阅读说明：本技术 一种聚酯材料的制备方法 (Preparation method of polyester material ) 是由 游怀 刘顺杰 王献红 于 2021-09-03 设计创作，主要内容包括：本发明提供一种聚酯材料的制备方法,包括以下步骤：在惰性气氛和催化剂存在下,将环状碳酸酯和环状酸酐进行共聚,得到聚酯材料；所述催化剂包括离子盐、金属氧化物、Lewis碱、Lewis碱-亲核试剂体系、Lewis酸、Lewis酸碱对、金属络合物和双金属氰化物中的一种或多种。该方法以高沸点、无毒性的环状碳酸酯以及廉价的酸酐作为原料,在上述种类的催化剂下一步法,高效且可控的制得聚酯,且产率高达99％以上。该方法通过改变催化剂以及聚合条件,投料比等来调节所得聚酯材料的分子量以及分子量分布；不同环状碳酸酯与不同的酸酐进行任意组合共聚,得到各种结构与性能的聚酯材料。(The invention provides a preparation method of a polyester material, which comprises the following steps: copolymerizing cyclic carbonate and cyclic anhydride in the presence of an inert atmosphere and a catalyst to obtain a polyester material; the catalyst comprises one or more of an ionic salt, a metal oxide, a Lewis base-nucleophile system, a Lewis acid-base pair, a metal complex, and a double metal cyanide. The method takes high-boiling-point non-toxic cyclic carbonate and cheap anhydride as raw materials, and efficiently and controllably prepares the polyester by a one-step method under the catalysis of the above-mentioned catalysts, and the yield is up to more than 99%. The method adjusts the molecular weight and the molecular weight distribution of the obtained polyester material by changing a catalyst, polymerization conditions, a feeding ratio and the like; different cyclic carbonates and different acid anhydrides are combined and copolymerized at will to obtain polyester materials with various structures and properties.)

1. A preparation method of a polyester material comprises the following steps:

copolymerizing cyclic carbonate and cyclic anhydride in the presence of an inert atmosphere and a catalyst to obtain a polyester material;

the catalyst comprises one or more of an ionic salt, a metal oxide, a Lewis base-nucleophile system, a Lewis acid-base pair, a metal complex, and a double metal cyanide.

2. The production method according to claim 1, wherein the cyclic carbonate is selected from one or more of five-membered cyclic carbonate, six-membered cyclic carbonate, seven-membered cyclic carbonate, and higher cyclic carbonate;

the five-membered cyclic carbonate has the structure of formula I:

the six-membered cyclic carbonate has a structure of formula II:

the seven-membered cyclic carbonate has the structure of formula iii:

the more cyclic carbonate has the structure of formula iv:

the R is₁、R₂、R₃And R₄Are independently selected from-H, -Me, -Et and-^tBu、-OH、-EtO、-ⁱPrO、-BnO、-^tBuO、-F、-Cl、-Br、-I、-NO₂and-CF₃One or more of;

in the formula IV, n is the number of carbon atoms.

3. The method according to claim 2, wherein the cyclic carbonate is one or more selected from the group consisting of a monocyclic carbonate, a bicyclic carbonate, and a polycyclic carbonate.

4. The production method according to claim 1, wherein the cyclic acid anhydride is selected from one or more of a monocyclic acid anhydride, a bicyclic acid anhydride, and a polycyclic acid anhydride;

the monocyclic anhydride is selected from one or more of succinic anhydride, maleic anhydride, glutaric anhydride and pimelic anhydride;

the bicyclo-phthalic anhydride is selected from one or more of phthalic anhydride, cyclohexene anhydride, cyclohexane anhydride, cyclopentane anhydride and camphor anhydride;

the polycyclic acid anhydride comprises norbornene dianhydride and derivatives thereof.

