CN104926649A - Preparation method of hydrogenated pyromellitic acid tetrapropyl ester and 1,2,3,4,5-cyclohexane tetracarboxylic acid dianhydride - Google Patents
Preparation method of hydrogenated pyromellitic acid tetrapropyl ester and 1,2,3,4,5-cyclohexane tetracarboxylic acid dianhydride Download PDFInfo
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Abstract
The invention discloses a preparation method of hydrogenated pyromellitic acid tetrapropyl ester and 1,2,3,4,5-cyclohexane tetracarboxylic acid dianhydride. The preparation method of the hydrogenated pyromellitic acid tetrapropyl ester comprises the step of under the action of a hydrogenation catalyst, hydrogenating pyromellitic acid tetrapropyl ester to compose the hydrogenated pyromellitic acid tetrapropyl ester, wherein a carrier of the hydrogenation catalyst is cocoanut active charcoal, and the active component of the cocoanut active charcoal is a composite metal consisting of the following components in percentage by mass: 1 to 5 percent of Ru, 0.5 to 2 percent of Pd and 0.3 to 2 percent of Ce. The invention also discloses a preparation method of the hydrogenation catalyst. The hydrogenation catalyst prepared by the invention is high in activity and long in service life, so that the reaction temperature and the reaction pressure are effectively reduced; hydrogenation is performed by using a fixed bed hydrogenation reactor, the requirement to equipment is low under low-pressure reaction, and discharged hydrogen is very easily reclaimed and reused through a low-pressure pressure pump.
Description
Technical field
The present invention relates to the preparation method of hydrogenated pyromellitic acid ester and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, particularly hydrogenation Pyromellitic Acid orthocarbonate preparation and prepared the method for 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride by it.
Background technology
1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is a kind of alicyclic acid anhydrides, polyimide prepared therefrom has the excellent transparency, low-k and dielectric loss, high breakdown strength, low rate of moisture absorption and the adhesivity good with base materials such as metals, has broad application prospects in fields such as aerospace, automobile, microelectronics, large-scale integrated circuit, semiconductor material and flat-panel monitors.The preparation of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride completes primarily of following reaction:
1, Pyromellitic Acid shortening obtains hydrogenation Pyromellitic Acid
2, hydrogenation Pyromellitic Acid cyclodehydration prepares 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride
Comprehensive prior art, 1,2,4, in the preparation of 5-cyclohexanetetracarboxylic acid dianhydride, key problem in technology is the preparation of hydrogenation Pyromellitic Acid, material choice can be Pyromellitic Acid or its ester class, with pyromellitic acid ester class for hydrogenating materials can reach high conversion, highly selective.For obtaining the High-efficient Production of hydrogenation pyromellitic acid ester, technology focuses on pyromellitic acid ester shortening and prepares hydrogenation pyromellitic acid ester.
Summary of the invention
One of technical problem that the present invention solves is to provide a kind of preparation method of hydrogenation Pyromellitic Acid orthocarbonate, described preparation method is, Pyromellitic Acid orthocarbonate is hydrogenation synthesis hydrogenation of benzene tetracarboxylic acid orthocarbonate under hydrogenation catalyst effect, the carrier of described hydrogenation catalyst is cocoanut active charcoal, and active ingredient is the composition metal of the metal Ru of massfraction 1-5%, the metal Pd of massfraction 0.5-2%, the metal Ce composition of massfraction 0.3-2%.
The preparation method of described hydrogenation catalyst comprises the steps:
1. get 94 weight part cocoanut active charcoals, adding equal-volume massfraction is soaked overnight in 3-5%HCl, filters, adds 400 parts by weight of deionized water and 100 weight part concentrated hydrochloric acids in the gac after filtration, drips 2-10 weight part RuCl
3, 0.9-3.5 weight part PdCl
2, the mixing solutions that is made into of 1-6.3 weight part six water cerous nitrate, 50 parts by weight of deionized water, 50 weight part concentrated hydrochloric acids;
2. add NaOH solution and be adjusted to pH=14, be heated to 60 DEG C, dripping 80-90 weight part massfraction is the formalin of 36%, finish and drip NaOH solution again, guarantee pH=14, be heated to 90 DEG C of insulated and stirred, cooling, filtration, filter cake adds deionized water and stirring, filters, with deionized water repeatedly drip washing until filtrate pH=7, to add massfraction be 1%AgNO
3till the constant muddiness of solution.
