CN110845513B - Synthetic method of aliphatic pentacyclic dianhydride - Google Patents
Synthetic method of aliphatic pentacyclic dianhydride Download PDFInfo
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Abstract
The invention discloses a method for synthesizing aliphatic pentacyclic dianhydride, in particular to pentacyclic [8.2.1.1 ]4,702,903,8]A synthesis method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride. The invention belongs to the field of fine chemical preparation methods. The method comprises the steps of taking maleic anhydride and cyclopentadiene as starting raw materials, synthesizing an intermediate product of norbornene anhydride through 1, 4-addition reaction at low temperature, then adding a solvent and a photocatalyst, monitoring the reaction process by HPLC under the illumination condition of a single wavelength light source, and after the reaction is finished, carrying out post-treatment to obtain a white solid. The method has the advantages of simple operation, high synthesis yield and few byproducts.
Description
Technical Field
The invention belongs to the field of fine chemical preparation methods, and particularly relates to a synthetic method of aliphatic pentacyclic dianhydride, particularly pentacyclic [8.2.1.1 ]4,702,903,8]A synthesis method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride; also relates to a device used in the synthesis method.
Background
Polyimides have many unique properties, such as excellent high temperature and mechanical resistance, good chemical resistance, low coefficient of thermal expansion and low dielectric constant, which make them useful in a wide range of applications in aerospace and microelectronics. However, aromatic polyimides prepared from aromatic tetracarboxylic acid anhydrides and aromatic amines have poor light transmittance due to their coloration. This problem severely limits the further applications of polyimides. Therefore, the synthesis of alicyclic dianhydride or diamine is of great significance to alicyclic polyimide.
Pentacyclic ring [8.2.1.14,702,903,8]Tetradecane-5, 6,11, 12-tetracarboxylic dianhydride is used as one of raw materials for synthesizing aliphatic polyimide materials, and the dianhydride reacts with 1, 3-diaminoadamantane to synthesize the aliphatic polyimide according to US 20020120090, Cheng and the like, due to the introduction of alicyclic groups, the flexibility of molecular chains is improved, fewer or no two electrons exist in the alicyclic polyimide, the conjugation effect on molecular main chains is destroyed, the charges among macromolecular chains are cut off, the acting force among the molecules is greatly reduced, and charge transfer complexes among the molecules and in the molecules are difficult to form, so that the effects of improving the solubility and the transparency are achieved.
In the prior art, five rings [8.2.1.1 ]4,702,903,8]Synthesis studies of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride have been reported less, and conventional preparation methods have been carried out by the photocyclization synthesis of nadic anhydride under irradiation of strong ultraviolet light [ Shaikhrazieva, V.S, Enikeev, R.S., Tolstikov, G.A. Zhurnal organic heskoi Khimi,1973,9,1458-]The light source of the photocatalytic device generally adopts a low-pressure or high-pressure mercury lamp which can provide ultraviolet light or visible light with a plurality of wavelength bands, and the product is irradiated by a multi-wavelength light source for a long time to cause the generation of a polymer byproduct, so that the reaction yield is reduced by 13-24%.
Therefore, there is a need to overcome the above-mentioned disadvantages of the above-mentioned method, and to provide a pentacyclic ring [8.2.1.1 ] with a high reaction yield and reduced formation of polymer by-products4,702,903,8]A synthesis method and a device of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride.
Disclosure of Invention
To overcome the above difficulties, the present inventionThe invention provides a method for synthesizing aliphatic pentacyclic dianhydride with high yield, in particular to pentacyclic [8.2.1.1 ]4,702,903,8]The synthesis method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride is shown in a reaction formula (1);
the invention also provides a device used in the synthesis method.
