CN111068774B - Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof - Google Patents

Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof Download PDF

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CN111068774B
CN111068774B CN201811214408.3A CN201811214408A CN111068774B CN 111068774 B CN111068774 B CN 111068774B CN 201811214408 A CN201811214408 A CN 201811214408A CN 111068774 B CN111068774 B CN 111068774B
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查晓钟
杨运信
朱庆才
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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Abstract

The invention relates to a catalyst for synthesizing 2, 6-naphthalenedicarboxylic acid and application thereof, mainly solving the problem of lower activity and selectivity of the 2, 6-naphthalenedicarboxylic acid catalyst in the prior art, and adopting the catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid, wherein the catalyst comprises a main catalyst, a cocatalyst and an accelerant, and the main catalyst adopts a compound containing Co and a compound containing Mn; the cocatalyst comprises bromide, and the promoter is N-heterocyclic carbene and derivatives, so that the technical problem is better solved, and the catalyst can be used in the industrial production of the poly (ethylene 2, 6-naphthalate).

Description

Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof
Technical Field
The invention relates to a catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof.
Background
2,6-naphthalene dicarboxylic acid (2, 6-NDA), known as a novel functional material of the 21 st century, is an important monomer for synthesizing high performance plastics as well as liquid crystal polyester resins. In recent years, the use of polyethylene 2, 6-naphthalate (PEN) in place of polyethylene terephthalate (PET) has become a trend due to its superior properties. The synthesis of 2,6-NDA becomes the bottleneck and key of PEN production, and how to research and develop an industrially feasible 2,6-NDA synthesis process route is favored by scientific research units at home and abroad.
As a method for synthesizing 2,6-NDA, there are a Henke method, an oxidation method, a carbonyl transfer method and the like. The Henke process is a synthesis using 2,6-NDA similar to that for the production of terephthalic acid, and mainly includes both disproportionation and isomerization. The disproportionation method obtains naphthoic acid by naphthalene carboxylation or direct oxidation of beta-methylnaphthalene, then reacts with potassium hydroxide to obtain potassium salt, and then the 2,6-NDA is prepared by the Henkel method disproportionation. The isomerization method comprises the steps of oxidizing disubstituted naphthalene obtained by extracting coal tar distillate or performing alkyl acylation on naphthalene (methylnaphthalene) into naphthalene dicarboxylic acid, and isomerizing potassium naphthalenedicarboxylate by a Henkel method to generate 2,6-NDA.
The carbonyl transfer method mainly uses diiodonaphthalene as a raw material to carry out carbonylation reaction in an acetic acid environment to obtain 2,6-NDA. U.S. Pat. No. 4,4845273 (titled: carbonylation process for production of aromatic) discloses a process for separating 2,6-NDA from naphthalenedicarboxylic acid isomers by crystallization from a mixture of 2,6-diiodonaphthalene and 2,7-diiodonaphthalene as starting materials by Carbonylation using an Rh-containing substance as a catalyst under a solvent acetic acid condition to obtain a mixture of naphthalenedicarboxylic acids.
The liquid phase oxidation method of 2, 6-dialkyl naphthalene has gradually become the key point of research and development at home and abroad because of mild reaction conditions and relatively simple process route. The oxidation method is mainly a 2,6-NDA (naphthalene-based anhydride) oxidation method by using 2, 6-dialkylnaphthalene, and adopts a Co-Mn-Br catalyst system, acetic acid as a solvent, the reaction temperature is about 200 ℃, and the reaction pressure is about 3MPa. The 2, 6-dialkylnaphthalene oxidation method includes a 2, 6-dimethylnaphthalene oxidation method, a 2, 6-isopropylnaphthalene oxidation method, a 2, 6-alkylacylnaphthalene oxidation method, and a 2, 6-diethylnaphthalene oxidation method. In the above-mentioned different 2, 6-dialkylnaphthalene liquid-phase oxidation methods, since 2, 6-dimethylnaphthalene and 2, 7-dimethylnaphthalene have similar physicochemical properties (e.g., a small difference in melting point and boiling point), separation is difficult and the operation cost is high; and 2,6-diisopropyl naphthalene (2, 6-DIPN) is easy to separate and purify from raw materials (isomer mixture), and the operation cost is lower. Thus, the oxidation of 2,6-diisopropylnaphthalene has long been a potentially competitive process route. The research on the liquid phase oxidation of 2,6-diisopropylnaphthalene to 2,6-NDA in Japan and U.S. was carried out earlier, focusing mainly on 3 aspects: (1) the proportion and the reaction conditions of a Co-Mn-Br main catalytic system; (2) a cocatalyst system; (3) a reaction solvent system. Guocha et al, in "Liquid phase catalytic oxidation of 2, 6-dimethylpropylnaphthalene to 2,6-naphthalene dicarboxylic acid over Co-Mn-B catalyst", teach that at a temperature of 185 ℃ and a pressure of 2.0MPa, the ratio of the amount of Co-Mn to Br is 5, the ratio of the amount of Co-Mn to 2,6-DIPN species is 15, and that under conditions of 1,2,6-DIPN to HOAc.
