CN110982054B - Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate - Google Patents
Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate Download PDFInfo
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- CN110982054B CN110982054B CN201911384859.6A CN201911384859A CN110982054B CN 110982054 B CN110982054 B CN 110982054B CN 201911384859 A CN201911384859 A CN 201911384859A CN 110982054 B CN110982054 B CN 110982054B
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 92
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 24
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 21
- 150000001413 amino acids Chemical class 0.000 claims abstract description 17
- -1 imidazole cations Chemical class 0.000 claims description 48
- 238000005809 transesterification reaction Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 22
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- 229960002479 isosorbide Drugs 0.000 claims description 20
- 235000001014 amino acid Nutrition 0.000 claims description 17
- 229940024606 amino acid Drugs 0.000 claims description 17
- 239000000920 calcium hydroxide Substances 0.000 claims description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 15
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 14
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
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- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
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- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 2
- DCBVRWAFSWCCCH-UHFFFAOYSA-N [3-(hydroxymethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalen-2-yl]methanol Chemical compound C1CCCC2CC(CO)C(CO)CC21 DCBVRWAFSWCCCH-UHFFFAOYSA-N 0.000 claims description 2
- RABVYVVNRHVXPJ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-adamantyl]methanol Chemical compound C1C(C2)CC3CC1(CO)CC2(CO)C3 RABVYVVNRHVXPJ-UHFFFAOYSA-N 0.000 claims description 2
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 claims description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 2
- RIBGZYZMHIANTO-UHFFFAOYSA-N [5-(hydroxymethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalen-1-yl]methanol Chemical compound OCC1CCCC2C(CO)CCCC21 RIBGZYZMHIANTO-UHFFFAOYSA-N 0.000 claims description 2
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/302—General preparatory processes using carbonates and cyclic ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
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- C08G64/307—General preparatory processes using carbonates and phenols
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Abstract
The invention relates to a composite catalyst for catalytically synthesizing polycarbonate and a method for catalytically synthesizing polycarbonate. The composite catalyst comprises a nano catalyst and an amino acid ionic liquid catalyst, and is used for an ester exchange reaction stage and a polycondensation reaction stage for synthesizing polycarbonate, wherein the nano catalyst is an oxide and/or a hydroxide. The composite catalyst selected by the invention has the advantages of excellent catalytic performance, good thermal stability, low residue and the like, and successfully solves the problem of polycarbonate synthesized by the traditional method; fries rearrangement reaction is effectively inhibited, and side reaction is reduced, so that high-quality polycarbonate is synthesized, and the application of the polycarbonate in high-end products is met; and the synthetic process is green and environment-friendly, and does not contain highly toxic raw material products such as phosgene and the like.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a composite catalyst for catalytically synthesizing polycarbonate and a method for catalytically synthesizing polycarbonate.
Background
Polycarbonate (PC) is the only thermoplastic plastic with good transparency in five general engineering plastics, has the advantages of good weather resistance, high toughness and the like, and is widely applied to the fields of electronic and electric appliances, building materials, automobile manufacturing, aerospace and the like. At present, the method for producing the polycarbonate mainly comprises the traditional interface phosgene method and the molten ester exchange method, wherein the traditional interface phosgene method for producing the bisphenol A polycarbonate not only uses the phosgene which is a highly toxic raw material, but also needs a large amount of dichloromethane solvent, generates a large amount of waste water to be treated, and causes serious influence on the environment. The melt transesterification method avoids the use of virulent phosgene and a large amount of methylene dichloride solvent, has small environmental pollution, and is green and environment-friendly, so the melt transesterification method becomes an important way for producing the polycarbonate in recent years.
Although the melt transesterification method is an environmentally friendly process for preparing polycarbonate, it is still difficult to prepare polycarbonate having a high molecular weight. Because the viscosity of the reactants is increased in the process of increasing the molecular weight of the polycarbonate along with the progress of the polymerization reaction under the conditions of high temperature and high pressure, the problems of overhigh local reaction temperature and the like are inevitably generated, more side reactions are caused, and the problems of thermal decomposition, dark color and the like of the polycarbonate are caused by overhigh temperature, thereby seriously affecting the quality of products. Therefore, the development of a high-activity catalytic system is crucial to the product quality of polycarbonate, and a high-efficiency catalytic system capable of synthesizing high-quality polycarbonate and enabling the product to have good color needs to be developed.