The primary process (the process that molecules absorb light to become excited molecules and generate intermediates such as various free radicals and atoms after dissociation) and quantum efficiency of the organic photochemical reaction are related to a light source; the ideal light source should be monochromatic, which greatly simplifies the determination of the absolute light intensity. The rate of reaction can be significantly increased by using the novel photocatalyst. The invention adopts a light source with single wavelength of lambda 245nm and a novel photocatalyst by the photocyclization reaction of the nadic anhydride. The process does not need to use a low-pressure or high-pressure mercury lamp as a light source, avoids rapid temperature caused by high energy of the light source, reduces by-products of the reaction, and improves the yield of the reaction to more than 70%.
The invention discloses a synthetic method of aliphatic pentacyclic dianhydride, which comprises the following steps:
1) placing maleic anhydride into a raw material bottle, adding ethyl acetate to dissolve, dropwise adding depolymerized cyclopentadiene, performing addition reaction, standing after the reaction is finished, filtering, and performing vacuum drying to obtain an intermediate product of norbornene anhydride;
2) adding a solvent and a photocatalyst into the obtained norbornene dianhydride in the step 1), then conveying the mixture into a capillary pipeline micro-channel of a photoreactor, vertically irradiating a light source under the illumination condition of a single-wavelength ultraviolet light source, allowing a reaction solution to flow through a cooling device through a capillary pipeline and be irradiated by ultraviolet light, and performing a photocyclization reaction in the process; white solid is continuously separated out from the reaction solution, the solid flows to a receiving bottle along with the reaction solution, and the solid is settled at the bottom of the bottle; after the reaction is finished, filtering, drying the precipitate, adding acetic anhydride into the precipitateHot reflux, filtering to obtain dianhydride product, washing with glacial acetic acid, and vacuum rotary steaming to remove glacial acetic acid to obtain pentacyclic ring [8.2.1.1 ]4,702,903,8]Tetradecane-5, 6,11, 12-tetracarboxylic dianhydride.
Preferably, the temperature of the addition reaction in the step 1) is-30 to 20 ℃.
2) The photocatalyst is any one of zinc porphyrin, copper trifluoromethanesulfonate, 5-aminolevulinic acid, tin protoporphyrin or phenyl porphyrin; a preferred catalyst is zinc porphyrin.
2) In the middle, the internal diameter of the capillary channel is 1-4 mm, and the length of the capillary microchannel is 1-20 m.
2) The solvent is any one of acetonitrile, acetone, ethyl acetate, carbon tetrachloride or dimethyl carbonate; the preferred solvent is acetone.
2) The wavelength of the ultraviolet light source is a single wavelength lambda 245nm, and the power of the ultraviolet light source for irradiation reaction is 100-500W.
2) The molar ratio of the norbornene dianhydride to the photocatalyst is 1: 0.01 to 0.05.
2) In the method, the light cyclization reaction temperature is-10 ℃ to 30 ℃, and the reaction time is 1 to 6 hours.
The device used in the synthesis method comprises a raw material bottle, wherein the raw material bottle is sequentially connected with a filtering container, a drying device, a solid product metering device, a feeding container and a photoreactor through pipelines; a first conveying pump and a second conveying pump are respectively and sequentially arranged on a pipeline between the raw material bottle and the filtering container and a pipeline between the feeding container and the photoreactor; the upper part of the charging container is communicated with a solvent metering device through a pipeline;
the raw material bottle is preferably a three-hole flask, so that different raw materials can be conveniently added;
the filtering container comprises a filtering bottle, a filtering plate with holes is arranged above the filtering bottle, a filtering membrane is arranged above the filtering plate, and the filtering bottle is connected with a vacuumizing device;
the photoreactor comprises a capillary pipeline micro-channel, a cooling circulating water tank and a single-wavelength ultraviolet light source;
valves are arranged among the pipelines; one end of the capillary pipeline micro-channel is connected with the outlet end of the feeding container, the other end of the capillary pipeline micro-channel is connected with the receiving bottle, the capillary pipeline micro-channel is wound on the plane glass plate in a continuous serpentine coil mode, and the capillary pipeline micro-channel and the plane glass plate are both arranged in the cooling device; a single wavelength uv light source is positioned vertically above the center of the cooling device.