5. The method of claim 1, wherein the ionic salt catalyst comprises one or more of a catalyst having a structure according to formula v, a quaternary ammonium salt having a structure according to formula vi, and an ionic liquid:

in the formula V, X^-Selected from Cl-, Br^-、CF₃COO-、N₃-or NO₃-；

R in formula VI₁、R₂、R₃And R₄Independently selected from-Et-ⁿBu₄Or-ⁿHept₄(ii) a Said Y is^-Selected from Cl^-、Br^-Or I^-；

The ionic liquid is selected from one or more of imidazoles, pyridines, quaternary amines, quaternary phosphonium, pyrroles and piperidines.

6. The production method according to claim 1, wherein the metal oxide is selected from one or more of cerium oxide, calcium oxide, manganese heptaoxide, manganese pentoxide, and aluminum oxide;

the metal complex is selected from porphyrins shown in a formula VII-1 and homologues thereof, beta-diimines shown in a formula VII-2 and homologues thereof, Salen shown in a formula VII-3 and homologues thereof, and [ NNO ] shown in a formula VII-4 and homologues thereof:

the M is₁Selected from Al, Co or Cr;the M is₂Selected from Zn, Mg or Al;

the M is₃Selected from Co, Cr or Fe;

the M is₄Selected from Zn, Mg or Al;

the R is₁、R₂、R₃、R₄、R₅、R₆And R₇Are independently selected from-H, -Me, -Et and-^tBu、-OH、-EtO、-ⁱPrO、-BnO、-^tBuO、-Cl、-Br、-I、-NO₂、-CF₃(ii) a X is selected from-Et, -EtO and-ⁱPrO、-BnO、-^tBuO, -Cl, -Br, -I or CH₃COO^-。

7. The method of claim 1, wherein said double metal cyanide compound has the general formula:

M^Π ₃[M^Ⅲ(CN)₆]₂·x M^ΠX₂·y L·z H₂O

M^Πis a divalent metal ion; m^ⅢIs a transition metal ion; x is F^-、Cl^-、Br^-、I^-、OH^-、CO₃ ²-or NO₃-; l is oxygen-containing organic ligand, such as small molecular alcohol, oligomer alcohol, aldehyde, ketone, ester, cyclic ether, etc.; x, y and z are respectively M in the catalyst^ΠX₂L and H₂The number of O.

8. The method according to claim 1, wherein the temperature of the copolymerization reaction is 0 to 500 ℃; the time of the copolymerization reaction is 0.1-100 h.

9. The production method according to claim 1, wherein the copolymerization reaction is bulk polymerization or solution polymerization;

the solvent adopted in the solution polymerization is one or more selected from toluene, xylene, DMF, chloroform, dichloromethane, propylene carbonate and ethylene carbonate;

the concentration of the cyclic carbonate in the solution polymerization is 10mol/L or less.

10. The production method according to claim 1, wherein a ratio of the mass of the catalyst to the amount of the total substance of the cyclic carbonate and the cyclic anhydride is 1:1 to 100000.

Technical Field

The invention belongs to the technical field of macromolecules, and particularly relates to a preparation method of a polyester material.

Background

Polyester is an important high molecular compound, and the diversity of the structure of the polyester endows the polyester with various excellent performances, so that the polyester can be widely applied to the fields of chemical fiber industry, bottles, films, packaging industry, electronic and electric appliances, medical sanitation, buildings, automobiles and the like. Therefore, in view of the importance of polyester materials, it is a very significant task to develop a new preparation method or technology to efficiently and controllably prepare polyesters with diversified structures and functions.

At present, the following methods are mainly used for preparing the polyester: step-by-step growth polymerization of diacid or dibasic ester and dihydric alcohol (A-A + B-type) and monomer (A-B type) with carboxyl or ester group and hydroxyl functional group is carried out, the method needs to discharge generated small molecular byproducts such as water, alcohol and the like out of a polymerization system in time, and a polymer with higher molecular weight can be obtained only when the conversion rate of the monomer is higher, meanwhile, the molecular weight distribution of the polymer is generally very wide, and the PDI is more than 2; ② the chain-growth ring-opening polymerization (ROP) of lactones, which produces essentially no small molecule by-products and the molecular weight of the polymer can be high at low monomer conversion. However, when the monomer conversion is high, side reactions such as transesterification and the like occur in the system, which limits further conversion of the lactone. In addition, due to the limited variety of ring-opening polymerizable lactones, the diversity of their functional groups and the lack of post-polymerization functionalization have limited functionality in the polyester materials produced. Due to the diversity of two comonomers, the performance of the obtained polyester material can be conveniently adjusted and the modification after polymerization can be conveniently carried out, but the defects in the art are that one of the raw materials used in the method is the epoxide with a lower boiling point, the requirement on equipment is higher, and meanwhile, certain potential safety hazards exist.

