CN114177900A - Catalyst for glycerol carbonate, synthesis method and application of glycerol carbonate - Google Patents
Catalyst for glycerol carbonate, synthesis method and application of glycerol carbonate Download PDFInfo
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- CN114177900A CN114177900A CN202111515001.6A CN202111515001A CN114177900A CN 114177900 A CN114177900 A CN 114177900A CN 202111515001 A CN202111515001 A CN 202111515001A CN 114177900 A CN114177900 A CN 114177900A
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- titanate
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- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 114
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 35
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- -1 alkaline earth metal salt Chemical class 0.000 claims description 14
- 150000005677 organic carbonates Chemical class 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910002971 CaTiO3 Inorganic materials 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008035 bio-based plasticizer Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 11
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 2
- 239000004621 biodegradable polymer Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 229920000954 Polyglycolide Polymers 0.000 description 13
- 239000004633 polyglycolic acid Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000004626 polylactic acid Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical group [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000171 calcio olivine Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for glycerol carbonate, a synthesis method and application of glycerol carbonate. A catalyst for glycerol carbonate, said catalyst being a perovskite titanate of formula A2TiO3、BTiO3Or A2‑2xBxTiO3(x is more than or equal to 0 and less than or equal to 1); wherein A is one of Na, K and Cs, and B is one of Mg and Ca. The invention also discloses a synthetic method for glycerol carbonate and glycerol carbonThe use of acid esters. In the technical scheme of the invention, the catalyst has the advantages of high activity and high stability, and provides a new application of the glycerol carbonate for plasticizing the fully biodegradable polymers PLA and PGA.
Description
Technical Field
The invention belongs to the technical field of glycerol carbonate, and particularly relates to a catalyst for glycerol carbonate, a synthesis method and application of glycerol carbonate.
Background
Glycerol Carbonate (GC) as a class of bio-based special chemicals has the characteristics of high boiling point, environmental protection, no toxicity, degradability and the like, and has been widely applied in the fields of organic synthesis, environmental protection, material science and the like. At present, GC can be urea and CO2CO or organic carbonate is obtained by reacting carbonylation reagent and glycerol. Among them, the process of synthesizing GC by transesterification of organic carbonate and glycerol has the advantages of simple process, environmental protection and high yield, thus gaining wide attention.
Currently, GC is synthesized industrially mainly with Na2CO3Strong bases such as NaOH and sodium methoxide are used as homogeneous catalysts. However, the homogeneous catalyst is difficult to separate, a large amount of three-waste pollutants are generated, and the quality of GC is influenced by the residual of the three-waste pollutants in the product. With researches, CaO replaces homogeneous alkali to be used as a catalyst to show excellent catalytic activity in a transesterification synthesis GC process, but CaO is easy to react with glycerol and water to generate inactive new compounds such as calcium glycerolate and the like, and the service life of the catalyst is greatly reduced.
In the prior art, alkali metal and alkaline earth metal are impregnated on the surface of metal oxide by an impregnation method to obtain a supported bimetallic heterogeneous catalyst for ester exchange synthesis GC, the glycerol yield can reach more than 90% under the optimal condition, but the catalytic efficiency is low, and the satisfactory GC yield can be obtained only after 10 hours of reaction. In addition, CaO-Al is used in the prior art2O3-SiO2、Ca2SiO4And KCl/ZIF-90 as catalysts for this reaction, but the catalysts still face lowPoor catalytic activity, low GC selectivity, poor stability and the like. Therefore, the development of a catalyst having both high activity and high stability is particularly important for the synthesis of glycerol carbonate.
Disclosure of Invention
It is a first object of the present invention to provide a catalyst for glycerol carbonate by introducing an alkali/alkaline earth metal oxide to TiO2The perovskite titanate catalyst with high activity and high stability is obtained by the lattice structure, so that the technical problems of difficult catalyst recovery and poor reusability in the process of synthesizing the glycerol carbonate by the existing ester exchange method can be solved.
In order to realize the purpose, the adopted technical scheme is as follows:
a catalyst for glycerol carbonate, said catalyst being a perovskite titanate of formula A2TiO3、BTiO3Or A2-2xBxTiO3(x is more than or equal to 0 and less than or equal to 1); wherein A is one of Na, K and Cs, and B is one of Mg and Ca.