In the photoreactor, the capillary tube microchannel is made of polytetrafluoroethylene; the cooling device is a cooling circulating water tank.
The invention has the following advantages and effects: the novel photocatalyst used in the invention is used as an energy donor, and the energy of the excited state of the sensitizer is higher than that of the excited state of the reactant molecule as an energy acceptor; the excited state has long enough life to make it have enough time to collide with reactant molecule to complete energy transfer and raise reaction rate. The single wavelength light source used in the present invention is determined by scanning the ultraviolet visible absorption spectrum. Compared with the wide wavelength range of a high-pressure or low-pressure mercury lamp, the single-wavelength light source reduces the energy loss, reduces the generation of polymer byproducts caused by long-time irradiation of the product by a multi-wavelength light source, and has the product purity of more than 99 percent and the product yield of more than 70 percent.
Drawings
FIG. 1 is a schematic view of a structure of a photoreactor in the present invention;
in the figure, 1-raw material bottle; 2-a first delivery pump; 3-single wavelength ultraviolet light source; 4-capillary channel microchannel; 5-receiving bottle, 6-cooling circulating water tank and 7-plane glass plate; 201-filtration vessel, 202-valve, 203-solid product metering device, 204-feeding vessel, 205-filter plate, 206-second transfer pump, 207-vacuum pumping device, 208-solvent metering device, 209-drying device.
Detailed Description
In order to further illustrate the synthesis method of the aliphatic pentacyclic dianhydride in the scheme, in particular to pentacyclic [8.2.1.1 ]4,702,903 ,8]The specific process of the preparation process of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride is shown in the following experimental scheme, but the scheme is not limited to the specific processThe specific numbers listed in the experimental cases, and the schemes of mass enlargement or mass reduction with the same proportion also belong to the disclosure of the experimental cases.
Example 1A
In the synthesis process of the product of the invention, the structure of the used device is as follows:
the device comprises a raw material bottle 1 (a three-hole flask), wherein the raw material bottle 1 is sequentially connected with a filtering container 201, a drying device 209, a solid product metering device 203, a feeding container 204 and a photoreactor through pipelines; a first conveying pump 2 and a second conveying pump 206 are respectively arranged on a pipeline between the raw material bottle 1 and the filtering container 201 and a pipeline between the feeding container 204 and the photoreactor in sequence; material transfer pumps may be optionally provided on the pipeline between the filtration vessel 201 and the drying device 209, the pipeline between the drying device 209 and the solid product metering device 203, and the pipeline between the solid product metering device 203 and the feed vessel 204;
the upper part of the feeding container 204 is communicated with a solvent metering device 208 through a pipeline, so that the amount of the solvent fed into the feeding container 204 can be conveniently metered;
the filtering container 201 comprises a filtering bottle, a filtering plate 205 with holes is arranged above the filtering bottle, a filtering membrane is arranged above the filtering plate 205, and the filtering bottle is connected with a vacuumizing device 207;
the photoreactor comprises a capillary pipeline micro-channel 4 made of polytetrafluoroethylene, a cooling circulating water tank 6 and a single-wavelength ultraviolet light source 3;
The principle of the device is as follows:
adding maleic anhydride into the raw material bottle 1, and adding ethyl acetateDissolving, dripping cyclopentadiene, reacting, standing after the reaction is finished, then conveying the materials to a filtering container 201 for filtering, drying the obtained precipitate by a drying device 209 to obtain an intermediate product, namely white solid nadic anhydride, the intermediate product is then metered by means of a solid product metering device 203, and the solvent is metered by means of a solvent metering device 208, and is transferred into a feed container 204, then adding the photocatalyst into the feeding container 204, finally conveying the material in the feeding container 204 to the capillary pipeline microchannel 4 in the photoreactor, irradiating by a single-wavelength ultraviolet light source 3 and cooling by a cooling circulating water tank 6, reacting to obtain crude dianhydride, and putting the crude product into a receiving bottle 5, adding acetic anhydride into the crude product, heating and refluxing, filtering to obtain a dianhydride product, washing with glacial acetic acid, and performing reduced pressure rotary evaporation to remove the glacial acetic acid to obtain a final product, namely pentacyclic [8.2.1.1 ].4,702,903,8]Tetradecane-5, 6,11, 12-tetracarboxylic dianhydride white solid.
