A catalyst for the synthesis of polycarbonate polyether polyols and a process for its preparation and use

Abstract

The present application relates to a kind of catalyst for synthesizing polycarbonate polyether polyol and its preparation method and use, the catalyst for synthesizing polycarbonate polyether polyol includes M1 / M2 double metal cyanide catalyst with tetracyclic acid as organic ligand;M1 and M2 represent different metal elements.The catalyst for synthesizing polycarbonate polyether polyol provided by the present application introduces tetracyclic acid into double metal cyanide catalyst, realizes the preparation of a kind of double metal cyanide catalyst for synthesizing polycarbonate polyether polyol, realizes green synthesis of catalyst using biomass material, while reducing preparation cost.

Description

Technical Field

[0001] This invention relates to the field of polymer preparation, specifically to a catalyst for synthesizing polycarbonate polyether polyols, its preparation method, and its uses. Background Technology

[0002] Currently, the copolymerization of epoxides and CO2 to prepare polycarbonate polyether polyols is a route that utilizes CO2 to convert it into a valuable product. Polycarbonate polyether polyols, as synthetic raw materials, have promising applications in the synthesis of polyurethane. It should be noted that polycarbonate polyether polyols synthesized from 1,2-epoxide butane (BO) possess excellent properties such as hydrophobicity and antioxidant activity due to their long side chains, making them suitable as raw materials for polyurethane synthesis and expanding their application areas. The preparation of polycarbonate from 1,2-epoxide butane requires a suitable catalytic system and reaction conditions. Commonly used catalysts in existing technologies include bimetallic cyanide catalysts and Salen-type catalysts. Bimetallic cyanide catalysts are one type of catalyst that can catalyze the copolymerization of CO2 and epoxides to prepare polycarbonate polyether polyols. Although they have disadvantages such as low catalytic efficiency and low CO2 fixation, their simple preparation process and insensitivity to the environment make them suitable for industrial development. In recent years, the application of this type of catalyst in the copolymerization of CO2 and epoxides to prepare polycarbonate polyether polyols has attracted widespread attention.

[0003] Although research on bimetallic cyanide catalysts is increasing, and the prepared bimetallic cyanide catalysts can improve the conversion rate of epoxides and the fixation rate of CO2, problems such as complex preparation processes and increased costs have also emerged.

[0004] For example, CN101979424A discloses a method for preparing a composite catalyst for synthesizing carbon dioxide copolymers. Although the catalyst prepared by combining a bimetallic cyanide catalyst with zinc carboxylate has a certain improvement in catalyst activity, the reaction time of at least 3 hours makes the preparation process complicated, and the addition of zinc carboxylate increases the preparation cost.

[0005] CN101942081A discloses a method for preparing a metal cyanide coordination catalyst. The preparation method requires the use of organic reagents such as N-alkylimidazolium, pyridine, aliphatic nitrile, sulfoxide or sulfone compounds, and solvents such as tetrahydrofuran. The preparation cost is high and the ligand raw materials are somewhat hazardous.

[0006] Therefore, developing a method for preparing a bimetallic cyanide catalyst that is low in cost, simple and green in preparation process, mild in conditions, and easy to industrialize, and achieving excellent catalytic performance when applied to the synthesis of polycarbonate polyether polyols, is an urgent problem to be solved in this field. Summary of the Invention

[0007] In view of the problems existing in the prior art, the purpose of the present invention is to provide a catalyst for synthesizing polycarbonate polyether polyols, its preparation method and uses. The bimetallic cyanide catalyst synthesized using biomass material fruit acid as organic ligand has high catalytic activity, the catalyst preparation process is simple and the cost is low, and the catalyst has high carbon dioxide fixation, high 1,2-epoxybutane conversion rate, mild reaction conditions and is conducive to industrial production when applied to the synthesis of epoxybutyl polycarbonate polyether polyols.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a catalyst for synthesizing polycarbonate polyether polyols, wherein the catalyst for synthesizing polycarbonate polyether polyols comprises an M1 / M2 bimetallic cyanide catalyst with fruit acid as an organic ligand.