Further, the perovskite type titanate is CaTiO3。
The second object of the present invention is to provide a method for preparing a catalyst for glycerol carbonate.
In order to realize the purpose, the adopted technical scheme is as follows:
the preparation method of the catalyst is a citric acid complexing method.
Further, the citric acid complexation method comprises the following steps: uniformly mixing the solution 1 and the solution 2, evaporating to form yellow gel, and roasting to obtain the catalyst;
wherein, the solution 1 is: adding titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution 1;
the solution 2 is as follows: dissolving alkali/alkaline earth metal salt, citric acid and glacial acetic acid in water, and uniformly stirring to obtain a solution 2.
Still further, the molar ratio of the alkali/alkaline earth metal salt to the citric acid to the glacial acetic acid is 1: 4: 1;
the evaporation temperature is 60-100 ℃;
the roasting temperature is 500-1200 ℃, and the time is 1-10 h;
the alkali/alkaline earth metal salt is NaNO3、KNO3、CsNO3、Mg(NO3)、Ca(NO3)2、CH3COONa、CH3COOK、CH3COCs、Ca(CH3COO)2、Mg(CH3COO)2At least one of;
the titanate is tetraethyl titanate, isopropyl titanate and tetrabutyl titanate.
The third purpose of the invention is to provide a synthetic method for glycerol carbonate, which has the advantages of high GC selectivity, good stability and the like.
In order to realize the purpose, the adopted technical scheme is as follows:
the synthesis method for the glycerol carbonate comprises the following steps: the above catalyst was used for synthesis by the transesterification method.
Further, the ester exchange method comprises the following steps: and (2) uniformly mixing the organic carbonate and the glycerol, adding the catalyst, and carrying out reflux reaction at the temperature of 40-120 ℃ for 1-10h to obtain the glycerol carbonate.
Still further, the organic carbonate is at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, dibutyl carbonate and diphenyl carbonate;
the molar ratio of the organic carbonate to the glycerol is 1-6: 1;
the dosage of the catalyst is 0.1-15 wt% of that of the glycerol.
The fourth object of the present invention is to provide a novel use of glycerol carbonate. According to the structural characteristics of GC, the polylactic acid/polylactic acid copolymer is used as a plasticizer for plasticizing PLA and PGA of full-biodegradable materials, has excellent plasticizing effect and solvent extraction resistance, and also maintains the excellent environmental friendliness of the materials.
In order to realize the purpose, the adopted technical scheme is as follows:
use of glycerol carbonate as a bio-based plasticizer.
Further, the glycerol carbonate is used to plasticize PLA and PGA.
Compared with the prior art, the invention has the beneficial effects that:
1. the perovskite titanate is used as the catalyst, the strong basicity of alkali metal and alkaline earth metal is reserved, the alkali metal/alkaline earth metal and titanium react to generate solid solution, so that the catalyst has excellent stability, and the catalyst has excellent catalytic activity and reusability in the GC synthesis reaction by the ester exchange method.
2. The invention uses the glycerol carbonate to replace esters and polyalcohol plasticizers to plasticize fully biodegradable polymers PLA and PGA, and expands a new application field of the glycerol carbonate. Under the synergistic effect of ester group and hydroxyl bifunctional group, the compatibility and interaction strength of the glycerol carbonate and the ester macromolecules can be obviously improved, the plasticizing effect and excellent extraction resistance of polylactic acid (PLA) and polyglycolic acid (PGA) are enhanced, and the environmental friendliness of the system can be maintained.
Drawings
FIG. 1 is a graph showing the effect of firing temperature on the phase structure of example 9;
FIG. 2 is a graph of the effect of calcination temperature on catalytic activity of example 9;
FIG. 3 is a graph showing the effect of the content of glycerol carbonate on the elongation at break of PLA and PGA in examples 10 and 11.
