CN104387233B - A kind of method of synthesizing tricyclic decane dimethanol - Google Patents
A kind of method of synthesizing tricyclic decane dimethanol Download PDFInfo
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- CN104387233B CN104387233B CN201410710821.4A CN201410710821A CN104387233B CN 104387233 B CN104387233 B CN 104387233B CN 201410710821 A CN201410710821 A CN 201410710821A CN 104387233 B CN104387233 B CN 104387233B
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/822—Rhodium
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
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- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
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Abstract
The present invention relates to a kind of method of synthesizing tricyclic decane dimethanol, the method is at next step hydroformylation dicyclopentadiene synthesizing tricyclic decane dimethanol of effect of catalyzer, catalyzer is the cobalt rhodium copper trimetallic catalyst of Phosphine ligands modification, catalyzer adopts sol-gel method preparation, catalyzer is mainly loaded solid catalyst, preparation process is relatively simple, catalyzer price is relatively low, reaction conditions is relatively gentle, catalytic activity and reaction preference high, reaction times is relatively short, catalyzer and reaction system are convenient to be separated, can reuse, be convenient to amplify and industrial application.By the catalyzer that the method for the invention obtains, the transformation efficiency of dicyclopentadiene can reach more than 99%, and the selectivity of Tricyclodecane Dimethanol can reach more than 90%.
Description
Technical field:
The present invention relates to a kind of method of synthesizing tricyclic decane dimethanol.
Background technology:
Tricyclodecane Dimethanol is a kind of important industrial chemicals, is widely used in aqueous based dispersions, coating composition, lubrication wet goods.And the important method of synthesizing tricyclic decane dimethanol mainly contains: 1) two-step approach: i.e. dicyclopentadiene (DCPD) hydroformylation synthesizing tricyclic decane dicarbaldehyde, then hydrogenation; 2) single stage method: i.e. dicyclopentadiene one step hydroformylation synthesizing tricyclic decane dimethanol.
The subject matter that two-step approach exists is complicated operation, needs through two-step reaction, and need use the gas that two classes are different.Single stage method is then relatively simple, only need use a class reactant gases.
In one-step synthesis method Tricyclodecane Dimethanol; United States Patent (USP) 4300002 is using the compound of cobalt and phosphine as catalyzer; saturated hydrocarbon polymer and aromatic hydrocarbon have studied dicyclopentadiene hydroformylation one-step synthesis method Tricyclodecane Dimethanol as solvent; reaction conditions is the temperature of reaction of 150-200 degree; the pressure of 70-150atm; the transformation efficiency of DCPD is 100%, and the selectivity of Tricyclodecane Dimethanol is more than 60%.There is the hypertonia that subject matter is reaction, other problem has the DCPD of quite a few to transform in order to single methanol.
First Chinese patent CN103396293 prepares the nano catalyst that tricobalt tetroxide supports, again by obtain catalyzer through Phosphine ligands modification, then the one-step synthesis of catalysis dicyclopentadiene at relatively low temperatures and pressures Tricyclodecane Dimethanol, can reach more than 99% by the transformation efficiency of the method DCPD, the selectivity of Tricyclodecane Dimethanol can reach more than 80%.There is subject matter is have the DCPD of quite a few to transform in order to single methanol.
Obviously, there is very large room for promotion in the selectivity of Tricyclodecane Dimethanol, wherein the most effective approach is the catalyzer of Development of Novel.
The research discovery that the present invention is nearest, with silica supported cobalt rhodium copper trimetallic catalyst, adopt one still process, the transformation efficiency of dicyclopentadiene can reach more than 99%, the selectivity of Tricyclodecane Dimethanol can reach more than 90%, and catalyzer is easy to be separated and reuse.
Summary of the invention:
The object of the invention is to; a kind of method of synthesizing tricyclic decane dimethanol is provided; the method is at next step hydroformylation dicyclopentadiene synthesizing tricyclic decane dimethanol of effect of catalyzer, and catalyzer is the cobalt rhodium copper trimetallic catalyst of Phosphine ligands modification, and catalyzer adopts sol-gel method preparation.By the catalyzer that the method for the invention obtains, the transformation efficiency of dicyclopentadiene can reach more than 99%, and the selectivity of Tricyclodecane Dimethanol can reach more than 90%, and catalyzer is easy to be separated and reuse.
