CN111138650B - High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof - Google Patents
High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof Download PDFInfo
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- CN111138650B CN111138650B CN202010049454.3A CN202010049454A CN111138650B CN 111138650 B CN111138650 B CN 111138650B CN 202010049454 A CN202010049454 A CN 202010049454A CN 111138650 B CN111138650 B CN 111138650B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention provides a high molecular weight high flexibility biology base polycarbonate copolymer and a preparation method thereofUnder nitrogen atmosphere, the mixture is prepared by mixing carbonic diester, 1,4:3, 6-dianhydrohexitol and dihydroxy compound as raw material, adding catalyst, and making them pass through two stages of ester exchange and polycondensation to obtain the high-molecular high-flexibility polycarbonate copolymer. The number average molecular weight of the polycarbonate copolymer obtained was 2.5X 104～12.1×104g/mol, glass transition temperature of 50-200 ℃, 5 percent thermal weight loss temperature of over 330 ℃, and excellent mechanical properties, and can be effectively used for multiple purposes. Compared with the homopolycarbonate, the polycarbonate copolymer provided by the invention has the advantages that the molecular weight, the polymerization degree, the mechanical property, the thermal stability and the like are obviously improved, meanwhile, the synthetic process is green and environment-friendly, and the highly toxic raw material products such as phosgene and the like are not contained.
Description
Technical Field
The invention relates to the field of preparation of polycarbonate, in particular to a high-molecular high-flexibility bio-based polycarbonate copolymer and a preparation method thereof.
Background
Most of the raw materials for producing the polycarbonate are derived from petroleum derivatives, but with the crisis of exhaustion of petroleum resources and the national green and environmental call, the raw materials derived from biomass resources have great development prospects. However, these plant-based monomers tend to have multiple functional groups, which results in the synthetic polycarbonates having an indeterminate structure and poor chemical stability.
1, 4; 3, 6-dianhydrohexitol is prepared from the starch of grains by catalytic decomposition, hydrogenation and further dehydration. 1, 4; the 3, 6-dianhydrohexitol has three isomers, namely isosorbide, isomannide and isoidide, and the isosorbide realizes large-scale industrial production at present, thereby laying a foundation for replacing petroleum-based raw materials. Use of 1, 4; 3, 6-dianhydrohexitol as a starting material for the preparation of polycarbonates has been described in a large number of documents. ACS Sustainable Chemistry & Engineering 2018,6,2684 & 2693 utilizes an ionic liquid catalyst melt transesterification process to obtain isosorbide-type polycarbonate having a number average molecular weight of 67000g/mol, a glass transition temperature of 176 ℃ and a thermal decomposition temperature (5% weight loss temperature) of 342 ℃. In the literature [ Journal of Molecular Catalysis: A,2016,424,77-84], a polycarbonate having a weight-average Molecular weight of 115000g/mol was obtained using a metal oxide as a catalyst. 1, 4; 3, 6-dianhydrohexitol has two hydroxyl groups and is fused from two tetrahydrofuran rings, based on 1, 4; the polycarbonate synthesized by 3, 6-dianhydrohexitol is a high molecular material with high molecular weight and high glass transition temperature, but has poor mechanical property and processability, and cannot meet the industrial application.
The introduction of aliphatic diols is an effective method for altering the mechanical properties thereof and has been reported in the literature. Documents [ CN 102746504; polymer Chemistry 2015,6(4),633-642] incorporated 1, 4-butanediol and yielded a polycarbonate copolymer with a weight average molecular weight of 36500g/mol, a glass transition temperature of 129 ℃ and a tensile strength significantly higher than that of homopolycarbonate. Introducing an aliphatic diol into 1, 4; 3, 6-dianhydrohexitol type polycarbonate can maintain its dimensional stability and contribute to improvement of its flexibility and processability, thereby satisfying its wide industrial application.
Disclosure of Invention
The invention provides a high molecular weight high flexibility biology base polycarbonate copolymer and a preparation method thereof, which solves the problems of 1, 4; 3, 6-dianhydrohexitol type polycarbonates have poor mechanical and processing properties.
