WO2022212124A1

WO2022212124A1 - Phosphonium-borane catalyst complexes and use thereof

Info

Publication number: WO2022212124A1
Application number: PCT/US2022/021318
Authority: WO
Inventors: Tzu-Pin Lin; Avery R. SMITH; Hua Zhou; Nikola S. LAMBIC; Carlos R. Lopez-Barron; Charles J. HARLAN; Matthew W. Holtcamp; Gursu CULCU; Timothy M. Boller; Jonathan J. Schaefer; Eryn G. LEE
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2021-03-30
Filing date: 2022-03-22
Publication date: 2022-10-06

Abstract

Embodiments described herein relate to phosphonium-boranes catalyst complexes comprising one or more di-/multi-anionic moieties and one or more cationic phosphonium-boranes, where the di-/multi-anionic moiety initiates the polymerization of one or more epoxides and one or more of CO₂, COS, and CS₂.

Description

TITLE: PHOSPHONIUM-BORANE CATALYST COMPLEXES AND USE THEREOF CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of and priority to US Provisional Application No. 63/167,861 filed March 30, 2021, the disclosure of which is incorporated herein by reference. TECHNOLOGICAL FIELD [0002] This invention relates to novel phosphonium-borane catalyst complexes uses thereof, such as the generation of telechelic and triblock copolymers. BACKGROUND [0003] Polymerization catalysts are of great use in industry. Hence there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties. [0004] Copolymerization of CO₂ and epoxide to produce telechelic polycarbonates is a challenging reaction. The more significant challenges include: (1) the polymerization is usually mediated by transition metal-based catalysts which are expensive, (2) the activity is usually low, typically with turnover numbers of less than 1,000 per catalyst, and (3) the conventional catalysts can only initiate CO₂ and epoxide copolymerization from a single chain- end, leading to mono-functionalized (as opposed to telechelic) polymers. [0005] US20210363297_A1 (2021) “ORGANIC METAL-FREE CATALYSTS WITH ELECTROPHILIC AND NUCLEOPHILIC DUAL-FUNCTIONS, PREPARATION METHODS OF MAKING THE SAME, AND USES THEREOF” [0006] Yang, G. et al. (2020) “Scalable Bifunctional Organoboron Catalysts for Copolymerization of CO₂ and Epoxides with Unprecedented Efficiency,” J. Am. Chem. Soc., v.142(28), pp. 12245–12255 discusses ammonium borane catalysts, such as (5-((1s,5s)-9- borabicyclo[3.3.1]nonan-9-yl)pentyl)triethyl-l4-azane, bromide salt, for CO₂/epoxide copolymerization. The reported catalysts are, however, not particularly active. [0007] Yang, G. et al. (2021) “Pinwheel-Shaped Tetranuclear Organoboron Catalysts for Perfectly Alternating Copolymerization of CO₂ and Epichlorohydrin,” J. Am. Chem. Soc., v.143(9), pp. 3455–3465 described ammonium borane catalysts that mediate CO2/epoxide copolymerization. [0008] Sulley, G. et al. (2020) “Switchable Catalysis Improves the Properties of CO₂- Adhesives, Elastomers, and Toughened Plastics,” J. Am. Chem. Soc., v.142(9), pp.4367–4378 describes a catalytic polymerization process to produce ABA-block polymers (poly(cyclohexene carbonate-b-decalactone-b-cyclohexene carbonate) [PCHC-PDL-PCHC]), incorporating 6–23 wt% CO₂) using an organometallic heterodinuclear Zn(II)/Mg(II) catalyst together with biobased ε-decalactone, cyclohexene oxide, and carbon dioxide. SUMMARY [0009] Exemplary embodiments described herein relate to a phosphonium-borane catalyst complex represented by the Formula (I): where (the n

B* is a group 13 metal, such as boron, aluminum, or gallium; Z is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups (such as dimer, trimers, etc.); T is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the anionic charge of X; Q is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the number of X present; each R¹, R², R³, R⁴, and R⁵ is independently a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), a hydrocarbyl group containing heteroatoms to form heteroatom-C or heteroatom-P or heteroatom-B* bonds, another B*, another P+, or a catalyst composition represented by the Formula (I), where one or more of R¹ and R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are optionally fused; and/or each Y is independently a linking group having 1 to 50 non-hydrogen atoms; and each X is independently a di-anionic group, a multi-anionic group, or a combination thereof. [0010] Exemplary embodiments described herein further relate to catalyst compositions represented by Formula (I) wherein the substituted hydrocarbyl (such as substituted alkyl, and substituted aryl) is substituted with a catalyst composition represented by the Formula (I), a group 13 metal-containing moiety of Formula (I) (such as a boron-containing moiety of Formula (I)), and/or a phosphonium-containing moiety of Formula (I). [0011] Exemplary embodiments described herein further relate to a phosphonium-borane catalyst compositions represented by the Formula (I) where one or more X are optionally independently tethered to the phospho-borane group, via one or more of B, P, Y, R¹, R², R³, R⁴, and/or R⁵. For example such a catalyst composition may be represented by the Formula (I-A):

where (the number of phosphonium moieties, P+) x Z = (L x M) + (G x J);

B* is a group 13 metal, such as boron, aluminum, or gallium;

Z is 1 to 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups (such as dimer, trimers, etc.);

G and L are, independently, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

J and M are, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; each R¹, R², R³, R⁴, and R⁵ is independently a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), a hydrocarbyl group containing heteroatoms to form heteroatom-C or heteroatom-P or heteroatom-B* bonds, another B*, another P+, or a catalyst composition represented by the Formula (I), where one or more of R'&R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are optionally fused; each Y is independently a linking group having 1 to 50 non-hydrogen atoms; and each X is independently a di-anionic group, a multi-anionic group, or a combination thereof.

[0012] Exemplary embodiments described herein further relate to processes for the copolymerization of epoxides and one or more of CO₂, COS, CS2, using phosphonium-borane catalyst complexes to produce polymers, such as polycarbonates, or sulfur-containing polycarbonate.

[0013] Exemplary embodiments described herein further relate to a transition metal catalyst compound represented by the Formula (II):

wherein,

E is NR2, OR, SR, or PR₂, where each R is, independently, hydrogen, or Ci to C50 hydrocarbyl or Ci to C₅₀ substituted hydrocarbyl (such as alkoxy); halogen, cyano, or silyl; each R⁸ and R¹² is, independently, an aryl group, or a substituted aryl group; and each R⁹, R¹⁰, and R^{1 1} is, independently, a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), where one or more of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is optionally fused (such as one or more of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, and R^{1 1} and R¹²are optionally fused) in cyclic or multicyclic rings. [0014] Exemplary embodiments described herein further relate to a method to produce polymers comprising contacting a catalyst composition represented by the Formula (II) with one or more lactones (such as caprolactones) to obtain a lactone homo-polymer (such as polycaprolactone or polydecalactone, or poly methylcaprolactone) or lactone copolymers (such as random copolymers of caprolactone and decalactone, or random copolymers of caprolactone and methylcaprolactone).

[0015] Exemplary embodiments described herein further relate to novel methods for producing polyesters by ring opening lactides and/or lactones, such as by using the transition metal compound represented by Formula (II) and then copolymerizing with anhydrides and/or epoxides and one or more of CO₂, COS, and CS₂ with a phosphonium-borane catalyst complex represented by Formula (I).

[0016] Exemplary embodiments described herein further relate to a method to produce block copolymers comprising: contacting a catalyst composition represented by the Formula (II) with one or more lactones (such as caprolactone, decalactone) and one or more polyols, to obtain a lactone -based homo- or co-polymer (such as polycaprolactone) having alcohol groups, such as alcohol end groups, and thereafter contacting the lactone homo- or co-polymer having alcohol groups (such as alcohol end groups) with a catalyst composition represented by Formula (I), one or more epoxides, and one or more of CO₂, COS, and CS₂, and obtaining block copolymer. [0017] Exemplary embodiments described herein further relate to polymer compositions produced by the methods described herein.

[0018] Exemplary embodiments described herein further relate to block copolymer compositions produced by the methods described herein.

BRIEF DESCRIPTION OF THE FIGURES

[0019] Fig. 1 depicts the crystal structure of transition metal catalyst compound Mn-N(SiMe3)2.

[0020] Fig. 2 is a dynamic mechanical thermal analysis (DMTA) plot regarding some triblock copolymers embodying the present technological advancement.

[0021] Fig. 3 is a tensile plot regarding some triblock copolymers embodying the present technological advancement.

[0022] Fig. 4 is a differential scanning calorimetry (DSC) plot regarding some triblock copolymers embodying the present technological advancement.

[0023] Figs. 5A, 5B, and 5C each depict an exemplary reaction scheme for making a triblock copolymer.

DETAILED DESCRIPTION

[0024] To address the above needs, among other things, a catalyst family based on phosphonium boranes has been developed. These catalysts are inexpensive and metal-free, often showing excellent activity for CHO/CO₂ copolymerization with turnover numbers of 1,000 or more. In the absence of chain- transfer-agents, these catalysts can produce di-telechelic or multi-telechelic polymers. In the presence of bifunctional or multi-functional chain-transfer- agents, these catalysts can produce additional telechelic polymer chains. Sequential monomer addition polymerization also allows for the synthesis of multi-block copolymers that, among other things, can be used as in adhesive, elastomers, and thermoplastic applications. Definitions

[0025] For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v.3(5), pg. 27 (1985). For example, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g. Hf, Ti, or Zr.

[0026] For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising a monomer (the monomer present in such polymer or copolymer is the polymerized form of the monomer). For example, when a copolymer is said to have a "caprolactone" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from caprolactone in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. A "polylactone" is a polymer where the mer unit(s) in the polymer are derived from one or more lactones (where the lactone mer units may be ring opened). A "caprolactone polymer" or "caprolactone copolymer" is a polymer or copolymer comprising at least 50 mol% of one or more caprolactone derived units (such as caprolactone, decalactone, or methylcaprolactone).

[0027] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are reported in units of g/mol (g mol ¹).

[0028] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec -butyl, tBu is tert-butyl, p-tBu is para-tertiary butyl, Hx is hexyl, Cy is cyclohex, Oct is octyl, Ph is phenyl, Cbz is Carbazole, p-Me is para-methyl, Bz and Bn are benzyl (i.e., CH₂Ph), dme is 1,2-dimethoxy ethane, tol is toluene, EtOAc is ethyl acetate, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is 23 °C unless otherwise indicated).

Phosphonium-Boranes Catalyst Complexes

[0029] Embodiments described herein relate to phosphonium-boranes catalyst complexes comprising one or more anionic moieties and one or more cationic phosphonium-boranes, where the anionic moiety initiates the polymerization and the phosphonium-borane catalyzes the polymerization of one or more epoxides and one or more of CO₂, COS, and CS2.

