A class of ether / alkali metal complex-based multi-active site catalysts, method of preparation and use in the preparation of polyesters, polycarbonates

Abstract

The application relates to a kind of multi-active site catalysts based on ether / alkali metal complex, preparation method and application in preparing polyester and polycarbonate, and belongs to the field of high polymer materials.The multi-active site catalysts based on ether / alkali metal complex are reticular structures with functional group terminated polyether polyol as main chain ligand and multiple main chains connected by coordination of alkali metal.The main chain has certain flexibility, and the relative position of multiple active centers can be regulated by changing the distance between ligand skeletons, so that single catalytic active center is changed into multiple active center cooperative catalysis, thereby greatly improving the alternating copolymerization activity of alkylene oxide and cyclic anhydride or carbon dioxide.The number average molecular weight of polyester or polycarbonate synthesized by the catalyst is 3.0-100.0 kg / mol, the molecular weight distribution is 1.1-1.5, the polyester or polycarbonate alternating degree is greater than 99%, the application range of such polymers is widened, and the catalyst has the prospect of realizing industrial production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a type of multi-active-site catalyst based on ether / alkali metal complexes, its preparation method, and its application in the preparation of polyesters and polycarbonates. Background Technology

[0002] Polyesters or polycarbonates are an important component in addressing the sustainability issues of petrochemical-based polymers, with bio-based polyesters or polycarbonates exhibiting good renewability, biocompatibility, and biodegradability. Despite the potential of polyester or polycarbonate materials, current technological limitations restrict their widespread application. These limitations primarily stem from a limited understanding of the structure-property relationship of polymers and the fact that synthetic methods are either too simplistic or unsuitable for industrial production.

[0003] This invention focuses on the alternating copolymerization reaction of epoxides with cyclic anhydrides or carbon dioxide. Based on currently reported catalytic systems, the reaction mechanism was thoroughly studied, and a class of multi-active-site catalysts based on ether / alkali metal complexes was designed and synthesized. Specifically, six catalysts were included: a bifunctional organoboron catalyst A, a β-iminoketone-based heteronuclear polymetallic catalyst B, a β-diimine-based heteronuclear polymetallic catalyst C, a phenoxy-based heteronuclear polymetallic catalyst D, a bifunctional dicarboxylic acid catalyst E, and a Schiff base-based heteronuclear polymetallic catalyst F. These catalysts use functionalized polyether polyols as the main chain ligands, forming a network structure where multiple main chains are linked through alkali metal coordination. The single catalytic active site is optimized into multi-active-site synergistic catalysis. The functionalized polyether polyol main chain has a certain degree of flexibility, allowing the relative positions of the multiple active sites to be controlled by changing the distance between the ligand backbones. Furthermore, the catalyst structure is more stable, giving this class of catalysts good tolerance. The number-average molecular weights of polyesters or polycarbonates synthesized by this catalyst are 3.0–100.0 kg / mol, the molecular weight distribution is 1.1–1.5, and the alternation of polyesters or polycarbonates is greater than 99%, which broadens the application range of such polymers and also has the prospect of realizing industrial production. Summary of the Invention

[0004] The main content of this invention is to provide a preparation technology for a class of multi-active-site catalysts based on ether / alkali metal complexes, based on the shortcomings of existing technologies, and to apply the technology to prepare polyesters and polycarbonates.

[0005] The technical solution of the present invention:

[0006] The aforementioned multi-active-site catalyst based on ether / alkali metal complexes is a network structure with functionalized group-terminated polyether polyols as the main chain ligands, and multiple main chains linked together through the coordination of alkali metals. The multi-active-site catalysts mainly include six types: bifunctional organoboron catalyst A, β-iminoketone-based heteronuclear multimetallic catalyst B, β-diimine-based heteronuclear multimetallic catalyst C, phenoxy-based heteronuclear multimetallic catalyst D, bifunctional dicarboxylic acid group catalyst E, and Schiff base-based heteronuclear multimetallic catalyst F, with the following structures:

[0007]

[0008] In the formula:

[0009] m = 0, 1, 2, 3;

[0010] n = 1, 2, 3, 4, 5, 6;

[0011] R is H, C1-C4 alkyl, C1-C4 alkoxy, F, Cl, Br or NO2 group;

[0012] M can be any one of Co, Al, Cr or Zn;

[0013] M1 is any one of Li, Na, or K;

[0014] X is Cl -1 NO3 -1 CF3COO -1 CH3COO -1 BF4 -1 or N3 -1 ;

[0015] Y is Cl -1 NO3 -1 CF3COO -1 CH3COO -1 BF4 -1 or N3 -1 .

[0016] The synthesis reaction equation for bifunctional organoboron catalyst A, one of the multi-active-site catalysts based on ether / alkali metal complexes, is as follows:

[0017]

[0018] The specific preparation steps of the bifunctional organoboron catalyst A are as follows:

[0019] Under inert gas protection, 9-boron bicyclo[3.3.1]nonane and olefin-terminated polyether polyols in a molar ratio of 2.5:1 were mixed and dissolved in an organic solvent. The mixture was then stirred at 0–100 °C for 5–7 h. The solvent was removed under reduced pressure to obtain a crude product. An organic solvent was added and the mixture was slurried for 2–3 h and then filtered. The filter cake was collected, and the reaction was repeated three times to obtain ligand A. Under inert gas protection, ligand A in a molar ratio of 1:1–6 was mixed with M1Y and dissolved in an organic solvent. The mixture was stirred at 0–100 °C for 5–24 h, and the reaction was stopped. The mixture was then filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain a bifunctional organoboron catalyst A.