[0010] M1 and M2 represent different metallic elements.

[0011] The catalyst for synthesizing polycarbonate polyether polyols provided by this invention introduces fruit acid into a bimetallic cyanide catalyst, realizing the preparation of a bimetallic cyanide catalyst that can be used to synthesize polycarbonate polyether polyols. It achieves green synthesis of the catalyst using biomass materials, while reducing the preparation cost.

[0012] As a preferred embodiment of the present invention, M1 includes one or a combination of at least two of Zn, Cu, Al or Fe.

[0013] Preferably, M2 comprises one or a combination of at least two of Fe, Co, or Ni.

[0014] In this invention, M1 and M2 are of different element types to ensure the achievement of a bimetallic composition. For example, when M1 is selected as Fe, M2 can only be selected as Co or Ni, and when M2 is selected as Fe, M1 can only be selected as one of Zn, Cu or Al.

[0015] Preferably, the fruit acid includes one or a combination of at least two of glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, mandelic acid, gluconolactone, lactobionic acid, and maltodextrin.

[0016] For example, the combination may be a combination of glycolic acid and lactic acid, a combination of lactic acid and malic acid, a combination of citric acid and tartaric acid, a combination of mandelic acid and gluconolactone, a combination of lactobionic acid and malic acid, a combination of lactic acid and maltodextrin, etc.

[0017] As a preferred technical solution of the present invention, the molar ratio of M1 to M2 in the catalyst for synthesizing polycarbonate polyether polyol is (1-10):2, for example, it can be 1:2, 2:2, 3:2, 4:2, 5:2, 6:2, 7:2, 8:2, 9:2 or 10:2, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] Preferably, the molar ratio of M1 to the organic ligand in the catalyst for synthesizing polycarbonate polyether polyol is 1:(1-10), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] In a second aspect, the present invention provides a method for preparing a catalyst for synthesizing polycarbonate polyether polyols as described in the first aspect, the method comprising:

[0020] According to the formula, provide M1 salt and fruit acid solution, and provide M2 ​​cyanate solution;

[0021] The M1 salt and fruit acid solution are first mixed with the M2 cyanate solution to obtain an intermediate material;

[0022] The obtained intermediate material was subjected to aging, solid-liquid separation, washing and drying in sequence to obtain a catalyst for synthesizing polycarbonate polyether polyol.

[0023] This invention incorporates fruit acid during catalyst preparation to obtain a bimetallic cyanide catalyst with fruit acid as the organic ligand. The active bimetallic cyanide catalyst with fruit acid as the organic ligand can be prepared at a relatively low temperature. The preparation conditions are mild, the reaction time is short, the preparation process is optimized, and the catalyst is not sensitive to air and is easy to use in industrial applications.

[0024] As a preferred technical solution of the present invention, the M1 salt and fruit acid solution is obtained by a second mixing of M1 salt, fruit acid and water.

[0025] Preferably, the M1 salt comprises one or a combination of at least two of the following: a halide, a sulfate, or an acetate.

[0026] In this invention, the halide salt can be a chloride salt, a bromide salt, such as zinc chloride, zinc bromide, ferric chloride, ferrous chloride, copper chloride, or aluminum chloride.

[0027] In this invention, the sulfate may be zinc sulfate, ferrous sulfate, ferric sulfate, copper sulfate, or aluminum sulfate, etc.

[0028] In this invention, the acetate can be zinc acetate, ferric acetate, copper acetate, aluminum acetate, or ferrous acetate, etc.

[0029] Preferably, the M2 cyanate solution is obtained by a third mixing of M2 cyanate and water.

[0030] In this invention, the M2 cyanate is a soluble metal cyanate corresponding to the M2 element, such as potassium ferrocyanide, potassium cobalt cyanide, or potassium tetracyanonitrile.

[0031] As a preferred technical solution of the present invention, the first mixing is to add M1 salt and fruit acid solution dropwise into M2 cyanate solution.