[0030] Embodiments described herein relate to a phosphonium-borane catalyst composition represented by the Formula (I):

where (the number of phosphonium moieties, P+) x Z = T x Q; each B* is, independently, a group 13 metal, such as one or more of boron, aluminum, gallium, indium;

Z is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups (such as dimer, trimers, etc.);

T is 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the anionic charge of X;

Q is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the number of X present; each R¹, R², R³, R⁴, and R⁵ is independently a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), a hydrocarbyl group containing heteroatoms to form heteroatom-C or heteroatom-P or heteroatom-B* bonds, another B*, another P+, or a catalyst composition represented by the Formula (I), where one or more of R¹ and R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are optionally fused; and/or each Y is independently a linking group having 1 to 50 non-hydrogen atoms, such as 2 to 40 non-hydrogen atoms, such as such as 3 to 30 non-hydrogen atoms; and each X is independently a di-anionic group, a multi-anionic group, or a combination thereof. [0031] Embodiments described herein relate to phosphonium-borane catalyst compositions represented by Formula (I) wherein the substituted hydrocarbyl (such as substituted alkyl, and substituted aryl) is substituted with a catalyst composition represented by the Formula (I), a group 13 metal-containing moiety of Formula (I) (such as a boron-containing moiety of Formula (I)), and/or a phosphonium-containing moiety of Formula (I). A "boron-containing moiety of Formula (I)" or a "group 13 metal-containing moiety of Formula (I)" is that part of Formula (I) not containing the phosphonium fragment, e.g., P(R³)(R⁴)(R⁵). A "phosphonium- containing moiety of Formula (I)" is that part of Formula (I) not containing the group 13 metal (such as boron) fragment, e.g., B*(R¹)(R²).

[0032] Embodiments described herein relate to a phosphonium-borane catalyst compositions represented by the Formula (I) where one or more X are optionally independently tethered to the phospho-borane group, via one or more of B, P, Y, R¹, R², R³, R⁴, and/or R⁵. For example the catalyst composition may be represented by the Formula (I-A): where

each B* is, independently, a group 13 metal, such as one or more of boron, aluminum, gallium, indium; Z is 1 to 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups (such as dimer, trimers, etc.); G and L are, independently, 2, 3, 4, 5, 6, 7, 8, 9, or 10; J and M are, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; each R¹, R², R³, R⁴, and R⁵ is independently a hydrocarbyl group, a hydrocarbyl group containing heteroatoms (preferably N, Si, O, or S), a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), another B*, another P+, or a catalyst composition represented by the Formula (I), where one or more of R¹ and R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are optionally fused; each Y is independently a linking group having 1 to 50 non-hydrogen atoms, such as 2 to 40 non-hydrogen atoms, such as such as 3 to 30 non-hydrogen atoms; and each X is independently a di-anionic group, a multi-anionic group, or a combination thereof. [0033] In some embodiments of Formula (I) or (I-A), Z is 1 or 2. R³, R⁴, R⁵ are hydrocarbons that contain 0, 1, or 2 B*. T is 2 and Q is 1 (see the catalyst section that shows all the catalysts that were tested). [0034] In any embodiment of Formula (I) or (I-A), each R¹, R², R³, R⁴, and R⁵ is independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aryl group. [0035] Alternately, in any embodiment of Formula (I) or (I-A), R¹, R², R³, R⁴, and R⁵ are independently selected from methyl, ethyl, propyl, butyl, pentyl, neopentyl, adamantyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 6eptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

[0036] In any embodiment of Formula (I) or (I-A), one or more of R¹ and R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are fused and may form saturated or aromatic cyclic or multicyclic groups.

[0037] In any embodiment of Formula (I) or (I-A), one or more of R¹, R², R³, R⁴, and R⁵ comprises one or more catalyst compositions selected form the group consisting of catalyst compositions represented by the Formula (I).

[0038] In any embodiment of Formula (I) or (I-A), each Y is independently a hydrocarbyl group, or substituted hydrocarbyl group, a group 14, 15 or 16 heteroatom, or a substituted group 13, 14, 15 or 16 heteroatom (such as a silyl group, a substituted silyl group, oxygen group, sulfur group, nitrogen group or phosphine group) such as an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C3 to C20) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aryl group.

[0039] Alternately, in any embodiment of Formula (I) or (I-A), each Y is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenylene, substituted phenylene (such as 1 ,2-phenylene, 1,3-phenylene, 1,4 — phenylene, 1,8-naphthalene, methylphenylene and dimethylphenylene), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

[0040] In any embodiment of Formula (I) or (I-A), each Y is independently -0-, (-CH2-)n, where n is 1 to 50, alternately n is 2 to 30, alternately n is 3 to 12 (alternately n is 1, e.g., -CH2-), -CR2-, -S1R2-, -GeR2-, (where each R is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbomyl, or substituted norbomyl. [0041] In any embodiment of Formula (I) or (I-A), Y is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15, or 16 element. Examples of suitable bridging groups include P(=S)R*, P(=Se)R*, P(=0)R*, R*2C, R*2Si, R*₂Ge, R*₂CCR*2, R*₂CCR*₂CR*2, R*2CCR*2CR*₂CR*2, R*C=CR*, R*C=CR*CR*₂, R*₂CCR*=CR*CR*2, R*C=CR*CR*=CR*, R*C=CR*CR*₂CR*2, R*₂CSiR*₂, R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*2, R*₂SiCR*₂SiR*2, R*C=CR*SiR*₂, R*₂CGeR*2, R*₂GeGeR*₂, R*2CGeR*₂CR*2, R*₂GeCR*₂GeR*2, R*₂SiGeR*₂, R*C=CR*GeR*₂, R*B, R*₂C-BR*, R*₂C-BR*-CR*₂, R*₂C-0-CR*2, R*2CR*2C-0-CR*₂CR*2,

R*2C-0-CR*₂CR*2, R*₂C-0-CR*=CR*, R*₂C-S-CR*₂, R*2CR*2C-S-CR*₂CR*2,

R*2C-S-CR*₂CR*2, R*₂C-S-CR*=CR*, R*₂C-Se-CR*2, R*2CR*2C-Se-CR*₂CR*2,

R*2C-Se-CR*₂CR*2, R*₂C-Se-CR*=CR*, R*₂C-N=CR*, R*₂C-NR*-CR*₂,

R*2C-NR*-CR*₂CR*2, R*₂C-NR*-CR*=CR*, R*2CR*2C-NR*-CR*₂CR*2, R*₂C-P=CR*, R*₂C-PR*-CR*2, O, S, Se, Te, NR*, PR*, AsR*, SbR*, O-O, S-S, R*N-NR*, R*P-PR*, O-S, O-NR*, O-PR*, S-NR*, S-PR*, and R*N-PR* where R* is hydrogen or a C1-C20 containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Preferred examples for the bridging group Y include CEb, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. In a preferred embodiment of the invention in any embodiment of any formula described herein, Y is represented by the formula ER^d ₂ or (ER^d ₂)2, where E is C, Si, or Ge, and each R^d is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^d can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. Preferably, Y is a bridging group comprising carbon or silica, such as di alkyl s ily 1 , preferably Y is selected from CEb, CEbCEb, C(CH₃)₂, SiMe₂, Me₂SiOSiMe₂, cyclotrimethylenesilylene (Si(CH₂)₃), cyclopentamethylenesilylene (Si(CEb)5) and cyclotetramethylenesilylene (Si(CH₂)₄).

[0042] In any embodiment of Formula (I) or (I-A), X is a di- or multi-anionic (such as tri-anionic) group that acts as an initiator for the polymerization. Alternately, each X is independently a halide, an alkoxide, aryloxide, a carboxylate, a carbonate, a sulfate, a phosphate, di-alkoxide, di-aryloxide, a di-carboxylate, a di-carbonate, a di-sulfate, a di-phosphate (such as a di-carboxylate) or tri-alkoxide, tri-aryloxide, a tri-carboxylate, a tri carbonate, a tri-sulfate, a tri-phosphate (such as a tri-carboxylate), or a combination thereof. Alternately, each X is independently a dicarboxylate (such as Norbomene di-carboxylate). Additionally, X can contain one or more than one alcohol groups (-OH) and thiol groups (-SH). X can be a group 13 to 16 heteroatom, such as B, Si, Ge, Sn, N, P, As, O, S, Se, Te, or the aforementioned elements with hydrogens attached, such as BH, B¾, S1H2, OH, NH, N¾, etc. X can be a substituted heteroatom, e.g., a heteroatom that has one or more of these hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group(s). X can be a substituted group 13 to 16 heteroatom, such as -0(R*), -0S(0)2(R*), -0S(0)2CF3, -S(R*), -N(R*)2, - NH(R*), -P(R*)2, -PH(R*), -Si(R*)₃, -SiH(R*)₂, -SiH₂(R*), -Ge(R*)₃, -B(R*)₂, -BH(R*) wherein R* is hydrocarbyl or substituted hydrocarbyl, such as, but not limited to, arylalkyl, alkylaryl, alkenyl, alkynyl, cycloalkyl, and the like, and wherein two or more adjacent R* may join together to form a cyclic or polycyclic structure.

[0043] For Complex 1, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = R⁴ = R⁵ = phenyl, X = Br.

[0044] For Complex 2, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = R⁴ = R⁵ = phenyl, X = 5-norbornene-2,3-dicarboxylate. [0045] For Complex 3, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0046] For Complex 4, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl, R⁴ = R⁵ = phenyl, X = 5-norbornene-2,3-dicarboxylate.

[0047] For Complex 5, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = R⁴ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl, R⁵ = phenyl, X = Br.

[0048] For Complex 6, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = R⁴ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl, R⁵ = phenyl, X = 5-norbornene-2,3-dicarboxylate.

[0049] For Complex 7, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl-diphenyl- phosphino-propyl, R⁴ = R⁵ = phenyl, X = Br.

[0050] For Complex 8, R¹ and R² formed a fused ring with boron namely 9-Borabicyclo(3.3.1)nonane, R³ = 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl-diphenyl- phosphino-propyl, R⁴ = R⁵ = phenyl, X = 5-norbornene-2,3-dicarboxylate.

[0051] For Complex 11, R¹ = R² = pentafluorophenyl, R³ = bis(perfluorophenyl)boraneyl)pentyl, R⁴ = R⁵ = phenyl, X = Br. [0052] For Complex 12, R¹ = R² = mesityl, R³ = (dimesitylboraneyl)pentyl,

R⁴ = R⁵ = phenyl, X = Br.

