US 11,965,062 B2
Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates
Michael Kember, Macclesfield Cheshire (GB); James Leeland, Macclesfield Cheshire (GB); Rakibul Kabir, Macclesfield Cheshire (GB); and Emmalina Hollis, Macclesfield Cheshire (GB)
Assigned to Econic Technologies LTD., Macclesfield (GB)
Appl. No. 16/757,870
Filed by Econic Technologies LTD, Macclesfield Cheshire (GB)
PCT Filed Oct. 24, 2018, PCT No. PCT/GB2018/053082
§ 371(c)(1), (2) Date Apr. 21, 2020,
PCT Pub. No. WO2019/081931, PCT Pub. Date May 2, 2019.
Claims priority of application No. 1717459 (GB), filed on Oct. 24, 2017.
Prior Publication US 2020/0339749 A1, Oct. 29, 2020
This patent is subject to a terminal disclaimer.
Int. Cl. C08G 65/26 (2006.01); C07F 15/04 (2006.01); C08G 18/44 (2006.01); C08G 64/34 (2006.01)
CPC C08G 65/2663 (2013.01) [C07F 15/045 (2013.01); C08G 18/44 (2013.01); C08G 64/34 (2013.01); C08G 65/2603 (2013.01); C08G 65/269 (2013.01)] 15 Claims
 
1. A method for preparing a polycarbonate ether polyol, the method comprising the steps of:
(I) (a) mixing catalyst of formula (I), double metal cyanide (DMC) catalyst and optionally carbon dioxide and/or solvent with epoxide and optionally starter compound and/or carbon dioxide to form mixture (α); or
(b) mixing double metal cyanide (DMC) catalyst and optionally starter compound, carbon dioxide and/or solvent with epoxide and optionally carbon dioxide and/or solvent to form mixture (α); or
(c) mixing epoxide, catalyst of formula (I), starter compound and carbon dioxide and optionally solvent to form mixture (α); or
(d) mixing catalyst of formula (I), double metal cyanide (DMC) catalyst and optionally starter compound, epoxide, carbon dioxide and/or solvent to form mixture (α); and
(II) adding one or more of starter compound, epoxide, catalyst of formula (I), double metal cyanide (DMC) catalyst and/or solvent, and optionally carbon dioxide, to mixture (α) to form mixture (β) comprising starter compound, epoxide, carbon dioxide, catalyst of formula (I), double metal cyanide (DMC) catalyst and optionally solvent,
wherein the catalyst of formula (I) has the following structure:

OG Complex Work Unit Chemistry
wherein M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2 or Ti(IV)-(X)2;
R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl; E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
E3, E4, E5 and E6 are selected from N, NR4, O and S, wherein when E3, E4, E5 or E6 are N, custom character is custom character, and wherein when E3, E4, E5 or E6 are NR4, O or S, custom character is custom character;
R4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR19 or -alkylC≡N or alkylaryl, wherein R19 is independently selected from hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group;
X is independently selected from OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, S(O)Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, wherein each X may be the same or different and wherein X may form a bridge between M1 and M2;
Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and
G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.