reaction was allowed to continue for 3 hours, after which PO (14 g) was added over 0.5 hours. The reaction was allowed to proceed for an additional 16 hours, after which the reactor was cooled to <10°C and the pressure was released. NMR and GPC were taken immediately.

[0225] Example 2: Comparative Example Using Polyether Initiator A 100 mL reactor was charged with PPG400 (15 mL) and DMC (9 mg) and heated under vacuum to 130°C. Four 6 g slugs of PO were added over several hours, with the DMC activity monitored during each addition. At 2 hour intervals, EO (3 x 9 mL) was added under CO pressure, ensuring that the DMC activity remained before each addition.

[0226] Example 3: Example 3 was carried out according to Example 1, except that hexanediol (2.75 g) was used to make the polyethylene carbonate-polyol (1200 g / mol), and PO (10 mL) and EtOAc (15 mL) were added to the Schlenk. Instead of the final PO addition in Reactor 2, EO (9 mL) was added to end-cap the polyol.

[0227] Example 4: Example 4 was carried out according to Example 1, except that hexanediol (2.75 g) was used to make the polyethylene carbonate-polyol (1200 g / mol), and EtOAc (15 mL) was added to the Schlenk. Instead of the final PO addition in Reactor 2, EO (9 mL) was added to end-cap the polyol.

[0228] [Table 1]

[0229] Two different literature methods were used to quantify the primary hydroxyl content of the polyols. Comparative Example 1 demonstrates that using propylene oxide as the sole epoxide in the second reaction produces a very low percentage of primary end groups. Method 1 yielded no primary hydroxyl groups, whereas Method 2 measured 12% primary hydroxyl groups. Since DMC catalysts are generally known to form approximately 3% primary end groups when reacted with PO alone, Method 1 appears to be more reliable. Comparative Example 2 was performed with ethylene oxide end-capping, except that a polyether was used as the initiator instead of polycarbonate. Method 1 measured only 56% primary hydroxyl end groups, whereas Method 2 measured a slightly higher 67%.

[0230] Examples 3 and 4 (inventive examples) used polycarbonate initiators prepared by reacting a carbonate catalyst, initiator, CO, and ethylene oxide. The difference between them is that Example 3 used a mixture of PO and EO in the second reactor, while Example 4 used only EO in the second reactor (apart from the 1 g of PO used to activate the DMC catalyst). Examples 3 and 4 showed approximately 80% primary hydroxyl end groups, despite the use of PO to activate the DMC catalyst. This indicates that the introduction of a polycarbonate initiator can substantially increase the primary hydroxyl content, even under identical conditions.

Claims

1. A (poly)ol block copolymer of the general structure B-A-(B)n, where block A is a polycarbonate block or a polyester block, n=t-1, and t=the number of reactive end residues on block A, and block B is a polyether carbonate block having less than 50% carbonate linkages and more than 70% of the copolymer chain ends are terminated with primary hydroxyl groups.

2. more than 75%, more preferably more than 80%, of the copolymer chain ends are terminated with primary hydroxyl groups; and / or the mol / mol ratio of block A to block B is in the range of (25:1) to (1:250); and / or The carbonate present in block A is CO ２ and / or derived from Block A is an alkylene oxide and CO ２ and / or derived from Block A is derived in part from an alkylene oxide, optionally the alkylene oxide being selected from the group consisting of cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (e.g., limonene oxide, C １０ H １６ O, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C １１ H ２２ 2. The (poly)ol block copolymer of claim 1, wherein the (poly)ol is selected from alkylene oxides (e.g., ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (e.g., oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, glycidyl esters, 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-dioxaepoxide.

3. Block A is a polyalkylene carbonate block, more typically an alkylene oxide and CO ２ and / or is derived from The alkylene oxide and CO ２ but providing at least 90% of the residues in said block that do not include any initiator, particularly at least 95% of the residues in said block, more particularly at least 99% of the residues in said block, and most particularly about 100% of the residues in said block that do not include any initiator, are alkylene oxide and CO ２ is a residue of:

3. The (poly)ol block copolymer according to claim 1 or claim 2, wherein the alkylene oxide residues of block A are ethylene oxide and / or propylene oxide residues, optionally in addition to other alkylene oxide residues.

