Method for terminating a polymerization process

Abstract

A method for terminating a polymerization process is described. The reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst to produce a polymer includes a termination step in which the catalyst is deactivated by contacting the catalyst with an acid effective to deactivate the catalyst. The deactivated catalyst can be removed from the polymer product by contacting the catalyst and polymer product with a solid phase and / or by precipitation, and the catalyst can also be optionally reactivated by contacting the deactivated catalyst with an anion. The acid can contain an anion that is effective to initiate the polymerization process and effective to deactivate the catalyst, and the molar ratio of acid to catalyst in the deactivation step can be 20:1 or less of the molar ratio of acid to catalyst for the reaction.

Description

[Technical Field]

[0001] The present invention relates to a method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide and a method for purifying the polymer product obtained therefrom. [Background technology]

[0002] Environmental and economic concerns associated with the depletion of petroleum resources have spurred momentum for the chemical conversion of carbon dioxide (CO2) so that it can be used as a renewable carbon source. CO2 is a highly attractive raw material due to its low reactivity, low cost, virtually nontoxicity, availability in high purity and in large quantities, and non-hazardous nature. Therefore, CO2 could be a promising substitute for carbon monoxide, phosgene, or other petrochemical feedstocks in many processes. One of the applications of CO2 that has been developed is its copolymerization with epoxides to obtain aliphatic polycarbonates.

[0003] A common method for producing aliphatic polycarbonates involves copolymerizing epoxides with CO2 in the presence of a metal complex catalyst. The polymerization process typically results in a crude product containing the catalyst, which can degrade the polymer product over time. The crude product may also discolor. Therefore, it is desirable to deactivate and / or remove the catalyst to prevent undesired degradation of the polymer product. Furthermore, many applications of aliphatic polycarbonates require colorless, metal-free polymers.

[0004] It is known that monometallic metal complex catalysts can be terminated (or deactivated) using strong acids, such as sulfonic acid or phosphoric acid, in polymerization reactions involving the reaction of carbon dioxide with epoxides. EP 2342257 and WO 2010 / 033703 each disclose monometallic transition metal complexes that can be terminated (or deactivated) using acids containing anions that are not polymerization initiators. Sulfonic acid and phosphoric acid are described, used in a 1:1 molar ratio of acid to catalyst. However, EP 2342257 also discloses deactivating the catalyst using acetic acid, but 800 molar equivalents of acetic acid relative to the catalyst were required to terminate (or deactivate) the catalyst. EP 2342257 and WO 2010 / 033703 do not disclose terminating (or deactivating) bimetallic catalysts.

[0005] Surprisingly, we have now found that a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst can be terminated using an acid containing an anion that is effective to function as an initiator for the polymerization reaction and that is also effective to deactivate the catalyst. We have also now found that a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a metal complex catalyst can be terminated using an acid containing an anion that is effective to function as an initiator for the polymerization process and that is also effective to deactivate the catalyst, at a molar ratio of acid to catalyst of 20:1 or less. We have also surprisingly found that the deactivated catalyst can be removed from the polymer product and, optionally, reactivated. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent No. 2342257 [Patent Document 2] International Publication No. 2010 / 033703 Summary of the Invention

[0007] In a first aspect of the present invention, there is provided a method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with an acid effective to deactivate the catalyst.

[0008] In a second aspect of the present invention, there is provided a method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst.

[0009] In a third aspect of the present invention, there is provided a method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with a carboxylic acid effective to deactivate the catalyst.

[0010] Preferably, the molar ratio of acid to catalyst in the deactivation step of the first, second and / or third aspects of the present invention is no more than 20:1 of the molar ratio of acid to catalyst for the deactivation reaction. In a fourth aspect of the present invention, there is provided a method for terminating a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is not more than 20:1 of the molar ratio of acid to catalyst for the deactivation reaction.

[0011] In a fifth aspect of the present invention, there is provided a method for terminating a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with a carboxylic acid effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is not more than 20:1 of the molar ratio of acid to catalyst for the deactivation reaction.

[0012] Preferably, the acids of the first, second, third, fourth and / or fifth aspects of the present invention have a pKa of at least 2.5, more preferably at least 3, most preferably at least 4.

[0013] In a sixth aspect of the present invention, there is provided a method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising: (i) terminating the polymerization process by contacting the catalyst with an acid effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally reactivating the deactivated catalyst by contacting the catalyst with an anion. Includes.

[0014] In a seventh aspect of the present invention, there is provided a method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising: (i) terminating the polymerization process by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally reactivating the deactivated catalyst by contacting the catalyst with an anion. Includes.

[0015] In an eighth aspect of the present invention, there is provided a method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising: (i) terminating the polymerization process by contacting the catalyst with a carboxylic acid effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally reactivating the deactivated catalyst by contacting the catalyst with an anion. Includes.

[0016] Preferably, the molar ratio of acid to catalyst in step (i) of the sixth, seventh and / or eighth aspects of the present invention is no more than 20:1 of the molar ratio of acid to catalyst for the deactivation reaction. In a ninth aspect of the present invention, there is provided a method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, the method comprising: (i) terminating the polymerization process by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally reactivating the deactivated catalyst by contacting the catalyst with an anion. Includes.

[0017] In a tenth aspect of the present invention, there is provided a method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, the method comprising: (i) terminating the polymerization process by contacting the catalyst with a carboxylic acid effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally reactivating the deactivated catalyst by contacting the catalyst with an anion. Includes.

[0018] Preferably, the acid in step (i) of the sixth, seventh, eighth, ninth and / or tenth aspects of the present invention has a pKa of at least 2.5, more preferably at least 3, most preferably at least 4. DETAILED DESCRIPTION OF THE INVENTION

[0019] catalyst The polymerization process in the first, second, third, sixth, seventh and / or eighth aspects of the present invention is carried out in the presence of a bimetallic metal complex catalyst represented by formula (I) or formula (II):

[0020] [ka] Preferably, In the formula, R 1 and R 2 are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR 13 R 14 , amine, ether-OR 15 , -R 16 OR 17 , ester group -OC(O)R 10 or -C(O)OR 10 , amide group -NR 9 C(O)R 9 or -C(O)-NR 9 (R 9 ), -COOH, -C(O)R 15, -OP(O)(OR 18 )(OR 19 ), -P(O)R 20 R 21 , -P(O)(OR)(OR), -OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 aryl, heteroaryl, alicyclic, or heteroalicyclic; R 4 are independently selected from H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R 9 , R 10 , R 13 , R 14 , R 18 , R 19 , R 20 and R 21 are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E 1 is C and E 2 is O, S or NH, or E 1 is N and E 2 is O, E 3 is N, NR 5 , O or S, and E 3 If is N, then

[0021] [ka] teeth,

[0022] [ka] and E 3 NR 5 , O or S,

[0023] [ka] teeth,

[0024] [ka] and R 5 are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 10 , -alkylnitrile or alkylaryl; X, if present, is independently OC(O)R x , OSO2R x , OSOR x , OSO(R x )2, S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R X are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y 1 and Y 2independently, if present, a metal M 2 is a neutral or anionic donor group capable of donating a lone pair of electrons to M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV).

[0025] For the avoidance of doubt, where a group is found in both formula (I) and formula (II), the definitions below apply to both formula (I) and formula (II) independently. Appearing group R 1 and R 2 Each of R can be the same or different. 1 and R 2 is preferably independently selected from the following: hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy or alkylthio. 2 are preferably the same and are hydrogen.

[0026] R 2 is hydrogen, and R 1 are even more preferably independently selected from the following: hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C 1~6Alkyl (e.g., haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl, and alkylthio, such as t-butyl, n-butyl, i-propyl, methyl, piperidinyl, methoxy, hexyl methyl ether, -SCH3, -S(C6H5), H, nitro, trimethylsilyl, methylsulfonyl (-SO2CH3), triethylsilyl, halogen, or phenyl.

[0027] Appearing R 1 may be the same or different, and R 1 and R 2 The R's may be the same or different. 1 Preferably, each occurrence of R is the same. 2 Preferably, each of R 1 and R 2 If and are identical, the R 1 and R 2 Preferably, each occurrence of R is methyl. 1 are identical and appearing R 2 are identical, and R 1 and R 2 It is preferable that the number of the saturation regions is different from the number of the saturation regions.

[0028] Appearing R 1 are preferably the same and selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, heteroalicyclic, alkoxy, aryloxy or alkylthio. 1 and R are the same and are selected from the following: halide, sulfoxide, silyl, and optionally substituted alkyl, heteroaryl, or alkoxy. 1 It is even more preferred that both occurrences of R are the same and are selected from: H, alkyl, aryl, alkoxy, trialkylsilyl, such as triethylsilyl, or halide. 1It is even more preferred that both occurrences of R are the same and are selected from: H, alkyl, phenyl, halide, or trialkylsilyl. 1 are the same and are selected from the following: H, methyl, ethyl, n-propyl, i-propyl n-butyl, t-butyl, t-amyl or t-octyl.

[0029] base R 3 It will be understood that R can be a divalent alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, or heteroalkynylene group (which may optionally be interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic groups), or a divalent arylene or cycloalkylene group that serves as a bridging group between two nitrogen centers in compounds of formula (I) and (II). Thus, R 3 When R is an alkylene group such as 2,2-dimethylpropane-1,3-diyl, 3 The group has the structure -CH-C(CH)-CH-. Thus, the definitions of alkyl, aryl, cycloalkyl, etc. groups referred to herein are defined as R 3 Further related to the divalent alkylene, arylene, cycloalkylene, etc. groups mentioned above, R may be optionally substituted. 3 Examples of R include ethane-1,2-diyl, 2,2-fluoropropane-1,3-diyl, 2,2-dimethylpropane-1,3-diyl, propane-1,3-diyl, butane-1,4-diyl, phenylene, cyclohexane-1,2-diyl, cyclohexane-1,4-diyl, or biphenylene. 3 When is cyclohexane-1,2-diyl or cyclohexane-1,4-diyl, it can be in the racemic, RR or SS form.

[0030] R 3can be independently selected from the following: substituted or unsubstituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene, arylene or cycloalkylene. 3 is preferably selected from the following: substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene. More preferably, R 3 is selected from the following: -CH2C(CH3)2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH2C6H5)2CH2-, -(C6H4)-, -CH2CH2-, -CH2-CH2CH2CH2-, -CH2CH2N(CH3)CH2CH2-, -(C6H 10 )- or -CH2CH2CH(C2H5)-. Even more preferably, R 3 is selected from the following: -CH2C(CH3)2CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH2C6H5)2CH2-, -CH2CH2CH(C2H5)-, -CH2CH2CH2CH2-. More preferably still, R 3 is selected from: -CH2C(CH3)2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2- and -CH2C(C2H5)2CH2-.

[0031] R 3 are independently selected from: substituted or unsubstituted alkylene and substituted or unsubstituted arylene, preferably substituted or unsubstituted propylene, such as propane-1,3-diyl and 2,2-dimethylpropane-1,3-diyl, and substituted or unsubstituted phenylene or biphenylene. 3 It is preferred that both R 3 is a substituted propane-1,3-diyl, such as 2,2-di(alkyl)propane-1,3-diyl, especially 2,2-dimethylpropane-1,3-diyl.

[0032] Each R 4are preferably independently selected from: hydrogen and optionally substituted aliphatic or aryl. 4 More preferably, R is independently selected from the following: hydrogen or optionally substituted alkyl or aryl. 4 Even more preferably, R are the same and are selected from hydrogen or optionally substituted alkyl or aryl. 4 Exemplary groups include hydrogen, methyl, ethyl, n-propyl, n-butyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. 4 Even more preferably, is hydrogen.

[0033] R 4 Group and R 1 In a preferred combination with the group R 1 is selected from H, methyl, ethyl, n-propyl, n-butyl, t-butyl, t-octyl, Cl, Br, F, nitro, trimethylsilyl, triethylsilyl, methylthio, and methoxy; R 4 is selected from H, methyl, ethyl, n-propyl, phenyl and trifluoromethyl.

[0034] E appears 1 Each of the occurrences of E can be the same or different. 1 Preferably, each occurrence of E is identical. 2 Each of the occurrences of E can be the same or different. 2 Preferably, each of E is the same. 1 is C and E 2 is O, S or NH, but more preferably E 1 is C and E 2 is O.

[0035] E appears 3 Each occurrence can be the same or different. 3 Preferably, each of R 5is preferably, when present, independently selected from the following: hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalkenyl, heteroalkynyl, heteroaryl, -alkylC(O)R 10 or -alkylnitrile. Each R 5 When present, R may be the same or different. 5 When present, is preferably selected from the following: hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl. Each R 5 More preferably, R, when present, are the same and are selected from hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl. 5 Exemplary groups include H, Me, Et, Bn, iPr, tBu, or Ph. Each R 5 Even more preferably, when present, is hydrogen or alkyl. 5 When present, is most preferably hydrogen.

[0036] Y in formula (II) 1 and Y 2 is metal M 2 Y is a group that can donate a lone pair to 1 and Y 2 The atoms of the group are typically each Y 1 and Y 2 and metal, M 2 Forms a bond between Y 1 and Y 2 and Y may be the same or different. 1 and Y 2 are preferably the same. 1 Group and / or Y 2 The atoms of the group are typically heteroatoms selected from oxygen, nitrogen, or sulfur, or carbene carbons.

[0037] Therefore, Y 1 and Y 2 can be a heteroatom or a group containing a heteroatom capable of donating a lone pair of electrons, the lone pair of electrons typically being donated by a nitrogen, sulfur, or oxygen atom, more typically by a nitrogen or oxygen atom, and most typically by a nitrogen atom.

[0038] Y 1 and Y 2 may independently contain 1 to 20 atoms, preferably 1 to 15 atoms, and more preferably 1 to 10 atoms. Y 1 and Y 2 are preferably independently selected from the following: O, S, - - NC(O)R 10 , -C(O)N - R 10 , -C(O)O - , -C(O)OR 10 , -C(O)R 10 , -C(R 10 )2C(O)N - (R 10 ), optionally substituted heteroaliphatic, e.g., -OR 10 , -SR 10 ,- - NR 10 , -N(R 10 )2, -C(R 10 )2N(R 10 )2, -C(R 10 )=N(R 10 ), or an optionally substituted heteroalicyclic, or heteroaryl, or an optionally substituted carbene structure, where R 10 is independently selected from the following: hydrogen or an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group. Y 1 and Y 2 More preferably, are independently selected from: - , S - , -OR 10 , -SR 10 ,- - N(R10 ), -N(R 10 )2, -C(R 10 )2N(R 10 )2, -C(R 10 )=N(R 10 ), - - NC(O)R 10 , -C(O)O, -C(O)OR 10 , C(O)R 10 or optionally imidazoline, "unusual" imidazoline (wherein "unusual" imidazoline has positive and negative charges on its heterocyclic ring depending on the position of the double bond), imidazolidine, pyrrolidine, pyrroline, triazoline, thiazoline, oxazole, oxazoline, imidazoylidene, imidazolinylidene, thiazolylidene, oxazolylidene, triazolylidene, benzimidazolylidene, pyrrolidinylidene, or "unusual" imidazolylidene, or N,N'-diamidocarbene, optionally substituted pyridine, imidazole, methylimidazole, benzimidazole, pyrrole, triazole, thiazole, benzimidazoline, benzotriazole (wherein R 10 are independently selected from the following: hydrogen or an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group.

[0039] Y 1 and Y 2 is independently selected from optionally substituted heteroaliphatic, heteroalicyclic, or heteroaryl, the optionally substituted heteroaliphatic, heteroalicyclic, or heteroaryl may also contain a metal M 2 It includes heteroatoms that can donate lone pairs to Y. 1 and Y 2 is independently selected from optionally substituted carbene structures (which may or may not be heteroaliphatic, heteroalicyclic, or heteroaryl), the optionally substituted carbene structures may also contain a metal M 2 It contains a carbon atom that can donate a lone pair of electrons to

[0040] Even more preferably, Y 1and Y 2 can be independently selected from: O, -OR 10 , -N(R 10 )2, -C(R 10 )2N(R 10 )2, -C(R 10 )=N(R 10 ), -C(O)O - , -C(O)R 10 , optionally substituted imidazolylidene, benzimidazolylidene, imidazolinylidene or pyrrole.