[0020] The synthesis reaction equation for the heteronuclear multimetallic catalyst B based on β-imino ketone in the aforementioned class of multi-active-site catalysts based on ether / alkali metal complexes is as follows:

[0021]

[0022] The specific preparation steps of the β-imino ketone-based heteronuclear multimetallic catalyst B are as follows:

[0023] Acetylacetone and amino-terminated polyether polyols in a molar ratio of 1.2:1 were mixed under inert gas protection, dissolved in an organic solvent, and stirred at 0–100 °C for 10–24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand B. Ligand B and MX in a molar ratio of 1:1 were mixed under inert gas protection, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Ligand B and MX in a molar ratio of 1:1–6 were then added, and the mixture was stirred at 0–100 °C for 5–24 h before the reaction was stopped. The mixture was filtered, and the filter cake was washed repeatedly with an organic solvent and dried under vacuum to obtain β-iminoketone-based heteronuclear multimetallic catalyst B.

[0024] The synthesis reaction equation for the heteronuclear multimetal catalyst C based on β-diimine in the aforementioned class of multi-active-site catalysts based on ether / alkali metal complexes is as follows:

[0025]

[0026] The specific preparation steps of the β-diimine-based heteronuclear multimetallic catalyst C are as follows:

[0027] Under inert gas protection, malondialdehyde and amino-terminated polyether polyols in a molar ratio of 1.5:1 were mixed, dissolved in an organic solvent, and stirred at 0–100 °C for 10–24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand C. Under inert gas protection, ligand C and MX in a molar ratio of 1:1 were mixed, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Then, ligand C and MX in a molar ratio of 1:1–6 were added, and the mixture was stirred at 0–100 °C for 5–24 h before the reaction was stopped. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain the β-diimine-based heteronuclear multimetallic catalyst C.

[0028] The synthesis reaction equation for the phenoxy-based heteronuclear multimetal catalyst D, one of the aforementioned multi-active-site catalysts based on ether / alkali metal complexes, is as follows:

[0029]

[0030] The specific preparation steps of the phenoloxy heteronuclear multimetallic catalyst D are as follows:

[0031] Under inert gas protection, o-hydroxybenzyl chloride and polyether polyol in a molar ratio of 2.1:1 were mixed and dissolved in an organic solvent. Triethylamine in a molar ratio of 1.5:1 to o-hydroxybenzyl chloride was then added, and the reaction was continued with stirring at 0–100 °C for 10–24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand D. Under inert gas protection, ligand D and MX in a molar ratio of 3:1 were mixed and dissolved in an organic solvent. The mixture was stirred at 0–100 °C for 5–24 h. Ligand D and MX in a molar ratio of 1:1–6 were then added, and the reaction was stopped after stirring at 0–100 °C for 5–24 h. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain phenoxy-based heteronuclear multimetallic catalyst D.

[0032] The synthesis reaction equation for the bifunctional dicarboxylic acid catalyst E in the aforementioned class of multi-active-site catalysts based on ether / alkali metal complexes is as follows:

[0033]

[0034] The specific preparation steps of the bifunctional dicarboxylic acid catalyst E are as follows:

[0035] Under inert gas protection, 80% nitric acid and polyether polyol in a molar ratio of 5:1 were mixed and dissolved in an organic solvent. The mixture was then stirred at 0–100 °C for 5–8 h. The solvent was removed under reduced pressure to obtain a crude product, which was then recrystallized to obtain ligand E. Under inert gas protection, ligand E and MX in a molar ratio of 2:1 were mixed and dissolved in an organic solvent. The mixture was stirred at 0–100 °C for 5–24 h. Then, ligand E and MX in a molar ratio of 1:1–6 were added. The mixture was stirred at 0–100 °C for 5–24 h, and the reaction was stopped. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain the bifunctional dicarboxylic acid catalyst E.

[0036] The synthesis reaction equation for the Schiff base-based heteronuclear multimetal catalyst F, one of the aforementioned multi-active-site catalysts based on ether / alkali metal complexes, is as follows:

[0037]

[0038] The specific preparation steps of the Schiff base-based heteronuclear multimetallic catalyst F are as follows:

[0039] Under inert gas protection, 3-R-salicylaldehyde and amino-terminated polyether polyols in a molar ratio of 2.1:1 were mixed, dissolved in an organic solvent, and then added... Molecular sieves were used, and the reaction was continued at 0–100 °C for 5–8 h with stirring. The solvent was removed under reduced pressure to obtain a crude product, which was then recrystallized to obtain ligand F. Under inert gas protection, ligand F and MX were mixed in a molar ratio of 2:1, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Then, ligand F and M1Y in a molar ratio of 1:1–6 were added, and the reaction was stopped after stirring at 0–100 °C for 5–24 h. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain Schiff base-based heteronuclear multimetallic catalyst F.

[0040] A method for preparing polyester and polycarbonate using a multi-active-site catalyst based on ether / alkali metal complexes, the specific reaction process is as follows: a multi-active-site catalyst based on ether / alkali metal complexes, epoxides and cyclic anhydrides (or carbon dioxide) are added to a high-pressure reactor, an organic solvent is selectively added, the mixture is stirred for a certain time, and the reaction is stopped; the crude product is first dissolved in dichloromethane, then methanol is added, and the mixture is stirred vigorously to precipitate the polymer. The precipitation process is repeated to obtain polyester or polycarbonate.