The above methods have the problems of low yield and low selectivity of 2,6-NDA in the process of preparing the 2,6-NDA.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low yield and low selectivity of the 2, 6-naphthalenedicarboxylic acid, and the invention provides a catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid, wherein the catalyst has the characteristics of high yield of the 2, 6-naphthalenedicarboxylic acid and high selectivity of the 2, 6-naphthalenedicarboxylic acid.
The second problem to be solved by the invention is the application of the catalyst.
The invention also provides a method for synthesizing 2,6-naphthalene dicarboxylic acid by using the catalyst.
In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid comprises a main catalyst, a cocatalyst and an accelerator, wherein the main catalyst adopts a compound containing Co and a compound containing Mn; the cocatalyst is bromide, and the accelerator is N-heterocyclic carbene and derivatives.
In the above technical solution, the compound of the main catalyst Co and/or the compound of Mn is preferably acetate.
In the above-mentioned embodiment, the cocatalyst preferably includes at least one selected from the group consisting of alkali metal bromide, HBr, and organic bromide, and more preferably potassium bromide.
The N-heterocyclic carbene and the derivative are beneficial to improving the selectivity and the yield of the 2, 6-naphthalenedicarboxylic acid.
In the above technical scheme, the accelerator is preferably selected from N-heterocyclic carbene and derivatives represented by the free structural formula I):
Figure GDA0001890555450000021
wherein R is 1 ～R 2 Independently from a hydrogen atom, a hydrocarbyl group having 1 to 5 carbon atoms, or an aromatic ring; y is at least one selected from a N-containing group, a P-containing group, or a hydrocarbylene group having from 1 to 12 carbon atoms.
In the above technical scheme, the structural formula I is preferably selected from the group consisting of R and 1 n, and R connected 2 The N, C and Y connected form a 4-to 8-membered ring structure. Such as, but not limited to, a 4-membered ring structure, a 5-membered ring structure, a 6-membered ring structure, a 7-membered ring structure, and the like.
In the above technical solution, the accelerator is more preferably at least one selected from the group consisting of compounds represented by structural formula II to compounds represented by structural formula IX:
Figure GDA0001890555450000031
in the above technical scheme, the most preferable accelerator comprises a compound shown in a structural formula VI and a compound shown in a structural formula VIII, and the two have synergistic effects on improving the yield of the 2, 6-naphthalenedicarboxylic acid and the selectivity of the 2, 6-naphthalenedicarboxylic acid. At this time, the ratio between the compound represented by structural formula VI and the compound represented by structural formula VIII is not particularly limited, and a comparable synergistic effect can be obtained. For example, but not limited to, the weight ratio of the compound of formula VI to the compound of formula VIII is from 0.10 to 10.00, and more specific non-limiting examples within this range can be 0.20, 0.40, 0.50, 0.60, 0.80, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and the like.
In the above technical solution, the weight part of the Co element in the catalyst is calculated as 100 parts, and the weight part of the Mn element is preferably 50 to 100 parts, for example, but not limited to, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, and the like, and more preferably 85 to 100 parts.
In the above technical solution, the weight part of the Co element in the catalyst is 100 parts, and the weight part of the bromide is preferably 50 to 250 parts, such as, but not limited to, 50 parts, 55 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 130 parts, 150 parts, 170 parts, 190 parts, 200 parts, 210 parts, 230 parts, 240 parts, 250 parts, and the like, and more preferably 170 to 210 parts, based on bromine.
In the technical scheme, the weight parts of the Co element in the catalyst are calculated by 100 parts, and the N-heterocyclic carbene and the derivative are calculated by R 1 N and to R 2 The total parts by weight of N attached preferably amounts to 10 to 100 parts by weight. Such as but not limited to10 parts, 11 parts, 15 parts, 18 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts and the like, more preferably 20 to 80 parts.
To solve the second technical problem, the technical solution of the present invention is as follows:
use of a catalyst according to any of the preceding claims for the synthesis of 2, 6-naphthalenedicarboxylic acid.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
a method for synthesizing 2, 6-naphthalenedicarboxylic acid comprising: 2,6-diisopropyl naphthalene and air are taken as raw materials, acetic acid is taken as a solvent, and the reaction is carried out in the presence of the catalyst in one technical scheme of the technical problems to generate the 2,6-naphthalene dicarboxylic acid.