[0041] Most preferably, Y 1 and Y 2 are independently selected from: O, —OCH3, —C(═O)H, —CH2N(CH3)2, —CH2N(H)(CH2CH(CH3)2), —CH═N(CH2CH(CH3)2), —CH2-piperidine or benzotriazine.

[0042] Y 1 and Y 2 The lone pair donor atoms of the groups may independently be bonded directly to the remainder of the catalyst of formula (II) through a bond to the respective aryl group, or may be bonded to the remainder of the catalyst of formula (II) through a linking group bonded to the respective aryl group. 1 and / or Y 2 When present in Y, it is preferably selected from the following: optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene, or cycloalkylene. 1 and / or Y 2 When present in Y, it is more preferably selected from optionally substituted alkylene, alkenylene, alkynylene or arylene, and even more preferably optionally substituted alkylene or arylene. 1 and / or Y 2 If present, preferably optionally substituted C1-C 10alkylene, more preferably optionally substituted C1-C6 alkylene, even more preferably optionally substituted C1-C4 alkylene, and most preferably methylene. 1 and / or Y 2 The lone pair donating atom in the group is a carbene carbon, which is not directly bonded to the remainder of the catalyst of formula (II).

[0043] Y 1 and Y 2 The heteroatoms of the group may be linked, via the linking group (if present), to each aryl group of the remainder of the catalyst of formula (II) by any suitable number of atoms, preferably 1 to 10 atoms, more preferably 1 to 6 atoms, even more preferably 1 to 4 atoms, and most preferably 1 to 2 atoms. 1 and / or Y 2 It will be understood that when the heteroatom of the group is directly bonded to the respective aryl group of the remainder of the catalyst of formula (II), the linking group will not be present.

[0044] It will be understood that X serves as a starting species for the process of the present invention. Each X is independently selected from: OC(O)R X , OSO2R X , OSO(R X )2, OR X , halide, nitrate, hydroxyl, carbonate, amide or optionally substituted aliphatic, heteroaliphatic (e.g., silyl), cycloaliphatic, heterocycloaliphatic, aryl or heteroaryl. R X are independently hydrogen or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl. X is OC(O)R X OR X Preferably, R Xare independently hydrogen, optionally substituted aliphatic, haloaliphatic, aryl, heteroaryl, silyl, or alkylaryl. Examples of X include: OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr)2, or N(SiMe3)2.

[0045] When G is not absent, it is a group capable of donating a lone pair of electrons (i.e., a Lewis base). Each G can be neutral or negatively charged. If G is negatively charged, one or more positive counterions are required to balance the charge of the complex. Suitable positive counterions include: Group 1 metal ions (Na + , K. + etc.), Group 2 metal ions (Mg 2+ , Ca 2+ etc.), ammonium ion (i.e., N(R 26 )4 + ), iminium ions (i.e., (R 12 )2C=N(R 26 )2 + , for example, bis(triphenylphosphine)iminium ion) or phosphonium ion (P(R 26 )4 + ) (where each R 26is independently selected from the following: hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl). Preferably, G is independently selected from the following: optionally substituted heteroaliphatic groups, optionally substituted heteroalicyclic groups, optionally substituted heteroaryl groups, halides, hydroxides, hydrides, carboxylates, and water. More preferably, G is independently selected from the following: Water, alcohols, substituted or unsubstituted heteroaryls (such as imidazole, methylimidazole, pyridine, 4-dimethylaminopyridine, pyrrole, and pyrazole), ethers (such as dimethyl ether, diethyl ether, and cyclic ethers), thioethers, carbenes, phosphines, phosphine oxides, substituted or unsubstituted heteroalicyclics (such as morpholine, piperidine, tetrahydrofuran, and tetrahydrothiophene), amines, alkylamines (such as trimethylamine and triethylamine), acetonitrile, esters (such as ethyl acetate), acetamides (such as dimethylacetamide), sulfoxides (such as dimethyl sulfoxide), carboxylates, hydroxides, hydrides, halides, nitrates, sulfonates, and the like. In some embodiments, one or both instances of G are independently selected from the following: Optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, ether, thioether, carbene, phosphine, phosphine oxide, amine, alkylamine, acetonitrile, ester, acetamide, sulfoxide, carboxylate, nitrate, or sulfonate. In some embodiments, one or both instances of G are negatively charged (e.g., halide). In further embodiments, one or both instances of G is optionally substituted heteroaryl.

[0046] In formula (II), the groups X and G are combined into a single M 1 or M 2 Although shown as being associated with a metal center of M, one or more X groups and G groups may be 1 and M 2It will also be understood that bridges may be formed between metal centers. For example, an X group may be associated with a single metal center of M, as shown in formula (II), or an X group may be associated with both metal centers, forming a bridge between two metal centers.

[0047] M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV).

[0048] In formulas (I) and (II) herein, M 1 and M 2 are independently preferably selected from Zn(II), Cr(III), Co(II), Mn(II), Mg(II), Fe(II) or Fe(III), most preferably Zn(II), Co(II) or Mg(II).

[0049] Preferably, M 1 or M 2 At least one of may be selected from the following: Ni(II), Ni(III), Co(II), Co(III), Cr(II), Cr(III), Fe(II), Fe(III), Mn(III), Al(III), Zn(II) or Mg(II).

[0050] In certain embodiments, the occurring M 1 and M 2 Preferably, each occurrence of M 1 and M 2 Unlike M 1 or M 2 is Ni(II) or Ni(III), and the other M 1 or M 2is preferably Fe(II), Fe(III), Cr(III), Al(III), Mg(II), Zn(II), Co(II) or Co(III), and M 1 or M 2 is Ni(II) and the other M 1 or M 2 More preferably, each occurrence of M is Mg(II), Zn(II), Co(II), Co(III) or Cr(III). 1 and M 2 Unlike M 1 or M 2 is Zn(II), and the other M 1 or M 2 is preferably Mg(II).

[0051] In certain embodiments, each occurrence of M 1 and M 2 and are identical. Preferably, each occurrence of M 1 and M 2 and may be identical and are preferably Ni(II), Ni(III), Fe(II), Fe(III), Mn(III), Cr(II), Cr(III), Co(II), Co(III), Zn(II) or Mg(II), with each occurrence of M 1 and M 2 and may be the same, and are more preferably Ni(II), Co(II), Zn(II) or Mg(II).

[0052] The catalyst preferably has an overall neutral charge. 1 and / or M 2 is M 1 and M 2 The oxidation state of the metal and the Y used 1 and Y 2 It will be understood that depending on the charge of the groups (if any), there may be one or more optional X groups (n and m), respectively, coordinated to the metal center (where X is as defined above). For example, if the ligand, excluding the Y group, has a charge of 2, then the M of the metal group 1 and M 2each is Ni(II), and each Y group is Y 1 and Y 2 are anionic (i.e., each has a single negative charge), the catalyst can have an overall charge of 0. In this case, no additional X groups are coordinated to the metal centers. However, if one or both of the metal centers have a ternary oxidation state with a 3+ charge, an additional X group is required on each M(III), even if the Y group is anionic. By way of further example, if each of the Y groups is neutral, the ligand can have a 2 - If both metal centers are M(II), then there can be a total of two X groups to achieve an overall neutral charge, and if both metal centers are M(III), then there can be a total of four X groups to achieve an overall neutral charge.

[0053] Suitable catalysts of formula (I) are:

[0054] [ka]

[0055] [ka]

[0056] [ka] More preferred catalysts of formula (I) are:

[0057] [ka] Suitable catalysts of formula (II) are:

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka] The polymerization process according to the fourth, fifth, ninth and / or tenth aspects of the present invention is carried out in the presence of a metal complex catalyst. The metal complex may be monometallic or bimetallic. Preferably, the metal complex is bimetallic, and more preferably, the metal complex is according to formula (I) and / or formula (II), as set forth above.

[0065] Double Metal Cyanide (DMC) Catalyst The polymerization process of the present invention may further comprise a double metal cyanide catalyst. 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 organic complexing agents (e.g., in non-stoichiometric amounts), water, a metal salt, and / or an acid.

[0066] The first two of the at least two metal centers may be represented by M' and M''. M' may be selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II) and Cr(III), M' is preferably selected from Zn(II), Fe(II), Co(II) and Ni(II), and even more preferably M' is Zn(II).

[0067] M" is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), preferably M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), more preferably M" is selected from Co(II) and Co(III).

[0068] It should be appreciated that the above preferred definitions for M' and M" may be combined. For example, M' may preferably be selected from Zn(II), Fe(II), Co(II) and Ni(II), and M" may preferably be selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). For example, M' may preferably be Zn(II), and M" may preferably be selected from Co(II) and Co(III).

[0069] If 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 are 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, and 7,811,958, the entire contents of which are incorporated by reference. , U.S. Pat. Nos. 6,835,687, 6,699,961, 6,716,788, 6,977,236, 7,968,754, 7,034,103, 4,826,953, 4,500,704, 7,977,501, 9,315,622, EP-A-1568414, EP-A-1529566 and WO 2015 / 022290.

[0070] DMC catalysts useful in the present invention can be produced by treating a solution (e.g., aqueous) of a metal salt with a solution (e.g., aqueous) of a metal cyanide salt in the presence of one or more organic complexing agents, water, and / or an acid. Suitable metal salts have the formula M'(X') pwherein M' is selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II), and Cr(III); M' is preferably selected from Zn(II), Fe(II), Co(II), and Ni(II); even more preferably, M' is Zn(II); X' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate; preferably, X' is a halide. p is an integer greater than or equal to 1, and the charge on the anion multiplied by p satisfies the valence of M'. Examples of suitable metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate, and mixtures thereof.

[0071] Suitable metal cyanide salts have 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), preferably M" is selected from Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II), more preferably M" is selected from Co(II) and Co(III). Y is a proton (H + ), or alkali metal ions, or alkaline earth metal ions (e.g., K +), and A is an anion selected from halide, oxide, hydroxide, sulfate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. q and b are integers equal to or greater than 1, and preferably b is 4 or 6. c can be an integer equal to or greater than 1. The sum of the charges on ions Y, CN, and A multiplied by q, b, and c, respectively (e.g., Y×q+CN×b+A×c) satisfies the valence of M″. Examples of suitable metal cyanide salts include potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), lithium hexacyanocobaltate(III), and mixtures thereof.

[0072] Suitable complexing agents include (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diol), ketones, esters, amides, alcohols, ureas, and the like. Exemplary complexing agents include propylene glycol, polypropylene glycol (PPG), (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, and the like. It should be recognized that the alcohols may be saturated or may contain unsaturated moieties (e.g., double or triple bonds). Multiple (i.e., multiple different types) complexing agents may be present in the DMC catalyst used in the present invention.

[0073] The DMC catalyst may include a complexing agent that is a polyether, a polyether carbonate, or a polycarbonate. Suitable polyethers for use in the present invention include those produced by ring-opening polymerization of cyclic ethers, including epoxide polymers, oxetane polymers, tetrahydrofuran polymers, and the like. Any method of catalysis can be used to make the polyethers. The polyethers can have any desired end groups, including, for example, hydroxyl, amine, ester, ether, and the like. Preferred polyethers for use in the present invention are polyether polyols having 2 to 8 hydroxyl groups. It is also preferred that the polyethers for use in the present invention have a molecular weight of about 1,000 daltons to about 10,000 daltons, more preferably about 1,000 daltons to about 5,000 daltons. Polyether polyols useful in the DMC catalyst of the present invention include PPG polyols, EO-capped PPG polyols, mixed EO-PO polyols, butylene oxide polymers, butylene oxide copolymers with ethylene oxide and / or propylene oxide, polytetramethylene ether glycol, and the like. Preferred polyethers include PPGs, such as PPG polyols, particularly diols and triols, said PPGs having a molecular weight of about 250 daltons to about 8,000 daltons, more preferably about 400 daltons to about 4,000 daltons.

[0074] Suitable polyether carbonates for use in the DMC catalyst of the present invention can also be obtained by the catalytic reaction of alkylene oxides and carbon dioxide in the presence of a suitable starter or initiator compound. Polyether carbonates used as complexing agents can also be produced by other methods known to those skilled in the art, such as the partial alcoholysis of polycarbonate polyols with difunctional or trifunctional hydroxy compounds. Polyether carbonates used as complexing agents preferably have an average hydroxyl functionality of 1 to 6, more preferably 2 to 3, and most preferably 2.

[0075] Suitable polycarbonates for use in the DMC catalyst of the present invention can also be obtained by polycondensation of difunctional hydroxy compounds (generally bis-hydroxy compounds, such as alkanediols or bisphenols) with carbonic acid derivatives, such as phosgene or bis[chlorocarbonyloxy] compounds, carbonic acid diesters (such as diphenyl carbonate or dimethyl carbonate) or urea. Methods for producing polycarbonates are generally known and are described, for example, in "Houben-Weyl, Methoden der organischen Chemie", Volume E20, Makromolekulare Stoffe, 4 th Edition,1987,p.1443-1457, “Ullmann's Encyclopedia of Industrial Chemistry”,Volume A21,5 th Edition, 1992, pp. 207-215 and "Encyclopedia of Polymer Science and Engineering", Volume 11, 2 ndEdition, 1988, pp. 648-718. Aliphatic polycarbonate diols having a molecular weight of about 500 to 5000 daltons, most preferably 1000 to 3000 daltons, are particularly preferably used. These are generally obtained from non-vicinity diols by reaction with diaryl carbonate, dialkyl carbonate, dioxolanone, phosgene, bischloroformate or urea (see, for example, EP-A-292772 and the references cited therein). Suitable non-adjacent diols are, in particular, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, bis-(6-hydroxyhexyl) ether, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-bis-hydroxymethylcyclohexane, diethylene glycol, triethylene glycol. Examples of diols include ethanol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, alkoxylation products of diols with ethylene oxide and / or propylene oxide and / or tetrahydrofuran, having a molar mass of up to 1000 daltons, preferably 200 to 700 daltons, and, more rarely, dimer diols obtainable by reducing both carboxyl groups of dimer acids obtainable by dimerization of unsaturated vegetable fatty acids. Non-adjacent diols can be used individually or in mixtures. The reaction can be catalyzed by bases or transition metal compounds in a manner known to those skilled in the art.

[0076] Other complexing agents that may be useful in the present invention include poly(tetramethylene ether diols). Poly(tetramethylene ether diols) are polyether polyols based on tetramethylene ether glycol, also known as polytetrahydrofuran (PTHF) or polyoxybutylene glycol. These poly(tetramethylene ether diols) contain two OH groups per molecule. They can be produced by cationic polymerization of tetrahydrofuran (THF) using a catalyst.

[0077] Complexing agents, as defined above, may be used to increase or decrease the crystallinity of the DMC catalyst thus obtained. Suitable acids for use in the DMC catalyst of the present invention are those 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; preferably, X''' is a halide. r is an integer corresponding to the charge on the counterion X'''. For example, when X''' is Cl - When , r is 1, i.e., the salt is HCl.

[0078] If present, the formula H r Particularly preferred acids for use in the DMC catalysts of the present invention having X''' include the following: HCl, H2SO4, HNO3, H3PO4, HF, HI, HBr, H3BO3, and HClO4. HCl, HBr, and H2SO4 are particularly preferred.

[0079] It should also be understood that an alkali metal salt (e.g., an alkali metal hydroxide, e.g., KOH, an alkali metal oxide, or an alkali metal carbonate) can be added to the reaction mixture. For example, a metal salt (M'(X') p ) into metal cyanide salts ((Y)q[M''(CN) b (A) c]), followed by the addition of the alkali metal salt to the reaction mixture.

[0080] In one common preparation, an aqueous solution of zinc chloride (in excess) is mixed with an aqueous solution of potassium hexacyanocobaltate, and an organic complexing agent (e.g., dimethoxyethane or tert-butyl alcohol) is added to the resulting slurry. After filtration and washing of the catalyst with an aqueous solution of the complexing agent (e.g., aqueous dimethoxyethane or aqueous tert-butyl alcohol), an active catalyst is obtained. Subsequent washing steps can be performed simply using the complexing agent to remove excess water. Each is followed by a filtration step.