[0041] The structural formulas of the cyclic anhydrides or carbon dioxide are as follows:

[0042]

[0043] The structural formula of the epoxide alkane is as follows:

[0044]

[0045] The mass ratio of the multi-active-site catalyst based on ether / alkali metal complex to the total of all monomers is 1:200 to 20000.

[0046] The molar ratio of the epoxide to the cyclic anhydride is 1:1.

[0047] The carbon dioxide pressure is 0.5–3.0 MPa.

[0048] The reaction temperature is 25–160°C.

[0049] The reaction time is 0.5 to 8.0 h.

[0050] The organic solvent is one of dichloromethane, dichloroethane, toluene, cyclohexane, n-hexane, 1,4-dioxane, and tetrahydrofuran.

[0051] The number-average molecular weight of the polyester or polycarbonate is 3.0 to 100.0 kg / mol.

[0052] The molecular weight distribution of the polyester or polycarbonate is 1.1 to 1.5.

[0053] The beneficial effects of this invention are:

[0054] (1) The multi-active-site catalyst based on ether / alkali metal complex of the present invention has a main chain ligand of a polyether polyol with functionalized groups at the end. The network structure that connects multiple main chains through the coordination of alkali metal can optimize a single catalytic active center into multi-active-site synergistic catalysis.

[0055] (2) The multi-active-site catalyst based on ether / alkali metal complex of the present invention has a stable structure, the ligands are tightly bound to the metal, and it has good tolerance, which greatly reduces the proportion of catalyst used.

[0056] (3) The multi-active-site catalyst based on ether / alkali metal complex described in this invention can adjust the relative position of multiple active sites by changing the distance between ligand skeletons, adapt to a variety of monomer structures, and can prepare a wide variety of polyesters or polycarbonates.

[0057] (4) The polyester or polycarbonate prepared using the multi-active-site catalyst based on ether / alkali metal complex described in this invention has mild reaction conditions, a polyester or polycarbonate alternation degree greater than 99%, a number-average molecular weight of 3.0 to 100.0 kg / mol, and a molecular weight distribution of 1.1 to 1.5. Detailed Implementation

[0058] The technical solution of the present invention will be further described below through embodiments.

[0059] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0060] In the following embodiments, the various processes and methods not described in detail are conventional methods known in the art. Furthermore, due to the large variety of catalysts and polymer structure ratios, not all preparation methods are described in detail; instead, typical examples are used to illustrate the specific process steps of the present invention.

[0061] Examples 1-6 are examples of methods for preparing catalyst AF:

[0062] Examples 7-12 are examples of the preparation of polyester and polycarbonate using the catalysis of the present invention. The epoxy alkane, cyclic anhydride, carbon dioxide and the multi-active-site catalyst based on ether / alkali metal complex used in the examples are all pure substances. The serial numbers of the epoxy alkane, cyclic anhydride, carbon dioxide and the multi-active-site catalyst based on ether / alkali metal complex are shown in the following formula.

[0063]

[0064]

[0065]

[0066] Example 1

[0067] Under inert gas protection, 10.0 g (82.0 mmol) of 9-boronbicyclo[3.3.1]nonane (mole ratio 2.5:1) and olefin-terminated polyether polyol (n=1, m=1, 4.6 g, 32.8 mmol) were mixed and dissolved in tetrahydrofuran (30.0 g) at a mass ratio of 3:1 to 9-boronbicyclo[3.3.1]nonane. The mixture was stirred at 40 °C for 6 h. The solvent was removed under reduced pressure to obtain a crude product. Hexane at a mass ratio of 5:1 to the crude product was added and stirred for 2 h. The mixture was then filtered, and the filter cake was collected. This process was repeated three times to obtain ligand A (n=1, m=1). The above steps constitute reaction stage 1. Under inert gas protection, ligand A (3.9 g, 10.1 mmol) and KCl (0.75 g, 10.1 mmol) in a 1:1 molar ratio were mixed and dissolved in dichloromethane (11.7 g) in a 3:1 mass ratio to the ligand. The mixture was stirred at 50 °C for 24 h, and then the reaction was stopped. The mixture was filtered, and the filter cake was washed several times with an organic solvent and dried under vacuum to obtain a bifunctional organoboron catalyst A (n = 1, m = 1, M1 = K, Y = Cl). -1 The above steps constitute reaction stage 2. 1H NMR (CDCl3, 400MHz): δ1.10(m,4H),1.21-1.25(m,8H),1.31(m,4H),1.40-1.46(m,8H),1.52(t,4H),1.56(m,4H),3.41(t,4H),3.50(t,4H).

