CN111205448A - Method for preparing polycarbonate by catalysis - Google Patents
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Abstract
The invention relates to a method for preparing polycarbonate by catalysis, which takes carbonic acid diester and dihydroxy compound as raw materials, and carries out ester exchange reaction under the catalysis of nitrogen-containing organic compound or compound of nitrogen-containing organic compound and cellulose, and the polycarbonate is generated by polycondensation; the method of the invention adopts the catalyst, which has the advantages of high catalytic activity, good selectivity and no influence on the quality of the polycarbonate, and the polycarbonate prepared by the method has large molecular weight and high glass transition temperature. The method has the advantages of wide raw material selection range, small catalyst dosage, mild reaction conditions, no environmental pollution in the reaction process, and no toxic substances in the product, and is an efficient, 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 through catalysis.
Background
Polycarbonate (PC) is a high-performance engineering plastic, has good transparency, excellent thermal stability and outstanding mechanical properties, and is widely used in the fields of optics, automobiles, buildings, electronics, aerospace and the like. In recent years, the application development of polycarbonate is developing towards high composition, high function, specialization and serialization, and the requirements on the safety and environmental protection of materials are higher and higher. However, the traditional polycarbonate preparation method is synthesized by petrochemical bisphenol A and highly toxic phosgene, the route not only seriously pollutes the environment, but also the estrogen effect of the bisphenol A causes some health problems, and in addition, the problem of shortage of petroleum resources is gradually serious. Therefore, the development of a green sustainable polycarbonate preparation process is a focus of research in this field.
The renewable bio-based monomer is an important way for green preparation of polycarbonate instead of the traditional petrochemical raw materials. 1,4:3, 6-Diglycidohexanol is considered to be the most potential bio-based monomer for the synthesis of polycarbonates, and its rigidity, chiral structure, enables it to impart high glass transition temperature and good transparency to the polymer. Although the conventional studies on the production of 1,4:3, 6-dianhydrohexitol (co) polycarbonate mostly employ a direct reaction with diphenyl carbonate (Journal of industrial and Engineering Chemistry,2016,37, 42-46), this method has severe reaction conditions, requires high temperature and high vacuum, and consumes much energy, and the by-product phenol is difficult to remove. In addition, the catalysts currently reported for the preparation of 1,4:3, 6-dianhydrohexitol (co) polycarbonates are mostly metal catalysts such as lithium acetylacetonate, sodium acetylacetonate (Journal of Polymer Science, Part A: Polymer Chemistry,2013,51, 1387-. Although these catalysts can improve the activity of 1,4:3, 6-diglycidyl hexanol to some extent and promote the synthesis of high molecular weight polycarbonate, the synthesized product has metal residue to pollute the environment, and the application of polycarbonate in the aspects of baby products, medical devices, food packaging and the like is limited.
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 catalysis, which takes carbonic acid diester and dihydroxy compound as raw materials, generates ester exchange reaction under the action of catalyst, and generates polycarbonate by polycondensation; the catalyst adopted by the method is a nitrogen-containing organic compound or a compound of the nitrogen-containing organic compound and cellulose, and has the advantages of high catalytic activity, good selectivity and no influence on the quality of polycarbonate. The method has the advantages of wide raw material selection range, small catalyst consumption and mild reaction conditions; the reaction process does not cause environmental pollution, and the product does not contain toxic substances, so the method is an efficient, environment-friendly and 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 catalysis, which comprises the following steps:
(1) and (3) ester exchange stage: carrying out ester exchange reaction on carbonic acid diester and dihydroxy compound under normal pressure and inert atmosphere to obtain 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 catalyst adopted by the method is a nitrogen-containing organic compound or a compound of the nitrogen-containing organic compound and cellulose.
When the method adopts the nitrogen-containing organic compound as the catalyst, the nitrogen-containing organic compound has high activity, good catalytic selectivity, alkalinity and nucleophilicity, can simultaneously activate the dihydroxy compound and the carbonic acid diester, improve the nucleophilic property of the hydroxyl oxygen atom of the dihydroxy compound and the electrophilic property of the carbonyl carbon of the carbonic acid diester, inhibit the occurrence of methylation side reaction, and further promote the forward progress of ester exchange reaction and polycondensation reaction; meanwhile, when the cellulose is adopted, the cellulose contains rich hydroxyl functional groups, so that intermolecular hydrogen bonds of the dihydroxy compound can be broken, the hydroxyl activity of the dihydroxy compound is successfully activated, and the ester exchange reaction of the dihydroxy compound and the carbonic acid diester is promoted; in addition, the nitrogen-containing organic compound and the cellulose interact with each other, as shown in fig. 1, as the content of the compound of the nitrogen-containing organic compound and the cellulose increases, hydrogen on methyl group of the dimethyl carbonate moves to a high field, which indicates that the compound of the nitrogen-containing organic compound and the cellulose can activate the dimethyl carbonate, and the reaction rate is accelerated; the compound of the nitrogen-containing organic compound and the cellulose solves the problem of poor universality of the traditional catalyst on the activation of different types of alcoholic hydroxyl groups, successfully realizes the preparation of the copolymerized polycarbonate by a one-pot method, reduces the reaction steps and simplifies the reaction process; and the cellulose and the nitrogenous organic compound have certain thermal stability, so that the cellulose and the nitrogenous organic compound can ensure that the cellulose and the nitrogenous organic compound have catalytic activity in an ester exchange reaction stage and a polycondensation stage, the nitrogenous organic compound can be thermally decomposed without residue in the final reaction stage, and the cellulose is a natural high molecular compound, so 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 nitrogen-containing organic compound includes any one of guanidine nitrogen-containing organic compounds, amidine nitrogen-containing organic compounds, amine nitrogen-containing organic compounds, imidazole nitrogen-containing organic compounds or pyridine nitrogen-containing organic compounds, and is preferably a guanidine nitrogen-containing organic compound.
