CN103880654A - Preparation method for 2,6-naphthalenedicarboxylic acid - Google Patents

Preparation method for 2,6-naphthalenedicarboxylic acid Download PDF

Info

Publication number
CN103880654A
CN103880654A CN201210553197.2A CN201210553197A CN103880654A CN 103880654 A CN103880654 A CN 103880654A CN 201210553197 A CN201210553197 A CN 201210553197A CN 103880654 A CN103880654 A CN 103880654A
Authority
CN
China
Prior art keywords
preparation
mol ratio
acetic acid
nda
dipn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201210553197.2A
Other languages
Chinese (zh)
Other versions
CN103880654B (en
Inventor
朱庆才
畅延青
陈大伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201210553197.2A priority Critical patent/CN103880654B/en
Publication of CN103880654A publication Critical patent/CN103880654A/en
Application granted granted Critical
Publication of CN103880654B publication Critical patent/CN103880654B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method for 2,6-naphthalenedicarboxylic acid, and mainly solves the problem that catalyst usage amount is too high in the prior art. According to the preparation method, Co-Mn-Br is employed as a catalyst, a mixture of acetic and water is taken as a solvent, the reaction temperature is 160-210 DEG C, the reaction pressure is 2-4 MPa, the reaction time is 3-7 h, and 2,6-naphthalenedicarboxylic acid is prepared by employing oxygen-containing gas to performing liquid-phase oxidation on 2,6-diisopropylnaphthalene. The preparation method is characterized in that the employed technical scheme comprises that the co-catalysts comprise a quaternary ammonium salt and at least one nitrogen oxide compound shown by the general formula I, II, III or IV, wherein the general formula I, II, III and IV are shown in the specification, R1 and R2 are same or different and both represent a hydrogen atom, a halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxy or acyl, and R3, R4 and R5 are same or different and all represent a hydrogen atom or acyl. The technical scheme relatively well solves the problem and is applicable to industrial production of 2,6-naphthalenedicarboxylic acid.