The technical scheme for realizing the invention is as follows:
a high molecular weight, high flexibility, bio-based polycarbonate copolymer, said polycarbonate copolymer having the formula:
wherein R is1、R2Is selected from CH2、C2H4、C3H6、C4H8、C5H10、C6H12、CH2CH(CH3)、CH2CH(CH3)CH2、(CH3)2C(CH2)2、(CH3)CHCH2、(CH3)CHCH2CH2、(CH3)CHCH2CH2、CH2C(CH3)CH2And CH (CH)3)CH2CH(CH3) At least one of (1), and n is 0 to 20;
and x and y are the number of the repeating units in the product, can be the same or different, are not zero at the same time, and are natural numbers of 0-100.
The polycarbonate copolymer is synthesized by taking carbonic diester and dihydroxy compound as raw materials, adding a catalyst in the reaction process and carrying out melt polymerization reaction.
The reaction conditions are as follows: heating to 90-150 ℃ under the nitrogen atmosphere and normal pressure, adding a catalyst, and reacting for 1-5 h to obtain a polycarbonate prepolymer; and then gradually heating to 200-260 ℃, reacting for 0.5-6 h when the pressure of the reaction system is less than 50pa, and obtaining the polycarbonate copolymer after the reaction is finished.
The carbonic acid diester is selected from any one or a mixture of more of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate.
The dihydroxy compound is at least one of 1,4:3, 6-diglycidyl hexanol or aliphatic dihydroxy compound.
The 1,4:3, 6-diglycidyl hexaol is at least one selected from isosorbide shown in formula I, isomannide shown in formula II and isoidide shown in formula III.
The aliphatic dihydroxy compound is at least one selected from the group consisting of tetraethylene glycol, triethylene glycol, diethylene glycol, tripropylene glycol, and ethylene glycol.
The catalyst is selected from an ionic liquid catalyst or a metal catalyst, wherein cations in the ionic liquid catalyst are selected from any one of quaternary phosphorus cations, quaternary ammonium cations, imidazole cations, piperidine cations and pyridine cations; the anion is one of hydroxide, formate, acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, palmitate, stearate, glycolate, lactate, benzoate, salicylate, succinate, citrate, tetrafluoroborate, hexafluorophosphate, dihydrogen phosphate, hydrogen sulfate, thiocyanate, chloroaluminate, choline chloride ion, ferric tetrachloride ion and imidazole anion.
The metal catalyst is at least one of lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, zinc acetylacetonate, dibutyltin oxide, tetrabutyl titanate, tetraisopropyl titanate, carbonate, acetate, alkaline earth metal, TBD or DBU.
The catalyst is used in an amount of 1X 10 times the molar amount of the carbonate-5～5×10-4The molar ratio of the dihydroxy compound to the carbonic acid diester is 1 (1-30). 1,4: the 3, 6-dianhydrohexitol accounts for 0-100% of the total amount of the copolymer structural unit, and the dihydroxy compound accounts for 0-100% of the total amount of the copolymer structural unit.
The invention has the beneficial effects that: because the dehydrated aliphatic diol has-C-O-C-bond and no atom is around the oxygen atom, the molecular rotation is easier, the dehydrated aliphatic diol is used as the comonomer, and compared with the traditional aliphatic diol monomer only containing carbon-carbon bond, the dehydrated aliphatic diol has more excellent molecular chain flexibility and is beneficial toThe mechanical properties of the homopolycarbonate are improved. The method used by the invention has mild reaction conditions, the prepolymerization temperature is lower than 150 ℃, the polycondensation temperature is lower than 260 ℃, and the total reaction time is not more than 10 h. The catalyst is used in a small amount of 1X 10 mol percent of the carbonate-5～5×10-4The synthetic process is green and environment-friendly, and does not contain phosgene and other highly toxic substances, and under the condition, the molecular weight of the prepared copolycarbonate is 2.5 multiplied by 104～12.1×104g/mol, much higher than 1,4:3, 6-dianhydrohexitol type homopolycarbonate maintains excellent thermal properties, the glass transition temperature is 50-200 ℃, and the 5% thermal weight loss temperature is above 330 ℃. Above all, compared with homopolycarbonates and aliphatic diol copolycarbonates without-C-O-C-bonds, they have excellent flexibility and retain the original rigidity, with elongations at break of more than 175% at the most. The copolycarbonate of the present invention can be effectively used for various purposes such as a back cover of a cellular phone, an electronic product, a medical instrument, and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram showing a polycarbonate copolymer of isosorbide, tetraethylene glycol and diphenyl carbonate prepared in example 1 of the present invention1H-NMR spectrum.
