CN118406219A - Copolymerization method of epoxy compound, anhydride and lactone - Google Patents

Abstract

The present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps: the epoxy compound and the acid anhydride are copolymerized under the catalytic conditions of an aminophenoloxy zinc halide catalyst, or the epoxy compound, the acid anhydride and the lactone are copolymerized under the catalytic conditions of an aminophenoloxy zinc halide catalyst in a one-pot method; the aminophenoloxy zinc halide catalyst is a mononuclear zinc catalyst, and its structure is shown in formula (I) or formula (II). Compared with the prior art, the copolymerization method provided by the present invention enables the two monomers of the epoxy compound and the acid anhydride to copolymerize at a very high rate, and simultaneously obtains a polymer with high polyester selectivity and a relatively high molecular weight, and secondly realizes the synthesis of a ternary two-block polymer of the epoxy compound, the acid anhydride and the lactone by a one-pot method.

Description

A copolymerization method of epoxy compound, acid anhydride and lactone

Technical Field

The invention relates to the technical field of polymers, and in particular to a copolymerization method of an epoxy compound, anhydride and lactone.

Background technique

The widespread use of polyolefin and other plastic products has not only caused serious environmental pollution, but also aggravated the consumption of oil resources and the energy crisis. Finding green and friendly materials to replace polyolefin materials has become a common goal of all walks of life.

As a new type of biodegradable polymer, polyester formed by ring-opening copolymerization of epoxy compounds and acid anhydrides not only has good biodegradability, but also has performance comparable to that of polyolefin materials. There are many types of epoxy compounds and acid anhydrides and they are widely available. Some of them are cheap and easy to obtain, so they have good economic advantages. At the same time, the functional groups on the monomers can realize the synthesis and post-modification of functional polyesters. For example, polyesters synthesized by ring-opening copolymerization of phthalic anhydride and epichlorohydrin and maleic anhydride and cyclohexene oxide can be further functionalized by sulfonation, etherification and other methods to improve the performance of polyesters. At present, the catalysts used to catalyze the copolymerization of epoxy compounds and acid anhydrides are mainly various metal complex catalysts, but there are still problems such as insufficient catalytic efficiency of the catalysts, unsatisfactory molecular weight level of the products, and certain polyether chain segments in the obtained polymers, which greatly reduce their thermodynamic and mechanical properties, which is not conducive to industrial application.

In 1985, the Inoue group used porphyrin aluminum complexes to catalyze the ring-opening copolymerization of propylene oxide and phthalic anhydride, and only obtained a polymer with a molecular weight of 3000 g/mol (Macromolecules, 1985, 18, 1049-1055). In 2007, the Coates group used β-diimino zinc catalysts to catalyze the copolymerization of cyclohexene oxide and phthalic anhydride to obtain a polymer with a molecular weight of 23 kg/mol, but the TOF was only 79 h ^-1 (J. Am. Chem. Soc., 2007, 129, 11330-11331). In 2011, the Sablong group applied the chromium complex of Salen ligand to the copolymerization of epoxy compounds and anhydrides, using DMAP as a co-catalyst, and obtained a polymer containing 73% polyester chain segments (Macromolecules, 2011, 44 (5): 1132-1139). In 2012, Nejad et al. studied the polymerization of cyclohexene oxide and cyclic anhydride catalyzed by Al, Cr, and Co complexes and found that Salen-Cr complex had the highest catalytic activity, but the number average molecular weight of the resulting polyester was between 8000-12000 and the PDI was between 1.2-1.3. (Macromolecules, 2012, 45(4): 1770-1776). In 2017, Nozaki's research group used a catalytic system consisting of binuclear Salen-Co and DMAP to catalyze the copolymerization of cyclohexene oxide and phthalic anhydride. The copolymerization reaction was efficiently catalyzed at 110°C to prepare a polyester material with a perfect alternating structure, with a TOF of 303h ^-1 (Macromolecules., 2017, 50: 7895-7900). In 2018, Li et al. used diethyl zinc, diphenyl zinc, DMAP, DBU and other Lewis acid-base pairs to catalyze the copolymerization of epoxy compounds and anhydrides to obtain polymers with high ester chain content, with the highest TOF reaching 210h ^-1 (Green Chem., 2018, 20(3): 641-648). In 2020, Mazzeo et al. used a binuclear aluminum complex with a naphthyl-bridged Schiff base ligand to catalyze the copolymerization of cyclohexene oxide and phthalic anhydride, with a polyester selectivity of up to 99%, but the polymer molecular weight was only 26kg/mol and the TOF was only 14h ^-1 (Organometallics, 2020, 39, 1213-1220). In 2021, the Jones group reported the catalyst (Salen)FeOAc, which can achieve copolymerization of cyclohexene oxide and phthalic anhydride without the need for a co-catalyst. Its polyester selectivity reaches 96% and the polymer molecular weight can reach 29 kg/mol (Macromolecules, 2021, 54, 8443-8452).

As can be seen from the above, the synthesis of polyester by copolymerization of epoxy compounds and anhydrides still faces many technical problems. The metal complex catalysts reported at present are difficult to take into account catalytic activity, product molecular weight and high polyester chain selectivity, and the metals involved in the catalysts with better performance are mainly chromium, cobalt, etc., which are not green and environmentally friendly. Therefore, it is urgent to develop efficient catalysts based on biocompatible metals to achieve high-activity catalytic epoxy compounds and highly controllable polymerization of anhydrides to obtain high molecular weight, high alternation polyester products to meet the needs of industrial applications. In addition, due to the slow decomposition speed of the polyester chain formed by epoxy compounds and anhydrides, the introduction of more easily degradable polylactones such as polylactide chain segments will increase the degradation speed while enhancing the physical properties of the polymer, making its performance more excellent.

Summary of the invention

The object of the present invention is to provide a copolymerization method of epoxy compounds, acid anhydrides and lactones.

In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

The present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps:

The epoxy compound and the acid anhydride are copolymerized under the catalytic condition of aminophenoloxy zinc halide catalyst;

The epoxy compound, the acid anhydride and the lactone are copolymerized under the catalytic condition of the aminophenoloxy zinc halide catalyst;

The aminophenoloxy zinc halide catalyst has a structure shown in formula (I) or (II):

In the formula (I):

R ¹ to R ² represent hydrogen, C ₁ to C ₂₀ straight chain, branched or cyclic alkyl, C ₇ to C ₃₀ single or multiple aromatic substituted alkyl, halogen;

R ³ represents a C ₁ ～C ₂₀ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₃₀ single or multiple aryl substituted alkyl group, a C ₆ ～C ₁₈ aryl group;

R ⁴ represents a C ₁ ～C ₂₀ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₃₀ single or multiple aromatic substituted alkyl group;

X represents a halogen.

More characteristically, in formula (I), R ¹ to R ² are hydrogen, C ₁ to C ₈ linear, branched or cyclic alkyl, C ₇ to C ₂₀ mono- or poly-aryl-substituted alkyl, halogen;

R ³ is a C ₁ ～C ₈ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₂₀ single or multiple aryl substituted alkyl group, a C ₆ ～C ₁₂ aryl group;

R ⁴ is a C ₁ ～C ₈ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₂₀ single or multiple aromatic substituted alkyl group;

X represents chlorine, bromine or iodine.

Preferably, in formula (I), R ¹ to R ² are hydrogen, methyl, tert-butyl, cumyl, trityl, or chlorine; R ³ is methyl, ethyl, isopropyl, n-butyl, tert-butyl, isopentyl, cyclohexyl, n-hexyl, n-octyl, benzyl, or phenethyl; R ⁴ is methyl, ethyl, isopropyl, n-butyl, cyclohexyl, benzyl, or phenethyl; and X represents chlorine.

Preferably, the aminophenoloxy zinc halide catalyst shown in formula (I) has one of the following structures:

In the formula (II):

R ⁵ to R ⁸ represent hydrogen, C ₁ to C ₂₀ straight chain, branched or cyclic alkyl, C ₇ to C ₃₀ single or multiple aromatic substituted alkyl, halogen;

R ⁹ represents ethylene or methylene;

X ¹ to X ² represent C ₁ to C ₁₂ linear, branched or cyclic alkoxy groups, or C ₁ to C ₁₂ linear, branched or cyclic alkyl substituted amino groups;

X ³ represents a halogen.