Preferably, the nitrogen-containing organic compound includes 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,3, 3-tetramethylguanidine, 1, 3-diphenylguanidine, formamidine, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicycloundec-7-ene, triazamidine, 1, 4-diazabicyclo [2.2.2] octane, monoethanolamine, diethanolamine, triethanolamine, triethylamine, diethylamine, imidazole, N-methylimidazole, N-ethylimidazole, 2-methylimidazole, 4-methylimidazole, 2-hydroxyimidazole, 4-hydroxyimidazole, 6-hydroxyimidazo [1, 2-B ] pyridazine, imidazo [1,2-A ] pyridin-8-ol, pyridine, 2, 6-diaminopyridine, 3-methylaminopyridine, 4-dimethylaminopyridine or 4-pyrrolidinylpyridine, preferably any of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene or 1, 5-diazabicyclo [4.3.0] non-5-ene.
The nitrogen-containing organic compound in the process of the invention is preferably 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene or 1, 5-diazabicyclo [4.3.0]Any one of non-5-alkene, the preferable nitrogen-containing organic compound not only has good catalytic selectivity, but also promotes the ester exchange reaction of the dihydroxy compound and the carbonic diester in the ester exchange stage, inhibits the side reaction of methylation, and the methylation is as low as 0.1%; and the thermal stability is good, the good catalytic activity is still kept under the high-temperature condition in the polycondensation stage, and the synergistic catalytic action can be formed with the cellulose, so that the polymerization positive reaction is promoted. In addition to the nitrogen-containing organic compound being highly basic, the dihydroxy compound is activated from the nitrogen-containing organic compound1As seen in an H NMR spectrum (shown in figure 2), the proton peak of the dihydroxy compound is obviously shifted to a high field, which indicates that the nitrogen-containing organic compound can effectively activate the dihydroxy compound, and indicates that the nitrogen-containing organic compound can enhance the hydroxyl activity of the dihydroxy compound and improve the nucleophilic property of a hydroxyl oxygen atom; and having excellent nucleophilicity, and activating a carbonic acid diester from a complex of the above nitrogen-containing organic compound and cellulose1It can be seen from the H NMR spectrum (FIG. 1) that the proton peak of the carbonic acid diester is also shifted to a high field, indicating that the above-mentioned nitrogen-containing organic compoundAnd the cellulose can synergistically activate the carbonic diester, so that the hydrophile property of the carbonyl carbon of the carbonic diester is improved. In addition, through the research combining molecular simulation and experiments, the nitrogen-containing organic compound and cellulose have higher activity matching property in the process of activating carbonyl carbon and hydroxyl oxygen, the condition that polymerization reaction is inhibited due to higher activity of a specific functional group is not caused, the polymerization reaction is carried out mildly, the catalytic activity and the selectivity can be improved, and therefore, the nitrogen-containing organic compound is superior to other nitrogen-containing organic compounds, and the polycarbonate with higher molecular weight and narrow molecular weight distribution is obtained.
Preferably, the transesterification reaction in step (1) is carried out at a temperature of 98 to 180 ℃, such as 98 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or the like, preferably 98 to 120 ℃.
Preferably, the transesterification reaction time in step (1) is 1 to 10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h, etc., preferably 5 to 7 h.
Preferably, the molar ratio of dihydroxy compound to carbonic acid diester in step (1) is 1 (1.75-20), such as 1:1.75, 1:3.5, 1:5.25, 1:7, 1:8, 1:10, 1:12, 1:14 or 1:18, etc., preferably 1 (3.5-7).
Preferably, the catalyst is used in an amount of 10 parts by mass of the dihydroxy compound-4-10-2E.g. 1X 10-4, 3X 10-4、5×10-4、8×10-4、1×10-3、3×10-3、5×10-3Or 1X 10-2And the like.
Preferably, the catalyst is a composite of a nitrogen-containing organic compound and cellulose, wherein the mass ratio of the cellulose to the nitrogen-containing organic compound is (10)-21) such as 0.05:1, 0.1:1, 0.3:1, 0.5:1, 0.8:1 or 1:1, etc.
Preferably, the inert atmosphere comprises nitrogen and/or argon.
Preferably, the degree of vacuum of the polycondensation reaction in step (2) is 50 to 1000Pa, such as 50Pa, 100Pa, 200Pa, 300Pa, 400Pa, 500Pa, 600Pa, 700Pa, 800Pa, 900Pa, 1000Pa, or the like.
Preferably, the temperature of the polycondensation reaction in step (2) is 180-.
Preferably, the time of the polycondensation reaction in step (2) is 1 to 11h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, etc., preferably 4 to 6 h.
Preferably, the carbonic acid diester in 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 in step (1) comprises any one of 1,4:3, 6-diglycidyl hexanol, an aliphatic dihydroxy compound, or an aromatic dihydroxy compound, or a combination of at least two thereof, which illustratively comprises a combination of 1,4:3, 6-diglycidyl hexanol and an aliphatic dihydroxy compound, or a combination of an aromatic dihydroxy compound and an aliphatic dihydroxy compound, or the like.