Example 1B
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at a low temperature, controlling the reaction temperature to be minus 10 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the addition of cyclopentadiene, standing for half an hour, filtering, and drying in vacuum to obtain 152.31g of white solid norbornadic anhydride with the purity of HPLC (high performance liquid chromatography) of 99.15 percent and the yield of 92.8 percent;
(2) 152.31g (0.93mol) of nadic anhydride is placed in a feeding container, 500.00g of acetone and 6.11g of zinc porphyrin are added, the mixture is pumped into a capillary tube microchannel (the inner diameter of the capillary tube is 4mm, the length of the capillary tube is 15m) of a photoreactor through a high-pressure constant-current pump, the reaction temperature is controlled to be-10 ℃ under the illumination condition of a lambda 245nm single-wavelength light source with the power of 500W, and a reaction solution flows through a water tank through the capillary tube microchannel and is irradiated by ultraviolet light to react. Continuously separating out white solid from the reaction solution, allowing the solid to flow to a receiving bottle along with the reaction solution, allowing the solid to settle at the bottom of the bottle, monitoring the reaction process by HPLC, reacting for 4 hours, performing reduced pressure rotary evaporation on part of the solvent after the reaction is finished, performing suction filtration on the obtained product by using a Buchner funnel to obtain a crude product of white solid dianhydride, drying the crude product, adding 200mL of acetic anhydride, heating and refluxing the obtained product, filtering the obtained product to obtain a dianhydride product, washing the crude product for 3 times by using 200mL of glacial acetic acid, and performing reduced pressure rotary evaporation on the obtained product to remove the glacial.
Example 1C
The difference from example 1B is that in (1), the reaction temperature was controlled to-15 ℃ and the same as in example 1B was maintained.
Example 1D
The difference from example 1B is that in (2), the reaction is carried out by ultraviolet irradiation under the irradiation of a single wavelength light source with a power of 400W and a wavelength of 245nm, and the rest is the same as example 1B.
Example 1E
The difference from example 1B is that in (2), 500.00g of ethyl acetate was used as a solvent to participate in the reaction, and the rest was the same as in example 1B.
The purity and yield of the products obtained in examples 1C to 1E are shown in tables 1 and 2, which are close to those of example 1B.
Example 2
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at low temperature, controlling the reaction temperature to be 0 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the dropwise adding of the cyclopentadiene, filtering, and performing vacuum drying to obtain 143.34g of white solid with the purity of HPLC (high performance liquid chromatography) of 99.12 percent and the yield of 87.4 percent;
(2) 143.34g (0.87mol) of nadic anhydride is placed in a feeding container, 500g of acetonitrile and 3.1g of benzoporphyrin are added, the mixture is pumped into a capillary pipeline micro-channel of a photoreactor through a high-pressure constant-current pump (the inner diameter of the capillary pipeline is 4mm, the length of the capillary pipeline is 15m), the reaction temperature is controlled to be 10 ℃ under the illumination condition of a lambda 245nm single-wavelength light source with the power of 400W, and a reaction solution flows through a water tank through the capillary pipeline micro-channel and is irradiated by ultraviolet light to react. Continuously separating out white solid from the reaction solution, allowing the solid to flow to a receiving bottle along with the reaction solution, allowing the solid to settle at the bottom of the bottle, monitoring the reaction process by HPLC, reacting for 4.5h, performing reduced pressure rotary evaporation on part of the solvent after the reaction is finished, performing suction filtration on a Buchner funnel to obtain a crude product of white solid dianhydride, drying, adding 200mL of acetic anhydride, heating and refluxing, filtering to obtain a dianhydride product, washing with 200mL of glacial acetic acid for 2 times, performing reduced pressure rotary evaporation to remove the glacial acetic acid to obtain 90.27g of white solid, wherein the purity of HPLC (high performance liquid chromatography) is.
