CN112812287B - Method for preparing polycarbonate by ionic liquid catalysis - Google Patents
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Abstract
The invention relates to a method for preparing polycarbonate by ionic liquid catalysis, which comprises the steps of carrying out melt polymerization reaction on carbonic diester and dihydroxy compounds under the action of an amide ionic liquid catalyst to generate polycarbonate; according to the method, the amide ionic liquid catalyst with high catalytic activity, good selectivity and good thermal stability is obtained by taking the amide group-containing compound as an anion and the tetraalkyl phosphorus as a cation, and the polycarbonate with high molecular weight and high glass transition temperature is obtained through catalysis. The method has mild reaction conditions, designable catalyst structure and high reaction rate; no solvent is needed in the reaction process, no virulent phosgene is used, and no environmental pollution is caused; the product obtained by the reaction has no catalyst residue and no toxic substances, and is a green and environment-friendly low-cost polycarbonate preparation process.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and relates to a method for preparing polycarbonate by ionic liquid catalysis.
Background
Polycarbonate (PC) is a high-performance polymer containing a carbonate group in a molecular chain, has good transparency, excellent dimensional stability and outstanding impact resistance due to its structural particularity, is widely used in the fields of optical elements, electronic and electric appliances, automobile parts, building and construction materials, aerospace and the like, and is a thermoplastic engineering plastic which is required to be speeded up most rapidly among five engineering plastics. However, the polycarbonate which is generally used at present is prepared by using bisphenol A which is a petrochemical product and phosgene which is a highly toxic chemical, and the application of the bisphenol A in the fields of food packaging, medical appliances and the like is limited because the bisphenol A which is a production raw material has estrogen effect and chronic toxic effect. In addition, with the increasing problems of shortage of petroleum resources and the increasing deterioration of the environment, the development of polymers derived from short-term renewable biological resources has attracted great interest. Therefore, the development of a green sustainable polycarbonate preparation process is a focus of research in this field.
As one of the most abundant biological raw materials, saccharides can be obtained from bio-based monomers required for preparing high molecular polymers by various methods. 1,4; in addition, the chiral structure of the compound makes the compound hopeful to synthesize high molecules with special selectivity; at the same time, its non-toxic properties make it possible to apply it to food packaging and medical equipment. Therefore, 1,4. The literature reports 1,4, 3,6-diglycidyl hexaol (co) polycarbonate was mostly studied by direct reaction with diphenyl carbonate (Green Chemistry,2019,21,3891-3901, acs sustamable Chemistry and engineering,2018,6,2684-2693, polymer,2017,116, 153-159. Although the method obtains high molecular weight polycarbonate, the diphenyl carbonate used has high purity and high price, and the phenol as a by-product of the reaction needs to be separated under the conditions of high temperature and high vacuum, thus increasing energy consumption. In addition, the catalysts currently reported for the preparation of 1,4, 3, 6-diglycidohexanol (co) polycarbonates are mostly metal catalysts such as sodium methoxide (Polymer, 2019,179, 1-6), metal acetylacetonate (CN 102746504A), metal hydroxide (Industrial & Engineering Chemistry Research,2018,57, 4824-4831), metal carbonate (CN 104031249A), and the like. However, these catalysts have a certain toxicity, which may not only cause environmental pollution, but also remain in the synthesized polycarbonate products, limiting the application of the products in the aspects of infant products, medical devices, food packaging, and the like.
Therefore, the development of an efficient and environmentally friendly, sustainable method for the preparation of polycarbonates is a major research focus in this field.
Disclosure of Invention
The invention aims to provide a method for preparing polycarbonate by ionic liquid catalysis, which is to develop an amide ionic liquid catalyst for efficiently catalyzing the melt polycondensation of carbonic acid diester and dihydroxy compounds to generate polycarbonate; the amide ionic liquid catalyst adopted by the method takes an amide group-containing compound as an anion and tetraalkyl phosphorus as a cation, has the advantages of designable structure, more catalytic sites, high activity, good selectivity and no influence on the quality of polycarbonate, and can catalyze to obtain the polycarbonate with high molecular weight and high glass transition temperature. The method has mild reaction conditions and wide raw material selection range; no solvent is needed in the reaction process, no virulent phosgene is used, and no environmental pollution is caused; the product obtained by the reaction has no catalyst residue and no toxic substances, and is a green and environment-friendly low-cost polycarbonate preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing polycarbonate by ionic liquid catalysis, which comprises the following steps:
(1) And (3) ester exchange stage: under the condition of normal pressure, carrying out ester exchange reaction on a reaction monomer carbonic acid diester and a dihydroxy compound to obtain a prepolymer;
(2) A polycondensation stage: carrying out polycondensation reaction on the prepolymer obtained in the step (1) under a vacuum condition to obtain polycarbonate;
the ionic liquid catalyst is amide ionic liquid and has the following structure:
wherein, the anion X - Is a compound containing an amide group, R in the cation of the ionic liquid 1 ，R 2 ，R 3 And R 4 Is C 1 -C 20 Alkyl of (C) 4 -C 20 Cycloalkyl and C 6 -C 20 Any one of the aryl groups of (1).