Preferably, the dihydroxy compound is a mixture of 1,4:3, 6-diglycidyl hexanol and an aliphatic dihydroxy compound or a mixture of 1,4:3, 6-diglycidyl hexanol and an aromatic dihydroxy compound.
Preferably, the molar ratio of 1,4:3, 6-diglycidyl hexanol to aliphatic dihydroxy compound in the mixture of 1,4:3, 6-diglycidyl hexanol and aliphatic dihydroxy compound is (1-8: 1), such as 1:1, 3.5:1, 4:1, 6:1, or 8:1, etc.
Preferably, the molar amount ratio of 1,4:3, 6-diglycidhexanehexol to the aromatic dihydroxy compound in the mixture of 1,4:3, 6-diglycidhexanehexol and the aromatic dihydroxy compound is (1-8: 1, such as 1:1, 3.5:1, 4:1, 6:1 or 8:1, etc.
The molecular weight of the product polycarbonate can be obviously improved by adopting the dihydroxy compound combination in the catalytic reaction process.
Preferably, the 1,4:3, 6-diglycidyl hexanol is selected from any one of isosorbide, isomannide or isoidide or a combination of at least two of the same, and the combination exemplarily includes a combination of isosorbide and isomannide, a combination of isoidide and isosorbide, or a combination of isomannide and isoidide, and the like, preferably isosorbide.
Preferably, the aliphatic dihydroxy compound is selected from any one or a combination of at least two of 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 3-cyclopentanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, hydrogenated dioleyl glycol, 1, 5-decalindiol, 2, 5-norbornanedimethanol, or 4, 8-bis (hydroxymethyl) tricyclodecane, which combination illustratively includes a combination of 1, 5-pentanediol and 1, 6-hexanediol, a combination of 1, 7-heptanediol and 1, 3-cyclopentanediol, 1, 3-cyclohexanediol, and 1, a combination of 4-cyclohexanediols, a combination of 1, 2-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol, a combination of diethylene glycol and triethylene glycol, a combination of tetraethylene glycol and hydrogenated dioleyl glycol, or a combination of 1, 5-decalindinol, 2, 5-norbornanedimethanol and 4, 8-bis (hydroxymethyl) tricyclodecane, and the like.
Preferably, the aromatic dihydroxy compound is selected from the group consisting of hydroquinone, 1, 4-benzenedimethanol, 1, 4-benzenediethanol, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cymene ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl ] fluorene, 9-bis 5[4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene, p-xylylene diamine, 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3, 5-dimethylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl ] fluorene, 9-bis [4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl ] fluorene, 4' - (1-phenylethyl) bisphenol, 2-bis (4-hydroxyphenyl) butane, 4' -ethylenebiphenol, 4' -dihydroxydiphenylmethane, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, p-xylene, 4,4' -dihydroxytetraphenylmethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, or 3- (4-hydroxyphenyl) -1-propanol, or a combination of at least two thereof, illustratively including a combination of hydroquinone and 1, 4-benzenedimethanol, a combination of 1, 4-benzenediethanol and 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene and 9, a combination of 9-bis [4- (2-hydroxyethoxy) -3-cymenylfluorene, a combination of 9, 9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl ] fluorene and 9, 9-bis 5[4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, a combination of 9, 9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene and 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene, a combination of 9, 9-bis [4- (2-hydroxyethoxy) -3, 5-dimethylphenyl ] fluorene and 9, 9-bis [4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl ] fluorene, a combination of a salt thereof and a salt thereof, A combination of 9, 9-bis [4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl ] fluorene and 4,4'- (1-phenylethyl) bisphenol, a combination of 2, 2-bis (4-hydroxyphenyl) butane and 4,4' -ethylenebiphenol, a combination of 4,4 '-dihydroxydiphenylmethane and 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, a combination of 4,4' -dihydroxytetraphenylmethane and 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, a combination of 2, 2-bis (4-hydroxy-3-tolyl) propane and 2, 2-bis (4-hydroxyphenyl) propane or a combination of 2, 2-bis (4-hydroxyphenyl) butane and 3- (4-hydroxyphenyl) -1-propane Combinations of alcohols, and the like.
Preferably, the method for catalytically preparing polycarbonate has the general reaction formula:
wherein R is1A benzene ring or an alkyl group having 1 to 10 carbon atoms, for example, 2, 3, 4, 5, 6, 7, 8 or 9; r1Illustratively including but not limited to any of methyl, ethyl, propyl, butyl, or pentyl.
R2Is a substituted or unsubstituted, straight or branched alkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35 or 40 carbon atoms,Any one or a combination of at least two of a cycloalkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35, or 40 carbon atoms, a heterocycloalkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35, or 40 carbon atoms, and an aryl group having 6 to 45 carbon atoms, for example, 10, 15, 20, 25, 30, 35, or 40 carbon atoms; m and m 'are each independently an integer of not less than 0, for example, 0, 1,6, 9, 20, 35, 45, 55, 75, 95, 110, 130, 150, or 200, etc., 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 is1A benzene ring or an alkyl group having 1 to 10 carbon atoms, for example, 2, 3, 4, 5, 6, 7, 8 or 9; r1Illustratively including but not limited to any of methyl, ethyl, propyl, butyl, or pentyl.
R2The alkyl group is any one or a combination of at least two of a substituted or unsubstituted straight-chain or branched alkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35 or 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35 or 40 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 45 carbon atoms, for example, 5, 10, 15, 20, 25, 30, 35 or 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 45 carbon atoms, for example, 10, 15, 20, 25, 30, 35 or 40 carbon atoms, and n is an integer greater than 0, for example, 20, 40, 60, 80, 100, 160, 180 or 200 carbon atoms.