Example 3
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at a low temperature, controlling the reaction temperature to be 10 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the dropwise adding of the cyclopentadiene, filtering, and drying in vacuum to obtain 133.78g of white solid with the purity of HPLC (high performance liquid chromatography) of 99.01 percent and the yield of 81.5 percent;
(2) 133.78g (0.82mol) of nadic anhydride is placed in a feeding container, 500g of ethyl acetate and 1.3g of 5-aminolevulinic acid are added, the mixture is pumped into a capillary pipeline micro-channel of a photoreactor through a high-pressure constant-current pump (the inner diameter of the capillary pipeline is 4mm, the length of the capillary pipeline is 15m), the reaction temperature is controlled to be 10 ℃ under the illumination condition of a lambda 245nm single-wavelength light source with the power of 300W, and a reaction solution flows through a water tank through the capillary pipeline micro-channel and is irradiated by ultraviolet light to carry out reaction. Continuously separating out white solid from the reaction solution, allowing the solid to flow to a receiving bottle along with the reaction solution, allowing the solid to settle at the bottom of the bottle, monitoring the reaction process by HPLC, reacting for 4.5h, performing reduced pressure rotary evaporation on part of the solvent after the reaction is finished, performing suction filtration on a Buchner funnel to obtain a crude product of white solid dianhydride, drying, adding 200mL of acetic anhydride, heating and refluxing, filtering to obtain a dianhydride product, washing with 200mL of glacial acetic acid for 2-3 times, performing reduced pressure rotary evaporation to remove the glacial acetic acid to obtain 73.10g of white solid, wherein the purity of HPLC is 99.12%, and the.
Example 4
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at a low temperature, controlling the reaction temperature to be 30 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the dropwise adding of the cyclopentadiene, filtering, and drying in vacuum to obtain 110.60g of white solid with the purity of HPLC (high performance liquid chromatography) of 99.14 percent and the yield of 67.4 percent;
(2) 110.60g (0.67mol) of nadic anhydride is placed in a feeding container, 500g of carbon tetrachloride and 3.6g of copper trifluoromethanesulfonate are added, the mixture is pumped into a capillary pipeline micro-channel of a photoreactor through a high-pressure constant-current pump (the inner diameter of the capillary pipeline is 4mm, the length of the capillary pipeline is 15m), the reaction temperature is controlled to be 30 ℃ under the illumination condition of a lambda 245nm single-wavelength light source with the power of 200W, and a reaction solution flows through a water tank through the capillary pipeline micro-channel and is irradiated by ultraviolet light to react. Continuously separating out white solid from the reaction solution, allowing the solid to flow to a receiving bottle along with the reaction solution, allowing the solid to settle at the bottom of the bottle, monitoring the reaction process by HPLC, reacting for 5 hours, performing reduced pressure rotary evaporation on part of the solvent after the reaction is finished, performing suction filtration on the white solid dianhydride crude product by using a Buchner funnel to obtain a white solid dianhydride crude product, drying the white solid dianhydride crude product, adding 200mL of acetic anhydride, heating and refluxing the white solid dianhydride crude product, filtering the white solid dianhydride crude product to obtain a dianhydride product, washing the white dianhydride product for 2 to 3 times by using 200mL of glacial acetic acid, and performing reduced.