[0068] The experimental procedures in Examples 1-1 to 1-8 of Table 1 are the same as those in Example 1, except for the temperature, reaction time, slurrying time, molar ratio of ligand A to M1Y, and the specific structure of the prepared bifunctional organoboron catalyst A. The obtained catalyst was then used in Examples 7-1 to 7-10 to prepare polyesters or polycarbonates. Details are as follows:

[0069] Table 1. Preparation of bifunctional organoboron catalyst A

[0070]

[0071] Example 2

[0072] Under inert gas protection, acetylacetone (10.0 g, 100.0 mmol) and amino-terminated polyether polyol (n = 1, m = 1, 12.3 g, 83.3 mmol) in a molar ratio of 1.2:1 were mixed and dissolved in n-hexane (50.0 g) in a mass ratio of 5:1 to acetylacetone. The mixture was stirred at 25 °C for 10 h. The solvent was removed under reduced pressure to obtain a crude product. The crude product was subjected to column chromatography (methanol:dichloromethane = 10:1) to obtain ligand B (n = 1, m = 1). This step constitutes reaction stage 1. Under inert gas protection, ligand B (3.1 g, 10.0 mmol) and CoCl2 (1.3 g, 10.0 mmol) in a molar ratio of 1:1 were mixed and dissolved in dichloroethane (12.4 g) in a mass ratio of 4:1 to ligand. The mixture was stirred at 55 °C for 5 h. This step constitutes reaction stage 2. Then, NaCl (0.58 g, 10.0 mmol) with a molar ratio of 1:1 to ligand B was added. The reaction was stopped after stirring at 75 °C for 24 h. The mixture was filtered, and the filter cake was washed several times with organic solvent and dried under vacuum to obtain the heteronuclear multimetallic catalyst B (n = 1, m = 1, M1 = K, M = Co, X = Cl) based on β-iminoketone. -1 ,Y=Cl -1 The above steps constitute reaction stage 3. 1 H NMR (CDCl3, 400MHz): δ1.99 (s, 6H), 2.08 (s, 6H), 3.41 (t, 4H), 3.51 (t, 4H), 3.63 (t, 4H), 5.10 (s, 2H).

[0073] The experimental procedures for Examples 2-1 to 2-9 in Table 2 are the same as those for Example 2, except for the temperature, reaction time, molar ratio of ligand B to M1Y, and the specific structure of the prepared β-iminoketone-based heteronuclear multimetallic catalyst B. The obtained catalyst was then used in Examples 8-1 to 8-10 to prepare polyesters or polycarbonates. Details are as follows:

[0074] Table 2. Preparation of heteronuclear multimetallic catalyst B based on β-imino ketone

[0075]

[0076] Example 3

[0077] Under inert gas protection, malondialdehyde (7.2 g, 100.0 mmol) and amino-terminated polyether polyol (n = 1, m = 0, 8.0 g, 66.7 mmol) in a molar ratio of 1.5:1 were mixed and dissolved in toluene (25.2 g) at a mass ratio of 3.5:1 to malondialdehyde (100.0 mmol). The mixture was stirred at 80 °C for 16 h. The solvent was removed under reduced pressure to obtain a crude product. The crude product was subjected to column chromatography (methanol:dichloromethane = 20:1) to obtain product ligand C (n = 1, m = 0). This step constitutes reaction stage 1. Under inert gas protection, ligand C (2.1 g, 13.5 mmol) and Zn(NO3)2 (2.5 g, 13.5 mmol) in a molar ratio of 1:1 were mixed and dissolved in dichloromethane at a mass ratio of 2:1 to ligand C. The mixture was stirred at 40 °C for 10 h. This step constitutes reaction stage 2. LiCl with a molar ratio of 1:1 to ligand C was added, and the reaction was stopped after stirring at 25°C for 24 h. The mixture was then filtered, and the filter cake was washed several times with organic solvent and dried under vacuum to obtain a heteronuclear polymetallic catalyst C(n=1,m=0,M1=Li,M=Zn,X=NO3) based on β-diimine. -1 ,Y=Cl -1 The above steps constitute reaction stage 3. 1 H NMR (CDCl3, 400MHz): δ3.40(s,2H),3.52(t,4H),3.76(s,2H),4.10(s,1H),6.95(s,1H),8.27(s,1H),8.75(s,1H).

[0078] The experimental procedures in Examples 3-1 to 3-8 in Table 3 are the same as in Example 3, except for the temperature, reaction time, molar ratio of ligand C to M1Y, and the specific structure of the prepared β-diimine-based heteronuclear multimetallic catalyst C. The obtained catalyst was then used in Examples 9-1 to 9-10 to prepare polyesters or polycarbonates. Details are as follows:

[0079] Table 3. Preparation of heteronuclear multimetallic catalyst C based on β-diimine

[0080]

[0081] Example 4

[0082] Under inert gas protection, o-hydroxybenzyl chloride (5.0 g, 35.2 mmol) and polyether polyol (n = 2, 1.8 g, 16.8 mmol) in a molar ratio of 2.1:1 were mixed and dissolved in toluene in a mass ratio of 3:1 to o-hydroxybenzyl chloride. Triethylamine (5.4 g, 52.8 mmol) in a molar ratio of 1.5:1 to o-hydroxybenzyl chloride was then added, and the mixture was stirred at 100 °C for 10 h. The solvent was removed under reduced pressure to obtain a crude product. The crude product was subjected to column chromatography (ethyl acetate: petroleum ether = 2:1) to obtain ligand D (n = 2). This step constitutes reaction stage 1. Under inert gas protection, ligand D (3.2 g, 10.0 mmol) and AlCl3 (0.44 g, 3.3 mmol) in a molar ratio of 3:1 were mixed and dissolved in toluene in a mass ratio of 1:1 to ligand D. The mixture was stirred at 100 °C for 24 h. This step constitutes reaction stage 2. Then, ligand D and KNO3 (2.0 g, 20.0 mmol) in a molar ratio of 1:2 were added. The reaction was stopped after stirring at 75 °C for 15 h. The mixture was filtered, and the filter cake was washed several times with organic solvent and dried under vacuum to obtain the phenoxy heteronuclear multimetallic catalyst D (n = 2, M1 = K, M = Al, X = Cl). -1 Y = NO3 -1 The above steps constitute reaction stage 3. 1 H NMR (CDCl3, 400MHz): δ3.55(t,8H),4.83(s,4H),6.86(m,2H),6.89(m,2H),7.10(m,2H),7.13(m,2H).