The method of a kind of synthesizing tricyclic decane dimethanol of the present invention, first the method prepares silica supported cobalt rhodium copper trimetallic catalyst, again by obtain catalyzer through Phosphine ligands modification, then the one-step synthesis of catalysis dicyclopentadiene at relatively low temperatures and pressures Tricyclodecane Dimethanol, concrete operations follow these steps to carry out:
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, tetraethoxy is dissolved in ethanol, is heated to temperature 60-80 DEG C under agitation condition, obtains mixed solution;
B, by cupric nitrate, cobalt chloride and Trichlororhodium are dissolved in distilled water, add the mixed solution of step a, then aqueous nitric acid is added, at temperature 60-80 DEG C of aging 24-72 hour, then air atmosphere at temperatures 400-600 DEG C of roasting 3-6 hour in retort furnace, obtain silica supported cobalt rhodium copper oxide, then by the silica supported cobalt rhodium copper oxide that obtains temperature 400-600 DEG C of reductase 12-4 hours in hydrogen, be cooled to room temperature, temperature 400-600 DEG C of roasting 3-6 hour in atmosphere again, temperature 400-600 DEG C of reductase 12-4 hours in hydrogen, obtain silica supported cobalt rhodium copper catalyst,
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, the silica supported cobalt rhodium copper catalyst obtained by step b and Phosphine ligands are triphenylphosphine, between tributylphosphine, triphen phosphine oxide or triphenylphosphine three, sodium sulfonate joins in tetrahydrofuran (THF), at room temperature stir 0.5-2 hour, then at temperature 20-45 DEG C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst of Phosphine ligands modification;
Synthesizing tricyclic decane dimethanol
D, be that toluene, normal hexane and tetrahydrofuran (THF) are incorporated in autoclave successively by the silica supported cobalt rhodium copper trimetallic catalyst of dicyclopentadiene and Phosphine ligands modification and organic solvent, airtight, then use N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 4-7MPa, and temperature of reaction is 150-170 DEG C, and reaction pressure is 7-9MPa, and the reaction times is 3-8 hour, can obtain Tricyclodecane Dimethanol.
The method of a kind of synthesizing tricyclic decane dimethanol of the present invention is compared with the method for the Tricyclodecane Dimethanol of existing synthesis, and the substantive distinguishing features had is:
1. catalyzer is mainly loaded solid catalyst, and preparation process is relatively simple, and catalyzer price is relatively low;
2. relatively gentle, the catalytic activity of reaction conditions and reaction preference is high, the reaction times is relatively short;
3. catalyzer and reaction system are convenient to be separated, and can reuse, and are convenient to amplify and industrial application.
Embodiment:
Embodiment 1
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, 20ml tetraethoxy to be dissolved in 14ml ethanol, to be heated to temperature 60 C under agitation, to obtain mixed solution;
B, 3g cupric nitrate, 0.3g cobalt chloride and 0.3g Trichlororhodium are dissolved in 10ml distilled water, add the mixed solution that step a obtains, then the mixing solutions of 5ml concentrated nitric acid and 5ml water is added, at temperature 60 C aging 24 hours, then air atmosphere at temperatures 400 DEG C of roastings 6 hours in retort furnace, obtain silica supported cobalt rhodium copper oxide; Then the silica supported cobalt rhodium copper oxide obtained temperature 400 DEG C in hydrogen is reduced 4 hours, be cooled to room temperature, temperature 400 DEG C of roastings 6 hours in atmosphere again, in hydrogen, temperature 400 DEG C reduction 4 hours, obtains silica supported cobalt rhodium copper catalyst;
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, the silica supported cobalt rhodium copper metal catalyst obtained by step b and 1g triphenylphosphine join in tetrahydrofuran (THF), at room temperature stir 0.5 hour, then at temperature 20 DEG C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst A of triphenylphosphine modification;
Synthesizing tricyclic decane dimethanol:
D, by the silica supported cobalt rhodium copper trimetallic catalyst A0.2g of dicyclopentadiene 5g and the modification of step c triphenylphosphine, tetrahydrofuran (THF) 20ml is incorporated in 200ml autoclave successively, airtight, then uses N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 5MPa, and temperature of reaction is 160 DEG C, and reaction pressure is 8MPa, and the reaction times is 6 hours, can obtain Tricyclodecane Dimethanol, the results are shown in Table 1.