Prepare the another kind of technical scheme of hydrogenation catalyst as the present invention, 2. the step of the preparation method of described hydrogenation catalyst is dropwise rear stirring, and filter, the deionized water drip washing of filter cake and catalyzer, until filtrate pH=6-7; Be added in fixed bed by above-mentioned catalyzer, be warmed up to 220-230 DEG C, pass into the mixed gas reducing catalyst of hydrogen or hydrogen and nitrogen, it is 2.5L/min that gas passes into speed, and reduction reaction pressure 0.1-0.2MPa, without HCl gas to tail gas.
In the present invention, the carrier of hydrogenation catalyst is 80 order cocoanut active charcoals, gac inner ratio surface area 1000-1500m
2/ g; Active ingredient is the composition metal of the metal Ru of massfraction 1-5%, the metal Pd of massfraction 0.5-2%, the metal Ce composition of massfraction 0.3-2%.Can allow the adding of metal Ce metal Ru, Pd dispersed, be adsorbed onto on gac, use metalloscope analysis to find, average 3-5 Pd, Ru atoms metal flocks together formation sosoloid nucleus, and dispersity is very high.So high dispersity not only allows catalyzer have outstanding catalytic activity, and prevents metal crystal nuclei in hydrogenation reaction from sintering because of heat release, improves catalyzer work-ing life.
The composition metal nucleus dispersion degree of depth is 100-150 micron under activated carbon surface, and in this degree of depth, precious metal sosoloid is easy to be adsorbed onto hydrogen and hydrogenating materials, and utilization ratio is the highest.The nitrogen BET surface area of hydrogenation catalyst reaches 1500 ~ 2000m
2/ g.Compared with the catalyzer that this reaction is conventional, catalyst activity prepared by the present invention and work-ing life higher, effectively reduce temperature of reaction and reaction pressure, hydrogenation reaction temperature is at 100-110 DEG C, and reaction pressure only has 0.2 ~ 0.5Mpa; Use fixed bed hydrogenation reactor hydrogenation, low pressure reaction is low for equipment requirements, and emptying hydrogen is easy to recycling by low pressure force (forcing) pump.
Described Pyromellitic Acid orthocarbonate be with Pyromellitic Acid and propyl alcohol be raw material, H-type mordenite for catalyzer, prepare through esterification.
The sulfuric acid used with usual esterification is compared with tetrabutyl titanate catalyst, esterification used catalyst in the present invention is acidic solid catalyst H-type mordenite, does not have corrodibility, and catalyzer can pass through simple filter method and product separation, simple to operate, do not produce any waste water.
Two of the technical problem that invention solves is to provide a kind of 1,2,4, the preparation method of 5-cyclohexanetetracarboxylic acid dianhydride, the hydrogenation Pyromellitic Acid orthocarbonate utilizing aforesaid method to prepare, through hydrolysis reaction system 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid prepares 1 through dehydration reaction, 2,4,5-cyclohexanetetracarboxylic acid dianhydride; Wherein, hydrolysis reaction used catalyst is H-type mordenite.
The present invention's propyl alcohol, as the raw material of esterification, has compared a lot of advantage with by methyl alcohol, esterified by butyl alcohol, and this is not only that a simple alcohols is replaced.The product generated with propyl alcohol esterification generates hydrogenation Pyromellitic Acid orthocarbonate through hydrogenation reaction, hydrogenation Pyromellitic Acid orthocarbonate is compared with hydrogenation Pyromellitic Acid four methyl esters, hydrogenation Pyromellitic Acid four butyl ester etc., more facile hydrolysis, hydrolysis reaction required time are shorter, and production efficiency is high, the more important thing is that cyclohexanetetracarboxylic acid ester compound has ship, chair form steric configuration, there are four hand-type atoms, Pyromellitic Acid methyl esters, Pyromellitic Acid ethyl ester, corresponding cyclohexanetetracarboxylic acid ester compound is become after the hydrogenation of Pyromellitic Acid butyl ester hydrogenation, steric isomer is a lot, only have the cyclohexanetetracarboxylic acid propyl ester stereoisomerism after hydrogenation little, wherein, that content is maximum is cis, cis, cis-1, 2, 4, 5-cyclohexanetetracarboxylic acid propyl ester, less four the little isomerized products of all the other content are cis, tran, tran,-1, 2, 4, 5-cyclohexanetetracarboxylic acid propyl ester, cis, cis, tran,-1, 2, 4, 5-cyclohexanetetracarboxylic acid propyl ester, tran, tran, tran,-1, 2, 4, 5-cyclohexanetetracarboxylic acid propyl ester, tran, cis, tran,-1, 2, 4, 5-cyclohexanetetracarboxylic acid propyl ester.