FIG. 2 is a diagram showing a polycarbonate copolymer of isosorbide, triethylene glycol and diphenyl carbonate prepared in example 17 of the present invention1H-NMR spectrum.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The molecular weight, thermal and mechanical properties in the following examples were determined as follows:
molecular weight: gel Permeation Chromatography (GPC) using N, N-Dimethylformamide (DMF) and monodisperse polystyrene as standard samples.
Thermal properties: characterized by Differential Scanning Calorimetry (DSC), thermogravimetric analyzer (TGA).
Mechanical properties: characterized by a Universal Tester (UTM).
Example 1
At room temperature, 6.43g of diphenyl carbonate, 3.07g of isosorbide and 1.75g of tetraethylene glycol (HO-CH)2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-OH) is added into a 250ml three-neck flask, the mixture is heated to 130 ℃ under the protection of nitrogen atmosphere, and then the catalyst 1-butyl-3-methylimidazolium lactate is added, wherein the using amount of the catalyst is 0.005mol percent of that of diphenyl carbonate. Stirring at 130 ℃ for transesterification reaction for 3 hours, then gradually raising the temperature and gradually reducing the pressure to 240 ℃ and 50pa, and keeping the temperature for 0.5 hour to finish the reaction to obtain the copolymer with the yield of 98 percent. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 121000 g/mol.
Of copolymers1The H-NMR spectrum is shown in figure 1, which shows that the copolymer has a correct structure; the glass transition temperature of the copolymer was 72 ℃ and the 5% thermogravimetric temperature was 334 ℃ as determined by DSC.
Example 2
In the same manner as in example 1, except that the temperature in the transesterification stage was 110 ℃, the copolymer was obtained in a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 60000 g/mol.
Example 3
In the same manner as in example 1, except that the temperature in the transesterification stage was 150 ℃, the copolymer was obtained in a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 65000 g/mol.
Example 4
In the same manner as in example 1, except that the time of the transesterification stage was 1 hour, the copolymer was obtained in a yield of 96%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 82100 g/mol.
Example 5
In the same manner as in example 1, except that the time of the transesterification stage was 5 hours, the copolymer was obtained in a yield of 95%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 72300 g/mol.
Example 6
In the same manner as in example 1, except that the amount of the catalyst used was 0.001% based on the amount of diphenyl carbonate, a copolymer was obtained in a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 49200 g/mol.
Example 7
In the same manner as in example 1, except that the amount of the catalyst used was 0.013% based on the diphenyl carbonate, a copolymer was obtained in a yield of 96%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 64200 g/mol.
Example 8
In the same manner as in example 1, except that the polycondensation temperature was 220 ℃ and the conditions were not changed, a copolymer was obtained in a yield of 97%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 64600 g/mol.
Example 9
In the same manner as in example 1, except that the polycondensation temperature was 260 ℃ and the conditions were not changed, a copolymer was obtained in a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 52300 g/mol.
Example 10
In the same manner as in example 1, except that the catalyst was changed to 1-ethyl-3-methylimidazolium lactate, a copolymer was obtained in a yield of 96%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 82500 g/mol.
Example 11
In the same manner as in example 1 except that the catalyst was changed to TBD, a copolymer was obtained in a yield of 95%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 51100 g/mol.
Example 12
In the same manner as in example 1 except that the catalyst was changed to lithium acetylacetonate, a copolymer was obtained in a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 46800 g/mol.
Example 13
In the same manner as in example 1 except that the catalyst was changed to tetraethylammonium lactate, the copolymer was obtained in a yield of 96% under the same conditions. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 60000 g/mol.
Example 14
In the same manner as in example 1 except that the catalyst was changed to 1-ethyl-3-methylimidazolium tetrafluoroborate, a copolymer was obtained in a yield of 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 47000 g/mol.