[0081] In an alternative preparation, several separate solutions may be prepared and then combined in sequence. For example, the following solutions may be prepared: 1. A solution of a metal cyanide (e.g., potassium hexacyanocobaltate) 2. A solution of a metal salt, such as zinc chloride (in excess) 3. Solution of first complexing agent (e.g., PPG diol) 4. A solution of a second complexing agent (e.g., tert-butyl alcohol).

[0082] In this method, Solutions 1 and 2 are immediately combined, followed by the slow addition of Solution 4, preferably with rapid stirring. Solution 3 can be added once or immediately after the addition of Solution 4 is complete. The catalyst is removed from the reaction mixture by filtration and subsequently washed with a solution of complexing agent.

[0083] When water is desired in the DMC catalyst, the above solutions (eg, solutions 1-4) can be aqueous solutions. However, it is understood that if the solutions described in the above preparations are anhydrous, anhydrous DMC catalysts (i.e., DMC catalysts free of water) can be prepared. Any further processing steps (washing, filtration, etc.) can be performed using anhydrous solvents to avoid hydrating the DMC catalyst and thereby introducing water molecules.

[0084] In one common preparation, several separate solutions may be prepared and then combined in sequence. For example, the following solutions may be prepared: 1. A solution of a metal salt (e.g., zinc chloride (in excess)) and a second complexing agent (e.g., tert-butyl alcohol) 2. A solution of a metal cyanide (e.g., potassium hexacyanocobaltate) 3. A solution of a first and a second complexing agent (for example, the first complexing agent can be a polymer (eg, PPG diol) and the second complexing agent can be tert-butyl alcohol).

[0085] In this method, Solution 1 and Solution 2 are slowly combined (e.g., over 1 hour) with stirring (e.g., at 450 rpm) at elevated temperature (e.g., above 25°C, e.g., about 50°C). After addition is complete, the stirring speed is increased for 1 hour (e.g., to 900 rpm). The stirring speed is then reduced to a low speed (e.g., to 200 rpm) and Solution 3 is rapidly added with weak stirring. The mixture is filtered.

[0086] The solid catalyst may be reslurried in a solution of the second complexing agent at a high stirring speed (e.g., about 900 rpm), followed by the addition of the first complexing agent at a low stirring speed (e.g., 200 rpm). The mixture is then filtered. This step may be repeated two or more times. The resulting catalyst cake may be dried under vacuum (e.g., while heating to 60°C).

[0087] Alternatively, the mixture can be first filtered, then reslurried in a solution of the first complexing agent (without the second or further complexing agent) at an elevated temperature (e.g., above 25°C, e.g., about 50°C), and then homogenized by stirring. This step is then followed by filtration. The solid catalyst is then reslurried in a mixture of the first and second complexing agents. For example, the solid catalyst is reslurried in the second complexing agent at an elevated temperature (e.g., above 25°C, e.g., about 50°C), followed by adding the first complexing agent and homogenizing the mixture by stirring. The mixture is filtered, and the catalyst is dried under vacuum while heating (e.g., to 100°C).

[0088] DMC catalysts are M' d [M'' e (CN) f ] g wherein M' and M" are as defined above, and d, e, f, and g are integers selected so that the DMC catalyst is electroneutral. Preferably, d is 3. Preferably, e is 1. Preferably, f is 6. Preferably, g is 2. Preferably, M' is selected from Zn(II), Fe(II), Co(II), and Ni(II), more preferably, M' is Zn(II). Preferably, M" is selected from Co(III), Fe(III), Cr(III), and Ir(III), more preferably, M" is Co(III).

[0089] It will be appreciated that any of these preferred features may be combined, e.g., d is 3, e is 1, f is 6, g is 2, M' is Zn(II), and M'' is Co(III).

[0090] Suitable DMC catalysts of the above formula may include zinc hexacyanocobaltate(III), zinc hexacyanoferrate(III), nickel hexacyanoferrate(II), and cobalt hexacyanocobaltate(III).

[0091] Many advances have been made in the field of DMC catalysts, and those skilled in the art will recognize that DMC catalysts may contain, in addition to the formula above, further additives that enhance the activity of the catalyst. Thus, while the formula above may form the "core" of the DMC catalyst, the DMC catalyst may further contain stoichiometric or non-stoichiometric amounts of one or more additional components, such as at least one organic complexing agent, acid, metal salt, and / or water.

[0092] For example, the DMC catalyst may have the formula: M' d [M'' e (CN) f ] g ·hM'''X'' i jR c kH2O lH r X'' where M', M'', X''', d, e, f, and g are as defined above. M''' can be M' and / or M''. X'' is an anion selected from halide, oxide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, preferably X'' is a halide. i is an integer equal to or greater than 1, and the charge on the anion X'' multiplied by i satisfies the valence of M'''. r is an integer corresponding to the charge on the counterion X'''. For example, when X''' is Cl, - When the formula is as follows, r is 1. l is 0 or a number of 0.1 to 5. Preferably, l is 0.15 to 1.5.

[0093] R c is a complexing agent and may be as defined above. For example, R c are (poly)ethers, polyether carbonates, polycarbonates, poly(tetramethylene ether diols), ketones, esters, amides, alcohols (e.g., C 1~8alcohol), urea, etc., for example, 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, for example, R c can be tert-butyl alcohol, dimethoxyethane or polypropylene glycol.

[0094] As indicated above, multiple complexing agents may be present in the DMC catalyst used in the present invention. The combination of complexing agents tert-butyl alcohol and polypropylene glycol is particularly preferred.

[0095] It should be appreciated that when water, complexing agents, acids, and / or metal salts are not present in the DMC catalyst, h, j, k, and / or l are each zero. When water, complexing agents, acids, and / or metal salts are present, h, j, k, and / or l are positive numbers, such as from 0 to 20. For example, h can be from 0.1 to 4. j can be from 0.1 to 6. k can be from 0 to 20, such as from 0.1 to 10, for example, from 0.1 to 5. l can be from 0.1 to 5, for example, from 0.15 to 1.5.

[0096] As shown above, DMC catalysts are complex structures, and thus the above formula, including additional components, is not intended to be limiting. Instead, those skilled in the art will recognize that this definition is not exhaustive of the DMC catalysts that can be used in the present invention.

[0097] An exemplary DMC catalyst is of the formula Zn3[Co(CN)6]2·hZnCl2·kH2O·j[(CH3)3COH], where h, k, and l 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).

[0098] Chain transfer agent The polymerization process of the present invention may optionally be carried out in the presence of a chain transfer agent. The chain transfer agent may be water or a compound of formula (III):

[0099] [ka] Preferably, it is selected from wherein Z is an optionally substituted residue selected from the group consisting of aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, polyolefin, polyester, polyether, polycarbonate, or combinations thereof; each W is independently selected from a hydroxyl, amine, thiol, or carboxylate group; a is an integer of at least 2.

[0100] The chain transfer agent (CTA) can be water or a compound having two or more groups independently selected from the following: hydroxyl (-OH), amine (-NHR W ), thiol (-SH) or carboxylate (-C(O)OH), (where R W is hydrogen, optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl, or combinations thereof (i.e., aliphatic aryl, aliphatic heteroaryl, heteroaliphatic aryl, etc.). It will be understood that although water does not have two distinct "-OH" groups, it exhibits chain transfer properties similar to molecules that have two distinct "-OH" groups and, therefore, may be encompassed by the term "chain transfer agent."

[0101] Z is the core of the chain transfer agent and can be any group capable of having two or more "W" groups attached thereto. In preferred embodiments, Z is an optionally substituted residue selected from the group consisting of aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, heteroaryl, polyolefin, polyester, polyether, polycarbonate, or a combination thereof. Z can be, for example, an optionally substituted araliphatic, heteroaraliphatic, aliphatic, cycloaliphatic, etc. group. Preferably, Z is selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or polyether.

[0102] When Z is a polymer (i.e., Z contains a polyolefin, polyester, polyether, or polycarbonate group), the molecular weight (Mn) of such a polymer is preferably less than 10,000 g / mol. Preferred polymers include poly(ethylene glycol) (PEG) and poly(lactic acid) (PLA).

[0103] The chain transfer agent, particularly the group Z, can be optionally substituted. In certain embodiments, Z is optionally substituted with halogen, nitrile, imine, nitro, aliphatic, acetyl, amido, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl.

[0104] n is an integer of at least 2. Preferably, n is an integer selected from 2 to 10 (inclusive). More preferably, a is an integer selected from 2 to 6 (inclusive).

[0105] Each occurrence of W can be the same or different. Preferably, each occurrence of W is the same. In certain embodiments, each occurrence of W is hydroxyl (i.e., the chain transfer agent is a polyol, e.g., a diol, triol, tetraol, etc.). In other embodiments, each occurrence of W is an amine (i.e., the chain transfer agent is a polyamine, e.g., a diamine, triamine, tetraamine, etc.). In other embodiments, each occurrence of W is a carboxylic acid (i.e., the chain transfer agent is a polycarboxylic acid, e.g., a diacid, triacid, tetraacid, etc.). In other embodiments, each occurrence of W is a thiol (i.e., the chain transfer agent is a polythiol, e.g., a dithiol, trithiol, tetrathiol, etc.). In other embodiments, the chain transfer agent is water.

[0106] When the chain transfer agent is water, X is preferably not OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2 or a halide, and more preferably CX is not OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, a halide, an alkyl, an alkoxy or an amide.

[0107] A single chain transfer agent may be used, or a mixture of chain transfer agents may be used. Examples of chain transfer agents useful in the second embodiment include water, mono-alcohols (i.e., alcohols having one OH group, such as 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, and cyclohexanol), diols (e.g., 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-diphenol, 1,4-diphenol ... ,3-diphenol, 1,4-diphenol, catechol and cyclohexene diol), triols (glycerol, benzenetriol, 1,2,4-butanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, preferably glycerol or benzenetriol), tetraols (e.g., calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, di(trimethylolpropane)), polyols (e.g., dipentaerythritol, D-(+)-glucose or D-sorbitol), dihydroxy-terminated polyesters (e.g., polylactic acid), dihydroxy-terminated polyethers (e.g., poly(ethylene glycol)), acids (e.g., diphenylphosphinic acid), starch, lignin, mono-amines (i.e., methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, amine, dipentylamine, hexylamine, dihexylamine), diamines (e.g., 1,4-butanediamine), triamines, diamine-terminated polyethers, diamine-terminated polyesters, mono-carboxylic acids (e.g., 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (e.g., maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (e.g., citric acid, 1,3,5-benzenetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid, preferably citric acid), mono-thiols, dithiols, trithiols and compounds with mixed hydroxyl, amine, carboxylic acid and thiol groups, such as lactic acid, glycolic acid, 3-hydroxypropionic acid, natural amino acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including pyranose and furanose forms). The chain transfer agent is preferably selected from: Cyclohexenediol, 1,2,4-butanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)nitropropane, tris(methyl alcohol)ethane, tri(methyl alcohol)propane, tri(methyl alcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and di-ethylene glycol, propylene glycol, 2,2-bis(methyl alcohol)-1,3-propanediol, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.

[0108] The chain transfer agent can be present in a molar ratio of at least 1:1 relative to the metal complex (monometallic or bimetallic metal complex catalyst). Preferably, the chain transfer agent is present in a molar ratio of about 1:1 to about 100:1 relative to the metal complex. More preferably, the chain transfer agent is present in a molar ratio of 1:1 to 9:1. Most preferably, the chain transfer agent is present in a molar ratio of at least 2:1 relative to the metal complex.

[0109] The halogenated X group reduces the amount of chain transfer agent required to produce polycarbonate chains terminated at both ends with hydroxyl groups. Indeed, water impurities present either in the carbon dioxide or during catalyst preparation (e.g., when hydrated metal acetates are used to produce catalysts useful in the first embodiment) can act as a sufficient amount of chain transfer agent (when the chain transfer agent is water) to terminate all polycarbonate chains with hydroxyl groups. Thus, excessive amounts of chain transfer agent are not required. Thus, in certain embodiments, X is a halogenated group and the molar ratio of chain transfer agent to metal complex is at least 0.1:1, preferably at least 1:1, more preferably 0.1:1 to 9:1, and even more preferably 0.1:1 to 1:1. Preferably, X is OC(O)Rx, OSO2Rx, OSO(Rx)2, ORx, or haloaliphatic, where one or both of the Rx groups is haloaliphatic, haloaryl, or haloalicyclic, more preferably haloaliphatic (e.g., fluoroaliphatic).

[0110] Chain transfer agents can be used to increase the molecular weight (M n ) can be adjusted. Reactant The polymerization process of the present invention involves the reaction of carbon dioxide with an epoxide. The epoxide can be any compound containing an epoxide residue. The epoxide can be aliphatic (including alicyclic) or aromatic. Examples of epoxides that can be used in the present invention include, but are not limited to: cyclohexene oxide, styrene oxide, unsubstituted or substituted alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, substituted cyclohexene oxides (e.g., limonene oxide, C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 220), 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, vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxapoxides. Examples of functionalized 3,5-dioxapoxides include:

[0111] [ka] The epoxide residue may be a glycidyl ether, a glycidyl ester, or a glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters, and glycidyl carbonates include:

[0112] [ka] The epoxide substrate may contain two or more epoxide residues, i.e., it may be a bis-epoxide, tris-epoxide, or multi-epoxide-containing residue. Examples of compounds containing two or more epoxide residues include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be appreciated that carrying out the reaction in the presence of one or more compounds having two or more epoxide residues may result in crosslinking in the resulting polymer.

[0113] As those skilled in the art will appreciate, epoxides can be obtained from "green" or renewable resources: Epoxides can be obtained from (poly)unsaturated compounds, such as those derived from fatty acids and / or terpenes, using standard oxidation reactions.

[0114] The epoxide residue may contain an -OH residue or a protected -OH residue. The -OH residue can be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzoyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (e.g., trimethylsilyl (TMS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), tri-isopropylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

[0115] The epoxide may be purified (e.g., by distillation over calcium hydride) before reacting with carbon dioxide. For example, the epoxide may be distilled before being added to the reaction mixture.

[0116] Preferably, the epoxide has a purity of at least 98%, more preferably greater than 99%. It will be understood that the term "epoxide" is intended to encompass one or more epoxides. In other words, the term "epoxide" refers to a single epoxide or a mixture of two or more different epoxides. For example, the epoxide substrate can be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide, and cyclohexene oxide.

[0117] Those skilled in the art will also understand that substituted and unsubstituted oxetanes can be used in place of or in addition to the epoxides of the second aspect of the present invention. Suitable oxetanes include the following: unsubstituted or substituted oxetanes (preferably those substituted at the 3-position with halogen, alkyl (unsubstituted or substituted with -OH or halogen), amino, hydroxyl, aryl (e.g., phenyl), alkylaryl (e.g., benzyl)). Examples of oxetanes include: oxetane, 3-ethyl-3-oxetanemethanol, oxetane-3-methanol, 3-methyl-3-oxetanemethanol, 3-methyloxetane, 3-ethyloxetane, etc.

[0118] Preferably, the epoxide may be aliphatic. 10 Preferably, the epoxide is an alkyl oxide. More preferably, the epoxide is ethylene oxide, propylene oxide, butylene oxide, or a combination thereof. Most preferably, the epoxide is ethylene oxide, propylene oxide, or a combination thereof. Such oxides are of particular interest because they can be used to prepare polymers with elastomeric properties (polyalkylene carbonates, e.g., PPC) that are useful in many applications, such as films.

[0119] Reaction conditions The polymerization process of the various embodiments of the present invention can be carried out at any suitable pressure, from 1 to 100 atmospheres, preferably from 1 to 40 atmospheres, for example, from 1 to 20 atmospheres, and more preferably from 1 atmosphere or 10 atmospheres.