4. at least 50% of the alkylene oxide residues of block A are ethylene oxide or propylene oxide residues, more typically at least 70% of the alkylene oxide residues of block A are ethylene oxide or propylene oxide residues, and most typically at least 90% of the alkylene oxide residues of block A are ethylene oxide or propylene oxide residues, especially at these levels ethylene oxide; and / or block A has between 70 and 100%, more typically between 80 and 100%, most typically between 90 and 100% carbonate linkages, and / or said polycarbonate block A of said (poly)ol block copolymer has at least 76% carbonate linkages, preferably at least 80% carbonate linkages, more preferably at least 85% carbonate linkages, and / or block A has less than 98% carbonate linkages, preferably less than 97% carbonate linkages, more preferably less than 95% carbonate linkages, and / or optionally block A has between 75% and 99% carbonate linkages, preferably between 77% and 95% carbonate linkages, more preferably between 80% and 90% carbonate linkages; and / or the block A has a high carbonate content and the block B has a low carbonate content, for example, the block A has more than 70% carbonate linkages; and / or The carbonate residue of block B is CO ２ and / or derived from Block B is an alkylene oxide and CO ２ and / or derived from Block B is derived in part from alkylene oxides, optionally the alkylene oxides being cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (e.g., limonene oxide, C １０ H １６ O, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C １１ H ２２ O), alkylene oxides (e.g., ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (e.g., oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, glycidyl esters, 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-dioxaepoxides; and / or Block B is a polyalkylene carbonate block; and / or block B comprises ethylene oxide residues and optionally other alkylene oxide residues, typically the alkylene oxide residues provide at least 90% of non-carbonate functional residues in said block, in particular at least 95% of non-carbonate functional residues in said block, more in particular at least 99% of non-carbonate functional residues in said block, and most in particular about 100% of the non-carbonate functional residues in said block are residues of alkylene oxide; and / or ethylene oxide residues form 5 to 100% of the alkylene oxide residues in block B, more typically 10 to 100%, most typically 10 to 50% of the alkylene oxide residues in block B, and / or at least 5%, 10%, 15%, 20%, 25%, or 30% of the alkylene oxide residues in block B are ethylene oxide residues; and / or Block B comprises a mixture of alkylene oxide residues, with other non-ethylene oxide residues being cyclohexene oxide, styrene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (e.g., limonene oxide, C １０ H １６ O, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C １１ H ２２ O), alkylene oxides (e.g., ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (e.g., oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, glycidyl esters, 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-dioxaepoxides; and / or at least 5% of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues, more typically at least 10% of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues, most typically at least 20% of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues, optionally at least 50% of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues, most particularly at least 70% or 90% of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues; and / or at least 70% of the terminal alkylene oxide residues are ethylene oxide residues, more typically at least 75%, and most typically at least 80% of the terminal alkylene oxide residues are ethylene oxide residues; and / or the polyether carbonate block B of the (poly)ol block copolymer has less than 40% carbonate linkages, preferably less than 35% carbonate linkages, more preferably less than 30% carbonate linkages, and / or block B has between 1% and 50% carbonate linkages, preferably between 5% and 45% carbonate linkages, more preferably between 10% and 40% carbonate linkages; and / or the polyethercarbonate block B of the (poly)ol block copolymer has at least 60% ether linkages, preferably at least 65% ether linkages, more preferably at least 70% ether linkages, and / or the polyethercarbonate block B of the (poly)ol block copolymer has less than 95% ether linkages, preferably less than 90% ether linkages, more preferably less than 85% ether linkages, and / or block B has between 50% and 99% ether linkages, preferably between 55% and 95% ether linkages, more preferably between 60% and 90% ether linkages; and / or the polycarbonate block A of the (poly)ol block copolymer further comprises an ether linkage; and / or 4. The (poly)ol block copolymer according to claim 2, wherein the polycarbonate block A of the (poly)ol block copolymer has less than 24% ether linkages, preferably less than 20% ether linkages, more preferably less than 15% ether linkages, such as less than 10%, for example less than 5%, and wherein block A may have at least 1% ether linkages, such as at least 2% ether linkages, or even at least 5% ether linkages, optionally block A may have between 0% and 25% ether linkages, preferably between 1% and 20% ether linkages, more preferably between 1% and 15% ether linkages.