Comparative example 1
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at low temperature, controlling the reaction temperature to be minus 10 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the dropwise adding of the cyclopentadiene, filtering, and performing vacuum drying to obtain 149.52g of white solid with the purity of HPLC (high performance liquid chromatography) 98.65% and the yield of 91.1%;
(2) 149.60g (0.91mol) of norbornene dianhydride is placed in a batch photoreactor, 500g of acetonitrile and 6.5g of protoporphyrin tin are added, under the condition of illumination of a light source of a high-pressure mercury lamp with the power of 500W, the reaction temperature is controlled to be 10 ℃, after 8 hours of reaction, HPLC detection raw materials are completely reacted, after the reaction is finished, partial solvent is evaporated in a rotary manner under reduced pressure, a white solid dianhydride crude product is obtained by suction filtration of a Buchner funnel, 200mL of acetic anhydride is added after drying, heating reflux is carried out, a dianhydride product is obtained by filtration, 200mL of glacial acetic acid is washed for 2-3 times, 56.32g of white solid is obtained by removing the glacial acetic acid under reduced pressure, the purity HPLC is 95..
Comparative example 2
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at low temperature, controlling the reaction temperature to be minus 10 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the dropwise adding of the cyclopentadiene, filtering, and performing vacuum drying to obtain 150.18g of white solid with the purity of HPLC (high performance liquid chromatography) 98.48 percent and the yield of 91.5 percent;
(2) 156.78g (0.96mol) of nadic anhydride is placed in a batch photoreactor, 500g of acetone and 6.5g of copper trifluoromethanesulfonate are added, the reaction temperature is controlled to be 10 ℃ under the illumination condition of a low-pressure mercury lamp light source with the power of 500W, after 7 hours of reaction, HPLC detection raw materials are completely reacted, after the reaction is finished, partial solvent is evaporated in a rotary manner under reduced pressure, a white solid dianhydride crude product is obtained by suction filtration of a Buchner funnel, 200mL of acetic anhydride is added after drying, heating reflux is carried out, a dianhydride product is obtained by filtration, 200mL of glacial acetic acid is washed for 2-3 times, the glacial acetic acid is removed by rotary evaporation under reduced pressure, 39.32g of white solid is obtained, the purity HPLC 97.16%.
Comparative example 3
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at a low temperature, controlling the reaction temperature to be minus 10 ℃, continuously precipitating white crystals in the reaction process, finishing the reaction after the addition of the cyclopentadiene is finished, standing for half an hour, filtering, and drying in vacuum to obtain 152.13g of white solid with the purity of 99.11 percent by HPLC and the yield of 92.7 percent;
(2) 152.13g (0.93mol) of norbornene dianhydride is placed in a batch type photoreactor, 500g of acetone without catalyst is added, under the illumination condition of a lambda 245nm single-wavelength light source with the power of 500W, the reaction temperature is controlled to be 10 ℃, after 7 hours of reaction, HPLC detection raw materials are completely reacted, after the reaction is finished, partial solvent is evaporated in a decompression rotary manner, a Buchner funnel is used for suction filtration to obtain a white solid dianhydride crude product, 200mL of acetic anhydride is added after drying, heating reflux is carried out, dianhydride product is obtained by filtration, 200mL of glacial acetic acid is washed for 2-3 times, 33.43g of white solid is obtained by evaporating glacial acetic acid in a decompression rotary manner, the purity is 96.25%, and the yield is 22.