Due to hydrogenation Pyromellitic Acid orthocarbonate facile hydrolysis, the present invention uses H-type mordenite to make hydrolyst, filters just energy thoroughly separating catalyst, does not need to add high boiling solvent.The disadvantage using sulfuric acid to make hydrolyst is, the sulfuric acid of meeting residual minim in product.
The preparation method of described H-type mordenite is as follows, gets 100 parts by weight of powder shape mordenites, adds 10 parts by weight of powder shape γ-aluminium sesquioxides, 10-15 weight part dust technology, stir into dried noodle shape, be extruded into strip, dry in 100-110 DEG C of baking oven, be ground into particulate state; Then use 10% aqueous ammonium chloride solution soaked overnight, filter, dry moisture, then roasting 3-4 hour in 500-600 DEG C of retort furnace, cooling.
Beneficial effect of the present invention is as follows:
(1) catalyst activity of Pyromellitic Acid orthocarbonate hydrogenation reaction prepared of the present invention and work-ing life higher, catalyzer can reach 2000 hours work-ing life, reaction conversion ratio 99.2%, hydrogenation reaction selects 98.2%, effectively reduce temperature of reaction and reaction pressure, hydrogenation reaction temperature is at 100-110 DEG C, and reaction pressure only has 0.2 ~ 0.5Mpa; Use fixed bed hydrogenation reactor hydrogenation, low pressure reaction is low for equipment requirements, and emptying hydrogen is easy to recycling by low pressure force (forcing) pump.
(2) the esterification used catalyst in the present invention is H-type mordenite, does not have corrodibility, and catalyzer can pass through simple filter method and product separation, simple to operate, does not produce any waste water;
(3) the present invention's propyl alcohol is as the raw material of esterification, and the hydrogenation Pyromellitic Acid orthocarbonate that the product generated with propyl alcohol esterification generates through hydrogenation reaction more facile hydrolysis, hydrolysis reaction required time is shorter, and production efficiency is high;
(4) due to hydrogenation Pyromellitic Acid orthocarbonate facile hydrolysis, the present invention uses H-type mordenite to make hydrolyst, filters just energy thoroughly separating catalyst, does not need to add high boiling solvent.
Embodiment
Following nonlimiting examples can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
1, Pyromellitic Acid lactate synthesis Pyromellitic Acid orthocarbonate
In 2L tetra-mouthfuls of reactors, add 218g Pyromellitic Acid, 380g propyl alcohol, 10gH-type mordenite, be warmed up to 110 DEG C, reaction refluxes at such a temperature, with gas-chromatography (GC) monitoring reaction, within about 5 hours, reaction conversion ratio reaches 90%, distills out moisture propyl alcohol.Add the new propyl alcohol of 300g and continue reaction, gas-chromatography monitoring reaction conversion ratio reaches 95%.
Cool to 30-40 DEG C, filter out catalyzer, with a small amount of propyl alcohol drip washing catalyzer, filtrate is lowered the temperature, and carry out recrystallization at 10-15 DEG C, filter out filter cake, filtrate recycle, filter cake dries to obtain 388g Pyromellitic Acid orthocarbonate, GC purity 99.3%, yield 93%.
2, Pyromellitic Acid orthocarbonate hydrogenation synthesis hydrogenation Pyromellitic Acid orthocarbonate
(1) preparation of catalyst for hydrogenation
1. the preparation of catalyst A
Get 94g cocoanut active charcoal (60-80 order), adding equal-volume massfraction is soaked overnight in the HCl solution of 3-5%, within second day, filters, adds 400g deionized water and 100g concentrated hydrochloric acid, drip 8.5gRuCl under stirring
2, 1.6g PdCl
2, the mixing solutions that is made into of 3.2g six water cerous nitrate, 50g deionized water, 50g concentrated hydrochloric acid, within 2-3 hour, drip off, finish stirring 1 hour.Adding massfraction is that 20%NaOH solution is adjusted to pH=14, be heated to 60 DEG C, dripping 80-90g massfraction is that 36% formalin reduces, finishing and dripping massfraction is again 20%NaOH solution, guarantees pH=14, is heated to 90 DEG C of insulated and stirred 1 hour, cooling, filtration, filter cake adds 400g deionized water and stirring 1 hour, filters, with deionized water repeatedly drip washing until filtrate pH=7, to add massfraction be 1%AgNO
3till the constant muddiness of solution.