At present, catalysts for synthesizing PC are reported to mainly comprise alkaline metal salt catalysts, heterocyclic nitrogen-containing catalysts, quaternary ammonium, quaternary phosphine, imidazole catalysts and the like. CN101125917 discloses the use of acetylacetone compounds and nitrogen-containing compounds as catalysts; CN 10594949451 discloses quaternary amine, quaternary phosphine catalysts as catalysts; CN109206606 discloses the use of imidazole amino acid ionic liquids as catalysts; CN109021221 discloses a nitrogen-containing heterocycle and inorganic nano-material composite catalyst as a catalyst; CN105085895 discloses a composite catalyst using acetylacetone compound and quaternary ammonium, quaternary phosphonium compound as catalyst; US2003022659 discloses the use of a quaternary phosphonium salt in combination with sodium hydroxide as a catalyst. However, these catalysts are difficult to activate the hydroxyl functional group of dihydroxy compounds during the synthesis of polycarbonate, so that the product quality, especially the synthesis of high quality polycarbonate and the color improvement are desired to be improved.
Therefore, there is a need in the art to develop a novel catalyst for catalytically synthesizing polycarbonate material, which has excellent catalytic performance, and the polycarbonate material catalytically synthesized by using the catalyst has better quality.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a composite catalyst for catalytically synthesizing polycarbonate and a method for catalytically synthesizing polycarbonate. The composite catalyst has the advantages of excellent catalytic performance, good thermal stability, low residue and the like, and the prepared polycarbonate product has better quality, and the synthesis process is green and environment-friendly and does not contain highly toxic raw material products such as phosgene and the like.
The invention aims to provide a composite catalyst for catalytically synthesizing polycarbonate, which comprises a nano catalyst and an amino acid ionic liquid catalyst, wherein the composite catalyst is used for a transesterification reaction stage and a polycondensation reaction stage for synthesizing the polycarbonate, and the nano catalyst is an oxide or a hydroxide.
The invention selects a composite catalyst catalysis system of a nano catalyst and amino acid ionic liquid to catalyze and synthesize polycarbonate, adopts the ionic liquid as the catalyst, and can better activate carbonyl and hydroxyl of carbonic diester and dihydroxy compounds due to the ionic liquid, so that the reaction activity of polymerization monomers can be improved, the polymerization reaction is facilitated, and meanwhile, the ionic liquid catalyst can be completely or partially degraded into micromolecules in the final polymerization stage and is removed together with phenol in vacuum, so that the residual quantity of the catalyst is reduced; the nano catalyst is selected as the catalyst, and has excellent thermal stability, so that the polymerization effect in the polycondensation stage can be effectively improved, the polycarbonate with high molecular weight can be synthesized, and meanwhile, the nano catalyst can be used as a polycarbonate additive without influencing the product quality. Through the synergistic effect of the two catalysts, fries rearrangement reaction can be effectively inhibited, and the occurrence of side reaction is reduced, so that high-quality polycarbonate (the number average molecular weight can reach 89000) is synthesized, and the application of the polycarbonate on high-end products is met.
The composite catalyst is used for an ester exchange reaction stage and a polycondensation reaction stage for synthesizing polycarbonate, namely, an amino acid ionic liquid catalyst is selected as a catalyst of the ester exchange stage, a nano catalyst is used as a catalytic system of the composite catalyst of the polycondensation stage to catalyze and synthesize the polycarbonate, and the ionic liquid is used as the ester exchange catalyst, so that the ionic liquid can better activate carbonyl and hydroxyl of carbonic diester and dihydroxy compounds, thereby improving the polymerization effect and reducing side reactions; however, the ionic liquid may be partially decomposed at high temperature to affect the polymerization reaction, so that the nano catalyst with better stability is adopted as the catalyst in the polycondensation stage, the polymerization effect can be effectively improved, and the polycarbonate with high molecular weight can be synthesized. The composite catalyst selected by the invention has excellent catalytic performance, good thermal stability and low residue, successfully overcomes the problem of polycarbonate synthesized by the traditional method, and the prepared polycarbonate product has higher quality, is green and environment-friendly in synthesis process, and does not contain highly toxic raw material products such as phosgene and the like.