More characteristically, R ⁵ to R ⁸ represent hydrogen, C ₁ to C ₈ linear, branched or cyclic alkyl, C ₇ to C ₂₀ mono- or poly-aryl-substituted alkyl, halogen;

R ⁹ represents ethylene;

X ¹ to X ² represent C ₁ to C ₆ straight chain, branched or cyclic alkoxy groups, or C ₁ to C ₆ straight chain, branched or cyclic alkyl substituted amine groups;

X ³ represents chlorine, bromine or iodine.

Preferably, in formula (II), R ⁵ to R ⁸ are independently selected from hydrogen, methyl, tert-butyl, cumyl, trityl, and chlorine; X ¹ to X ² are independently selected from methoxy, dimethylamino, and diethylamino; and X ³ is chlorine.

Preferably, the aminophenoloxy zinc halide catalyst shown in formula (II) has one of the following structures:

Preferably, the molar ratio of the aminophenoloxy zinc halide catalyst to the epoxy compound is 1:(500-150000).

The molar ratio of the aminophenoloxy zinc halide catalyst to the acid anhydride is 1:(50-100000).

The molar ratio of the aminophenoloxy zinc halide catalyst to the lactone is 1:(200-1000).

Preferably, the epoxy compound is one or more of propylene oxide, epichlorohydrin and cyclohexene oxide.

Preferably, the acid anhydride is one or more of phthalic anhydride, maleic anhydride and succinic anhydride.

Preferably, the lactone is one or more of L-lactide, D-lactide, rac-lactide, meso-lactide and ε-caprolactone.

Preferably, the copolymerization reaction temperature is 25 to 250°C;

The copolymerization reaction time is 0.1 to 200 hours;

The copolymerization reaction is carried out under an inert atmosphere.

Preferably, the raw materials for the copolymerization reaction further include a co-catalyst;

The molar ratio of the aminophenoloxy zinc halide catalyst to the co-catalyst is 1:(0-20).

Preferably, the co-catalyst is one or more of bis(triphenylphosphorane)ammonium chloride, 4-dimethylaminopyridine and tetrabutylammonium bromide.

The present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps: copolymerizing the epoxy compound and the acid anhydride under the catalytic conditions of an aminophenoloxy zinc halide catalyst, and simultaneously achieving copolymerization of three monomers, namely, the epoxy compound, the acid anhydride and the lactone. Compared with the prior art, the copolymerization method provided by the present invention enables the catalyst to have a higher activity for the copolymerization of the epoxy compound and the acid anhydride, and simultaneously obtains a polymer with a high polyester chain segment and a high molecular weight; and achieves the one-pot copolymerization of the three monomers of the epoxy compound, the acid anhydride and the lactone. The results of the examples of the present application show that the copolymer obtained by the present invention is a single polymer.

Detailed ways

The present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps:

The epoxy compound and the acid anhydride are copolymerized under the catalytic condition of aminophenoloxy zinc halide catalyst;

The epoxy compound, the acid anhydride and the lactone are copolymerized under the catalytic condition of the aminophenoloxy zinc halide catalyst;

The aminophenoloxy zinc halide catalyst has a structure shown in formula (I) or (III):

In the formula (I):

R ¹ to R ² represent hydrogen, C ₁ to C ₂₀ straight chain, branched or cyclic alkyl, C ₇ to C ₃₀ single or multiple aromatic substituted alkyl, halogen;

R ³ represents a C ₁ ～C ₂₀ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₃₀ single or multiple aryl substituted alkyl group, a C ₆ ～C ₁₈ aryl group;

R ⁴ represents a C ₁ ～C ₂₀ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₃₀ single or multiple aromatic substituted alkyl group;

X represents a halogen.

More characteristically, in formula (I), R ¹ to R ² are hydrogen, C ₁ to C ₈ linear, branched or cyclic alkyl, C ₇ to C ₂₀ mono- or poly-aryl-substituted alkyl, halogen;

R ³ is a C ₁ ～C ₈ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₂₀ single or multiple aryl substituted alkyl group, a C ₆ ～C ₁₂ aryl group;

R ⁴ is a C ₁ ～C ₈ straight chain, branched or cyclic alkyl group, a C ₇ ～C ₂₀ single or multiple aromatic substituted alkyl group;

X represents chlorine, bromine or iodine.

Preferably, in formula (I), R ¹ to R ² are hydrogen, methyl, tert-butyl, cumyl, trityl, or chlorine; R ³ is methyl, ethyl, isopropyl, n-butyl, tert-butyl, isopentyl, cyclohexyl, n-hexyl, n-octyl, benzyl, or phenethyl; R ⁴ is methyl, ethyl, isopropyl, n-butyl, cyclohexyl, benzyl, or phenethyl; and X represents chlorine.

Preferably, the aminophenoloxy zinc halide catalyst shown in formula (I) has one of the following structures:

In the formula (II):

R ⁵ to R ⁸ represent hydrogen, C ₁ to C ₂₀ straight chain, branched or cyclic alkyl, C ₇ to C ₃₀ single or multiple aromatic substituted alkyl, halogen;

R ⁹ represents ethylene or methylene;

X ¹ to X ² represent C ₁ to C ₁₂ linear, branched or cyclic alkoxy groups, or C ₁ to C ₁₂ linear, branched or cyclic alkyl substituted amino groups;

X ³ represents a halogen.

More characteristically, R ⁵ to R ⁸ represent hydrogen, C ₁ to C ₈ linear, branched or cyclic alkyl, C ₇ to C ₂₀ mono- or poly-aryl-substituted alkyl, halogen;

R ⁹ represents ethylene;

X ¹ to X ² represent C ₁ to C ₆ straight chain, branched or cyclic alkoxy groups, or C ₁ to C ₆ straight chain, branched or cyclic alkyl substituted amine groups;

X ³ represents chlorine, bromine or iodine.

Preferably, in formula (II), R ⁵ to R ⁸ are independently selected from hydrogen, methyl, tert-butyl, cumyl, trityl, and chlorine; X ¹ to X ² are independently selected from methoxy, dimethylamino, and diethylamino; and X ³ is chlorine.

Preferably, the aminophenoloxy zinc halide catalyst shown in formula (II) has one of the following structures:

The aminophenoloxy zinc halide catalyst shown in formula (I) or (II) of the present invention can be synthesized by referring to the methods disclosed in patents CN202210076002.3 and CN202210075972.1, and its corresponding multi-dentate aminophenol ligand can be synthesized by referring to the methods disclosed in patents ZL201910187042.3 and ZL200910197687.1.

The aminophenoloxy zinc halide catalyst of the present invention introduces metal zinc as a catalytic center in its structure, which is more environmentally friendly, so that the complex has higher activity than a large number of metal aluminum chloride catalysts reported, and at the same time, due to the electronic effect of the ligand, the homopolymerization reaction of the epoxide is slower, the generation of polyether can be reduced, and the polyester selectivity is better. The aminophenoloxy zinc halide catalyst has good anti-sensitivity, is not easy to be deactivated in the catalytic multi-polymerization process, and can form a single polymer.

The present invention has no special restrictions on the sources of the epoxy compound, acid anhydride, lactone and aminophenoloxy zinc halide catalyst. The epoxy compound, acid anhydride, lactone and aminophenoloxy zinc halide catalyst well known to those skilled in the art can be used. Specifically, the epoxy compound, acid anhydride, lactone and aminophenoloxy zinc halide catalyst can be commercially available products or homemade products. The present invention has no special restrictions on the homemade method of the epoxy compound, acid anhydride, lactone and aminophenoloxy zinc halide catalyst. The epoxy compound, acid anhydride, lactone and aminophenoloxy zinc halide catalyst can be obtained. The present invention has no special requirements on the mixing order of the epoxy compound, acid anhydride, lactone and catalyst. The epoxy compound, acid anhydride, lactone and catalyst can be mixed in any order.

In the present invention, the molar ratio of the aminophenoloxy zinc halide catalyst to the epoxy compound is preferably 1:(500-150000), more preferably 1:(1000-60000), and most preferably 1:(1000-10000).

In the present invention, the molar ratio of the aminophenoloxy zinc halide catalyst to the acid anhydride is preferably 1:(50-100000), more preferably 1:(100-60000), and most preferably 1:(200-10000).

In the present invention, the ratio of the aminophenoloxy zinc halide catalyst to the lactone substance is preferably 1:(50-5000), more preferably 1:(100-1000), and most preferably 1:(150-500).

The present invention has no special requirements on the molar ratio of the epoxy compound, the acid anhydride and the lactone. In the present invention, the molar ratio of the epoxy compound, the acid anhydride and the lactone can be any value.