[0032] In this invention, the solution is mixed by dripping, which enhances the reaction process in the liquid phase, ensures complete reaction of the materials, and thus guarantees the performance of the resulting catalyst. The dripping rate is 1 drop every 5-10 seconds, such as 1 drop every 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, or 10 seconds, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. A dropper commonly used in this field can be used for the dripping process.

[0033] Preferably, the temperature of the first mixing is 40-60°C, for example, it can be 40°C, 45°C, 50°C, 55°C or 60°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] As a preferred technical solution of the present invention, the aging temperature is 40-60℃, for example, it can be 40℃, 45℃, 50℃, 55℃ or 60℃, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0035] Preferably, the aging time is 0.5-2 h, for example, it can be 0.5 h, 0.8 h, 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h or 2 h, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0036] Preferably, the solid-liquid separation method is centrifugation.

[0037] As a preferred technical solution of the present invention, the preparation method includes:

[0038] According to the formula, provide M1 salt and fruit acid solution, and provide M2 ​​cyanate solution;

[0039] The M1 salt and fruit acid solution are first mixed with the M2 cyanate solution to obtain an intermediate material;

[0040] The obtained intermediate material was subjected to aging, solid-liquid separation, washing and drying in sequence to obtain a catalyst for synthesizing polycarbonate polyether polyol;

[0041] Wherein, the M1 salt and fruit acid solution is obtained by a second mixing of M1 salt, fruit acid and water; the M1 salt includes one or a combination of at least two of the following: halide salt, sulfate salt or acetate salt; the M2 cyanate solution is obtained by a third mixing of M2 cyanate and water; the first mixing is achieved by adding the M1 salt and fruit acid solution dropwise into the M2 cyanate solution; the temperature of the first mixing is 40-60℃; the aging temperature is 40-60℃; the aging time is 0.5-2 h; and the solid-liquid separation method is centrifugation.

[0042] Thirdly, the present invention provides the use of a catalyst for synthesizing polycarbonate polyether polyols as described in the first aspect, the use including the preparation of polycarbonate polyether polyols using the catalyst for synthesizing polycarbonate polyether polyols;

[0043] Specifically, 1,2-epoxybutane and carbon dioxide are copolymerized under a carbon dioxide atmosphere using an initiator and a catalyst for synthesizing polycarbonate polyether polyols to obtain polycarbonate polyether polyols.

[0044] As a preferred embodiment of the present invention, the initiator includes one or a combination of at least two of polypropylene glycol, sebacic acid, or 1,4-butanediol.

[0045] Preferably, the absolute pressure of the carbon dioxide atmosphere is 1-10 MPa, for example, it can be 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa or 10 MPa, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0046] Preferably, the temperature of the copolymerization reaction is ≥70℃, for example, it can be 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0047] Preferably, the copolymerization reaction time is 1-48 h, for example, it can be 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, 32 h, 34 h, 36 h, 38 h, 40 h, 42 h, 44 h, 46 h or 48 h, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0048] Compared with existing technical solutions, the present invention has the following beneficial effects:

[0049] (1) This invention introduces fruit acid, a biomass material, as an organic ligand into a bimetallic cyanide catalyst, which simplifies and greens the preparation process of the bimetallic cyanide catalyst, reduces the preparation cost, and provides mild preparation conditions, making it easy to industrialize.

[0050] (2) In the process of preparing the catalyst, fruit acid is added to prepare a bimetallic cyanide catalyst with fruit acid as organic ligand. The conversion rate of 1,2-epoxybutane monomer can reach more than 87% and up to 99.9% in the copolymerization reaction of 1,2-epoxybutane and CO2 to synthesize polycarbonate polyether polyol, and the CO2 fixation rate can reach 33.5%. Attached Figure Description

[0051] Figure 1 This is the 1H NMR spectrum of the epoxy butyl poly(carbonate-ether) polyol and byproduct BC obtained in Application Example 1 of this invention.

[0052] The present invention will now be described in further detail. However, the examples described below are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims. Detailed Implementation

[0053] To better illustrate the present invention and facilitate understanding of its technical solutions, typical but non-limiting embodiments of the present invention are as follows:

[0054] Unless otherwise specified, the experimental raw materials used in the preparation methods described in the embodiments and comparative examples of this invention can be obtained by purchasing commercially available materials or by using conventional preparation methods.