Disclosure of Invention

In view of the above, the present invention aims to provide a method for preparing a polyester material, which can efficiently and controllably prepare polyester in a one-step method.

The invention provides a preparation method of a polyester material, which comprises the following steps: copolymerizing cyclic carbonate and cyclic anhydride in the presence of an inert atmosphere and a catalyst to obtain a polyester material; the catalyst comprises one or more of an ionic salt, a metal oxide, a Lewis base-nucleophile system, a Lewis acid-base pair, a metal complex, and a double metal cyanide. The method is characterized in that under the action of catalysts comprising ionic salts, metal oxides, Lewis bases, Lewis base-nucleophilic reagent systems, Lewis acids, Lewis acid-base pairs, metal complexes, double metal cyanides and the like, cyclic carbonate and cyclic anhydride are subjected to one-step method to efficiently and controllably prepare the polyester.

In the present invention, the cyclic carbonate is selected from one or more of five-membered cyclic carbonate, six-membered cyclic carbonate, seven-membered cyclic carbonate and higher cyclic carbonate;

the five-membered cyclic carbonate has the structure of formula I:

the six-membered cyclic carbonate has a structure of formula II:

the seven-membered cyclic carbonate has the structure of formula iii:

the more cyclic carbonate has the structure of formula iv:

the R is₁、R₂、R₃And R₄Are independently selected from-H, -Me, -Et and-^tBu、-OH、-EtO、-ⁱPrO、-BnO、-^tBuO、-F、-Cl、-Br、-I、-NO₂and-CF₃One or more of;

in the formula IV, n is the number of carbon atoms.

In the present invention, the cyclic carbonate is selected from one or more of monocyclic carbonate, bicyclic carbonate and polycyclic carbonate.

In the present invention, the cyclic anhydride is selected from one or more of monocyclic anhydride, bicyclic anhydride and polycyclic anhydride;

the monocyclic anhydride is selected from one or more of succinic anhydride, maleic anhydride, glutaric anhydride and pimelic anhydride;

the bicyclo-phthalic anhydride is selected from one or more of phthalic anhydride, cyclohexene anhydride, cyclohexane anhydride, cyclopentane anhydride and camphor anhydride;

the polycyclic acid anhydride comprises norbornene dianhydride and derivatives thereof.

In the invention, the ionic salt catalyst comprises one or more of a catalyst with a structure shown in a formula V, a quaternary ammonium salt with a structure shown in a formula VI and an ionic liquid:

in the formula V, X^-Selected from Cl^-、Br^-、CF₃COO^-、N₃ ^-Or NO₃ ^-；

R in formula VI₁、R₂、R₃And R₄Independently selected from-Et-ⁿBu₄Or-ⁿHept₄(ii) a Said Y is^-Selected from Cl^-、Br^-Or I^-；

The ionic liquid is selected from one or more of imidazoles, pyridines, quaternary amines, quaternary phosphonium, pyrroles and piperidines.