Preferably, the nano-catalyst comprises any one or a combination of at least two of nano-calcium hydroxide, nano-zinc oxide, nano-titanium dioxide, nano-silicon dioxide, nano-zirconium oxide and nano-cerium dioxide.
Preferably, the particle size of the nano-catalyst is 10-100 nm, such as 15nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90 nm.
Preferably, the cation in the amino acid ionic liquid catalyst is any one or a combination of at least two of quaternary ammonium cations, quaternary phosphine cations, imidazole cations, piperidine cations and pyridine cations, preferably any one of quaternary ammonium cations, pyridine cations, piperidine cations or imidazole cations, and more preferably is 1-ethyl-3-methylimidazole cation, 1-propyl-3-methylimidazole cation, 1-butyl-3-methylimidazole cation, 1-pentyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-benzyl-3-methylimidazole cation, 1-ethyl acetate-3-methylimidazole cation, 1-allyl-3-methylimidazole cation, piperidine cations and pyridine cations, and the like, 1-2 (hydroxyethyl) -3-methylimidazolium cation, tetraethylammonium cation, tetrabutylammonium cation, choline cation, tetrabutylphosphine cation, trihexyl (tetradecyl) phosphine cation, N-ethylpyridine cation or N-butyl-N-methylpiperidine cation.
Preferably, the anion in the amino acid-based ionic liquid catalyst is any one or a combination of at least two of glycine anion, alanine anion, valine anion, leucine anion, isoleucine anion, phenylalanine anion, proline anion, tryptophan anion, tyrosine anion, serine anion, cysteine anion, methionine anion, aspartic acid anion, glutamic acid anion, lysine anion, arginine anion, and histidine anion, preferably any one of lysine anion, threonine anion, valine anion, alanine anion, serine anion, histidine anion, or aspartic acid anion combination.
The amino acid ionic liquid catalyst adopted by the invention can better activate carbonyl and hydroxyl of carbonic diester and dihydroxy compound, thereby improving the reaction activity of the polymerization monomer and being beneficial to the polymerization reaction.
Another object of the present invention is to provide a method for preparing a polycarbonate, comprising: under the condition that the composite catalyst for catalyzing and synthesizing the polycarbonate exists, the dihydroxy compound and the carbonic diester are subjected to an ester exchange reaction stage and a polycondensation reaction stage in sequence to obtain the polycarbonate.
The invention adopts the synergy of two catalystsEffectively inhibits fries rearrangement reaction and reduces side reaction, thereby synthesizing high-quality polycarbonate (the number average molecular weight can reach 89000), and the molecular weight of the finally prepared polycarbonate is 1.0 multiplied by 104～1.8×105g/mol, the glass transition temperature is 150-175 ℃, and the application of the polycarbonate in high-end products is met.
The formula of the reaction for synthesizing polycarbonate by using dihydroxy compound and carbonic diester as raw materials is as follows:
wherein R is1Alkylene, a total number of carbon atoms in the main chain of 2-10, cycloalkylene or an aromatic group; r2Is benzene ring or linear alkyl such as methyl, ethyl or propyl; m and n are the molar ratio of the two hydroxyl compounds, m and n cannot be 0 at the same time, and m and n are any integers from 0 to 50.
Preferably, the nano-catalyst and the amino acid ionic liquid catalyst in the composite catalyst are added simultaneously in the ester exchange reaction stage;
or, the amino acid ionic liquid catalyst is added in the stage of ester exchange reaction, and the nano catalyst is added in the stage of polycondensation reaction.
Preferably, the temperature in the transesterification stage is 80 to 180 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ or 170 ℃.
Preferably, the time of the transesterification reaction stage is 0.1 to 6 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or 5.5 hours, and the like.
Preferably, the atmosphere of the transesterification reaction stage is a nitrogen atmosphere.
Preferably, the transesterification reaction stage is carried out at atmospheric pressure.
Preferably, the temperature in the polycondensation reaction stage is 180 to 300 ℃, such as 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃ or 290 ℃.
Preferably, the time of the polycondensation reaction stage is 0.1 to 6 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or 5.5 hours, and the like.
Preferably, the pressure in the polycondensation reaction stage is 20 to 120Pa, such as 25Pa, 30Pa, 35Pa, 40Pa, 45Pa, 50Pa, 55Pa, 60Pa, 65Pa, 70Pa, 75Pa, 80Pa, 85Pa, 90Pa or 95Pa, 100Pa, 105Pa, 110Pa or 115 Pa.