[0053] For Complex 13, R¹ = R² = cyclohexyl, R³ = (dicyclohexylboraneyl)pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0054] For Complex 14, R¹ = R² = n-hexyl, R³ = (di-n-hexylboraneyl)pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0055] For Complex 15, R¹ and R² form a fused ring with boron namely (4, 4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl), R³ = (5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0056] For Complex 16, R¹ and R² formed a fused ring with boron namely 9-Borabicyclo(3.3.1)nonane, R³ = pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0057] For Complex 17, R¹ and R² form a fused ring with boron namely

(benzo[d][l,3,2]dioxaborol-2-yl), R³ = 5-(benzo[d][l,3,2]dioxaborol-2-yl)pentyl, R⁴ = R⁵ = phenyl, X = Br.

[0058] Specific examples of phosphonium-borane catalyst complexes useful herein are shown below:

[0059] Non-limiting examples of anionic catalysts include complexes 2, 4, 6, 8, and 22. Complex 23 is a non-limiting example of a tri-anionic complex. Complex 24 is a non-limiting example of a tetra- anionic complex.

[0060] Phosphonium-borane catalyst compounds that are particularly useful in this invention include one or more of: Complex 1, named as “(5-(9-borabicyclo[3.3.1]nonan-9- yl)pentyl)triphenyl phosphonium bromide” complex 3 named as “bis-(5-(9- borabicyclo[3.3.1]nonan-9-yl)pentyl)diphenyl phosphonium bromide”, complex 5 named as “tris-(5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl)phenyl phosphonium bromide”, complex 7 named as propane- l,3-diylbis((5-((ls,5s)-9-borabicyclo[3.3. l]nonan-9- yl)pentyl)diphenylphosphonium) dibromide” are particularly of interest.

[0061] In alternate embodiments in any of the processes described herein one phosphonium-borane catalyst complex is used, e.g. the catalyst complexes are not different. For purposes of this invention one catalyst complex is considered different from another if they differ by at least one atom.

[0062] In some embodiments, two or more different phosphonium-borane catalyst complexes are present in the catalyst system used herein. In some embodiments, two or more different catalyst complexes are present in the reaction zone where the process(es) described herein occur. It is optional to use the same initiator for the compounds, however, two different initiators can be used in combination.

[0063] The two phosphonium-borane catalyst complexes may be used in any ratio. Preferred molar ratios of (A) catalyst complex to (B) catalyst complex fall within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The particular ratio chosen will depend on the exact complex chosen, the method of initiation, and the end product desired. In a particular embodiment, when using the two catalysts, useful mole percents, based upon the molecular weight of the catalysts, are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.

Methods to Prepare the Phosphonium-Borane Catalyst Compounds.

[0064] Phosphine is allowed to react with alkenyl bromide (or halide) in acetonitrile (MeCN) at 50-60°C for 24 - 96 hours to afford phosphonium bromide (or halide) as the product. The phosphonium bromide (or halide) is then allow to react with dialkyl hydrido borane in THF at 20-65°C for 24 - 96 hours, affording phosphonium borane as the product.

[0065] In any embodiment of Formula (I) or (I- A), X is a di- or multi-anionic (such as tri-anionic) group that acts as an initiator for the polymerization. Alternately, each X is independently a di-alkoxide, di-aryloxide, a di-carboxylate, a di-carbonate, a di-sulfate, a diphosphate (such as a di-carboxylate), or tri-alkoxide, tri-aryloxide, a tri-carboxylate, a tricarbonate, a tri-sulfate, a tri-phosphate (such as a tri-carboxylate), or a combination thereof. The identity of X can affect the structures, end groups, and molecular weight of the polymers as illustrated in the figure below. For example, di-anionic initiator such as 5-norbomene-2,3- dicarboxylate will result in a di-telechelic polymer. Such polymer will feature OH end groups on both ends, after the polymerization was quenched with an acid or water. Similarly, a trianionic initiator will lead to a tri-telechelic polymer. Di-anionic or multi-anionic initiator can result in polymers with higher molecular weights, compared to those generated by a monoanionic initiator (see polymerization Example 15 and Example 16).

[0066] An initiator, which is part of the catalyst structure, is not to be confused with a chain-transfer-agent (CTA), which is an optional reagent that can produce more polymer chains, in addition to the ones initiated by the initiators.

[0067] Chain-Transfer Agents In general, chain-transfer-agents (CTAs) allow the polymerization to produce additional polymer chains. CTAs can be used to produce additional polymer chains. CTA's can also be used to control the molecular weights. CTAs useful with the phosphonium-borane catalyst complexes can include water, alcohols (such as di-alcohols), carboxylic acids (such as dicarboxylic acids), carboxylates, or thio groups. Examples include: water, ethanol, methanol, 1,4-benzenedimethanol, 1,2-trans- dihydroxycyclohexane, and terephthalic acid. CTAs can also be an oligomer or a polymer featuring one or more than one alcohol or carboxylic acid end groups.

[0068] In embodiments, bifunctional chain-transfer agents (such as polyols) can be used with the phosphonium-borane catalyst complexes described herein to produce additional telechelic polymers with multiple functional groups (such as poly-ols). Useful bifunctional chain transfer agents include 1,4-benzenedimethanol, 1,2-trans- dihydroxycyclohexane, terephthalic acid, or telechelic poly-ols.

Co-Activators

[0069] Co-activators may be used with the phosphonium-borane catalyst complexes. A co-activator, may be used in conjunction with an initiator in order to form an active catalyst complex. In some embodiments a co-activator can be pre-mixed with the catalyst complex before introduction into a reaction zone or may be introduced separately into the reaction zone. Compounds which may be utilized as co-activators with the phosphonium-borane catalyst complexes include, for example, phosphonium halide and bis(triphenylphosphine)iminium halide, or triethyl borane, tricyclohexyl borane, tri-n-hexyl borane, etc.

Transition Metal Compounds

[0070] Embodiments described herein also relate to a catalyst composition represented by the Formula (II):

wherein,

E is NR₂, OR, SR, or PR₂, where each R is, independently, hydrogen, or Ci to C₅₀ (such as C₆ to C_30, such as G to C₂₀) hydrocarbyl or Ci to C₅₀ (such as G to C_30, such as G to C₂₀) substituted hydrocarbyl (such as alkoxy); halogen, cyano, or silyl; each R⁸ and R¹² is, independently, an aryl group or a substituted aryl group, such as C₅ to C₅₀ (such as Ce to C_30, such as Ce to C₂₀) aryl, or C₅ to C₅₀ (such as G to C_30, such as Ce to C₂₀) substituted aryl group; and each R⁹, R¹⁰, and R¹¹ is, independently, a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), where one or more of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is optionally fused (such as one or more of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, and R¹¹ and R¹² are optionally fused) in cyclic or multicyclic rings. [0071] Alternately, in any embodiment of Formula (II), R⁸ and R¹² are independently selected from phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, norbornyl, substituted norbornyl (such as methyl norbornyl) and isomers thereof.

[0072] In any embodiment of Formula (II), each R⁹, R¹⁰, and R¹¹ is independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C_30, such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C_30, such as G to C₂₀) aryl, or C₅ to C₅₀ (such as G to C_30, such as G to C₂₀) substituted aryl group.

[0073] Alternately, in any embodiment of Formula (II), R⁹, R¹⁰, and R¹¹ are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

[0074] In any embodiment of Formula (II), one or more of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, and R¹¹ and R¹² are fused and may form saturated or aromatic cyclic or multicyclic groups. [0075] Examples of useful transition metal compounds include (the crystal structure of which is discussed below):

[0076] In alternate embodiments in any of the processes described herein one transition metal catalyst compound is used, e.g. the catalyst compounds are not different. For purposes of this invention one catalyst compound is considered different from another if they differ by at least one atom.

[0077] In some embodiments, two or more different transition metal catalyst compound are present in the catalyst system used herein. In some embodiments, two or more different transition metal catalyst compound are present in the reaction zone where the process(es) described herein occur.

[0078] The two transition metal catalyst compound may be used in any ratio. Preferred molar ratios of (A) catalyst complex to (B) catalyst complex fall within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The particular ratio chosen will depend on the exact complex chosen, the method of initiation, and the end product desired. In a particular embodiment, when using the two catalysts, useful mole percents, based upon the molecular weight of the catalysts, are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.

Methods to Prepare the Transition Metal Catalyst Compounds.

[0079] Synthesis of BDI-A Mn-N(SiMe3)2 (hereafter denoted as BDI-Mn). A 0.97 gram amount of BDI-A was combined with a 0.5 gram amount of Mn(N(SiMe3)2)2 in 5 milliliters of toluene. The solution was heated overnight (~16 hours) at 110°C in a sand bath open to a nitrogen drybox atmosphere. Evaporation of solvent overnight during heating yielded a quantitative amount of red crystals. ¹ H NMR (400 MHz, CD2CI2) of crystals yielded no discernable peaks due to the paramagnetic properties of the complex. The crystal structure shown in Fig. 4 was obtained by single-crystal X-ray diffraction using a Bruker AXS eco D8Quest A30 to verify atom connectivity and depicting a Mn(II) trigonal planar metal atom center.

Polymerization Processes

[0080] In embodiments herein, the invention relates to polymerization processes where one or more epoxide monomers and one or more of CO₂, COS, CS2, are contacted with one or more phosphonium-borane catalyst compositions as described above, to form oxygen containing polymers, such as polycarbonates.

[0081] In embodiments herein, the invention relates to polymerization processes where one or more lactone monomers and, are contacted with one or more transition metal catalyst compounds as described above, to form polylactone polymers, such as polycaprolactone, polydecalactone, polymethylcaprolactone, or copolymers thereof.

[0082] In embodiments herein, the invention relates to polymerization processes where one or more lactone monomers and, optionally, one or more caprolactone monomers are contacted with one or more transition metal catalyst compounds as described above, to form polylactone polymers, such as polycaprolactone, polydecalactone, polymethylcaprolactone, or copolymers thereof and thereafter said polymer is contacted with one or more epoxide monomers, one or more of CO₂, COS, CS2, and one or more phosphonium-borane catalyst compositions as described above, to form copolymers, such as block copolymers.

[0083] A embodiment of the present technological advancement relates to a method to produce polymers comprising: contacting a catalyst composition represented by the Formula (II) with one or more caproloctones, to obtain polycaprolactones.

[0084] Epoxide monomers useful herein include epoxides, substituted epoxides, and isomers thereof. Examples of epoxides include, but are not limited to, cyclohexene oxide, methyl cyclohexene oxide, dimethyl cyclohexene oxide, ethyl cyclohexene oxide, vinyl cyclohexene oxide, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, pentene oxide, hexene oxide, heptane oxide, octene oxide, epichlorohydrin, glycidyl methyl ether, glycidyl ethyl ether, glycidyl n-butyl ether, glycidyl isobutyl ether, glycidyl allyl ether, glycidyl 2-ethylhexyl ether, glycidyl benzyl ether, glycidyl phenyl ether, norbornene oxide. [0085] Exemplary epoxide monomers include cyclohexne oxide and vinyl cyclohexene oxide and their respective homologs and derivatives.