When the amide ionic liquid catalyst with the amide-containing compound as the anion and the tetraalkyl phosphorus as the cation is adopted, the catalytic activity and selectivity of the catalyst are improved, the reaction rate is accelerated, and the reaction time is greatly reduced; the structure of the amide ionic liquid catalyst can be designed, and the molecular weight of the polymer can be regulated and controlled by changing the structure of anions and cations or the combination of anions and cations, so that polycarbonate products with different molecular weights are obtained; in addition, the amide ionic liquid catalyst can simultaneously activate hydroxyl of a dihydroxy compound and carbonyl carbon of a carbonic diester, promote hydroxyl oxygen atoms of the dihydroxy compound to attack the carbonyl carbon of the carbonic diester, thereby inhibiting the occurrence of methylation side reaction and promoting forward progress of ester exchange reaction and polycondensation reaction; as shown in fig. 1, when the content of the amide-based ionic liquid increases, all proton peaks of isosorbide move to a high field, which indicates that the amide-based ionic liquid can efficiently activate isosorbide, break hydrogen bonds in isosorbide and improve the activities of internal and external hydroxyl groups of isosorbide; in addition, the amide ionic liquid catalyst has good thermal stability, so that the amide ionic liquid catalyst can keep good catalytic activity in an ester exchange stage and a polycondensation stage of a melt polymerization reaction, can be thermally decomposed in the final stage of the reaction, is not remained in a polycarbonate product, does not influence the color of the product, and ensures that the prepared polycarbonate polymer is safer and has wider application.
The polycarbonate obtained by the method does not contain toxic substances, and byproducts are easy to separate and can be recycled.
Preferably, the anion of the amide-based ionic liquid catalyst comprises any one of N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-azahexacyclone, 1, 8-naphthalimide, 1, 2-cyclopentaditimide, 3-pentamethyleneglutarimide, 3-tetramethyleneglutarimide, 1,2,3, 6-tetrahydrophthalimide, hexahydrophthalimide, diethylamide, succinimide, glutarimide, adipimide, maleimide, succinimide, phthalimide, or bistrifluoroacetamide.
Preferably, the cation of the amide-type ionic liquid catalyst comprises any one of tetradecyl trihexylphosphine, butyl trihexylphosphine, propyl trihexylphosphine, ethyl tributyl phosphonium, tetramethyl phosphonium, tetrapropyl phosphonium or tetrabutyl phosphonium.
Preferably, the amide ionic liquid is any one of the following compounds 1 to 18:
the amide ionic liquid in the method has high catalytic activity, not only can effectively activate the hydroxyl of a dihydroxy compound, increase the nucleophilicity of the hydroxyl and improve the capability of the hydroxyl in attacking the carbonyl of the carbonic diester, but also can activate the carbonyl carbon of the carbonic diester and increase the electrophilicity of the carbonyl carbon, so that the carbonyl carbon is more easily attacked by the hydroxyl, the selectivity of an ester exchange product is improved in an ester exchange reaction stage, and the generation of a methylated byproduct is inhibited. In addition, the amide ionic liquid has good thermal stability, can still maintain excellent catalytic performance under the conditions of high temperature and high vacuum in the polycondensation reaction stage, promotes the reaction of terminal groups, and accelerates the growth of molecular chains. Meanwhile, the amide ionic liquid can obtain products with different molecular weights by changing the structure of amide anions, so that the regulation and control of the polymerization reaction process and the product structure are realized. In addition, through DFT simulation calculation of the interaction between the catalyst and the reaction monomer, and by combining experimental data, the amide ionic liquid catalyst can simultaneously activate the dihydroxy compound and the carbonic acid diester, the condition that the polymerization reaction is inhibited due to higher activity of a specific functional group is avoided, the forward progress of the reaction is promoted, and the catalytic efficiency and selectivity are improved, so that the amide ionic liquid catalyst is superior to other amide ionic liquid catalysts, and the polycarbonate with higher molecular weight and narrow molecular weight distribution is obtained.
Preferably, the molar ratio of dihydroxy compound and carbonic acid diester in step (1) is 1 (0.95-11), such as 1.
Preferably, the transesterification reaction in step (1) is carried out for a period of 1 to 7 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or 7 hours.
Preferably, the transesterification reaction in step (1) is carried out at a temperature of 120 to 175 ℃, for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or 175 ℃, etc.
Preferably, the dosage of the amide ionic liquid catalyst is 1 x 10 -6 -1×10 -2 mol, e.g. 1X 10 - 6 mol、5×10 -6 mol、8×10 -6 mol、2×10 -5 mol、6×10 -5 mol、9×10 -5 mol、1×10 -4 mol、5×10 -4 mol、1×10 -3 mol、3×10 -3 mol、5×10 -3 mol、8×10 -3 mol or 1X 10 -2 mol, and the like.
Preferably, the degree of vacuum of the polycondensation reaction in step (2) is 50 to 1000Pa, such as 50Pa, 200Pa, 350Pa, 500Pa, 600Pa, 700Pa, 800Pa, 900Pa, 1000Pa, or the like.
Preferably, the temperature of the polycondensation reaction in step (2) is 220-290 ℃, such as 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃ or 290 ℃ and the like.