Description

The preparation method of NDA
Technical field
The present invention relates to a kind of method of being prepared NDA by the liquid-phase oxidation of 2,6-isopropyl naphthalene.
Background technology
2,6-naphthalic acid (2,6-NDCA) and derivative be the important monomer of preparation various polyester, polyurethane material and liquid crystalline polymers (LCP) etc., particularly 2, the PEN (PEN) that 6-NDCA and ethylene glycol polycondensation make has broad application prospects in film, packaging vessel (especially Beer Bottle) and industrial fiber.Due to the structural high symmetry of 2,6-NDCA.Making PEN have the characteristic of straight-chain polymer, is a kind of good rigidly, intensity is large, hot workability is excellent high performance material.Compared with polyethylene terephthalate (PET), the performances such as PEN thermotolerance, barrier, mechanical property, chemical proofing, uvioresistant are more superior.At present industrial main by dialkyl group naphthalene air oxidation in liquid phase synthetic 2 under Co-Mn-Br catalyzer, 6-NDCA, as US Patent No. 5183933(title is: Process for preparing 2,6-naphthalene-dicarboxylic acid) adopt 2,6-dimethylnaphthalene (2,6-DMN) make 2,6-NDCA, its yield is 93%.Various 2, in 6-dialkyl group naphthalene liquid phase oxidation, due to the physical properties of 2,6-dimethylnaphthalene and the physicochemical property of 2,7-dimethylnaphthalene similar, separate more difficultly, running cost is higher; And 2,6-DIPN (2,6-DIPN) is easy to separate, purify with raw material (isomer mixture), running cost is lower.Therefore,, from industrial production and Financial cost, the operational path that 2,6-DIPN oxidation style is prepared 2,6-NDCA has more development prospect.US Patent No. 4681978(title is: Process for producing 2,6-naphthalene-dicarboxylic acid) in (Co+Mn)/2, the mol ratio of 6-DIPN is up to 2 of acquisition in 3.897 o'clock, 6-NDCA yield is 91.7%, if but reducing (Co+Mn)/2, the mol ratio of 6-DIPN significantly reduces the yield that causes product, and high catalyst levels like this, from an economic point of view, described technique is disadvantageous.
Summary of the invention
Technical problem to be solved by this invention is the too high problem of catalyst levels in the NDA preparation existing in prior art.Provide a kind of 2,6-DIPN liquid-phase oxidation to prepare the method for 2,6 naphthalic acids, it is few that the method has catalyst levels, the feature that target product NDA yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of 2, the preparation method of 6-naphthalic acid, taking Co-Mn-Br as catalyzer, the mixture of acetic acid and water is solvent, it is 160～210 DEG C in temperature of reaction, reaction pressure is 2～4MPa, reaction times is under the condition of 3～7h, with oxygenous gas liquid phase oxidation 2,6-diisopropylnaphthalene is prepared NDA, and described catalyzer is taking quaternary ammonium salt and select at least one oxynitrides that free general formula I, II, III or IV represent as promotor:
Figure 135107DEST_PATH_IMAGE001
Figure 549907DEST_PATH_IMAGE002
（I） （II）
Figure 492456DEST_PATH_IMAGE003
Figure 743439DEST_PATH_IMAGE004
（III） （IV）
Wherein, R 1and R 2for identical or different, represent separately hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group; R 3, R 4and R 5for identical or different, be expressed as hydrogen atom or acyl group.
In such scheme, the preferred Tetrabutyl amonium bromide of described quaternary ammonium salt, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, C 12-16any in alkyl trimethyl ammonium bromide and triethyl benzyl ammonia chloride; Described quaternary ammonium salt and the mol ratio of acetic acid are preferably 0.0001～0.01, and more preferably 0.003～0.0045; Described oxynitrides and the mol ratio of acetic acid are preferably 0.01～0.1, and more preferably 0.025～0.075; In described acetic acid and the mixture of water, the mol ratio of water and acetic acid is preferably 0.1～0.15; In described Co-Mn-Br catalyst proportion, the mol ratio that (Co+Mn) is preferably 0.015～0.04, Co:Mn:Br with the mol ratio of acetic acid is preferably 1:(0.5～2): (1～10); Described (Co+Mn)/2, the mol ratio of 6-DIPN is preferably 0.1～4, and more preferably 0.5～2; The described preferred air of oxygenous gas, the mol ratio of air and raw material 2,6-DIPN is preferably 20～60, and more preferably 30～50.
The discovery that contriver is surprised, adopts after aforesaid method, in the situation that catalyst levels is less, still obtained very high by 2,6-NDCA yield.Experimental result shows, prior art is in (Co+Mn)/2, the mol ratio of 6-DIPN be within 0.2 o'clock, obtain 2,6-NDCA yield is 72.6%, and the inventive method under equal conditions can make 2, the yield of 6-NDCA is 92.6%, has obtained good technique effect.
Embodiment
[embodiment 1]
The preparation of NDA: by 2.5mol Glacial acetic acid, 0.25mol water, 0.02molCo (OAc) 2, 0.02mol Mn (OAc) 2, 0.1mol Potassium Bromide, 0.0075mol Tetrabutyl amonium bromide, 0.0625molN-hydroxyphthalimide (NHPI) and 0.2mol2,6-diisopropylnaphthalene adds in titanium material reactor, first discharge in still and be pressurized to 2.5MPa after air with nitrogen, improve stirring velocity to 800rpm, supply with continuously pressurized air to reaction pressure 3.0MPa, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 200 DEG C, reaction pressure 3.0MPa, air and 2, the mol ratio of 6-diisopropylnaphthalene is 40, after sustained reaction 3h, and stopped reaction.
Product analysis: reaction mixture that above-mentioned reaction is obtained is cooling, filter, gained solid first after through the Glacial acetic acid of 60 DEG C and the hot distilled water washing of 80 DEG C, then dry 5h at 85 DEG C, obtains reaction product.Adopt the methods analyst reaction product of document (2,6-DIPN liquid phase air oxidation NDA processed, Journal of Chemical Industry and Engineering, 2007,8:1996-2003), the yield that obtains as calculated NDA is 92.6%.
[embodiment 2-6]
Only change quaternary ammonium salt and oxynitrides kind, do not change it and drop into molar weight, all the other operate with embodiment 1, and the yield of the NDA of each embodiment gained is as shown in table 1.
[embodiment 7-14]
Only change the input amount of Tetrabutyl amonium bromide and HP (NHPI), do not change the input amount of all the other raw materials, all the other operate with embodiment 1, and the yield of the NDA of each embodiment gained is as shown in table 2.
[embodiment 15-18]
Only change the input amount of water, do not change the input amount of all the other raw materials, all the other operate with embodiment 1, and the yield of the NDA of each embodiment gained is as shown in table 2.
[embodiment 19-28]
Only change Co (OAc) 2, Mn (OAc) 2and the input amount of Potassium Bromide, not changing the input amount of all the other raw materials, all the other operate with embodiment 1, and the yield of the NDA of each embodiment gained is as shown in table 2.
[comparative example 1]
Only add Tetrabutyl amonium bromide, do not add HP, all the other operate with embodiment 1, and the yield of the NDA of comparative example 1 gained is as shown in table 1.
[comparative example 2]
Only add HP, do not add Tetrabutyl amonium bromide, all the other operate with embodiment 1, and the yield of the NDA of comparative example 2 gained is as shown in table 1.
[comparative example 3]
Do not add Tetrabutyl amonium bromide and HP, all the other operate with embodiment 1, and the yield of the NDA of comparative example 3 gained is as shown in table 1.
1(is continued for table)
Figure 164057DEST_PATH_IMAGE005
Table 1(is continuous)
Figure 698943DEST_PATH_IMAGE006
2(is continued for table)
Quaternary ammonium salt/acetic acid mol ratio Oxynitrides/acetic acid mol ratio Water/acetic acid mol ratio
Embodiment 7 0.0001 0.025 0.1
Embodiment 8 0.0020 0.025 0.1
Embodiment 9 0.0045 0.025 0.1
Embodiment 10 0.0080 0.025 0.1
Embodiment 11 0.0045 0.010 0.1
Embodiment 12 0.0045 0.020 0.1
Embodiment 13 0.0045 0.075 0.1
Embodiment 14 0.0045 0.100 0.1
Embodiment 15 0.0030 0.025 0
Embodiment 16 0.0030 0.025 0.05
Embodiment 17 0.0030 0.025 0.15
Embodiment 18 0.0030 0.025 0.2
Embodiment 19 0.0030 0.025 0.1
Embodiment 20 0.0030 0.025 0.1
Embodiment 21 0.0030 0.025 0.1
Embodiment 22 0.0030 0.025 0.1
Embodiment 23 0.0030 0.025 0.1
Embodiment 24 0.0030 0.025 0.1
Embodiment 25 0.0030 0.025 0.1
Embodiment 26 0.0030 0.025 0.1
Embodiment 27 0.0030 0.025 0.1
Embodiment 28 0.0030 0.025 0.1
Table 2(is continuous)
Figure 123977DEST_PATH_IMAGE007