The heteroatom in the heterocycloalkyl group is O, S, P or N, or a combination of at least two of these, and the combination illustratively includes a combination of O and S, or a combination of P and N, or the like, preferably O.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) and (3) ester exchange stage: carrying out ester exchange reaction on carbonic acid diester and dihydroxy compound under normal pressure and inert atmosphere to obtain prepolymer, wherein a catalyst adopted in the ester exchange reaction is a compound of a nitrogen-containing organic compound and cellulose; the temperature of the ester exchange reaction is 98-180 ℃, and the time of the ester exchange reaction is 1-10 h; the nitrogen-containing organic compound in the catalyst comprises any one of guanidine nitrogen-containing organic compounds, amidine nitrogen-containing organic compounds, amine nitrogen-containing organic compounds, imidazole nitrogen-containing organic compounds and pyridine nitrogen-containing organic compounds;
(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 180-300 ℃, and the time of the polycondensation reaction is 1-11 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method takes a nitrogen-containing organic compound as a catalyst, and utilizes the alkalinity and nucleophilicity of the nitrogen-containing organic compound to simultaneously activate a dihydroxy compound and a carbonic diester, so that the nucleophilicity of a hydroxyl oxygen atom of the dihydroxy compound and the electrophilicity of a carbonyl carbon of the carbonic diester are improved, the occurrence of methylation side reaction is inhibited, and the forward progress of an ester exchange reaction and a polycondensation reaction is promoted; the nitrogen-containing organic compound is compounded with the cellulose, and the rich hydroxyl functional groups in the cellulose break the intermolecular hydrogen bond of the dihydroxy compound, improve the hydroxyl activity of the dihydroxy compound and promote the hydroxyl oxygen atoms of the dihydroxy compound to attack the carbonyl carbon of the carbonic diester, thereby promoting the ester exchange reaction and accelerating the reaction rate; in addition, the interaction of the nitrogen-containing organic compound and the cellulose improves the catalytic activity and selectivity, enhances the reaction activity of the dihydroxy compound and the carbonic diester, solves the problem of poor universality of the traditional catalyst on the activation of different types of alcoholic hydroxyl groups, successfully realizes the one-pot method for preparing the copolymerized polycarbonate, simplifies the reaction steps and reduces the reaction flow;
(2) the cellulose and the nitrogenous organic compound in the catalyst adopted by the method have excellent thermal stability, so that the catalyst can ensure that the catalyst has catalytic activity in an ester exchange stage and a polycondensation stage; the nitrogenous organic compound can be thermally decomposed without residue at the final stage of the reaction, and the cellulose is a natural high molecular compound, so that the obtained polymer is safer and has wider application;
(3) the polycarbonate prepared by the method has the characteristics of large molecular weight and high glass transition temperature, and has the advantages of wide selection range of preparation raw materials, small using amount of catalyst, mild reaction conditions, no environmental pollution in the reaction process and no toxic substances in the product.
Drawings
FIG. 1 is a drawing of cellulose and 1,5, 7-triazabicyclo [4.4.0]]Method for activating dimethyl carbonate by deca-5-ene1H NMR spectrum;
FIG. 2 is 1,5, 7-triazabicyclo [4.4.0]]Process for preparing isosorbides activated by dec-5-ene1H 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 limitations of the present invention.
Example 1
In the embodiment, isosorbide and dimethyl carbonate are used as raw materials, and a polycarbonate is prepared under the composite catalysis of cellulose and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, wherein the reaction formula is as follows:
the preparation method comprises the following steps:
(1) and (3) ester exchange stage: a reaction flask was charged with 14.6g (0.1mol) of isosorbide and 63g (0.7mol) of dimethyl carbonate in the presence of a composite catalyst of 1,5, 7-triazabicyclo [ 4.4.0%]The mass of dec-5-ene was 1.46X 10-2g, the mass of cellulose is 1.46X 10-3g, reacting for 6 hours at the temperature of 98 ℃ under normal pressure in the nitrogen atmosphere, then slowly raising the temperature to 180 ℃ and reacting for 1 hour to volatilize unreacted dimethyl carbonate and low-boiling-point product methanol to obtainA prepolymer;
(2) a polycondensation stage: raising the temperature in the step (1) from 180 ℃ to 240 ℃, slowly reducing the vacuum degree to 50Pa, and carrying out reaction for 4 hours to obtain a product isosorbide type polycarbonate;
and (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonaten18000g/mol, weight average molecular weight MwIs 30000 g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonategWas 151 ℃.
Example 2
This example is different from example 1 in that the mass of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene in the composite catalyst was replaced with 4-dimethylaminopyridine, 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 polycarbonatenIs 17000g/mol, weight average molecular weight MwIs 30000 g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonategThe temperature was 148 ℃.
Example 3
This example is different from example 1 in that the mass of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene in the composite catalyst was replaced with 4-pyrrolidinylpyridine, 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 polycarbonaten16000g/mol, a weight-average molecular weight MwIt was 28000 g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonategThe temperature was 150 ℃.
Example 4
This example is different from example 1 in that the same mass of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene in the composite catalyst was replaced with 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 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 polycarbonatenHas a weight average molecular weight M of 15000g/molw26000 g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonategThe temperature was 150 ℃.
Example 5
This example is different from example 1 in that 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and the like in the composite catalyst were replaced by 1, 5-diazabicyclo [4.3.0] non-5-ene, 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 polycarbonatenIs 14000g/mol, a weight-average molecular weight MwIt was 23000 g/mol.
