POLYOL BLOCK COPOLYMER, COMPOSITIONS AND PROCESSES THEREFOR

Abstract

A polyol block copolymer including a polycarbonate block, A(AZZ(ZA).sub.n), and polyethercarbonate blocks, B. The polyol block copolymer has the polyblock structure:

##STR00001##

wherein n=t1 and wherein t=the number of terminal OH group residues on the block A; and wherein each A is independently a polycarbonate chain having at least 70% carbonate linkages, and wherein each B is independently a polyethercarbonate chain having 50-99% ether linkages and at least 1% carbonate linkages; and wherein ZZ(Z).sub.n is a starter residue. The process of producing a polyol block copolymer from a two step process carried out in two reactors, and products and compositions incorporating such copolymers.

Claims

1. A process for producing a polycarbonate ethercarbonate polyol block copolymer comprising a first reaction in a first reactor and a second reaction in a second reactor; wherein the first reaction is the reaction of a carbonate catalyst with CO.sub.2 and epoxide, in the presence of a starter and/or solvent to produce a polycarbonate polyol copolymer and the second reaction is the reaction of a DMC catalyst with the polycarbonate polyol copolymer of the first reaction and CO.sub.2 and epoxide to produce the polyol block copolymer.

2. The process according to claim 1 further comprising a third reaction comprising the reaction of the poly block copolymer of the second reaction with a monomer or further polymer in the absence of a DMC catalyst to produce a higher polymer, optionally wherein the monomer or further polymer is a (poly)isocyanate and the product of the third reaction is a polyurethane.

3. A process for producing a polyol block copolymer in a multiple reactor system; the system comprising a first and second reactor wherein a first reaction takes place in the first reactor and a second reaction takes place in the second reactor; wherein the first reaction is the reaction of a carbonate catalyst with CO.sub.2 and epoxide, in the presence of a starter and/or solvent to produce a polycarbonate polyol copolymer and the second reaction is the reaction of a DMC catalyst with the polycarbonate polyol compound of the first reaction and CO.sub.2 and epoxide to produce the polyol block copolymer.

4. The process according to claim 1, wherein the DMC catalyst is pre-activated, optionally in the second reactor or separately, optionally wherein the DMC is pre-activated with a starter compound or with the reaction product of the first or second reaction; or wherein the product of the first reaction is a low molecular weight polycarbonate polyol product having a molecular weight (Mn) in the range 200 to 4000 Daltons as measured by Gel Permeation Chromatography (GPC); or wherein the first reaction produces generally alternating polycarbonate polyol product; or wherein the epoxide is asymmetric and wherein the reaction produces a polycarbonate having between 40-100% head to tail linkages, preferably more than 70%, more than 80% or more than 90% head to tail linkages; or wherein the first reaction is carried out under CO.sub.2 pressure of less than 20 bar, more preferably, less than 10 bar, most preferably, less than 8 bar; or wherein the second reaction is carried out under CO.sub.2 pressure of less than 60 bar, preferably less than 20 bar, more preferably less than 10 bar, most preferably, less than 5 bar.

5. The process according to claim 1, wherein the CO.sub.2 is added continuously in the first reaction, preferably in the presence of a starter; or wherein the first reaction can be a batch, semi-batch, or continuous process; or wherein the second reaction can be a continuous process or semi batch process.

6. The process according to claim 1, wherein the product of the first reaction is fed into the second reactor as a crude reaction mixture, wherein said second reactor contains a pre-activated DMC catalyst.

7. The process according to claim 6, wherein the crude reaction mixture fed into the second reactor includes an amount of unreacted epoxide and/or CO.sub.2 and/or starter; or wherein the carbonate catalyst is present in the crude reaction mixture; or wherein the carbonate catalyst has been removed from the crude reaction mixture prior to the addition to the second reactor; or wherein the crude reaction mixture is stabilised by an acid prior to addition to the second reactor.

8. The process according to claim 1, wherein the temperature of reaction in the first reactor is in the range about 0 C. to 250 C., preferably from about 40 C. to about 160 C., more preferably from about 50 C. to 120 C.; or wherein the temperature of reaction in the second reactor is in the range from about 50 to about 160 C., preferably in the range from about 70 to about 140 C., more preferably from about 70 to about 110 C.; or wherein the reactors are located in series; or wherein the reactors are nested, optionally wherein the first and second reactors are effective to provide different reaction conditions, such as temperature and/or pressure, to each other simultaneously.