The key of the invention is the selection of the catalyst, and the skilled person knows how to determine the appropriate reaction temperature, reaction time, reaction pressure and material ratio according to the actual needs. However:
the reaction temperature in the technical scheme is preferably 120-200 ℃;
the reaction pressure in the technical scheme is preferably 1.5-3.0 MPa;
the reaction time in the technical scheme is preferably 2.0-5.0 h.
In the above technical scheme, 2,6-diisopropylnaphthalene =1 (0.02-0.10) is preferred as the acetic acid in terms of molar ratio.
In a specific embodiment, the number of moles of the catalyst refers to the sum of the number of moles of all metal element atoms in the main catalyst.
The product of the invention is cooled, decompressed and separated, the crude product is washed by hot distilled water after centrifugal separation and then dried, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water, and the conversion rate of 2,6-diisopropyl naphthalene and the yield and the selectivity of 2,6-naphthalene dicarboxylic acid are calculated according to the following formulas:
Figure GDA0001890555450000051
Figure GDA0001890555450000052
Figure GDA0001890555450000053
compared with the prior art, the key of the invention is that the N-heterocyclic carbene and the derivative are adopted as the catalyst, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield and selectivity of the 2,6-naphthalene dicarboxylic acid.
Experimental results show that the yield of the 2, 6-naphthalenedicarboxylic acid prepared by the invention can reach 79.45%, the selectivity can reach 94.50%, a good technical effect is achieved, particularly, the catalyst simultaneously comprises the compounds shown in the structural formulas VI and VIII, a more prominent technical effect is achieved, and the catalyst can be used in industrial production of the poly (ethylene 2, 6-naphthalenedicarboxylate). The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr and a compound shown as a structural formula II. Wherein the weight portion of Co element is 100 portions, the weight portion of Mn element is 95 portions, the weight portion of bromide is 190 portions counted by bromine, and the weight portion of the compound shown in the structural formula II is 48 portions counted by N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.45% and the selectivity was calculated to be 94.50%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ COMPARATIVE EXAMPLE 1 ]
Is a comparative example of [ example 1 ].
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O and KBr. Wherein the weight part of the Co element is 100 parts, the weight part of the Mn element is 95 parts, and the weight part of the bromide is 190 parts counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 65.64% and the selectivity was calculated to be 90.13%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from comparison with example 1, the catalyst of the present invention, using the catalyst of formula II, performed better than the catalyst without the promoter, and had high selectivity and yield of 2, 6-naphthalenedicarboxylic acid.
[ example 2 ] A method for producing a polycarbonate
Catalyst and process for preparing sameThe composition of (A): weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The catalyst comprises O, KBr and a compound shown in a structural formula III, wherein the weight portion of Co is 100 parts, the weight portion of Mn is 95 parts, the weight portion of bromide is 190 parts counted by bromine, and the weight portion of the compound shown in the structural formula III is 48 parts counted by N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.63% and the selectivity was calculated to be 94.41%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 3 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr and a compound shown in a structural formula IV, wherein the weight part of Co is 100, the weight part of Mn is 95, the weight part of bromide is 190 according to the weight part of bromine, and the compound shown in the structural formula IV corresponds to the compound shown in the structural formula I and R 1 N and to R 2 The total weight part of the N is 48 parts.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.53% and the selectivity was calculated to be 94.45%, and the catalyst composition, reaction conditions, amounts of materials fed, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 4 ] A method for producing a polycarbonate
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The material comprises 100 parts by weight of Co element, 95 parts by weight of Mn element, 190 parts by weight of bromide calculated by bromine and 48 parts by weight of compound shown in structural formula V calculated by N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.55% and the selectivity was calculated to be 94.38%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 5 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The catalyst comprises O, KBr and a compound shown in a structural formula VI, wherein the weight portion of Co is 100 parts, the weight portion of Mn is 95 parts, the weight portion of bromide is 190 parts counted by bromine, and the weight portion of the compound shown in the structural formula VI is 48 parts counted by N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.47% and the selectivity was calculated to be 94.55%, and the catalyst composition, reaction conditions, amounts of materials fed, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 6 ] A method for producing a polycarbonate