Detailed Description
In order to further illustrate the catalyst, the synthesis method and the application of the present invention for glycerol carbonate, and to achieve the intended purpose, the following detailed description is given for the catalyst, the synthesis method and the application of glycerol carbonate according to the present invention, together with the preferred embodiments, the detailed description, the structure, the characteristics and the efficacy thereof. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The catalyst, synthesis method and application of glycerol carbonate according to the present invention will be further described in detail with reference to the following specific examples:
the technical scheme of the invention is as follows:
a catalyst for glycerol carbonate, said catalyst being a perovskite titanate of formula A2TiO3、BTiO3Or A2-2xBxTiO3(x is more than or equal to 0 and less than or equal to 1); wherein A is one of Na, K and Cs, and B is one of Mg and Ca.
Preferably, the perovskite type titanate is CaTiO3。
The preparation method of the catalyst is a citric acid complexing method.
Preferably, the citric acid complexation method comprises the following steps: uniformly mixing the solution 1 and the solution 2, evaporating to form yellow gel, and roasting to obtain the catalyst;
wherein, the solution 1 is: adding titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution 1;
the solution 2 is as follows: dissolving alkali/alkaline earth metal salt, citric acid and glacial acetic acid in water, and uniformly stirring to obtain a solution 2.
Further preferably, the molar ratio of the alkali/alkaline earth metal salt to the citric acid to the glacial acetic acid is 1: 4: 1;
the evaporation temperature is 60-100 ℃;
the roasting temperature is 500-1200 ℃, and the time is 1-10 h;
the alkali/alkaline earth metal salt is NaNO3、KNO3、CsNO3、Mg(NO3)、Ca(NO3)2、CH3COONa、CH3COOK、CH3COCs、Ca(CH3COO)2、Mg(CH3COO)2At least one of (1). Preferably Ca (NO)3)2And Ca (CH)3COO)2。
The titanate is one of tetraethyl titanate, isopropyl titanate and tetrabutyl titanate.
The invention adopts high-temperature treatment to introduce alkali/alkaline earth metal into TiO2The composite oxide with the perovskite structure formed by the lattice structure retains the excellent catalytic activity of alkali metal and alkaline earth metal on one hand, can well inhibit the loss of active sites on the other hand, and obviously improves the stability and the reusability of the catalyst.
The synthesis method for the glycerol carbonate comprises the following steps: the above catalyst was used for synthesis by the transesterification method.
Preferably, the ester exchange method comprises the following steps: and (2) uniformly mixing the organic carbonate and the glycerol, adding the catalyst, and carrying out reflux reaction at the temperature of 40-120 ℃ for 1-10h to obtain the glycerol carbonate.
More preferably, the organic carbonate is at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, dibutyl carbonate and diphenyl carbonate;
the molar ratio of the organic carbonate to the glycerol is 1-6: 1;
the dosage of the catalyst is 0.1-15 wt% of that of the glycerol.
Use of glycerol carbonate as a bio-based plasticizer.
Further preferably, the glycerol carbonate is used to plasticize PLA and PGA.
The specific method comprises the following steps: mixing the glycerol carbonate and the high molecular polymer on a high-speed mixer until the mixture is uniform, wherein the mixing temperature is 150 ℃ and 250 ℃, and the mixing time is 10-20min, putting the mixed material into an extruder, and performing extrusion granulation to obtain the glycerol carbonate plasticized high molecular material.
The glycerol carbonate has both ester group and hydroxyl group, is easy to generate hydrogen bond with carbonyl group in polyester high molecular polymer structure, and has the characteristics of ester and polyether polyol compound. In view of special structural characteristics, the invention also uses glycerol carbonate as a plasticizer to replace ester and polyether polyol compounds for plasticizing and modifying PLA and PGA, and improves the flexibility of the polymer. The glycerol carbonate has excellent degradation characteristics, and can be used as a plasticizer to efficiently plasticize and modify a polymer and maintain the environmental friendliness of a system.
In the following examples, the glycerol conversion and glycerol carbonate yield were determined by gas chromatography (GC-2014), and specific methods were referred to in the literature (Applied Catalysis A General,2017,542: 174-181). The catalyst and reaction product are then separated, washed and dried for further performance testing for reusability, as described in Journal of the Taiwan Institute of Chemical Engineers,2018,87: 131-.
Example 1.