Claims (10)

1. one kind 2, the preparation method of 6-naphthalic acid, taking Co-Mn-Br as catalyzer, the mixture of acetic acid and water is solvent, is 160～210 DEG C in temperature of reaction, reaction pressure is 2～4MPa, reaction times is under the condition of 3～7h, prepares 2 with oxygenous gas liquid phase oxidation 2,6-DIPN, 6-naphthalic acid, is characterized in that described catalyzer taking quaternary ammonium salt and selects at least one oxynitrides that free general formula I, II, III or IV represent as promotor:
Figure 264264DEST_PATH_IMAGE002
（I） （II）
Figure 848960DEST_PATH_IMAGE003
（III） （IV）
Wherein, R 1and R 2for identical or different, represent separately hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group; R 3, R 4and R 5for identical or different, be expressed as hydrogen atom or acyl group.
2. the preparation method of a kind of NDA according to claim 1, is characterized in that described quaternary ammonium salt is Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, C 12-16any in alkyl trimethyl ammonium bromide and triethyl benzyl ammonia chloride.
3. the preparation method of a kind of NDA according to claim 1, is characterized in that described quaternary ammonium salt and the mol ratio of acetic acid are 0.0001～0.01, and the mol ratio of oxynitrides and acetic acid is 0.01～0.1.
4. according to the preparation method of a kind of NDA described in claim 1 or 3, it is characterized in that described quaternary ammonium salt and the mol ratio of acetic acid are 0.003～0.0045, the mol ratio of oxynitrides and acetic acid is 0.025～0.075.
5. the preparation method of a kind of NDA according to claim 1, in the acetic acid described in it is characterized in that and the mixture of water, the mol ratio of water and acetic acid is 0.1～0.15.
6. according to claim 1 a kind of 2, the preparation method of 6-naphthalic acid, it is characterized in that in described Co-Mn-Br catalyst proportion, (Co+Mn) be 0.015～0.04, Co:Mn:Br mol ratio is 1:(0.5～2 with the mol ratio of acetic acid): (1～10).
7. the preparation method of a kind of NDA according to claim 1, is characterized in that described (Co+Mn)/2, and the mol ratio of 6-DIPN is 0.1～4.
8. the preparation method of a kind of NDA according to claim 1, is characterized in that described (Co+Mn)/2, and the mol ratio of 6-DIPN is 0.5～2.
9. the preparation method of a kind of NDA according to claim 1, is characterized in that described oxygenous gas is air, and the mol ratio of air and raw material 2,6-DIPN is 20～60.
10. the preparation method of a kind of NDA according to claim 9, is characterized in that described air and the mol ratio of raw material 2,6-DIPN are 30～50.
CN201210553197.2A 2012-12-19 2012-12-19 The preparation method of NDA Active CN103880654B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210553197.2A CN103880654B (en) 2012-12-19 2012-12-19 The preparation method of NDA