[0086] In embodiments of the invention, the epoxide monomer (such as cyclohexene oxide and vinyl cyclohexene oxide) is combined with one or more of CO₂, COS, CS2, such as CO₂. [0087] Lactone monomers include lactones and substituted lactones such as methyl caprolactone and decalactone. Lactone comprises caprolactone.

[0088] Lactones are cyclic carboxylic esters, containing a l-oxacycloalkan-2-one structure (-C("0)-0--), "substituted lactones" are lactones that have one or more hydrogen groups replaced by hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group and or have one or more ring atoms replaced by a heteroatom.

[0089] Lactone monomers useful herein include caprolactone, substituted caprolactone (such as alkyl-caprolactone, where the alkyl is a Ci to C30 alkyl), such as methyl-caprolactone), valerolactone, propiolactone, butyrolactone, hexalactone, decalactone. [0090] Monomers and comonomers used herein may be linear, branched, or cyclic, and if cyclic may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Polymerization

[0091] A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where polymer product is dissolved in the polymerization medium, such as 80 wt% or more, 90 wt% or more or 100% of polymer product is dissolved in the reaction medium. Such systems are preferably not turbid as described in Oliveira, J. V. C. et al. (2000), Ind. Eng. Chem. Res., v.29, pg. 4627.

[0092] A bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system typically contains less than 25 wt% of inert solvent or diluent, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.

[0093] Polymerization processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, or solution polymerization process known in the art can be used. Such processes can be ran in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes are typically useful, such as homogeneous polymerization process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is also useful, such as a process where monomer concentration in all feeds to the reactor is 70 volume % or more. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer.).

[0094] Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™ fluids); perhalogenated hydrocarbons, such as perfluorinated C₄_ I_Q alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the solvents. [0095] In a preferred embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, based on the total volume of the feedstream, or preferably no solvent. Preferably the polymerization is run in a bulk process.

[0096] Preferred polymerizations can be ran at any temperature and/or pressure suitable to obtain the desired polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0°C to about 300°C, preferably about 20°C to about 200°C, preferably about 35 °C to about 150°C, preferably from about 40 °C to about 120°C, preferably from about 45°C to about 100°C; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.

[0097] In a typical polymerization, the ran time of the reaction is up to 960 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.

[0098] In an alternate embodiment, the activity of the catalyst is at least 50 g/g of cat, preferably 500 or more g/g of cat, preferably 5,000 or more g/g of cat, preferably 50,000 or more g/g of cat. In an alternate embodiment, the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more. [0099] Sequential monomer addition polymerization allows the synthesis of multi-block copolymers that can be used in adhesives, elastomers, and thermoplastics, among other things. [0100] In alternate embodiments, the catalyst complexes described herein may be used to prepare block copolymers, typically diblock and triblock copolymers. This may done by sequential monomer addition to the same catalyst complexes or by sequential polymerization reactions with different catalysts. This may also done by sequential monomer addition to multiple catalyst complexes or addition of new catalyst complexes and monomer in the same or different reaction zones.

[0101] In alternate embodiments, the phosphonium-borane catalyst complex as described herein can be used in combination with a non-phosphonium-borane polymerization catalyst, such as a transition metal catalyst compound (such as tin 2-ethylhexanoate ) or the transition metal compounds represented by Formula (II), to produce block copolymers. For example such transition metal catalyst compounds can produce telechelic poly-ols of polylactones (such as polycaprolactone) in the first stage of polymerization. The phosphonium borane catalysts can then be introduced at the second stage polymerization which enables the copolymerization with epoxides/CCk, COS, CS2. The epoxide can be introduced at either the first or second stage.

[0102] For example a tri-block polymer can be prepared by: 1) polymerizing a lactone monomer (such as caprolactone, or methyl-caprolactone) in the presence of a transition metal polymerization catalyst such as a manganese transition metal catalyst complex represented by Formula (II) described below such as

or optionally an organic catalyst such as sodium alkoxide that can catalyze the polymerization of lactones, and a chain transfer agent (such as a polyol, such as (MeOH)2Ph, such as 1,2-trans- dihydroxycyclohexane), to form "B blocks", where the B block is homo- or co-polymers of lactone monomers. The reaction is optionally conducted in the presence of optional monomer to be used in the second stage such as epoxide for catalysts that are tolerant of epoxide. This B block polymer is then reacted with one or more phosphonium-borane catalyst complexes described herein in the presence of one or more epoxides (such as cyclohexene oxide, vinyl cyclohexene oxide) and one or more of CO₂, COS, and CS2 to form ABA block copolymers, where the A blocks are at least 30 mol% polycarbonates. Examples appear the in the reaction schemes shown in Figs. 5 A, 5B, and 5C.

[0103] In a preferred embodiment, a polymerization reaction for catalyst composition represented by Formula (I) and /or (II): 1) is conducted at temperatures of 0 to 300°C (preferably 25 to 150°C, preferably 40 to 120°C, preferably 45 to 100°C);

2) is conducted at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa);

3) is conducted in solvent, or may be conducted in neat epoxides (without or with added solvents such as dichloromethane or toluene;

4) the polymerization reaction is preferred to be formed under an inert atmosphere such as nitrogen or argon;

5) occurs in one reaction zone; and

6) has a turnover number for the catalyst composition of 100 or more, (preferably at least 200, preferably at least 500, preferably at least 5,000).

[0104] In a preferred embodiment, the catalyst composition used in the polymerization comprises no more than one catalyst complex. A "reaction zone" also referred to as a "polymerization zone" is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23 °C unless otherwise noted.

[0105] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, silanes, or chain transfer agents.

Polymer Products

[0106] This invention also relates to compositions of matter produced by the methods described herein.

[0107] In a preferred embodiment, the process described herein produces polycarbonates, polylactones, or block copolymers of polycarbonates and polylactones. In some embodiment, the produced polymers are blended mixtures of polycarbonates, polylactones, di-(tri-, or multi- )block copolymers of polycarbonates and polylactones. For the B block, it is preferred to have two or more comonomers with one of the comonomers being caprolactone. For example, B block can be copolymers of caprolactone and methyl caprolactone, or copolymers of caprolactone and decalactone. The caprolactone composition can be between 0.5 to 99.5 mol%, preferably between 10 to 80 mol%, preferably between 30 to 70 mol%, preferably between 40 to 60 mol%.

[0108] Lactone monomers include lactones and substituted lactones. Lactones are cyclic carboxylic esters, containing a l-oxacycloalkan-2-one structure (-C(=0)-0-), "substituted lactones" are lactones that have one or more hydrogen groups replaced by hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group and or have one or more ring atoms replaced by a heteroatom.

[0109] Lactone monomers useful herein include caprolactone, substituted caprolactone (such as alkyl-caprolactone, where the alkyl is a Ci to C30 alkyl), such as methyl-caprolactone), valerolactone, propiolactone, butyrolactone, hexalactone, or decalactone.

[0110] In a preferred process the polymerization catalysts described herein are used to produce polycarbonate.

[0111] The phosphonium borane catalysts disclosed herein are capable of copolymerizing CO₂ with epoxide, affording polycarbonates, polyethers, and copolymers of polycarbonates and polyethers. When CO₂ strictly alternatively copolymerize with epoxide, carbonate linkage is formed in every repeating unit, thus affording polycarbonate. On the other hand, it is possible that the catalyst to produce polyether as a result of polymerizing epoxide without CO₂, or to produce copolymers of polycarbonates and polyethers as a result of copolymerizing epoxide in a non-strictly alternating manner.

[0112] A desirable process can produce a polymer with CCk/epoxide from 50/50 mol% ratio (polycarbonate), to 0/100 mol% ratio (polyether), and every composition in between such as 40/60, 30/70, 20/80, 10/90 mol% ratios. Preferably, the catalysts described herein can produce a polymer with a 50/50 to 25/75 CCL/expoxide mol ratio. When CCL/epoxide perfectly alternates, the polymer has 50/50 mol ratio (100% polycarbonate). However, it is sometimes not perfect, for example 45/55 mol ratio polymer. The extreme of imperfection is CCk/epoxide mol ratio of 0/100 (100% polyether) where no CO₂ is incorporated into the polymer, leading to formation of polyether.

Polymer Properties

[0113] Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000 g/mol (preferably 10,000 to 750,000 g/mol, preferably 20,000 to 500,000 g/mol) as determined by LT THF GPC-1D (see procedure below).

[0114] Typically, the polymers produced herein have an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20, alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5 to 3), as determined by the GPC methods. [0115] The triblock copolymers feature A-B-A (hard-soft-hard) block compositions. Each block is linked covalently. It is possible and sometimes desirable to simultaneously form A-B diblock copolymer, or homopolymers of A during the polymerization processes, thus affording a mixture of A-B-A, A-B, and A polymers in the same process.

[0116] The polymer composition of A block should be polycarbonate (CCVepoxide = 50/50 mol ratio) or copolymers of polycarbonate and polyether (with an epoxide content ranging 50 to 95 mol%. For example A block can be polycyclohexene carbonate.

[0117] The B block polymer is made of caprolactone (CL) and at least one or more lactones (L) such as methyl caprolactone (MCL) or decalactone (DL). The mol% of CL should range from 99.5% to 0.5%, preferably from 95% to 5%, preferably from 90% to 10%, preferably from 80% to 20%, preferably from 60% to 40%, preferably from 55% to 45%.

[0118] The glass transition temperatures of B block should be below 20°C, preferably below 0°C, preferably below -10°C, and preferably below -70°C. The glass transition temperatures of A block should be above 30°C, preferably above 50°C, preferably above 450°C, and preferably above 100°C. Any of these values can provide upper and/or lower bounds for ranges of glass transition values.

[0119] The weight ratios of A/B block should range from 95/5 to 5/95, preferably from 90/10 to 10/90, preferably from 80/20 to 20/80, preferably from 60/40 to 40/60, preferably from 55/45 to 45/55. Changing the weight ratio can result in significant change in tensile properties, rheological properties, and other physical properties such as order-to-disorder transition temperature (a temperature the polymer undergoes transition from ordered to disordered.

[0120] In a preferred process the polymerization catalysts described herein are used to produce polycarbonate block copolymers.