Preferably, the carbonic acid diester includes any one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dioctyl carbonate, and diphenyl carbonate, or a combination of at least two thereof.
Preferably, the dihydroxy compound comprises any one of isosorbide, isomannide, isoidide, an aliphatic dihydroxy compound, and an aromatic dihydroxy compound, or a combination of at least two thereof.
Preferably, the aromatic dihydroxy compound comprises 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 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, 4' -dihydroxytetraphenylmethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2, 9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, Any one or a combination of at least two of 2, 2-bis (4-hydroxyphenyl) propane and hydroquinone.
Preferably, the aliphatic dihydroxy compound includes ethylene glycol, 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, 2-methyl-1, 4-cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, isosorbide, hydrogenated dioleyl glycol, 2-ethyl-1, 6-hexanediol, 2, 4-trimethyl-1, 6-hexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, any one or a combination of at least two of 4-cyclohexanedimethanol, 1, 5-decalindimethanol, 2, 3-decalindimethanol, 2, 6-decalindimethanol, 2, 3-norbornanedimethanol, 2, 5-norbornanedimethanol and 1, 3-adamantanedimethanol.
Preferably, the molar ratio of dihydroxy compound to carbonic acid diester is 1 (0.5-10), preferably 1 (0.95-5), such as 1:0.6, 1:0.8, 1: 0.95, 1:1, 1: 1.05, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9, etc.
Preferably, the composite catalyst is used in an amount of 1X 10 based on 1mol of the dihydroxy compound-9～1×10- 2mol, e.g. 1X 10-8mol、1×10-7mol、1×10-6mol、1×10-5mol、1×10-4mol or 1X 10-3mol, and the like.
Preferably, the molar ratio of the amino acid ionic liquid catalyst to the nano catalyst in the composite catalyst is 1 (10)-410), e.g. 1:10-4mol、1:10-3mol、1:10-2mol, 1:0.1mol, 1:1mol, 1:2mol, 1:4mol, 1:6mol, 1:8mol, 1:10mol, or the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite catalyst selected by the invention has excellent catalytic performance, good thermal stability and low residue, successfully overcomes the problem of polycarbonate synthesized by the traditional method, prepares a high-quality polycarbonate product, is green and environment-friendly in synthesis process, and does not contain highly toxic raw material products such as phosgene and the like.
(2) The invention effectively inhibits fries rearrangement reaction and reduces side reaction by the synergistic action of the two catalysts, thereby synthesizing high-quality polycarbonate (the number average molecular weight can reach 89000), and the finally prepared polycarbonate has the molecular weight of 1.0 multiplied by 104～1.8×105g/mAnd the glass transition temperature of the ol is 150-175 ℃, so that the application of the polycarbonate in high-end products is met.
Drawings
FIG. 1 is a drawing showing a polycarbonate resin composition provided in example 1 of the present invention1H-NMR spectrum.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. 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
A method for preparing polycarbonate by using a composite catalyst has the following reaction equation:
the method comprises the following steps:
4.38g of isosorbide and 6.42g of diphenyl carbonate (isosorbide: diphenyl carbonate: 1, molar ratio) were put into a 250mL three-necked glass flask equipped with a mechanical stirrer under nitrogen atmosphere, heated to 130 ℃ and charged with 5X 10-5mol of 1-ethyl-3-methylimidazole lysine ethanol solution and nano zinc oxide composite catalyst (the molar ratio of 1-ethyl-3-methylimidazole lysine to nano zinc is 1:10-9) And carrying out ester exchange reaction for 0.5h in a nitrogen atmosphere at normal pressure to synthesize a prepolymer, then increasing the reaction temperature to 180 ℃, adjusting the temperature to 240 ℃ and gradually reducing the pressure, reducing the vacuum degree to 100Pa, and carrying out polycondensation reaction for 0.5h to finally obtain the polycarbonate, wherein the number average molecular weight is 113000g/mol, and the molecular weight distribution is 1.63.