9. The process according to claim 1, wherein the process employs a total amount of epoxide, and wherein about 1 to 100% of the total amount of epoxide is mixed in the first reaction, with any remainder added in the second reaction; optionally with about 5 to 90% being mixed in the first reaction, optionally with about 10 to 90%, optionally with about 20 to 90%, optionally with about 40 to 90%, optionally with about 40 to 80%, optionally with about 5 to 50%; or wherein the epoxides are selected from cyclohexene oxide, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C.sub.10H.sub.16O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C.sub.11H.sub.22O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides), unsubstituted or substituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers, glycidyl esters, glycidyl carbonates, vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides; or wherein between 0.1 and 20% of the total epoxide in the first reaction is an epoxide substrate containing more than one epoxide moiety, preferably a bis-epoxide; or wherein the carbonate catalyst is a catalyst capable of producing polycarbonate chains with greater than 76% carbonate linkages; or wherein the carbonate catalyst is a metal catalyst comprising phenol or phenolate ligands; or wherein the carbonate catalyst is a bimetallic complex comprising phenol or phenolate ligands; or wherein the carbonate catalyst is a catalyst of Formula (IV): ##STR00016## wherein M is a metal cation represented by M(L).sub.v; x is an integer from 1 to 4, ##STR00017## is a multidentate ligand or plurality of multidentate ligands; L is a coordinating ligand; v is an integer that satisfies the valency of M, and/or the preferred coordination geometry of M or is such that the complex represented by formula (IV) above has an overall neutral charge; or wherein the carbonate catalyst has the following structure: ##STR00018## wherein M.sub.1 and M.sub.2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)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).sub.2 or Ti(IV)(X).sub.2; R.sub.1 and R.sub.2 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; R.sub.3 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; R.sub.5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl; E.sub.1 is C, E.sub.2 is O, S or NH or E.sub.1 is N and E.sub.2 is O; E.sub.3, E.sub.4, E.sub.5 and E.sub.6 are selected from N, NR.sub.4, O and S, wherein when E.sub.3, E.sub.4, E.sub.5 or E.sub.6 are N, is , and wherein when E.sub.3, E.sub.4, E.sub.5 or E.sub.6 are NR.sub.4, O or S, is ; R.sub.4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR.sub.19 or -alkylCN or alkylaryl; X is independently selected from OC(O)R.sub.x, OSO.sub.2R.sub.x, OSOR.sub.x, OSO(R.sub.x).sub.2, S(O)R.sub.x, OR.sub.x, 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 M.sub.1 and M.sub.2; R.sub.xis 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; or wherein the carbonate catalyst is selected from catalysts of formula (IV), metal salen catalysts, metal porphyrin catalysts, metal tetraaza annulene catalysts and metal beta-diiminate catalysts as defined herein.