And (3) testing thermal performance: the DSC test result of the product shows that the glass transition temperature T of the polycarbonategThe temperature was 149 ℃.
Example 6
This example is different from example 1 in that the mass of cellulose in the composite catalyst is changed from 1.46X 10-3g is replaced by 1.46X 10-2g, 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 polycarbonatenIs 17000g/mol, weight average molecular weight MwIt was 28000 g/mol.
Example 7
This example differs from example 1 in that the initial reaction temperature of the transesterification reaction was changed from 98 ℃ 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 polycarbonaten16000g/mol, a weight-average molecular weight MwIt was 28000 g/mol.
Example 8
This example differs from example 1 in that the initial reaction temperature of the transesterification reaction was changed from 98 ℃ to 140 ℃ 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 polycarbonatenHas a weight average molecular weight M of 15000g/molw24000 g/mol.
Example 9
This example differs from example 1 in that the transesterification reaction time was changed from 6h 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 polycarbonatenIs 5100g/mol, weight average molecular weight Mw6500 g/mol.
Example 10
This example differs from example 1 in that the transesterification reaction time was changed from 6h to 5h, 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 polycarbonatenHas a weight average molecular weight M of 15000g/molwIs 21000 g/mol.
Example 11
This example differs from example 1 in that the transesterification reaction time was changed from 6h 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 polycarbonaten16000g/mol, a weight-average molecular weight MwIs 21000 g/mol.
Example 12
This example differs from example 1 in that the transesterification reaction time was changed from 6h to 10h, 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 polycarbonaten13000g/mol, weight-average molecular weight MwIs 21000 g/mol.
As can be seen from comparative examples 1 and 9 to 12, 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 5 to 7 hours.
Example 13
This example differs from example 1 in that the mass of dimethyl carbonate was changed from 63g to 15.75g (0.175mol), 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 polycarbonatenIs 4300g/mol, weight average molecular weight Mw5100 g/mol.
Example 14
This example differs from example 1 in that the mass of dimethyl carbonate was changed from 63g to 31.5g (0.35mol), 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 polycarbonatenIs 17000g/mol, weight average molecular weight MwIs 27000 g/mol.
Example 15
This example differs from example 1 in that the mass of dimethyl carbonate was changed from 63g to 47.25g (0.525mol), and the other conditions were exactly 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 polycarbonaten24000g/mol, weight average molecular weight Mw39000 g/mol.
Example 16
This example differs from example 1 in that the mass of dimethyl carbonate was changed from 63g to 126g (1.4mol), 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 polycarbonatenIs 17000g/mol, weight average molecular weight MwIs 30000 g/mol.
As can be seen from comparative examples 1 and 13 to 16, when the molar ratio of the dihydroxy compound to the carbonic acid diester is 1 (3.5 to 7), the number average molecular weight and the weight average molecular weight of the polycarbonate obtained by the catalytic preparation are large.
Example 17
This example differs from example 1 in that carbonic acid bisThe amount of methyl ester used was adjusted to 47.25g (0.525mol), and 1,5, 7-triazabicyclo [4.4.0] in the composite catalyst]The amount of dec-5-ene was replaced by 1.46X 10-3g, replacing the amount of cellulose with 1.46X 10-4g, 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 polycarbonaten9000g/mol, weight-average molecular weight MwIt was 14000 g/mol.
Example 18
This example differs from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol) and 1,5, 7-triazabicyclo [4.4.0] in the composite catalyst]The amount of dec-5-ene was replaced by 7.3X 10-3g, replacing the amount of cellulose by 7.3X 10-4g, 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 polycarbonaten20000g/mol, weight average molecular weight MwIs 32000 g/mol.
Example 19
This example differs from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol) and 1,5, 7-triazabicyclo [4.4.0] in the composite catalyst]The amount of dec-5-ene was replaced by 4.38X 10-2g, replacing the amount of cellulose with 4.38 × 10-3g, 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 polycarbonatenA weight average molecular weight M of 23000g/molwIs 38000 g/mol.
Example 20
This example differs from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol) and 1,5, 7-triazabicyclo [4.4.0] in the composite catalyst]The dose of dec-5-ene was replaced with 0.146g, and the dose of cellulose was replaced with 1.46X 10-2g, 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 of the polycarbonateMn18000g/mol, weight average molecular weight MwIs 30000 g/mol.
Example 21
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), 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 polycarbonatenIs 4900g/mol, weight average molecular weight Mw5800 g/mol.
Example 22
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the degree of vacuum of the polycondensation reaction in step (2) was changed to 80Pa, 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 polycarbonatenIs 11000g/mol, the weight average molecular weight Mw19000 g/mol.
Example 23
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the temperature of the polycondensation reaction in step (2) was 180 ℃, and other conditions were exactly 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 polycarbonaten12000g/mol, a weight-average molecular weight MwIs 20000 g/mol.
Example 24
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the temperature of the polycondensation reaction in step (2) was 220 ℃, and other conditions were exactly 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 polycarbonaten20000g/mol, weight average molecular weight MwIs 32000 g/mol.
Example 25
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the temperature of the polycondensation reaction in step (2) was 280 ℃, 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 polycarbonaten33000g/mol, weight-average molecular weight MwIt was 53000 g/mol.
Example 26
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the temperature of the polycondensation reaction in step (2) was 300 ℃, and other conditions were exactly 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 polycarbonatenIs 22000g/mol, weight average molecular weight Mw37000 g/mol.
