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Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof

A technology of tetraaminobenzene hydrochloride and tetraaminobenzene, which is applied in the application field of high-performance materials PDBI, can solve the problems of high TAP monomer preparation cost, difficulty in industrialization implementation and promotion, and restrictions on the preparation of polymerization-grade monomers. , to enhance the effect of realizing industrialized production, controllable amount of by-products, and good fiber spinnability

Inactive Publication Date: 2013-05-15
ZHEJIANG UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The most important thing is that 2,3,5,6-tetraaminopyridine hydrochloride (TAP), one of the two monomers used to make M5 resin and fiber, is nitrated with 2,6-diaminopyridine and reduction, there are defects such as more by-products and lower yields, which limit the preparation of polymerization-grade monomers; although domestic TAP synthesis patents [CN101289419A] and PIPD resin preparation technology [CN101418073A], but by The price restriction of 2,6-diaminopyridine and the complexity of the process lead to the extremely high cost of TAP monomer preparation, making it difficult to implement and promote industrialization
Although there is also the research [CN101358385A] of adding a small amount of TAP and DHTA in PBO polymerization to carry out PBO modification, the preparation technology of low-cost 2,3,5,6-tetraaminopyridine or the development of similar tetraaminoaromatic new monomers still imminent

Method used

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  • Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof
  • Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof
  • Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Example 1: Preparation and application of a kind of 1,2,4,5-tetraaminobenzene hydrochloride

[0037] 1) Weigh 17.5g (0.0735mol) of 4,6-dinitro-m-dichlorobenzene (DCDNB) in a 500mL autoclave, add 1,4-dioxane 175mL, weigh ammonia water (29%) 42g ( 0.70mol), the glass rod was stirred evenly and then the kettle was installed to ensure its sealing, and the nitrogen gas was passed three times to remove the air, the stirring speed was controlled to be 500 rpm, and the ammonolysis reaction was heated to 150°C for 5h (the maximum temperature and pressure were respectively 160°C and 1.5MPa). After the reaction was completed, the temperature was cooled, the reaction solution was taken out, a large amount of water was added, and a yellow solid was precipitated. After filtration and drying, 13.3 g of the product 4,6-dinitrom-phenylenediamine (DADNB) was obtained, with a melting point of 150° C. and a purity of 96.3%. The rate is 90.9%. IR (KBr, cm -1 ): 3476.6(s), 3367.5(s), 1605...

Embodiment 2

[0042] Embodiment 2: intermediate 4, the technical scope of 6-dinitro-m-diphenylamine (V) synthesis

[0043] Change the molar ratio RO of ammonia water and 4,6-dinitro-m-dichlorobenzene in step 1) in Example 1, the reaction temperature T (℃), and the reaction preset pressure P 1 (MPa), reaction control pressure P 2 (MPa), reaction solvent, reaction time t (h), all the other steps are with the step 1 in embodiment 1), synthetic 4, the test result list 1 of 6-dinitro-m-diphenylamine (V):

[0044] Table 1:

[0045]

Embodiment 3

[0046] Embodiment 3: Intermediate 1,2,4,5-tetraaminobenzene (I) synthetic process scope

[0047] Change the percentage ω1 of reaction solvent, catalyzer and raw material weight in step 2) in embodiment 1, reaction temperature T (℃), reaction pressure P (MPa), reaction time t (h), all the other steps are with the steps in embodiment 1 1), step 2), the results are shown in Table 2.

[0048] Table 2

[0049]

[0050]

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Abstract

The invention provides a method of preparing 1,2,4,5-tetra amino benzene and hydrochloride thereof. 4,6-dinitro m-dichlorobenzene is used as a raw material, and the 1,2,4,5-tetra amino benzene is prepared through aminolysis and catalysis hydrogenation reduction and the hydrochloride of the 1,2,4,5-tetra amino benzene is prepared by adding hydrochloric acid. The method has advantages of easily-available raw materials for the reaction, few side reactions and controllable amount of byproducts. The hydrochloride of the 1,2,4,5-tetra amino benzene has a purity up to a polymer grade requirement, and a total yield of more than 75 %. A thermal decomposition temperature of the 1,2,4,5-tetra amino benzene is 200-282 DEG C detected by a thermal gravimetric method. The 1,2,4,5-tetra amino benzene is good in thermal stability. As a new synthetic material monomer, the 1,2,4,5-tetra amino benzene with a purity of more than 99 % is used to polymerize with 2,5-dihydroxy terephthalic acid to prepare poly-1,4-(2.5-dihydroxy) phenylene benzo diimidazole resin with an intrinsic viscosity Eta of more than 12 dL*g<-1> and a good spinnability.

Description

(1) Technical field [0001] The invention relates to a synthesis method of 1,2,4,5-tetraaminobenzene and 1,2,4,5-tetraaminobenzene hydrochloride and their application in high-performance material PDBI. (2) Background technology [0002] PBO fiber is a high-performance fiber made of PBO polymer through liquid crystal spinning technology. It is the organic fiber with the highest strength and modulus at present. Polycondensation and spinning products of terephthalic acid (TPA). However, its application in composite materials is limited due to its chemical inert surface and poor axial compressive strength of fibers. In recent years, there have been studies on the hydroxyl (OH) modification of the PBO molecular structure by using hydroxyterephthalic acid monomers (HTA or 2,5-dihydroxyterephthalic acid DHTA [CN1594398A]) to replace TPA. The results show that : The polarity of the hydroxyl group can significantly improve the composite cohesion, but because it cannot form hydrogen ...

Claims

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Application Information

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IPC IPC(8): C07C211/50C07C209/36C07C209/00C08G73/18D01F6/74
Inventor 金宁人张建庭陈汉庚金婷婷金菁
Owner ZHEJIANG UNIV OF TECH
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