10. The process according to claim 1 wherein the DMC catalyst, in addition to at least two metal centres and cyanide ligands, also comprises at least one of: one or more complexing agents, water, a metal salt and/or an acid, optionally in non-stoichiometric amounts; or wherein the DMC catalyst is prepared by treating a solution of a metal salt with a solution of a metal cyanide salt in the presence of at least one of: complexing agent, water, and/or an acid, optionally wherein the metal salt is of the formula M(X).sub.p, wherein M is selected from Zn(II), Ru(II), Ru(III), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(VI), Sr(II), W(IV), W(VI), Cu(II), and Cr(III), X is an anion selected from halide, oxide, hydroxide, sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, p is an integer of 1 or more, and the charge on the anion multiplied by p satisfies the valency of M; the metal cyanide salt is of the formula (Y).sub.qM(CN).sub.b(A).sub.c, wherein M is selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V), Y is a proton or an alkali metal ion or an alkaline earth metal ion (such as K.sup.+), A is an anion selected from halide, oxide, hydroxide, sulphate, cyanide oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate; q and b are integers of 1 or more; c may be 0 or an integer of 1 or more; the sum of the charges on the anions Y, CN and A multiplied by q, b and c respectively (e.g. Yq+CNb+Ac) satisfies the valency of M; the at least one complexing agent is selected from a (poly)ether, a polyether carbonate, a polycarbonate, a poly(tetramethylene ether diol), a ketone, an ester, an amide, an alcohol, a urea or a combination thereof, optionally wherein the at least one complexing agent is selected from propylene glycol, polypropylene glycol, (m)ethoxy ethylene glycol, dimethoxyethane, tert-butyl alcohol, ethylene glycol monomethyl ether, diglyme, triglyme, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and sec-butyl alcohol, 3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, or a combination thereof; and wherein the acid, if present, has the formula H.sub.rX, where X is an anion selected from halide, sulfate, phosphate, borate, chlorate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, and r is an integer corresponding to the charge on the counterion X; or wherein the DMC catalyst comprises the formula: ##STR00019## wherein M and M are as defined above, and d, e, f and g are integers, and are chosen such that the DMC catalyst has electroneutrality, optionally, d is 3, e is 1, f is 6 and g is 2; or wherein the DMC catalyst comprises the formula: ##STR00020## wherein M, M, d, e, f and g are as defined above, M is M and/or M, X is an anion selected from halide, oxide, hydroxide, sulphate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, i is an integer of 1 or more, and the charge on the anion X multiplied by i satisfies the valency of M, h, j, k and l are each independently zero or a positive number, r is an integer that corresponds to the charge on the counterion X, and R.sup.c is a complexing agent or a combination of one or more complexing agents, optionally wherein the one or more complexing agents are selected from dimethoxyethane, tert-butyl alcohol, polyethylene glycol, polypropylene glycol, polyethercarbonate, poly (tetramethylene glycol), polycarbonate; or wherein the DMC catalyst is upon Zn.sub.3[Co(CN).sub.6].sub.2 (zinc based hexacyanocobaltate); or wherein the DMC catalyst is zinc hexacyanocobaltate and the one or more ligands are selected from alcohols and polyols.

11. The process according to claim 1, wherein the product of the first reaction is fed into the second reactor in a single portion or in a continuous or discontinuous manner, optionally wherein the product of the first reaction comprises unreacted epoxide and/or carbonate catalyst; or wherein the product of the first reaction is used to pre-activate the DMC catalyst in the second reaction, prior to addition of epoxide and CO.sub.2; or wherein the same or different epoxides are used in the first or second reactions; or wherein the epoxide used in the first or second reaction comprises propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide; or wherein the polycarbonate ethercarbonate polyol block copolymer comprises a polycarbonate block, A (AZZ(ZA).sub.n), and polyethercarbonate blocks, B, wherein the polyol block copolymer has the polyblock structure: ##STR00021## wherein n=t1 and wherein t=the number of terminal OH group residues on the block A; and wherein each A is independently a polycarbonate chain having at least 70% carbonate linkages, and wherein each B is independently a polyethercarbonate chain having 50-99% ether linkages and at least 1% carbonate linkages; and wherein ZZ(Z), is a starter residue.

12. A polyurethane comprising a block copolymer residue having a polycarbonate block, A (AZZ(ZA).sub.n), wherein A is a polycarbonate chain having at least 70% carbonate linkages, and polyethercarbonate blocks, B, each having up to 50% carbonate linkages and at least 50% ether linkages, wherein the residue has a polyblock structure BAZZ(ZA B).sub.n, wherein n=t1 and wherein t=the number of terminal OH group residues on the block A and wherein ZZ(Z).sub.nis a starter residue.

13. The polyurethane according to claim 12, wherein the starter residue depends on the nature of the starter compound, and wherein the starter compound has the formula (III): ##STR00022## wherein Z can be any group which can have 1 or more, typically, 2 or more R.sup.z groups attached to it and may be selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, cycloalkenylene, hererocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or Z may be a combination of any of these groups, for example Z may be an alkylarylene, heteroalkylarylene, heteroalkylheteroarylene or alkylheteroarylene group; a is an integer which is at least 1, typically, at least 2, optionally a is in the range of between 1 or 2 and 8, optionally a is in the range of between 2 and 6; wherein each R.sup.Z may be OH, NHR, SH, C(O)OH, P(O)(OR)(OH), PR(O)(OH).sub.2 or PR(O)OH, optionally R.sup.Z is selected from OH, NHR or C(O)OH, optionally each R.sup.z is OH, C(O)OH or a combination thereof (e.g. each R.sup.z is OH); wherein R may be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, optionally R is H or optionally substituted alkyl; and wherein Z corresponds to R.sup.z, except that a bond replaces the labile hydrogen atom.