5. The (poly)ol block copolymer according to any one of claims 1 to 4, wherein the (poly)block structure of the copolymer is defined by the following formula: B-A’-Z’-Z-(Z’-A’-B) ｎ wherein n=t−1 and t=the number of residues of terminal OH groups on block A; each A′ is independently a polycarbonate chain having at least 70% carbonate linkages; each B is independently a polyethercarbonate chain having 50-99% ether linkages and at least 1% carbonate linkages; and Z′-Z-(Z′) ｎ is the initiator residue].

6. -A'- has the structure: 【Chemical 1】 wherein the ratio of (p:q) is at least (7:3); Block B has the following structure: 【Chemistry 2】 wherein the ratio of w:v is 1:1 or greater; R ｅ１ , R ｅ２ , R ｅ３ and R ｅ４ depends on the identity of the alkylene oxides used to prepare blocks A and B, and optionally Each R ｅ１ , R ｅ２ , R ｅ３ , or R ｅ４ are independently H, halogen, hydroxyl, or optionally substituted alkyl (e.g., methyl, ethyl, propyl, butyl, —CH ２ Cl, —CH ２ -OR ２０ , -CH ２ -OC(O)R １２ , or -CH ２ -OC(O)OR １８ ), alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl, or heteroalkenyl, preferably selected from H or optionally substituted alkyl; and / or R ｅ１ and R ｅ２ , or R ｅ３ and R ｅ４ are joined to form a saturated, partially unsaturated or unsaturated ring comprising carbon and hydrogen atoms and optionally one or more heteroatoms.

7. The initiator residue depends on the nature of the initiator compound, which may be of formula (III): 【Chemistry 3】 wherein Z has one or more, usually two or more, -R Ｚ Z may be any group capable of carrying a group, and may be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, heterocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z may be any combination of these groups, for example, Z may be an alkylarylene group, a heteroalkylarylene group, a heteroalkylheteroarylene group, or an alkylheteroarylene group; a is an integer that is at least 1, typically at least 2, optionally a is 1 or in the range of 2 to 8, optionally a is in the range of 2 to 6; R Ｚ are respectively -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), and -PR'(O)(OH). ２ or —PR′(O)OH, optionally R Ｚ is selected from —OH, —NHR′, or —C(O)OH, and optionally, R ｚ are each —OH, —C(O)OH, or a combination thereof (e.g., R ｚ are each —OH); R' may be H or an optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, or heterocycloalkyl, optionally R' is H or an optionally substituted alkyl; Z' is the same as R except that the highly reactive hydrogen atom is replaced with a bond. ｚ and optionally, a is an integer of at least 2, or optionally the initiator compound is a monofunctional initiator such as alcohols, phenols, amines, thiols, and carboxylic acids, for example, alcohols, e.g., methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, linear or branched C ３ ~C ２０ Monoalcohols, for example, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol , 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, monoethers or esters of ethylene, propylene, polyethylene, and polypropylene glycol, such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, phenols, such as linear or branched C ３ ~C ２０ alkyl-substituted phenols such as nonylphenol or octylphenol, monofunctional carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and acrylic acid, and monofunctional thiols such as ethanethiol, propane-1-thiol, propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol, or amines such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine;and / or diols, for example, 1,2-ethanediol (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-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, Licorice, catechol, cyclohexenediol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol (PPG) or polyethylene glycol (PEG) having an Mn of about 1500 g / mol or less, for example, PPG425, PPG725, PPG1000, triols, for example, glycerol, benzenetriol, The (poly)ol block copolymer according to claim 5 or 6, wherein the (poly)ol is selected from 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, polyethylene oxide triol, polypropylene oxide triol, and polyester triol, tetraols such as calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, erythritol, pentaerythritol, or polyalkylene glycols (PEG or PPG) having four -OH groups, polyols such as sorbitol or polyalkylene glycols (PEG or PPG) having five or more -OH groups, or compounds having mixed functional groups such as ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine;