[0083] The experimental procedures for Examples 4-1 to 4-9 in Table 4 are the same as those for Example 4, except for the temperature, reaction time, molar ratio of ligand D to M1Y, and the specific structure of the prepared phenoxy heteronuclear multimetallic catalyst D. The obtained catalyst was then used in Examples 10-1 to 10-10 to prepare polyesters or polycarbonates. Details are as follows:

[0084] Table 4. Preparation of Phenoxy-based Heteronuclear Multimetallic Catalyst D

[0085]

[0086] Example 5

[0087] Under inert gas protection, 80% nitric acid (3.2 g, 50.5 mmol) and polyether polyol (n = 1, m = 2, 2.1 g, 10.1 mmol) in a molar ratio of 5:1 were mixed and dissolved in cyclohexane (6.4 g) in a mass ratio of 1:2 to nitric acid. The mixture was then stirred at 80 °C for 8 h. The solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized in n-hexane in a mass ratio of 4:1 to obtain ligand E (n = 1, m = 2). The above steps constitute reaction stage 1. Under an inert gas atmosphere, ligand E (2.3 g, 9.9 mmol) and ZnCl2 (0.67 g, 5.0 mmol) in a molar ratio of 2:1 were mixed and dissolved in toluene in a mass ratio of 3:1 to ligand E. The mixture was stirred at 100 °C for 5 h, which constitutes reaction stage 2. Then, NaBF4 (1.1 g, 9.9 mmol) in a molar ratio of 1:1 to ligand E was added, and the mixture was stirred at 60 °C for 24 h. The reaction was then stopped, filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain the bifunctional dicarboxylic acid catalyst E (n = 1, m = 2, M1 = Na, M = Zn, X = Cl). -1 Y = BF4 -1 The above steps constitute reaction stage 3. 1 H NMR (DMSO-d6, 400MHz): δ1.78(m,4H), 2.35(t,4H), 3.39(t,4H), 3.58(t,4H).

[0088] The experimental procedures for Examples 5-1 to 5-10 in Table 5 are the same as those for Example 5, except for the temperature, reaction time, molar ratio of ligand E to M1Y, and the specific structure of the prepared bifunctional dicarboxylic acid catalyst E. The obtained catalysts were then used in Examples 11-1 to 11-10 to prepare polyesters or polycarbonates. Details are as follows:

[0089] Table 5. Preparation of bifunctional dicarboxylic acid catalyst E

[0090]

[0091] Example 6

[0092] Under inert gas protection, salicylaldehyde (2.6 g, 21.2 mmol) and amino-terminated polyether polyol (n = 1, m = 1, 1.5 g, 10.1 mmol) in a molar ratio of 2.1:1 were mixed and dissolved in dichloromethane (13.0 g) in a mass ratio of 5:1 to salicylaldehyde. Molecular sieves were used, and the reaction was continued at 0°C with stirring for 8 hours. The solvent was removed under reduced pressure to obtain a crude product, which was recrystallized with n-hexane in a 3:1 ratio to obtain ligand F (n=1, m=1). This step constitutes reaction stage 1. Under inert gas protection, ligand F (3.6 g, 10.2 mmol) and CrCl2 (0.63 g, 5.1 mmol) in a 2:1 molar ratio were mixed and dissolved in tetrahydrofuran in a 3:1 mass ratio to ligand F. The mixture was stirred at 25°C for 24 hours. This step constitutes reaction stage 2. KCl (0.86 g, 10.2 mmol) in a 1:1 molar ratio to ligand F was then added, and the mixture was stirred at 25°C for 24 hours. The reaction was then stopped, filtered, and the filter cake was washed multiple times with organic solvent and dried under vacuum to obtain the Schiff base-based heteronuclear multimetallic catalyst F (n=1, m=1, M1=K, M=Cr, X=Cl). -1 ,Y=Cl -1 The above steps constitute reaction stage 3. 1 H NMR (CDCl3, 400MHz): δ3.54(t,4H),3.75(t,4H),5.94(t,4H),6.98(m,2H)7.20(m,2H)7.35(m,2H)7.69(m,2H)8.45(s,2H).

[0093] The experimental procedures for Examples 6-1 to 6-9 in Table 6 are the same as those for Example 6, except for the temperature, reaction time, molar ratio of ligand F to M1Y, and the specific structure of the prepared Schiff base-based heteronuclear multimetallic catalyst F. The obtained catalyst was then used in Examples 12-1 to 12-10 to prepare polyesters or polycarbonates. Details are as follows:

[0094] Table 6. Preparation of Schiff base-based heteronuclear multimetallic catalyst F

[0095]

[0096] Example 7

[0097] A 100mL high-pressure reactor equipped with magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of bifunctional organoboron catalyst 1a (Y=CF3COO) was weighed at room temperature. -1 The bifunctional organoboron catalyst 1a, along with 1g of epoxide and 5g of cyclic anhydride, were reacted at a mass ratio of 1:500, with a molar ratio of 1g of epoxide and 5g of cyclic anhydride of 1:1. 1,4-dioxane was added at a mass ratio of 2:1 to the epoxide, the mixture was heated to 150°C, and reacted for 0.5 hours. Stirring was then stopped, and a very small amount of the reaction mixture was collected for further processing. 1 H NMR and GPC tests. 1¹H NMR analysis showed that the polyester had a degree of alternation of 99.5%, and GPC analysis showed that the polymer molecular weight was 47.3 kg / mol with a molecular weight distribution of 1.3. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polyester was obtained by vacuum drying.