Preferably, the time of the polycondensation reaction in step (2) is 0.5 to 6.0h, such as 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, or 6.0h, and the like.
Preferably, the carbonic acid diester in the step (1) includes any one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate or dinaphthyl carbonate or a combination of at least two thereof, and the combination illustratively includes a combination of dimethyl carbonate and diethyl carbonate, a combination of dipropyl carbonate and dibutyl carbonate, a combination of diphenyl carbonate and ditolyl carbonate or a combination of dinaphthyl carbonate and dimethyl carbonate, and the like.
Preferably, the dihydroxy compound of step (1) comprises any one of 1, 4.
Preferably, the dihydroxy compound is a mixture of 1, 4.
Preferably, the molar ratio of 1, 4.
Preferably, the molar ratio of 1, 4.
The molecular weight of the product polycarbonate can be obviously improved by adopting the dihydroxy compound combination in the catalytic reaction process.
Preferably, the 1, 4.
The aliphatic dihydroxy compound is selected from at least one of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2-methyl-1, 4-cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, hydrogenated dioleyl glycol, hydrogenated dilinoleyl glycol, 2-ethyl-1, 6-hexanediol, 2, 4-trimethyl-1, 6-hexanediol, 1, 5-decalindian dimethanol, 2, 3-decalindian dimethanol, 2, 6-decalindian dimethanol, 2, 3-norbornandimethanol, 2, 5-norbornane dimethanol, 1, 3-adamantane or 4, 8-bis (hydroxymethyl) or a combination of any two or more thereof;
<xnotran> ,1,4- ,1,4- ,9,9- [4- (2- ) ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3,5- ] ,9,9- [4- (2- ) -3- -6- ] ,9,9- [4- (3- -2,2 ) ] ,9,9- (3- -4- (2- ) ) ,9,9- (5- -1- ) ,9,9- (5- (2- ) -1- ) , </xnotran> 9,9-bis (6- (2-hydroxypropoxy) naphthyl) fluorene, 9,9-bis (6- (2- (2-hydroxyethoxy) ethoxy) naphthyl) fluorene, 9,9-bis (5- (2- (2-hydroxyethoxy) ethoxy) -1-naphthyl) fluorene, 4,4'- (1-phenylethyl) bisphenol, 2,2-bis (4-hydroxyphenyl) butane, 4,4' -ethylenebiphenol, 4 '-dihydroxydiphenylmethane, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, 4' -dihydroxytetraphenylmethane, 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2 '-bis (2-hydroxypropoxy) -1,1' -binaphthyl, and a mixture thereof 2,2 '-bis (2- (2-hydroxyethoxy) ethoxy) -1,1' -binaphthyl, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) propane, or 3- (4-hydroxyphenyl) -1-propanol, or a combination of at least two thereof.
Preferably, the method for preparing polycarbonate by catalysis has a general reaction formula:
wherein R is 1 A phenyl ring or an alkyl group having 1 to 15 carbon atoms, for example, 2,5, 6, 8, 10, 11, 13 or 15; r is 1 Exemplary include, but are not limited to, any of methyl, ethyl, propyl, butyl, or pentyl.
R 2 Is any one or a combination of at least two of a substituted or unsubstituted straight-chain or branched-chain alkyl group having 2 to 20 carbon atoms, for example, 2,4, 5, 8, 10, 11, 13, 16, 18 or 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, for example, 3,5, 7, 10, 12, 14, 15, 17 or 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, for example, 3,5, 7, 10, 12, 14, 15, 17 or 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, for example, 6, 10, 13, 15, 16, 18, 20 or 24 carbon atoms; m and m 'are each independently an integer of not less than 0, for example, 0, 1,5, 10, 20, 30, 40, 50, 65, 75, 90, 110, 130, 150, or the like, and m' are not both 0.
When m is 0, m' is represented by n, and the reaction formula of the method for preparing the polycarbonate by catalysis is as follows:
wherein R is 1 A phenyl ring or an alkyl group having 1 to 15 carbon atoms, for example, 2,5, 6, 8, 10, 11, 13 or 15; r is 1 Exemplary include, but are not limited to, any of methyl, ethyl, propyl, butyl, or pentyl.
R 2 The alkyl group is any one or a combination of at least two of a substituted or unsubstituted straight-chain or branched-chain alkyl group having 2 to 20, for example, 2,4, 5, 8, 10, 11, 13, 16, 18 or 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20, for example, 3,5, 7, 10, 12, 14, 15, 17 or 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 20, for example, 3,5, 7, 10, 12, 14, 15, 17 or 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24, for example, 6, 10, 13, 15, 16, 18, 20 or 24 carbon atoms, and n is an integer greater than 0, for example, 10, 30, 50, 70, 90, 150, 170 or 200 carbon atoms.
The hetero atom in the above-mentioned heterocycloalkyl group is any one of O, S, P or N or a combination of at least two thereof, and the combination illustratively includes a combination of O and S or a combination of P and N, and the like.