8. the molecular weight (Mn) of said (poly)ol is in the range of 300 to 20,000 Da, optionally the molecular weight (Mn) of block A is in the range of 200 to 4000 Da, optionally the molecular weight (Mn) of block B is in the range of 100 to 20,000 Da, more typically the molecular weight (Mn) of block A is in the range of 200 to 2000 Da, more typically in the range of 200 to 1000 Da, most typically in the range of 400 to 800 Da, and / or the molecular weight (Mn) of block B is typically 200 to 10,000 Da, more typically 200 to 5000 Da, and optionally the molecular weight (Mn) is measured by gel permeation chromatography (GPC); and / or ethylene oxide residues form 0 to 100% of the alkylene oxide residues in the (poly)ol block copolymer, typically 5 to 70%, more typically 10 to 60%, and most typically 10 to 40% of the alkylene oxide residues in the (poly)ol block copolymer, and / or at least 5%, 10%, 15%, 20%, 25%, or 30% of the alkylene oxide residues in the (poly)ol block copolymer are ethylene oxide residues; and / or 8. The (poly)ol block copolymer according to claim 1, wherein block A is a substantially alternating polycarbonate (poly)ol residue.

9. A composition comprising the (poly)ol block copolymer according to any one of claims 1 to 8 and one or more additives selected from catalysts, blowing agents, stabilizers, plasticizers, fillers, flame retardants, and antioxidants, and optionally further comprising a (poly)isocyanate.

10. 10. A polyurethane, optionally isocyanate-terminated, produced from the reaction of a (poly)ol block copolymer according to any one of claims 1 to 8, or a composition according to claim 9, with a (poly)isocyanate.

11. A polyurethane comprising residues of the block copolymer of any one of claims 1 to 8.

12. An isocyanate-terminated polyurethane prepolymer comprising the reaction product of a block copolymer according to any one of claims 1 to 8 or a composition according to claim 9 with an excess of a (poly)isocyanate.

13. An isocyanate-terminated polyurethane prepolymer comprising the residue of a block copolymer according to any one of claims 1 to 8.

14. the catalyst for the reaction of the (poly)isocyanate with the (poly)ol block copolymer comprises a suitable urethane catalyst, such as a tertiary amine compound and / or an organometallic compound; or A trimerization catalyst is present; or 10. The composition of claim 9, wherein there is an excess of (poly)isocyanate, more typically an excess of polymeric isocyanate, relative to polyol to allow for the formation of polyisocyanurate rings in the presence of the trimerization catalyst.

15. A lubricant composition comprising the (poly)ol block copolymer according to any one of claims 1 to 8.

16. A surfactant composition comprising the (poly)ol block copolymer according to any one of claims 1 to 8.

17. A process for producing a (poly)ol block copolymer, comprising: mixing a DMC catalyst with a polycarbonate or polyester (poly)ol (co)polymer according to block A of any one of claims 1 to 8, ２ with ethylene oxide and optionally one or more other alkylene oxides to produce the (poly)ol block copolymer of any one of claims 1 to 8.

18. 1. A process for producing a (poly)ol block copolymer, comprising a first reaction in a first reactor and a second reaction in a second reactor, wherein the first reaction comprises reacting a carbonate catalyst with CO in the presence of an initiator and optionally a solvent. ２ and an alkylene oxide to produce a polycarbonate (poly)ol copolymer according to any one of claims 1 to 8, wherein the second reaction comprises reacting a DMC catalyst with the polycarbonate (poly)ol copolymer of the first reaction, CO ２ with ethylene oxide and optionally one or more other alkylene oxides to produce the (poly)ol block copolymer of any one of claims 1 to 8.