In the present invention, the Lewis base catalyst mainly includes inorganic base, organic base, and the like. The inorganic base includes lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide Mg (OH)₂Nickel hydroxide Ni (OH)₂Sodium carbonate (Na)₂CO₃) Potassium carbonate (K)₂CO₃) Sodium bicarbonate (NaHCO)₃) Disodium hydrogen phosphate (Na)₂HPO₄) Etc.; the organic base comprises an alkoxide RO^-M⁺Such as potassium methoxide (CH)₃O^-K⁺) Sodium ethoxide (EtO-Na)⁺) And phenolates such as sodium phenolate and the like, amine salts such as lithium bis (trimethylsilyl) amide ([ (CH)₃)₃Si]₂NLi), bis (bistrimethylsilyl) amine zinc ([ [ (CH)₃)₃Si]₂N]₂Zn), etc., carboxylates such as stannous octoate Sn (Oct)₂Potassium acetate (CH)₃COO-K⁺) Etc., 1-tert-butyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphoranylideneamino]-2 λ 5,4 λ 5-bis (phosphazene compound) (tBu-P4), 1-tert-butyl-2, 2,4,4, 4-pentakis (dimethylamino) -2 λ 5,4 λ 5-bis (phosphazene compound) (tBu-P2), 1, 8-diazabicycloundec-7-ene (DBU), 4-Dimethylaminopyridine (DMAP), 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene (MTBD), N-methylimidazole (N-MeIm), etc.;

in the Lewis base-nucleophilic reagent catalytic system, the Lewis base comprises: 1-tert-butyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) -phosphoranylideneamino ] -2. lambda.5, 4. lambda.5-bis (phosphazene) (tBu-P4), 1-tert-butyl-2, 2,4,4, 4-pentakis (dimethylamino) -2. lambda.5, 4. lambda.5-bis (phosphazene) (tBu-P2), 1, 8-diazabicycloundec-7-ene (DBU), 4-Dimethylaminopyridine (DMAP), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), N-methylimidazole (N-MeIm), etc., nucleophiles include alcohols, thiols, phenols, amines, and the like;

the Lewis acid catalyst comprises dibutyl dimethoxy stannane Bu₂Sn(OMe)₂Tetrabutyl titanate [ Ti (OBu) ]₄]Boron trifluoride BF₃Organoboranes such as triethylboron (BEt)₃、BPh₃Etc.), tris (pentafluorophenyl) aluminum, and acetic acid, trifluoroacetic anhydride, etc.;

in the Lewis acid-base pair catalyst, the Lewis acid comprises various substances contained in the Lewis acid in the technical scheme, and the Lewis base comprises various substances contained in the Lewis base in the technical scheme;

in the present invention, the metal oxide is selected from one or more of cerium oxide, calcium oxide, manganese heptaoxide, manganese pentoxide, and aluminum oxide;

the metal complex is selected from porphyrins shown in a formula VII-1 and homologues thereof, beta-diimines shown in a formula VII-2 and homologues thereof, Salen shown in a formula VII-3 and homologues thereof, and [ NNO ] shown in a formula VII-4 and homologues thereof:

the M is₁Selected from Al, Co or Cr;

the M is₂Selected from Zn, Mg or Al;

the M is₃Selected from Co, Cr or Fe;

the M is₄Selected from Zn, Mg or Al;

the R is₁、R₂、R₃、R₄、R₅、R₆And R₇Are independently selected from-H, -Me, -Et, -tBu, -OH, -EtO and-ⁱPrO、-BnO、-^tBuO、-Cl、-Br、-I、-NO₂、-CF₃(ii) a X is selected from-Et, -EtO and-ⁱPrO, -BnO, -tBuO, -Cl, -Br, -I or CH₃COO^-。

In the present invention, the double metal cyanide compound has the following general formula:

M^Π ₃[M^Ⅲ(CN)₆]₂·x M^ΠX₂·y L·z H₂O

M^Πis a divalent metal ion; m^ⅢIs a transition metal ion; x is F^-、Cl^-、Br^-、I^-、OH^-、CO₃ ^2-Or NO₃ ^-(ii) a L is an oxygen-containing organic ligand; x, y and z are respectively M in the catalyst^ΠX₂L and H₂The number of O. Preferably, the value of x is 0-50; y takes a value of 0-50; and z is 0-50.

In the invention, the temperature of the copolymerization reaction is 0-500 ℃; the time of the copolymerization reaction is 0.1-100 h. The reaction formula of the copolymerization is as follows:

wherein R is₁Ethyl, isopropyl, n-propyl, cyclohexyl, etc.; r₂Ethyl, vinyl, isopropyl, n-propyl, phenyl, and the like. The value of n is preferably 1-10000.