14. The polyurethane according to claim 12, wherein A has the following structure: ##STR00023## wherein the ratio of p:q is at least 7:3; and block B has the following structure: ##STR00024## wherein the ratio of w:v is greater or equal to 1:1; and R.sup.e1, R.sup.e2, R.sup.e3 and R.sup.e4 depend on the nature of the epoxide used to prepare blocks A and B, optionally wherein each R.sup.e1, R.sup.e2, R.sup.e3, or R.sup.e4 is independently selected from H, halogen, hydroxyl, or optionally substituted alkyl (such as methyl, ethyl, propyl, butyl, CH.sub.2Cl, CH.sub.2OR.sub.20, CH.sub.2OC(O)R.sub.12, or CH.sub.2OC(O)OR.sub.18), alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl or heteroalkenyl, preferably selected from H or optionally substituted alkyl.

15. The polyurethane according to any one of claims 13, wherein a is an integer which is at least 2; or wherein a is 1 and accordingly the copolymer residue is of formula BAZZ; or wherein the starter compound is selected from monofunctional starter substances such as alcohols, phenols, amines, thiols and carboxylic acid, for example, alcohols such as methanol, ethanol, 1- and 2-propanol, 1- and 2-butanol, linear or branched C.sub.3-C.sub.20-monoalcohol such as tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, mono-ethers or esters of ethylene, propylene, polyethylene, polypropylene glycols such as ethylene glycol mono-methyl ether and propylene glycol mono-methyl ether, phenols such as linear or branched C.sub.3-C.sub.20 alkyl substituted phenols, for example nonyl-phenols or octyl phenols, monofunctional carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, fatty acids, such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid and acrylic acid, and monofunctional thiols such as ethanethiol, propane-1-thiol, propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol, or amines such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, and morpholine; and/or selected from diols such as 1,2-ethanediol (ethylene glycol), 1-2-propanediol, 1,3-propanediol (propylene glycol), 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl glycol, catechol, cyclohexenediol, 1,4-cyclohexanedimethanol, dipropylene glycol, diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycols (PPGs) or polyethylene glycols (PEGs) having an Mn of up to about 1500 g/mol, such as PPG 425, PPG 725, PPG 1000 and the like, triols such as glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methylalcohol)propane, tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylol propane, polyethylene oxide triols, polypropylene oxide triols and polyester triols, tetraols such as calix[4]arene, 2,2-bis(methylalcohol)-1,3-propanediol, erythritol, pentaerythritol or polyalkylene glycols (PEGs or PPGs) having 4OH groups, polyols, such as sorbitol or polyalkylene glycols (PEGs or PPGs) having 5 or more OH groups, or compounds having mixed functional groups including ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine.

16. The polyurethane according to claim 12, wherein the block copolymer residue molecular weight (Mn) is in the range 300-20,000 Da and the molecular weight (Mn) of block A is in the range 200-4000 Da, and wherein the molecular weight (Mn) of block B is in the range 100-20,000 Da, more typically, the molecular weight (Mn) of block A is 200-2000 Da, more typically 200-1000 Da, most typically 400-800 Da and/or the molecular weight (Mn) of block B is typically 200-10,000 Da, more typically 200-5000 Da, optionally wherein the molecular weight (Mn) is measured by Gel Permeation Chromatography (GPC); or wherein block A has at least 76%, more typically, at least 80% or most typically at least 85% carbonate linkages; and/or wherein block A has less than 98% carbonate linkages, more typically, less than 97% carbonate linkages or most typically less than 95% carbonate linkages; and/or wherein block A has between 75% and 99% carbonate linkages, more typically, between 77% and 95% carbonate linkages, most typically between 80 and 90% carbonate linkages; or wherein block B has at least 5% carbonate linkages, more typically at least 10% carbonate linkages, most typically at least 15% carbonate linkages; and/or wherein block B has between 1% and 50% carbonate linkages, more typically between 5% and 45% carbonate linkages, most typically, between 10% and 40% carbonate linkages; and/or wherein block B has at least 60% ether linkages, more typically, at least 65% ether linkages, most typically at least 70% ether linkages; and/or wherein block B has less than 95% ether linkages, more typically, less than 90% ether linkages, most typically less than 85% ether linkages; and/or wherein block B has between 50% and 99% ether linkages, more typically between 55% and 95% ether linkages, most typically, between 60% and 90% ether linkages; or wherein block A further comprises ether linkages, optionally wherein block A has less than 24% ether linkages, more typically, less than 20% ether linkages, most typically, less than 15% ether linkages; and/or wherein block A has at least 1% ether linkages, more typically, at least 3% ether linkages, most typically, at least 5% ether linkages; and/or wherein block A has between 1% and 25% ether linkages, typically between 5% and 20% ether linkages, more typically, between 10% and 15% ether linkages.

