A POLYOL BLOCK COPOLYMER, COMPOSITIONS AND PROCESSES THEREFOR

Abstract

A process for producing a polyol block copolymer in a multiple reactor system including a first and second reactor in which a first reaction takes place in the first reactor and a second reaction takes place in the second reactor. The first reaction is the reaction of a carbonate catalyst with CO.sub.2 and epoxide, in the presence of starter and/or solvent to produce polycarbonate polyol copolymer and the second reaction is the reaction of DMC catalyst with the polycarbonate polyol compound of the first reaction and epoxide to produce polyol block copolymer. The product of the first reaction is fed into the second as crude reaction mixture, the epoxide and the polycarbonate polyol compound of the first reaction are fed in a continuous or semi-batch manner, and/or the product of the first reaction has neutral or alkaline pH on addition to the second. The invention further relates to the copolymers and products incorporating such copolymers.

Claims

1. 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 epoxide to produce a polyol block copolymer, wherein (i) the product of the first reaction is fed into the second reactor as a crude reaction mixture, (ii) the epoxide and the polycarbonate polyol compound of the first reaction are fed into the second reactor in a continuous or semi-batch manner, and/or (iii) the product of the first reaction has a neutral or alkaline pH on addition to the second reaction.

2. 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 polyfunctional starter, and optionally a solvent, to produce a polycarbonate polyol and the second reaction is the semi-batch or continuous reaction of a DMC catalyst with the polycarbonate polyol compound of the first reaction and epoxide to produce a polyol block copolymer.

3. A process for producing a polyol block copolymer according to claim 2, wherein the starter compound has the formula (III):
Z—(R.sup.Z).sub.a(III) wherein Z can be any group which can have 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 2; 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.

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 with a polycarbonate polyol copolymer or with a polyol block copolymer.

5. (canceled)

6. (canceled)

7. The process according to claim 1, 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).

8. (canceled)

9. (canceled)

10. 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.

11. The process according to claim 1, wherein the polycarbonate copolymer is fed into the reaction with the DMC catalyst, as a crude reaction mixture, wherein said reaction contains a pre-activated DMC catalyst.

12. The process according to claim 1, wherein the first reaction is carried out under CO.sub.2 pressure of less than 20 bar.

13. (canceled)

14. The process according to claim 1, wherein the first reaction is a batch, semi-batch, or continuous process.

15. The process according to claim 1, wherein the second reaction is a continuous process or semi batch process.

16. The process according to claim 1, wherein the crude reaction mixture fed into the second reactor includes an amount of unreacted epoxide and/or starter.

17. The process according to claim 1, wherein the carbonate catalyst is present in the crude reaction mixture.

18. The process according to claim 1, wherein the carbonate catalyst has been removed from the crude reaction mixture prior to the addition to the second reactor.

19. 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.

20. The process according to claim 1, wherein the temperature of reaction in the second reactor is in the range from about 50 to about 160° C.

21. The process according to claim 1, wherein the reactors are located in series.

22. The process according to claim 1, wherein the reactors are nested.

23. The process according to claim 1, wherein the first and second reactors are effective to provide different reaction conditions, such as temperature and/or pressure, to each other simultaneously.

24. (canceled)

25. The process according to claim 1, 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.

26. (canceled)

27. The process according to claim 1, wherein the carbonate catalyst is a catalyst capable of producing polycarbonate chains with greater than 76% carbonate linkages.

28. The process according to claim 1, wherein the carbonate catalyst is a metal catalyst comprising phenol or phenolate ligands.

29-36. (canceled)

37. The process according to claim 1, wherein the DMC catalyst is based upon Zn.sub.3[Co(CN).sub.6].sub.2 (zinc hexacyanocobaltate).

38-40. (canceled)

41. The process according to claim 1, wherein the product of the first reaction is used to pre-activate the DMC catalyst in the second reaction, prior to addition of epoxide.

42. The process according to claim 1, wherein the same or different epoxides are used in the first or second reactions.

43. The process according to claim 1, wherein the epoxide used in the first or second reaction comprises propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide.

44. (canceled)

45. The process according to claim 1, wherein the second reaction is carried substantially in the absence of CO.sub.2.

46. The process according to claim 1, wherein the polyol block copolymer produced in the second reaction is a polycarbonate block polyether polyol block copolymer.

47. A polyol block copolymer comprising a polycarbonate block, A (-A′-Z′—Z—(Z′-A′).sub.n-), and polyether 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 t=at least 2; and wherein each A′ is independently a polycarbonate chain having at least 70% carbonate linkages, and wherein each B is independently a polyether chain; and wherein Z′—Z—(Z′).sub.n is a starter residue.

48. The polyol block copolymer according to claim 47, wherein -A′- has the following structure: ##STR00008## wherein the ratio of p:q is at least 7:3; and block B has the following structure: ##STR00009## 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.

49-69. (canceled)

70. A polyurethane produced from the reaction of a polyol block copolymer produced according to the process of claim 1 and a (poly)isocyanate.

71. A polyurethane comprising a block copolymer residue having a polycarbonate block, A (-A′-Z′—Z—(Z′-A′).sub.n-), wherein A′ is a polycarbonate chain having at least 70% carbonate linkages, and polyether blocks, B, wherein the residue has a 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 Z′—Z—(Z′)n is a starter residue.

72-83. (canceled)

84. A lubricant composition comprising a polyol block copolymer of claim 47.

85. A surfactant composition comprising a polyol block copolymer of claim 47.

Description

EXAMPLES

Example 1

[0244] ##STR00007##

[0245] Hexanediol (2.6 g) was taken into a 100 mL reactor and dried at 120° C. under vacuum for 1 hour. 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 10 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 (3 mL) and EtOAc (9 mL) and kept under N.sub.2.

[0246] 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 N.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 70° C. whilst pressurising to 1 bar with N.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.

TABLE-US-00001 TABLE 1 Experimental results from Example 1 Overall Mn Example CO.sub.2 wt % g/mol PDI 1 10.8 1850 1.10

Examples 2-10

[0248] Examples 2-10 were carried out as per example 1 except they were performed in a 2 L reactor. Reaction 1 was carried out using the quantities detailed in Table 2.

[0249] Reaction 2 was carried out in a 2 L reactor using the quantities shown in Table 3. The reactor minimum fill requirements met by addition of either Ethyl acetate (280 mL) or polycarbonate ether polyol from a preceding dual reactor reaction. The mixture was stirred and heated to 130° C. DMC catalyst was activated using 15 g of propylene oxide was added in 3 bursts (5 g each) with −10 minutes between each to confirm activity of the DMC catalyst. The PPC/PO mixture from above was then added at 85° C. via a HPLC pump added over 1-3 hours.

[0250] 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 any pressure released. NMR and GPC were measured immediately.

TABLE-US-00002 TABLE 2 Reagent quantities and conditions for reaction 1 Reaction 1 Cat- Set Set alyst Starter/ EtOAc/ Temp/ Pressure/ E.g PO/g (1)/g Starter g g C. barg  2 544 6.0 DPG 114 150 75 20  3 544 4.3 DPG 42.43 0 75 20  4 544 2.5 DPG 47 0 75 20  5 544 2.9 Hex 40 180 74 20  6 664 2.7 DPG 47.5 0 71 7.7  7 415 4.0 TMPEO450 55 0 65 10  8 300 2.9 TMPEO450 54.59 0 65 10  9 300 2.9 TMPEO450 85.22 0 65 10 10 498 1.4 TMPEO450 42.33 0 65 10

TABLE-US-00003 TABLE 3 Reagent quantities and conditions for reaction 2 Reaction 2 Final Minimum Post PPC Cookout CO2 PCE E.g. Starter Starter/g DMC/g fill PO/g time (h) wt % length PDI  2 DPG 2.5 0.15 EtOAc 30 2 17.3%  700 1.13  3 DPG 2.5 0.07 EtOAc 30 1   24% 2000 1.14  4 DPG 2.5 0.07 EtOAc 90 1   17% 2000 1.12  5 Hex 2.2 0.15 EtOAc 23 2   21% 1900 1.12  6 N/A N/A 0.10 PCE polyol  0 1 16.1% 2000 1.15  7 PPG400 2.2 0.10 EtOAc 30 1   26% 3700 1.56  8 PPG400 2.2 0.10 EtOAc 30 1   16% 3400 1.50  9 PPG400 2.2 0.10 EtOAc 30 1   9% 2700 1.19 10 PPG400 2.2 0.10 EtOAc 30 1 10.8% 4100 1.33

[0251] 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 in reactor 1 (see examples 6 to 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.

[0252] Examples 7-10 demonstrate the process can be used to produce polyols with higher functionality as trimethylolpropane ethoxylate (Mn 450, triol) was used as the starter in reaction 1.

[0253] Example 6 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.

[0254] 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 5 (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.