As a preferable technical scheme of the invention, the method comprises the following steps:
(1) And (3) ester exchange stage: under the condition of normal pressure, carrying out ester exchange reaction on carbonic acid diester and dihydroxy compound to obtain a prepolymer, wherein a catalyst adopted in the ester exchange reaction is amide ionic liquid; the time of the ester exchange reaction is 1-7h, and the temperature of the ester exchange reaction is 120-175 ℃; the anion of the amide ionic liquid catalyst comprises any one of N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-azahexacyclic ketone, 1, 8-naphthalimide, 1, 2-cyclopentanedicarboximide, 3-pentamethylene glutarimide, 3-tetramethylene glutarimide, 1,2,3, 6-tetrahydrophthalimide, hexahydrophthalimide, diethylamide, succinimide, glutarimide, adipimide, maleimide, succinimide, phthalimide or bistrifluoroacetamide; the cation of the amide ionic liquid catalyst comprises any one of tetradecyl trihexylphosphine, butyl trihexylphosphine, propyl trihexylphosphine, ethyl tributyl phosphonium, tetramethyl phosphonium, tetrapropyl phosphonium or tetrabutyl phosphonium;
(2) A polycondensation stage: carrying out polycondensation reaction on the prepolymer obtained in the step (1) under a vacuum condition to obtain polycarbonate; the vacuum degree of the polycondensation reaction is 50-1000Pa, the temperature of the polycondensation reaction is 220-290 ℃, and the time of the polycondensation reaction is 0.5-6.0h.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, the amide ionic liquid is used as a catalyst, and the high catalytic activity and selectivity of the amide ionic liquid are utilized, so that the intermolecular hydrogen bond of the dihydroxy compound is broken, the hydroxyl activity of the dihydroxy compound is improved, the carbonyl group of the carbonic diester is activated, and the carbonyl group of the carbonic diester is easily attacked by the hydroxyl of the dihydroxy compound, so that the generation of a methylation byproduct is inhibited, the selectivity of an ester exchange product is improved, and the forward progress of the reaction of the dihydroxy compound and the carbonic diester is promoted;
(2) The structure of the amide ionic liquid catalyst adopted by the method can be designed, the catalytic activity and selectivity of the amide ionic liquid catalyst can be adjusted by changing the structure of anions and cations and the combination of anions and cations, polycarbonate products with different molecular weights are obtained, and the directional regulation and control of a polymerization reaction process and products are realized; in addition, by optimizing the anion and cation structure and combination of the amide ionic liquid catalyst, the problem of poor universality of the traditional catalyst on the activation of different types of alcohol hydroxyl groups is solved, the preparation of the copolymerized polycarbonate by a one-pot method is successfully realized, the reaction steps are simplified, the reaction flow is reduced, and the synthesis efficiency is improved;
(3) The amide ionic liquid catalyst adopted by the method is green and environment-friendly, has a small using amount, enables the obtained polymer to be safer and more widely applied, has excellent thermal stability, can keep good catalytic activity in both an ester exchange stage and a polycondensation stage, and accelerates the reaction rate;
(4) The method adopts a melt polymerization process, has mild reaction conditions, does not generate organic wastewater and solid wastes in the reaction process, prepares the polycarbonate with large molecular weight, narrow molecular weight distribution and high glass transition temperature, does not contain toxic substances, and has wider application.
Drawings
FIG. 1 shows that the amide ionic liquid activates isosorbide 1 H NMR spectrum.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
An example of the synthesis of the amide ionic liquid used in the present invention is as follows:
(1) Synthesis of
(Tetrabutylphosphonophthalimide)
Tetrabutyl phosphonium hydroxide aqueous solution (0.01mol, 6.9 g) and phthalimide (0.01mol, 1.47g) were added to a 50mL single-necked round-bottomed flask equipped with magnetons, the flask was placed in a water bath, the reaction mixture was stirred at room temperature for 24 hours, and after the reaction was completed, the mixture was rotary evaporated under reduced pressure at 70 ℃ for 4 hours, and then dried under vacuum at 60 ℃ for 12 hours to obtain 3.85g of a product at a yield of 95%.
(2) Synthesis of
(Tetrabutylphosphorylglutarimide)
Tetrabutyl phosphonium hydroxide aqueous solution (0.01mol, 6.9 g) and glutarimide (0.01mol, 1.13g) were added to a 50mL single-neck round-bottom flask charged with magnetons, the flask was placed in a water bath, the reaction mixture was stirred at room temperature for 24h, after the reaction was completed, rotary evaporated at 70 ℃ under reduced pressure for 4h, and further dried under vacuum at 60 ℃ for 12h to obtain 3.34g of a product at 90% yield.
(3) Synthesis of
(Tetrabutylphosphonium hexahydrophthalimide)
Tetrabutyl phosphonium hydroxide aqueous solution (0.01mol, 6.9 g) and hexahydrophthalimide (0.01mol, 1.53g) were added to a 50mL single-necked round-bottomed flask equipped with magnetons, the flask was placed in a water bath, the reaction mixture was stirred at room temperature for 24 hours, and after the reaction was completed, it was rotary-evaporated at 70 ℃ under reduced pressure for 4 hours and then dried under vacuum at 60 ℃ for 12 hours to obtain 3.95g of a product in 96% yield.