Comparative example 4
Pentacyclic ring [8.2.1.14,702,903,8]The preparation method of tetradecane-5, 6,11, 12-tetracarboxylic dianhydride specifically comprises the following steps:
(1) placing 98.00g (1.00mol) of maleic anhydride into a three-mouth raw material bottle, adding 300.00g of ethyl acetate to dissolve, slowly dropwise adding 72.71g (1.10mol) of cyclopentadiene at low temperature, controlling the reaction temperature to be minus 10 ℃, continuously separating out white crystals in the reaction process, finishing the reaction after the addition of cyclopentadiene is finished, standing for half an hour, filtering, and drying in vacuum to obtain 152.31g of white solid norbornadic anhydride with the purity of HPLC (high performance liquid chromatography) of 99.08 percent and the yield of 92.6 percent;
(2) 152.31g (0.93mol) of nadic anhydride is placed in a feeding container, 500.00g of acetone is added, no catalyst is added in the process, the mixture is pumped into a capillary pipeline micro-channel of a photoreactor through a high-pressure constant-current pump (the inner diameter of the capillary pipeline is 4mm, the length of the capillary pipeline is 15m), the reaction temperature is controlled to be-10 ℃ under the illumination condition of a lambda 245nm single-wavelength light source with the power of 500W, and a reaction solution flows through a water tank through the capillary pipeline micro-channel and is irradiated by ultraviolet light to react. Continuously separating out white solid from the reaction solution, allowing the solid to flow to a receiving bottle along with the reaction solution, allowing the solid to settle at the bottom of the bottle, monitoring the reaction process by HPLC, reacting for 4 hours, performing reduced pressure rotary evaporation on part of the solvent after the reaction is finished, performing suction filtration on the obtained product by using a Buchner funnel to obtain a crude product of white solid dianhydride, drying the crude product, adding 200mL of acetic anhydride, heating and refluxing the obtained product, filtering the obtained product to obtain a dianhydride product, washing the crude product with 200mL of glacial acetic acid for 3 times, performing reduced pressure rotary evaporation on the obtained product to remove the glacial acetic acid.
The following tables 1 and 2 are the results of the purity and yield, respectively, of the product, which is determined by HPLC as the purity test method: chromatography column SinoChromODS-BP, C18, 4.6 mm. times.250 mm. times.5 μm; the flow rate is 0.8 mL/min; the column temperature is 25 ℃; mobile phase V (methanol) V (water) 80: 20; the sample injection amount is 5 mu L; a detector Diode Array Detector (DAD); the detection wavelength is 254 nm.
The yield was calculated as Y/% - (-) M2/M1X 100 wherein (M)1Theoretical yield, M2For post-treatment pure quality)
TABLE 1 comparison of yields of products in examples and comparative examples
TABLE 2 comparison table of purities of products in examples and comparative examples
As can be seen from the data in tables 1 and 2, the yield and purity of the intermediate product and the final product of each example are high, the yield reaches about 72% at most, and the purity reaches about 99%, but the purity of the product in each proportion is lower than that of the product in the example. This shows that the process of the invention produces a product with a yield and purity superior to the product of the comparative example.
Through comparison between the above examples and comparative examples, the inventors found that the product yield in the examples of the present invention is much higher than that in the comparative examples, and the purity is higher than that in each comparative example by about 2 to 3 percentage points. In examples 1B to 1E, the yields of both the intermediate product and the final product were comparable, indicating that the product yields were relatively stable. The other examples are slightly different from the example 1B in yield, which shows that the invention has a remarkable effect on improving the yield and purity of the product after adopting a specific photoreactor and a specific process method.
Comparative example 4 differs from example 1B in that no catalyst was used in comparative example 4 and the final product was obtained in significantly lower yield and purity than example 1B. It can be seen that the introduction of the catalyst improves the yield and purity of the product to some extent.
In each proportion, a batch photoreactor is adopted, or a low-pressure mercury lamp light source illumination condition is adopted for reaction or a high-pressure mercury lamp light source illumination condition is adopted for reaction, and the yield of the obtained product is far lower than that of the products in the embodiments 1B to 1E. This is because the apparatus used in the present invention realizes continuous production, and the single-wavelength light source used reduces energy loss compared with a wide wavelength range of a high-pressure or low-pressure mercury lamp, reduces the generation of a poly-byproduct due to long-time irradiation of the product by a multi-wavelength light source, and increases the yield.