[0055] The experimental materials used in the implementation of this invention are as follows:

[0056] (1) 1,2-Epoxybutane: CAS No. 106-88-7, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; after reflux in calcium hydride for 8 hours, it was redistilled for use.

[0057] (2) Polypropylene glycol-400: CAS No. 25322-69-4, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; it was dehydrated for 48 hours in an inert gas atmosphere in a container containing molecular sieves, and the molecular sieves were activated by holding at 500℃ in a muffle furnace for 4 hours.

[0058] (3) Potassium cobalt cyanide: CAS No. 13963-58-1, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0059] (4) Zinc chloride: CAS No. 13963-58-1, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0060] (4) Glycolic acid: CAS No. 79-14-1, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0061] (4) Malic acid: CAS number 97-67-6, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0062] (4) Citric acid: CAS number 77-92-9, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0063] (4) Gluconolactone: CAS No. 90-80-2, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0064] Example 1

[0065] This embodiment provides a bimetallic cyanide catalyst, and the specific preparation process is as follows:

[0066] (1) Dissolve 11.42 g ZnCl2 and 0.1 mol gluconolactone in 60 mL of deionized water to obtain the first solution;

[0067] (2) Dissolve 1.33 g K3[Co(CN)6] in 20 mL of deionized water to obtain a second solution;

[0068] (3) At 50°C, the first solution obtained in step (1) is added dropwise to the second solution obtained in step (2) over a time of 0.5 h at a rate of 1 drop every 7 s to obtain an intermediate slurry.

[0069] (4) The intermediate slurry obtained in step (3) is aged at 50°C for 1 h, filtered, washed, and dried at 50°C for 3 days to constant weight to obtain the bimetallic cyanide catalyst of gluconolactone organic ligand.

[0070] The molar ratio of zinc to cobalt in the bimetallic cyanide catalyst of the obtained gluconolactone organic ligand is 2:1, and the molar ratio of zinc to gluconolactone is 1:1.

[0071] Example 2

[0072] This embodiment provides a bimetallic cyanide catalyst, and the specific preparation process is as follows:

[0073] (1) Dissolve 13.6 g FeCl3 and 0.1 mol malic acid in 60 mL of deionized water to obtain the first solution;

[0074] (2) Dissolve 1.33 g K3[Co(CN)6] in 20 mL of deionized water to obtain a second solution;

[0075] (3) At 60°C, the first solution obtained in step (1) is added dropwise to the second solution obtained in step (2) over a time of 0.5 h at a rate of 1 drop every 8 s to obtain an intermediate slurry.

[0076] (4) The intermediate slurry obtained in step (3) is aged at 80°C for 2 h, filtered, washed, and dried at 50°C for 3 days to constant weight to obtain a bimetallic cyanide catalyst with malic acid organic ligand.

[0077] The molar ratio of iron to cobalt in the obtained malic acid organic ligand bimetallic cyanide catalyst is 2:1, and the molar ratio of iron to malic acid is 1:1.

[0078] Example 3

[0079] This embodiment provides a bimetallic cyanide catalyst, and the specific preparation process is as follows:

[0080] (1) Dissolve 13.6 g FeCl3 and 0.1 mol citric acid in 60 mL of deionized water to obtain the first solution;

[0081] (2) Dissolve 1.33 g K3[Co(CN)6] in 20 mL of deionized water to obtain a second solution;

[0082] (3) At 30°C, the first solution obtained in step (1) is added dropwise to the second solution obtained in step (2) over a time of 0.5 h, and the rate of addition is 1 drop every 5 s to obtain an intermediate slurry.

[0083] (4) The intermediate slurry obtained in step (3) is aged at 50°C for 1 h, filtered, washed, and dried at 50°C for 3 days to constant weight to obtain the bimetallic cyanide catalyst of citric acid organic ligand.

[0084] The molar ratio of iron to cobalt in the obtained bimetallic cyanide catalyst with citric acid organic ligand is 2:1, and the molar ratio of iron to citric acid is 1:1.