17. A polyurethane according to claim 12, wherein block A is a generally alternating polycarbonate polyol residue; and/or wherein the mol/mol ratio of block A to block B is in the range 25:1 to 1:250; or wherein at least 30% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, typically, at least 50% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, more typically, at least 75% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, most typically, at least 90% of the epoxide residues of block A are ethylene oxide or propylene oxide residues, and/or wherein at least 30% of the epoxide residues of block B are ethylene oxide or propylene oxide residues, typically, at least 50% of the epoxide residues of block B are ethylene oxide or propylene oxide residues, more typically, at least 75% of the epoxide residues of block B are ethylene oxide or propylene oxide residues, most typically, at least 90% of the epoxide residues of block B are ethylene oxide or propylene oxide residues.

18. The polyurethane according to claim 12 wherein the polyurethane is in the form of a soft foam, a flexible foam, an integral skin foam, a high resilience foam, a viscoelastic or memory foam, a semi-rigid foam, a rigid foam (such as a polyurethane (PUR) foam, a polyisocyanurate (PIR) foam and/or a spray foam), an elastomer (such as a cast elastomer, a thermoplastic elastomer (TPU) or a microcellular elastomer), an adhesive (such as a hot melt adhesive, pressure sensitive or a reactive adhesive), a sealant or a coating (such as a waterborne or solvent dispersion (PUD), a two-component coating, a one component coating, a solvent free coating), optionally wherein the polyurethane is formed via a process that involves extruding, moulding, injection moulding, spraying, foaming, casting and/or curing; further optionally wherein the polyurethane is formed via a one pot or pre-polymer process.

19. An isocyanate terminated polyurethane prepolymer comprising a block copolymer residue having a polycarbonate block, A (AZZ(ZA).sub.n), wherein A is a polycarbonate chain having at least 70% carbonate linkages and polyethercarbonate blocks, B, each having up to 50% carbonate linkages and at least 50% ether linkages wherein the residue has a polyblock structure BAZZ(ZA B).sub.n, wherein n=t1 and wherein t=the number of terminal OH group residues on the block A and wherein ZZ(Z).sub.n is a starter residue.

Description

EXAMPLES

Example 1

##STR00014##

[0237] Hexanediol (2.6 g) was added into a 100 mL reactor and a mixture of catalyst (1) (0.15 g) in PO (12.45 g) injected into the vessel. The vessel was heated to 75 C. and pressurised to 20 bar and stirred for 16 hours after which it was cooled and vented, resulting in a ca. 550 g/mol PPC-polyol. The contents of the reactor were then transferred to a clean, dry Schlenk along with PO (2 mL) and EtOAc (6 mL).

[0238] In a separate 100 mL reactor, 9.2 mg of DMC catalyst as made in WO2017/037441, example 1 and hexanediol (0.26 g) were dried at 120 C. under vacuum for 1 hour. Ethyl acetate (12 mL) was injected into the vessel via a syringe under continuous flow of CO.sub.2 gas. The vessel was heated to the desired temperature (130 C.). 3.75 g of propylene oxide was added in 3 bursts 1.25 g each with 30 minutes between each to confirm activity of the DMC catalyst.

[0239] The reactor was cooled to 85 C. whilst pressurising to 4.5 bar with CO.sub.2 and PO (1.25 g) was added. The Schlenk mixture from above was then added via a HPLC pump. added over 1 hour. The reaction continued for 5 hours. The reactor was cooled to below 10 C. and the pressure was released. NMR and GPC were measured immediately.