Embodiment 2
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, 20ml tetraethoxy is dissolved in 14ml ethanol, is heated to temperature 80 DEG C under agitation, obtains mixed solution;
B, 3g cupric nitrate, 0.3g cobalt chloride and 0.3g Trichlororhodium are dissolved in 10ml distilled water, add the mixed solution that step a obtains, then the mixing solutions of 5ml concentrated nitric acid and 5ml water is added, temperature 80 DEG C aging 72 hours, then air atmosphere at temperatures 600 DEG C of roastings 3 hours in retort furnace, obtain silica supported cobalt rhodium copper oxide; Then the silica supported cobalt rhodium copper oxide temperature 600 DEG C of reductase 12s hour in hydrogen will obtained, be cooled to room temperature, temperature 600 DEG C of roastings 3 hours in atmosphere again, temperature 600 DEG C of reductase 12s hour in hydrogen, obtain silica supported cobalt rhodium copper catalyst;
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, the silica supported cobalt rhodium copper catalyst obtained by step b and 1g tributylphosphine join in tetrahydrofuran (THF), at room temperature stir 2 hours, then under temperature 45 C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst B of tributylphosphine modification;
Synthesizing tricyclic decane dimethanol:
D, the silica supported cobalt rhodium copper trimetallic catalyst B0.2g of dicyclopentadiene (DCPD) 5g and the modification of step c tributylphosphine and organic solvent-normal hexane 20ml is incorporated in 200ml autoclave successively, airtight, then use N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 6MPa, and temperature of reaction is 150 DEG C, and reaction pressure is 8MPa, and the reaction times is 3 hours, can obtain Tricyclodecane Dimethanol, the results are shown in Table 1.
Embodiment 3
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, 20ml tetraethoxy to be dissolved in 14ml ethanol, to be heated to temperature 70 C under agitation, to obtain mixed solution;
B, by 3g cupric nitrate, 0.3g cobalt chloride and 0.3g Trichlororhodium are dissolved in 10ml distilled water, add the mixed solution that step a obtains, then the mixing solutions of 5ml concentrated nitric acid and 5ml water is added, at temperature 70 C aging 48 hours, then air atmosphere at temperatures 500 DEG C of roastings 4 hours in retort furnace, obtain silica supported cobalt rhodium copper oxide, then the silica supported cobalt rhodium copper oxide obtained temperature 500 DEG C in hydrogen is reduced 3 hours, be cooled to room temperature, temperature 500 DEG C of roastings 4 hours in atmosphere again, temperature 500 DEG C reduction 3 hours in hydrogen, obtain silica supported cobalt rhodium copper catalyst,
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, the silica supported cobalt rhodium copper metal catalyst obtained by step b and triphen phosphine oxide join in tetrahydrofuran (THF), at room temperature stir 1 hour, then at temperature 35 DEG C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst C of triphen phosphine oxide modification;
Synthesizing tricyclic decane dimethanol:
D, dicyclopentadiene (DCPD) 5g and step c catalyzer C0.2g and organic solvent toluene 20ml is incorporated in 200ml autoclave successively, airtight, then use N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 4MPa, and temperature of reaction is 160 DEG C, and reaction pressure is 7MPa, and the reaction times is 8 hours, can obtain Tricyclodecane Dimethanol, the results are shown in Table 1.
Embodiment 4
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, 20ml tetraethoxy to be dissolved in 14ml ethanol, to be heated to temperature 60 C under agitation, to obtain mixed solution;
B, by 3g cupric nitrate, 0.3g cobalt chloride and 0.3g Trichlororhodium are dissolved in 10ml distilled water, add the mixed solution that step a obtains, then the mixing solutions of 5ml concentrated nitric acid and 5ml water is added, at temperature 60 C aging 24 hours, then air atmosphere at temperatures 400 DEG C of roastings 6 hours in retort furnace, obtain silica supported cobalt rhodium copper oxide, then the silica supported cobalt rhodium copper oxide obtained temperature 400 DEG C in hydrogen is reduced 4 hours, be cooled to room temperature, temperature 400 DEG C of roastings 6 hours in atmosphere again, temperature 400 DEG C reduction 4 hours in hydrogen, obtain silica supported cobalt rhodium copper catalyst,
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, between the silica supported cobalt rhodium copper trimetallic catalyst obtained by step b and 1g triphenylphosphine three, sodium sulfonate joins in tetrahydrofuran (THF), at room temperature stir 0.5 hour, then at temperature 35 DEG C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst D of triphenylphosphine three sodium sulfonate modifications;
Synthesizing tricyclic decane dimethanol:
D, the silica supported cobalt rhodium copper trimetallic catalyst D0.2g of sodium sulfonate modification between dicyclopentadiene (DCPD) 5g and step c triphenylphosphine three and organic solvent ethanol 20ml is incorporated in 200ml autoclave successively, airtight, then use N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 4MPa, and temperature of reaction is 150 DEG C, and reaction pressure is 9MPa, and the reaction times is 3 hours, can obtain Tricyclodecane Dimethanol, the results are shown in Table 1.