[0120] The polymerization process can be carried out at any suitable temperature, from about 0°C to about 250°C, preferably from about 40°C to about 160°C, and even more preferably from about 50°C to about 120°C.

[0121] The duration of the polymerization process can be up to 168 hours, preferably from about 1 minute to about 24 hours, more preferably from about 5 minutes to about 12 hours, and most preferably from about 1 hour to about 6 hours. When the polymerization process involves the reaction of carbon dioxide with an epoxide, the temperature of the process (i.e., the temperature at which the polymerization process is carried out) can be used to control the composition of the reaction product. Increasing the temperature also increases the selectivity of the catalysts of formulas (I) and (II) towards the production of cyclic carbonates. The catalysts and polymerization processes of formulas (I) and (II) can be operated at temperatures up to 250°C.

[0122] The polymerization process can be carried out at low catalyst loadings. For example, when the polymerization involves the reaction of carbon dioxide with an epoxide, the catalyst loading for the process is preferably a catalyst:epoxide ratio of about 1:1,000 to 100,000, more preferably about 1:1,000 to 300,000, even more preferably about 1:10,000 to 100,000, and most preferably about 1:50,000 to 100,000. When the polymerization process involves the reaction of a hydride with an epoxide, the catalyst loading for the process is preferably a catalyst:total monomer content ratio of about 1:1,000 to 300,000, more preferably about 1:10,000 to 100,000, and most preferably about 1:50,000 to 100,000. For the avoidance of doubt, the above ratios are molar ratios.

[0123] The polymerization process can be carried out in the presence of a solvent, examples of which include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, etc.

[0124] The polymerization process can be carried out in a batch reactor or in a continuous reactor. reaction products The polymer product of the polymerization process of various embodiments of the present invention can be a polycarbonate or polyether carbonate polyol. For example, the polymer product can be a polyether carbonate polyol, such as poly(cyclohexene carbonate) (PCHC) or poly(propylene carbonate) (PPC).

[0125] It will be understood that the polymer product is a polycarbonate or polyether carbonate polyol. If the polymer product is a polyethercarbonate polyol, the polyethercarbonate polyol may contain n ether linkages and m carbonate linkages, where n and m are integers and m / (n+m) is greater than zero and less than 1. If the polymer product is a polycarbonate, the polycarbonate may contain n ether linkages and m carbonate linkages, where n and m are integers and m / (n+m) is equal to 1. Thus, as those skilled in the art will appreciate, when m / (n+m) is 1, the polymer product is a polycarbonate, and when m / (n+m) is greater than zero and less than 1, the polymer product is a polyethercarbonate polyol.

[0126] Typically, when the polymerization process is carried out in the presence of a DMC catalyst, as described above, the ratio of m / (n+m) is greater than 0 to less than 1. Typically, when the polymerization process of the present invention is carried out in the absence of a DMC catalyst, i.e., in the presence of a monometallic or bimetallic metal complex catalyst, as described above, m / (n+m) is 0.05 to 0.95.

[0127] For example, the polymerization process of the present invention can prepare polycarbonates having m / (n+m) values ​​equal to 1. As one skilled in the art will recognize, in this case the polymer product will have perfect alternation of epoxide and CO2 monomers.

[0128] For example, the polymerization process of the present invention can prepare polyether carbonate polyols having a wide range of m / (n+m) values, where m / (n+m) can be less than 0.05, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, greater than 0.95, or any range when prepared in a specific example. For example, m / (n+m) can be about 0.5 to 0.95, about 0.10 to 0.90, about 0.15 to 0.85, about 0.20 to about 0.80, or about 0.25 to about 0.75. In certain embodiments, when the polymer product is a polyethercarbonate polyol, the polyethercarbonate polyol can have a high proportion of carbonate linkages, for example, m / (n+m) can be greater than about 0.50, such as greater than about 0.55 to less than about 0.95, such as from about 0.65 to about 0.90, such as from about 0.75 to about 0.90. The polymerization process of the present invention can prepare polyethercarbonate polyols having high m / (n+m) ratios under mild conditions, for example, at pressures of 20 atmospheres or less, for example, 10 atmospheres or less.

[0129] The polyether carbonate polyol has the formula (IV):

[0130] [ka] where Z and W' depend on the identity of the chain transfer agent, R' and R" depend on the identity of the epoxide, and m and n define the amount of carbonate and polyether linkages in the polyethercarbonate polyol. It will be understood that the polyethercarbonate polyol must contain at least one carbonate linkage and at least one ether linkage. It will therefore be understood that the number of ether and carbonate linkages in the polyol (n+m) is greater than or equal to a. The sum of n+m must be greater than or equal to a.

[0131] It is understood that in the polymer of formula (IV), adjacent epoxide monomer units in the backbone can be head-to-tail, head-to-head, or tail-to-tail linked. It is also understood that formula (IV) does not require that the carbonate and ether linkages be in two separate "blocks" in each of the sections defined by "a," but instead, the carbonate and ether repeat units can be statistically distributed along the polymer backbone or arranged such that the carbonate and ether linkages are not in two separate blocks.

[0132] Thus, polyether polyols (e.g., polymers of formula (IV)) may be referred to as random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers. It should be understood that the weight percent of carbon dioxide incorporated into a polymer cannot be used definitively to determine the amount of carbonate linkages in the polymer backbone. For example, two polymers incorporating the same weight percent of carbon dioxide may have very different ratios of carbonate and ether linkages. This is because the "weight percent incorporation" of carbon dioxide does not take into account the length and nature of the chain transfer agent. For example, if one polymer (Mn, 2000 g / mol) is prepared using a chain transfer agent with a molar mass of 100 g / mol and another polymer (Mn, also 2000 g / mol) is prepared using a chain transfer agent with a molar mass of 500 g / mol, and both resulting polymers have the same m / n ratio, the weight percent of carbon dioxide in the polymers will differ due to the different proportions of the chain transfer agent's mass in the overall polymer molecular weight (Mn). For example, when m / (m+n) is 0.5, the two polyether carbonate polyols described have carbon dioxide contents of 26.1 wt % and 20.6 wt %, respectively.

[0133] As demonstrated above, the polymerization process of the present invention is capable of producing polyethercarbonate polyols having a wide range of carbonate to ether linkage ratios (e.g., m / (n+m) can be greater than zero to 1), which corresponds to incorporation of up to about 43% by weight of carbon dioxide when propylene oxide is used. Similarly, when m / (n+m) is 1, polycarbonates can be formed.

[0134] As previously mentioned, the polymerization process of the present invention can produce polyether carbonate polyols that are random copolymers, statistical copolymers, alternating copolymers, or periodic copolymers. Therefore, if the carbonate linkages are not present in a single block, this results in a polymer product with improved properties, such as thermal degradation resistance, compared to polycarbonate polyols. The polymers prepared by the process of the present invention are preferably random or statistical copolymers.

[0135] Each R' may be independently selected from: H, halogen, hydroxyl, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group. Preferably, R' is selected from H or an optionally substituted alkyl. Each R" may be independently selected from: H, halogen, hydroxyl, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group. Preferably, R" is selected from H or an optionally substituted alkyl.

[0136] R' and R" can together form a saturated, partially unsaturated, or unsaturated ring containing carbon and hydrogen atoms and, optionally, one or more heteroatoms (e.g., O, N, or S). For example, R' and R" can together form a 5- or 6-membered ring.

[0137] As indicated above, the nature of R' and R" depends on the epoxide used in the reaction. If the epoxide is cyclohexene oxide (CHO), R' and R" together form a 6-membered alkyl ring (e.g., a cyclohexyl ring). If the epoxide is ethylene oxide, R' and R" are both H. If the epoxide is propylene oxide, R' is H and R" is methyl (or R' is methyl and R" is H, depending on how the epoxide is incorporated into the polymer backbone). If the epoxide is butylene oxide, R' is H and R" is ethyl (or vice versa). If the epoxide is styrene oxide, R' can be hydrogen and R" can be phenyl (or vice versa).

[0138] It is also understood that each occurrence of R' and / or R'' can be different, for example, when a mixture of ethylene oxide and propylene oxide is used, R' can independently be hydrogen or methyl, and R'' can independently be hydrogen or methyl.

[0139] Thus, R' and R'' may be independently selected from hydrogen or alkyl, or R' and R'' may together form a cyclohexyl ring, preferably R' and R'' may be independently selected from hydrogen, methyl, or ethyl, or R' and R'' may together form a cyclohexyl ring.

[0140] W' corresponds to W described above, except that a bond is replaced by a transferable hydrogen atom. Therefore, the identity of each W' depends on the definition of W in the chain transfer agent. The variable a will similarly depend on the identity of the chain transfer agent. It will be understood that the value of a in formula (IV) will be the same as in formula (III). Thus, in formula (IV), a is an integer that is at least 2, preferably a is in the range of 2 to 8, and preferably a is in the range of 2 to 6.

[0141] The value of a will affect the shape of the polyether carbonate polyol reaction product. For example, when a is 2, the polyol of formula (IV) can have the following structure:

[0142] [ka] wherein Z, W', m, n, R' and R'' are as defined above for formula (IV).

[0143] For example, when a is 3, the polyether carbonate polyol of formula (IV) can have the formula:

[0144] [ka] wherein Z, W', m, n, R' and R'' are as defined above for formula (IV).

[0145] The polymer product can have any suitable number average molecular weight (Mn). n The number average molecular weight (Mn) of the polymer product can be measured by gel permeation chromatography (GPC), for example, using a Polymer Labs GPC-60 with a Polymer Labs Mixed B column and THF as the eluent at a flow rate of 1 mL / min. Narrow molecular weight distribution polystyrene standards can be used to calibrate the instrument.

[0146] Chain transfer agents are used to increase the molecular weight (M n For example, by adding a chain transfer agent to the polymerization process, it is possible to control the M of about 200 g / mol to about 20,000 g / mol, preferably less than about 10,000 g / mol. n It is possible to prepare polyether carbonate polyols and polyester polyols having the following structure:

[0147] The polymer product can have a polydispersity index (PDI) of less than about 2, preferably less than about 1.5, and even more preferably less than about 1.2. Advantageously, the molecular weight distribution can be controlled to produce multimodal or broad molecular weight distribution polymers by adding one or more chain transfer agents.

[0148] The polymer products are useful molecular building blocks in the preparation of various copolymer materials. The polymer products can be further reacted to produce, for example, polymeric reaction products such as polyureas or polyamines. These processes and reactions are known to those skilled in the art (see, for example, WO 2013 / 034750).

[0149] These polyether carbonate polyols or polyester polyols can be used in a variety of applications and products where polyols are traditionally used, including, but not limited to: adhesives (e.g., hot melt adhesives and structural adhesives), binders (e.g., binders for agricultural products, binders for foundry cores, and binders for rubber crumb), coatings (e.g., powder coatings, transportation coatings, e.g., automotive or marine coatings, fast cure coatings, self-healing coatings, topcoats and primers, varnishes, and coatings for marine applications, e.g., oil drilling rigs), elastomers (e.g., cast elastomers, elastomers for fibers / spandex, elastomers for footwear, elastomers for RIM / RRIM, elastomers for synthetic leather, industrial microcellular elastomers, and TPU elastomers), flexible foams (e.g., viscoelastic foams), rigid foams (e.g., rigid and flexible panels, cast rigid foams, aerosol gap-fill foams, spray foams, refrigeration foams, pour-in-place foams, and foam slabs), and sealants (e.g., polish sealants and construction sealants for consumer, industrial, and transportation (e.g., automotive) applications). The polyamines and polyureas can be processed using standard techniques known to those skilled in the art, such as, for example, foaming.

[0150] It will be understood that the polyether carbonate polyols and polyester polyols produced by the polymerization of the present invention or the polymers of the fourth aspect of the present invention may be mixed with other polyols before further use or reaction.

[0151] Polyether carbonate polyols have various advantageous properties compared to LDPE, including high strength, high toughness, high gloss, high transparency, low haze, high barrier properties to gases (e.g., oxygen and carbon dioxide) or water, flame retardancy, UV resistance, high durability, rigidity and stiffness, compatibility with plasticizers, a wide dimensional stability temperature range, biodegradability and biocompatibility, and high modulus and yield strength. Therefore, these polymers can be used in a variety of applications and products, including, for example, electronic components, building materials, data storage products, automotive and aircraft products, safety parts, medical applications, mobile phones, packaging (including bottles), and optical applications (e.g., safety glass, windshields, etc.).

[0152] acid The method of the present invention includes contacting the catalyst with an acid effective to deactivate the catalyst. Advantageously, contacting the catalyst with the acid stabilizes the polymer product. Without being bound by theory, it is believed that a complex forms between the catalyst and the anion of the acid (e.g., acetate anion when acetic acid is used as the acid), which may or may not be in equilibrium with the catalyst-polymer complex, depending on the acid used. Removal (or lack of addition) of carbon dioxide from the polymerization reaction can initiate degradation of the polymer chains due to the presence of the catalyst-polymer complex. Formation of the complex between the catalyst and the anion of the acid reduces the amount of catalyst-polymer complex present, advantageously reducing the amount of polymer degradation.

[0153] The processes of the first and sixth aspects of the invention include contacting the catalyst with an acid effective to deactivate the catalyst. The acid of the first and sixth aspects of the invention can be any suitable acid effective to deactivate the catalyst. Preferably, the acid of the first and sixth aspects of the invention is an acid containing an anion effective as an initiator for the polymerization process. Thus, the acid is an acid having an anion of OC(O)R X , OSO2R X , OSO(R X )2, an acid containing an anion selected from halide, nitrate or carbonate. X are independently hydrogen or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl. The anion is OC(O)R X More preferably, R X are independently hydrogen, optionally substituted aliphatic, haloaliphatic, aryl, heteroaryl, silyl, or alkylaryl. Examples of anions include: OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, Cl, Br, I, F. Most preferably, the acid comprises an anion selected from: OC(O)CH3, OC(O)CH2CH3, OC(O)(CH2)2CH3, OC(O)(CH2)3CH3, OC(O)(CH2)4CH3, OC(O)(CH2)5CH3, OC(O)(CH2)6CH3, OC(O)C(CH3)3, OC(O)C6H5, OC(O)CCCl3, and / or OC(O)CF3, most preferably OC(O)CH3.

[0154] The acid of the first and sixth aspects of the present invention is preferably selected from a sulfonic acid, a phosphoric acid, an organic acid, such as a carboxylic acid, or any combination of such acids. More preferably, the acid is a carboxylic acid. The carboxylic acid can be any suitable carboxylic acid. Preferably, the acid is a functionalized organic acid, which is an organic acid that, in addition to the acid group, has one or more other functional groups that are effective to form a stable bond or interaction with one or more of the metal centers of the catalyst. The one or more other functional groups can be any suitable group that is effective to form a stable bond with one or more of the metal centers of the catalyst. For example, the functional group can be —OH, —SO3H, —P(O)(OH), —N(R 9 )2 or -COOH, where R 9 can be independently selected from hydrogen, aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl groups. More preferably, the acid is a functionalized carboxylic acid containing one or more other functional groups effective to form a stable bond or interaction with one or more of the metal centers of the catalyst, as previously described. More preferably, the acid is a functionalized carboxylic acid containing one or more additional —COOH groups and one or more —OH groups, or a polyfunctional carboxylic acid containing two or more —COOH groups. Most preferably, the acid is a polyfunctional carboxylic acid, such as, for example, a dicarboxylic acid, a tricarboxylic acid, or salicylic acid.

[0155] Advantageously, these carboxylic acids can be used in the process of the present invention in amounts less than typically expected to deactivate the catalyst and / or stabilize the polymer product, e.g., in substantially stoichiometric amounts.

[0156] When the acid is a carboxylic acid, the carboxylic acid may be an optionally substituted C1-C 20 Alkyl or optionally substituted C5-C 20 Aryl carboxylic acids, preferably optionally substituted C1-C 10 Alkyl or optionally substituted C-C 12The carboxylic acid may be an arylcarboxylic acid, more preferably an optionally substituted C1-C6 alkyl or an optionally substituted C6 arylcarboxylic acid, more preferably an optionally substituted C1-C4 alkyl or an optionally substituted C6 arylcarboxylic acid. Most preferably, the carboxylic acid may be formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, stearic acid, pivalic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 1-adamantanecarboxylic acid, benzoic acid, and / or salicylic acid. For example, those skilled in the art will recognize that salicylic acid is also a functional carboxylic acid due to the fact that it has a -COOH group and an -OH group.