In the present invention, the lactide is preferably one or more of L-lactide, D-lactide, rac-lactide, meso-lactide and ε-caprolactone, and specifically may be one, two, three or four.

In the present invention, the temperature of the copolymerization reaction is preferably 25 to 250° C., more preferably 50 to 200° C., and most preferably 80 to 180° C. In the present invention, the time of the copolymerization reaction is preferably 0.1 to 200 hours, more preferably 0.2 to 80 hours, and most preferably 0.5 to 50 hours. The present invention has no special requirements for the heating method of the copolymerization reaction, and the heating method well known to those skilled in the art can be used for heating.

In the present invention, the copolymerization reaction is preferably carried out under an inert atmosphere. The present invention has no special requirements for the inert atmosphere, and any inert atmosphere known to those skilled in the art can be used, specifically argon.

In the present invention, the raw materials of the copolymerization reaction preferably also include a co-catalyst. In the present invention, the co-catalyst is preferably one or more of bis(triphenylphosphorane)ammonium chloride, 4-dimethylaminopyridine and tetrabutylammonium bromide. In the present invention, the molar ratio of the aminophenoloxy zinc halide catalyst to the co-catalyst is preferably 1:(0-20), more preferably 1:(0-10), and most preferably 1:(1-5). The present invention has no special requirements for the order of adding the co-catalyst, and it can be mixed with the epoxy compound, acid anhydride, lactone and catalyst in any order.

In the present invention, the raw materials of the copolymerization reaction preferably also include a solvent, and the solvent is preferably one or more of propylene oxide, epichlorohydrin, and cyclohexene oxide, and specifically can be one, two or three. The present invention has no special requirements for the order of adding the solvent, and can be mixed with the monomer and the catalyst in any order. The present invention preferably dissolves the catalyst in the solvent and configures it into a catalyst solution so that the amount of catalyst added is more controllable. In the present invention, the amount of the solvent added is preferably measured by the concentration of the catalyst. In the present invention, the molar concentration of the aminophenoloxy zinc halide catalyst in the solvent is preferably 0.010-0.030 mol/L; more preferably 0.01-0.028 mol/L, and most preferably 0.010 mol/L.

The present invention has no special requirements for the device used in the copolymerization reaction, and any device known to those skilled in the art that can meet the technical requirements of this application can be used. In the present invention, the copolymerization reaction is preferably carried out in a polymerization bottle.

In the present invention, it is preferred to add a chain terminator to terminate the copolymerization reaction after the copolymerization reaction time is reached. The present invention has no special requirements on the type of the chain terminator, and a chain terminator that can terminate the copolymerization reaction of epoxy compounds, acid anhydrides and lactones known to those skilled in the art can be used. Specifically, it can be a commercially available conventional solvent, such as petroleum ether, dichloromethane, n-hexane, tetrahydrofuran, methanol, etc. The present invention has no special requirements on the amount of the chain terminator, and it can be added according to the conventional technical content in this field.

After the reaction is terminated, the present invention preferably uses dichloromethane or other highly polar low boiling point solvents such as chloroform to dissolve the reactants. The present invention has no special requirements for the amount of dichloromethane used, as long as it can completely dissolve all the reactants.

After adding the dichloromethane and concentrating, the present invention preferably adds methanol, ethanol, isopropanol or benzyl alcohol and other alcohols to precipitate the copolymerization product. The present invention has no special requirements on the amount of methanol added, until the precipitate no longer increases.

After the copolymerization product is precipitated, the present invention preferably dries the copolymerization product at 60°C to obtain the target product. The present invention has no special requirements for the specific implementation of the drying, and the drying can be carried out by a drying method of solid substances well known to those skilled in the art, specifically vacuum drying (less than 0.1 mmHg). In the present invention, the drying time is preferably 16 to 28 hours, more preferably 20 to 26 hours, and most preferably 24 hours.

The present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps: copolymerization of the epoxy compound and the acid anhydride under the catalytic condition of aminophenoloxy zinc halide; copolymerization of the epoxy compound, the acid anhydride and the lactone under the catalytic condition of aminophenoloxy zinc halide. Compared with the prior art, the copolymerization method provided by the present invention enables the copolymerization reaction of the epoxy compound and the acid anhydride to have extremely high catalytic activity and extremely high polyester selectivity, and the obtained polymer has a higher molecular weight, and can also realize the one-pot copolymerization of the epoxy compound, the acid anhydride and the lactone to obtain a diblock polymer.

The copolymerization method of epoxy compounds, acid anhydrides and lactones provided by the present invention is described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

Example 1

Synthesis of catalyst 17

Under argon protection, NaH (24 mg, 1.0 mmol) was added in batches to a 20 mL tetrahydrofuran solution of ligand L ¹ H (200 mg, 0.540 mmol) and reacted for 12 hours. Excess NaH was filtered to remove, and then anhydrous zinc chloride tetrahydrofuran complex (152 mg, 0.540 mmol) was added to the reaction solution and the reaction was continued for 12 hours. After filtering, the solid was drained to obtain a light yellow solid, which was recrystallized from dichloromethane and n-hexane to obtain a white solid (130 mg, 51%).

¹ H NMR (400MHz, CDCl ₃ ): δ7.38–7.29 (m, 2H, ArH), 7.19 (d, ³ J＝7.3Hz, 1H, ArH), 6.95 (t, ³ J＝7.5Hz, 1H, ArH),6.92–6.85(m,2H,ArH),5.30(s,0.3×2H,0.3CH ₂ Cl ₂ ),5.13–4.02(very br s,2H,ArCH ₂ ),3.80(s,3H,ArOCH ₃ ),3.69(br s,2H,CH ₃ OCH ₂ ),3.60–2.70(very br,7H,CH ₃ OCH ₂ &ArCH ₂ &NCH ₂ CH ₂ ),1.34–1.19(m,0.1×8H,0.1Hexane),0.90–0.78(m,0.1×6H,0.1Hexane).Anal.Calcd.for C ₁₈ H ₂₀ Cl ₃ NO ₃ Zn·0.3CH ₂ Cl ₂ ·0.1C ₆ H ₁₄ : C, 45.02; H, 4.40; N, 2.78. Found: C, 44.57; H, 4.37; N, 2.76%.

Example 2

Synthesis of Catalyst 18

The remaining steps were the same as Example 1 except that the raw materials used were ligand L ² H (174 mg, 0.470 mmol), NaH (23 mg, 0.94 mmol) and anhydrous zinc chloride tetrahydrofuran complex (132 mg, 0.470 mmol). The white powder (105 mg, 47%) was obtained by recrystallization from dichloromethane and n-hexane.

¹ H NMR (400MHz, CDCl ₃ ): δ7.37 (td, ³ J＝7.6Hz, ⁴ J＝1.8Hz, 1H, ArH), 7.20 (dd, ³ J＝7.4Hz, ⁴ J＝1.8Hz, 1H ,ArH),7.04(d, ⁴ J＝2.4Hz,1H,ArH),6.98(td, ³ J＝7.5Hz, ⁴ J＝1.1Hz,1H,ArH),6.94(dd, ³ J＝8.3, ⁴ J＝1.0Hz, 1H, ArH), 6.60 (d, ⁴ J＝2.4Hz, 1H, ArH), 4.48 (d, ² J＝13.1Hz, 1H, ArCH ₂ ), 3.94 (d, ² J＝12.1Hz ,1H,ArCH ₂ ),3.81(s,3H,ArOCH ₃ ),3.75(m,0.2×4H,0.2THF),3.72–3.63(m,3H,ArCH ₂ &CH ₃ OCH ₂ ),3.56(d, ² J＝13.1Hz, 1H,ArCH ₂ ), 3.53 (s, 3H, CH ₃ OCH ₂ ), 3.16 (ddd, ² J＝13.2, ³ J＝8.1, ³ J＝5.2Hz, 1H, NCH ₂ CH ₂ ), 2.60 (dt, ² J＝13.2, ³ J＝4.4Hz,1H,NCH ₂ CH ₂ ),2.19(s,3H,ArCH ₃ ),1.85(m,0.2×4H,0.2THF),1.47(s,9H,C(CH ₃ ) ₃ ). ¹³ C{ ¹ H} NMR (100MHz, CDCl ₃ ): δ157.9,139.3,133.0,130.9,130.0,128.4,123.0,121.4,121.2,121.0,120.4,112.0(all Ar-C),68.2 (CH ₂ OCH ₃ ),67.9(THF),60.0(CH ₂ OCH ₃ ),59.5(ArCH ₂ ),56.2(ArCH ₂ ),55.4(ArOCH ₃ ),52.1(NCH ₂ CH ₂ ),35.2(C( CH ₃ ) ₃ ),29.9(C(CH ₃ ) ₃ ),25.7(THF),20.8(ArCH ₃ ).Anal.Calcd.for C ₂₃ H ₃₂ ClNO ₃ Zn·0.2C ₄ H ₈ O:C,58.85;H,6.97;N,2.88.Found:C,58.35;H,7.44;N,2.49%.