FIG. 1 shows a polycarbonate obtained in the present example1The H-NMR spectrum showed that the peaks at δ 4.07, 5.11, 4.89, 4.54, 5.07 and 3.91ppm of isosorbide moieties in the repeating units were assigned to H-1, H-2, H-3, H-4, H-5 and H-6, respectively. The peaks of the terminal functional groups were assigned to the hydrogen atoms c, e and a at δ 4.39, 3.58 and 7.38ppm, respectively. Hydrogen atom c is the peak of the external hydroxyl group of isosorbide at the end of the polymer, and hydrogen atome is the peak of the hydroxyl groups in isosorbide at the end of the polymer. Nuclear magnetism also proves that the ionic liquid can activate the internal hydroxyl of isosorbide to enable the internal hydroxyl/external hydroxyl<1。
Example 2
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol nano zinc oxide and 1-ethyl-3-methylimidazolamine composite catalyst (1-ethyl-3-methylimidazolamine: nano zinc oxide ═ 1:10-5) The polycarbonate obtained had a number average molecular weight of 88000g/mol and a molecular weight distribution of 1.59.
Example 3
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of nano-cerium dioxide and 1-ethyl-3-methylimidazole tryptophan composite catalyst (the molar ratio of 1-ethyl-3-methylimidazole tryptophan to nano-cerium dioxide is 1: 10)-7) The polycarbonate obtained had a number average molecular weight of 82000g/mol and a molecular weight distribution of 1.65.
Example 4
The difference from example 1 is that the transesterification stage is charged with 5X 10-5mol of nano-cerium dioxide and 1-ethyl-3-methylimidazolium aspartic acid composite catalyst (the molar ratio of 1-ethyl-3-methylimidazolium aspartic acid to nano-cerium dioxide is 1: 10)-2) The obtained polycarbonate had a number average molecular weight of 79000g/mol and a molecular weight distribution of 1.61.
Example 5
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol tetraethyl ammonium alanine and nano cerium dioxide composite catalyst (the mol ratio of tetraethyl alanine to nano cerium dioxide is 1: 10)-9) The polycarbonate obtained had a number average molecular weight of 91000g/mol and a molecular weight distribution of 1.67.
Example 6
The transesterification stage is followed by addition of 5X 10-5mol of N-ethylpyridine lysine and nano-cerium dioxide composite catalyst (the molar ratio of the N-ethylpyridine lysine to the nano-cerium dioxide is 1: 10)-4) The polycarbonate obtained had a number average molecular weight of 69000g/mol and a molecular weight distribution of1.59。
Example 7
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5The mol ratio of the 1-2 (hydroxyethyl) -3-methylimidazolitone to the nano-cerium dioxide composite catalyst (1-2 (hydroxyethyl) -3-methylimidazolitone: nano-cerium dioxide is 1:10-3) The polycarbonate obtained had a number average molecular weight of 94000g/mol and a molecular weight distribution of 1.62.
Example 8
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol trihexyl (tetradecyl) phosphine threonine glutamic acid and nano calcium hydroxide composite catalyst (the molar ratio of trihexyl (tetradecyl) phosphine threonine to nano calcium hydroxide is 1:10-6) The polycarbonate obtained had a number average molecular weight of 89000g/mol and a molecular weight distribution of 1.58.
Example 9
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-4mol choline valine and nano calcium hydroxide composite catalyst (the mol ratio of choline valine to nano calcium hydroxide is 1:10-2) The obtained polycarbonate had a number average molecular weight of 75000g/mol and a molecular weight distribution of 1.65.
Example 10
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol tetraethyl ammonium lysine and nano cerium dioxide composite catalyst (the molar ratio of tetraethyl lysine to nano cerium dioxide is 1: 10)-2) The polycarbonate obtained had a number average molecular weight of 87000g/mol and a molecular weight distribution of 1.59.
Example 11
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of 1-ethyl-3-methylimidazolium glutamic acid and nano calcium hydroxide composite catalyst (the molar ratio of 1-ethyl-3-methylimidazolium glutamic acid to nano calcium hydroxide is 1: 10)-9) The polycarbonate obtained had a number average molecular weight of 65000g/mol and a molecular weight distribution of 1.52.
Example 12
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of composite catalyst of tetrabutyl phosphine lysine and nano cerium dioxide (the molar ratio of tetrabutyl phosphine lysine to nano cerium dioxide is 1: 10)-9) The polycarbonate obtained had a number average molecular weight of 91000g/mol and a molecular weight distribution of 1.64.
Example 13
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of tetrabutyl phosphine glycine and nano calcium hydroxide composite catalyst (the molar ratio of tetrabutyl phosphine glycine to nano calcium hydroxide is 1: 10)-5) The polycarbonate obtained had a number average molecular weight of 88000g/mol and a molecular weight distribution of 1.58.