[0157] When the acid is a dicarboxylic acid, the dicarboxylic acid may be an optionally substituted C0-C 20 Alkyl or optionally substituted C-C 20 Aryl dicarboxylic acids, preferably optionally substituted C0-C 10 Alkyl or optionally substituted C-C 12 The dicarboxylic acid may be an aryl dicarboxylic acid, more preferably an optionally substituted C0-C6 alkyl or an optionally substituted C6 aryl dicarboxylic acid, more preferably an optionally substituted C0-C4 alkyl or an optionally substituted C6 aryl dicarboxylic acid. Most preferably, the dicarboxylic acid may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaconic acid, aspartic acid, tartaric acid, glutamic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenic acid, or 2,6-naphthalenedicarboxylic acid.

[0158] When the acid is a tricarboxylic acid, the tricarboxylic acid may be an optionally substituted C0-C 20 Alkyl or optionally substituted C-C 20 Aryl tricarboxylic acids, preferably optionally substituted C0-C 10 Alkyl or optionally substituted C-C 12Preferably, the dicarboxylic acid is an optionally substituted C0-C6 alkyl or optionally substituted C6 aryltricarboxylic acid, more preferably an optionally substituted C0-C4 alkyl or optionally substituted C6 aryltricarboxylic acid. Most preferably, the dicarboxylic acid is citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, or trimesic acid, and even more preferably, the dicarboxylic acid is citric acid, isocitric acid, aconitic acid, or propane-1,2,3-tricarboxylic acid.

[0159] The processes of the second, fourth, seventh and ninth aspects of the present invention comprise the step of contacting the catalyst with an acid containing an anion that is effective to initiate the polymerization process and that is effective to deactivate the catalyst.

[0160] Preferably, the acid of the second, fourth, seventh, and ninth aspects of the invention is selected from a sulfonic acid, a phosphoric acid, an organic acid, such as a carboxylic acid, or a combination of any such acids, provided that the acid is also effective to initiate the polymerization process. Acids containing anions that are effective to initiate the polymerization process and that are effective to deactivate the catalyst are as defined above in connection with the first and sixth aspects of the invention. Accordingly, it is most preferred that the acid comprises an anion selected from the following: OC(O)CH3, OC(O)CH2CH3, OC(O)(CH2)2CH3, OC(O)(CH2)3CH3, OC(O)(CH2)4CH3, OC(O)(CH2)5CH3, OC(O)(CH2)6CH3, OC(O)C(CH3)3, OC(O)C6H5, OC(O)CCCl3, and / or OC(O)CF3, most preferably OC(O)CH3.

[0161] The acid of the second, fourth, seventh and ninth aspects of the invention is preferably an organic acid, such as a carboxylic acid. Suitable carboxylic acids are as defined above in relation to the first and third aspects of the invention.

[0162] The processes of the third, fifth, eighth, and tenth aspects of the present invention include contacting the catalyst with a carboxylic acid effective to deactivate the catalyst. Suitable carboxylic acids are as defined above in connection with the first and sixth aspects of the present invention. Preferably, the carboxylic acid is effective to initiate the polymerization process and is effective to deactivate the catalyst. Accordingly, it is most preferred that the acid contains an anion selected from the following: OC(O)CH3, OC(O)CH2CH3, OC(O)(CH2)2CH3, OC(O)(CH2)3CH3, OC(O)(CH2)4CH3, OC(O)(CH2)5CH3, OC(O)(CH2)6CH3, OC(O)C(CH3)3, OC(O)C6H5, OC(O)CCCl3, and / or OC(O)CF3, most preferably OC(O)CH3.

[0163] The acids of the various embodiments of the present invention preferably have a pKa of at least 2.5, more preferably at least 3, and most preferably at least 4. For the avoidance of doubt, pKas referred to herein refer to pKas measured in dilute aqueous solutions at 25°C, unless otherwise specified, where for the purposes of the present invention, the pKas may be measured by any suitable method known to those skilled in the art.

[0164] In the fourth, fifth, ninth, and tenth aspects of the present invention, and preferably in the first, second, third, sixth, seventh, and / or eighth aspects of the present invention, the molar ratio of acid to catalyst for the deactivation reaction is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction. Preferably, the molar ratio of acid to catalyst is 18:1 or less, 16:1 or less, 14:1 or less, 12:1 or less, 10:1 or less, 5:1 or less, 4:1 or less, 3:1 or less, or 2:1 or less of the molar ratio of acid to catalyst for the reaction. More preferably, the molar ratio of acid to catalyst is 10:1 or less of the molar ratio of acid to catalyst for the reaction. Even more preferably, the molar ratio of acid to catalyst is 5:1 or less of the molar ratio of acid to catalyst for the reaction. Most preferably, the molar ratio of acid to catalyst is 2:1 to 1:1 of the molar ratio of acid to catalyst for the reaction.

[0165] For the avoidance of doubt, as used herein, the molar ratio of acid to catalyst for a reaction and like terms refer to the stoichiometric ratio of acid to catalyst for a reaction, which reaction can be represented by the following reaction scheme:

[0166] [ka] The number of polymer chains of a catalyst-O polymer complex will typically depend on the number of X groups, i.e., the number of initiating species present in the catalyst at the start of the polymerization reaction. This is because polymer chains will typically grow from each initiating species present in the catalyst at the start of the polymerization reaction. It will therefore be understood that the stoichiometric ratio of acid to catalyst for a reaction will typically depend on the number of X groups in the catalyst at the start of the polymerization reaction, and therefore the number of polymer chains present at the end of the polymerization reaction, and the acid used. For example, if the acid is monobasic, twice as much acid will be required to deactivate a metal complex catalyst with two X groups present at the start of the polymerization reaction compared to a metal complex catalyst with one X group present at the start of the polymerization reaction (due to the fact that the metal complex catalyst has two initiating species present at the start of the polymerization reaction, and therefore typically has two polymer chains present at the end of the polymerization reaction, compared to a metal complex catalyst with one initiating species present at the start of the polymerization reaction, and therefore typically has one polymer chain present at the end of the polymerization reaction). For example, if the catalyst is a metal complex catalyst in which two X groups are present at the start of the polymerization reaction, twice as much monobasic acid will be required to deactivate the catalyst as compared to a dibasic acid (due to the fact that a dibasic acid has two acid groups compared to a monobasic acid which has a single acid group). It will be understood that the reaction will either proceed to completion or remain at equilibrium. However, in either case, the stoichiometry of the reaction will be the same. However, as those skilled in the art will understand, polymer chains will not necessarily grow from all of the X groups, i.e., the initiating species present in the catalyst at the start of the polymerization reaction. In this case, the stoichiometric ratio of acid to catalyst for the reaction will depend on the number of polymer chains present at the end of the polymerization reaction and the acid used.

[0167] Advantageously, the process of the present invention allows for the use of less organic acid than typically expected to deactivate the catalyst and / or stabilize the polymer product. For example, a substantially stoichiometric amount can be used. The ability to deactivate the catalyst with an organic acid is a further advantage. Advantageously, an acid containing an anion that is the initiating species for the polymerization process of the present invention, such as O(C)OR, is used. X It has surprisingly been found that the catalyst can be deactivated by contact with an anion-containing acid (eg, acetic acid).

[0168] The acid of the present process can be in any suitable form. For example, the acid can be in a solid and / or liquid state. In certain embodiments, the acid can be present on a solid support, such as an acidic ion exchange resin. The acid can be contacted with the catalyst in any suitable manner. For example, a solid and / or liquid acid can be added directly to the polymerization reaction medium. For example, if the acid is present on a solid, the solid can be added directly to the polymerization reaction mixture, or the polymerization reaction mixture can be passed over and / or through the solid.

[0169] Catalyst removal The processes of the sixth through tenth aspects of the present invention include removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation. The mixture containing the deactivated catalyst and polymer product (which will typically also include acid and / or other by-products added to the process to stop the catalyst) is referred to herein as the "crude polymer product."

[0170] When the acid used to deactivate the catalyst is present on a solid, the solid (having the acid thereon) can also function as a solid phase for the step of removing the deactivated catalyst from the polymer product. Thus, in certain embodiments, step (i), in which the catalyst is contacted with an acid effective to deactivate the catalyst, can be carried out simultaneously with step (ii), in which the deactivated catalyst and polymer product are contacted with a solid phase. Those skilled in the art will recognize that contact with the acid deactivates the catalyst, and that if the acid is present on a solid, the deactivated catalyst will also be in contact with the solid simultaneously with deactivation. Advantageously, when the acid used to deactivate the catalyst is present on a solid, the deactivation and removal steps can be carried out simultaneously.

[0171] The deactivated catalyst can be removed from the crude polymer product by contacting the deactivated catalyst and polymer product with a solid phase effective to remove the deactivated catalyst from the polymer product. The solid phase can be any suitable solid phase. Preferably, the solid phase is an inorganic solid phase or an ion exchange resin, more preferably an inorganic solid phase or an acidic ion exchange resin.

[0172] The inorganic solid phase can be any suitable inorganic solid phase. For example, the inorganic solid phase can be silica, alumina, zirconia, molecular sieves, zeolites, clays, or derivatives or combinations thereof. Preferably, the inorganic solid phase can be silica, magnesium silicate, or alumina. Preferably, the inorganic solid phase can be surface functionalized with functional groups effective to form stable bonds with one or more metal centers of the deactivated catalyst, such as hydroxyl, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphate, thiol, and / or amine functional groups. More preferably, the inorganic solid phase comprises sulfonic acid, sulfonate, carboxylic acid, and / or carboxylate functional groups, most preferably sulfonate or carboxylic acid functional groups.

[0173] The acidic ion exchange resin may be in any suitable form. For example, the acidic ion exchange resin may be a gel or a macroreticular resin. Preferably, the acidic ion exchange resin is a macroreticular resin. Preferably, the acidic ion exchange resin comprises a porous polymer-based resin. For example, the acidic ion exchange resin may comprise a resin in the form of polymer beads, such as a cross-linked polystyrene resin in the form of spherical beads.

[0174] Preferably, the acidic ion exchange resin is in the form of polymer beads ("free" polymer beads), which may optionally be in the form of a packed resin bed. When the acidic ion exchange resin is in the form of "free" polymer beads, the crude polymer product is typically contacted with the ion exchange resin by mixing the "free" polymer beads into the crude polymer product. When the acidic ion exchange resin is in the form of polymer beads in a packed resin bed, the crude polymer product is typically contacted with the ion exchange resin by passing a volume of crude polymer product through the packed resin bed.

[0175] The acidic ion exchange material can be either strongly acidic or weakly acidic. For example, the acidic ion exchange resin can be a strongly acidic resin, such as a phosphonic acid ion exchange resin or a sulfonic acid ion exchange resin. Preferably, the strongly acidic resin is a sulfonic acid ion exchange resin. Conversely, the acidic ion exchange resin can be a weakly acidic resin, such as an ion exchange resin containing -COOH functional groups. Preferably, the weakly acidic resin contains iminodiacetic acid groups, and more preferably, the weakly acidic resin is a polymethacrylic acid resin or an iminodiacetic acid chelating cation exchange resin containing -COOH functional groups.

[0176] Preferred acidic ion exchange resins include those sold under the trade name Amberlite®, such as Amberlite IRC 748, those sold under the trade name Amberlyst®, such as Amberlyst 15, and those sold under the trade name Dowex®, such as Dowex Marathon MSC.

[0177] The crude polymer product may be contacted with the solid phase for any suitable period of time. Preferably, the crude polymer product may be contacted with the solid phase for at least 1 minute, such as at least 10 minutes, for example at least 30 minutes, for example at least 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, 48 ​​hours, or 72 hours. For the avoidance of doubt, the length of time for which the crude polymer product is contacted with the solid phase corresponds to the residence time of the crude polymer product with the solid phase.

[0178] Those skilled in the art will recognize that when the crude polymer product is contacted with the solid phase, the deactivated catalyst typically becomes bound to the solid phase and is removed from the liquid phase containing the polymer product. Typically, after contacting the solid phase with the crude polymer product as described above, the solid phase is removed from the liquid phase. The solid phase can be removed from the liquid phase by any suitable method. For example, if the solid phase is in the form of polymer beads, it is preferred to remove the solid phase by filtration. For example, if the solid phase is in the form of a packed resin bed, the liquid phase can be removed from the solid phase by a suitable washing step. Suitable washing steps will be known to those skilled in the art.

[0179] Advantageously, it has been found that the use of an organic carboxylic acid and / or organic dicarboxylic acid to deactivate the catalyst in the process of the present invention allows for easier removal of the deactivated catalyst from the crude polymer product compared to, for example, the use of a sulfonic acid to deactivate the catalyst.

[0180] Alternatively, the deactivated catalyst can be removed from the polymer product by precipitation. The precipitation can be carried out in any suitable manner. For example, the deactivated catalyst can be precipitated from the crude polymer product by adding one or more precipitating agents, or can be precipitated automatically (i.e., without adding one or more precipitating agents). For example, the deactivated catalyst can be precipitated from the crude polymer product by adding one or more acids effective to precipitate the deactivated catalyst. The acid effective to precipitate the deactivated catalyst can be any suitable acid. The acid effective to precipitate the deactivated catalyst is preferably a carboxylic acid, more preferably a functional or polyfunctional carboxylic acid (i.e., a carboxylic acid having one or more additional functional groups, the additional functional groups being, for example, —OH, —SO3H, —P(O)(OH)2, —N(R 9 )2 or -COOH, where R 9 may be independently selected from hydrogen, aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl groups), most preferably a dicarboxylic acid or salicylic acid. The acid effective to precipitate the deactivated catalyst may be the same as or different from the acid effective to deactivate the catalyst. Alternatively, the crude polymer product may be allowed to stand for a suitable period of time to allow the deactivated catalyst to automatically precipitate from the crude polymer product. The crude polymer product may be allowed to stand for any suitable period of time. Preferably, the crude polymer product may be allowed to stand for at least 1 hour, for example, at least 2 hours, for example, at least 4 hours, for example, at least 6 hours, for example, at least 8 hours, for example, at least 12 hours, for example, at least 18 hours, for example, at least 24 hours.

[0181] In the various precipitation methods described above, heat may be applied. Heat may be applied for any suitable time. For example, heat may be applied for up to 1 minute, for example, up to 2 minutes, for example, up to 5 minutes, for example, up to 10 minutes, for example, up to 15 minutes, for example, up to 30 minutes, for example, up to 1 hour, for example, up to 2 hours, for example, up to 5 hours. Heat may be applied at any suitable temperature. For example, heat may be applied to a temperature of at least 30°C, for example, at least 40°C, for example, at least 50°C, for example, at least 60°C, for example, at least 70°C, for example, at least 80°C, for example, at least 90°C, for example, at least 100°C.

[0182] The precipitated deactivated catalyst can be removed from the crude polymer product by any suitable method, preferably by filtration or centrifugation, more preferably by filtration, optionally followed by contact with a further solid phase, wherein the further solid phase is as defined above.

[0183] Surprisingly and advantageously, the inventors have found that the use of organic carboxylic acids, functionalized carboxylic acids (including di- or tricarboxylic acids) to deactivate the catalyst in the process of the present invention means that the deactivated catalyst is particularly suitable for removal by precipitation. Without being bound by theory, it is hypothesized that these bulky and / or polyvalent organic acids bind to vacant metal sites on the catalyst, possibly as aggregates, reducing their solubility.

[0184] reactivation The processes of the sixth, seventh, eighth, ninth and tenth aspects of the present invention optionally include a step of reactivating the deactivated catalyst by contacting it with a suitable anion. Preferably, the processes of the sixth, seventh, eighth, ninth and tenth aspects of the present invention include a step of reactivating the deactivated catalyst by contacting it with a suitable anion. However, those skilled in the art will recognize that if the catalyst is removed from the crude polymer product in a substantially reactivated form, i.e., a form effective to catalyze the process of the present invention, no reactivation step is required.