The metal chloride now adsorbed on the activated carbon is reduced into metallic state by alkali and formaldehyde, is added in 400g ethanol by the catalyzer after reduction and stirs 1 hour, filter, be kept in dehydrated alcohol stand-by.
2. the preparation of catalyst B
Identical with the preparation process of catalyst A, difference is only not add cerous nitrate in the preparation of catalyst B, and rest materials proportioning, reducing process condition etc. are constant.
3. the preparation of catalyzer C
Get 94g cocoanut active charcoal (60-80 order), adding equal-volume massfraction is soaked overnight in the HCl solution of 3-5%, within second day, filters, adds 400g deionized water and 100g concentrated hydrochloric acid, drip 8.5gRuCl under stirring
2, 1.6g PdCl
2, the mixing solutions that is made into of 3.2g six water cerous nitrate, 50g deionized water, 50g concentrated hydrochloric acid, within 2-3 hour, drip off, finish stirring 1 hour, filter, catalyzer deionized water drip washing, until filtrate pH=6-7.
Be added to by above-mentioned for 40g catalyzer in 30cm length, diameter 2cm fixed bed, catalyzer hair plates support, hair plates, at 5cm place, fixed bed lower end, adds 5cm magnet ring and does preheating section above catalyzer.With heating by electric cooker fixed bed to 100-110 DEG C, with air in nitrogen replacement reactor, there is no oxygen until analyze in tail gas.Be warmed up to 220-230 DEG C, passing into volume ratio is 1; The hydrogen of 9 and nitrogen mixed gas reducing catalyst, it is 2.5L/min that mixed gas passes into speed, reduction reaction pressure 0.1-0.2MPa, and tail gas massfraction is emptying after the 3%NaOH aqueous solution absorbs.Reduce after 5-6 hour, improve hydrogen intake, in mixed gas, hydrogen, nitrogen volume ratio are 3; 7, mixed gas passes into speed 2.5L/min, and reduction reaction temperature, reduction pressure are constant.After 5 hours, keep reduction temperature, reduction pressure constant, improve hydrogen intake, hydrogen, nitrogen volume ratio are 1; 1.Make pure hydrogen reduction after 5 hours into, reduction temperature, pressure are constant.To reduce after 10 hours without HCl gas in tail gas, reduction terminates.
(2) hydrogenation reaction
1. the hydrogenation reaction of catalyst A is utilized
Above-mentioned for 40g catalyst A be added in 30cm length, diameter 2cm fixed bed, catalyzer hair plates support, hair plates, at 5cm place, fixed bed lower end, adds 5cm magnet ring and does preheating section above catalyzer.With heating by electric cooker fixed bed to 100-110 DEG C, first then use hydrogen exchange reactor with nitrogen, there is no oxygen, ethanol until analyze in tail gas.
Be Pyromellitic Acid orthocarbonate and the propyl alcohol of 3:7 by weight ratio, per hourly add 200-220g.Hydrogen passes into speed and remains on 2.5L/min, reaction pressure 0.2-0.5MPa, and temperature of reaction remains on 200-220 DEG C.Product solution is lowered the temperature through condenser, collects in receiving tank, and the pressurization of hydrogen barrier film pressure pump is recovered in steel cylinder for subsequent use.The solution collected distills out propyl alcohol, and propyl alcohol can reuse, and in still kettle, material is exactly product hydrogenated cyclohexyl alkane tetracarboxylic acid propyl ester.
GC monitors in hydrogenation reaction, and the activity rating of catalyst A is as follows;
2. the hydrogenation reaction of catalyst B is utilized
Use above-mentioned catalyst B, other processing condition are constant, reaction operation 500 hours, and gas-chromatography GC monitors, reaction conversion ratio 98%, and the little isomer of main product purity 97%, four adds up to 1%; Be warmed up to 230-240 DEG C of reaction, GC monitoring in 1000 hours, reaction conversion ratio 99%, the little isomer of main product purity 94%, four adds up to 3%.