Example 14
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of N-butyl-N-methylpiperidine lysine and nano cerium dioxide composite catalyst (the molar ratio of N-butyl-N-methylpiperidine lysine to nano cerium dioxide is 1: 10)-5) The polycarbonate obtained had a number average molecular weight of 69000g/mol and a molecular weight distribution of 1.68.
Example 15
The difference from example 1 is that the transesterification stage is supplemented with 5X 10-5mol of N-butylpyridinyl lysine and nano-cerium dioxide composite catalyst (the molar ratio of N-butylpyridinyl lysine to nano-cerium dioxide is 1: 10)-3) The polycarbonate obtained had a number average molecular weight of 67000g/mol and a molecular weight distribution of 1.51.
Example 16
The difference from example 1 is that the polycondensation time is 1h, the number-average molecular weight of the polycarbonate obtained is 121000g/mol and the molecular weight distribution is 1.72.
Example 17
The difference from example 1 is that the polycondensation time is 2h, the number-average molecular weight of the polycarbonate obtained is 117000g/mol and the molecular weight distribution is 1.77.
Example 18
The difference from example 1 is that the polycondensation temperature is 280 ℃ and the polycarbonate obtained has a number-average molecular weight of 121000g/mol and a molecular weight distribution of 1.71.
Example 19
The difference from example 1 is that the polycondensation temperature is 250 ℃ and the polycarbonate obtained has a number average molecular weight of 123000g/mol and a molecular weight distribution of 1.68.
Example 20
The difference from example 1 is that the polycondensation temperature is 220 ℃ and the polycarbonate obtained has a number-average molecular weight of 89000g/mol and a molecular weight distribution of 1.58.
Example 21
The difference from example 1 is that when isosorbide (4.38g) was replaced with isomannide (4.38g), a polycarbonate having a number average molecular weight of 74000g/mol and a molecular weight distribution of 1.74 was obtained.
Example 22
The difference from example 1 is that when isosorbide (4.38g) was replaced with bisphenol A (6.85g), polycarbonate having a number average molecular weight of 63000g/mol and a molecular weight distribution of 1.65 was obtained.
Example 23
The difference from example 1 is that isosorbide (4.38g) and diphenyl carbonate (4.49g) isosorbide: diphenyl carbonate at a molar ratio of 1: 0.7), the number average molecular weight was 39000g/mol and the molecular weight distribution was 1.68, all conditions remaining unchanged.
Example 24
The difference from example 1 was that isosorbide (3.06g) and diphenyl carbonate (6.42g) (isosorbide: diphenyl carbonate: 0.7:1, molar ratio) were used as starting materials, and the number average molecular weight was 41000g/mol and the molecular weight distribution was 1.55, without changing the other conditions.
Example 25
A method for preparing polycarbonate by using a composite catalyst has the following reaction equation:
the implementation method comprises the following steps: under nitrogen atmosphere, 2.19g of isosorbide, 6.42g of diphenyl carbonate and 1.35g of 1, 4-butanediol were added with mechanical stirringInto a 250mL three-necked glass flask, heated to 130 ℃ and charged with 5X 10-6mol of 1-butyl-3-methylimidazolium lysine and nano calcium hydroxide composite catalyst (the molar ratio of 1-butyl-3-methylimidazolium lysine to nano calcium hydroxide is 1:10-9) And carrying out ester exchange reaction for 0.5h in a nitrogen atmosphere at normal pressure to synthesize a prepolymer, reacting for 1h at 180 ℃, slowly raising the reaction temperature to 240 ℃, reducing the vacuum degree to 100Pa, and reacting for 1h to obtain the polycarbonate with the number average molecular weight of 49000g/mol and the molecular weight distribution of 1.63.
Example 26
A method for preparing polycarbonate by using a composite catalyst comprises the following steps:
2.19g of isosorbide, 6.42g of diphenyl carbonate and 2.16g of 1, 4-cyclohexanedimethanol were added under nitrogen to a 250mL three neck glass flask equipped with mechanical stirring, heated to 130 ℃ and charged with 5X 10-6The tetrabutyl phosphine lysine and nano calcium hydroxide composite catalyst (the molar ratio of tetrabutyl phosphine lysine to nano calcium hydroxide is 1: 10)-9) And (3) carrying out ester exchange reaction for 0.5h in a nitrogen atmosphere at normal pressure to synthesize a prepolymer, slowly raising the reaction temperature to 240 ℃ after 1h at 180 ℃, reducing the vacuum degree to 100Pa, and reacting for 1h to obtain the polycarbonate with the number average molecular weight of 64000g/mol and the molecular weight distribution of 1.66.