Blends and End Uses

[0121] In another embodiment, the polymer produced herein is combined with one or more additional polymers prior to being formed into an article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

[0122] In a preferred embodiment, the polymer is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, preferably 20 to 95 wt%, even more preferably at least 30 to 90 wt%, even more preferably at least 40 to 90 wt%, even more preferably at least 50 to 90 wt%, even more preferably at least 60 to 90 wt%, even more preferably at least 70 to 90 wt%.

[0123] The blends described above may be produced by mixing the polymers of the invention with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.

[0124] The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti -blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.

[0125] Any of the foregoing polymers and compositions in combination with optional additives (anti-oxidants, colorants, dyes, stabilizers, filler, etc.) may be used in a variety of end- use applications produced by methods known in the art. Exemplary end uses are as articles formed by molding techniques, e.g., injection or blow molding, extrusion coating, foaming, casting, and combinations thereof.

Experimental

GPC Method

[0126] The equipment used is as follows:

Agilent 1260 Infinity II Multi-Detector GPC/SEC System;

Pump - Quaternary Pump (up to four different solvents);

Operation temperature range: 30 - 60 °C; and Detectors:

• Differential Refractive Index (DRI) detector at 658 nm,

• Viscometer detector (Inlet Pressure and Differential Pressure),

• Light Scattering (LS) detector at 658 nm (dual channel MALS: 90° and 15°), and

• UV Diode Array Detector (Up to eight wavelengths from 190-950 nm).

[0127] All detectors were plumbed in series: UV to Light Scattering to Refractive Index to Viscometer.

[0128] Agilent Multi-Detector GPC/SEC Instrument control and Data Analysis Software Suite was used.

[0129] The chromatographic conditions were as follows:

• Column: 2 x PLgel 5 pm Mixed-C, 7.5 x 300 mm with a Guard column;

• Eluent: Tetrahydrofuran (stabilized with 250 ppm BHT);

• Operation temperature: 40 °C;

• Injection volume: 25 pL;

• Run flow rate: 1.0 mL/min; and

• Run time: 36 minutes with 3-minute post ran time.

[0130] The detectors calibration was performed by using a traceable 50,000 g/mole polystyrene narrow standard. The column calibration was performed by using twenty-three traceable polystyrene narrow standards range from 200 to 4,000,000 g/mole.

Dynamic Mechanical Thermal Analysis

[0131] Fig. 2 is a dynamic mechanical thermal analysis (DMTA) plot regarding some triblock copolymers embodying the present technological advancement. Dynamic mechanical thermal analysis (“DMTA”) was performed using a rheometer ARES-G2 (TA Instruments). The samples were prepared as small discs with 8 mm in diameter and 4 mm in height. The polymer samples were molded at approximately 190°C on either a Carver Lab Press or Wabash Press. The polymer samples are then loaded into the open oven of the instrument between two serrated parallel plates. The temperature is controlled with a forced convection oven. Dynamic temperature ramps are conducted at a heating rate of 2°C/min using a frequency of 1 Hz and strain of 0.1%. The elastic and viscous moduli (G’ and G”) are measured as a function of temperature.

Tensile Properties.

[0132] Fig. 3 is a tensile plot regarding some triblock copolymers embodying the present technological advancement. Tensile tests are performed using a solid analyzed RSA-G2 (TA Instruments) Small dogbone specimens (with dimensions 15 mm X 3 mm X 0.5 mm) are cut with a die from a molded plaque of thickness 0.5 mm. The specimens are clamped to the RSA-G2 using the film tool and uniaxial deformation is applied at a linear rate of 0.1 rnm/s. The normal force (F) applied during the deformation is recorded in the instrument and the stress is calculated as F/a, where a is the cross-section area of the dogbone specimen.

Differential Scanning Calorimetry (DSC)

[0133] Fig. 4 is a differential scanning calorimetry (DSC) plot regarding some triblock copolymers embodying the present technological advancement. Crystallization temperature (T_c) and melting temperature (or melting point, T_m) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2500 DSC). Typically, 6 to 10 mg of molded polymer are sealed in an aluminum pan and loaded into the instrument at room temperature. Melting data (first heat) is acquired by heating the sample to at least 30°C above its melting temperature, at a heating rate of 10°C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history. Crystallization data are acquired by cooling the sample from the melt to at least 50°C below the crystallization temperature at a cooling rate of 10°C/min. The sample is held at this temperature for at least 5 minutes, and finally heated at 10°C/min to acquire additional melting data (second heat). The endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures. The melting temperatures reported are the peak melting temperatures from the second heat unless otherwise specified.

Materials

[0134] Cyclohexene oxide (CHO), butylene oxide (BO), propylene oxide (PO), dicholoromethane (DCM), caprolactone (CL), and decalactone (DL) were purchased from Aldrich, and purified by distilling over CaH2 under N2. Phenylene dimethanol (PDM) is purchased from Aldrich and recrystallized from anhydrous toluene. Methyl caprolactone (MCL) were synthesized according to literature procedures (. Macromolecules 2011, v.44, pp. 8537-8545).

Examples

[0135] Catalyst Complex Synthesis: pent-4-en- l-yldiphenylphosphane

To the potassium diphenylphosphide THF solution (0.5M, 75 mmol) was slowly added 5-Bromo-l-pentene (12.3 g, 82.5 mmol). The red color discharged after 30 minutes of stirring. The reaction was stirred overnight at room temperature. Most THF was then removed by rotary evaporator. The crude reaction was diluted with hexane (100 ml) and then washed by water. The organic phase was separated and dried over magnesium sulfate. All solvents were then removed under vacuo. The pure product was collected by vacuum distillation as a clear oil (17.3 g, 91%). ¾ NMR (400 MHz, Chloroform-d) d 7.54 - 7.30 (m, 10H), 5.83 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.31 - 4.82 (m, 2H), 2.24 (q, J = 7.2 Hz, 2H), 2.11 (dd, J = 9.8, 6.3 Hz, 2H), 1.61 (q, J = 7.9 Hz, 2H). ³¹P NMR (162 MHz, Chloroform-d) d -16.29 (p, J = 7.8 Hz). ¹³C NMR (101 MHz, Chloroform-d) d 138.89 (d, J = 12.9 Hz), 138.14, 132.75 (d, J = 18.4 Hz), 128.52, 128.42 (d, J = 6.6 Hz), 115.16, 35.16 (d, J = 13.2 Hz), 27.49 (d, J = 11.4 Hz), 25.29 (d, J = 16.7 Hz).

[0136] di(pent-4-en- l-yl)diphenylphosphonium bromide

Mix pent-4-en- l-yldiphenylphosphane (8.0 g, 31.5 mmol) and 5-Bromo-l-pentene (5.16 g, 34.6 mmol) in acetonitrile (50 ml) and stir at 70°C for 2 days. The solvent was then removed under vacuo. Diethyl ether (~10ml) was added to the crude product. The pure product slowly crushed out as white solid (12.4 g, 98%). ¹ H NMR (400 MHz, Chloroform-d) d 7.83

(dd, J = 12.3, 7.7 Hz, 4H), 7.76 - 7.58 (m, 6H), 5.61 (ddt, J = 16.9, 10.1, 6.7 Hz, 2H), 5.04 - 4.82 (m, 4H), 3.23 (dd, J = 16.5, 12.5 Hz, 4H), 2.21 (q, J = 7.1 Hz, 4H), 1.52 (q, J = 7.9 Hz, 4H). ³¹P NMR (162 MHz, Chloroform-d) d 28.02. ¹³C NMR

(101 MHz, Chloroform-d) d 136.09, 134.80 (d, J = 2.8 Hz), 133.02 (d, J = 9.4 Hz), 130.37 (d, J = 12.2 Hz), 117.61 (d, J = 82.6 Hz), 116.96, 33.80 (d, J = 16.4 Hz), 21.34 (d, J = 3.7 Hz), 20.89 (d, J = 49.8 Hz).

[0137] bis(5-(9-borabicyclor3.3.1 |nonan-9-yl )pentyl )diphenyl-X⁴-phosphonium bromide

Mix di(pent-4-en-l-yl)diphenylphosphonium bromide (2.0 g, 5.0 mmol) and 9-BBN (1.24 g, 10.2 mmol) in THF (5 ml) and stir at 65°C for 16 hours. The solvent was then removed under vacuo. The crude product was washed by diethyl ether (~5ml). The pure product was collected as white solid (3.1 g, 97%). ^lH NMR (400 MHz, Chloroform-7) d 7.89 (dd, 7 = 12.2, 7.7 Hz, 4H), 7.80 - 7.61 (m, 6H), 3.28 (dq, 7 = 15.2, 5.6 Hz, 4H), 1.88 - 1.66 (m, 12H), 1.66 - 1.33 (m, 24H), 1.24 (t, 7 = 7.5 Hz, 4H), 1.12 (dq, 7 = 13.0, 5.6, 4.2 Hz, 4H). ¹³C NMR (126 MHz, Chloroform-7) d 134.67 (d, 7= 3.1 Hz), 133.09 (d, 7 = 9.5 Hz), 130.31 (d, 7= 12.0 Hz), 117.96 (d, 7 = 82.4 Hz), 33.53 (d, 7 = 15.0 Hz), 33.04, 30.91(br), 27.59(br), 23.99, 23.12, 22.11 (d, 7 = 4.5 Hz), 21.82 (d, 7 = 48.6 Hz).

[0138] pent-4-en- 1 - vKpentvDdiphenylphosphonium bromide

Mix pent-4-en-l-yldiphenylphosphane (0.5 g, 2.0 mmol) and 5-Bromo-l-pentene (0.36 g, 2.4 mmol) in acetonitrile (5 ml) and stir at 65 °C for 2 days. The solvent was then removed under vacuo. Diethyl ether (~ 10ml) was added to the crude product. The pure product slowly crushed out as white solid (0.74 g, 93%). ¹ H NMR (400 MHz, Chloroform- 7) d 7.93 - 7.79 (m, 4H), 7.78 - 7.57 (m, 6H), 5.62 (ddt, 7 = 17.0, 10.1, 6.7 Hz, 1H), 5.02 - 4.87 (m, 2H), 3.37 - 3.12 (m, 4H), 2.22 (q, 7 = 7.1 Hz, 2H), 1.53 (h, 7 = 7.8 Hz, 2H), 1.46 - 1.34 (m, 4H), 1.21 (q, 7= 7.1 Hz, 2H), 0.74 (t, 7 = 7.3 Hz, 3H). ¹³C NMR (126 MHz, Chloroform-7) d 136.13, 134.75 (d, 7 = 3.1 Hz), 133.05 (d, 7 = 9.5 Hz), 130.34 (d, 7= 12.2 Hz), 117.73 (d, 7= 82.2 Hz),

116.92, 33.81 (d, 7 = 16.3 Hz), 32.36 (d, 7 = 15.4 Hz), 22.01 (d, 7 = 1.0 Hz), 21.79 (d, 7 = 2.3 Hz), 21.55 (d, 7 = 48.2 Hz), 21.40 (d, 7 = 2.0 Hz), 21.02 (d, 7 = 49.8 Hz), 13.62. ³¹P NMR (202 MHz, Chloroform-7) d 28.01.