Example 3

Synthesis of catalyst 19

Except that the reactants were L ³ H (539 mg, 1.00 mmol), NaH (48 mg, 2.0 mmol) and anhydrous zinc chloride tetrahydrofuran complex (281 mg, 1.00 mmol), the other synthetic steps were the same as Example 1. The crude product was recrystallized from tetrahydrofuran/n-hexane to obtain colorless crystals, which were dried to obtain white powder (236 mg, 37%).

¹ H NMR (400MHz, CDCl ₃ ): δ7.35 (td, ³ J＝7.9Hz, ⁴ J＝1.7Hz, 1H, ArH), 7.31–7.27 (dd, ³ J＝7.3Hz, ⁴ J＝1.5Hz ,2H,PhH),7.25–7.21(m,5H,ArH&PhH),7.19(t, ³ J＝7.5Hz,2H,PhH),7.16–7.09(m,2H,ArH&PhH),7.07(t, ³ J＝ 7.3Hz, 1H, PhH), 6.96 (td, ³ J＝7.5Hz, ² J＝1.1Hz, 1H, ArH), 6.90 (d, ³ J＝8.4Hz, 1H, ArH), 6.56 (d, ⁴ J＝2.5Hz, 1H, ArH), 4.27 (d, ² J＝13.6Hz, 1H, ArCH ₂ ), 3.85 (d, ² J＝12.4Hz, 1H, ArCH ₂ ), 3.71 (d, ² J＝13.6 Hz,1H,ArCH ₂ ),3.63(s,3H,ArOCH ₃ ),3.67–3.56(m,1H,CH ₃ OCH ₂ ,parfially overlapped with the signal ofArOCH ₃ ),3.52(d, ² J＝12.4Hz, 1H, ArCH ₂ ), 3.45 (ddd, ² J＝9.9Hz, ³ J＝6.0, 4.0Hz, 1H, CH ₃ OCH ₂ ), 3.21 (s, 3H, CH ₃ OCH ₂ ), 2.85 (ddd, ² J＝13.3Hz, ³ J＝6.0,4.3Hz,1H,NCH ₂ CH ₂ ),2.51(ddd, ² J＝13.3Hz, ³ J＝7.0,4.0Hz,1H,NCH ₂ CH ₂ ),1.77(s ,3H,C(CH ₃ ) ₂ Ph),1.66(s,3H,C(CH ₃ ) ₂ Ph),1.63(s,3H,C(CH ₃ ) ₂ Ph),1.62(s,3H,C( CH ₃ ) ₂ Ph). ¹³ C{ ¹ H}NMR (100MHz, CDCl ₃ ):162.7,158.0,152.1,152.0,138.3,135.6,133.4,130.8,128.2,127.8,127.4,126.8,126.7,126.4,125.3,124.3,121.1,120.5,120.3,111.6(all Ar-C),68.2( CH ₂ OCH ₃ ),60.2(ArCH ₂ ),59.4(CH ₂ OCH ₃ ),55.8(ArCH ₂ ),54.2(ArOCH ₃ ),50.7(NCH ₂ CH ₂ ),42.4(C(CH ₃ ) ₂ Ph) ,42.3(C(CH ₃ ) ₂ Ph),31.3(C(CH ₃ ) ₂ Ph),31.2(C(CH ₃ ) ₂ Ph),30.3(C(CH ₃ ) ₂ Ph),28.3(C(CH ₃ ) ₂ Ph).Anal.Calcd.for C ₃₆ H ₄₂ ClNO ₃ Zn :C,67.82;H,6.64;N,2.20.Found:C,67.47;H,6.59;N,2.10%.

Example 4

Synthesis of Catalyst 20

(1) Synthesis of ligand

Add N-(2-methoxybenzyl)-2-methoxyethylamine (4.68 g, 24.0 mmol) and 30 mL of N,N-dimethylformamide (DMF) to a 100 mL eggplant-shaped bottle and stir to dissolve. Add K ₂ CO ₃ (4.20 g, 30.0 mmol) to the bottle and stir for a while before adding 2-bromomethyl-4-tert-butyl-6-tritylphenol (9.71 g, 20.0 mmol). After reacting for 14 hours, add 150 mL of water, extract with ethyl acetate, and wash the organic phase with saturated brine. Dry over anhydrous Na ₂ SO ₄ , filter, spin dry the solvent, and recrystallize with dichloromethane and methanol to obtain a white solid (9.7 g, 81%).

¹ H NMR (400MHz, CDCl ₃ ): δ10.65(br s,1H,OH),7.24–7.16(m,13H,ArH),7.16–7.11(m,3H,ArH),7.09(d, ⁴ J ＝2.4Hz,1H,ArH),6.92–6.85(m,2H,ArH),6.81(td, ³ J＝7.4Hz, ⁴ J＝1.1Hz,1H,ArH),6.76(dd, ³ J＝8.2Hz , ⁴ J＝1.0Hz,1H,ArH),3.74(s,2H,ArCH ₂ ),3.61(s,2H,ArCH ₂ ),3.58(s,3H,ArOCH ₃ ),3.19(m,5H,CH ₂ OCH ₃ &CH ₂ CH ₂ N), 2.51 (t, ³ J＝6.3Hz, 2H, CH ₂ CH ₂ N), 1.14 (s, 9H, C (CH ₃ ) ₃ ). ¹³ C{ ¹ H} NMR (100MHz, CDCl ₃ ): δ158.0,154.0,146.4,139.9,133.2,131.8,131.3,128.8,127.6,126.9,125.3,125.1,124.5,121.8,120.4,110.3(allAr-C),70.4(CH ₂ OCH ₃ ),63.6( CPh ₃ ) ,58.7(CH ₂ OCH ₃ ),58.7(ArCH ₂ ),55.1(ArCH ₂ ),53.1(NCH ₂ CH ₂ ),51.6(ArOCH ₃ ),34.1(C(CH ₃ ) ₃ ),31.6(C(CH ₃ ) ₃ ).Anal.Calcd.for C ₄₁ H ₄₅ NO ₃ :C,82.10;H,7.56;N ,2.34.Found:C,82.21;H,7.64;N,2.34%.

(2) Synthesis of Catalyst 20

Except that the reactants were ^L4H (368 mg, 0.600 mmol), NaH (29 mg, 1.2 mmol) and anhydrous zinc chloride tetrahydrofuran complex (169 mg, 0.600 mmol), the other synthetic steps were the same as those in Example 1. The crude product was recrystallized from dichloromethane/n-hexane or tetrahydrofuran/n-hexane system to obtain colorless crystals, which were dried to obtain white powder (181 mg, 43%).

¹ H NMR (400MHz, CDCl ₃ ): δ7.38 (t, ³ J＝8.0Hz, 1H, ArH), 7.28 (d, ³ J＝7.6Hz, 6H, PhH), 7.22–7.12 (m, 8H, PhH&ArH),7.05(t, ³ J＝4.2Hz,3H,PhH),6.99(t, ³ J＝7.4Hz,1H,ArH),6.90(d, ³ J＝8.4Hz,1H,ArH),6.71( d, ⁴ J＝2.8Hz, 1H, ArH), 5.28 (s, 0.2×2H, CH ₂ Cl ₂ ), 4.14 (d, ² J＝13.7Hz, 1H, ArCH ₂ ), 4.05 (d, ² J＝ 12.5Hz,1H,ArCH ₂ ),3.95(d, ² J＝13.7Hz,1H,ArCH ₂ ),3.74(m,0.2×4H,0.2THF),3.59(s,3H,ArOCH ₃ ),3.62–3.54(m,1H,ArCH ₂ ,parfiallyoverlapped with the signal of ArOCH ₃ ),3.38(dt, ² J＝12.5Hz, ³ J＝4.2Hz,2H,CH ₃ OCH ₂ ),2.92(s,3H,CH ₃ OCH ₂ ),2.80(dt, ² J＝13.3Hz, ³ J＝4.0Hz,1H,NCH ₂ CH ₂ ),2.67-2.58(m,1H,NCH ₂ CH ₂ ),1.85(m,0.2×4H,0.2THF),1.12(s,9H,C(CH ₃ ) ₃ ). ¹³ C{ ¹ H}NMR (100MHz, CDCl ₃ ): δ162.8,158.2,147.1,135.9, 135.7,133.6,131.3,130.8,129.5,126.7,126.4,124.7,121.0,120.3,120.2,111.5(all Ar-C),68.3(CH ₂ OCH ₃ ),68.1(THF),63.9(CPh ₃ ),60.0 (CH ₂ OCH ₃ ),59.4(ArCH ₂ ),55.6(ArCH ₂ ),54.5(ArOCH ₃ ),53.6(CH ₂ Cl ₂ ),50.8(NCH ₂ CH ₂ ),34.0(C(CH ₃ ) ₃ ),31.8(C(CH ₃ ) ₃ ),25.7(THF).Anal.Calcd.For C ₄₁ H ₄₄ ClNO ₃ Zn·0.2CH ₂ Cl ₂ ·0.2THF: C, 69.01; H, 6.34; N, 1.92. Found: C, 69.07; H, 6.77; N, 1.91%.

Example 5

Synthesis of catalyst 21

(1) Synthesis of ligand

Add N-(2-methoxybenzyl)-2-methoxyethylamine (2.77 g, 14.2 mmol) and 30 mL of N,N-dimethylformamide (DMF) to a 100 mL eggplant-shaped bottle. Add K ₂ CO ₃ (2.68 g, 19.4 mmol) and 2-bromomethyl-4,6-di-tert-butylphenol (3.85 g, 12.9 mmol). After reacting for 14 hours, add 150 mL of water, extract with ethyl acetate, and wash the organic phase with saturated brine. Dry over anhydrous Na ₂ SO ₄ , filter, spin dry the solvent, and purify by column chromatography (PE:EA=10:1) to obtain a yellow oil (5.0 g, 90%).

¹ H NMR (400MHz, CDCl ₃ ): δ10.82 (br s, 1H, OH), 7.24 (m, 2H, ArH), 7.17 (d, ⁴ J＝2.4Hz, 1H, ArH), 6.95–6.85 ( m,2H,ArH),6.83(d, ⁴ J＝2.4Hz,1H,ArH),3.85(s,3H,ArOCH ₃ ),3.79(s,2H,ArCH ₂ ),3.76(s,2H,ArCH ₂ ),3.49(t, ³ J＝6.0Hz,2H,CH ₂ CH ₂ N),3.26(s,3H,CH ₃ OCH ₂ ),2.69(t, ³ J＝6.0Hz,2H,CH ₂ CH ₂ N ),1.41(s,9H,C(CH ₃ ) ₃ ),1.26(s,9H,C(CH ₃ ) ₃ ). ¹³ C{ ¹ H}NMR (100MHz, CDCl ₃ ): δ158.2,154.5,140.2,135.5,131.7,128.9,125.5,123.6,122.7, 121.8,120.4,110.5(all Ar-C),70.4(CH ₂ OCH ₃ ),58.9(CH ₂ OCH ₃ ),58.7(ArCH ₂ ),55.2(ArCH ₂ ),53.5(NCH ₂ CH ₂ ),52.1( ArOCH ₃ ),35.0(C(CH ₃ ) ₃ ),34.2(C(CH ₃ ) ₃ ),31.8(C(CH ₃ ) ₃ ),29.7(C(CH ₃ ) ₃ ).Anal.Calcd.for C ₂₆ H ₃₉ NO ₃ :C,75.50;H,9.50;N,3.39.Found:C,75.66;H,9.66;N, 3.41%.

(2) Synthesis of Catalyst 21

Except that the reactants were L ⁵ H (290 mg, 0.700 mmol), NaH (34 mg, 1.4 mmol) and anhydrous zinc chloride tetrahydrofuran complex (196 mg, 0.700 mmol), the other synthetic steps were the same as in the example. The crude product was recrystallized from tetrahydrofuran/n-hexane to obtain colorless crystals, which were dried to obtain white powder (180 mg, 47%).

¹ H NMR (400MHz, CDCl ₃ ): δ7.38 (td, ³ J＝7.0Hz, ⁴ J＝1.5Hz, 1H, ArH), 7.25 (d, ⁴ J＝2.6Hz, 1H, ArH), 7.22( dd, ³ J＝7.5Hz, ⁴ J＝1.7Hz, 1H, ArH), 7.00 (td, ³ J＝7.5Hz, ⁴ J＝1.1Hz, 1H, ArH), 6.95 (d, ³ J＝8.2Hz, 1H, ArH), 6.74 (d, ⁴ J＝2.6Hz, 1H, ArH), 4.45 (d, ² J＝13.1Hz, 1H, ArCH ₂ ), 3.93 (d, ² J＝12.2Hz, 1H, ArCH ₂ ),3.82(s,3H,ArOCH ₃ ),3.75(m,0.5×4H,0.5THF),3.71–3.65(m,3H,ArCH ₂ &CH ₃ OCH ₂ ),3.62(d, ² J＝13.1Hz,1H,ArCH ₂ ),3.50(s, 3H,CH ₃ OCH ₂ ), 3.19 (dt, ² J＝13.3Hz, ³ J＝6.7Hz, 1H, NCH ₂ CH ₂ ), 2.61 (dt, ² J＝13.2Hz, ³ J＝4.3Hz, 1H, NCH ₂ CH ₂ ),1.85(m,0.5×4H,0.5THF),1.48(s,9H,C(CH ₃ ) ₃ ),1.25(s,9H,C(CH ₃ ) ₃ ). ¹³ C{ ¹ H}NMR (100MHz, CDCl ₃ ): δ163.1,158.0,138.5,136.5,133.0,130.9,125.9,124.6,121.2,121.1,120.5,112.0(all Ar-C),68.1(CH ₂ OCH ₃ ),67.9( THF),60.0(CH ₂ OCH ₃ ),59.8(ArCH ₂ ),56.2(ArCH ₂ ),55.6(ArOCH ₃ ),52.4(NCH ₂ CH ₂ ),35.5(C(CH ₃ ) ₃ ),34.0(C (CH ₃ ) ₃ ),31.9(C(CH ₃ ) ₃ ),29.9(C(CH ₃ ) ₃ ),25.7(THF).Anal.Calcd.for C ₂₆ H ₃₈ ClNO ₃ Zn·0.5THF:C,61.21;H,7.70;N,2.55.Found:C,61.40;H,7.64;N,2.37%.

Example 6

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14 mg, 0.024 mmol) were added to the polymerization bottle. 0.5 mL of the cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.01 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 5. The reaction temperature was controlled at 25 ° C, the reaction was carried out for 24 hours, and petroleum ether was added to terminate the reaction.

Dissolved in dichloromethane, sampled and measured H NMR spectrum. Calculation showed that the conversion rate of phthalic anhydride was 89%, TOF = 7.4h ^-1 ; the polyester chain segments in the polymer were 99%.

The remaining solution was concentrated and methanol was added to precipitate the polymer, which was then dried in vacuum for 24 hours. A sample was taken for GPC measurement, and _Mn = 5.7 × ¹⁰³ g/mol and molecular weight distribution PDI = 1.16.

Example 7

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14 mg, 0.024 mmol) were added to the polymerization bottle. 0.5 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle, [Cat.] ₀ = 0.01 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 1. The reaction temperature was controlled at 80°C, the reaction was carried out for 103 min, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 67%, TOF = 73 h ^-1 ; polyester chain segments in the polymer were 99%; M _n = 8.3 × 10 ³ g/mol, and molecular weight distribution PDI = 1.13.

Example 8

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14 mg, 0.024 mmol) were added to the polymerization bottle. 0.5 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle, [Cat.] ₀ = 0.01 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 2. The reaction temperature was controlled at 80°C, the reaction was continued for 55 min, and petroleum ether was added to terminate the reaction. Other operations were the same as those in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 63%, TOF = 137 h ^-1 ; polyester chain segments in the polymer were 99%; M _n = 7.5 × 10 ³ g/mol, and molecular weight distribution PDI = 1.11.

Example 9

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14 mg, 0.024 mmol) were added to the polymerization bottle. 0.5 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle, [Cat.] ₀ = 0.01 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 5. The reaction temperature was controlled at 80°C, the reaction was continued for 24 min, and petroleum ether was added to terminate the reaction. Other operations were the same as those in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 97%, TOF = 485 h ^-1 ; polyester chain segments in the polymer were 99%; M _n = 6.1×10 ³ g/mol, and molecular weight distribution PDI = 1.21.