Example 2

[0240] PPG400 (7.26 g) was taken into a 100 mL reactor and dried at 120 C. under vacuum for 1 hour. A mixture of catalyst (1) (0.12 g) in PO (12.45 g) injected into the vessel. The vessel was heated to 75 C. and pressurised to 10 bar and stirred for 16 hours after which it was cooled and vented, resulting in a ca. 1000 g/mol PPC-polyol. The contents of the reactor were then transferred to a clean, dry Schlenk along with PO (3 mL) and EtOAc (9 mL) and kept under N.sub.2.

[0241] In a separate 100 mL reactor, 9.2 mg of DMC catalyst as per WO2017/037441 example 1 and PPG400 (0.88 g) were dried at 120 C. under vacuum for 1 hour. The reactor was cooled down to room temperature and ethyl acetate (12 mL) was injected into the vessel via a syringe under continuous flow of CO.sub.2 gas. The vessel was heated to the desired temperature (130 C.). 3.75 g of propylene oxide was added in 3 bursts (1.25 g each) with 30 minutes between each to confirm activity of the DMC catalyst.

[0242] The reactor was cooled to 85 C. whilst pressurising to 4.5 bar with CO.sub.2 and PO (1.25 g) was added. The Schlenk mixture from above was then added via a HPLC pump. added over 1 hour. The reaction was carried outover 5 hours. The reactor was cooled to below 10 C. and the pressure was released. NMR and GPC were measured immediately.

Example 3

[0243] Hexanediol (93.9 g) was taken into a 2 L reactor and dried at 120 C. under vacuum for 1 hour. The reactor was cooled and catalyst (1) (4.38 g) and PO (544 g) were added to the vessel. The vessel was heated to 75 C. and pressurised to 20 bar and stirred for 16 hours after which anhydrous EtOAc (225 g) was added and the mixture cooled and vented, resulting in a ca. 550 g/mol PPC-polyol. The contents of the reactor were stored under nitrogen until used in reaction 2.

[0244] In a separate 2 L reactor, DMC catalyst as per WO2017/037441 example 1 (50 mg) and PPG400 (0.4 mL) were dried at 120 C. under vacuum for 1 hour. The vacuum was broken with CO.sub.2 (0.2 barg), ethyl acetate (250 g) added via HPLC pump and the mixture heated to the desired temperature (130 C.). 17 g of propylene oxide was added in 3 bursts (10 g, 5 g, 2 g) each time observing the rise and fall of pressure indicating DMC activation.

[0245] The reactor was cooled to 85 C. and pressurising to 4.5 bar with CO.sub.2. An additional 15 g PO was added. The reaction 1 mixture was then added via a HPLC pump over 2 hours after which additional PO (10 g) was added. The reaction was completed overnight. The reactor was cooled to below 10 C. and the pressure was released. NMR and GPC were measured immediately.

Example 4

[0246] Example 4 was carried out as per example 3, except hexanediol (48.7 g) and catalyst (1) (3.16 g) were used to make a ca. 1100 g/mol PPC-polyol.

Example 5

[0247] Example 5 was carried out as per example 4 except hexanediol (39.8 g) was used to make a ca. 1300 g/mol PPC polyol.

Example 6

##STR00015##

[0248] Above: catalyst (2) and co-catalyst PPNCI

[0249] Hexanediol (1.4475 g) was added into a 100 mL reactor and a mixture of catalyst (2) (28.6 mg) and co-catalyst PPNCI (bis(triphenylphosphine) iminiumchloride, 23.4 mg) in EtOAc (10 mL) injected into the vessel followed by PO (20 mL). The vessel was heated to 70 C. and pressurised to 15 bar and stirred for 16 hours after which it was cooled and vented, resulting in a ca. 1200 g/mol polyol with approximately 85% carbonate linkages. The contents of the reactor were then transferred to a clean, dry Schlenk along with PO (6 mL).

[0250] In a separate 100 mL reactor, 9.2 mg of DMC catalyst as per WO2017/037441 example 1 and PPG 400 (0.49 mL) were dried at 120 C. under vacuum for 1 hour. Ethyl acetate (15 mL) was injected into the vessel via a syringe. The vessel was heated to the desired temperature (130 C.). 0.9 g of propylene oxide was added in 2 bursts 0.45 g each with 30 minutes between each to confirm activity of the DMC catalyst.