[0098] The experimental procedures for Examples 7-1 to 7-10 in Table 7 are the same as those for Example 7, except for the experimental conditions: cyclic anhydride, epoxide alkane, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0099] Table 7. Test results of polymers prepared by bifunctional organoboron catalysts

[0100]

[0101] Example 8

[0102] A 100mL high-pressure reactor equipped with magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of the β-iminoketone-based heteronuclear multimetallic catalyst 1b (X=Cl) was weighed at room temperature. -1 Y = N3 -1 The mass ratio of β-iminoketone-based heteronuclear multimetallic catalyst 1b to 2g of epoxide and 10g of carbon dioxide was 1:10000. The carbon dioxide pressure was 0.5MPa, the temperature was raised to 140℃, and the reaction was carried out for 5.0h. After stirring was stopped, a very small amount of the reaction mixture was taken out for further processing. 1 H NMR and GPC tests. 1 ¹H NMR analysis showed that the polycarbonate had a degree of alternation of 99.4%, and GPC analysis showed that the polymer molecular weight was 71.2 kg / mol with a molecular weight distribution of 1.3. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polycarbonate was obtained by vacuum drying.

[0103] The experimental procedures for Examples 8-1 to 8-10 in Table 8 are the same as those for Example 8, except for the experimental conditions: cyclic anhydride, epoxide, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0104] Table 8. Test results of polymers prepared using β-iminoketone-based heteronuclear multimetallic catalysts.

[0105]

[0106] Example 9

[0107] A 100mL high-pressure reactor equipped with magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of β-diimine-based heteronuclear multimetallic catalyst 1c(X=Cl) was weighed at room temperature. -1 Y = NO3 -1 The mass ratio of β-diimine-based heteronuclear polymetallic catalyst 1c to 9g of epoxide and 10g of carbon dioxide was 1:1000. The carbon dioxide pressure was 1.5MPa. Toluene was added in a mass ratio of 2:1 to epoxide. The temperature was raised to 100℃, and the reaction was carried out for 1.0h. Stirring was stopped, and a very small amount of the reaction mixture was taken out for further processing. 1 H NMR and GPC tests. 1 ¹H NMR analysis showed that the polycarbonate had a degree of alternation of 99.1%, and GPC analysis showed that the polymer molecular weight was 65.3 kg / mol with a molecular weight distribution of 1.4. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polycarbonate was obtained by vacuum drying.

[0108] The experimental procedures for Examples 9-1 to 9-10 in Table 9 are the same as those for Example 9, except for the experimental conditions: cyclic anhydride, epoxide, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0109] Table 9. Test results of polymers prepared using β-diimine-based heteronuclear multimetallic catalysts.

[0110]

[0111] Example 10

[0112] A 100mL high-pressure reactor equipped with a magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of phenoloxy heteronuclear polymetallic catalyst 1d (X=CH3COO) was weighed at room temperature. -1 Y = NO3 -1 The mass ratio of phenoxy heteronuclear polymetallic catalyst 1d to the total of epoxide 2h and cyclic anhydride 3g was 1:1000, and the molar ratio of epoxide 2h to cyclic anhydride 3g was 1:1. Dichloroethane was added in a mass ratio of 2:1 to epoxide, the temperature was raised to 80℃, and the reaction was carried out for 3.0h. Stirring was stopped, and a very small amount of the reaction mixture was taken out for further processing. 1 H NMR and GPC tests.1 HNMR analysis showed that the polyester had a degree of alternation of 99.2%, and GPC analysis showed that the polymer molecular weight was 67.1 kg / mol with a molecular weight distribution of 1.3. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polyester was obtained by vacuum drying.

[0113] The experimental procedures for Examples 10-1 to 10-10 in Table 10 are the same as those for Example 10, except for the experimental conditions: cyclic anhydride, epoxide, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0114] Table 10. Test results of polymers prepared by phenoxy heteronuclear multimetallic catalysts

[0115]

[0116] Example 11

[0117] A 100mL high-pressure reactor equipped with magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of the bifunctional dicarboxylic acid catalyst 1e(X=CH3COO) was weighed at room temperature. -1 ,Y=Cl -1 The bifunctional dicarboxylic acid catalyst 1e, the total mass ratio of 2g of epoxide and 5g of cyclic anhydride was 1:6000, and the molar ratio of 2g of epoxide and 5g of cyclic anhydride was 1:1. Cyclohexane was added in a mass ratio of 3:1 to the epoxide, the temperature was raised to 80℃, and the reaction was carried out for 4.0h. Stirring was stopped, and a very small amount of the reaction mixture was taken out for further processing. 1 H NMR and GPC tests. 1 ¹H NMR analysis showed that the polyester had a degree of alternation of 99.8%, and GPC analysis showed that the polymer molecular weight was 78.7 kg / mol with a molecular weight distribution of 1.3. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polyester was obtained by vacuum drying.

[0118] The experimental procedures for Examples 11-1 to 11-10 in Table 11 are the same as those for Example 11, except for the experimental conditions: cyclic anhydride, epoxide, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0119] Table 11. Test results of polymers prepared by bifunctional dicarboxylic acid catalysts.