Example 10

Except that the catalyst was replaced with 3, the reaction temperature was controlled at 80°C and the reaction time was 48 min, other operations were the same as in Example 9. Calculation and detection revealed that the conversion rate of phthalic anhydride was 84%, TOF = 234 h ^-1 ; polyester segments in the polymer were 99%; M _n = 6.4×10 ³ g/mol, and molecular weight distribution PDI = 1.20.

Embodiment 11

Except that the catalyst was replaced with 5, the reaction temperature was controlled at 80°C and the reaction time was 39 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 97%, TOF = 255h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.1×10 ³ g/mol, and molecular weight distribution PDI = 1.17.

Example 12

Except that the catalyst was replaced with 7, the reaction temperature was controlled at 80°C and the reaction time was 36 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 84%, TOF = 280h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.5×10 ³ g/mol, and molecular weight distribution PDI = 1.20.

Example 13

Except that the catalyst was replaced with 9, the reaction temperature was controlled at 80°C and the reaction time was 57 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 83%, TOF = 175h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.0×10 ³ g/mol, and molecular weight distribution PDI = 1.18.

Embodiment 14

Except that the catalyst was replaced with 10, the reaction temperature was controlled at 80°C and the reaction time was 26 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 91%, TOF = 420h ^-1 ; polyester segments in the polymer were 99%; M _n = 6.0×10 ³ g/mol, and molecular weight distribution PDI = 1.19.

Embodiment 15

Except that the catalyst was replaced with 11, the reaction temperature was controlled at 80°C and the reaction time was 47 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 91%, TOF = 232h ^-1 ; polyester segments in the polymer were 99%; M _n = 6.1×10 ³ g/mol, and molecular weight distribution PDI = 1.18.

Example 16

Except that the catalyst was replaced with 13, the reaction temperature was controlled at 80°C and the reaction time was 26 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 87%, TOF = 402h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.2×10 ³ g/mol, and molecular weight distribution PDI = 1.22.

Embodiment 17

Except that the catalyst was replaced with 14, the reaction temperature was controlled at 80°C and the reaction time was 29 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 93%, TOF = 384 h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.6×10 ³ g/mol, and molecular weight distribution PDI = 1.14.

Embodiment 18

Except that the catalyst was replaced with 16, the reaction temperature was controlled at 80°C and the reaction time was 21 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 90%, TOF = 514h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.5×10 ³ g/mol, and molecular weight distribution PDI = 1.16.

Embodiment 19

Except that the catalyst was replaced with 17, the reaction temperature was controlled at 80°C and the reaction time was 10 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 90%, TOF = 1080h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.9×10 ³ g/mol, and molecular weight distribution PDI = 1.16.

Embodiment 20

Except that the catalyst was replaced with 18, the reaction temperature was controlled at 80°C and the reaction time was 12 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 92%, TOF = 920h ^-1 ; polyester segments in the polymer were 99%; M _n = 3.5×10 ³ g/mol, and molecular weight distribution PDI = 1.20.

Embodiment 21

Except that the catalyst was replaced with 19, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 96%, TOF = 822 h ^-1 ; polyester segments in the polymer were 99%; M _n = 3.2×10 ³ g/mol, and molecular weight distribution PDI = 1.18.

Embodiment 22

Except that the catalyst was replaced with 20, the reaction temperature was controlled at 80°C and the reaction time was 16 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 91%, TOF = 682h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.9×10 ³ g/mol, and molecular weight distribution PDI = 1.26.

Embodiment 23

Except that the catalyst was replaced with 21, the reaction temperature was controlled at 80°C and the reaction time was 13 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 90%, TOF = 830h ^-1 ; polyester segments in the polymer were 99%; M _n = 3.3×10 ³ g/mol, and molecular weight distribution PDI = 1.22.

Embodiment 24

Except that the catalyst was replaced with 27, the reaction temperature was controlled at 80°C and the reaction time was 26 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 84%, TOF = 388h ^-1 ; polyester segments in the polymer were 99%; M _n = 4.8×10 ³ g/mol, and molecular weight distribution PDI = 1.22.

Embodiment 25

Except that the catalyst was replaced with 28, the reaction temperature was controlled at 80°C and the reaction time was 27 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 82%, TOF = 364h ^-1 ; polyester segments in the polymer were 99%; M _n = 4.2×10 ³ g/mol, and molecular weight distribution PDI = 1.24.

Embodiment 26

Except that the catalyst was replaced with 30, the reaction temperature was controlled at 80°C and the reaction time was 23 min, other operations were the same as in Example 9. Calculation and detection showed that the conversion rate of phthalic anhydride was 82%, TOF = 427h ^-1 ; polyester segments in the polymer were 99%; M _n = 4.8×10 ³ g/mol, and molecular weight distribution PDI = 1.24.

Embodiment 27

Under argon protection, phthalic anhydride (189 mg, 1.3 mmol) and bis(triphenylphosphorane)ammonium chloride (18 mg, 0.0315 mmol) were added to the polymerization bottle. 0.5 mL of the epichlorohydrin solution of catalyst 3 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0128 M, [ECH]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 5. The reaction temperature was controlled at 80°C, the reaction was carried out for 15 min, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 79%, TOF = 630 h ^-1 ; polyester chain segments in the polymer were 99%; M _n = 2.1 × 10 ³ g/mol, and molecular weight distribution PDI = 1.39.

Embodiment 28

Except that the catalyst was replaced with 4, the reaction temperature was controlled at 80°C and the reaction time was 11 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 81%, TOF = 972 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.1×10 ³ g/mol, and molecular weight distribution PDI = 1.42.

Embodiment 29

Except that the catalyst was replaced with 5, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 82%, TOF = 702 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.2×10 ³ g/mol, and molecular weight distribution PDI = 1.37.

Embodiment 30

Except that the catalyst was replaced with 7, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 87%, TOF = 745 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.4×10 ³ g/mol, and molecular weight distribution PDI = 1.31.

Embodiment 31

Except that the catalyst was replaced with 9, the reaction temperature was controlled at 80°C and the reaction time was 20 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 85%, TOF = 510 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.3×10 ³ g/mol, and molecular weight distribution PDI = 1.40.

Embodiment 32

Except that the catalyst was replaced with 1, the reaction temperature was controlled at 80°C and the reaction time was 15 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 83%, TOF = 664h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.1×10 ³ g/mol, and molecular weight distribution PDI = 1.44.

Embodiment 33

Except that the catalyst was replaced with 11, the reaction temperature was controlled at 80°C and the reaction time was 15 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 83%, TOF = 664 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.1×10 ³ g/mol, and molecular weight distribution PDI = 1.44.

Embodiment 34

Except that the catalyst was replaced with 13, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 87%, TOF = 745 h ^-1 ; polyester segments in the polymer were 99%; M _n = 3.0×10 ³ g/mol, and molecular weight distribution PDI = 1.43.

Embodiment 35

Except that the catalyst was replaced with 14, the reaction temperature was controlled at 80°C and the reaction time was 16 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 89%, TOF = 668h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.3×10 ³ g/mol, and molecular weight distribution PDI = 1.48.

Embodiment 36

Except that the catalyst was replaced with 15, the reaction temperature was controlled at 80°C and the reaction time was 15 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 89%, TOF = 710 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.3×10 ³ g/mol, and molecular weight distribution PDI = 1.37.

Embodiment 37

Except that the catalyst was replaced with 16, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 99%, TOF = 848h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.9×10 ³ g/mol, and molecular weight distribution PDI = 1.49.

Embodiment 38

Except that the catalyst was replaced with 17, the reaction temperature was controlled at 80°C and the reaction time was 9 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 99%, TOF = 1320 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.8×10 ³ g/mol, and molecular weight distribution PDI = 1.39.

Embodiment 39

Except that the catalyst was replaced with 18, the reaction temperature was controlled at 80°C and the reaction time was 11 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 95%, TOF = 1036h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.1×10 ³ g/mol, and molecular weight distribution PDI = 1.32.

Embodiment 40

Except that the catalyst was replaced with 19, the reaction temperature was controlled at 80°C and the reaction time was 12 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 96%, TOF = 960h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.6×10 ³ g/mol, and molecular weight distribution PDI = 1.24.