3. the hydrogenation reaction of catalyzer C is utilized
Use catalyzer C, be added to by above-mentioned for 40g catalyzer C in 30cm length, diameter 2cm fixed bed, catalyzer hair plates support, hair plates, at 5cm place, fixed bed lower end, adds 5cm magnet ring and does preheating section above catalyzer.With heating by electric cooker fixed bed to 100-110 DEG C, with air in nitrogen replacement reactor, there is no oxygen until analyze in tail gas.
Be Pyromellitic Acid orthocarbonate and the propyl alcohol of 3:7 by weight ratio, per hourly add 200-220g.Hydrogen passes into speed and remains on 2.5L/min, reaction pressure 0.2-0.5MPa, and temperature of reaction remains on 200-220 DEG C.Product solution is lowered the temperature through condenser, collects in receiving tank, and the pressurization of hydrogen barrier film pressure pump is recovered in steel cylinder for subsequent use.The solution collected distills out propyl alcohol, and propyl alcohol can reuse, and in still kettle, material is exactly product hydrogenated cyclohexyl alkane tetracarboxylic acid propyl ester.
GC monitors in hydrogenation reaction, and the activity rating of catalyzer C is as follows;
3, hydrogenation Pyromellitic Acid orthocarbonate is through hydrolysis reaction system 1,2,4,5-cyclohexanetetracarboxylic acid
Add 10gH-type mordenite catalyst, 500g water, 100g hydrogenation Pyromellitic Acid orthocarbonate at 1000ml reactor, be warmed up to 102-103 DEG C, reaction starts backflow, reacts after 5 hours, makes distillation into.Distillation speed 1g/min, control temperature 100-150 DEG C, when distilling out 300g cut, add 300g water, continues distillation, goes out cut alcohol content monitoring reaction by analytical distillation.In time distilling out cut not containing propyl alcohol, get organic layer in reactor, with high performance liquid chromatography (HPLC) monitoring reaction, until product spectrogram content reaches more than 99% stop distillation.
Cool to room temperature, filter out catalyzer, then liquid pressure-reducing is distilled pulpous state, filter, filtrate is containing product reuse, and filter cake vacuum drying, oven temperature 100-120 DEG C, vacuum-0.09MPa, until product moisture < 0.2%.
Single batch obtains product 50g, yield 80%, and filtrate cycle uses, and yield can reach 90%.。
4,1,2,4,5-cyclohexanetetracarboxylic acid is through dehydration reaction system 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride
200g acetic acid, 240g diacetyl oxide, 140g1 is added, 2,4 in 1L reactor, 5-cyclohexanetetracarboxylic acid, is warmed up to 110-120 DEG C, and reaction starts backflow, insulation reaction 5 minutes, cooling, filters, filter cake is dried and is obtained 69g product that is 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, yield 80%, filtrate can reuse.
Wherein, being prepared as follows of the H-type mordenite in step 1 and step 3;
Get the Powdered mordenite of 100g ZSM-8, add the Powdered γ-aluminium sesquioxide of 10g, 10-15g massfraction is 5% dust technology, stir into dried noodle shape, be extruded into diameter 2mm strip with banded extruder, dry in 100-110 DEG C of baking oven, be ground into the particulate state of diameter 2mm, long 2mm.Then with massfraction be 10% aqueous ammonium chloride solution soak 10-12 hour, carry out Na ion and NH
4ion-exchange.Ion-exchange terminates to filter.First in the baking oven of 100-110 DEG C, dry moisture, then roasting 3-4 hour in 500-600 DEG C of retort furnace, by-NH
4ion roasting becomes-H ion, stores stand-by after cooling to room temperature.
Claims (6)
1. the preparation method of hydrogenation Pyromellitic Acid orthocarbonate, described preparation method is, Pyromellitic Acid orthocarbonate is hydrogenation synthesis hydrogenation of benzene tetracarboxylic acid orthocarbonate under hydrogenation catalyst effect, it is characterized in that, the carrier of described hydrogenation catalyst is cocoanut active charcoal, and active ingredient is the composition metal of the metal Ru of massfraction 1-5%, the metal Pd of massfraction 0.5-2%, the metal Ce composition of massfraction 0.3-2%.