As can be seen from comparison of examples 1 and 23 to 26, when the temperature of the polycondensation reaction is controlled to 240 ℃ and 280 ℃, the number average molecular weight and the weight average molecular weight of the polycarbonate obtained by the catalytic preparation are large.
Example 27
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the polycondensation reaction temperature in step (2) was 280 ℃, the polycondensation reaction time was changed to 1 hour, 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 polycarbonatenIs 22000g/mol, weight average molecular weight MwThe concentration was 36000 g/mol.
Example 28
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the polycondensation reaction temperature in step (2) was 280 ℃, the polycondensation reaction time was changed to 6 hours, 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 polycarbonatenIs 32000g/mol, weight average molecular weight MwIt was 51000 g/mol.
Example 29
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the polycondensation reaction temperature in step (2) was 280 ℃, the polycondensation reaction time was changed to 8 hours, 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 polycarbonatenIs 31000g/mol, weight average molecular weight MwIt was 52000 g/mol.
Example 30
This example is different from example 1 in that the amount of dimethyl carbonate used was adjusted to 47.25g (0.525mol), the polycondensation reaction temperature in step (2) was 280 ℃ and the polycondensation reaction time was changed to 11 hours, 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 polycarbonatenIs 29000g/mol, weight average molecular weight MwIt was 49000 g/mol.
As can be seen from comparison of examples 1 and 27 to 30, when the polycondensation reaction time is 4 to 6 hours, the number average molecular weight and the weight average molecular weight of the polycarbonate produced by the catalysis are large, and the reaction time is short.
Example 31
This example differs from example 1 in that dimethyl carbonate was replaced with 0.525mol of diphenyl carbonate, 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 polycarbonaten20000g/mol, weight average molecular weight MwIs 32000 g/mol.
Example 32
This example differs from example 1 in that the isosorbide is replaced with an equimolar amount of isomannide, and the other conditions are 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 polycarbonaten13000g/mol, weight-average molecular weight MwIs 21000 g/mol.
Example 33
In the embodiment, isosorbide, dimethyl carbonate and 1, 4-benzenedimethanol are used as raw materials, and a polycarbonate is prepared under the composite catalysis of cellulose and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, wherein the reaction formula is as follows:
the preparation method comprises the following steps:
(1) and (3) ester exchange stage: 11.68g (0.08mol) of isosorbide, 47.25g (0.525mol) of dimethyl carbonate and 2.76g (0.02mol) of 1, 4-benzenedimethanol are added into a reaction flask, and 1,5, 7-triazabicyclo [4.4.0] is added into the composite catalyst]The mass of dec-5-ene was 1.168X 10-2g (1.0X 10 of isosorbide mass)-3) The mass of the cellulose is 1.168X 10-2g, reacting at the normal pressure and the temperature of 98 ℃ for 6 hours in the nitrogen atmosphere, then 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 ℃, slowly reducing the vacuum degree to 50Pa, and carrying out reaction for 4 hours to obtain a product of isosorbide type copolycarbonate;
and (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn27000g/mol, weight average molecular weight MwIt was 47000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 136 ℃.
Example 34
This example differs from example 33 in that 2.12g (0.02mol) of diethylene glycol were added before the reaction in step (1) was started, and the other conditions were exactly the same as in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn26000g/mol, weight average molecular weight MwIt was 43000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 109 ℃.
Example 35
This example is different from example 33 in that 3.00g (0.02mol) of triethylene glycol was added before the reaction in step (1) and the other conditions were exactly the same as in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn26000g/mol, weight average molecular weight Mw39000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 94 ℃.
Example 36
This example differs from example 33 in that 2.88g (0.02mol) 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 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight MnIs 22000g/mol, weight average molecular weight MwIt was 34000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 120 ℃.
Example 37
This example differs from example 33 in that 3.92g (0.02mol) of 4, 8-bis (hydroxymethyl) tricyclodecane was added before the reaction in step (1) and the other conditions were exactly the same as in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn20000g/mol, weight average molecular weight MwIt was 34000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategIt was 129 ℃.
Example 38
This example differs from example 33 in that 2.32g (0.02mol) of 1, 4-cyclohexanediol were added before the start of the reaction in step (1), and the other conditions were exactly the same as in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn18000g/mol, weight average molecular weight MwIt was 31000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 138 ℃.
Example 39
This example differs from example 33 in that 2.36g (0.02mol) of 1, 6-hexanediol were added before the start of the reaction in step (1), and the other conditions were exactly the same as in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight MnHas a weight average molecular weight M of 15000g/molw26000 g/mol.
And (3) testing thermal performance: the results of DSC tests of the product show the glass transition temperature T of isosorbide-type copolycarbonategThe temperature was 88 ℃.
As can be seen from examples 33 to 39, the dihydroxy compound used in the preparation was a mixture of 1,4:3, 6-diglycidyl hexanol and an aliphatic dihydroxy compound or a mixture of 1,4:3, 6-diglycidyl hexanol and an aromatic dihydroxy compound; which is advantageous for improving the number average molecular weight and the weight average molecular weight of the polycarbonate obtained by the preparation.
Example 40
This example differs from example 1 in that only 1.46 × 10 was used-2g of 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene was used as a catalyst, i.e., no cellulose was added, and the other conditions were exactly the same as compared with example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight MnHas a weight average molecular weight M of 15000g/molw26500 g/mol.