[0185] When the deactivated catalyst is removed from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase, the anion is preferably capable of releasing the catalyst from the solid phase.

[0186] The anion can be any suitable anion. Preferably, the anion is derived from an acid. Preferably, the anion is derived from an acid selected from the following: nitric acid; sulfuric acid; organic acids, such as optionally substituted C 0~20 Alkyl carboxylic acids and optionally substituted C 6~20 aryl carboxylic acids; sulfonic acids such as methanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acids such as p-toluenesulfonic acid, t-butylsulfonic acid and 2-hydroxypropanesulfonic acid; perhalogen acids such as perchloric acid; halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; phosphonic acids such as benzenephosphonic acid; and acids derived from the interaction between a Lewis acid and a Bronsted acid; or metal salts of each of the above acids.

[0187] Preferably, the anion is derived from a carboxylic acid selected from: optionally substituted C 0~20 Alkyl carboxylic acid or optionally substituted C 6~20Aryl carboxylic acids, more preferably optionally substituted C 0~10 Alkyl carboxylic acid or optionally substituted C 6~12 Arylcarboxylic acids, more preferably optionally substituted C0-C6 alkylcarboxylic acids or optionally substituted C6 arylcarboxylic acids, more preferably optionally substituted C0-C4 alkylcarboxylic acids or optionally substituted C6 arylcarboxylic acids, the anions of which are most preferably derived from the following: acetic acid, oxalic acid, salicylic acid; metal salts of acetic acid, oxalic acid and / or salicylic acid, or combinations thereof.

[0188] The anion may preferably be derived from a functional carboxylic acid (as defined above), a metal salt of a functional carboxylic acid, or a combination thereof, more preferably a functional carboxylic acid.

[0189] Preferably, the anion can be derived from an acid having a pKa of at least 2.5, more preferably at least 3, and most preferably at least 4. More preferably, the anion can be derived from a carboxylic acid having a pKa of at least 2.5, more preferably at least 3, and most preferably at least 4. Most preferably, the anion can be derived from a monocarboxylic acid having a pKa of at least 2.5, more preferably at least 3, and most preferably at least 4.

[0190] Preferably, the anion is capable of functioning as an initiating species for the process of the present invention. Accordingly, the anion may be selected from: OC(O)R X , OSO2R X , OSO(R X )2, OR X , halide, nitrate, hydroxyl, carbonate, amide or optionally substituted aliphatic, heteroaliphatic (e.g., silyl), cycloaliphatic, heterocycloaliphatic, aryl or heteroaryl. R Xare independently hydrogen or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl, or heteroaryl. The anion is OC(O)R X OR X More preferably, R X are independently hydrogen, optionally substituted aliphatic, haloaliphatic, aryl, heteroaryl, silyl, or alkylaryl. Examples of anions include: OCOCH3, OCOCF3, OSO2C7H7, OSO(CH3)2, Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr)2, or N(SiMe3)2. Preferably, the anion is: OC(O)CH3, OC(O)CH2CH3, OC(O)(CH2)2CH3, OC(O)(CH2)3CH3, OC(O)(CH2)4CH3, OC(O)(CH2)5CH3, OC(O)(CH2)6CH3, OC(O)C(CH3)3, OC(O)C6H5, OC(O)CCCl3, and / or OC(O)CF3, more preferably OC(O)CH3.

[0191] More preferably, the anion may be selected from anions derived from monocarboxylic acids, such as monocarboxylic acids having a pKa of at least 2.5, more preferably at least 3, and most preferably at least 4, and / or from anions capable of functioning as initiating species for the process of the present invention.

[0192] Most preferably, the anion is acetic acid and / or a metal salt of acetic acid. Advantageously, if the anion can function as an initiating species for the process of the present invention, the reactivated catalyst can be directly used in a further polymer polymerization process. For example, if the anion is derived from acetic acid, the OC(O)CH anion of acetic acid can function as an initiating species in a further polymerization process, and as such, the reactivated catalyst can be directly used in said further polymerization process. Advantageously, this means that no further purification step is required, i.e., no further purification of the reactivated catalyst is required.

[0193] definition For the purposes of this invention, an aliphatic group is a hydrocarbon residue that may be linear or branched and may be fully saturated or contain one or more units of unsaturation, provided that it is not aromatic. The term "unsaturated" refers to a residue having one or more double and / or triple bonds. Thus, the term "aliphatic" is intended to encompass alkyl, alkenyl, or alkynyl groups (including their polyvalent equivalents, such as alkylene, alkenylene, and alkynylene), as well as combinations thereof. Aliphatic groups are preferably C 1~20 It is an aliphatic group, that is, an aliphatic group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. The aliphatic group is preferably C 1~15 Aliphatic, more preferably C 1~12 Aliphatic, more preferably C 1~10 Aliphatic, even more preferably C 1~8 Aliphatic, e.g., C 1~6 It is an aliphatic group.

[0194] The alkyl group is preferably "C 1~20"Alkyl group" means an alkyl group that is a straight or branched chain having from 1 to 20 carbon atoms. Thus, the alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, the alkyl group is C 1~15 Alkyl, preferably C 1~12 Alkyl, more preferably C 1~10 Alkyl, even more preferably C 1~8 Alkyl, even more preferably C 1~6 It is an alkyl group. 1~20 Examples of the "alkyl group" include the following: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, and 1,1-dimethylpropyl. group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, etc.

[0195] The alkenyl and alkynyl groups are preferably each 2~20 alkenyl" and "C 2~20 alkynyl," more preferably "C 2~15 alkenyl" and "C 2~15 alkynyl," and even more preferably "C 2~12 alkenyl" and "C 2~12 alkynyl," and even more preferably "C 2~10 alkenyl" and "C 2~10alkynyl," and even more preferably "C 2~8 alkenyl" and "C 2~8 alkynyl," most preferably "C 2~6 alkenyl" and "C 2~6 alkynyl group.

[0196] Alkylene is as defined above for alkyl, except that it is divalent. Similarly, alkenylene and alkynylene are defined as the divalent equivalents of alkenyl and alkynyl above.

[0197] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl, and heteroalkynyl) are aliphatic groups as described above, further comprising one or more heteroatoms. Thus, heteroaliphatic groups preferably contain 2 to 21 atoms, preferably 2 to 16 atoms, more preferably 2 to 13 atoms, more preferably 2 to 11 atoms, more preferably 2 to 9 atoms, and even more preferably 2 to 7 atoms, of which at least one atom is a carbon atom. Particularly preferred heteroatoms are selected from O, S, N, P, and Si. When a heteroaliphatic group has two or more heteroatoms, the heteroatoms can be the same or different.

[0198] Heteroalkylene is as defined above for heteroalkyl groups, except that it is divalent. Similarly, heteroalkenylene and heteroalkynylene are defined as the divalent equivalents of heteroalkenyl and heteroalkynyl, respectively. Alicyclic groups are saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic (including fused, bridged, and spiro-fused) ring structures having 3 to 20 carbon atoms, i.e., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Alicyclic groups preferably have 3 to 15, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8, and even more preferably 3 to 6 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl, and cycloalkynyl groups. It will be understood that an alicyclic group can include an aliphatic ring bearing one or more linking or non-linking alkyl substituents, for example, -CH2-cyclohexyl. 3~20 Illustrative examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0199] Heteroalicyclic groups are alicyclic groups as defined above which, in addition to carbon atoms, have one or more ring heteroatoms, preferably selected from O, S, N, P, and Si. Heteroalicyclic groups preferably contain 1 to 4 heteroatoms, which may be the same or different. Heteroalicyclic groups preferably contain 5 to 20 atoms, more preferably 5 to 14 atoms, and even more preferably 5 to 12 atoms.

[0200] The aryl group is a monocyclic or polycyclic ring structure having 5 to 20 carbon atoms. The aryl group is preferably a "C 6~12 "C is an aryl group" and is an aryl group composed of 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and includes monocyclic groups and fused ring groups such as bicyclic groups. 6~10Specific examples of the "aryl group" include a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an azulenyl group, and the like. Note that this also includes fused-ring aryl groups such as indane and tetrahydronaphthalene.

[0201] Heteroaryl groups are aryl groups having, in addition to carbon atoms, 1 to 4 ring heteroatoms, preferably selected from O, S, N, P, and Si. Heteroaryl groups preferably have 5 to 20, more preferably 5 to 14, ring atoms. Specific examples of heteroaryl groups include pyridine, imidazole, methylimidazole, and dimethylaminopyridine.

[0202] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxane, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazole, ox ... thiazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quionolidine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole and trithiane.

[0203] Arylene is as defined above for aryl groups, except that it is divalent. Similarly, heteroarylene is defined as the divalent equivalent of heteroaryl, and cycloalkylene is defined as the divalent equivalent of alicyclic and heteroalicyclic groups above.

[0204] The term "halide" or "halogen" is used interchangeably and as used herein means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., preferably a fluorine atom, a bromine atom, or a chlorine atom, more preferably a fluorine atom.

[0205] The haloalkyl group is preferably "C 1~20 haloalkyl group," more preferably "C 1~15 haloalkyl group," more preferably "C 1~12 haloalkyl group," more preferably "C 1~10 haloalkyl group," and even more preferably "C 1~8 haloalkyl group," and even more preferably "C 1~6 haloalkyl group" and substituted with at least one halogen atom, preferably 1, 2 or 3 halogen atoms, each of which is C 1~20 Alkyl, C 1~15 Alkyl, C 1~12 Alkyl, C 1~10 Alkyl, C 1~8 Alkyl or C 1~6 It is an alkyl group. 1~20 Specific examples of the "haloalkyl group" include the following: 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.

[0206] The alkoxy group is preferably "C 1~20 alkoxy group”, more preferably “C 1~15 alkoxy group”, more preferably “C 1~12 alkoxy group”, more preferably “C 1~10 alkoxy group”, and even more preferably “C 1~8alkoxy group”, and even more preferably “C 1~6 C is an alkoxy group, each of which is 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. 1~20 Specific examples of the "alkoxy group" include the following: methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, and n-hexadecyloxy group. , n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2-methylbutoxy group, 1-ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, and the like.

[0207] The aryloxy group is preferably "C 5~20 aryloxy group”, more preferably “C 6~12 aryloxy group," and even more preferably "C 6~10 aryloxy group" and each of which is defined as C 5~20 Aryl, C 6~12 Aryl or C 6~10 It is an oxy group bonded to an aryl group.

[0208] The alkylthio group is preferably "C 1~20 alkylthio group," more preferably "C 1~15 alkylthio group," more preferably "C 1~12 alkylthio group," more preferably "C 1~10 alkylthio group," and even more preferably "C 1~8 alkylthio group," and even more preferably "C 1~6 alkylthio group" and each of which 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 A thio (-S-) group is bonded to an alkyl group. The alkylthio group used as a substituent as defined herein can be bonded either through a carbon atom of the alkyl group as defined above or through the sulfur atom of the thio group. The arylthio group is preferably bonded through the "C 5~20 arylthio group”, more preferably “C 6~12 arylthio group,” and even more preferably “C 6~10 arylthio group" and each of which 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.

[0209] The alkylaryl group is preferably "C 6~12 Aryl C 1~20 alkyl group”, more preferably “C 6~12 Aryl C 1~16 alkyl group,” and even more preferably, “C 6~12 Aryl C 1~6 The alkylaryl group is an "alkyl group" and an aryl group, as defined above, attached at various positions to the alkyl group, as defined above. The point of attachment of the alkylaryl group to the molecule can be through the alkyl position, and thus preferably the alkylaryl group is -CH2-Ph or -CH2CH2-Ph. The alkylaryl group can also be referred to as an "aralkyl."

[0210] The silyl ether group is preferably a group OSi(R 7 )3, where each R 7 are independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. In certain embodiments, each R 7 may independently be unsubstituted aliphatic, alicyclic, or aryl. Preferably, each R 7 is an alkyl group selected from optionally substituted phenyl or optionally substituted methyl, ethyl, propyl, or butyl (e.g., n-butyl or tert-butyl (tBu)). Examples of silyl ether groups include: OSi(CH), OSi(C,H), OSi(C,H), OSi(CH),C(CH), OSi(tBu), and OSi(C,H)C(CH).

[0211] A nitrile group (also called a cyano group) is the group CN. The imine group is the group -CR 8 NR 8 , preferably the group —CHNR 8 where R 8 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 8 R is an unsubstituted aliphatic, alicyclic, or aryl. 8 is preferably an alkyl group selected from methyl, ethyl or propyl.

[0212] The amide group is preferably —NR 9 C(O)R 9 or -C(O)-NR 9 (R 9 ), where R 9 can be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. In certain embodiments, R 9 R is an unsubstituted aliphatic, alicyclic, or aryl. 9is preferably hydrogen, methyl, ethyl, propyl or phenyl. The amide group may be terminated by hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups.

[0213] The ester group is preferably —OC(O)R 10 or -C(O)OR 10 where R 10 can be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. In certain embodiments, R 10 R is an unsubstituted aliphatic, alicyclic, or aryl. 10 is preferably hydrogen, methyl, ethyl, propyl or phenyl. The ester group may be terminated by hydrogen, aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl or heteroaryl groups.

[0214] The acetylide group has a triple bond -C≡CR 11 and preferably, where R 11 may be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. For purposes of the present invention, R 11 When R is alkyl, the triple bond can be anywhere in the alkyl chain. 11 R is an unsubstituted aliphatic, alicyclic, or aryl. 11 is preferably methyl, ethyl, propyl or phenyl.

[0215] The amino group is preferably -NH2, -NHR 12 or -N(R 12 )2, where R 12 may be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, silyl, aryl, or heteroaryl group as defined above. 12 )2, then each R 12 It will be understood that the groups can be the same or different. In certain embodiments, each R19 R is independently an unsubstituted aliphatic, alicyclic, silyl, or aryl. 12 is preferably methyl, ethyl, propyl, butyl, Si(CH3)3 or phenyl.

[0216] The ether group is preferably -OR 15 or -R 16 OR 17 where R 15 , R 16 and R 17 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. In certain embodiments, R 15 , R 16 and R 17 R is an unsubstituted aliphatic, alicyclic, or aryl. 15 , R 16 and R 17 are preferably methyl, ethyl, propyl or phenyl, respectively. The ether group may be terminated by hydrogen, aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl or heteroaryl groups.

[0217] base R 13 , R 14 , R 18 , R 19 , R 20 and R 21 can be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. 13 , R 14 , R 18 , R 19 , R 20 and R 21 R is an unsubstituted aliphatic, alicyclic, or aryl. 13 , R 14 , R 18 , R 19 , R 20 and R 21 is preferably hydrogen, methyl, ethyl, propyl or phenyl.

[0218] The sulfoxide is preferably —S(O)R 22 and the sulfonyl group is preferably —S(O)R 22 where R 22 can be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. In certain embodiments, R 22 R is an unsubstituted aliphatic, alicyclic, or aryl. 22 is preferably hydrogen, methyl, ethyl, propyl or phenyl.

[0219] The sulfinate group is preferably -OSOR 23 where R 23 may be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. 23 R is an unsubstituted aliphatic, alicyclic, or aryl. 23 is preferably hydrogen, methyl, ethyl, propyl or phenyl.

[0220] As used herein, the term “phosphonium” refers to a group of the formula P(R 24 )4 + , typically pH 4 + where R 24 can be hydrogen, an aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, or heteroaryl group as defined above. 24 R is an unsubstituted aliphatic, alicyclic, or aryl. 24 is preferably hydrogen, methyl, ethyl, propyl or phenyl.

[0221] The silyl group is preferably the group -Si(R 25 )3, where each R 25 are independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group as defined above. In certain embodiments, each R 25are independently unsubstituted aliphatic, alicyclic, or aryl. 25 is preferably an alkyl group selected from methyl, ethyl or propyl.