Example 15
In the same manner as in example 1 except that the catalyst was changed to 1-ethyl-3-methylimidazolium iron tetrachloride salt, the copolymer was obtained in a yield of 89% under the same conditions. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 48300 g/mol.
Example 16
In the same manner as in example 1, except that the catalyst was changed to cesium carbonate, a copolymer was obtained in a yield of 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 38700 g/mol.
Example 17
The same procedure as in example 1 was repeated, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 13.52g of triethylene glycol (HO-CH) were used as starting materials2CH2-O-CH2CH2-O-CH2CH2-OH), the remaining conditions were unchanged to obtain a copolymer with a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 83000 g/mol.
Of copolymers1The H-NMR spectrum is shown in FIG. 2, which shows that the copolymer has a correct structure; the glass transition temperature of the copolymer was 83 ℃ and the 5% thermogravimetric temperature was 340 ℃ as determined by DSC. The elongation at break of the copolymer was 114% as determined by UTM.
Example 18
The same procedure as in example 1 was repeated, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 9.56g of diethylene glycol (HO-CH) were used as starting materials2CH2-O-CH2CH2-OH), the remaining conditions were unchanged to obtain a copolymer with a yield of 99%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 60700 g/mol.
The glass transition temperature of the copolymer was 105 ℃ and the 5% thermogravimetric temperature was 332 ℃ as determined by DSC. The elongation at break of the copolymer was 176% as determined by UTM.
Example 19
A copolymer was obtained in the same manner as in example 1 except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 17.30g of tripropylene glycol were used as starting materials, and the yield was 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 51500 g/mol. The glass transition temperature of the copolymer was measured by DSC to be 78 ℃.
Example 20
In the same manner as in example 1, except that 64.23g of diphenyl carbonate, 21.92g of isosorbide and 29.14g of tetraethylene glycol were used as raw materials, the transesterification temperature was 120 ℃ and the other conditions were changed, a copolymer was obtained at a yield of 95%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 75600 g/mol.
Example 21
In the same manner as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 15.92g of diethylene glycol were used as raw materials, the transesterification temperature was 120 ℃ and the other conditions were changed, a copolymer was obtained at a yield of 98%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 60000 g/mol.
Example 22
In the same manner as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 22.53g of triethylene glycol were used as raw materials, the transesterification temperature was 120 ℃ and the conditions were not changed, a copolymer was obtained at a yield of 96%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 72000 g/mol.
Example 23
In the same manner as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 28.84g of tripropylene glycol were used as raw materials, the transesterification temperature was 120 ℃ and the conditions were not changed, a copolymer was obtained with a yield of 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 26800 g/mol.
Example 24
In the same manner as in example 1, except that 6.43g of diphenyl carbonate and 4.07g of isosorbide were used as starting materials, the transesterification temperature was 120 ℃ and the conditions were not changed, a polymer was obtained at a yield of 99%. The reaction product was characterized to give a polycarbonate having a number average molecular weight of 84300 g/mol.
Example 25
In the same manner as in example 1, except that 6.43g of diphenyl carbonate and 5.83g of tetraethylene glycol were used as starting materials, a polymer was obtained in a yield of 88%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 52800 g/mol.
Example 26
In the same manner as in example 1, except that 6.43g of diphenyl carbonate and 4.51g of triethylene glycol were used as starting materials, a polymer was obtained in a yield of 95%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 102500 g/mol.
Example 27
In the same manner as in example 1, except that 6.43g of diphenyl carbonate and 3.18g of diethylene glycol were used as starting materials, a polymer was obtained in a yield of 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 70600 g/mol.
Example 28
The procedure is as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 6.85g of 1, 3-propanediol were used as starting materials. The remaining conditions were unchanged to give a copolymer with a yield of 94%. The reaction product was characterized to give a polycarbonate copolymer having a number average molecular weight of 41000 g/mol.
Example 29
The procedure is as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 6.85g of 1, 2-propanediol were used as starting materials. The remaining conditions were unchanged to give a copolymer in 88% yield. The reaction product was characterized to give a polycarbonate copolymer having a weight average molecular weight of 26100 g/mol.