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The catalyst comprises O, KBr and a compound shown in a structural formula VII, wherein the weight portion of Co is 100 parts, the weight portion of Mn is 95 parts, the weight portion of bromide is 190 parts counted by bromine, and the weight portion of the compound shown in the structural formula VII is 48 parts counted by N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.39% and the selectivity was calculated to be 94.54%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 7 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The catalyst comprises O, KBr and a compound shown as a structural formula VIII, wherein the weight part of Co is 100 parts, the weight part of Mn is 95 parts, the weight part of bromide is 190 parts by weight of bromine, and the weight part of the compound shown as the structural formula VIII is 48 parts by weight of N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.64% and the selectivity was calculated to be 94.40%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 8 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 The catalyst comprises O, KBr and a compound shown in a structural formula IX, wherein the weight part of Co is 100 parts, the weight part of Mn is 95 parts, the weight part of bromide is 190 parts by weight of bromine, and the weight part of the compound shown in the structural formula IX is 48 parts by weight of N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.41% and the selectivity was calculated to be 94.37%, and the catalyst composition, reaction conditions, amounts of materials fed, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 9 ] A method for producing a polycarbonate
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr and a compound shown in a structural formula II. Wherein the weight portion of the Co element is 100, the weight portion of the Mn element is 85, the weight portion of the bromide is 170 according to the weight portion of the bromine, and the weight portion of the compound shown in the structural formula II is 20 according to the weight portion of the N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.05mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 1.5MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 120 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 2.0 hours.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 76.85% and the selectivity was calculated to be 94.15%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 10 ]
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr and a compound shown in a structural formula II. Wherein the weight portion of the Co element is 100, the weight portion of the Mn element is 100, the weight portion of the bromide is 210 in terms of bromine, and the weight portion of the compound shown in the structural formula II is 80 in terms of N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.25mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 3.0MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 200 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 5.0 hours.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.54% and the selectivity was calculated to be 93.88%, and the catalyst composition, reaction conditions, amounts of materials fed, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 11 ] A method for producing a polycarbonate
Composition of the catalyst: weighing Co (OAc) according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr, a compound shown as a structural formula VI and a compound shown as a structural formula VIII. Wherein, the weight portion of Co element is 100, the weight portion of Mn element is 95, the weight portion of bromide is 190 according to bromine, the weight portion of the compound shown in structural formula VI is 27 according to N, and the weight portion of the compound shown in structural formula VIII is 21 according to N.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.10mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 2.75MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to 178 ℃, controlling the air flow to 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 81.39% and the selectivity was calculated to be 95.32%, and the catalyst composition, reaction conditions, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from example 11 in comparison with examples 5 and 7, the catalyst used in the present invention has a synergistic effect between the compound represented by the structural formula VI and the compound represented by the structural formula VIII as a promoter in terms of increasing the selectivity and yield of 2, 6-naphthalenedicarboxylic acid.
TABLE 1
Figure GDA0001890555450000121