19. 1. A process for producing a (poly)ol block copolymer in a multiple reactor system, the system including first and second reactors, a first reaction being carried out in the first reactor and a second reaction being carried out in the second reactor; the first reaction being carried out by reacting a carbonate catalyst with CO in the presence of an initiator and optionally a solvent. ２ and alkylene oxide to produce a polycarbonate (poly)ol copolymer according to any one of claims 1 to 8, wherein the second reaction is carried out by reacting a DMC catalyst with the polycarbonate (poly)ol compound of the first reaction, CO ２ with ethylene oxide and optionally one or more other alkylene oxides to produce the (poly)ol block copolymer of any one of claims 1 to 8.

20. The method further comprises reacting the block copolymer of any one of claims 1 to 8 with a monomer or a further polymer to produce a higher molecular weight polymer, optionally comprising: The process according to any one of claims 17 to 19, wherein the monomer or further polymer is a (poly)isocyanate and the product of the reaction is a polyurethane.

21. the DMC catalyst is optionally preactivated in the reactor or separately, optionally the DMC being preactivated with an initiator compound or with the polycarbonate or polyester (poly)ol (co)polymer according to block A of any one of claims 1 to 8, or with a (poly)ol block copolymer according to any one of claims 1 to 8; and / or and / or when one or more other alkylene oxides are added in addition to ethylene oxide to the reaction of claim 20 or the second reaction of any one of claims 18 to 20, the addition of the ethylene oxide at the end of the reaction is in a mol / mol excess over the other alkylene oxides; and / or 21. The process of any one of claims 18 to 20, wherein ethylene oxide forms 5 to 100% (mol / mol), more typically 10 to 100%, most typically 10 to 50% (mol / mol) of the alkylene oxide added to the reaction of claim 20 or the second reaction of any one of claims 18 to 20, and / or at least 5%, 10%, 15%, 20%, 25%, or 30% (mol / mol) of the alkylene oxide added.

22. 22. The process of any one of claims 18 to 21, wherein when an asymmetric alkylene oxide is added, the reaction is capable of forming a polycarbonate having between 40 and 100% head-to-tail linkages, preferably greater than 70%, greater than 80%, or greater than 90% head-to-tail linkages.

23. 23. The process according to any one of claims 18 to 22, wherein the polycarbonate or polyester(poly)ol copolymer according to block A of any one of claims 1 to 8 is fed as a crude reaction mixture to the reactor, or a second reactor, optionally continuously or semi-continuously, for the reaction with the DMC catalyst, wherein the reactor or the second reactor contains a pre-activated DMC catalyst.

24. The first reaction is carried out at a CO pressure of less than 20 bar (2 MPa), more preferably less than 10 bar (1 MPa), and most preferably less than 8 bar (0.8 MPa). ２ carried out under pressure; and / or The second reaction is carried out at a CO pressure of less than 60 bar (6 MPa), preferably less than 20 bar (2 MPa), more preferably less than 10 bar (1 MPa), and most preferably less than 5 bar (0.5 MPa). ２ carried out under pressure; and / or CO ２ is added continuously to the first reaction, preferably in the presence of an initiator; and / or The first reaction can be a batch, semi-batch, or continuous process; and / or 24. The process of any one of claims 18 to 23, wherein the second reaction can be a continuous process or a semi-batch process.

25. The crude reaction mixture fed to the reactor or second reactor may contain an amount of unreacted alkylene oxide and / or CO ２ and / or containing an initiator; and / or 25. The process of any one of claims 23 to 24, wherein the carbonate catalyst is present in the crude reaction mixture or the carbonate catalyst is removed from the crude reaction mixture prior to addition to the reactor or second reactor.