[0085] Example 4

[0086] This embodiment provides a bimetallic cyanide catalyst, and the specific preparation process is as follows:

[0087] (1) Dissolve 11.42 g ZnCl2 and 0.1 mol glycolic acid in 60 mL of deionized water to obtain the first solution;

[0088] (2) Dissolve 1.33 g K3[Co(CN)6] in 20 mL of deionized water to obtain a second solution;

[0089] (3) At 80°C, the first solution obtained in step (1) is added dropwise to the second solution obtained in step (2) over a time of 0.5 h at a rate of 1 drop every 10 s to obtain an intermediate slurry.

[0090] (4) The intermediate slurry obtained in step (3) is aged at 80°C for 1.5 h, filtered, washed, and dried at 50°C for 3 days to constant weight to obtain a bimetallic cyanide catalyst with glycolic acid organic ligand.

[0091] The molar ratio of zinc to cobalt in the bimetallic cyanide catalyst with the obtained glycolic acid organic ligand is 2:1, and the molar ratio of zinc to glycolic acid is 1:1.

[0092] Example 5

[0093] The only difference from Example 1 is that the amount of gluconolactone added is 0.5 mol. The resulting bimetallic cyanide catalyst with gluconolactone organic ligand has a zinc to cobalt molar ratio of 2.5:1 and a zinc to gluconolactone molar ratio of 1.5:1.

[0094] Example 6

[0095] The only difference from Example 1 is that the amount of gluconolactone added is 0.8 mol. The resulting bimetallic cyanide catalyst with gluconolactone organic ligand has a zinc to cobalt molar ratio of 3:1 and a zinc to gluconolactone molar ratio of 2:1.

[0096] Example 7

[0097] The only difference from Example 1 is that the aging temperature is 40°C.

[0098] Example 8

[0099] The only difference from Example 1 is that the aging temperature is 60°C.

[0100] Comparative Example 1

[0101] The only difference from Example 1 is that no gluconolactone is added during the preparation process, that is, no fruit acid is added during the preparation process.

[0102] Comparative Example 2

[0103] The only difference from Example 2 is that malic acid is not added during the preparation process.

[0104] Comparative Example 3

[0105] The only difference from Example 3 is that citric acid is not added during the preparation process.

[0106] Comparative Example 4

[0107] The only difference from Example 4 is that glycolic acid is not added during the preparation process.

[0108] Comparative Example 5

[0109] The only difference from Example 1 is that gluconolactone is replaced with an equal amount of acetic acid during the preparation process.

[0110] Comparative Example 6

[0111] The only difference from Example 1 is that gluconolactone is replaced with an equal amount of tert-butanol during the preparation process.

[0112] Comparative Example 7

[0113] The only difference from Example 1 is that gluconolactone is replaced with an equal amount of a mixture of acetic acid and methanol during the preparation process to ensure that the molar amounts of hydroxyl and carboxyl groups are the same as those in gluconolactone.

[0114] Application Example 1

[0115] This application example uses the bimetallic cyanide catalyst obtained in Example 1 to prepare polycarbonate polyether polyols. The specific process is as follows:

[0116] 30 mg of bimetallic cyanide catalyst and 0.4 g of polypropylene glycol-400 initiator were added to a 50 mL dehydrated reactor. The reactor was evacuated, and 10 mL of 1,2-epoxybutane was added. CO2 was introduced and purged 6 times. The reactor was stirred at 500 r / min with an absolute pressure of 3 MPa. The polymerization temperature was 100℃ and the reaction time was 8 h. After the reaction was completed, the unreacted 1,2-epoxybutane was evaporated to obtain polycarbonate polyether polyol.