Claims (12)

  1. The catalyst for synthesizing the 1.2, 6-naphthalenedicarboxylic acid comprises a main catalyst, a cocatalyst and an accelerant, wherein the main catalyst adopts a compound containing Co and a compound containing Mn; the cocatalyst is bromide, the accelerator is N-heterocyclic carbene and a derivative, and the accelerator is selected from the N-heterocyclic carbene and the derivative shown in the structural formula I:
    Figure FDA0003850940150000011
    wherein R is 1 ～R 2 Independently from a hydrogen atom, a hydrocarbyl group having 1 to 5 carbon atoms, or an aromatic ring; y is at least one selected from a N-containing group, a P-containing group, or a hydrocarbylene group having from 1 to 12 carbon atoms.
  2. 2. The catalyst according to claim 1, characterized in that the compound of the procatalyst Co and/or the compound of Mn is an acetate.
  3. 3. The catalyst of claim 1, wherein the promoter comprises at least one member selected from the group consisting of alkali metal bromide, HBr, and organic bromide.
  4. 4. The catalyst of claim 1, wherein the promoter is of the formula I 1 N, and R connected to each other 2 The N, C and Y connected form a 4-to 8-membered ring structure.
  5. 5. The catalyst of claim 4, wherein the promoter is at least one member selected from the group consisting of compounds represented by structural formula II through compounds represented by structural formula IX:
    Figure FDA0003850940150000012
    Figure FDA0003850940150000021
  6. 6. the catalyst of claim 4 wherein the promoter comprises a compound of formula VI and a compound of formula VIII.
  7. 7. The catalyst of claim 6, wherein the weight ratio of the compound of formula VI to the compound of formula VIII is from 0.10 to 10.00.
  8. 8. The catalyst of claim 1, wherein the weight portion of Co element in the catalyst is calculated as 100 portions, and the weight portion of Mn element is 50-100 portions.
  9. 9. The catalyst of claim 1, wherein the weight portion of Co element in the catalyst is 100, and the weight portion of bromide in the catalyst is 50-250.
  10. 10. The catalyst of claim 1, wherein the weight portion of Co element in the catalyst is 100, and the N-heterocyclic carbene and the derivative thereof and R in the catalyst are 1 N and to R bound 2 The total weight part of the connected N is 10 to 100 parts.
  11. 11. Use of a catalyst according to any one of claims 1 to 10 in the synthesis of 2, 6-naphthalenedicarboxylic acid.
  12. A method for synthesizing 2, 6-naphthalenedicarboxylic acid comprising: 2,6-diisopropyl naphthalene and air are used as raw materials, acetic acid is used as a solvent, 2,6-naphthalene dicarboxylic acid is synthesized in the presence of the catalyst of any one of claims 1 to 10, the reaction temperature is 120 to 200 ℃, the reaction pressure is 1.5 to 3.0MPa, the reaction time is 2.0 to 5.0h, and the molar ratio of the acetic acid to the 2,6-diisopropyl naphthalene =1 (0.02 to 0.10).
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4709088A (en) * 1983-10-24 1987-11-24 Teijin Petrochemical Industries, Ltd. Process for producing 2,6-naphthalene-dicarboxylic acid
CN101402644A (en) * 2008-10-31 2009-04-08 浙江大学 Production method for metal aza ring carbene complex
CN103242371A (en) * 2013-05-29 2013-08-14 洛阳师范学院 Aryl-pyridine cyclic Pd-N heterocyclic carbene compound as well as preparation method and application thereof
CN104549523A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst used in synthesis of ethylidene diacetate

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Publication number Priority date Publication date Assignee Title
ES2279117T3 (en) * 2002-01-22 2007-08-16 Universiteit Gent METALLIC COMPLEXES TO USE IN A METATESIS.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4709088A (en) * 1983-10-24 1987-11-24 Teijin Petrochemical Industries, Ltd. Process for producing 2,6-naphthalene-dicarboxylic acid
CN101402644A (en) * 2008-10-31 2009-04-08 浙江大学 Production method for metal aza ring carbene complex
CN103242371A (en) * 2013-05-29 2013-08-14 洛阳师范学院 Aryl-pyridine cyclic Pd-N heterocyclic carbene compound as well as preparation method and application thereof
CN104549523A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst used in synthesis of ethylidene diacetate

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