26. the reaction temperature in the first reactor is in the range of about 0°C to 250°C, preferably in the range of about 40°C to about 160°C, more preferably in the range of about 50°C to 120°C; and / or the reaction temperature in the reactor or second reactor is in the range of about 50 to about 160°C, preferably in the range of about 70 to about 140°C, more preferably in the range of about 70 to about 110°C; and / or the reactors are arranged in series or the reactors are nested, and optionally the first and second reactors are effective to simultaneously provide different reaction conditions, such as temperature and / or pressure, to each other; and / or The crude reaction mixture is stabilized with an acid before being added to the reactor or a second reactor; and / or the process employs a total amount of alkylene oxide, wherein about 1-100% of the total amount of alkylene oxide is mixed in the first reaction, and any remainder is added in the second reaction; optionally, about 5-90%, optionally about 10-90%, optionally about 20-90%, optionally about 40-90%, optionally about 40-80%, optionally about 5-50% is mixed in the first reaction; and / or 0.1 to 20% of the total alkylene oxide in the first reaction is an alkylene oxide substrate containing more than one epoxide moiety, preferably a bis-epoxide; and / or The carbonate catalyst is a catalyst capable of producing polycarbonate chains having more than 76% carbonate linkages; and / or the carbonate catalyst is a metal catalyst containing a phenol or phenolate ligand; and / or 26. The process of any one of claims 18 to 25, wherein the carbonate catalyst is a binuclear metal complex containing a phenol or phenolato ligand.

27. The carbonate catalyst has the formula (IV): 【Chemistry 4】 (Wherein M is M-(L) ｖ is a metal cation represented by x is an integer from 1 to 4, 【Chemistry 5】 is one or more multidentate ligands; L is a coordinating ligand; v is an integer that satisfies the valence of M and / or the preferred coordination geometry of M, or that results in an overall charge neutrality of the complex represented by formula (IV) above; and / or The carbonate catalyst has the structure shown below: 【Chemistry 6】 (In the formula, M １ and M ２ are Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III) )-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) ２ , or Ti(IV)-(X) ２ are independently selected from R １ and R ２ are independently selected from hydrogen, halide, nitro, nitrile, imine, amine, ether, silyl, silyl ether, sulfoxide, sulfonyl, sulfinate, or acetylide groups, or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic groups; R ３ are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene, wherein the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene can be optionally interrupted by an aryl, heteroaryl, aliphatic ring, or heteroaliphatic ring; R ５ are independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; E １ is C and E ２ is O, S, or NH, or E １ is N and E ２ is O; E ３ , E ４ , E ５ , and E ６ is N, NR ４ , O, and S; ３ , E ４ , E ５ , or E ６ If is N, then 【Chemistry 7】 teeth 【Chemistry 8】 and E ３ , E ４ , E ５ , or E ６ NR ４ , O, or S, 【Chemistry 9】 teeth 【Chemistry 10】 and R ４ is H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １９ or -alkylC≡N, or alkylaryl; X is OC(O)R ｘ , OSO ２ R ｘ , OSOR ｘ , OSO (R ｘ ) ２ , S(O)R ｘ , OR ｘ , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl, each X may be the same or different, and X is selected from M １ and M ２ may form a bridge between; R ｘ is independently hydrogen or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl; 27. The process of any one of claims 18 to 26, wherein G is independently selected from neutral or anionic donor ligands that are absent or Lewis bases.

28. 27. The process of any one of claims 18 to 26, 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 tetraazaannulene catalyst, and a metal β-diiminate catalyst.