The specific operation steps are as follows:
(1) preparing a catalyst:
adding titanate into absolute ethyl alcohol to form a uniform solution 1, and mixing the titanate with the absolute ethyl alcohol according to a molar ratio of 1: 4: dissolving the alkali/alkaline earth metal salt of 1, citric acid and glacial acetic acid in water, uniformly stirring to obtain a solution 2, mixing the solutions 1 and 2 under rapid stirring, and rapidly stirring to form a uniformly mixed solution. Evaporating at 60-100 ℃ to form yellow gel, and roasting the yellow gel at 500-1200 ℃ for 1-10h to obtain the perovskite titanate catalyst.
Wherein the perovskite titanate has a general formula A2TiO3、BTiO3And A2-2xBxTiO3(x is more than or equal to 0 and less than or equal to 1), wherein A is one of Na, K and Cs, and B is one of Mg and Ca.
The alkali/alkaline earth metal salt is NaNO3、KNO3、CsNO3、Mg(NO3)、Ca(NO3)2、CH3COONa、CH3COOK、CH3COOCs、Ca(CH3COO)2And Mg (CH)3COO)2At least one of (1).
The titanate is one of tetraethyl titanate, isopropyl titanate and tetrabutyl titanate.
(2) Synthesis of glycerol carbonate:
adding organic carbonate and glycerol in a certain material ratio into a reactor, heating to a set temperature, uniformly stirring, then adding a perovskite titanate catalyst, and continuously stirring and refluxing at 40-120 ℃ for 1-10h to obtain a glycerol carbonate product.
Wherein the organic carbonate is at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, dibutyl carbonate and diphenyl carbonate.
The molar ratio of organic carbonate to glycerol is 1-6: 1.
The amount of the catalyst is 0.1-15 wt% of the amount of the glycerol.
(3) Applications of
Mixing 10-50 parts of glycerol carbonate and 100 parts of high molecular polymer on a high-speed mixer until the mixture is uniform, wherein the mixing temperature is 150 ℃ and 250 ℃, the mixing time is 10-20min, putting the mixed material into an extruder, and performing extrusion granulation to obtain the glycerol carbonate plasticized high molecular material.
Example 2.
6.81g of tetrabutyl titanate was added to absolute ethanol to form a homogeneous solution 1, the molar ratio was 1: 4: dissolving the calcium nitrate, the citric acid and the glacial acetic acid of the solution 1 in water, and uniformly stirring to obtain a solution 2. And (3) mixing and stirring the solution 1 and the solution 2 under rapid stirring to form a uniform mixed solution, wherein the molar ratio of titanium to calcium in the mixed solution is 1: 1. evaporating at 80 deg.C to form yellow gel, and calcining the yellow gel at 700 deg.C for 3.0h to obtain CaTiO3A catalyst.
Mixing a mixture of 1: 2 glycerol and dimethyl carbonate are put into a reactor, and then CaTiO is added3The catalyst accounts for 3 wt% of the mass of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 2 hours at the temperature of 80 ℃.
Example 3.
Preparation of the catalyst CaTiO was prepared in the same manner as in example 23A catalyst.
Mixing a mixture of 1: 3 glycerol and dimethyl carbonate are put into a reactor, and then CaTiO is added3The catalyst accounts for 5 wt% of the mass of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 5 hours at the temperature of 100 ℃.
Example 4.
The catalyst was prepared as in example 2.
Mixing a mixture of 1: 4 glycerol and dimethyl carbonate are put into a reactor, and then CaTiO is added3The mass of the catalyst is 4 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 3 hours at the temperature of 90 ℃.
Example 5.
The catalyst preparation procedure was the same as in example 2, except that: the potassium nitrate 4.04g is used to replace the calcium acetate to prepare the K2TiO3A catalyst.
Mixing a mixture of 1: 3 glycerol and dimethyl carbonate are fed into a reactor, and then K is added2TiO3The mass of the catalyst is 3 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 2 hours at the temperature of 85 ℃.
Example 6.
The catalyst was prepared as in example 2, with a molar ratio of 1: 5 glycerol and dimethyl carbonate are fed into a reactor, and then CaTiO is added3And the mass of the catalyst is 7 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 4 hours at the temperature of 85 ℃.