[0117] The 1H NMR spectra of the obtained epoxy-butyl poly(carbonate-ether) polyol and byproduct BC are as follows: Figure 1As shown in the figure, signals e (4.7-4.9 ppm) and f (4.0-4.3 ppm) represent the absorption peaks of H on the methylene and methine groups of the polycarbonate units in the polymer chain, while signals c and d (3.2-3.8 ppm) represent the absorption peaks of H on the methylene and methine groups of the polyether units in the polymer. Characteristic signals a (0.9-1.0 ppm) and b (1.4-1.7 ppm) represent the absorption peaks of H on the ethyl side chain in the polymer. The peaks at h (4.6 ppm) and g (4.5 ppm, 4.0 ppm) are characteristic absorption peaks of H on the byproduct BC.

[0118] Application Example 2

[0119] This application example uses the bimetallic cyanide catalyst obtained in Example 2 to prepare polycarbonate polyether polyols. The specific process is as follows:

[0120] 30 mg of bimetallic cyanide catalyst and 0.4 g of polypropylene glycol-400 initiator were added to a 50 mL dehydrated reactor. The reactor was evacuated, and 10 mL of 1,2-epoxybutane was added. CO2 was introduced and purged 6 times. The reactor was stirred at 500 r / min with an absolute pressure of 1 MPa. The polymerization temperature was 120 °C and the reaction time was 12 h. After the reaction was completed, the unreacted 1,2-epoxybutane was evaporated to obtain polycarbonate polyether polyol.

[0121] Application Example 3

[0122] This application example uses the bimetallic cyanide catalyst obtained in Example 3 to prepare polycarbonate polyether polyols. The specific process is as follows:

[0123] 30 mg of bimetallic cyanide catalyst and 0.4 g of polypropylene glycol-400 initiator were added to a 50 mL dehydrated reactor. The reactor was evacuated, and 10 mL of 1,2-epoxybutane was added. CO2 was introduced and purged 6 times. The reactor was stirred at 500 r / min with an absolute pressure of 5 MPa. The polymerization temperature was 90 °C and the reaction time was 8 h. After the reaction was completed, the unreacted 1,2-epoxybutane was evaporated to obtain polycarbonate polyether polyol.

[0124] Application Example 4

[0125] This application example uses the bimetallic cyanide catalyst obtained in Example 4 to prepare polycarbonate polyether polyols. The specific process is as follows:

[0126] 30 mg of bimetallic cyanide catalyst and 0.4 g of polypropylene glycol-400 initiator were added to a 50 mL dehydrated reactor. The reactor was evacuated, and 10 mL of 1,2-epoxybutane was added. CO2 was introduced and purged 6 times. The reactor was stirred at 500 r / min with an absolute pressure of 10 MPa. The polymerization temperature was 90 °C and the reaction time was 8 h. After the reaction was completed, the unreacted 1,2-epoxybutane was evaporated to obtain polycarbonate polyether polyol.

[0127] Application Example 5

[0128] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Example 5 is used to prepare polycarbonate polyether polyol.

[0129] Application Example 6

[0130] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Example 6 is used to prepare polycarbonate polyether polyol.

[0131] Application Example 7

[0132] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Example 7 is used to prepare polycarbonate polyether polyol.

[0133] Application Example 8

[0134] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Example 8 is used to prepare polycarbonate polyether polyol.

[0135] Application Example 9

[0136] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 1 is used to prepare polycarbonate polyether polyol.

[0137] Application Example 10

[0138] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 2 is used to prepare polycarbonate polyether polyol.

[0139] Application Example 11

[0140] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 3 is used to prepare polycarbonate polyether polyol.

[0141] Application Example 12

[0142] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 4 is used to prepare polycarbonate polyether polyol.

[0143] Application Example 13

[0144] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 5 is used to prepare polycarbonate polyether polyol.

[0145] Application Example 14

[0146] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 6 is used to prepare polycarbonate polyether polyol.

[0147] Application Example 15

[0148] The only difference from Application Example 1 is that the bimetallic cyanide catalyst in Comparative Example 7 is used to prepare polycarbonate polyether polyol.

[0149] Application Example 16

[0150] The only difference from Application Example 1 is that the reaction temperature is 60°C.

[0151] Application Example 17

[0152] The only difference from Application Example 1 is that the reaction temperature is 70°C.

[0153] Application Example 18

[0154] The only difference from Application Example 1 is that the reaction temperature is 100°C.