Example 1
In the embodiment, isosorbide and dimethyl carbonate are used as raw materials, and a polycarbonate is prepared under the catalysis of an amide ionic liquid, wherein the reaction formula is as follows:
the preparation method comprises the following steps:
(1) And (3) ester exchange stage: under the nitrogen atmosphere and normal pressure, adding 7.3g (0.05 mol) of isosorbide, 22.5g (0.25 mol) of dimethyl carbonate and tetrabutyl phosphorus phthalimide (0.0005mol, 0.2025g) into a reaction bottle, reacting the reaction mixture at 160 ℃ for 2h, slowly raising the temperature to 180 ℃, and reacting for 0.5h to volatilize unreacted dimethyl carbonate and low-boiling-point product methanol to obtain a prepolymer;
(2) A polycondensation stage: raising the temperature in the step (1) from 180 ℃ to 250 ℃, slowly reducing the vacuum degree to 50Pa, and carrying out reaction for 1.5h to obtain a product isosorbide type polycarbonate;
and (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 25000g/mol, weight average molecular weight M w It was 41000g/mol.
And (3) testing thermal performance: the DSC results of the product show the glass transition temperature T of the polycarbonate g The temperature was 165 ℃.
Nuclear magnetic testing: the methylation selectivity is 0.4 percent, and the methyl esterification selectivity is 99.6 percent.
Example 2
This example is different from example 1 in that tetrabutylphosphonium glutarimide (0.0005 mol,0.1855 g) was used as a catalyst, and the other conditions were exactly the same as those in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n At 22000g/mol, a weight-average molecular weight M w 37000g/mol.
And (3) testing thermal performance: the DSC results of the product show the glass transition temperature T of the polycarbonate g The temperature was 163 ℃.
Nuclear magnetic testing: the methylation selectivity is 0.7 percent, and the methyl esterification selectivity is 99.3 percent.
Example 3
This example is different from example 1 in that tetrabutylphosphonium hexahydrophthalimide (0.0005 mol,0.2055 g) was used as a catalyst, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 20000g/mol, weight average molecular weight M w 33000g/mol.
Thermal performanceAnd (3) testing: the DSC results of the product show the glass transition temperature T of the polycarbonate g The temperature was 160 ℃.
Nuclear magnetic testing: the methylation selectivity is 1.3 percent, and the methyl esterification selectivity is 98.7 percent.
Example 4
This example is different from example 1 in that tetrabutylphosphonium 1, 8-naphthalimide (0.0005mol, 0.2275g) was used as a catalyst, and the other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 17000g/mol, weight-average molecular weight M w Is 29000g/mol.
And (3) testing thermal performance: the DSC results of the product show the glass transition temperature T of the polycarbonate g It was 159 ℃.
Nuclear magnetic testing: the methylation selectivity is 1.8 percent, and the methyl esterification selectivity is 98.2 percent.
Example 5
This example differs from example 1 in that tetrabutylphosphonium succinimide (0.0005mol, 0.1785g) was used as the catalyst, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Has a weight average molecular weight M of 15000g/mol w 25000g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonate g The temperature was 155 ℃.
Nuclear magnetic testing: the methylation selectivity is 2.0 percent, and the methyl esterification selectivity is 98.0 percent.
Example 6
This example differs from example 1 in that tetrabutylphosphonium 1, 2-cyclopentadiylimide (0.0005 mol,0.1985 g) is used as the catalyst, and the other conditions are exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 13000g/mol, weight-average molecular weight M w Is 20000g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonate g The temperature was 150 ℃.
Nuclear magnetic testing: the methylation selectivity is 3.7 percent, and the methyl esterification selectivity is 96.3 percent.
Example 7
This example is different from example 1 in that propyltrihexylphosphatimide (0.0005 mol, 0.2375g) was used as a catalyst, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 11000g/mol, the weight average molecular weight M w It was 18000g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonate g The temperature was 148 ℃.
Nuclear magnetic testing: the methylation selectivity is 4.7 percent, and the methyl esterification selectivity is 95.3 percent.
Example 8
This example differs from example 1 in that tetradecyltrihexylphosphine 3, 3-tetramethyleneglutarimide (0.0005 mol, 0.3245g) was used as the catalyst, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 10000g/mol, weight average molecular weight M w 16000g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonate g The temperature was 146 ℃.
Nuclear magnetic testing: the methylation selectivity is 5.1 percent, and the methyl esterification selectivity is 94.9 percent.
Example 9
This example is different from example 1 in that the mass of dimethyl carbonate was changed from 22.5g to 4.275g (0.0475 mol), and the other conditions were completely the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n A weight average molecular weight of 5000g/molM w 5400g/mol.
Example 10
This example is different from example 1 in that the mass of dimethyl carbonate was changed from 22.5g to 40.5g (0.45 mol), and the other conditions were completely the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 31000g/mol, weight average molecular weight M w It was 50000g/mol.
Example 11
This example is different from example 1 in that the mass of dimethyl carbonate was changed from 22.5g to 49.5g (0.55 mol), and the other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 24000g/mol, weight average molecular weight M w 40000g/mol.
As can be seen from comparative examples 1 and 9 to 11, when the molar ratio of the dihydroxy compound to the carbonic acid diester is 1 (5-9), the polycarbonate obtained by the catalytic preparation has a large number average molecular weight and a large weight average molecular weight.