Claims (11)
1. A synthetic method of aliphatic pentacyclic dianhydride comprises the following steps:
1) placing maleic anhydride into a raw material bottle, adding ethyl acetate to dissolve, dropwise adding depolymerized cyclopentadiene, performing addition reaction, standing after the reaction is finished, filtering, and performing vacuum drying to obtain an intermediate product of norbornene anhydride;
2) adding solvent and photocatalyst into the obtained norbornene dianhydride in the step 1), conveying the mixture into a capillary pipeline micro-channel of a photoreactor, vertically irradiating a light source under the illumination condition of a single-wavelength ultraviolet light source, allowing the reaction solution to flow through a cooling device through a capillary pipeline and be irradiated by ultraviolet light, and performing light irradiation in the processCyclization reaction; white solid is continuously separated out from the reaction solution, the solid flows to a receiving bottle along with the reaction solution, and the solid is settled at the bottom of the bottle; after the reaction is finished, filtering, drying and precipitating, then adding acetic anhydride into the precipitate, heating and refluxing, filtering to obtain dianhydride product, washing with glacial acetic acid, decompressing and rotary-steaming to remove the glacial acetic acid to obtain the product pentacyclic [8.2.1.1 ]4,702,903,8]Tetradecane-5, 6,11, 12-tetracarboxylic dianhydride;
the photocatalyst is any one of zinc porphyrin, copper trifluoromethanesulfonate, 5-aminolevulinic acid, protoporphyrin tin or benzoporphyrin; the wavelength of the ultraviolet light source is a single wavelength lambda 245nm, and the power of the ultraviolet light source for irradiation reaction is 100-500W.
2. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein the temperature of the addition reaction in 1) is-30 to 20 ℃.
3. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the photocatalyst is zinc porphyrin.
4. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the internal diameter of the capillary micro-channel is 1-4 mm, and the length of the capillary micro-channel is 1-20 m.
5. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein the flow rate of the reaction solution in the capillary channel microchannel of 2) is 1-10 mL/min.
6. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the solvent is any one of acetonitrile, acetone, ethyl acetate, carbon tetrachloride or dimethyl carbonate.
7. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the solvent is acetone.
8. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the molar ratio of the nadic anhydride to the photocatalyst is 1: 0.01 to 0.05.
9. The method for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein in 2), the photocyclization reaction temperature is-10 ℃ to 30 ℃ and the reaction time is 1 to 6 hours.
10. The apparatus for synthesizing aliphatic pentacyclic dianhydride according to claim 1, wherein the apparatus comprises a raw material bottle (1), and the raw material bottle (1) is connected with a filtering container (201), a drying device (209), a solid product metering device (203), a feeding container (204) and a photoreactor sequentially through pipelines; a first conveying pump (2) is arranged on a pipeline between the raw material bottle (1) and the filtering container (201), and a second conveying pump (206) is arranged on a pipeline between the feeding container (204) and the photoreactor;
the solvent metering device (208) is connected with the upper part of the feeding container (204) through a pipeline;
the filtering container (201) comprises a filtering bottle, a filtering plate (205) with holes is arranged above the filtering bottle, a filtering membrane is arranged above the filtering plate (205), and the filtering bottle is connected with a vacuumizing device (207);
the photoreactor comprises a capillary pipeline micro-channel (4), a cooling circulating water tank (6) and a single-wavelength ultraviolet light source (3);
valves (202) are arranged among the pipelines; one end of the capillary pipeline microchannel (4) is connected with the outlet end of the feeding container (204), the other end of the capillary pipeline microchannel (4) is connected with the receiving bottle (5), the capillary pipeline microchannel (4) is wound on the plane glass plate (7) in a continuous serpentine coil mode, and the capillary pipeline microchannel (4) and the plane glass plate (7) are both arranged in the cooling device; a single wavelength ultraviolet light source (3) is arranged vertically above the center of the cooling device.
11. The apparatus for synthesizing aliphatic pentacyclic dianhydride according to claim 10, wherein in the photoreactor, the capillary micro-channels (4) are made of polytetrafluoroethylene; the cooling device is a cooling circulating water tank (6).
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