[0139] (5-(9-borabicvclol3.3.1 lnonan-9-yl Ipentyl )( pentyl )diphenyl-X⁴-phosphonium bromide

Mix pent-4-en-l-yl(pentyl)diphenylphosphonium bromide (0.68 g, 1.7 mmol) and 9-BBN (0.23 g, 1.8 mmol) in THF (5 ml) and stir at ambient temperature for 2 days. The solvent was then removed under vacuo. Diethyl ether (~10ml) was added to the crude product. The pure product slowly crushed out as white solid. Fully dissolve all product into dichloromethane and then remove all solvents. The process was repeated 3 times in order to fully remove all oxygen containing solvents. The final isolation yield is 680 mg (77%). ¹ H NMR (400 MHz,

Chloroform-7) d 7.91 (dd, 7 = 12.1, 7.6 Hz, 4H), 7.83 - 7.61 (m, 6H), 3.46 - 3.23 (m, 4H), 1.92 - 1.73 (m, 6H), 1.68 - 1.38 (m, 16H), 1.28 (t, 7 = 7.6 Hz, 4H), 1.17 (dq, 7 = 9.7, 5.2, 4.0 Hz, 2H), 0.82 (t, 7 = 13 Hz, 3H). ¹³C NMR (126 MHz, Chloroform-7) d 134.64 (d, 7 = 3.1

Hz), 133.16 (d, 7 = 9.2 Hz), 130.29 (d, 7 = 11.8 Hz), 118.02 (d, 7 = 82.2 Hz), 33.53 (d, 7 = 15.2 Hz), 33.07, 32.42 (d, 7 = 15.7 Hz), 30.94, 27.61, 24.01, 23.15, 22.17, 22.11 (d, 7 = 7.8 Hz), 22.09 (d, 7 = 0.9 Hz), 21.90 (d, 7 = 4.5 Hz), 21.74 (d, 7= 13.0 Hz), 13.65. ³¹PNMR (162 MHz, Chloroform-7) d 28.32. ⁿB NMR (160 MHz, Chloroform-7) d 88.55. [0140] di(pent-4-en-l-yl)(phenyl)phosphane

To the THF (50 ml) solution of 5-Bromo-l-pentene (9.2 g, 61 mmol) and magnesium (1.7 g, 70 mmol) powder was catalytic amount of iodine to initiate the Grignard reaction. The reaction was then stirred at 70 °C for 3 hours. Then cool the reaction to 0°C and p.p-dichlorophenylphosphine (5.0 g, 28 mmol) was slowly added. The reaction was allowed to stir at room temperature for 1 hour. THF was then removed under vacuo and the reaction was redissolved into dichloromethane (100 ml). A few drops NH4Cl(_aq) was added and the raction was stirred for 15 minutes until the excess Grignard reactant was fully quenched. The reaction was then dried with MgS0₄ and filtered by a silica pad. After solvent removal, the pure product was collected by vacuum distillation as a clear oil (2.0 g, 29%). ¹ H NMR (400 MHz, Chloroform-7) d 7.54 (td, 7 = 7.3, 2.6 Hz, 2H), 7.43 - 7.30 (m, 3H), 5.77 (ddt, 7 = 16.9, 10.1, 6.7 Hz, 2H), 5.14 - 4.86 (m, 4H), 2.14 (q, 7 = 7.2 Hz, 4H), 1.74 (t, 7 = 6.5 Hz, 4H), 1.69 - 1.28 (m, 4H). ³¹P NMR (162 MHz, Chloroform-7) d -24.81.

[0141] tri(pent-4-en- l-yl)(phenyl)phosphonium bromide

Mix di(pent-4-en-l-yl)(phenyl)phosphane (2.1 g, 8.1 mmol) and 5-Bromo-l-pentene (1.33 g, 8.9 mmol) in acetonitrile (5 ml) and stir at 80°C for 16 hours. The solvent was then removed under vacuo. Diethyl ether (~10ml) was added to the crude product. The pure product slowly crushed out as white solid (2.66 g, 83%). ¹ H NMR (400 MHz, Chlorol^'ornw/) d 7.94

(dd, 7 = 11.8, 7.1 Hz, 2H), 7.73 (dtd, 7 = 18.3, 7.9, 4.3 Hz, 3H), 5.90 - 5.58 (m, 3H), 5.16 - 4.91 (m, 6H), 3.03 - 2.78 (m, 6H), 2.27 (q, 7 = 7.1 Hz, 6H), 1.62 (q, 7 = 7.8 Hz, 6H). ³¹P NMR (162 MHz, Chlorol^'ornw/) d 30.44.

[0142] tris(5-(9-horahicyclo|3.3.1 |nonan-9-yl Inentyl Knhenyl )-X⁴-nhosphonium bromide

Mix tri(pent-4-en-l-yl)(phenyl)phosphonium bromide (2.62 g, 6.6 mmol) and 9-BBN (2.59 g, 21 mmol) in THF (5 ml) and stir at 65°C for 16 hours. The solvent was then removed under vacuo. The crude product was washed by diethyl ether (~5ml). The pure product was collected as white solid (4.65 g, 92%). ¹ H NMR (400 MHz, Chlorol^'ornw/) d 8.02 (dd, 7 = 1 1.6, 7.5 Hz, 2H), 7.72 (ddt, 7 = 14.7, 9.8, 4.4 Hz, 3H), 2.91 (dt, 7 = 14.3, 7.0 Hz, 6H), 1.83 (dt, 7 = 12.8,

4.9 Hz, 18H), 1.72 - 1.43 (m, 36H), 1.35 (d, 7 = 7.0 Hz, 6H), 1.20 (dq, 7 = 9.5, 5.5, 4.0 Hz, 6H). ³¹P NMR (162 MHz, Chloroform-7) d 29.89. ⁿB NMR (128 MHz, Chloroform-7) d 86.96. [0143] propane- l,3-diylbis(pent-4-en-l-yldiphenylphosphonium) bromide

Mix l,3-bis(diphenylphosphaneyl)propane (2.0 g, 4.85 mmol) and 5-Bromo-l-pentene (1.59 g, 10.7 mmol) in acetonitrile (10 ml) and stir at 80°C for 2 days. The solvent was then removed under vacuo. Diethyl ether (~10ml) was added to the crude product. The pure product slowly crushed out as white solid (3.44 g, 94%). ¹ H NMR (400 MHz, Chloroform-*:/) d 7.94

(dd, J = 12.0, 7.6 Hz, 8H), 7.75 - 7.54 (m, 12H), 5.64 (ddt, J = 17.0, 10.2, 6.7 Hz, 2H),

5.16 - 4.76 (m, 4H), 3.81 (dd, / = 16.0, 12.6 Hz, 4H), 3.29 (dd, / = 16.4, 12.2 Hz, 4H), 2.26 (q, J = 7.1 Hz, 4H), 2.08 - 2.01 (m, 2H), 1.55 (q, J = 7.9 Hz, 4H). ³¹P NMR (162 MHz, Chlorol^'orrrw/) d 27.18.

[0144] propane- 1, 3-diylbis((5-((ls, 5s)-9-borabicYclor3.3. Hnonan-9- yl Ipentyl Idiphenylphosphonium ) bromide

Mix propane- l,3-diylbis(pent-4-en-l-yldiphenylphosphonium) bromide (3.24 g, 4.6 mmol) and 9-BBN (1.17 g, 9.6 mmol) in THF (5 ml) and stir at 65°C for 16 hours. The solvent was then removed under vacuo. Diethyl ether (~10 ml) was added to the crude product. The pure product slowly crushed out as white solid (4.22 g, 97%). ¹ H NMR (400 MHz, Chloroform-*/) d 7.97 (dd, /= 12.1, 7.5 Hz, 8H), 7.79 - 7.52 (m, 12H), 3.93 - 3.66 (m, 4H), 3.31 (dq, J= 11.9, 6.5 Hz, 4H), 2.18 - 1.95 (m, 2H), 1.89 - 1.68 (m, 12H), 1.67 - 1.34 (m, 24H), 1.32 - 1.07 (m, 8H). ³¹P NMR (162 MHz, Chloroform-*/) d 27.19. ⁿB NMR (128 MHz, Chlorolbrnw/) d 86.46.

[0145] propane- 1, 3-diylbis((5-((ls, 5s)-9-borabicvclor3.3.11nonan-9- vDpentvDdiphenylphosphonium) (2R,3R)-bicyclor2.2.11hept-5-ene-2,3-dicarboxylate

The THF (5 ml) solution of propane-1, 3-diylbis((5-((ls,5s)-9-borabicyclo[3.3. l]nonan-9- yl)pentyl)diphenylphosphonium) bromide (1.38 g, 1.45 mmol) and (2R,3R)- bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate sodium (0.38 g, 1.45 mmol) was stirred at room temperature for 2 days. All THF was then removed under vacuo and the crude product was dissolved into dichloromethane. Sodium bromide solid was then removed by gravity filtration on celite. And the solvent was removed under vacuo. The product was redissolved into dichloromethane which was then removed. The step was repeated a few times until all THF was fully removed. The product was then placed under vacuum till full dryness and was isolated as white solid (1.21 g, 86%). ³¹P NMR (162 MHz, Chloroform-_<i) d 27.20. [0146] bis(5-(dimesitylboraneyl)pentyl)diphenylphosphonium bromide

Mix di(pent-4-en-l-yl)diphenylphosphonium bromide (0.20 g, 0.5 mmol) and dimesityl borane (0.26 g, 1.1 mmol) in THF (5 ml) and stir at 60°C for 2 days. All THF was then removed under vacuo and the crude product was dissolved into dichloromethane. Solid residues were then removed by gravity filtration on celite. And the solvent was removed under vacuo. The product was redissolved into dichloromethane which was then removed. The step was repeated a few times until all THF was fully removed. The product was then placed under vacuum till full dryness and was isolated as white solid (0.28 g, 65%). ¹ H NMR (400 MHz, Chloroform- d) δ 7.89 - 7.72 (m, 6H), 7.67 (dt, /= 8.1, 4.1 Hz, 4H), 6.76 (s, 8H), 3.22 (td, J= 12.4, 6.5 Hz, 4H), 2.24 (s, 12H), 2.16 (s, 24H), 1.82 (t, J = 7.8 Hz, 4H), 1.52 (d, J = 7.1 Hz, 4H), 1.38 (q, J

= 8.3, 7.7 Hz, 8H). ¹¹B NMR (128 MHz, Chloroform-d) δ 2.05. ³¹P NMR (162 MHz, Chloroform-d) δ 28.18. ¹³C NMR (126 MHz, Chloroform-d) δ 142.26, 138.83, 138.26, 134.63 (d, J = 3.0 Hz), 133.14 (d, J = 9.4 Hz), 130.25 (d, J = 11.9 Hz), 128.36, 117.80 (d, J = 82.1 Hz), 34.15, 33.69 (d, J = 15.4 Hz), 25.26, 22.72, 22.28 (d, J = 4.6 Hz), 21.97 (d, J = 48.5 Hz), 21.06.