Example 12
This example differs from example 1 in that the transesterification reaction time was changed from 2h to 1h, and the other conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 20000g/mol, weight average molecular weight M w 33000g/mol.
Example 13
This example differs from example 1 in that the transesterification reaction time was changed from 2h to 3h, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 33000g/mol, weight-average molecular weight M w Is 55000g/mol.
Example 14
This example differs from example 1 in that the transesterification reaction time was changed from 2h to 5h, and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 30000g/mol, weight-average molecular weight M w It was 49000g/mol.
Example 15
This example differs from example 1 in that the transesterification reaction time was changed from 2h to 7h, and the other conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 21000g/mol, weight average molecular weight M w It was 34000g/mol.
As can be seen by comparing examples 1 and 12 to 15, the number average molecular weight and the weight average molecular weight of the polycarbonate obtained by the catalytic preparation are large when the transesterification reaction time is 3 to 5 hours.
Example 16
This example differs from example 1 in that the initial reaction temperature of the transesterification reaction was changed from 160 ℃ to 120 ℃ and the other conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 19000g/mol, weight average molecular weight M w Is 32000g/mol.
Example 17
This example differs from example 1 in that the initial reaction temperature of the transesterification reaction was changed from 160 ℃ to 175 ℃ and otherwise the conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 21000g/mol, a weight-average molecular weight M w It was 34000g/mol.
Example 18
This example differs from example 1 in that the amount of catalyst used was varied from 5X 10 -4 mol is replaced by 1X 10 -6 mol, other conditions are exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average of the polycarbonateMolecular weight M n 18000g/mol, weight-average molecular weight M w It was 30000g/mol.
Example 19
This example differs from example 1 in that the amount of catalyst used was varied from 5X 10 -4 mol replacement to 1X 10 -2 mol, otherwise exactly the same conditions as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n At 22000g/mol, a weight-average molecular weight M w 37000g/mol.
Example 20
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the degree of vacuum of the polycondensation reaction in step (2) was changed to 1000Pa, and other conditions were completely the same as those in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 4700g/mol, weight average molecular weight M w Was 5600g/mol.
Example 21
The present example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the degree of vacuum of the polycondensation reaction in step (2) was changed to 100Pa, and other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 21000g/mol, a weight-average molecular weight M w It was 34000g/mol.
Example 22
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the temperature of the polycondensation reaction in step (2) was changed to 220 ℃ and other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 28000g/mol, weight-average molecular weight M w It was 46000g/mol.
Example 23
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the temperature of the polycondensation reaction in step (2) was changed to 240 ℃ and the other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 34000g/mol, weight-average molecular weight M w It was 57000g/mol.
Example 24
This example differs from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the temperature of the polycondensation reaction in step (2) was changed to 270 ℃ and the other conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 30000g/mol, a weight-average molecular weight M w It was 49000g/mol.
Example 25
This example differs from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the temperature of the polycondensation reaction in step (2) was replaced with 290 ℃ and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 27000g/mol, weight-average molecular weight M w It was 46000g/mol.
As can be seen from comparison of examples 1 and 22 to 25, when the temperature of the reaction in the polycondensation stage is controlled to 240 to 270 ℃, the number average molecular weight and the weight average molecular weight of the polycarbonate produced by the catalysis are large.
Example 26
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the time for the polycondensation reaction in step (2) was changed to 0.5h, and other conditions were completely the same as those in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 16000g/mol, weight-average molecular weight M w And the concentration was 26000g/mol.
Example 27
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 40.5g (0.45 mol), the time for the polycondensation reaction in step (2) was changed to 6.0 hours, and other conditions were completely the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 28000g/mol, weight average molecular weight M w It was 46000g/mol.
Example 28
This example is different from example 1 in that dimethyl carbonate was replaced with an equimolar amount of diphenyl carbonate, and the other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n At 45000g/mol, weight average molecular weight M w It was 75000g/mol.
Example 29
This example differs from example 1 in that dimethyl carbonate was replaced by equimolar diphenyl carbonate and tetrabutylphosphonium glutarimide (0.0005 mol,0.1855 g) was used as the catalyst, but otherwise the conditions were exactly the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 44000g/mol, a weight-average molecular weight M w It was 71000g/mol.
Example 30
This example is different from example 1 in that dimethyl carbonate was replaced with equimolar diphenyl carbonate, tetrabutylphosphonium hexahydrophthalimide (0.0005 mol,0.2055 g) was used as a catalyst, and the other conditions were completely the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 40000g/mol, a weight-average molecular weight M w It was 66000g/mol.
Example 31
This example is different from example 1 in that isosorbide is replaced with isomolar isomannide, and other conditions are exactly the same as in example 1.
Molecular weightAnd (3) testing: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 17000g/mol, weight average molecular weight M w Was 28000g/mol.
Example 32
This example is different from example 1 in that isosorbide was replaced with equimolar bisphenol A, dimethyl carbonate was replaced with equimolar diphenyl carbonate, the catalyst used was tetrabutylphosphonium 1, 8-naphthalimide (0.0005 mol, 0.2275g), and the other conditions were completely the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 41000g/mol, weight average molecular weight M w It was 67000g/mol.