Example 27
A method for preparing polycarbonate by using a composite catalyst comprises the following steps:
3.42g of bisphenol A, 6.42g of diphenyl carbonate, 2.61g of 1, 10-decanediol were placed in a 250mL three-neck glass flask equipped with mechanical stirring under nitrogen, heated to 130 ℃ and charged with 5X 10-6mol 1-butyl-3-methylimidazolamine ethanol and nano calcium hydroxide composite catalyst (the molar ratio of 1-butyl-3-methylimidazolamine to nano calcium hydroxide is 1:10-9) And carrying out ester exchange reaction for 0.5h in a nitrogen atmosphere at normal pressure to synthesize a prepolymer, slowly raising the reaction temperature to 240 ℃ after 1h at 180 ℃, reducing the vacuum degree to 100Pa, and reacting for 1h to obtain the polycarbonate with the number average molecular weight of 73000g/mol and the molecular weight distribution of 1.61.
Example 28
A method for preparing polycarbonate by using a composite catalyst comprises the following steps:
2.19g of isosorbide, 6.42g of diphenyl carbonate, 2.07g (0.015mol) of 1, 4-terephthalyl alcohol were placed in a 250mL three-necked glass flask equipped with a mechanical stirrer under nitrogen, heated to 130 ℃ and charged with 5X 10-6mol of 1-butyl-3-methylimidazolium glutamic acid and nano-cerium dioxide (the molar ratio of 1-butyl-3-methylimidazolium glutamic acid to nano-cerium dioxide is 1: 10)-9) And carrying out ester exchange reaction for 0.5h in a nitrogen atmosphere at normal pressure to synthesize a prepolymer, reacting for 1h at 180 ℃, slowly raising the reaction temperature to 240 ℃, reducing the vacuum degree to 100Pa, and reacting for 1h to obtain the polycarbonate with the number average molecular weight of 65000g/mol and the molecular weight distribution of 1.71.
Comparative example 1
The method for preparing polycarbonate by using other compound catalysts has the following reaction equation:
4.38g of isosorbide and 6.42g of diphenyl carbonate were placed in a 250mL three-neck glass flask equipped with mechanical stirring, heated to 130 ℃ and charged with 5X 10 under nitrogen atmosphere-6Performing ester exchange reaction on mol nano calcium carbonate solution for 0.5h in nitrogen atmosphere at normal pressure to synthesize prepolymer, raising the reaction temperature to 180 ℃, and adding 5 multiplied by 10-6mol of imidazo [1,2-a]After pyridine reaction for 1h, the temperature is adjusted to 240 ℃, the pressure is gradually reduced to 100Pa, polycondensation reaction is carried out for 0.5h, and finally the polycarbonate with the number average molecular weight of 45000g/mol and the molecular weight distribution of 1.73 is obtained.
Comparative example 2
A method for preparing polycarbonate by using other compound catalysts comprises the following steps:
4.38g of isosorbide and 6.42g of diphenyl carbonate were placed in a 250mL three-neck glass flask equipped with mechanical stirring, heated to 130 ℃ and charged with 5X 10 under nitrogen atmosphere-6mol of lithium acetylacetonate under nitrogen atmosphere at normal pressureEster exchange reaction is carried out in the enclosure for 0.5h to synthesize prepolymer, then the reaction temperature is raised to 180 ℃ and is replenished with 5 multiplied by 10-6After the reaction of mol tetraethylammonium hydroxide for 1h, adjusting the temperature to 240 ℃ and gradually reducing the pressure to 100Pa, and carrying out polycondensation for 0.5h to finally obtain the polycarbonate with the number average molecular weight of 39000g/mol and the molecular weight distribution of 1.58.
As can be seen from comparison of comparative examples 1-2 with example 1, the number average molecular weight of the obtained polycarbonate is low without the interaction of the composite catalysts of the present invention, and the technical effects of the present invention are not achieved.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
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