2. the preparation method of hydrogenation Pyromellitic Acid orthocarbonate according to claim 1, it is characterized in that, the preparation method of described hydrogenation catalyst comprises the steps:
1. get 94 weight part cocoanut active charcoals, adding equal-volume massfraction is soaked overnight in 3-5%HCl, filters, adds 400 parts by weight of deionized water and 100 weight part concentrated hydrochloric acids in the gac after filtration, drips 2-10 weight part RuCl
3, 0.9-3.5 weight part PdCl
2, the mixing solutions that is made into of 1-6.3 weight part six water cerous nitrate, 50 parts by weight of deionized water, 50 weight part concentrated hydrochloric acids;
2. add NaOH solution and be adjusted to pH=14, be heated to 60 DEG C, dripping 80-90 weight part massfraction is the formalin of 36%, finish and drip NaOH solution again, guarantee pH=14, be heated to 90 DEG C of insulated and stirred, cooling, filtration, filter cake adds deionized water and stirring, filters, with deionized water repeatedly drip washing until filtrate pH=7, to add massfraction be 1%AgNO
3till the constant muddiness of solution.
3. the preparation method of hydrogenation Pyromellitic Acid orthocarbonate according to claim 2, it is characterized in that, 2. the step of the preparation method of described hydrogenation catalyst is, dropwise rear stirring, filter, the deionized water drip washing of filter cake and catalyzer, until filtrate pH=6-7; Be added in fixed bed by above-mentioned catalyzer, be warmed up to 220-230 DEG C, pass into the mixed gas reducing catalyst of hydrogen or hydrogen and nitrogen, it is 2.5L/min that gas passes into speed, and reduction reaction pressure 0.1-0.2MPa, without HCl gas to tail gas.
4. the preparation method of hydrogenation Pyromellitic Acid orthocarbonate according to claim 1, is characterized in that, described Pyromellitic Acid orthocarbonate be with Pyromellitic Acid and propyl alcohol be raw material, H-type mordenite for catalyzer, prepare through esterification.
5. the preparation method of hydrogenation Pyromellitic Acid orthocarbonate according to claim 4, it is characterized in that, the preparation method of described H-type mordenite is as follows: get 100 parts by weight of powder shape mordenites, add 10 parts by weight of powder shape γ-aluminium sesquioxides, 10-15 weight part dust technology, stir into dried noodle shape, be extruded into strip, dry in 100-110 DEG C of baking oven, be ground into particulate state; Then use 10% aqueous ammonium chloride solution soaked overnight, filter, dry moisture, then roasting 3-4 hour in 500-600 DEG C of retort furnace, cooling.
6.1,2,4, the preparation method of 5-cyclohexanetetracarboxylic acid dianhydride, is characterized in that, utilizes hydrogenation Pyromellitic Acid orthocarbonate prepared by method described in claim 1-5 any one claim, through hydrolysis reaction system 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid prepares 1 through dehydration reaction, and 2,4,5-cyclohexanetetracarboxylic acid dianhydride; Wherein, hydrolysis reaction used catalyst is H-type mordenite.
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Application Number | Priority Date | Filing Date | Title |
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CN110461851A (en) * | 2017-03-29 | 2019-11-15 | 三菱瓦斯化学株式会社 | The manufacturing method of 1,2,4,5- cyclopentanetetracarboxylic's dianhydride |
CN114163449A (en) * | 2021-12-20 | 2022-03-11 | 大连奇凯医药科技有限公司 | Preparation and characterization method of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride |
CN115894512A (en) * | 2022-12-21 | 2023-04-04 | 大连奇凯医药科技有限公司 | Synthesis and detection method of 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
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CN110461851A (en) * | 2017-03-29 | 2019-11-15 | 三菱瓦斯化学株式会社 | The manufacturing method of 1,2,4,5- cyclopentanetetracarboxylic's dianhydride |
US11174269B2 (en) | 2017-03-29 | 2021-11-16 | Mitsubishi Gas Chemical Company, Inc. | Method for producing 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
CN114163449A (en) * | 2021-12-20 | 2022-03-11 | 大连奇凯医药科技有限公司 | Preparation and characterization method of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride |
CN114163449B (en) * | 2021-12-20 | 2023-03-17 | 大连奇凯医药科技有限公司 | Preparation and characterization method of 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
CN115894512A (en) * | 2022-12-21 | 2023-04-04 | 大连奇凯医药科技有限公司 | Synthesis and detection method of 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
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Inventor after: Yuanfeng Inventor after: Jiang Dianbao Inventor after: Li Chengbin Inventor after: Pei Xiong Inventor before: Yuanfeng Inventor before: Jiang Dianping Inventor before: Li Chengbin Inventor before: Pei Xiong |