EXAMPLE 41
This example differs from example 1 in that only 1.46 × 10 was used-2g of 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene was used as a catalyst, i.e., no cellulose was added, and the other conditions were exactly the same as compared with example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonatenIs 14000g/mol, a weight-average molecular weight Mw24000 g/mol.
Example 42
This example differs from example 1 in that only 1.46 × 10 was used-2g of 1, 5-diazabicyclo [4.3.0]Non-5-ene, i.e. no cellulose was added, the other conditions were exactly the same as compared to example 1.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonaten12000g/mol, a weight-average molecular weight MwIs 20000 g/mol.
Example 43
This example differs from example 33 in that only 1.168X 10 is used-2g of 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene was used as a catalyst, i.e., no cellulose was added, and the other conditions were exactly the same as those in example 33.
And (3) testing molecular weight: GPC measurement of the product showed that the isosorbide-type copolycarbonate had a number average molecular weight Mn25000g/mol, weight average molecular weight MwIt was 43000 g/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 potassium acetylacetonate catalyst;
the preparation method comprises the following steps:
(1) and (3) ester exchange stage: adding 36.5g (0.25mol) of isosorbide and 168.75g (1.875mol) of dimethyl carbonate into a reaction bottle, adding 36.5mg of potassium acetylacetonate catalyst, reacting at the normal pressure of 98 ℃ for 6 hours under the atmosphere of nitrogen, 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 isosorbide type polycarbonate;
and (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the polycarbonaten8800g/mol, weight average molecular weight Mw17500 g/mol.
Comparative example 2
In the comparative example, isosorbide, dimethyl carbonate and 1, 4-cyclohexanedimethanol are used as raw materials, and a polycarbonate is prepared under the catalytic action of a catalyst, and the reaction formula is as follows:
the preparation method comprises the following steps:
(1) transesterification stage 1: 44g (0.30mol) of isosorbide, 27g (0.3mol) of dimethyl carbonate and 5X 10-3g transesterification catalyst (sodium hydroxide as catalyst, denoted as catalyst 1), N2Under the protection of air flow, reacting for 7.5h at the temperature of 110 ℃ under normal pressure, then slowly raising the temperature to 220 ℃ until the reaction is complete and no methanol is distilled off any more, thus obtaining the isosorbide polycarbonate prepolymer;
(2) transesterification stage 2: into a reaction flask were charged 35g (0.30mol) of 1, 4-cyclohexanedimethanol, 27g (0.3mol) of dimethyl carbonate, 4X 10-3g transesterification catalyst (Potassium carbonate as catalyst, noted catalyst 2), N2Under the protection of gas flow, reacting at 105 ℃ for 8h under normal pressure, slowly raising the temperature to 210 ℃ until the reaction is complete and no methanol is distilled off any more, thus obtaining the poly (1, 4-cyclohexanedimethanol polycarbonate) prepolymer;
(3) and (3) polycondensation reaction stage: mixing the prepolymers obtained in the step (1) and the step (2), adding 0.01g of polycondensation catalyst lithium hydroxide (recorded as catalyst 3), slowly reducing the vacuum degree to 200Pa, and carrying out reaction at 260 ℃ for 10 hours to obtain the product copolycarbonate.
And (3) testing molecular weight: GPC measurement of the product showed that the number average molecular weight M of the copolycarbonatenIs 20000 g/mol.
Using cellulose and 1,5, 7-triazabicyclo [ 4.4.0%]Method for activating dimethyl carbonate by using deca-5-ene compound as catalyst1The H NMR spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that as the molar ratio of complex to dimethyl carbonate increases from 0:3 to 9:3, the proton peak of dimethyl carbonate shifts from 3.78ppm to 3.65 ppm. The proton peak of the dimethyl carbonate obviously moves to a high field, which indicates that the composite catalyst can efficiently activate the dimethyl carbonate;
using 1,5, 7-triazabicyclo [4.4.0]Process for preparing isosorbides activated by dec-5-ene1The H NMR spectrum is shown in FIG. 2, and it can be seen from FIG. 2 that 1,5, 7-triazabicyclo [4.4.0] is accompanied by 1,5, 7-triazabicyclo]The molar ratio of dec-5-ene to isosorbide increases from 0:1 to 1:1, and the proton peaks of the hydrogens in the 1-, 2-, 3,5-, and 6-positions of isosorbide are clearly shifted to high fields. The peak of isosorbide proton is shifted, indicating that 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene is highly effective in activating 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 catalytically preparing polycarbonate, comprising the steps of:
(1) and (3) ester exchange stage: carrying out ester exchange reaction on carbonic acid diester and dihydroxy compound under normal pressure and inert atmosphere to obtain 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 catalyst adopted by the method is a nitrogen-containing organic compound or a compound of the nitrogen-containing organic compound and cellulose.
2. The process of claim 1 wherein the catalyst is a nitrogen-containing organic compound, the catalyst being added during the transesterification stage;
preferably, the catalyst is a compound of a nitrogen-containing organic compound and cellulose, and the catalyst is placed in a mode that the nitrogen-containing organic compound and the cellulose are added in a transesterification stage;
or the nitrogen-containing organic compound is added in the transesterification stage followed by the addition of the cellulose in the polycondensation stage.
3. The method according to claim 1 or 2, wherein the nitrogen-containing organic compound comprises any one of guanidine nitrogen-containing organic compounds, amidine nitrogen-containing organic compounds, amine nitrogen-containing organic compounds, imidazole nitrogen-containing organic compounds or pyridine nitrogen-containing organic compounds, and is preferably guanidine nitrogen-containing organic compounds.