Example 7.
6.81g of tetrabutyl titanate was added to absolute ethanol to form a homogeneous solution 1, the molar ratio was 0.4: 1.2: 4: dissolving the calcium acetate, the potassium nitrate, the citric acid and the glacial acetic acid of the solution 1 in water, and uniformly stirring to obtain a solution 2. Then under the condition of rapid stirring, mixing and stirring the solution 1 and the solution 2 to form a uniform mixed solution, evaporating at 80 ℃ to form yellow gel, roasting the yellow gel at 700 ℃ for 3.0h to obtain K1.2Ca0.4TiO3A catalyst.
Mixing a mixture of 1: 2 glycerol and dimethyl carbonate are fed into a reactor, and then K is added1.2Ca0.4TiO3The mass of the catalyst is 3 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 2 hours at the temperature of 80 ℃.
Example 8.
The catalyst was prepared as in example 2.
Mixing a mixture of 1: 3 isPutting glycerol and diethyl carbonate into a reactor, uniformly mixing, and adding CaTiO3And the mass of the catalyst is 7 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 2 hours at the temperature of 80 ℃.
Example 9.
5.71g of isopropyl titanate was added to absolute ethanol to form a homogeneous solution 1, the molar ratio was 1: 4: dissolving the calcium acetate, the citric acid and the glacial acetic acid of the solution 1 in water, and uniformly stirring to obtain a solution 2. Under rapid stirring, the solution 1 and the solution 2 are mixed and stirred to form a uniform mixed solution. Evaporating at 80 deg.C to form yellow gel, and calcining the yellow gel at set temperature (500, 600, 700, 800, 900, 1000, 1100 deg.C) for 3.0h to obtain CaTiO3A catalyst.
Mixing a mixture of 1: 3, adding glycerol and dimethyl carbonate into a reactor, and then adding CaTiO at different roasting temperatures3The mass of the catalyst is 3 wt% of that of the glycerol, and the glycerol carbonate product can be obtained after reflux reaction for 2 hours at the temperature of 80 ℃.
The results of phase structure analysis of the catalysts at different calcination temperatures are shown in FIG. 1, and when the temperature is over 600 ℃, CaO enters TiO2Formation of lattice structure CaTiO3CaO-TiO formed at 500-600 ℃2A composite oxide.
The yield of the glycerol carbonate was measured by the catalytic reaction of the catalyst at different calcination temperatures, and the results are shown in FIG. 2. From FIG. 2, it can be seen that the catalyst calcined at 700 ℃ has the best catalytic effect, and the yield corresponding to GC is CaO-TiO25 times of the composite oxide.
Comparative example 1: taking CaO as a catalyst, and mixing the components in a molar ratio of 1: 2, putting the glycerol and the dimethyl carbonate into a reactor, then adding CaO with the glycerol amount of 3 wt%, and carrying out reflux reaction for 2h at the temperature of 80 ℃ to obtain the product glycerol carbonate.
Comparative example 2: with Ba-Li/CeO2As a catalyst, mixing a mixture of 1: 2 into the reactor, and then adding Ba-Li/CeO with the amount of glycerol being 3 wt%2Reflux reaction at 80 deg.c for 2 hr to obtain sweet productAn oily carbonate.
TABLE 1 catalytic Performance and stability of the catalysts in the different examples
| Examples | Glycerol conversion (%) | GC yield (%) | GC yield after five-time reuse (%) |
| Example 2 | 88.3 | 87.5 | 86.8 |
| Example 3 | 99.8 | 98.7 | 96.4 |
| Example 4 | 99.6 | 98.4 | 92.9 |
| Example 5 | 98.9 | 97.4 | 93.3 |
| Example 6 | 92.5 | 91.3 | 84.4 |
| Example 7 | 96.7 | 95.4 | 93.6 |
| Example 8 | 88.1 | 86.5 | 78.5 |
| Example 9 | 87.4 | 86.3 | 79.4 |
| Comparative example 1 | 95.6 | 88.4 | 35.6 |
| Comparative example 2 | 75.4 | 73.7 | 36.4 |
As is apparent from table 1, the perovskite titanate prepared according to the present invention shows not only excellent catalytic activity but also excellent stability in the ester exchange process synthesis GC reaction, as compared to CaO and the supported catalyst. Compared with the existing catalyst, the catalyst system of the invention has the advantages of high activity and good reusability, and can still maintain good catalytic activity after being used for many times.