Example 30
The procedure is as in example 1, except that 64.23g of diphenyl carbonate, 30.67g of isosorbide and 5.59g of ethylene glycol are used as starting materials. The remaining conditions were unchanged to give a copolymer with a yield of 86%. The reaction product was characterized to give a polycarbonate copolymer having a weight average molecular weight of 52000 g/mol.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a high molecular weight high-flexibility bio-based polycarbonate copolymer is characterized in that the structural formula of the polycarbonate copolymer is as follows:
wherein R is1、R2Is selected from C3H6、C4H8、C5H10、C6H12、CH2CH(CH3)、CH2CH(CH3)CH2、(CH3)2C(CH2)2、(CH3)CHCH2、(CH3)CHCH2CH2、(CH3)CHCH2CH2、CH2C(CH3)CH2And CH (CH)3)CH2CH(CH3) N is a natural number of 20 or less, and n is not 0;
x and y are the number of the repeating units in the product, can be the same or different, are not zero at the same time, and are natural numbers of 0-100;
the preparation method of the high-molecular-weight high-flexibility bio-based polycarbonate copolymer comprises the steps of taking carbonic acid diester and dihydroxy compounds as raw materials, heating to 90-150 ℃ under nitrogen atmosphere and normal pressure, adding a catalyst, and reacting for 1-5 hours to obtain a polycarbonate prepolymer; then gradually heating to 200-260 ℃, reacting for 0.5-6 h when the pressure of the reaction system is less than 50pa, and obtaining a polycarbonate copolymer after the reaction is finished; the molecular weight of the copolycarbonate is 2.5 x 104～12.1×104g/mol；
The catalyst is selected from an ionic liquid catalyst or a metal catalyst, wherein cations in the ionic liquid catalyst are selected from any one of imidazole cations, piperidine cations and pyridine cations; the metal catalyst is at least one of lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, zinc acetylacetonate, dibutyltin oxide, tetrabutyl titanate, tetraisopropyl titanate, carbonate, acetate, alkaline earth metal, TBD or DBU;
the catalyst is used in an amount of 1X 10 times the molar amount of the carbonate-5～1.3×10-4The molar ratio of the dihydroxy compound to the carbonic acid diester is 1 (1-30).
2. The method for preparing a high molecular weight high flexibility bio-based polycarbonate copolymer according to claim 1, wherein: the carbonic acid diester is selected from any one or a mixture of more of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate.
3. The method for preparing a high molecular weight high flexibility bio-based polycarbonate copolymer according to claim 1, wherein: the dihydroxy compound is at least one of 1,4:3, 6-diglycidyl hexanol or aliphatic dihydroxy compound.
4. The method of claim 1, wherein the 1,4:3, 6-dianhydrohexitol is at least one selected from the group consisting of isosorbide, isomannide, and isoidide.
5. The method for preparing a high molecular weight high flexibility bio-based polycarbonate copolymer according to claim 1, wherein: the aliphatic dihydroxy compound is at least one selected from the group consisting of tetraethylene glycol, triethylene glycol, diethylene glycol, and tripropylene glycol.
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| CN102666677A (en) * | 2009-11-19 | 2012-09-12 | 三菱化学株式会社 | Polycarbonate resin film, transparent film, and process for producing same |
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| CN107573497A (en) * | 2017-09-30 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of method that makrolon is prepared based on ionic liquid efficient catalytic |
| CN108727578A (en) * | 2018-03-15 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of preparation method of isobide base makrolon |
| CN110003458A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院成都有机化学有限公司 | A kind of load type solid body base catalyst and its application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102666677A (en) * | 2009-11-19 | 2012-09-12 | 三菱化学株式会社 | Polycarbonate resin film, transparent film, and process for producing same |
| CN105949451A (en) * | 2016-07-14 | 2016-09-21 | 中国科学院过程工程研究所 | Method for preparing polycarbonate through basic ionic liquid catalysis |
| CN107573497A (en) * | 2017-09-30 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of method that makrolon is prepared based on ionic liquid efficient catalytic |
| CN108727578A (en) * | 2018-03-15 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of preparation method of isobide base makrolon |
| CN110003458A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院成都有机化学有限公司 | A kind of load type solid body base catalyst and its application |
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