[0251] The reactor was cooled to 85 C. whilst pressurising to 4.5 bar with CO.sub.2 and PO (2 g) was added. The Schlenk mixture from above was then added via a HPLC pump. over 1 hour. Extra EtOAc was added (5 mL). The reaction continued for 16 hours. The reactor was cooled to below 10 C. and the pressure was released. NMR and GPC were measured immediately.

TABLE-US-00001 TABLE 1 Results from Example 1-6 Overall CO.sub.2 Example Conversion % wt % Mn g/mol PDI 1 100 17.6 750 1.10 2 100 17.3 1600 1.10 3 100 19.5 760 1.11 4 100 21.1 2060 1.60 5 100 24.5 1830 1.30 6 100 18.5 1850 1.26

[0252] The overall CO.sub.2 wt % was calculated according to the method set out in WO2017/037441.

[0253] The examples demonstrate that the low molecular weight polycarbonate polyols, which have poor stability, do not have to be stored or purified but can be produced and used in situ to produce more stable polyols with high overall CO.sub.2 contents containing a mixture carbonate and ether linkages, under low CO.sub.2 pressures. Furthermore, the process can produce polymers with CO.sub.2 contents in the core of the polymer and higher ether contents at the end of the polyols.

Examples 7-11

[0254] Example 7-11 were carried out as per example 1, except they were carried out in a 2L reactor. Reaction 1 was carried out using the quantities detailed in Table 2.

[0255] In a separate 2 L reactor reaction 2 was carried out using the quantities detailed in table 3. The reactor minimum fill requirements during DMC activation were met by addition of either ethyl acetate (280 mL) or polycarbonate ether polyol product from a preceding dual reactor reaction. DMC catalyst was activated using 15 g bursts of PO. The PPC/PO mixture from above was then added at 85 C. via a HPLC pump added over 1-3 hours. Following PPC addition, a further quantity of PO was then added to the mixture via HPLC at 5 mL/min. The reaction was cooked out for a further 1-16 hours before being cooled to below 10 C. and pressure released. NMR and GPC were measured immediately.

TABLE-US-00002 TABLE 2 Quantities and conditions used for reactor 1 in experiments 7-11 Reaction 1 Set Pressure/ E.g. PO/g Catalyst (1)/g Starter Starter/g EtOAc/g Set Temp/C. barg 7 544 3.16 Hexanediol 35.0 400 75 18 8 544 2.48 DPG 47.0 0 75 20 9 544 2.20 Hexanediol 43.5 0 65 7.7 10 544 3.16 Hexanediol 40.0 150 65 8 11 544 2.8 Hexanediol 44 150 74 20

TABLE-US-00003 TABLE 3 Quantities and conditions used for reactor 2 in experiments 7-11 Reaction 2 Cookout Final PCE PCE E.g Starter Starter/g DMC/g Min. fill PO/g time (h) CO2 wt % Mn PDI 7 Hex 2.2 0.3 EtOAc 40 2 26% 2650 1.14 8 DPG 2.5 0.073 EtOAc 95 16 20% 2000 1.40 9 Hex 2.2 0.15 EtOAc 80 1 17% 2050 1.17 10 Hex 2.2 0.1 EtOAc 60 16 21% 2000 1.19 11 N/A N/A 0.15 PCE 45 2.5 23% 1900 1.14 polyol

[0256] The examples demonstrate that the low molecular weight polycarbonate polyols, which have poor stability, do not have to be stored or purified but can be produced and used in situ to produce more stable polyols with high overall CO.sub.2 contents containing a mixture carbonate and ether linkages, under low CO.sub.2 pressures (see examples 9 and 10).

[0257] Furthermore, the process can produce polymers with CO.sub.2 contents in the core of the polymer and higher ether contents at the end of the polyols.

[0258] Example 11 demonstrates the process tolerates using the final polyol product as the starter to activate the DMC catalyst in reactor 2. This method demonstrates that the reaction heel of a previous reaction can be left in the reactor to activate the DMC for the next reaction and satisfy the minimum fill of the reactor. This is particularly useful in manufacturing to eliminate the need for solvent or a different starter to pre-activate the DMC with.

[0259] The thermal stability of a PPC polyol as produced in reaction 1 (Mn 2000) was compared against a polyol of the invention produced by example 10 (FIG. 1). It can be clearly seen that the block copolymer polyol produced by the dual reaction has enhanced thermal stability compared to the PPC polyol.