[0222] Any of the aliphatic (including alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene), heteroaliphatic (including heteroalkyl, heteroalkenyl, heteroalkynyl, heteroalkylene, heteroalkenylene, and heteroalkynylene), alicyclic, cycloalkylene, heteroalicyclic, aryl, arylene, heteroaryl, heteroarylene haloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylaryl, silyl, silyl ether, ester, sulfoxide, sulfonyl, imine, acetylide, amino, sulfonate, or amido groups mentioned anywhere above, particularly if referred to above as "optionally substituted," Optionally substituted with halogen, hydroxy, nitro, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, sulfonate, or with an optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl group (e.g., optionally substituted with halogen, hydroxy, nitro, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, sulfonate, or acetylide).

[0223] When the phrase "optionally substituted" is used at the beginning of a list of chemical species, it means that all chemical species in the list that can be substituted can be optionally substituted, not that only the first chemical species in the list can be optionally substituted. The term "optionally substituted," as used herein, means unsubstituted or substituted with a suitable group. Suitable groups will be known to those skilled in the art. Generally, such groups will not significantly adversely affect the function of the substituted group or the larger residue to which the substituted group is attached. In some cases, those skilled in the art will expect the substituent to improve the function of the substituted group.

[0224] All features contained herein may be combined with all of the above aspects in any combination. Embodiments of the present invention will now be described with reference to the following non-limiting examples. [Example]

[0225] catalyst Catalyst 1 and catalyst 2 used in the examples are as follows.

[0226] [ka] Example 1: Stabilization of Mn2000 PPC Diol with Varying Acids Five different aliquots of approximately 70-80 g each were withdrawn from 600 g of crude reactor product containing approximately 78 wt. % polypropylene carbonate polyol (PCC polyol) with Mn of 2243 g / mol (GPC), 20 wt. % propylene oxide, and approximately 4.8 g of catalyst 1. The crude PCC polyol contained approximately 2.6 (mol) % cyclic carbonate. One aliquot was left untreated, while the other four aliquots were treated with various acids at 2.2 molar equivalents relative to the molar amount of catalyst present in each sample (1.1 equivalents per metal site on the catalyst). For these five samples, 1The samples were analyzed by H NMR and GPC initially and after 13 days, and the results are summarized in Table 1.

[0227] [Table 1] The data clearly show that after 13 days, the unacid-stabilized crude material deteriorated significantly, going from 2.6% to approximately 70% cyclic carbonate, while the molecular weight was halved and the dispersity increased significantly. Surprisingly, 2.2 equivalents of each of the acids tested (just 1.1 equivalents per metal center) were shown to effectively stabilize the PPC polyol.

[0228] Example 2: Stabilization of Mn1600 PPC diol with varying acids Example 1 was repeated, except that 30 g of the polymer mixture (60% PPC polyol reaction product with Mn of 1574 g / mol (containing 66% PPC and 34% cyclic carbonate), 40% propylene oxide, and 0.16 g of catalyst 2) was divided into approximately 4 g portions. One sample was left untouched, while the others received various acids at 2.5 molar equivalents relative to the molar amount of catalyst present in each sample (1.25 equivalents per metal site on the catalyst). After 3 days, the samples were analyzed and compared to the crude product. The results are shown in Table 2.

[0229] [Table 2] This indicates that the various acids stabilize the mixture similarly as selectivity and molecular weight remain substantially unchanged.

[0230] Example 3: Stabilization of Mn900 PPC diol with varying acids Example 1 was repeated except that the PPC polyol had an Mn of 922 g / mol and 5.9 mol% cyclic carbonate. Samples were drawn in 11 approximately 40 g aliquots. One sample was left intact, while the remaining samples had several different acids added to them in varying amounts relative to the catalyst. The results are shown in Table 3.

[0231] [Table 3] Surprisingly, polymer molecular weight and selectivity were shown to be substantially maintained even when substoichiometric amounts of acid per metal center (e.g., 1.2 equivalents of oxalic acid or pTSA) were used. Although catalyst 1, in its active form, features acetate initiating groups, the deactivation process appears to be independent of whether the acid's conjugate anion is a viable initiator for the polymerization reaction.

[0232] Example 4: Stabilization of Mn500 PPC Diol with Varying Acids 600 g of PPC polyol having 522 g / mol Mn and 15.1 mol % cyclic carbonate was stabilized with 5 equivalents of acetic acid relative to catalyst 1 (2.5 equivalents per metal site). The selectivity of the sample was measured over a 6-day period and found to be unchanged over this period. The results are shown in Table 4.

[0233] [Table 4] Example 5: Stabilization 600 g of polyether carbonate polyol containing 59% carbonate linkages (28.7 wt. % CO), 1395 g / mol Mn, 2 g of catalyst 1, and 0.3 g of DMC catalyst were stabilized with several different acids added at different amounts relative to the catalyst. After 6 days, the molecular weight and cyclic content were reevaluated. The results are shown in Table 5.

[0234] [Table 5] The various acids all showed comparable levels of stabilization, with no observed increase in cyclic carbonates, and all samples exhibited stabilized molecular weights. The samples stabilized with pTSA showed a very marginal decrease in molecular weight, likely due to the known degradation of polyethers by pTSA. This indicates that, as in polycarbonates, catalyst deactivation can be achieved satisfactorily in polyethercarbonate polyols and that acids containing initiator conjugated anions can be used satisfactorily to post-quench the catalyst.

[0235] Some samples were heated at 120° C. for 16 hours in the presence of deactivated Catalyst 1 to evaluate the extent to which the polyol was stabilized. The results are shown in Table 5a.

[0236] [Table 6] After heating the crude sample in the presence of deactivated catalyst at 120°C for 16 hours, the sample was found to be remarkably robust considering the catalyst was still present. Without being bound by theory, the extra degradation caused by pTSA is believed to be due to degradation of the polyether linkages by pTSA.

[0237] Example 6: Catalyst removal using a weakly acidic resin To 500 g of polycarbonate polyol with Mn of approximately 550 g / mol, stabilized with 5 equivalents of p-TSA, and containing approximately 4 g of catalyst 1 and 8 wt% cyclic carbonate, was added EtOAc (500 mL) and dried, acidified Amberlite IRC748 resin (functionalized with iminodiacetic acid, 300 g, acidified, dried).

[0238] The mixture was stirred overnight, then the resin was removed by filtration and washed with 2×200 mL of EtOAc, resulting in the isolation of a blue-colored resin and a colorless polyol / cyclic carbonate / EtOAc mixture with a metal (UV-Vis) content of less than 20 ppm in nearly quantitative yield.

[0239] Example 7: Catalyst removal using a strongly acidic resin To 500 g of polycarbonate polyol with Mn of approximately 550 g / mol, stabilized with 5 equivalents of p-TSA, and containing approximately 4 g of catalyst 1 and 8 wt% cyclic carbonate, was added EtOAc (500 mL) and dried, acidified Amberlyst 15 resin (functional, sulfonic acid, 300 g, pre-washed).

[0240] The mixture was stirred overnight, then the resin was removed by filtration and washed with 2×200 mL of EtOAc, resulting in the isolation of a blue-colored resin and a colorless polyol / cyclic carbonate / EtOAc mixture with a metal (UV-Vis) content of less than 20 ppm in nearly quantitative yield.

[0241] Example 8: Catalyst Removal Using Magnesium Silicate To 600 g of a polycarbonate polyol containing approximately 4 g of catalyst 2 and 9 wt. % cyclic carbonate, stabilized with 5 equivalents of p-TSA and having a Mn of approximately 2000 g / mol, was added 300 mL of EtOAc. A column was packed with Florisil (600 g, prewetted with EtOAc), and the polyol solution was added overhead. After thorough washing of the polyol mixture with EtOAc and drying, a colorless polyol / cyclic carbonate mixture (metal content less than 5 ppm by ICP-OES) was obtained in near quantitative yield.

[0242] Example 9: Catalyst Removal Using Alumina To 2 g of polycarbonate polyol, stabilized with 5 equivalents of p-TSA and containing approximately 0.01 g of catalyst 2 and 30 wt% cyclic carbonate, with Mn approximately 2000 g / mol, was added 2 mL of EtOAc. A column was packed with neutral or basic alumina (20 g, prewetted with EtOAc), and the polyol solution was added to the top of the column. After thorough washing of the polyol mixture with EtOAc and drying, a colorless polyol / cyclic carbonate mixture (metal content less than 5 ppm by ICP-OES) was obtained in nearly quantitative yield.

[0243] Example 10: Catalyst Removal Using Silica To 2 g of a polycarbonate polyol containing approximately 0.01 g of catalyst 2 and 30 wt. % cyclic carbonate, stabilized with 5 equivalents of p-TSA and having a Mn of approximately 2000 g / mol, was added 2 mL of DCM. A column was packed with silica (12 g, prewetted with DCM), and the polyol solution was added to the top of the column. After thorough washing of the polyol mixture with CHCl3 and drying, a colorless polyol / cyclic carbonate mixture (metal content less than 20 ppm by ICP-OES) was obtained in nearly quantitative yield.

[0244] Example 11: Catalyst Removal Using Polymer Beads Aliquots from the samples prepared in Example 1 were dissolved in a volume of ethyl acetate and stirred using a Dowex Marathon MSC for the times indicated in Table 7 below, after which the samples were filtered and the ethyl acetate removed under vacuum. The samples were analyzed for metal content using either ICP-OES or UV-Visible spectrophotometry. The results are shown in Table 7.

[0245] [Table 7] Surprisingly, it was found that samples quenched with carboxylic acids were easily removed from solution with Dowex resin. In contrast, samples quenched with pTSA required significantly more Dowex resin and time, yet still failed to remove most of the metal.

[0246] Example 12: Catalyst Removal by Precipitation and Filtration A second aliquot of the sample from Example 1 was allowed to stand overnight, at which point a green / blue precipitate was observable in the polyol. The polyol was filtered and analyzed for metal content by ICP-OES. The results are shown in Table 8.

[0247] [Table 8] It was found that using salicylic acid in a single precipitation step removed over 92% of the catalyst, while precipitation using oxalic acid removed over 85%. Both acids are polyfunctional. Therefore, without being bound by theory, it is theorized that multidentate anions can block metal vacancies on the catalyst or form aggregates, either of which reduces the solubility of the catalyst.

[0248] Example 13: Regeneration of Catalyst 1 (Method 1) To a bed of Amberlite IRC-748 beads (500 g, approximately 1.6 wt. % catalyst) contained in a filter was added 400 mL of EtOAc. The beads were allowed to soak for 5 minutes with occasional agitation in each portion, after which a vacuum was applied below the filter to drain the EtOAc filtrate. Glacial acetic acid (400 mL) was added to the beads and allowed to soak for 15 minutes before applying a vacuum to collect the blue filtrate. The filtrate was layered with 400 mL of EtOAc and 700 mL of water, which was centrifuged and combined in a separatory funnel. The organic layer was washed with excess water and reduced in vacuo to give Catalyst 1 (6.26 g). MS(ESI or APCI)767.3[M-2OAc+HCOO]+ and 781.3[M-OAc] + . Example 14: Regeneration of Catalyst 1 (Method 2) Purolite C106 (84 g / g of recovered catalyst) was added to the crude polymerization reaction mixture. The resulting suspension was stirred at 23 °C for 90 min. The mixture was filtered. The resin was dried on a sinter and then transferred to a clean glass jar. 30% formic acid in EtOAc (10 mL / g resin) was added to the resin and the suspension was stirred for 4 h. The mixture was filtered to collect the resin. The organics were dried over Na2SO4, filtered, MeOH was added to the mixture, and the solvent was evaporated under vacuum. This gave catalyst 1 as a solid (260 mg). MS(ESI or APCI)767.3[M+HCOO] + . Example 15: Regeneration of Catalyst 1 (Method 3) Purolite C106 (84 g / g of recovered catalyst) was added to the crude polymerization reaction mixture. The resulting suspension was stirred at 23°C for 3 hours. The mixture was filtered. The resin was dried on a sinter and then transferred to a clean glass jar. 1 L of acetic acid and 1 L of EtOH were added to the resin, and the suspension was stirred at 23°C for 2 hours. The mixture was filtered to remove the resin, and the solvent was removed in vacuo to give a blue suspension. The resulting suspension was filtered and washed with water (100 mL) to give Catalyst 1 as a solid (2.37 g). MS(ESI or APCI)767.3[M-2OAc+HCOO] + and 781.3[M-OAc] + Example 16: Copolymerization using recovered catalyst Dodecanediol (1.05 g, 5.2 mmol) was placed in a reactor and dried under vacuum at 100°C for 30 minutes. After cooling to room temperature, the reactor was pressurized with 0.2 bar of CO2 and the vacuum / CO2 cycle was repeated three times. The recovered catalyst (0.086 mmol) was placed in a Schlenk tube and dried under vacuum for 30 minutes. Propylene oxide (15 mL, 0.214 mol) was then added to the reactor via syringe under CO2. The reactor was heated to 75°C, pressurized with 20 bar of CO2, and heated to 75°C. The set temperature and pressure were maintained for 16 hours. The reactor was cooled to below 10°C and the pressure was gradually released. Immediately 1 H NMR and GPC were measured.