[0147] Tetra(pent-4-en-l-yl)phosphonium bromide (C oH PBr). Mix tri(pent-4-en-l- yl)phosphane (6.44 g, 27.0 mmol) and 5-Bromo-l-pentene (4.83 g, 32.4 mmol) in acetonitrile (20 ml) and stir at 75°C for 1 day. The solvent was then removed under vacuo. The crude product was stirred with pentane (15 ml). And then all pentane was decanted away. The product was placed under vacuum till full dryness and was collected as foamy solid (10.4 g, 99%). ¾ NMR (400 MHz, Chloroform-d) d 5.70 (ddt, J = 17.0, 10.2, 6.8 Hz, 4H), 5.12 - 4.95 (m, 8H), 2.58 - 2.32 (m, 8H), 2.21 (q, J = 7.0 Hz, 8H), 1.74 - 1.49 (m, 8H). ¹³C NMR (126 MHz, Chloroform- ) d 135.83, 116.93, 33.99 (d, /= 15.5 Hz), 20.88 (d, / = 4.2 Hz), 18.35 (d, J = 47.7 Hz). ³¹P NMR (162 MHz, Chlorol^'orn /) d 33.77.

[0148] Tetra(5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl)phosphonium bromide

(C H B BrP). Mix tetra(pent-4-en-l-yl)(phenphosphonium bromide (10.0 g, 25.8 mmol) and 9-BBN (12.9 g, 106 mmol) in THF (100 ml) and stir at 70°C for 16 hours. The reaction solution was filtered onto celite and was washed by dichloromethane. All Solvents were then removed under vacuo. The crude product was stirred with pentane (~20 ml) for 30 minutes. After solvent removal, the crude product was stirred with more pentane and Et₂0 mixture. And then all solvent was decanted away. The pure product was collected as clear oil (20.0 g, 88 %). ¾ NMR (400 MHz, Chloroform-^/) d 2.49 (tt, J = 8.7, 5.3 Hz, 8H), 1.83 (dq, J = 7.6, 3.5 Hz, 24H), 1.75 - 1.44 (m, 48H), 1.37 (t, J= 6.7 Hz, 8H), 1.26 - 1.09 (m, 8H). ¹³C NMR (126 MHz,

Chloroform-d) d 33.96 (d, J = 14.3 Hz), 33.15, 31.06, 27.66, 24.04, 23.19, 22.00 (d, J = 4.9 Hz), 19.53 (d, / = 46.8 Hz). ⁿB NMR (160 MHz, CDC1₃) d 33.36. ³¹PNMR (162 MHz, CDCb) d 32.68.

[0149] Tetra(5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl)phosphonium (2R,3R)- bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (C₁₁₃H₂₀₀B₈O₄P₂). Mix tetra(5-(9- borabicyclo[3.3. l]nonan-9-yl)pentyl)phosphonium bromide (9.75 g, 10.4 mmol) and (2R,3R)- bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate sodium (1.36 g, 5.19 mmol) in dichloromethane (50 ml) and stir at ambient temperature for 48 hours. Sodium Bromide was removed by gravity filtration on celite. Then dichloromethane was removed under vacuo. The crude product was stirred in Et₂0 for 16 hours. All Et₂0 was decanted away. The pure product (9.40 g, 95 %) was collected as white solid. ¹ H NMR (400 MHz, Chloroform-d ) δ 6.19 (s, 2H), 3.09-2.92 (m, 2H), 2.56 - 2.07 (m, 16H), 1.89-1.74 (m, 48H), 1.70 - 1.40 (m, 98H), 1.30 (br, 16H), 1.25 - 1.09 (m, 16H), 0.91 (d, J = 1.3 Hz, 2H). ¹³C NMR (126 MHz, Chloroform-d) δ 177.94 (d, J = 37.0 Hz), 176.56 (d, J = 27.5 Hz), 137.56 (d, J = 39.0 Hz), 135.12 (d, J = 61.2 Hz), 50.68 (d, J = 4.4 Hz), 50.40, 48.39 (d, J = 8.1 Hz), 43.01 (d, J = 12.7 Hz), 42.45 (d, J = 12.6 Hz), 33.96 (d, J = 13.7 Hz), 33.10, 30.62, 27.11, 24.01, 23.38 (d, J = 3.6 Hz), 21.82 (d, J = 4.5 Hz), 19.33 (d, J = 46.7 Hz). ³¹P NMR (162 MHz, CDCl₃) d 32.88.

[0150] (5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl)tributylphosphonium bromide

(C₂₅H₅₁BBrP). Mix tributyl(pent-4-en-l-yl)phosphonium bromide (2.00 g, 5.48 mmol) and 9- BBN (0.69 g, 5.69 mmol) in THF (20 ml) and stir at 70°C for 16 hours. All solvent was then removed under vacuo. The crude product was stirred in pentane (20 ml) for 30 minutes. The pure product () was obtained by filtration as white solid and was washed by pentane and Et20. ^lH NMR (400 MHz, Chloroform-d) δ 2.56 - 2.36 (m, 8H), 1.88-1.77 (m, 4H), 1.70 - 1.44 (m, 24H), 1.36 (dd, 7 = 8.3, 6.5 Hz, 4H), 1.39-1.33 (m, 2H), 1.02 - 0.89 (m, 9H). ¹³C NMR (126 MHz, Chloroform-7) d 33.05, 32.03, 30.93, 30.65 (d, 7 = 14.5 Hz), 27.83, 24.00 (d, 7 = 13.7 Hz), 23.82 (d, 7 = 2.3 Hz), 23.45 (d, 7= 81.6 Hz), 21.81 (d, 7 = 4.7 Hz), 19.34 (d, 7 = 46.9 Hz), 19.13 (d, 7 = 47.4 Hz), 13.44. ³¹P NMR (162 MHz, CDC1₃) d 32.75.

[0151] (5-(9-borabicyclo[3.3.1]nonan-9-yl)pentyl) tris(dimethylamino)phosphonium bromide (Ci9H42BrBP). Mix tris(dimethylamino)(pent-4-en-l-yl)phosphonium bromide (2.50 g, 8.01 mmol) and 9-BBN (1.03 g, 8.41 mmol) in THF (20 ml) and stir at 70°C for 16 hours. All Solvent was then removed under vacuo. The crude product was stirred in pentane (20 ml) for 30 minutes. The pure product () was obtained by filtration as white solid and was washed by pentane and Et₂0. ¹ H NMR (400 MHz, Chloroform- 7) d 2.81 (d, 7 = 9.8 Hz, 18H),

2.68 - 2.51 (m, 2H), 1.90 - 1.70 (m, 6H), 1.70 - 1.41 (m, 12H), 1.32 (t, 7 = 6.4 Hz, 2H), 1.23 - 1.00 (m, 2H). ¹³C NMR (126 MHz, Chloroform-7) d 37.46 (d, 7= 3.6 Hz), 33.84 (d, 7 = 17.3 Hz), 33.07, 30.95, 27.64, 24.29 (d, 7 = 46.4 Hz), 23.87 (d, 7 = 55.9 Hz), 23.13, 22.17 (d, 7 = 4.5 Hz). ³¹P NMR (162 MHz, CDCI3) d 59.80. ⁿB NMR (128 MHz, CDCI3) d 87.94.

[0152] (3-(9-borabicyclo[3.3.1]nonan-9-yl)propyl)tributylphosphonium bromide

(C₂₃H₄₇BBrP). Mix allyltributylphosphonium bromide (2.00 g, 6.18 mmol) and 9-BBN (0.78 g, 6.43 mmol) in THF (20 ml) and stir at 70°C for 16 hours. All solvent was then removed under vacuo. The crude product was stirred in pentane (20 ml) for 30 minutes. The pure product was obtained by filtration as white solid and was washed by pentane and diethyl ether. ^lH NMR (400 MHz, CDCI₃) δ 2.59 - 2.37 (m, 8H), 1.95 - 1.71 (m, 8H), 1.71 - 1.58 (m, 8H), 1.54 (dt, 7 = 7.5, 3.9 Hz, 12H), 1.28 - 1.15 (m, 2H), 1.02 - 0.90 (m, 9H). ¹³C NMR (126 MHz, CDCb) d 33.09, 30.92, 29.08 (d, 7= 14.0 Hz), 23.95, 23.81 (d, 7 = 4.4 Hz), 23.01, 22.12 (d, 7 = 45.2 Hz), 19.12 (d, 7 = 47.2 Hz), 17.40 (d, 7 = 4.8 Hz), 13.44. ³¹P NMR (162 MHz, CDCb) d 32.15. Polymerization

[0153] The polymerization of CO₂ and cyclohexene oxide (CHO) are performed in a stainless steel vessel. The catalyst was firstly dissolved in 100 uL epoxide with respective epoxide/catalyst mole ratios. Then, the vessel was pressurized with 450 psi CO₂, isolated, and heated at respective temperatures for 12 hours. The reaction was then brought back to ambient temperature and depressurized. An aliquot was then extracted and dissolved in 1 mL CDCI3 containing l,3-bis(trimethylsilyl)benzene (5 mM) as an internal standard for quantification. The conversion and tune over number (TON) was determined by 1H NMR spectroscopy.

Table 1: CO₂ and cyclohexene oxide (CHO) polymerization Examples.

Polymerization Examples in the Parr reactors (large scale)

[0154] AF6407B is a PCHC-P(CL/MCL)-PCHC triblock copolymer (Example 11).

Catalyst BDI-Mn (24.0 mg) was dissolved in 1 mL dicholoride methane. The catalyst solution was quickly transferred to a mixture of CL (25.0 mL), MCL (9.3 mL), CHO (20 mL), and 1,4-phenylene dimethanol (PDM, 50.3 mg). The polymerization was performed at 120°C for 3 hours. After 3 hours, the solution was brought to 50°C. A DCM solution (1 mL) of catalyst 2 (42.7 mg) was added to the mixture. The reaction was pressurized with 450 psig CO₂ and heated to 80°C for 16 hours in a 600 mL vessel. After 16 hours, the vessel was depressurized. The polymer was dissolved in DCM and then precipitated into methanol. The polymer was isolated by filtration and dried under vacuum at 90°C for 12 hours (yield: 45.24 g). The ¹ H NMR analysis indicated PCL/PMCL/PCHC mol ratio of 63/18/19. THF GPC revealed an Mw/Mn of 45,874/27,133.