[0155] Application Example 19

[0156] The only difference from Application Example 1 is that the reaction temperature is 120°C.

[0157] The relevant indicators of the products obtained from Application Example 1-19 are detailed in Table 1. The calculation formulas for the relevant indicators during the process are as follows:

[0158] (1) Carbon dioxide fixation: ;

[0159] (2) Monomer conversion rate: ;

[0160] In the formula: A 1.1 and A 4.5 It is the peak area of ​​the characteristic absorption peak of cyclic carbonates; A 4.2It is the peak area of ​​the hydrogen absorption peak at position d in the NMR spectrum of the polycarbonate; A 4.8 It is the peak area of ​​the hydrogen absorption peak at position e in the NMR spectrum of the polycarbonate; A 3.5 It is the peak area of ​​the hydrogen absorption peak at position c in the NMR spectrum of the polycarbonate.

[0161] Table 1

[0162]

[0163] As shown in the table above, this invention provides a method for preparing and applying a bimetallic cyanide catalyst for synthesizing polycarbonate polyether polyols. The method uses biomass material fruit acid as an organic ligand to prepare the bimetallic cyanide catalyst, achieving a simplified and green preparation process with low cost, mild preparation conditions, and ease of industrialization. The application to 1,2-epoxybutane and carbon dioxide in the preparation of epoxybutyl polycarbonate polyether polyols increases the amount of carbon dioxide fixed, achieves high monomer conversion, and the mild reaction conditions facilitate industrial production.

[0164] As shown in Application Examples 1-4, the preparation method uses different fruit acids as organic ligands to synthesize bimetallic cyanide catalysts. When applied to the copolymerization of 1,2-epoxybutane and carbon dioxide to prepare epoxybutyl polycarbonate polyether polyols, differences exist in the amount of carbon dioxide fixed and the monomer conversion rate, with the highest carbon dioxide fixation reaching 30% and the highest monomer conversion rate reaching 99%. Comparing Application Examples 1 with Application Examples 5-6 shows that increasing the amount of fruit acid used in the bimetallic cyanide catalyst reduces both the carbon dioxide fixation rate and the monomer conversion rate. Comparing Application Examples 1 with Application Examples 7-8 shows that the preparation temperature of the bimetallic cyanide catalyst can achieve good results within a suitable range. Comparing Application Examples 1 with Application Examples 9-15 shows that when no fruit acid ligand is added or other ligands are added, the catalyst is inactive, proving that fruit acid, as an organic ligand, plays an important role in the activity of the bimetallic catalyst of this application. Comparing Application Examples 1 with Application Examples 16-19 shows that a good effect can be achieved within a certain polymerization temperature range.

[0165] In summary, this invention provides a bimetallic cyanide catalyst for synthesizing polycarbonate polyether polyols, its preparation method, and its applications. The bimetallic cyanide catalyst prepared using biomass material fruit acid as an organic ligand achieves a simplified and green preparation process with low cost, mild preparation conditions, and ease of industrialization. Its application to the preparation of epoxide-butane and carbon dioxide processes yields epoxide-butyl polycarbonate polyether polyols, improving carbon dioxide fixation and monomer conversion rates.

[0166] The present invention is described in detail through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the components used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0167] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0168] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0169] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A catalyst for synthesizing polycarbonate polyether polyols, characterized in that, The catalyst for synthesizing polycarbonate polyether polyols includes an M1 / M2 bimetallic cyanide catalyst with fruit acid as an organic ligand. The fruit acids include one or a combination of at least two of glycolic acid, lactic acid, malic acid, citric acid, and tartaric acid. M1 and M2 represent different metallic elements; The preparation method of the catalyst for synthesizing polycarbonate polyether polyols includes: According to the formula, provide M1 salt and fruit acid solution, and provide M2 ​​cyanate solution; The M1 salt and fruit acid solution are first mixed with the M2 cyanate solution at a temperature of 40-60℃ to obtain an intermediate material; The obtained intermediate material is subjected to aging, solid-liquid separation, washing and drying in sequence to obtain a catalyst for synthesizing polycarbonate polyether polyol, wherein the aging temperature is 40-60℃.

2. The catalyst for synthesizing polycarbonate polyether polyols as described in claim 1, characterized in that, M1 includes one of Zn, Cu, Al, or Fe.

3. The catalyst for synthesizing polycarbonate polyether polyols as described in claim 1, characterized in that, The M2 includes one of Fe, Co, or Ni.

4. The catalyst for synthesizing polycarbonate polyether polyols as described in claim 1, characterized in that, The molar ratio of M1 to M2 in the catalyst for synthesizing polycarbonate polyether polyol is (1-10):

2.

5. The catalyst for synthesizing polycarbonate polyether polyols as described in claim 1, characterized in that, The molar ratio of M1 to the organic ligand in the catalyst for synthesizing polycarbonate polyether polyols is 1:(1-10).

6. A method for preparing a catalyst for synthesizing polycarbonate polyether polyols as described in any one of claims 1-5, characterized in that, The preparation method includes: According to the formula, provide M1 salt and fruit acid solution, and provide M2 ​​cyanate solution; The M1 salt and fruit acid solution are first mixed with the M2 cyanate solution at a temperature of 40-60℃ to obtain an intermediate material; The obtained intermediate material is subjected to aging, solid-liquid separation, washing and drying in sequence to obtain a catalyst for synthesizing polycarbonate polyether polyol, wherein the aging temperature is 40-60℃.

7. The preparation method according to claim 6, characterized in that, The M1 salt and fruit acid solution is obtained by a second mixing of M1 salt, fruit acid, and water.

8. The preparation method according to claim 6, characterized in that... The M1 salt includes one or a combination of at least two of the following: halide, sulfate, or acetate.

9. The preparation method according to claim 6, characterized in that, The M2 cyanate solution is obtained by a third mixing of M2 cyanate and water.

10. The preparation method according to claim 6, characterized in that, The first mixing involves adding M1 salt and fruit acid solution dropwise into M2 cyanate solution.

11. The preparation method according to claim 6, characterized in that, The aging time is 0.5-2 hours.

12. The preparation method according to claim 6, characterized in that, The solid-liquid separation method is centrifugation.

13. The preparation method according to claim 6, characterized in that, The preparation method includes: According to the formula, provide M1 salt and fruit acid solution, and provide M2 ​​cyanate solution; The M1 salt and fruit acid solution are first mixed with the M2 cyanate solution to obtain an intermediate material; The obtained intermediate material was subjected to aging, solid-liquid separation, washing and drying in sequence to obtain a catalyst for synthesizing polycarbonate polyether polyol; Wherein, the M1 salt and fruit acid solution is obtained by a second mixing of M1 salt, fruit acid and water; the M1 salt includes one or a combination of at least two of the following: halide salt, sulfate salt or acetate salt; the M2 cyanate solution is obtained by a third mixing of M2 cyanate and water; the first mixing is achieved by adding the M1 salt and fruit acid solution dropwise into the M2 cyanate solution; the temperature of the first mixing is 40-60℃; the aging temperature is 40-60℃; the aging time is 0.5-2 h; and the solid-liquid separation method is centrifugation.

14. Use of a catalyst for synthesizing polycarbonate polyether polyols as described in any one of claims 1-5, characterized in that, The applications include the preparation of polycarbonate polyether polyols using catalysts for the synthesis of polycarbonate polyether polyols; Specifically, 1,2-epoxybutane and carbon dioxide are copolymerized under a carbon dioxide atmosphere using an initiator and a catalyst for synthesizing polycarbonate polyether polyols to obtain polycarbonate polyether polyols. The copolymerization reaction is carried out at a temperature of ≥70℃.

15. The use as described in claim 14, characterized in that, The initiator includes one or a combination of at least two of polypropylene glycol, sebacic acid, or 1,4-butanediol.

16. The use as described in claim 14, characterized in that, The absolute pressure of the carbon dioxide atmosphere is 1-10 MPa.

17. The use as described in claim 14, characterized in that, The copolymerization reaction takes 1-48 hours.

Images