[0120]

[0121] Example 12

[0122] A 100mL high-pressure reactor equipped with magnetic stir bar was dried at 120℃ for more than 12 hours, then evacuated and cooled to room temperature before being purged with nitrogen for use. Under nitrogen protection, a certain amount of Schiff base-based heteronuclear multimetallic catalyst 1f(X=CH3COO) was weighed at room temperature. -1 Y = CH3COO -1 The mass ratio of the Schiff base-based heteronuclear multimetallic catalyst 1f to the total amount of 3g of epoxide and 8g of cyclic anhydride was 1:5000, and the molar ratio of 3g of epoxide and 8g of cyclic anhydride was 1:1. Cyclohexane with a mass ratio of 3:1 to epoxide was added, the temperature was raised to 100℃, and the reaction was carried out for 5.0h. Stirring was stopped, and a very small amount of the reaction mixture was taken out for further processing. 1 HNMR and GPC tests. 1 ¹H NMR analysis showed that the polyester had a degree of alternation of 99.3%, and GPC analysis showed that the polymer molecular weight was 92.1 kg / mol with a molecular weight distribution of 1.4. The remaining reactant polymer was purified by dissolving the crude product in a small amount of dichloromethane, then adding a large amount of methanol and stirring vigorously to precipitate the polymer. This process was repeated, and the polyester was obtained by vacuum drying.

[0123] The experimental procedures for Examples 12-1 to 12-10 in Table 12 are the same as those for Example 12, except for the experimental conditions: cyclic anhydride, epoxide, catalyst structure, solvent, mass ratio of catalyst to total, temperature, time, product transpiration rate, molecular weight, and molecular weight distribution. Details are as follows:

[0124] Table 12 Test results of polymers prepared by heteronuclear multimetallic catalysts based on Schiff bases

[0125]

Claims

1. A class of multi-active-site catalysts based on ether / alkali metal complexes, characterized in that, The multi-active-site catalyst is a network structure in which polyether polyols with functionalized groups at the end are used as the main chain ligands, and multiple main chains are connected by the coordination of alkali metals. The multi-active-site catalysts include six types of catalysts, namely bifunctional organoboron catalyst A, based on... β -Imine heteronuclear multimetallic catalyst B, based on β The structures of the following heteronuclear multimetallic catalysts are as follows: C (diimine), D (phenoxy-based), E (bifunctional dicarboxylic acid group), and F (Schiff base-based). In the formula: m = 0，1，2，3； n = 1，2，3，4，5，6； R is H, C1-C4 alkyl, C1-C4 alkoxy, F, Cl, Br or NO2 group; M can be any one of Co, Al, Cr or Zn; M1 is any one of Li, Na, or K; X is Cl -1 NO3 -1 CF3COO -1 CH3COO -1 BF4 -1 or N3 -1 ; Y is Cl -1 NO3 -1 CF3COO -1 CH3COO -1 BF4 -1 or N3 -1 .