Embodiment 41

Except that the catalyst was replaced with 20, the reaction temperature was controlled at 80°C and the reaction time was 14 min, other operations were the same as in Example 27. Calculation and detection revealed that the conversion of phthalic anhydride was 91%, TOF = 780 h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.4×10 ³ g/mol, and molecular weight distribution PDI = 1.32.

Embodiment 42

Except that the catalyst was replaced with 21, the reaction temperature was controlled at 80°C and the reaction time was 12 min, other operations were the same as in Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 97%, TOF = 970h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.2×10 ³ g/mol, and molecular weight distribution PDI = 1.28.

Embodiment 43

Except that the catalyst was replaced with 27, the reaction temperature was controlled at 80°C and the reaction time was 15 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 90%, TOF = 720h ^-1 ; polyester segments in the polymer were 99%; M _n = 2.2×10 ³ g/mol, and molecular weight distribution PDI = 1.43.

Embodiment 44

Except that the catalyst was replaced with 28, the reaction temperature was controlled at 80°C and the reaction time was 18 min, other operations were the same as Example 27. Calculation and detection showed that the conversion rate of phthalic anhydride was 90%, TOF = 640, polyester segments in the polymer were 99%, _Mn = 2.8 × ¹⁰³ g/mol, and molecular weight distribution PDI = 1.36.

Embodiment 45

Under argon protection, phthalic anhydride (216 mg, 1.4 mmol) and bis(triphenylphosphorane)ammonium chloride were added to the polymerization bottle. 0.5 mL of propylene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0146 M, [PO]: [PA]: [Cat.]: [PPNCl] = 1000: 200: 1: 5. The reaction temperature was controlled at 25 ° C, the reaction was carried out for 13 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 77%; the polyester chain segments in the polymer were 99%; M _n = 4.5 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.11.

Embodiment 46

Under argon protection, succinic anhydride (100 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (2.87 mg, 0.005 mmol) were added to the polymerization bottle. 0.5 mL of the cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.002 M, [CHO]: [SA]: [Cat.]: [PPNCl] = 5000: 1000: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was carried out for 6 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of succinic anhydride was 80%; the polyester chain segments in the polymer were 90%; M _n = 2.4 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.79.

Embodiment 47

Under argon protection, maleic anhydride (98 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (2.87 mg, 0.005 mmol) were added to the polymerization bottle. 0.5 mL of cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.002 M, [CHO]: [MA]: [Cat.]: [PPNCl] = 5000: 1000: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was carried out for 6 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 55%; the polyester chain segments in the polymer were 23%; and the polymer was cross-linked.

Embodiment 48

Under argon protection, succinic anhydride (102 mg, 1.02 mmol) and bis(triphenylphosphorane)ammonium chloride (2.92 mg, 0.0051 mmol) were added to the polymerization bottle. 0.4 mL of the epichlorohydrin solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00255 M, [ECH]: [SA]: [Cat.]: [PPNCl] = 5000: 1000: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was continued for 2.7 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of succinic anhydride was 90%; the polyester chain segments in the polymer were 93%; M _n = 4.4 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.54.

Embodiment 49

Under argon protection, maleic anhydride (100 mg, 1.02 mmol) and bis(triphenylphosphorane)ammonium chloride (2.92 mg, 0.0051 mmol) were added to the polymerization bottle. 0.5 mL of the epichlorohydrin solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00255 M, [ECH]: [MA]: [Cat.]: [PPNCl] = 5000: 1000: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was continued for 2.7 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of maleic anhydride was 70%; the polyester chain segments in the polymer were 31%; and the polymer was cross-linked.

Embodiment 50

Under argon protection, phthalic anhydride (148 mg, 1.0 mmol), rac-lactide (144 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14.35 mg, 0.025 mmol) were added to the polymerization bottle. 0.4 mL of the epichlorohydrin solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0125 M, [ECH]: [PA]: [rac-LA]: [Cat.]: [PPNCl] = 1000: 200: 200: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was carried out for 60 min, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 100%; the conversion rate of rac-lactide was 73%; M _n = 5.3 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.37.

Embodiment 51

Under argon protection, phthalic anhydride (148 mg, 1.0 mmol), rac-lactide (144 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14.35 mg, 0.025 mmol) were added to the polymerization bottle. 0.35 mL of propylene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0143 M, [PO]: [PA]: [rac-LA]: [Cat.]: [PPNCl] = 1000: 200: 200: 1: 5. The reaction temperature was controlled at 25 ° C, the reaction was carried out for 86 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 100%; the conversion rate of rac-lactide was 59%; M _n = 6.0 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.33.

Embodiment 52

Under argon protection, succinic anhydride (100 mg, 1.0 mmol), rac-lactide (144 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14.35 mg, 0.025 mmol) were added to the polymerization bottle. 0.5 mL of propylene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.01 M, [CHO]: [SA]: [rac-LA]: [Cat.]: [PPNCl] = 1000: 200: 200: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was continued for 5.2 h, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 100%; the conversion rate of rac-lactide was 82%; M _n = 4.6 × 10 ³ g/mol, and the molecular weight distribution PDI = 1.43.

Embodiment 53

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol), rac-lactide (144 mg, 1.0 mmol), ε-caprolactone (114 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (14.35 mg, 0.025 mmol) were added to the polymerization bottle. 0.5 mL of propylene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.01 M, [PO]: [PA]: [rac-LA]: [ε-CL]: [Cat.]: [PPNCl] = 1000: 200: 200: 200: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was carried out for 8.0 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and testing revealed that the conversion rate of phthalic anhydride was 100%, the conversion rate of rac-lactide was 100%, the conversion rate of ε-caprolactone was 37%, M _n =2.1×10 ³ g/mol, and the molecular weight distribution PDI was 1.54.

Embodiment 54

Except for controlling the reaction temperature at 100°C and the reaction time for 7.2 min, other operations were the same as in Example 9. Calculation and detection revealed that the conversion rate of phthalic anhydride was 99%, TOF = 1650 h ^-1 ; polyester segments in the polymer were 99%; M _n = 5.6×10 ³ g/mol, and molecular weight distribution PDI = 1.22.

Embodiment 55

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (2.9 mg, 0.005 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0033 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 3000: 1000: 1: 5. The reaction temperature was controlled at 80°C, the reaction was continued for 114 min, and petroleum ether was added to terminate the reaction. Other operations were the same as those in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 83%, TOF = 434 h ^-1 ; polyester chain segments in the polymer were 94%; M _n = 10.7 × 10 ³ g/mol, and molecular weight distribution PDI = 1.19.

Embodiment 56

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and 4-dimethylaminopyridine (0.6 mg, 0.005 mmol) were added to the polymerization bottle. 0.3 mL of the cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0033 M, [CHO]: [PA]: [Cat.]: [DMAP] = 3000: 1000: 1: 5. The reaction temperature was controlled at 80 ° C, the reaction was carried out for 125 min, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 66%, TOF = 317 h ^-1 ; polyester chain segments in the polymer were 96%; M _n = 1.16 × 10 ⁴ g/mol, and molecular weight distribution PDI = 1.12.

Embodiment 57

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.58 mg, 0.001 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00067 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 15000: 5000: 1: 5. The reaction temperature was controlled at 80°C, the reaction was continued for 12 h, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 95%, TOF = 396 h ^-1 ; polyester chain segments in the polymer were 93%; M _n = 3.15×10 ⁴ g/mol, and molecular weight distribution PDI = 1.18.

Embodiment 58

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.29 mg, 0.0005 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00033 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 30000: 10000: 1: 5. The reaction temperature was controlled at 110°C, the reaction was carried out for 12 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 84%, TOF = 700h ^-1 ; polyester chain segments in the polymer were 91%; M _n = 3.46×10 ⁴ g/mol, and molecular weight distribution PDI = 1.29.

Embodiment 59

Under argon protection, phthalic anhydride (146 mg, 1.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.29 mg, 0.0005 mmol) were added to the polymerization bottle. 0.5 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.0002M, [CHO]: [PA]: [Cat.]: [PPNCl] = 50000: 10000: 1: 5. The reaction temperature was controlled at 110°C, the reaction was carried out for 12 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 99%, TOF = 825h ^-1 ; polyester chain segments in the polymer were 87%; M _n = 3.19×10 ⁴ g/mol, and molecular weight distribution PDI = 1.31.

Embodiment 60

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.84 mg, 0.0015 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.001 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 10000: 10000: 1: 5. The reaction temperature was controlled at 110 ° C, the reaction was carried out for 18 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 91%, TOF = 450h ^-1 ; polyester chain segments in the polymer were 97%; M _n = 3.85 × 10 ⁴ g/mol, and molecular weight distribution PDI = 1.28.