[0249] [Table 9] This data demonstrates that the recaptured catalyst is active to produce polypropylene carbonate polyol and can be recovered with activity approaching that of the fresh catalyst. Appendix 1 1. A method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, the method comprising the step of deactivating the catalyst by contacting the catalyst with an acid effective to deactivate the catalyst. Appendix 2 1. A method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising: (i) terminating the polymerization process by contacting the catalyst with an acid effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally, reactivating the deactivated catalyst by contacting the catalyst with an anion. Appendix 3 3. The method of claim 1 or 2, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction. Appendix 4 4. The method of claim 3, wherein the molar ratio of acid to catalyst in the deactivation step is 10:1 or less of the molar ratio of acid to catalyst for the deactivation reaction. Appendix 5 5. The method of any one of claims 1 to 4, wherein the acid contains an anion effective to initiate the polymerization process. Appendix 6 1. A method for terminating a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, comprising the step of deactivating said catalyst by contacting said catalyst with an acid containing an anion effective to initiate said polymerization process and effective to deactivate said catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction. Appendix 7 1. A method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a complex metal catalyst, comprising: (i) terminating the polymerization process by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the reaction; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or by precipitation; and (iii) optionally, reactivating the deactivated catalyst by contacting the catalyst with an anion. Appendix 8 8. The method of claim 7, wherein the molar ratio of acid to catalyst in the quenching step is 10:1 or less of the molar ratio of acid to catalyst for the reaction. Appendix 9 10. The method according to any one of claims 1 to 9, wherein the acid is a carboxylic acid. Appendix 10 10. The method of claim 9, wherein the acid is a functionalized carboxylic acid and, in addition to an acid group, contains one or more other functional groups effective to form stable bonds or interactions with one or more metal centers of the catalyst. Appendix 11 The functional groups are -OH, -SO 3 H, -P(O)(OH) 2 , -N(R 9 ) 2 or -COOH, and R 9 are independently selected from hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. Appendix 12 12. The method of claim 11, wherein the functionalized carboxylic acid is a dicarboxylic acid, a tricarboxylic acid, or a hydroxycarboxylic acid. Appendix 13 The acid is OC(O)CH 3 , OC(O)CH 2 CH 3 , OC(O)(CH 2 ) 2 CH 3 , OC(O)(CH 2 ) 3 CH 3 , OC(O)(CH 2 ) 4 CH 3 , OC(O)(CH 2 ) 5 CH 3 , OC(O)(CH 2 ) 6 CH 3 , OC(O)C(CH 3 ) 3 , O.C.(O.)C 6 H 5 , OC(O)CCCl 3 and / or OC(O)CF 3 anions selected from, most preferably OC(O)CH 3 13. The method of any one of appendix 1 or 12, comprising: Appendix 14 14. The method of any one of claims 1 to 13, wherein the acid has a pKa of at least 2.5. Appendix 15 The metal complex catalyst is represented by formula (I) or formula (II): JPEG0007811440000034.jpg221170 It is of In the formula, R1 and R 2 are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR 13 R 14 , amine, ether-OR 15 、-R 16 OR 17 , ester group -OC(O)R 10 or -C(O)OR 10 , amide group -NR 9 C(O)R 9 or -C(O)-NR 9 (R 9 ), -COOH, -C(O)R 15 , -OP(O)(OR 18 )(OR 19 ), -P(O)R 20 R 21 , -P(O)(OR)(OR), -OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 aryl, heteroaryl, alicyclic, or heteroalicyclic; R 4 are independently selected from H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R 9 、R 10 、R 13 、R 14 、R 18 、R 19 、R 20 and R 21 are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E 1 is C and E 2 is O, S or NH, or E 1 is N and E 2 is O, E 3 is N, NR 5 , O or S, and E 3 If is N, then JPEG0007811440000035.jpg7170 teeth, JPEG0007811440000036.jpg7170 and E 3 NR 5 , O or S, JPEG0007811440000037.jpg7170 teeth, JPEG0007811440000038.jpg7170 and R 5 are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 10 , -alkylnitrile or alkylaryl; X, if present, is independently 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, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R X are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y 1 and Y 2 independently, if present, a metal M 2 is a neutral or anionic donor group capable of donating a lone pair of electrons to M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III), or Ti(IV). Appendix 16 16. The method according to any one of appendices 2 to 5 or 7 to 15, wherein the solid phase is an inorganic solid phase or an ion exchange resin. Appendix 17 17. The method of claim 16, wherein the ion exchange resin is an acidic ion exchange resin. Appendix 18 Item 16. The method of any one of items 2-5 or 7-15, wherein the deactivated catalyst is precipitated or spontaneously precipitated from the crude polymer product by addition of one or more precipitating agents. Appendix 19 19. The method of any one of Appendices 2 to 5 or 7 to 18, wherein the anion is derived from an acid. Appendix 20 20. The method of claim 19, wherein the anion is derived from one or more carboxylic acids. Appendix 21 17. The method of claim 16, wherein the anion is derived from a functionalized carboxylic acid, a metal salt of a functional carboxylic acid, or a combination thereof, wherein the functionalized carboxylic acid comprises, in addition to the acid, one or more other functional groups effective to form a stable bond or interaction with one or more of the metal centers of the catalyst, and the metal salt of the functional carboxylic acid comprises one or more other functional groups effective to form a stable bond or interaction with one or more of the metal centers of the catalyst. Appendix 22 The functional groups are -OH, -SO 3 H, -P(O)(OH) 2 , -N(R 9 ) 2 or -COOH, and R 9 are independently selected from hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group. Appendix 23 23. The method of claim 22, wherein the functionalized carboxylic acid is a dicarboxylic acid, a tricarboxylic acid, or a hydroxycarboxylic acid. Appendix 24 24. The method of any one of claims 19 to 23, wherein the anion is derived from an acid having a pKa of at least 2.5. Appendix 25 25. The method of any one of claims 1 to 5 or 7 to 24, wherein the anion is capable of functioning as an initiator for the polymerization process. Appendix 26 The anion is OC(O)CH 3 , OC(O)CH 2 CH 3 , OC(O)(CH 2 ) 2 CH 3 , OC(O)(CH 2 ) 3 CH 3 , OC(O)(CH 2 ) 4 CH 3 , OC(O)(CH 2 ) 5 CH 3 , OC(O)(CH 2 ) 6 CH 3 , OC(O)C(CH 3 ) 3 , O.C.(O.)C 6 H 5 , OC(O)CCCl 3 and / or OC(O)CF 3 and most preferably OC(O)CH 3 26. The method according to claim 25, Appendix 27 27. The method of any one of claims 1 to 26, wherein the acid does not include trimesic acid.

Claims

1. 1. A method for terminating a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising the step of deactivating the catalyst by contacting the catalyst with an acid effective to deactivate the catalyst, wherein the metal complex catalyst is represented by Formula (I) or Formula (II): It is of In the formula, R １ and R ２ are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR １３ R １４ , amine, ether -OR １５ , -R １６ OR １７ , an ester group —OC(O)R １０ Or -C(O)OR １０ , an amide group -NR ９ C(O)R ９ or —C(O)—NR ９ (R ９ ), -COOH, -C(O)R １５ , -OP(O)(OR １８ ) (OR １９ ), -P(O)R ２０ R ２１ , —P(O)(OR)(OR), —OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 interrupted by aryls, heteroaryls, alicyclics, or heteroalicyclics; R ４ are independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R ９ , R １０ , R １３ , R １４ , R １８ , R １９ , R ２０ and R ２１ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E １ is C and E ２ is O, S or NH, or E １ is N and E ２ is O, E ３ is N, NR ５ , O or S, and E ３ If is N, then teeth, and E ３ NR ５ , O or S, teeth, and R ５ are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １０ , -alkylnitrile or alkylaryl, X, if present, is independently 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, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R Ｘ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y １ and Y ２ are, if present, independently a metal M ２ is a neutral or anionic donor group capable of donating a lone pair of electrons to M １ and M ２ are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV); A process wherein the acid used to deactivate the catalyst is present on a solid support and / or the acid is selected from a sulfonic acid, a phosphoric acid, a carboxylic acid, or a combination thereof.

2. 1. A method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising: (i) terminating the polymerization process by contacting the catalyst with an acid effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or precipitating the catalyst; The metal complex catalyst is represented by formula (I) or formula (II): It is of In the formula, R １ and R ２ are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR １３ R １４ , amine, ether -OR １５ , -R １６ OR １７ , an ester group —OC(O)R １０ Or -C(O)OR １０ , an amide group -NR ９ C(O)R ９ or —C(O)—NR ９ (R ９ ), -COOH, -C(O)R １５ , -OP(O)(OR １８ ) (OR １９ ), -P(O)R ２０ R ２１ , —P(O)(OR)(OR), —OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 interrupted by aryls, heteroaryls, alicyclics, or heteroalicyclics; R ４ are independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R ９ , R １０ , R １３ , R １４ , R １８ , R １９ , R ２０ and R ２１ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E １ is C and E ２ is O, S or NH, or E １ is N and E ２ is O, E ３ is N, NR ５ , O or S, and E ３ If is N, then teeth, and E ３ NR ５ , O or S, teeth, and R ５ are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １０ , -alkylnitrile or alkylaryl, X, if present, is independently 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, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R Ｘ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y １ and Y ２ are, if present, independently a metal M ２ is a neutral or anionic donor group capable of donating a lone pair of electrons to M １ and M ２ are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV); A process wherein the acid used to deactivate the catalyst is present on a solid support and / or the acid is selected from a sulfonic acid, a phosphoric acid, a carboxylic acid, or a combination thereof.

3. 3. The process of claim 1 or 2, wherein the molar ratio of acid to catalyst in the quenching step is 20:1 or less of the molar ratio of acid to catalyst for the quenching reaction, and / or the acid contains an anion effective to initiate the polymerization process.

4. 1. A method for terminating a polymerization process involving the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising the step of deactivating said catalyst by contacting said catalyst with an acid containing an anion effective to initiate said polymerization process and effective to deactivate said catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less than the molar ratio of acid to catalyst for the deactivation reaction; The bimetallic metal complex catalyst is represented by formula (I) or formula (II): It is of wherein R 1 and R 2 are independently hydrogen, halide, nitro group, nitrile group, imine group, —NCR 13 R 14 , amine, ether —OR 15 , —R 16 OR 17 , ester group —OC(O)R 10 or —C(O)OR 10 , amide group —NR 9 C(O)R 9 or —C(O)—NR 9 (R 9 ), —COOH, —C(O)R 15 , —OP(O)(OR 18 )(OR 19 ), —P(O)R 20 R 21 , —P(O)(OR)(OR), —OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; R 3 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 can be interrupted by aryls, heteroaryls, alicyclics, or heteroalicyclics; R 4 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R 9 , R 10 , R 13 , R 14 , R 18 , R 19 , R 20 and R 21 are independently selected from hydrogen or an aliphatic, heteroaliphatic, cycloaliphatic, heteroalicyclic, aryl or heteroaryl group; E 1 is C and E 2 is O, S or NH, or E 1 is N and E 2 is O; E 3 is N, NR 5 , O or S, and when E 3 is N, teeth, and when E 3 is NR 5 , O or S, teeth, and R 5 is independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 10 , -alkylnitrile, or alkylaryl; X, if present, is independently selected from OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, S(O)Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R x is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y 1 and Y 2 , if present, are independently neutral or anionic donor groups capable of donating a lone pair of electrons to the metal M 2 ; M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV); A process wherein the acid used to deactivate the catalyst is present on a solid support and / or the acid is selected from a sulfonic acid, a phosphoric acid, a carboxylic acid, or a combination thereof.

5. 1. A method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising: (i) terminating the polymerization process by contacting the catalyst with an acid containing an anion effective to initiate the polymerization process and effective to deactivate the catalyst, wherein the molar ratio of acid to catalyst in the deactivation step is 20:1 or less of the molar ratio of acid to catalyst for the deactivation reaction; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or precipitating the catalyst; The metal complex catalyst is represented by formula (I) or formula (II): It is of In the formula, R １ and R ２ are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR １３ R １４ , amine, ether -OR １５ , -R １６ OR １７ , an ester group —OC(O)R １０ Or -C(O)OR １０ , an amide group -NR ９ C(O)R ９ or —C(O)—NR ９ (R ９ ), -COOH, -C(O)R １５ , -OP(O)(OR １８ ) (OR １９ ), -P(O)R ２０ R ２１ , —P(O)(OR)(OR), —OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 interrupted by aryls, heteroaryls, alicyclics, or heteroalicyclics; R ４ are independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R ９ , R １０ , R １３ , R １４ , R １８ , R １９ , R ２０ and R ２１ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E １ is C and E ２ is O, S or NH, or E １ is N and E ２ is O, E ３ is N, NR ５ , O or S, and E ３ If is N, then teeth, and E ３ NR ５ , O or S, teeth, and R ５ are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １０ , -alkylnitrile or alkylaryl, X, if present, is independently 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, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R Ｘ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y １ and Y ２ are, if present, independently a metal M ２ is a neutral or anionic donor group capable of donating a lone pair of electrons to M １ and M ２ are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV); A process wherein the acid used to deactivate the catalyst is present on a solid support and / or the acid is selected from a sulfonic acid, a phosphoric acid, a carboxylic acid, or a combination thereof.

6. The method of any one of claims 1 to 5, wherein the acid is a carboxylic acid.

7. 7. The method of claim 6, wherein the acid is a functionalized carboxylic acid that, in addition to an acid group, contains one or more other functional groups effective to form stable bonds or interactions with one or more metal centers of the catalyst.

8. The acid is OC(O)CH ３ , OC(O)CH ２ CH ３ , OC(O)(CH ２ ) ２ CH ３ , OC(O)(CH ２ ) ３ CH ３ , OC(O)(CH ２ ) ４ CH ３ , OC(O)(CH ２ ) ５ CH ３ , OC(O)(CH ２ ) ６ CH ３ ,OC(O)C(CH ３ ) ３ , O.C.(O.C.) ６ H ５ ,OC(O)CCCl ３ and / or OC(O)CF ３ anions selected from, most preferably OC(O)CH ３ 8. The method of claim 1, comprising:

9. 9. The method of any one of claims 2 or 5 to 8, wherein the solid phase is an inorganic solid phase or an ion exchange resin.

10. 10. The method of claim 9, wherein the ion exchange resin is an acidic ion exchange resin.

11. 9. The method of any one of claims 2 or 5 to 8, wherein the deactivated catalyst is precipitated or spontaneously precipitated from the crude polymer product by addition of one or more precipitating agents.

12. 12. The method of any one of claims 2 or 5 to 11, wherein the anion is derived from an acid.

13. 11. The method of claim 9 or 10, wherein the anion is derived from a functionalized carboxylic acid, a metal salt of a functional carboxylic acid, or a combination thereof, wherein the functionalized carboxylic acid comprises, in addition to the acid, one or more other functional groups effective to form a stable bond or interaction with one or more of the metal centers of the catalyst, and the metal salt of the functional carboxylic acid comprises one or more other functional groups effective to form a stable bond or interaction with one or more of the metal centers of the catalyst.

14. 14. The method of claim 12 or 13, wherein the anion is derived from an acid having a pKa of at least 2.

5.

15. 15. The method of any one of claims 1, 2 or 5-14, wherein the anion is capable of functioning as an initiator for the polymerization process.

16. The method of any one of claims 1 to 15, wherein the acid does not comprise trimesic acid.

17. The method of claim 1, wherein the acid used to deactivate the catalyst is present on a solid support, and the solid support serves as a solid phase for the step of removing the deactivated catalyst from the polymer product.

18. 1. A method for purifying a polymer product formed from a polymerization process comprising the reaction of carbon dioxide with an epoxide in the presence of a bimetallic metal complex catalyst, comprising: (i) terminating the polymerization process by contacting the catalyst with an acid effective to deactivate the catalyst; (ii) removing the deactivated catalyst from the polymer product by contacting the deactivated catalyst and polymer product with a solid phase and / or precipitating the catalyst, wherein the acid used to deactivate the catalyst is present on a solid support, and the solid support serves as the solid phase for the step of removing the deactivated catalyst from the polymer product; The bimetallic metal complex catalyst is represented by formula (I) or formula (II): It is of In the formula, R １ and R ２ are independently hydrogen, halide, nitro group, nitrile group, imine group, -NCR １３ R １４ , amine, ether -OR １５ , -R １６ OR １７ , an ester group —OC(O)R １０ Or -C(O)OR １０ , an amide group -NR ９ C(O)R ９ or —C(O)—NR ９ (R ９ ), -COOH, -C(O)R １５ , -OP(O)(OR １８ ) (OR １９ ), -P(O)R ２０ R ２１ , —P(O)(OR)(OR), —OP(O)R(OR), a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group, or an acetylide group, or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic, or heteroalicyclic group; 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 interrupted by aryls, heteroaryls, alicyclics, or heteroalicyclics; R ４ are independently selected from H or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, or alkylaryl; R ９ , R １０ , R １３ , R １４ , R １８ , R １９ , R ２０ and R ２１ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; E １ is C and E ２ is O, S or NH, or E １ is N and E ２ is O, E ３ is N, NR ５ , O or S, and E ３ If is N, then teeth, and E ３ NR ５ , O or S, teeth, and R ５ are independently H or optionally substituted aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR １０ , -alkylnitrile or alkylaryl, X, if present, is independently 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, nitro, amido, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl; m and n are independently integers selected from the range of 0 to 3, such that the sum of m and n is 0 to 5; R Ｘ are independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, or heteroaryl group; each G is independently absent or a neutral or anionic donor ligand that is a Lewis base; Y １ and Y ２ are, if present, independently a metal M ２ is a neutral or anionic donor group capable of donating a lone pair of electrons to M １ and M ２ are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III), Co(III), Mn(III), Ni(III), Fe(III), Ca(II), Ge(II), Al(III), Ti(III), V(III), Ge(IV), Y(III), Sc(III) or Ti(IV); A process wherein the acid used to deactivate the catalyst is present on a solid support and / or the acid is selected from a sulfonic acid, a phosphoric acid, a carboxylic acid, or a combination thereof.

19. 20. The method of any one of claims 2, 5 or 18, comprising the step of (iii) reactivating the deactivated catalyst by contacting the catalyst with an anion.

20. The method according to any one of claims 1 to 18, wherein the deactivation step and the removal step are carried out simultaneously.

21. 21. The method of any one of claims 2, 3 or 5 to 20, wherein the solid phase is an inorganic solid phase.

22. 22. The method of claim 21, wherein the solid phase is an inorganic solid phase selected from silica, alumina, zirconia, molecular sieves, zeolites, clays or derivatives or combinations thereof, preferably silica, magnesium silicate or alumina.

23. 23. The method of claim 21 or 22, wherein the inorganic solid phase is surface functionalized with functional groups effective to form stable bonds with one or more metal centers of the deactivated catalyst, such as, for example, hydroxyl, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphate, thiol and / or amine functional groups, more preferably the inorganic solid phase comprises sulfonic acid, sulfonate, carboxylic acid and / or carboxylate functional groups, most preferably sulfonate or carboxylic acid functional groups.

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