29. The DMC catalyst, in addition to at least two metal centers and cyanide ligands, also comprises, optionally in non-stoichiometric amounts, at least one of: one or more complexing agents, water, metal salts, and / or acids; and / or 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 has the formula M'(X'): ｐ (In the formula, M' is Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(II I), 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 a halide ion, an oxide ion, a hydroxide ion, a sulfate ion, a carbonate ion, a cyanide ion, an oxalate ion, a thiocyanate ion, an isocyanate ion, an isothiocyanate ion, a carboxylate ion, and a nitrate ion; p is an integer of 1 or greater, and the charge of the anion multiplied by p satisfies the valence of M'; the metal cyanide salt has the formula (Y): ｑ M'' (CN) ｂ (A) ｃ wherein M″ is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V); Y is a proton or an alkali metal ion or an alkaline earth metal ion (K ＋ etc.), 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 may be 0 or an integer equal to or greater than 1; the sum of the charges of the anions Y, CN, and A multiplied by q, b, and c, respectively (e.g., Y x q + CN x b + A x c) satisfies the valence of M''); the at least one complexing agent is selected from (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols, ureas, or combinations thereof; Optionally, the at least one complexing agent is chosen from propylene glycol, polypropylene glycol, (meth)ethoxyethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or combinations thereof; When the acid is present, it is a compound of formula H ｒ X''', where X''' is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and r is an integer corresponding to the charge of the counterion X''', and / or The DMC catalyst has the formula: M' ｄ [M'' ｅ (CN) ｆ ] ｇ wherein M′ and M″ are as defined in claim 28, and d, e, f, and g are integers selected such that the DMC catalyst is electroneutral; optionally, d is 3, e is 1, f is 6, and g is 2; and / or The DMC catalyst has the formula: M' ｄ [M'' ｅ (CN) ｆ ] ｇ ・hM'''X'' ｌ ・jR ｃ ・kH ２ O・lH ｒ X''' (wherein M', M'', d, e, f, and g are as defined in claim 28, M''' is M' and / or M'', X'' is an anion selected from a halide ion, an oxide ion, a hydroxide ion, a sulfate ion, a carbonate ion, a cyanide ion, an oxalate ion, a thiocyanate ion, an isocyanate ion, an isothiocyanate ion, a carboxylate ion, and a nitrate ion, i is an integer of 1 or more, and the charge of the anion X'' multiplied by i satisfies the valence of M''', h, j, k, and l are each independently 0 or a positive number, r is an integer corresponding to the charge of the counter ion X''', and R ｃ is a complexing agent or a combination of one or more complexing agents, optionally wherein the one or more complexing agents are selected from dimethoxyethane, tert-butyl alcohol, polyethylene glycol, polypropylene glycol, polyether carbonate, poly(tetramethylene glycol), polycarbonate; and / or The DMC catalyst is Zn ３ [Co(CN) ６ ] ２ (zinc hexacyanocobaltate) based; and / or the DMC catalyst is zinc hexacyanocobaltate and the one or more ligands are selected from alcohols and polyols; and / or The polycarbonate or polyester(poly)ol copolymer according to block A of any one of claims 1 to 8 is fed continuously or semi-continuously into the reactor or a second reactor in one operation, optionally with the product of the first reaction comprising unreacted alkylene oxide and / or carbonate catalyst; and / or The polycarbonate or polyester (poly)ol copolymer according to block A of any one of claims 1 to 8 or the (poly)ol block copolymer according to any one of claims 1 to 8 is a (poly)ol copolymer comprising an alkylene oxide and CO ２ is used to preactivate the DMC catalyst in the reactor or a second reactor prior to the addition of the same or different alkylene oxides are used in the first or second reaction; and / or the alkylene oxide used in the first or second reaction comprises propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide; and / or The polycarbonate or polyester (poly)ol (co)polymer is ２ , ethylene oxide, and optionally other alkylene oxides are added to the reaction mixture; and / or the polycarbonate or polyester (poly)ol (co)polymer is added continuously or semi-continuously to the DMC catalyst, preferably the polycarbonate or polyester (poly)ol (co)polymer is added continuously; and / or 29. The process of any one of claims 18 to 28, wherein at least one separate portion of the polycarbonate or polyester (poly)ol (co)polymer is added after the start of the reaction.

30. 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 (e.g., polyurethane (PUR) foam, polyisocyanurate (PIR) foam, and / or spray foam), elastomer (e.g., cast elastomer, thermoplastic elastomer (TPU), or microcellular elastomer), adhesive (e.g., hot melt adhesive, pressure sensitive adhesive, or reactive adhesive), sealant, or coating (e.g., water-based or solvent dispersion (PUD), two-component coating, one-component coating, solventless coating), and optionally 12. The polyurethane of claim 10 or 11, wherein the polyurethane is formed via a process including extrusion, molding, injection molding, spraying, foaming, casting and / or vulcanization, and further optionally, the polyurethane is formed via a "one-pot" process or a "prepolymer" process.

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