Example 10.
And (3) mixing different amounts of glycerol carbonate with 100 parts of PLA respectively on a high-speed mixer until the mixture is uniform, wherein the mixing temperature is 180 ℃, the mixing time is 15min, putting the mixed material into an extruder, and performing extrusion granulation to obtain the glycerol carbonate plasticized PLA material.
Example 11.
And (3) mixing different amounts of glycerol carbonate and 100 parts of PGA on a high-speed mixer until the mixture is uniform, wherein the mixing temperature is 250 ℃, the mixing time is 10min, feeding the mixed material into an extruder, and performing extrusion granulation to obtain the glycerol carbonate plasticized PGA material.
In examples 9-10, the content of glycerol carbonate was 0, 10, 20, 30, 40, 50%, respectively, and the elongation at break was measured (in a manner conventional in the art), and the results are shown in FIG. 3. As can be seen from fig. 3, the elongation at break of PLA and PGA can be significantly increased after GC is added to PLA, and the plasticizing and toughening effects of GC on PLA and PGA are significant.
Further, in the prior art, PLA is plasticized by adding a plasticizer, and at the same time, PLA cannot be completely degraded. The glycerol carbonate synthesized by the invention has ester group and hydroxyl double-active functional groups, not only can play a good plasticizing effect and excellent extraction resistance for PLA and PGA, but also can maintain the environmental friendliness of the system.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. Catalyst for glycerol carbonate characterized in that said catalyst is a perovskite titanate of formula A2TiO3、BTiO3Or A2-2xBxTiO3(x is more than or equal to 0 and less than or equal to 1); wherein A is one of Na, K and Cs, and B is one of Mg and Ca.
2. The catalyst according to claim 1,
the perovskite type titanate is CaTiO3。
3. The method of claim 1, wherein the method of preparation is citric acid complexation.
4. A process for preparing a catalyst according to claim 3,
the citric acid complexation method comprises the following steps: uniformly mixing the solution 1 and the solution 2, evaporating to form yellow gel, and roasting to obtain the catalyst;
wherein, the solution 1 is: adding titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution 1;
the solution 2 is as follows: dissolving alkali/alkaline earth metal salt, citric acid and glacial acetic acid in water, and uniformly stirring to obtain a solution 2.
5. A process for preparing the catalyst according to claim 4,
the molar ratio of the alkali/alkaline earth metal salt to the citric acid to the glacial acetic acid is 1: 4: 1;
the evaporation temperature is 60-100 ℃;
the roasting temperature is 500-1200 ℃, and the time is 1-10 h;
the alkali/alkaline earth metal salt is NaNO3、KNO3、CsNO3、Mg(NO3)、Ca(NO3)2、CH3COONa、CH3COOK、CH3COCs、Ca(CH3COO)2、Mg(CH3COO)2At least one of;
the titanate is tetraethyl titanate, isopropyl titanate and tetrabutyl titanate.
6. The synthesis method for the glycerol carbonate is characterized by comprising the following steps: the synthesis is carried out by transesterification using the catalyst of claim 1.
7. The synthetic method of claim 6, wherein,
the ester exchange method comprises the following steps: after mixing organic carbonate and glycerol uniformly, adding the catalyst of claim 1, and carrying out reflux reaction at 40-120 ℃ for 1-10h to obtain the glycerol carbonate.
8. The synthesis method according to claim 7,
the organic carbonate is at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, dibutyl carbonate and diphenyl carbonate;
the molar ratio of the organic carbonate to the glycerol is 1-6: 1;
the dosage of the catalyst is 0.1-15 wt% of that of the glycerol.
9. Use of glycerol carbonate as a bio-based plasticizer.
10. Use according to claim 9, characterized in that said glycerol carbonate is used for plasticizing PLA and PGA.
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