A POLYOL BLOCK COPOLYMER, COMPOSITIONS AND PROCESSES THEREFOR

Abstract

A polyol block copolymer comprising a polycarbonate block, A (-A′-Z′—Z—(Z′-A′).sub.n-), and polyethercarbonate blocks, B. The polyol block copolymer has the polyblock structure:

B-A′-Z′—Z—(Z′-A′-B).sub.n

wherein n=t−1 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 Z′—Z—(Z′).sub.n is a starter residue. A 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 polyol block copolymer comprising a polycarbonate block, A (-A′-Z′—Z—(Z′-A′).sub.n-), and polyethercarbonate blocks, B, wherein the polyol block copolymer has the polyblock structure:
B-A′-Z′—Z—(Z′-A′-B).sub.n wherein n=t−1 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 Z′—Z—(Z′).sub.n is a starter residue.

2. The polyol block copolymer according to claim 1, wherein the starter residue depends on the nature of the starter compound, and wherein the starter compound has the formula (III):
ZR.sup.Z).sub.a  (III) wherein Z can be any group which can have 1 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; a is an integer which is at least 1, typically; 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.

3. A polyol block copolymer according to claim 1, wherein -A′- has the following structure: ##STR00010## wherein the ratio of p:q is at least 7:3; and block B has the following structure: ##STR00011## 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.

4. (canceled)

5. (canceled)

6. The polyol block copolymer according to claim 2, wherein a is an integer which is at least 2.

7. (canceled)

8. The polyol block copolymer according to claim 1, 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 4-OH 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.

9. The polyol block copolymer according to claim 1, wherein the polyol 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.

10. (canceled)

11. (canceled)

12. (canceled)

13. The polyol block copolymer according to claim 1, wherein block A has between 75% and 99% carbonate linkages.

14. (canceled)

15. (canceled)

16. The polyol block copolymer according to claim 1, wherein block B has between 1% and 50% carbonate linkages.

17. (canceled)

18. (canceled)

19. A polyol block copolymer according to claim 1, wherein block B has between 50% and 99% ether linkages.

20. A polyol block copolymer according to claim 1, wherein block A further comprises ether linkages.

21. (canceled)

22. (canceled)

23. The polyol block copolymer according to claim 1, wherein block A has between 1% and 25% ether linkages.

24. The polyol block copolymer according to claim 20, wherein the epoxide is asymmetric and the polycarbonate has between 40-100% head to tail linkages.

25. The polyol block copolymer according to claim 20, wherein between 0.1 and 20% of the total epoxide in block A is an epoxide substrate containing more than one epoxide moiety.

26. The polyol block copolymer according to claim 1, wherein block A is a generally alternating polycarbonate polyol residue.

27. The polyol block copolymer according to claim 1, wherein the mol/mol ratio of block A to block B is in the range 25:1 to 1:250.

28. The polyol block copolymer according to claim 1, wherein at least 30% of the epoxide residues of block A are ethylene oxide or propylene oxide residues.

29. The polyol block copolymer according to claim 1, wherein at least 30% of the epoxide residues of block B are ethylene oxide or propylene oxide residues.

30. (canceled)

31. A composition comprising the polyol block copolymer of claim 1 and one or more additives selected from catalysts, blowing agents, stabilizers, plasticisers, fillers, flame retardants, and antioxidants.

32. The composition according to claim 31, further comprising a (poly)isocyanate.

33. (canceled)

34. (canceled)

35. (canceled)

36. A polyurethane produced from the reaction of a polyol block copolymer according to claim 1.

37. (canceled)

38. (canceled)

39. The polyurethane according to claim 36, 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).

40. (canceled)

41. (canceled)

42. An isocyanate terminated polyurethane prepolymer comprising the composition according to claim 31 with an excess of (poly)isocyanate.

43. (canceled)

44. (canceled)

45. A lubricant composition comprising a polyol block copolymer of a claim 1.

46. A surfactant composition comprising a polyol block copolymer of a claim 1.

47. 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.

48. The process according to claim 47 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.

49. The process according to claim 48 wherein the monomer or further polymer is a (poly)isocyanate and the product of the third reaction is a polyurethane.

50. 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.

51. (canceled)

52. (canceled)

53. (canceled)

54. (canceled)

55. (canceled)

56. (canceled)

57. The process according to cam 47, 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.

58. (canceled)

59. (canceled)

60. (canceled)

61. (canceled)

62. (canceled)

63. (canceled)

64. (canceled)

65. (canceled)

66. (canceled)

67. (canceled)

68. (canceled)

69. (canceled)

70. (canceled)

71. (canceled)

72. (canceled)

73. (canceled)

74. The process according to claim 47, 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.

75. (canceled)

76. The process according to claim 47, wherein the carbonate catalyst is a catalyst capable of producing polycarbonate chains with greater than 76% carbonate linkages.

77. A process according to claim 47, wherein the carbonate catalyst is a metal catalyst comprising phenol or phenolate ligands.

78-85. (canceled)

86. The process according to claim 47, wherein the DMC catalyst is based upon Zn.sub.3[Co(CN).sub.6].sub.2 (zinc hexacyanocobaltate).

87. (canceled)

88. (canceled)

89. The process according to claim 47, 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.

90-93. (canceled)

Description

EXAMPLES

Example 1

[0244] ##STR00008##

[0245] 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).

[0246] 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.

[0247] 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

[0248] 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.

[0249] 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.

[0250] 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 out over 5 hours. The reactor was cooled to below 10° C. and the pressure was released. NMR and GPC were measured immediately.

Example 3

[0251] 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.

[0252] 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.

[0253] 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

[0254] 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

[0255] 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

[0256] ##STR00009##

[0257] Above: catalyst (2) and co-catalyst PPNCI

[0258] 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).

[0259] 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.

[0260] 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

[0261] The overall CO.sub.2 wt % was calculated according to the method set out in WO2017/037441.

[0262] 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

[0263] Example 7-11 were carried out as per example 1, except they were carried out in a 2 L reactor. Reaction 1 was carried out using the quantities detailed in Table 2.

[0264] 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

[0265] 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). 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.

[0266] 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.

[0267] 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.