Table 1:DCPD hydroformylation one-step synthesis Tricyclodecane Dimethanol
As can be seen from Table 1, the nanometer gold supported with the tricobalt tetroxide of Phosphine ligands modification is catalyzer, can single stage method efficient catalysis dicyclopentadiene synthesizing tricyclic decane dimethanol, the transformation efficiency of dicyclopentadiene can reach 100%, and the selectivity of Tricyclodecane Dimethanol can reach more than 90%.
Claims (1)
1. the method for a synthesizing tricyclic decane dimethanol, first the method prepares silica supported cobalt rhodium copper trimetallic catalyst, again by obtain catalyzer through Phosphine ligands modification, then the one-step synthesis of catalysis dicyclopentadiene at relatively low temperatures and pressures Tricyclodecane Dimethanol, concrete operations follow these steps to carry out:
Prepare silica supported cobalt rhodium copper trimetallic catalyst:
A, tetraethoxy is dissolved in ethanol, is heated to temperature 60-80 DEG C under agitation condition, obtains mixed solution;
B, by cupric nitrate, cobalt chloride and Trichlororhodium are dissolved in distilled water, add the mixed solution of step a, then aqueous nitric acid is added, at temperature 60-80 DEG C of aging 24-72 hour, then air atmosphere at temperatures 400-600 DEG C of roasting 3-6 hour in retort furnace, obtain silica supported cobalt rhodium copper oxide, then by the silica supported cobalt rhodium copper oxide that obtains temperature 400-600 DEG C of reductase 12-4 hours in hydrogen, be cooled to room temperature, temperature 400-600 DEG C of roasting 3-6 hour in atmosphere again, temperature 400-600 DEG C of reductase 12-4 hours in hydrogen, obtain silica supported cobalt rhodium copper catalyst,
The silica supported cobalt rhodium copper trimetallic catalyst preparation of Phosphine ligands modification:
C, the silica supported cobalt rhodium copper catalyst obtained by step b and Phosphine ligands are triphenylphosphine, between tributylphosphine, triphen phosphine oxide or triphenylphosphine three, sodium sulfonate joins in tetrahydrofuran (THF), at room temperature stir 0.5-2 hour, then at temperature 20-45 DEG C, vacuumize removing tetrahydrofuran (THF), obtain the silica supported cobalt rhodium copper trimetallic catalyst of Phosphine ligands modification;
Synthesizing tricyclic decane dimethanol:
D, be that toluene, normal hexane or tetrahydrofuran (THF) are incorporated in autoclave successively by the silica supported cobalt rhodium copper trimetallic catalyst of dicyclopentadiene and Phosphine ligands modification and organic solvent, airtight, then use N
2purge 3 times, synthetic gas purges 3 times, fills synthetic gas to 4-7MPa, and temperature of reaction is 150-170 DEG C, and reaction pressure is 7-9MPa, and the reaction times is 3-8 hour, can obtain Tricyclodecane Dimethanol.
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| CN110330421B (en) * | 2019-08-26 | 2021-09-28 | 重庆化工职业学院 | Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material |
| CN114685281B (en) * | 2022-03-11 | 2024-05-28 | 广东希必达新材料科技有限公司 | Process for preparing tricyclodecane dimethylamine from dicyclopentadiene and application thereof |
| CN116102401A (en) * | 2022-12-30 | 2023-05-12 | 广东希必达新材料科技有限公司 | Continuous production method for synthesizing tricyclodecane dimethanol by dicyclopentadiene |
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