2. The method for preparing a multi-active-site catalyst based on an ether / alkali metal complex as described in claim 1, characterized in that, The synthesis reaction equation for bifunctional organoboron catalyst A is as follows: The specific preparation steps for bifunctional organoboron catalyst A are as follows: Under inert gas protection, 9-boron bicyclo[3.3.1]nonane and olefin-terminated polyether polyols with a molar ratio of 2.5:1 were mixed, dissolved in an organic solvent, and stirred at 0-100℃ for 5-7 h. The solvent was removed under reduced pressure to obtain a crude product. An organic solvent was added and the mixture was slurried for 2-3 h and filtered. The filter cake was collected and the process was repeated three times to obtain ligand A. Under inert gas protection, ligand A with a molar ratio of 1:1-6 was mixed with M1Y, dissolved in an organic solvent, stirred at 0-100℃ for 5-24 h, and the reaction was stopped. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain bifunctional organoboron catalyst A. based on β The synthesis reaction equation for -imino ketone using heteronuclear polymetallic catalyst B is: based on β The specific preparation steps for the heteronuclear multimetallic catalyst B of -imino ketone are as follows: Acetylacetone and amino-terminated polyether polyols in a molar ratio of 1.2:1 were mixed under inert gas protection, dissolved in an organic solvent, and stirred at 0–100 °C for 10–24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand B. Ligand B and MX in a molar ratio of 1:1 were mixed under inert gas protection, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Then, M1Y in a molar ratio of 1–6:1 to ligand B was added, and the mixture was stirred at 0–100 °C for 5–24 h before the reaction was stopped. The mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain the product based on… β -Imine heteronuclear polymetallic catalyst B; based on β The synthesis reaction equation for the heteronuclear polymetallic catalyst C of -diimine is: based on β The specific preparation steps for the heteronuclear multimetallic catalyst C of -diimine are as follows: Under inert gas protection, malondialdehyde and amino-terminated polyether polyols in a molar ratio of 1.5:1 were mixed, dissolved in an organic solvent, and stirred at 0–100 °C for 10–24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand C. Under inert gas protection, ligand C and MX in a molar ratio of 1:1 were mixed, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Then, M1Y in a molar ratio of 1–6:1 to ligand C was added, and the reaction was stopped after stirring at 0–100 °C for 5–24 h. The mixture was filtered, and the filter cake was washed several times with an organic solvent and dried under vacuum to obtain the product based on… β -Diimine heteronuclear polymetallic catalyst C; The synthesis reaction equation based on the phenoloxy heteronuclear polymetallic catalyst D is as follows: The specific preparation steps for phenoxy-based heteronuclear multimetallic catalyst D are as follows: Under inert gas protection, o-hydroxybenzyl chloride and polyether polyol in a molar ratio of 2.1:1 were mixed and dissolved in an organic solvent. Triethylamine in a molar ratio of 1.5:1 to o-hydroxybenzyl chloride was then added, and the reaction was continued to be stirred at 0-100℃ for 10-24 h. The solvent was removed under reduced pressure to obtain a crude product, which was then subjected to column chromatography to obtain ligand D. Under inert gas protection, ligand D and MX in a molar ratio of 3:1 were mixed and dissolved in an organic solvent. The mixture was stirred at 0-100℃ for 5-24 h, and then M1Y in a molar ratio of 1-6:1 to ligand D was added. The reaction was stopped after stirring at 0-100℃ for 5-24 h, the mixture was filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain phenoloxy heteronuclear polymetallic catalyst D. The synthesis reaction equation for the bifunctional dicarboxylic acid catalyst E is as follows: The specific preparation steps for the bifunctional dicarboxylic acid catalyst E are as follows: Under inert gas protection, 80% nitric acid and polyether polyol with a molar ratio of 5:1 were mixed and dissolved in an organic solvent. The mixture was then stirred at 0–100 °C for 5–8 h. The solvent was removed under reduced pressure to obtain a crude product, which was then recrystallized to obtain ligand E. Under inert gas protection, ligand E and MX with a molar ratio of 2:1 were mixed and dissolved in an organic solvent. The mixture was stirred at 0–100 °C for 5–24 h. Then, M1Y with a molar ratio of 1–6:1 to ligand E was added. The mixture was stirred at 0–100 °C for 5–24 h, and the reaction was stopped. The mixture was then filtered, and the filter cake was washed multiple times with an organic solvent and dried under vacuum to obtain the bifunctional dicarboxylic acid catalyst E. The synthesis reaction equation for the heteronuclear polymetallic catalyst F based on Schiff bases is as follows: The specific preparation steps of the Schiff base-based heteronuclear multimetallic catalyst F are as follows: Under inert gas protection, 3- (molar ratio 2.1:1) R - Salicylic aldehyde and amino-terminated polyether polyols are mixed, dissolved in an organic solvent, and 5 Å molecular sieves are added. The mixture is then stirred at 0–100 °C for 5–8 h. The solvent is removed under reduced pressure to obtain a crude product. The crude product is recrystallized to obtain ligand F. Under inert gas protection, ligand F and MX are mixed in a molar ratio of 2:1, dissolved in an organic solvent, and stirred at 0–100 °C for 5–24 h. Then, M1Y in a molar ratio of 1–6:1 to ligand F is added. The mixture is stirred at 0–100 °C for 5–24 h and the reaction is stopped. The mixture is filtered, and the filter cake is washed multiple times with an organic solvent and dried under vacuum to obtain Schiff base-based heteronuclear polymetallic catalyst F.

3. A method for preparing polyesters and polycarbonates using the multi-active-site catalyst based on an ether / alkali metal complex as described in claim 1 or the multi-active-site catalyst based on an ether / alkali metal complex prepared by the method described in claim 2, characterized in that, The specific reaction process is as follows: a multi-active-site catalyst based on ether / alkali metal complex, epoxide, and cyclic acid anhydride or carbon dioxide are added to a high-pressure reactor, and an organic solvent is selectively added. The mixture is stirred for a certain period of time and then the reaction is stopped. The crude product is first dissolved in dichloromethane, then methanol is added and stirred vigorously to precipitate the polymer. The precipitation process is repeated to obtain polyester or polycarbonate.

4. The method according to claim 3, characterized in that, The structural formulas of the cyclic anhydrides or carbon dioxide are as follows: 。 5. The method according to claim 3, characterized in that, The structural formula of the epoxide alkane is as follows: 。 6. The method according to claim 3, characterized in that, When the system raw materials are alkyl epoxides and cyclic anhydrides, the mass ratio of the multi-active-site catalyst based on ether / alkali metal complex to the total mass of alkyl epoxides and cyclic anhydrides is 1:200 to 20000; when the system raw materials are alkyl epoxides, cyclic anhydrides, and carbon dioxide, the mass ratio of the multi-active-site catalyst based on ether / alkali metal complex to the total mass of alkyl epoxides and cyclic anhydrides is 1:200 to 20000; when the system raw materials are alkyl epoxides and carbon dioxide, the mass ratio of the multi-active-site catalyst based on ether / alkali metal complex to alkyl epoxides is 1:200 to 20000; the molar ratio of alkyl epoxides to cyclic anhydrides is 1:1; when carbon dioxide is added, the carbon dioxide pressure is 0.5 to 3.0 MPa.

7. The method according to claim 3, characterized in that, The reaction temperature is 25~160 ℃; the reaction time is 0.5~8.0 h.

8. The manufacturing method according to claim 2 or the method according to claim 3, characterized in that, The organic solvent is one of dichloromethane, dichloroethane, toluene, cyclohexane, n-hexane, 1,4-dioxane, and tetrahydrofuran.

9. The method according to claim 3, characterized in that, The polyester or polycarbonate has a number-average molecular weight of 3.0~100.0 kg / mol and a molecular weight distribution of 1.1~1.5.

Images