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210553197.2A CN103880654B (en) 2012-12-19 2012-12-19 The preparation method of NDA

Publications (2)

Publication Number Publication Date
CN103880654A true CN103880654A (en) 2014-06-25
CN103880654B CN103880654B (en) 2015-09-09

Family

ID=50949824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210553197.2A Active CN103880654B (en) 2012-12-19 2012-12-19 The preparation method of NDA

Country Status (1)

Country Link
CN (1) CN103880654B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111068790A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof
CN112441909A (en) * 2019-09-04 2021-03-05 中国石油化工股份有限公司 Synthesis method of 2,6-naphthalene dicarboxylic acid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496264A2 (en) * 1991-01-21 1992-07-29 Mitsubishi Chemical Corporation Process for preparing 2,6-naphthalenedicarboxylic acid
JPH06211732A (en) * 1992-06-12 1994-08-02 Osaka City Production of 2,6-naphthalene dicarboxylic acid
CN101244997A (en) * 2007-02-16 2008-08-20 北京石油化工学院 Process for producing 2,6-naphthalenedicarboxylic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496264A2 (en) * 1991-01-21 1992-07-29 Mitsubishi Chemical Corporation Process for preparing 2,6-naphthalenedicarboxylic acid
JPH06211732A (en) * 1992-06-12 1994-08-02 Osaka City Production of 2,6-naphthalene dicarboxylic acid
CN101244997A (en) * 2007-02-16 2008-08-20 北京石油化工学院 Process for producing 2,6-naphthalenedicarboxylic acid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111068790A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof
CN111068790B (en) * 2018-10-18 2023-05-02 中国石油化工股份有限公司 Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof
CN112441909A (en) * 2019-09-04 2021-03-05 中国石油化工股份有限公司 Synthesis method of 2,6-naphthalene dicarboxylic acid
CN112441909B (en) * 2019-09-04 2023-04-07 中国石油化工股份有限公司 Method for synthesizing 2,6-naphthalene dicarboxylic acid

Also Published As

Publication number Publication date
CN103880654B (en) 2015-09-09

Similar Documents

Publication Publication Date Title
EP3941896B1 (en) Process for the depolymerization of polyethylene terephthalate (pet)
CN103965039B (en) The method of synthesis NDA
CN107915833B (en) Fiber-grade bio-based polyester and preparation method thereof
CN107868238A (en) A kind of preparation method and application of heavy metal free polyester polycondensation catalyst
CN112955425B (en) Preparation method and preparation system of ester composition
CN102126957A (en) Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis
CN103880654B (en) The preparation method of NDA
CN112876359B (en) Preparation method of dimethyl 2, 6-naphthalene dicarboxylate
CN100420668C (en) Process for synthesizing dimethylacetamide by ethyl acetate and dimethylamine
CN110479234B (en) Catalyst for synthesizing dimethylaminoethyl methacrylate, preparation method and application thereof
CN113801311A (en) Process for preparing polyester
CN114456062A (en) Method for converting terephthalic acid into terephthalic acid diester through catalytic esterification
CN103772191B (en) The preparation method of terephthalic acid
CN111068790B (en) Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof
CN111848692B (en) Preparation method of biomass organic guanidine complex and application of biomass organic guanidine complex in catalytic synthesis of PET or PEIT polyester
CN103772152B (en) The preparation method of terephthalyl alcohol
CN102746193A (en) Preparation method of 2-cyano-4'-bromomethylphenylbenzene
CN112441909B (en) Method for synthesizing 2,6-naphthalene dicarboxylic acid
KR101544513B1 (en) Method for PolyTrimethyleneTerephthalate Having Invaliable Thermal Behavior Using Terephthalic acid from Biomass
US6323305B1 (en) Process for preparing polyethylene naphthalate based polymers by using NDCA or its derivates
CN114315728A (en) Imidazole ionic liquid and application thereof in alcoholysis polymerization of 2, 5-furandicarboxylic acid ester
CN1551865A (en) Process for the production of 2,6-naphthalenedicarboxylic acid
CN102219678B (en) Starting-up method for producing oxalic acid ester with CO
CN112441908B (en) Method for synthesizing 2,6-naphthalene dicarboxylic acid
CN112645811A (en) Method for preparing 2,6-naphthalene dicarboxylic acid by oxidizing 2, 6-diisopropyl naphthalene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant