Process for the preparation of carbon dioxide-based polyether carbonate polyols from flue gas and carbon dioxide-based polyether carbonate polyols

Abstract

This invention relates to the field of polymer synthesis technology, and discloses a method for preparing carbon dioxide-based polyether carbonate polyols from flue gas as raw material, as well as the carbon dioxide-based polyether carbonate polyols. The method includes: in the presence of a catalyst and an initiator, wherein the catalyst is a bimetallic cyanide complex, copolymerizing carbon dioxide in flue gas with an epoxide to prepare carbon dioxide-based polyether carbonate polyols. This invention, using flue gas as raw material to prepare carbon dioxide-based polyether carbonate polyols, can solve the problem of high-value utilization of flue gas, and the prepared carbon dioxide-based polyether carbonate polyols have adjustable molecular weight and low dispersion coefficient.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology, specifically relating to a method for preparing carbon dioxide-based polyether carbonate polyols using flue gas as raw material, and the carbon dioxide-based polyether carbonate polyols. Background Technology

[0002] Flue gas refers to the gaseous substances that pollute the environment, produced during the combustion of fossil fuels such as coal. These substances are typically emitted through flues or chimneys. The carbon dioxide concentration in flue gas is usually between 6% and 15%. Currently, flue gas is mainly treated through environmental protection facilities to meet emission standards before being released.

[0003] Polyether carbonate polyols are obtained by copolymerizing carbon dioxide with epoxides. Carbon dioxide is stable in this reaction, requiring a highly active catalyst. Current research mainly focuses on catalyst development. Among them, bimetallic cyanide coordination catalysts are the most widely used heterogeneous catalysts (J. Polym. Sci., Part A: Polym. Chem, 2013, 51(22), 4811; and Polymer, 2011, 52, 5494-5502). Chen Liban et al. and Liu Baohua et al. prepared polyether carbonate polyols (CN1044663A, CN100484984C) under 100% carbon dioxide conditions using high molecular weight organic complexing agents and bimetallic complex catalysts, respectively.

[0004] Therefore, if high-value products can be produced directly from carbon dioxide in waste gas, it will have high economic value. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem that existing technologies do not use flue gas as a raw material to prepare polyether carbonate polyols, and to provide a method for preparing carbon dioxide-based polyether carbonate polyols using flue gas as a raw material, as well as the carbon dioxide-based polyether carbonate polyols. This method can solve the problem of high-value utilization of flue gas, and the prepared carbon dioxide-based polyether carbonate polyols have adjustable molecular weight and low dispersion coefficient.

[0006] To achieve the above objectives, the first aspect of the present invention provides a method for preparing carbon dioxide-based polyether carbonate polyols from flue gas as raw material, wherein the method comprises: in the presence of a catalyst and an initiator, wherein the catalyst is a bimetallic cyanide complex, copolymerizing carbon dioxide in flue gas with an epoxide to prepare carbon dioxide-based polyether carbonate polyols.

[0007] A second aspect of the present invention provides a carbon dioxide-based polyether carbonate polyol prepared by the method described above.

[0008] The beneficial effects of the present invention through the above technical solution include:

[0009] (1) When the carbon dioxide content in the simulated flue gas is as low as 5%, the epoxy conversion rate and selectivity are both greater than 90%.

[0010] (2) The catalyst has a simple structure, low preparation cost, and simple process.

[0011] (3) The reaction time of carbon dioxide and epoxide copolymerization in simulated flue gas is short, the molecular weight of carbon dioxide-based polyether carbonate polyol products is adjustable, and the dispersion coefficient is low. Attached Figure Description

[0012] Figure 1 This is the NMR spectrum of the carbon dioxide-based polyether carbonate polyol prepared in Example 3. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] As previously stated, the first aspect of the present invention provides a method for preparing carbon dioxide-based polyether carbonate polyols using flue gas as raw material, wherein the method comprises: in the presence of a catalyst and an initiator, wherein the catalyst is a bimetallic cyanide complex, copolymerizing carbon dioxide in flue gas with an epoxide to prepare carbon dioxide-based polyether carbonate polyols.

[0015] The inventors of this invention discovered that there are no reports in the prior art on the preparation of polyether carbonate polyols using flue gas as a raw material. Furthermore, if high-value products could be prepared directly from carbon dioxide in flue gas (waste gas), it would have significant economic value. Based on this, the inventors of this invention use a bimetallic cyanide complex as a catalyst to copolymerize carbon dioxide from flue gas with epoxides in the presence of an initiator. This process utilizes flue gas waste while simultaneously producing carbon dioxide-based polyether carbonate polyols with adjustable molecular weight and low dispersion coefficient.

[0016] According to the present invention, the bimetallic cyanide complex has the structure shown in formula (1);

[0017] M a [Co b (CN) c ] d mNe X f ·nH2O·oL,(1);

[0018] Wherein, M and N may be the same or different, and each is selected from at least one of iron, nickel, copper, zinc and chromium, preferably at least one of iron, nickel, zinc and chromium;

[0019] Wherein, X is at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and / or bromine;

[0020] Wherein, the L ligand is at least one of a compound of oxygen, nitrogen, phosphorus, and sulfur; preferably, the L ligand is at least one of ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol, 1,2-propanediol, tert-butanol, 1,4-dioxane, polyethylene glycol, polyether polyol, polyvinyl alkyl ether, polyoxymethylene, and polyester.

[0021] Where a is 1-5, b is 1-5, c is 1-10, d is 1-5, e is 1-5, and f is a positive number from 1 to 10. Preferably, a is 1-3, b is 1-3, c is 5-10, d is 1-3, e is 1-3, and f is a positive number from 2 to 10. a, b, c, d, e, and f are positive numbers and can make the sum of the valences of the corresponding elements in equation (1) zero.

[0022] Wherein, m is any value between 0.7 and 2, n is any value between 0.1 and 2, and o is any value between 0.1 and 2; preferably, m is any value between 0.8 and 1.8, n is any value between 0.2 and 1.5, and o is any value between 0.2 and 1.5; more preferably, m is any value between 0.87 and 1.2, n is any value between 0.45 and 0.88, and o is any value between 0.5 and 0.77.

[0023] According to the present invention, preferably, the bimetallic cyanide complex is selected from at least one of the following structures:

[0024] Zn3[Co(CN)6]2·0.92FeCl2·0.45H2O·0.51t-BuOH,

[0025] Zn3[Co(CN)6]2·1.2NiCl2·0.88H2O·0.7t-BuOH,

[0026] Zn3[Co(CN)6]2·0.92CrCl2·0.45H2O·0.51t-BuOH,

[0027] Zn3[Co(CN)6]2·0.87CrBr2·0.75H2O·0.61t-BuOH,

[0028] Zn3[Co(CN)6]2·1.4NiCl2·0.68H2O·0.77t-BuOH.

[0029] According to the present invention, the amount of catalyst used is 0.01-10% by weight of the amount of epoxide used, preferably 0.1-5% by weight.

[0030] In this invention, the flue gas is simulated flue gas, wherein the flue gas also contains nitrogen; preferably, based on the total volume of the flue gas, the carbon dioxide content is 5-90% by volume and the nitrogen content is 10-95% by volume.

[0031] According to the present invention, the epoxide is selected from one or more of propylene oxide, ethylene oxide, cyclohexene oxide, butane oxide, isobutylene oxide, and cyclopentene oxide; preferably, the epoxide is selected from propylene oxide and / or ethylene oxide.

[0032] According to the present invention, the initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, hydroxyl-containing polymers and hydroxyl-containing oligomers; preferably, the initiator is selected from alcohols and / or hydroxyl-containing polymers.

[0033] According to the present invention, the amount of the initiator is 0.01-20% by weight of the amount of the epoxide, preferably 1-10% by weight.

[0034] According to the present invention, the conditions for the copolymerization reaction include: a reaction pressure of 0.1-10 MPa, a reaction temperature of 25-150°C, and a reaction time of 0.5-50 h; preferably, the reaction pressure is 3-5 MPa, the reaction temperature is 80-120°C, and the reaction time is 1-12 h. Furthermore, in the present invention, the copolymerization reaction is carried out in a high-pressure reactor.

[0035] According to the present invention, the method further includes purifying and drying the crude product obtained by copolymerization to prepare a polyether carbonate polyol. The purification is performed by distillation.

[0036] The drying process is carried out in a vacuum drying oven at a temperature of 20-80°C for 6-24 hours.

[0037] A second aspect of the present invention provides a carbon dioxide-based polyether carbonate polyol prepared by the method described above.

[0038] According to the present invention, the number average molecular weight of the carbon dioxide-based polyether carbonate polyol is 500-9000 g / mol, preferably 1000-2800 g / mol.

[0039] According to the present invention, the dispersion coefficient of the carbon dioxide-based polyether carbonate polyol is 1.03-2.4, preferably 1.03-2, and more preferably 1.03-1.4.

[0040] According to the present invention, the carbon dioxide content in the carbon dioxide-based polyether carbonate polyol is 10-30%, preferably 15-25%, and more preferably 17-25%.

[0041] According to a particularly preferred embodiment of the present invention, a method for preparing carbon dioxide-based polyether carbonate polyols from flue gas includes the following steps:

[0042] In a high-pressure reactor, using flue gas as raw material and bimetallic cyanide complexes and their derivatives as catalysts, carbon dioxide in the flue gas is copolymerized under the condition of adding an initiator. The reaction is carried out at a certain temperature and pressure for a certain period of time. The crude product is purified and dried to obtain polyether carbonate polyol. The flue gas used as raw material is simulated using syngas of carbon dioxide and nitrogen, with a carbon dioxide content of 5-90% by volume.

[0043] The present invention will be described in detail below through embodiments.

[0044] In the following examples and comparative examples:

[0045] The conversion rate and carbon dioxide content were measured by 1H NMR spectroscopy; the tert-butanol and octanediol raw materials were commercially available products from McLean Company.

[0046] Preparation Example 1

[0047] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts and their derivatives.

[0048] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL tert-butanol containing 0.49 g ZnCl₂ and 0.47 g NiCl₂. After reacting at 25 °C for 3 h, the resulting suspension was washed and centrifuged with water and tert-butanol at a volume ratio of 1:1. This process was repeated at least three times. Finally, the mixture was washed with tert-butanol, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.12 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0049] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·1.1NiCl2·0.67H2O·0.45t-BuOH.

[0050] Preparation Example 2

[0051] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts and their derivatives.

[0052] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL tert-butanol containing 0.49 g ZnCl₂ and 0.57 g CrCl₂. After reacting at 25 °C for 3 h, the resulting suspension was washed with water and tert-butanol at a volume ratio of 1:1 and centrifuged. This process was repeated at least three times. Finally, the mixture was washed with tert-butanol, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.28 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0053] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·0.92CrCl2·0.45H2O·0.51t-BuOH.

[0054] Preparation Example 3

[0055] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts and their derivatives.

[0056] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL tert-butanol containing 0.81 g ZnBr₂ and 1.05 g CrBr₂. After reacting at 25 °C for 3 h, the resulting suspension was washed and centrifuged with water and tert-butanol at a volume ratio of 1:1. This process was repeated at least three times. Finally, the mixture was washed with tert-butanol, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.88 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0057] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·0.87CrBr2·0.75H2O·0.61t-BuOH.

[0058] Preparation Example 4

[0059] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts and their derivatives.

[0060] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL ethylene glycol dimethyl ether containing 0.49 g ZnCl₂ and 0.47 g NiCl₂. After reacting at 25 °C for 3 h, the resulting suspension was washed with water and ethylene glycol dimethyl ether at a volume ratio of 1:1 and centrifuged. This process was repeated at least three times. Finally, the mixture was washed with ethylene glycol dimethyl ether, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.19 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0061] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·1.2NiCl2·0.88H2O·0.7t-BuOH.

[0062] Preparation Example 5

[0063] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts and their derivatives.

[0064] Under stirring, 4.0 mL of a deionized solution of 0.3 g K3Co(CN)6 was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water containing 0.49 g ZnCl2 and 0.47 g NiCl2, and 1 mL of polyether polyol (molecular weight 1000 g / mol). After reacting at 25 °C for 3 h, the resulting suspension was washed and centrifuged with water and polyether polyol (molecular weight 1000 g / mol) at a volume ratio of 1:1. This process was repeated at least three times. Finally, the mixture was washed with polyether polyol (molecular weight 1000 g / mol), centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.08 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0065] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·1.4NiCl2·0.68H2O·0.77t-BuOH.

[0066] Comparative Preparation Example 1

[0067] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts.

[0068] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL tert-butanol containing 0.49 g ZnCl₂. After reacting at 25 °C for 3 h, the resulting suspension was washed and centrifuged with water and tert-butanol at a volume ratio of 1:1. This process was repeated at least three times. Finally, the mixture was washed with tert-butanol, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.54 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0069] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Zn3[Co(CN)6]2·0.55H2O·0.41t-BuOH.

[0070] Comparative Preparation Example 2

[0071] This preparation example illustrates the preparation of bimetallic cyanide coordination catalysts.

[0072] Under stirring, 4.0 mL of a deionized solution of 0.3 g K₃Co(CN)₆ was added dropwise at a rate of 0.5 mL / min to a mixed solution of 5.0 mL deionized water and 1 mL tert-butanol containing 0.46 g FeCl₂. After reacting at 25 °C for 3 h, the resulting suspension was washed and centrifuged with water and tert-butanol at a volume ratio of 1:1. This process was repeated at least three times. Finally, the mixture was washed with tert-butanol, centrifuged, and vacuum dried at 50 °C to constant weight to obtain 1.31 g of solid powder, i.e., the bimetallic cyanide coordination catalyst.

[0073] The resulting bimetallic cyanide coordination catalyst has the following structural formula: Fe3[Co(CN)6]2·0.65H2O·0.44t-BuOH.

[0074] Example 1

[0075] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0076] Raw materials: The flue gas used contains 5% carbon dioxide.

[0077] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 115 °C with stirring, and 5% carbon dioxide from the flue gas was added to bring the temperature to 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 90%, and the selectivity was 91%, yielding 32 g of carbon dioxide-based polyether carbonate polyol.

[0078] The carbon dioxide-based polyether carbonate polyol contains 23% carbon dioxide, has a number-average molecular weight of 2000 g / mol, and a dispersion coefficient of 1.13.

[0079] Example 2

[0080] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0081] Raw materials: The flue gas used contains 40% carbon dioxide.

[0082] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 25 ml of ethylene oxide. The mixture was heated to 115 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the ethylene oxide feedstock and byproducts were removed under vacuum. The epoxide conversion rate was 90%, and the selectivity was 93%, yielding 28 g of carbon dioxide-based polyether carbonate polyol.

[0083] The carbon dioxide-based polyether carbonate polyol contains 25% carbon dioxide, has a number-average molecular weight of 1800 g / mol, and a dispersion coefficient of 1.13.

[0084] Example 3

[0085] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0086] Raw materials: The flue gas used contains 90% carbon dioxide.

[0087] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 50.6 ml of cyclohexene oxide. The mixture was heated to 115 °C with stirring, and 90% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as ethylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 96%, and the selectivity was 93%, yielding 47 g of carbon dioxide-based polyether carbonate polyol.

[0088] The carbon dioxide-based polyether carbonate polyol contains 21% carbon dioxide, has a number-average molecular weight of 1900 g / mol, and a dispersion coefficient of 1.09.

[0089] Figure 1 This is the 1H NMR spectrum of the carbon dioxide-based polyether carbonate polyol prepared in Example 3. Figure 1It can be seen that: the chemical shift values ​​in the 1H NMR spectrum, ranging from 1.1 to 1.2 ppm, represent the active hydrogen on the methyl group in the polyether unit of the polyether carbonate polyol; the characteristic peaks at chemical shifts of 4.7-5.0 ppm, 3.8-4.3 ppm, and 1.2-1.4 ppm represent the characteristic peaks of the methylene, methylene, and methyl groups in the polyester unit of the polyether carbonate polyol, respectively. Figure 1 It can be seen that carbon dioxide-based polyether carbonate polyol was successfully prepared.

[0090] Example 4

[0091] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0092] Raw materials: The flue gas used contains 40% carbon dioxide.

[0093] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 4.6 g of dried 1,4-butanediol and 35 ml of propylene oxide. The mixture was heated to 115 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 92%, and the selectivity was 96%, yielding 33 g of carbon dioxide-based polyether carbonate polyol.

[0094] The carbon dioxide-based polyether carbonate polyol contains 16% carbon dioxide, has a number-average molecular weight of 2100 g / mol, and a dispersion coefficient of 1.10.

[0095] Example 5

[0096] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0097] Raw materials: The flue gas used contains 40% carbon dioxide.

[0098] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 20.4 g of dried polyether polyol (400 g / mol) and 35 ml of propylene oxide. The mixture was heated to 115 °C with stirring, and 40% carbon dioxide was added to the flue gas to 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 95%, and the selectivity was 92%, yielding 45 g of carbon dioxide-based polyether carbonate polyol.

[0099] The carbon dioxide-based polyether carbonate polyol contains 23% carbon dioxide, has a number-average molecular weight of 2500 g / mol, and a dispersion coefficient of 1.08.

[0100] Example 6

[0101] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0102] Raw materials: The flue gas used contains 40% carbon dioxide.

[0103] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 115 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 5 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 90%, and the selectivity was 91%, yielding 30 g of carbon dioxide-based polyether carbonate polyol.

[0104] The carbon dioxide-based polyether carbonate polyol contains 17% carbon dioxide, has a number-average molecular weight of 1000 g / mol, and a dispersion coefficient of 1.14.

[0105] Example 7

[0106] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0107] Raw materials: The flue gas used contains 40% carbon dioxide.

[0108] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 115 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 95 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 95%, and the selectivity was 92%, yielding 36 g of carbon dioxide-based polyether carbonate polyol.

[0109] The carbon dioxide-based polyether carbonate polyol contains 19% carbon dioxide, has a number-average molecular weight of 2800 g / mol, and a dispersion coefficient of 1.03.

[0110] Example 8

[0111] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0112] Raw materials: The flue gas used contains 40% carbon dioxide.

[0113] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 50 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 10 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 90%, and the selectivity was 92%, yielding 30 g of carbon dioxide-based polyether carbonate polyol.

[0114] The carbon dioxide-based polyether carbonate polyol contains 22% carbon dioxide, has a number-average molecular weight of 1600 g / mol, and a dispersion coefficient of 1.06.

[0115] Example 9

[0116] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0117] Raw materials: The flue gas used contains 40% carbon dioxide.

[0118] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 150 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 1 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 94%, and the selectivity was 95%, yielding 33 g of carbon dioxide-based polyether carbonate polyol.

[0119] The carbon dioxide-based polyether carbonate polyol contains 24% carbon dioxide, has a number-average molecular weight of 2100 g / mol, and a dispersion coefficient of 1.10.

[0120] Example 10

[0121] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0122] Raw materials: The flue gas used contains 40% carbon dioxide.

[0123] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 150 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 0.5 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 90%, and the selectivity was 90%, yielding 35 g of carbon dioxide-based polyether carbonate polyol.

[0124] The carbon dioxide-based polyether carbonate polyol contains 19% carbon dioxide, has a number-average molecular weight of 2500 g / mol, and a dispersion coefficient of 1.03.

[0125] Example 11

[0126] This embodiment illustrates the preparation of carbon dioxide-based polyether carbonate polyols using flue gas as a raw material through the method of the present invention.

[0127] Raw materials: The flue gas used contains 40% carbon dioxide.

[0128] 18 mg of the catalyst prepared in Preparation Example 1 was added to a thoroughly dried 100 ml high-pressure reactor, along with 7.2 g of dried octanediol and 35 ml of propylene oxide. The mixture was heated to 150 °C with stirring, and 40% carbon dioxide from the flue gas was added to a pressure of 25 bar. After reacting for 50 h, the apparatus was cooled, and volatile substances such as the propylene oxide feedstock and byproducts were removed under vacuum. The epoxy conversion rate was 95%, and the selectivity was 96%, yielding 34 g of carbon dioxide-based polyether carbonate polyol.

[0129] The carbon dioxide-based polyether carbonate polyol contains 21% carbon dioxide, has a number-average molecular weight of 2000 g / mol, and a dispersion coefficient of 1.11.

[0130] Example 12

[0131] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that "catalyst prepared in Example 1" was replaced with "catalyst prepared in Example 2".

[0132] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 2500 g / mol, a dispersion index of 1.3, and a carbon dioxide content of 17%.

[0133] Example 13

[0134] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that "the catalyst prepared in Example 1" was replaced with "the catalyst prepared in Example 3".

[0135] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 3000 g / mol, a dispersion index of 1.32, and a carbon dioxide content of 19%.

[0136] Example 14

[0137] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that "catalyst prepared in Example 1" was replaced with "catalyst prepared in Example 4".

[0138] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 3200 g / mol, a dispersion index of 1.2, and a carbon dioxide content of 20%.

[0139] Example 15

[0140] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that "the catalyst prepared in Example 1" was replaced with "the catalyst prepared in Example 5".

[0141] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 3100 g / mol, a dispersion index of 1.4, and a carbon dioxide content of 24%.

[0142] Comparative Example 1

[0143] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that “catalyst prepared in Example 1” was replaced with “catalyst prepared in Comparative Example 1”.

[0144] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 2000 g / mol, a dispersion index of 2.41, and a carbon dioxide content of 15%.

[0145] Comparative Example 2

[0146] Carbon dioxide-based polyether carbonate polyols were prepared from flue gas using the same method as in Example 1, except that “catalyst prepared in Example 1” was replaced with “catalyst prepared in Comparative Example 2”.

[0147] The prepared carbon dioxide-based polyether carbonate polyol had a number average molecular weight of 2100 g / mol, a dispersion index of 2.5, and a carbon dioxide content of 13%.

[0148] In summary, the method of this invention for preparing carbon dioxide-based polyether carbonate polyols using flue gas as raw material can solve the problem of high-value utilization of flue gas. Moreover, the prepared carbon dioxide-based polyether carbonate polyols have adjustable molecular weight, low dispersion coefficient, and high carbon dioxide content. In addition, when the carbon dioxide-based polyether carbonate polyols prepared by this invention are applied to polyurethane, the polyurethane exhibits superior material properties, achieving the performance of polyurethanes prepared by traditional polyols.

[0149] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing carbon dioxide-based polyether carbonate polyols from flue gas, characterized in that, The method includes: in the presence of a catalyst and an initiator, wherein the catalyst is a bimetallic cyanide complex, copolymerizing carbon dioxide in flue gas with an epoxide to prepare a carbon dioxide-based polyether carbonate polyol.

2. The method according to claim 1, wherein, The bimetallic cyanide complex has the structure shown in formula (1); M a [Co b (CN) c ] d mN e X f ·nH2O·oL,(1); Wherein, M and N may be the same or different, and each is selected from at least one of iron, nickel, copper, zinc and chromium, preferably at least one of iron, nickel, zinc and chromium; X is at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and / or bromine; The L-ligand is at least one of a compound containing oxygen, nitrogen, phosphorus, and sulfur; preferably, the L-ligand is at least one of ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol, 1,2-propanediol, tert-butanol, 1,4-dioxane, polyethylene glycol, polyether polyol, polyvinyl alkyl ether, polyoxymethylene, and polyester, and more preferably at least one of tert-butanol, polyethylene glycol, and ethylene glycol; a is 1-5, b is 1-5, c is 1-10, d is 1-5, e is 1-5, and f is a positive number from 1 to 10; m is any value between 0.7 and 2, n is any value between 0.1 and 2, and o is any value between 0.1 and 2.

3. The method according to claim 2, wherein, The bimetallic cyanide complex is selected from at least one of the following structures: Zn3[Co(CN)6]2·0.92FeCl2·0.45H2O·0.51t-BuOH, Zn3[Co(CN)6]2·1.2NiCl2·0.88H2O·0.7t-BuOH, Zn3[Co(CN)6]2·0.92CrCl2·0.45H2O·0.51t-BuOH, Zn3[Co(CN)6]2·0.87CrBr2·0.75H2O·0.61t-BuOH, Zn3[Co(CN)6]2·1.4NiCl2·0.68H2O·0.77t-BuOH.

4. The method according to any one of claims 1-3, wherein, The amount of catalyst used is 0.01-10% by weight of the amount of epoxide used.

5. The method according to claim 1, wherein, The flue gas also contains nitrogen. Preferably, based on the total volume of the flue gas, the carbon dioxide content is 5-90% by volume and the nitrogen content is 10-95% by volume.

6. The method according to claim 1, wherein, The epoxide is selected from one or more of propylene oxide, ethylene oxide, cyclohexene oxide, butane oxide, isobutylene oxide, and cyclopentene oxide.

7. The method according to claim 1, wherein, The initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, hydroxyl-containing polymers, and hydroxyl-containing oligomers; Preferably, the amount of the initiator is 0.01-20% by weight of the amount of the epoxide.

8. The method according to claim 1, wherein, The conditions for the copolymerization reaction include: a reaction pressure of 0.1-10 MPa, a reaction temperature of 25-150℃, and a reaction time of 0.5-50 h.

9. A carbon dioxide-based polyether carbonate polyol prepared by the method of any one of claims 1-8.

10. The carbon dioxide-based polyether carbonate polyol according to claim 9, wherein, The number average molecular weight of the carbon dioxide-based polyether carbonate polyol is 500-9000 g / mol, preferably 1000-3100 g / mol; And / or, the dispersion coefficient of the carbon dioxide-based polyether carbonate polyol is 1.03-2.4, preferably 1.03-1.4; And / or, the carbon dioxide content in the carbon dioxide-based polyether carbonate polyol is 10-30%, preferably 15-25%.

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