In the invention, the copolymerization reaction adopts bulk polymerization or solution polymerization;

the solvent adopted in the solution polymerization is one or more selected from toluene, xylene, DMF, chloroform, dichloromethane, propylene carbonate and ethylene carbonate; in specific embodiments, the solvent is toluene, xylene, propylene carbonate, or the like.

The concentration of the cyclic carbonate in the solution polymerization is 10mol/L or less.

In the present invention, the ratio of the mass of the catalyst to the total mass of the cyclic carbonate and the cyclic anhydride is 1:1 to 100000.

In a particular embodiment of the invention, the catalyst is preferably selected from the group consisting of PPNCl, PPNTFA,ⁿBu₄NBr、ⁿHept₄NBr、^tBu-P₄MTBD, potassium methoxide CH₃O^-K⁺And sodium ethoxide EtO^-Na⁺One or more of;

the cyclic anhydride is selected from one or more of phthalic anhydride, succinic anhydride, camphoric anhydride CPA and norbornene anhydride;

the cyclic carbonate is selected from one or more of propylene carbonate PC, ethylene carbonate EC and trimethylene carbonate TMC;

in the invention, the temperature of the copolymerization reaction is 180 ℃, 200 ℃ and 140 ℃; the time is 2h, 1h, 10min, 30min or 12 h.

The invention provides a preparation method of a polyester material, which comprises the following steps: copolymerizing cyclic carbonate and cyclic anhydride in the presence of an inert atmosphere and a catalyst to obtain a polyester material; the catalyst comprises one or more of an ionic salt, a metal oxide, a Lewis base-nucleophile system, a Lewis acid-base pair, a metal complex, and a double metal cyanide. The method takes high-boiling-point non-toxic cyclic carbonate and cheap anhydride as raw materials, and efficiently and controllably prepares the polyester by a one-step method under the catalysis of the above-mentioned catalysts, and the yield is up to more than 99%. The method adjusts the molecular weight and the molecular weight distribution of the obtained polyester material by changing the catalyst and polymerization conditions such as reaction temperature, reaction time, feeding ratio and the like, and simultaneously, different cyclic carbonates participating in copolymerization reaction and different acid anhydrides can be randomly combined and copolymerized to obtain the polyester material with various structures and performances, thereby providing a simple, efficient and controllable novel preparation method for the preparation of the polyester material. The conversion rate of the cyclic carbonate and the anhydride is up to more than 99%. The yield of the polyester is up to more than 99%. The molecular weight of the polyester can be 1-500kg mol^-1And optionally adjusting. The molecular weight distribution of the polyester material can be adjusted at will between 1.1 and 5.0.

Drawings

FIG. 1 is a drawing showing the preparation of a polyester poly (PA-alt-PO) prepared in example 1 of the present invention¹H NMR Spectrum (300MHz, CDCl)₃)；

FIG. 2 is a drawing showing the preparation of a polyester poly (PA-alt-PO) prepared in example 1 of the present invention¹³C NMR spectrum;

FIG. 3 is a drawing showing the results of preparing polyester poly (SA-alt-PO) obtained in example 9 of the present invention¹H NMR spectrum;

FIG. 4 is a diagram showing the results of production of poly (CPA-alt-PO) polyester obtained in example 10 of the present invention¹H NMR spectrum;

FIG. 5 shows an embodiment 11 of the present inventionTo obtain poly (NA-alt-PO) polyester¹H NMR spectrum;

FIG. 6 shows the preparation of poly (PA-alt-EO) polyester obtained in example 12 of the present invention¹H NMR spectrum;

FIG. 7 shows the results of the preparation of the polyester poly (PA-alt-TMO) obtained in example 13 of the present invention¹H NMR spectrum;

FIG. 8 shows the results of the preparation of poly (CPA-alt-EO) polyester obtained in example 16 of the present invention¹H NMR spectrum.

Detailed Description

In order to further illustrate the present invention, the following examples are provided to describe the preparation method of a polyester material of the present invention in detail, but they should not be construed as limiting the scope of the present invention.

Example 1

And (2) pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 180 ℃ oil bath kettle, reacting for 2 hours, and opening the kettle to obtain the polyester poly (PA-alt-PO). Of the resulting polyester poly (PA-alt-PO)¹H NMR(300MHz,CDCl₃)、¹³C NMR(300MHz,CDCl₃) The number average molecular weight M is shown in FIG. 1 and FIG. 2 respectively_n＝13.5kg mol^-1The molecular weight distribution PDI was 1.53.

Example 2

A10 mL autoclave was purged three times under argon atmosphere and transferred to a glove box while hot, to which PPNTFA (32.6mg,0.05mmol), phthalic anhydride PA (1.481g,10mol), propylene carbonate PC (1.021g,10mmol), and 2mL of toluene were sequentially added. Sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle into an oil bath kettle at 180 ℃, reacting for 2 hours, and opening the kettle to obtain the polyester poly (PA-alt-PO) with the number average molecular weight M_n＝13.5kg mol^-1The molecular weight distribution PDI was 1.53.

Example 3

The 10mL autoclave was purged three times under argon atmosphere and transferred to a glove box while hot, to which nBu4NBr (16.1mg,0.05mmol), phthalic anhydride PA (1.481g,10mol), propylene carbonate PC were added in order(1.021g,10mmol), 2mL of xylene. The high-pressure reaction kettle is sealed and then transferred into an oil bath kettle at 180 ℃, and after 2 hours of reaction, the kettle is opened to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝10kg mol^-1The molecular weight distribution PDI was 1.43. Example 4

And (2) pumping air of a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding nHept4NBr (21.7mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to an oil bath kettle at 180 ℃, and opening the kettle after reacting for 2 hours to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝9.5kg mol^-1The molecular weight distribution PDI was 1.46.

Example 5

The method comprises the steps of pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding tBu-P4(63 mu L of a 0.8mol/L n-hexane solution, 0.05mmol), benzyl alcohol BnOH (5.2 mu L, 0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle to a 180 ℃ oil bath kettle, and opening the kettle after reacting for 2 hours to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝12.8kg mol^-1The molecular weight distribution PDI was 1.66.

Example 6

The method comprises the steps of pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding MTBD (7.2 muL, 0.05mmol), benzyl alcohol BnOH (5.2 muL, 0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to an oil bath kettle at 180 ℃, and opening the kettle after reacting for 2 hours to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝7.5kg mol^-1The molecular weight distribution PDI was 1.57.

Example 7

Pumping and ventilating a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, and sequentially adding potassium methoxide CH₃O-K⁺(3.5mg,0.05mmol), phthalic anhydride PA (1.481g,10mol), propylene carbonate PC (1.021g,10mmol), sealing the autoclave, transferring to an oil bath pan at 180 DEG CAnd opening the kettle after reacting for 2 hours to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝6.5kg mol^-1The molecular weight distribution PDI was 1.53.

Example 8

And (2) pumping air of a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding sodium ethoxide EtO-Na + (3.4mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to an oil bath kettle at 180 ℃, and opening the kettle after reacting for 2 hours to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝6.8kg mol^-1The molecular weight distribution PDI was 1.73.

Example 9

And (2) pumping and ventilating a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the high-pressure reaction kettle to a glove box while the high-pressure reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), succinic anhydride SA (1.001g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle to a 180 ℃ oil bath kettle, and opening the kettle after reacting for 1h to obtain the polyester poly (SA-alt-PO). Of the resulting polyester poly (SA-alt-PO)¹H NMR(300MHz,CDCl₃) As shown in fig. 3. Number average molecular weight M_n＝7.2kg mol^-1The molecular weight distribution PDI was 1.53.

Example 10

And (2) pumping gas of a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), camphoric anhydride CPA (1.822g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to an oil bath kettle at 180 ℃, and opening the kettle after reacting for 30min to obtain polyester poly (CPA-alt-PO). Of the resulting polyester poly (CPA-alt-PO)¹H NMR(300MHz,CDCl₃) As shown in fig. 4. Number average molecular weight M_n＝17.0kg mol^-1The molecular weight distribution PDI was 1.42.

Example 11

Pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), norbornene anhydride NA (1.642g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 180 ℃ oil bath kettle,after reacting for 1h, opening the kettle to obtain the polyester poly (NA-alt-PO). Of the resulting polyester poly (NA-alt-PO)¹H NMR(300MHz,CDCl₃) As shown in fig. 5. Number average molecular weight M_n＝200.2kg mol^-1The molecular weight distribution PDI was 1.33.

Example 12

And (2) pumping air of a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and ethylene carbonate EC (0.881g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 180 ℃ oil bath kettle, and opening the kettle after reacting for 10min to obtain the polyester poly (PA-alt-EO). Of the resulting polyester poly (PA-alt-EO)¹H NMR(300MHz,CDCl₃) As shown in fig. 6. Number average molecular weight M_n＝25.9kg mol^-1The molecular weight distribution PDI was 1.71.

Example 13

And (2) pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and trimethylene carbonate TMC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 180 ℃ oil bath kettle, and opening the kettle after reacting for 30min to obtain the polyester poly (PA-alt-TMO). Of the resulting polyester poly (PA-alt-TMO)¹H NMR(300MHz,CDCl₃) As shown in fig. 7. Number average molecular weight M_n＝4.8kg mol^-1The molecular weight distribution PDI is 1.54.

Example 14

And (2) pumping a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), phthalic anhydride PA (1.481g,10mol) and propylene carbonate PC (1.021g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 200 ℃ oil bath kettle, reacting for 30min, and opening the kettle to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝9.1kg mol^-1The molecular weight distribution PDI was 1.75.

Example 15

A10 mL autoclave was purged three times under argon atmosphere and transferred to a glove box while hot, to which PPNCl (28.7mg,0.05mmol) and phthalic anhydride PA (1) were added in this order481g,10mol) and propylene carbonate PC (3.573g,35mmol), sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle into an oil bath kettle at 140 ℃, and opening the kettle after 12 hours of reaction to obtain the polyester poly (PA-alt-PO). Number average molecular weight M_n＝4.1kg mol^-1The molecular weight distribution PDI was 1.33.

Example 16

And (2) pumping and ventilating a 10mL high-pressure reaction kettle for three times in an argon atmosphere, transferring the reaction kettle to a glove box while the reaction kettle is hot, sequentially adding PPNCl (28.7mg,0.05mmol), camphoric anhydride CPA (1.822g,10mol) and ethylene carbonate EC (0.881g,10mmol), sealing the high-pressure reaction kettle, transferring the reaction kettle to a 180 ℃ oil bath kettle, and opening the kettle after reacting for 10min to obtain the polyester poly (CPA-alt-EO). Of the resulting polyester poly (CPA-alt-EO)¹H NMR(300MHz,CDCl₃) As shown in fig. 8. Number average molecular weight M_n＝53.0kg mol^-1The molecular weight distribution PDI was 1.84.

From the above examples, the present invention provides a method for preparing a polyester material, comprising the following steps: copolymerizing cyclic carbonate and cyclic anhydride in the presence of an inert atmosphere and a catalyst to obtain a polyester material; the catalyst comprises one or more of an ionic salt, a metal oxide, a Lewis base-nucleophile system, a Lewis acid-base pair, a metal complex, and a double metal cyanide. The method catalyzes the copolymerization of the cyclic carbonate and the cyclic anhydride in one step under the catalysts of the types to prepare the polyester efficiently and controllably. The method adjusts the molecular weight and the molecular weight distribution of the obtained polyester material by changing the catalyst and polymerization conditions such as reaction temperature, reaction time, feeding ratio and the like, and simultaneously, different cyclic carbonates participating in copolymerization reaction and different acid anhydrides can be randomly combined and copolymerized to obtain the polyester material with various structures and performances, thereby providing a simple, efficient and controllable novel preparation method for the preparation of the polyester material.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.