Embodiment 61

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.17 mg, 0.0003 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle, and 0.5 mL of toluene was added. [Cat.] ₀ = 0.001 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 10000: 10000: 1: 1. The reaction temperature was controlled at 110 ° C, the reaction was carried out for 73 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 99%, TOF = 127h ^-1 ; polyester chain segments in the polymer were 93%; M _n = 5.0×10 ⁴ g/mol, and molecular weight distribution PDI = 1.38.

Embodiment 62

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.34 mg, 0.00059 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexane oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.001 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 10000: 10000: 1: 2. The reaction temperature was controlled at 110 ° C, the reaction was continued for 29 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 54%, TOF = 186 h ^-1 ; polyester chain segments in the polymer were 95%; M _n = 3.30 × 10 ⁴ g/mol, and molecular weight distribution PDI = 1.43.

Embodiment 63

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.34 mg, 0.00059 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00049 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 20000: 20000: 1: 1. The reaction temperature was controlled at 110 ° C, the reaction was carried out for 96 hours, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 57%, TOF = 119 h ^-1 ; polyester chain segments in the polymer were 90%; M _n = 3.21 × 10 ⁴ g/mol, and molecular weight distribution PDI = 1.49.

Embodiment 64

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.11 mg, 0.0002 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexene oxide solution of catalyst 4 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.00016 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 60000: 60000: 1: 1. The reaction temperature was controlled at 130 ° C, the reaction was carried out for 127 h, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 73%, TOF = 344 h ^-1 ; polyester chain segments in the polymer were 87%; M _n = 3.23 × 10 ⁴ g/mol, and molecular weight distribution PDI = 1.41.

Embodiment 65

Under argon protection, phthalic anhydride (435 mg, 3.0 mmol) and bis(triphenylphosphorane)ammonium chloride (0.84 mg, 0.0015 mmol) were added to the polymerization bottle. 0.3 mL of cyclohexene oxide solution of catalyst 17 was measured and added to the polymerization bottle. [Cat.] ₀ = 0.001 M, [CHO]: [PA]: [Cat.]: [PPNCl] = 10000: 10000: 1: 5. The reaction temperature was controlled at 110°C, the reaction was continued for 15 h, and petroleum ether was added to terminate the reaction. Other operations were the same as in Example 6. Calculation and detection showed that the conversion rate of phthalic anhydride was 91%, TOF = 606 h ^-1 ; polyester chain segments in the polymer were 97%; M _n = 3.15×10 ⁴ g/mol, and molecular weight distribution PDI = 1.32.

As can be seen from the above embodiments, the present invention provides a copolymerization method of an epoxy compound, an acid anhydride and a lactone, comprising the following steps: an epoxy compound and an acid anhydride are copolymerized under the catalytic conditions of an aminophenoloxy zinc halide catalyst; an epoxy compound, an acid anhydride and a lactone are copolymerized in one pot under the catalytic conditions of an aminophenoloxy zinc halide catalyst; the aminophenoloxy zinc halide catalyst is a mononuclear catalyst. Compared with the prior art, the copolymerization method provided by the present invention enables the copolymerization of epoxy compounds and acid anhydrides to have high catalytic activity, and the polyester selectivity is good, a copolymer with a higher molecular weight can be synthesized, and the one-pot copolymerization of three monomers can be achieved. The results of the embodiments of the present application show that the copolymer obtained by the present invention is a single polymer.

The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims (10)

1. A method for copolymerizing an epoxy compound, an acid anhydride and a lactone, comprising the steps of:

Carrying out copolymerization reaction on an epoxy compound and anhydride under the catalysis of an aminophenoxy zinc halide catalyst;

Carrying out copolymerization reaction on an epoxy compound, anhydride and lactone under the catalysis of an aminophenoxy zinc halide catalyst;

The aminophenoxy zinc halide catalyst has a structure shown in formula (I) or (II):

In the formula (I):

R ¹～R² independently represents hydrogen, C ₁～C₂₀ straight-chain, branched-chain or cyclic alkyl, C ₇～C₃₀ mono-or polyaryl substituted alkyl, halogen;

r ³ represents C ₁～C₂₀ straight-chain, branched-chain or cyclic alkyl, C ₇～C₃₀ single-or multi-aryl substituted alkyl and C ₆～C₁₈ aryl;

R ⁴ represents C ₁～C₂₀ straight-chain, branched-chain or cyclic alkyl, C ₇～C₃₀ mono-or poly-aryl substituted alkyl;

x represents halogen;

In the formula (II):

R ⁵～R⁸ independently represents hydrogen, C ₁～C₂₀ straight-chain, branched-chain or cyclic alkyl, C ₇～C₃₀ mono-or polyaryl substituted alkyl, halogen;

r ⁹ represents ethylene or methylene;

X ¹～X² represents an alkoxy group of C ₁～C₁₂ linear, branched or cyclic structure, an alkyl-substituted amine group of C ₁～C₁₂ linear, branched or cyclic structure;

x ³ represents halogen.

2. The copolymerization process according to claim 1, wherein in formula (I), R ¹～R² is hydrogen, alkyl of C ₁～C₈ linear, branched or cyclic structure, mono-or poly-aryl substituted alkyl of C ₇～C₂₀, halogen; r ³ is C ₁～C₈ straight-chain, branched-chain or cyclic alkyl, C ₇～C₂₀ single or multiple aryl substituted alkyl, C ₆～C₁₂ aryl; r ⁴ is C ₁～C₈ straight-chain, branched-chain or cyclic alkyl, C ₇～C₂₀ mono-or poly-aryl substituted alkyl; x represents chlorine, bromine or iodine.

3. The copolymerization process according to claim 2, wherein in (I), R ¹～R² is hydrogen, methyl, t-butyl, cumyl, trityl, chlorine; r ³ is methyl, ethyl, isopropyl, n-butyl, tert-butyl, isopentyl, cyclohexyl, n-hexyl, n-octyl, benzyl, phenethyl; r ⁴ is methyl, ethyl, isopropyl, n-butyl, cyclohexyl, benzyl, phenethyl; x represents chlorine.

4. The copolymerization process according to claim 1, wherein in the formula (II), R ⁵～R⁸ represents hydrogen, alkyl of C ₁～C₈ linear, branched or cyclic structure, mono-or poly-aryl substituted alkyl of C ₇～C₂₀, halogen, respectively; r ⁹ represents ethylene; x ¹～X² represents an alkoxy group of C ₁～C₆ linear, branched or cyclic structure, an alkyl-substituted amine group of C ₁～C₆ linear, branched or cyclic structure; x ³ represents chlorine, bromine or iodine.

5. The copolymerization process according to claim 4, wherein in the formula (II), the R ⁵～R⁸ is independently selected from hydrogen, methyl, tert-butyl, cumyl, trityl, chlorine; the X ¹～X² is independently selected from methoxy, dimethylamino, diethylamino; and X ³ is chlorine.

6. The copolymerization method according to claim 1, wherein:

the ratio of the amount of the aminophenoxy zinc halide catalyst to the amount of the epoxy compound is 1 (500 to 150000);

The ratio of the amount of the amino phenol oxygen zinc halide catalyst to the amount of the acid anhydride is 1 (50-100000);

the ratio of the amount of the aminophenoxy zinc halide catalyst to the amount of the lactone substance is 1 (200-1000).

7. The copolymerization method according to claim 1, wherein the epoxy compound is one or more of propylene oxide, epichlorohydrin and epoxycyclohexane; the anhydride is one or more of phthalic anhydride, maleic anhydride and succinic anhydride; the lactone is one or more of L-lactide, D-lactide, rac-lactide, meso-lactide and epsilon-caprolactone.

8. The copolymerization method according to claim 1, wherein the temperature of the copolymerization reaction is 25 to 250 ℃; the time of the copolymerization reaction is 0.1-200 hours; the copolymerization is carried out under an inert atmosphere.

9. The copolymerization method according to any one of claims 1 to 8, wherein the raw material for the copolymerization reaction further comprises a cocatalyst; the ratio of the amount of the substances of the aminophenoxy zinc halide catalyst to the cocatalyst is 1 (0-20).

10. The copolymerization method according to claim 9, wherein the cocatalyst is one or more of bis (triphenylphosphine) ammonium chloride, 4-dimethylaminopyridine and tetrabutylammonium bromide.