4. The method of any of claims 1-3, wherein the nitrogen-containing organic compound comprises 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,3, 3-tetramethylguanidine, 1, 3-diphenylguanidine, formamidine, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicycloundec-7-ene, triazamidine, 1, 4-diazabicyclo [2.2.2] octane, monoethanolamine, diethanolamine, triethanolamine, triethylamine, diethylamine, imidazole, N-methylimidazole, N-ethylimidazole, 2-methylimidazole, 4-methylimidazole, 2-hydroxyimidazole, 4-hydroxyimidazole, 6-hydroxyimidazo [1, 2-B ] pyridazine, imidazo [1,2-A ] pyridin-8-ol, pyridine, 2, 6-diaminopyridine, 3-methylaminopyridine, 4-dimethylaminopyridine or 4-pyrrolidinylpyridine, preferably any of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene or 1, 5-diazabicyclo [4.3.0] non-5-ene.
5. The process according to any one of claims 1 to 4, wherein the temperature of the transesterification reaction in step (1) is between 98 and 180 ℃, preferably between 98 and 120 ℃;
preferably, the transesterification reaction time in step (1) is 1-10h, preferably 5-7 h;
preferably, the molar ratio of dihydroxy compound to carbonic acid diester in step (1) is 1 (1.75-20), preferably 1 (3.5-7);
preferably, the catalyst is used in an amount of 10 parts by mass of the dihydroxy compound-4-10-2；
Preferably, the catalyst is a composite of a nitrogen-containing organic compound and cellulose, wherein the mass ratio of the cellulose to the nitrogen-containing organic compound is (10)-2-1):1；
Preferably, the inert atmosphere comprises nitrogen and/or argon.
6. The process according to any one of claims 1 to 5, wherein the degree of vacuum of the polycondensation reaction in the step (2) is 50 to 1000 Pa;
preferably, the temperature of the polycondensation reaction in step (2) is 180-300 ℃, preferably 240-280 ℃;
preferably, the time of the polycondensation reaction in step (2) is 1 to 11 hours, preferably 4 to 6 hours.
7. The method of any one of claims 1-6, 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.
8. The method of any one of claims 1-7, wherein the dihydroxy compound of step (1) comprises any one of or a combination of at least two of 1,4:3, 6-diglycidyl hexanol, an aliphatic dihydroxy compound, or an aromatic dihydroxy compound;
preferably, the dihydroxy compound is a mixture of 1,4:3, 6-diglycidyl hexanol and an aliphatic dihydroxy compound or a mixture of 1,4:3, 6-diglycidyl hexanol and an aromatic dihydroxy compound;
preferably, the molar amount ratio of 1,4:3, 6-diglycidyl hexanol to aliphatic dihydroxy compound in the mixture of 1,4:3, 6-diglycidyl hexanol and aliphatic dihydroxy compound is (1-8: 1;
preferably, the molar amount ratio of 1,4:3, 6-diglycidyl hexanol to aromatic dihydroxy compound in the mixture of 1,4:3, 6-diglycidyl hexanol and aromatic dihydroxy compound is (1-8: 1;
preferably, the 1,4:3, 6-diglycidyl hexanol is selected from any one or a combination of at least two of isosorbide, isomannide or isoidide;
preferably, the aliphatic dihydroxy compound is selected from any one or a combination of at least two of 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 3-cyclopentanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, hydrogenated dioleyl glycol, 1, 5-decalindiol, 2, 5-norbornanedimethanol, or 4, 8-bis (hydroxymethyl) tricyclodecane;
preferably, the aromatic dihydroxy compound is selected from the group consisting of hydroquinone, 1, 4-benzenedimethanol, 1, 4-benzenediethanol, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cymene ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl ] fluorene, 9-bis 5[4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene, p-xylylene diamine, 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3, 5-dimethylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl ] fluorene, 9-bis [4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl ] fluorene, 4' - (1-phenylethyl) bisphenol, 2-bis (4-hydroxyphenyl) butane, 4' -ethylenebiphenol, 4' -dihydroxydiphenylmethane, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, p-xylene, Any one or a combination of at least two of 4,4' -dihydroxytetraphenylmethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, or 3- (4-hydroxyphenyl) -1-propanol.
9. The process according to any one of claims 1 to 8, characterized in that the process has the general reaction formula:
wherein R is1Is a benzene ring or an alkyl group having 1 to 10 carbon atoms, R2The aryl group is any one or a combination of at least two of a substituted or unsubstituted straight-chain or branched-chain alkyl group with 3-45 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-45 carbon atoms, a substituted or unsubstituted heterocycloalkyl group with 3-45 carbon atoms and a substituted or unsubstituted aryl group with 6-45 carbon atoms; m and m 'are each independently an integer of not less than 0, and m' are not both 0.
10. The method according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) and (3) ester exchange stage: carrying out ester exchange reaction on carbonic acid diester and dihydroxy compound under normal pressure and inert atmosphere to obtain prepolymer, wherein a catalyst adopted in the ester exchange reaction is a compound of a nitrogen-containing organic compound and cellulose; the temperature of the ester exchange reaction is 98-180 ℃, and the time of the ester exchange reaction is 1-10 h; the nitrogen-containing organic compound in the catalyst comprises any one of guanidine nitrogen-containing organic compounds, amidine nitrogen-containing organic compounds, amine nitrogen-containing organic compounds, imidazole nitrogen-containing organic compounds and pyridine nitrogen-containing organic compounds;
(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 180-300 ℃, and the time of the polycondensation reaction is 1-11 h.
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