Example 33
The present example is different from example 1 in that isosorbide was replaced with equimolar bisphenol a, dimethyl carbonate was replaced with equimolar diphenyl carbonate, the catalyst used was tetrabutylphosphonium succinimide (0.0005mol, 0.1785g), and the other conditions were completely the same as in example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n Is 42000g/mol, weight-average molecular weight M w 69000g/mol.
Example 34
This example differs from example 1 in that isosorbide was replaced by equimolar bisphenol A, dimethyl carbonate was replaced by equimolar diphenyl carbonate, the catalyst used was tetrabutylphosphonium 1, 2-cyclopentyldiimide (0.0005 mol,0.1985 g), and the other conditions were exactly the same as in example 1.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n 38000g/mol, weight average molecular weight M w 63000g/mol.
Example 35
In the embodiment, isosorbide, dimethyl carbonate and 1, 4-benzenedimethanol are used as raw materials to prepare polycarbonate under the catalysis of tetrabutyl phosphorus phthalimide, and the reaction formula is as follows:
the preparation method comprises the following steps:
(1) And (3) ester exchange stage: under nitrogen atmosphere and normal pressure, 5.84g (0.04 mol) of isosorbide, 40.5g (0.45 mol) of dimethyl carbonate, 1.38g (0.01 mol) of 1, 4-benzenedimethanol and 0.2025g (0.0005 mol) of tetrabutyl phosphorothioimide are added into a reaction bottle, the reaction mixture is reacted for 2 hours at 160 ℃, then the temperature is slowly raised to 180 ℃, and the reaction is carried out for 0.5 hour, so that the unreacted dimethyl carbonate and the low boiling point product methanol are volatilized, and a prepolymer is obtained;
(2) A polycondensation stage: raising the temperature in the step (1) from 180 ℃ to 250 ℃, slowly reducing the vacuum degree to 50Pa, and carrying out reaction for 1.5h to obtain a product isosorbide type copolycarbonate;
and (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the isosorbide-type copolycarbonate n 37000g/mol of the molecular weight M w 61000g/mol.
Example 36
This example is different from example 35 in that 1.06g (0.01 mol) of diethylene glycol was added before the reaction in step (1) was started, and the other conditions were exactly the same as in example 35.
And (3) testing the molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight M n 36000g/mol, weight average molecular weight M w It was 59000g/mol.
Example 37
This example differs from example 35 in that 1.44g (0.01 mol) of 1, 4-cyclohexanedimethanol was added before the start of the reaction in step (1), and the other conditions were exactly the same as in example 35.
And (3) testing the molecular weight: GPC measurement of the product showed that the number average molecular weight M of the isosorbide-type copolycarbonate n 34000g/mol, weight-average molecular weight M w It was 57000g/mol.
Example 38
This example differs from example 35 in that 1.18g (0.01 mol) of 1, 6-hexanediol was added before the reaction in step (1) and the other conditions were exactly the same as in example 35.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight M n 33000g/mol, weight-average molecular weight M w It was 54000g/mol.
Example 39
This example is different from example 35 in that dimethyl carbonate was replaced with equimolar diphenyl carbonate, and the other conditions were exactly the same as example 35.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the isosorbide-type copolycarbonate n 49000g/mol, weight-average molecular weight M w 81000g/mol.
Example 40
This example is different from example 35 in that isosorbide is replaced with bisphenol A in an equimolar amount, and the other conditions are exactly the same as example 35.
And (3) testing molecular weight: GPC measurement of the product showed that bisphenol A type copolycarbonate had number average molecular weight M n Is 47000g/mol, weight average molecular weight M w 78000g/mol.
Comparative example 1
In the comparative example, isosorbide and dimethyl carbonate are used as raw materials, and a polycarbonate is prepared under the catalytic action of a sodium acetylacetonate catalyst;
the preparation method comprises the following steps:
(1) And (3) ester exchange stage: under the atmosphere of nitrogen and normal pressure, adding 36.5g (0.25 mol) of isosorbide, 168.75g (1.875 mol) of dimethyl carbonate and 36.5mg of sodium acetylacetonate catalyst into a reaction bottle, reacting for 6 hours at 98 ℃, slowly raising the temperature to 180 ℃, and reacting for 1 hour to volatilize unreacted dimethyl carbonate and low-boiling-point product methanol to obtain a prepolymer;
(2) A polycondensation stage: raising the temperature in the step (1) from 180 ℃ to 240 ℃ and carrying out reaction for 5 hours at the temperature to obtain a product, namely isosorbide type polycarbonate;
molecular weightAnd (3) testing: GPC measurement of the product showed that the number average molecular weight M of the polycarbonate n At 15300g/mol, a weight-average molecular weight M w It was 25400g/mol.