[0155] AF6410B is a PCHC-P(CL/MCL)-PCHC triblock copolymer (Example 12).

Catalyst BDI-Mn (19.0 mg) was dissolved in 1 mL dicholoride methane. The catalyst solution was quickly transferred to a mixture of CL (16.0 mL), MCL (2.6 mL), CHO (40 mL), and 1,4- phenylene dimethanol (PDM, 39.9 mg). The polymerization was performed at 120°C for 3 hours. After 3 hours, the solution was brought to 50°C. A DCM solution (1 mL) of catalyst 2 (42.7 mg) was added to the mixture. The reaction was pressurized with 450 psig CO₂ and heated to 80°C for 16 hours in a 600 mL vessel. After 16 hours, the vessel was depressurized. The polymer was dissolved in DCM and then precipitated into methanol. The polymer was isolated by filtration and dried under vacuum at 90°C for 12 hours (yield: 41.90 g). The ¹ H NMR analysis indicated PCL/PMCL/PCHC mol ratio of 43/7/50. THF GPC revealed an Mw/Mn of 22,414/15,570.

[0156] AF6411B is a PCHC-P(CL/DL)-PCHC triblock copolymer (Example 13). Catalyst BDI-Mn (23.8 mg) was dissolved in 1 mL CHO. The catalyst solution was quickly transferred to a mixture of CL (20.0 mL), DL (6.2 mL), and 1 ,4-phenylene dimethanol (PDM, 50.0 mg). The polymerization was performed at 120°C for 3 hours. After 3 hours, the solution was brought to 50°C. A CHO solution (20 mL) of catalyst 2 (51.2 mg) was added to the mixture. The reaction was pressurized with 450 psig CO₂ and heated to 80°C for 16 hours in a 600 mL vessel. After 16 hours, the vessel was depressurized. The polymer was dissolved in DCM and then precipitated into methanol. The polymer was isolated by filtration and dried under vacuum at 90°C for 12 hours (yield: 33.34 g). The ¹ H NMR analysis indicated PCL/PDL/PCHC mol ratio of 57/9/34. THF GPC revealed an Mw/Mn of 99,684/81,462.

PVCHC [0157] Synthesis of polyvinylcyclohexene carbonate (PVCHC) polyol (Example 14).

To a Parr reactor was charged with Catalyst 4 (50.4 mg), vinyl cyclohexene oxide VCHO (40 mL), and trans-dihydroxycyclohexane DHCH (89.1 mg). The reactor was then pressurized with a steady-state CO₂ pressure of 500 psi and heated at 80°C for 16 hours. The polymerization was terminated by cooling down to ambient temperatures, followed by the release of CO₂. An aliquot was extracted for ¹ H NMR analysis (CDCI3), revealing that 70.5 % of vinyl cyclohexene oxide was converted into polyvinylcyclohexene carbonate. Around 120 mL dichloromethane was added. The mixture was transferred into a large beaker, and all volatiles were removed under reduced pressure at 90°C, yielding a white solid. The solid was further washed with methanol and dried under vacuum at 90°C to give 32.68 g polymer. THF GPC revealed Mw and Mn of 33,662 g/mol and 32,852 g/mol, respectively.

[0158] Synthesis of polycyclohexene carbonate (PCHC) (Example 15). To a Parr reactor was charged with Catalyst 20 (346.1 mg) and CHO (40 mL). The reactor was then pressurized with a steady-state CO₂ pressure of 400 psi and heated at 80°C for 3.5 hours. The polymerization was terminated by cooling down to ambient temperatures, followed by the release of CO₂. An aliquot was extracted for ¹ H NMR analysis (CDCL), revealing that 82.4% of cyclohexene oxide was converted into polycyclohexene carbonate. Around 100 mL dichloromethane was added. The mixture was transferred into a large beaker containing 500 mL methanol (with 1 wt% water), leading to the precipitation of the polymer. The polymer was isolated by filtration, and all volatiles were removed under reduced pressure at 90°C, yielding 41.34 g polymer. THF GPC revealed Mw and Mn of 19,845 g/mol and 15,976 g/mol, respectively.

[0159] Synthesis of telechelic polycyclohexene carbonate (PCHC) (Example 16). To a

Parr reactor was charged with Catalyst 22 (350.1 mg) and CHO (40 mL). The reactor was then pressurized with a steady-state CO₂ pressure of 400 psi and heated at 80°C for 3.5 hours. The polymerization was terminated by cooling down to ambient temperatures, followed by the release of CO₂. An aliquot was extracted for ¹ H NMR analysis (CDCL), revealing that 75.8 % of cyclohexene oxide was converted into polycyclohexene carbonate. Around 100 mL dichloromethane was added. The mixture was transferred into a large beaker containing 500 mL methanol (with 1 wt% water), leading to the precipitation of the polymer. The polymer was isolated by filtration, and all volatiles were removed under reduced pressure at 90°C, yielding 39.66 g polymer. THF GPC revealed Mw and Mn of 23,549 g/mol and 20,259 g/mol, respectively.

[0160] Synthesis of polybutylene carbonate (Example 17). To a Parr reactor was charged with Catalyst 20 (453.5 mg). The reactor was charged with 100 psi CO₂ at ambient temperatures. Butylene oxide (BO) was added with CO₂ (200 psig) to initiate the polymerization. The reactor was then pressurized with a steady-state CO₂ pressure of 400 psi and heated at 50°C for 7 hours. The polymerization was terminated by cooling down to ambient temperatures, followed by the release of CO₂. An aliquot was extracted for ¹ H NMR analysis (CDCb), revealing that 33.3% of butylene oxide was converted into polybutylene carbonate. Around 120 mL dichloromethane was added. The mixture was transferred into a large beaker, and all volatiles were removed under reduced pressure at 40°C, yielding 17.7 g polymer.

[0161] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including." Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase "comprising", it is understood that we also contemplate the same composition or group of elements with transitional phrases "consisting essentially of," "consisting of", "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or elements and vice versa.

Claims

PCT CLAIMS: What is claimed is:

1. A catalyst complex represented by the Formula (I):

where (the number of phosphonium moieties, P+) x Z = T x Q;

B* is a group 13 metal

Z is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups;

T is 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the anionic charge of X; Q is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the number of X present; each R¹, R², R³, R⁴, and R⁵ is independently a hydrocarbyl group, a substituted hydrocarbyl group, (such as an alkyl, substituted alkyl, aryl, substituted aryl group), a hydrocarbyl group containing heteroatoms (preferably N, Si, O, or S) to form heteroatom-C or heteroatom-P or heteroatom-B* bonds, another B*, another P+, or a catalyst composition represented by the Formula (I), where one or more of R¹ and R², R³ and R⁴, R⁴ and R⁵, and R³ and R⁴ and R⁵ are optionally fused; each Y is independently a linking group having 1 to 50 non-hydrogen atoms; and each X is independently a di-anionic group, a multi-anionic group, or a combination thereof.

2. The catalyst complex of claim 1, wherein at least one of R¹, R², R³, R⁴, and R⁵ is independently the substituted hydrocarbyl that is substituted with another catalyst composition represented by Formula (I), a group 13 metal-containing moiety of Formula (I), or a phosphonium-containing moiety of Formula (I).

3. The catalyst complex of claim 2, wherein the group 13 metal-containing moiety is a boron-containing moiety of Formula (I).

4. The catalyst complex of any preceding claim, wherein the catalyst complex is one or more of:

5. The catalyst complex any preceding claim, wherein the catalyst complex is one or more of:

6. The catalyst complex of any one of claims 1-4, wherein the catalyst complex is represented by Formula (I-A):

(I-A) where (the number of phosphonium moieties, P+) x Z = (L x M) + (G x J);

B* is a group 13 metal;

Z is 1 to 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups;

G and L are, independently, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

7. The catalyst complex of any preceding claim, wherein Z is 1 or 2, R³, R⁴, and R⁵ are each independently hydrocarbons that contain 0, 1, or 2 B*, T is 1 or 2, and Q is 1.

8. The catalyst complex of any preceding claim, wherein one or more of R¹, R², R³, R⁴, and R⁵ comprises one or more catalyst compositions selected form the group consisting of catalyst compositions represented by the Formula (I).

9. The catalyst complex of any preceding claim, wherein each Y is independently selected from group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenylene, substituted phenylene, benzyl, substituted benzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

10. The catalyst complex of any preceding claim, wherein each Y is a bridging group containing at least one Group 13, 14, 15, or 16 element.

11. The catalyst complex of claim 10, wherein Y is represented by the formula ERd2 or (ERd2)2, where E is C, Si, or Ge, and each Rd is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl or a Ci to C20 substituted hydrocarbyl, and two Rd optionally form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

12. The catalyst complex of any preceding claim, wherein X is a group 13 to 17 heteroatom, substituted heteroatom, monovalent heteroatom, or monovalent substituted group 13 to 16 heteroatom.

13. A composition comprising a triblock copolymer of blocks A-B-A, wherein the blocks are covalently linked, the block A includes polycarbonate or copolymers of polycarbonate and poly ether, and the block B includes caprolactone and at least one or more lactones.

14. The composition of claim 13, wherein the block A is polycyclohexene carbonate, polymethylcyclohexene carbonate, or polyvinylcyclohexene carbonate.

15. The composition of claim 13 or 14, wherein the block A includes C0₂/epoxide in a mol ratio that ranges from 50/50 to 25/75.

16. The composition of claim 13, 14, or 15, wherein the block B includes methyl caprolactone or decalactone, and the mol% of the caprolactone is from 0.5% to 99.5%.

17. The composition of any one of claims 13-16, wherein a glass transition temperature of block B is from 20°C to -70°C, and a glass transition temperature of block A is from 30°C to 450°C.

18. The composition of any one of claims 13-17, wherein a Mw of the triblock copolymer ranges from 5,000 to 1,000,000, with a weight ratio of block A to block B ranging from 95/5 to 5/95.

19. The composition of any one of claims 13-18, wherein the triblock copolymer is PCHC- P(CL/MCL)-PCHC, PCHC-P(CL/MCL)-PCHC, or PCHC-P(CL/DL)-PCHC, where PCHC is polycyclohexene carbonate, P(CL/MCL) is copolymers of caprolactone and methylcaprolactone, P(CL/DL) is copolymers of caprolactone and decalactone.