Method for activating isosorbide by using amide ionic liquid 1 The H NMR spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that as the molar ratio of the amide-based ionic liquid is increased from 0. The proton peak of the isosorbide shifts to the right, which shows that the amide ionic liquid can effectively activate the isosorbide.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing polycarbonate by ionic liquid catalysis, which is characterized by comprising the following steps:
(1) And (3) ester exchange stage: under the condition of normal pressure, catalyzing carbonic diester and dihydroxy compound to perform ester exchange reaction by using an ionic liquid catalyst to obtain a prepolymer;
(2) A polycondensation stage: carrying out polycondensation reaction on the prepolymer obtained in the step (1) under a vacuum condition to obtain polycarbonate;
the ionic liquid catalyst is amide ionic liquid and has the following structure:
wherein, the anion X - Is 1, 8-naphthalimide, 1, 2-cyclopentanedicarboximide, 3-pentamethyleneglutarimide, 3-tetramethyleneglutarimide, 1,2,3, 6-tetrahydrophthalimide, hexahydrophthalimide, succinimide, glutarimide, adipimide, succinimide, a,Any one of maleimide, succinimide or phthalimide, R in ionic liquid cation 1 ，R 2 ，R 3 And R 4 Is C 1 -C 20 Any one of the alkyl groups of (1).
2. The method of claim 1, wherein the cation of the amide-based ionic liquid comprises any one of tetradecyltrihexylphosphine, butyltrihexylphosphine, propyltrihexylphosphine, ethyltributylphosphine, tetramethylphosphine, tetrapropylphosphine, or tetrabutylphosphonium.
3. The process according to claim 1 or 2, wherein the molar ratio of the dihydroxy compound to the carbonic acid diester in step (1) is 1 (0.95-11), the transesterification reaction time is 1-7 hours, the transesterification reaction temperature is 120-175 ℃, and the amount of the amide-based ionic liquid catalyst is 1X 10 -6 -1×10 -2 mol。
4. The method of claim 3, wherein the degree of vacuum of the polycondensation reaction in step (2) is 50 to 1000Pa, the temperature of the polycondensation reaction is 220 to 290 ℃, and the time of the polycondensation reaction is 0.5 to 6.0 hours.
5. The method of claim 3, wherein the carbonic acid diester of step (1) comprises any one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate, or dinaphthyl carbonate, or a combination of at least two thereof.
6. The method of claim 3, wherein the dihydroxy compound of step (1) comprises any one of 1, 4.
7. The method of claim 6, wherein the aliphatic dihydroxy compound is selected from the group consisting of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2-methyl-1, 4-cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, hydrogenated dioleyl glycol, hydrogenated dilinoleyl glycol, 2-ethyl-1, 6-hexanediol, 2, 4-trimethyl-1, 6-hexanediol, 1, 5-decalindimethanol, 2, 3-decalindimethanol, 2, 6-decalindimethanol, 2, 3-norbornanedimethanol, 2, 5-norbornanedimethanol, 1, 3-adamantanedimethanol, or a bis (4-hydroxymethyl) bis (methyl) diol, or a combination of any one or two or more thereof.
8. <xnotran> 6 , , ,1,4- ,1,4- ,9,9- [4- (2- ) ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3- ] ,9,9- [4- (2- ) -3,5- ] ,9,9- [4- (2- ) -3- -6- ] ,9,9- [4- (3- -2,2 ) ] ,9,9- (3- -4- (2- ) ) ,9,9- (5- -1- ) ,9,9- (5- (2- ) -1- ) , </xnotran> 9,9-bis (6- (2-hydroxypropoxy) naphthyl) fluorene, 9,9-bis (6- (2- (2-hydroxyethoxy) ethoxy) naphthyl) fluorene, 9,9-bis (5- (2- (2-hydroxyethoxy) ethoxy) -1-naphthyl) fluorene, 4,4'- (1-phenylethyl) bisphenol, 2,2-bis (4-hydroxyphenyl) butane, 4,4' -ethylenebiphenol, 4,4 '-dihydroxydiphenylmethane, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, 4,4' -dihydroxytetraphenylmethane, 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2 '-bis (2-hydroxypropoxy) -1,1' -binaphthyl, and mixtures thereof 2,2 '-bis (2- (2-hydroxyethoxy) ethoxy) -1,1' -binaphthyl, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) propane, or 3- (4-hydroxyphenyl) -1-propanol, or a combination of at least two thereof.
9. The process of claim 1, wherein the process has the general reaction formula:
wherein R is 1 Is a benzene ring or an alkyl group having 1 to 15 carbon atoms, R 2 Is any one or the combination of at least two of substituted or unsubstituted straight-chain or branched-chain alkyl with 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl with 3 to 20 carbon atoms and substituted or unsubstituted aryl with 6 to 24 carbon atoms; m and m 'are each independently an integer of not less than 0, and m' are not both 0.
10. The method of claim 1, wherein the method comprises the steps of:
(1) And (3) ester exchange stage: under the condition of normal pressure, under the action of an amide ionic liquid catalyst, carrying out ester exchange reaction on carbonic diester and a dihydroxy compound to obtain a prepolymer; the time of the ester exchange reaction is 1-7h, and the temperature of the ester exchange reaction is 120-175 ℃;
(2) A polycondensation stage: carrying out polycondensation reaction on the prepolymer obtained in the step (1) under a vacuum condition to obtain polycarbonate; the vacuum degree of the polycondensation reaction is 50-1000Pa, the temperature of the polycondensation reaction is 220-290 ℃, and the time of the polycondensation reaction is 0.5-6.0h.
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