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Monomers and intermediates of AB type hydroxyl modified high polymer and preparation methods of monomers and intermediates

A technology of hydroxyl and hydroxyl terephthalic acid, applied in the preparation of organic compounds, chemical instruments and methods, preparation of carboxylic acid esters, etc., can solve the problems such as weakening of the positive charge of the carbonyl carbonyl group of acyl chloride, difficulty in carrying out, and reduction in reaction ability.

Inactive Publication Date: 2014-03-26
ZHEJIANG UNIV OF TECH +1
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  • Summary
  • Abstract
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

With the idea of ​​converting one into a less active ester group and the other into a more active acid chloride, such as 3-hydroxy p-methoxycarbonylbenzoyl chloride (α-MHBC) between formulas (1) and (2), press The process of the dotted arrow can control the acid chloride group to react with PPD first, and the new monomer of AB type H-PPTA can be prepared with high selectivity, which has been used in p-methoxycarbonylbenzoyl chloride and 4-amino-6-nitroisophthaloyl dichloride. In the ring condensation reaction of phenol hydrochloride, the effective control of the selective reaction of acid chlorides has been realized, and the corresponding AB type PBO monomer has been successfully prepared; if the isomer β-MHBC of α-MHBC is used (the hydroxyl group is meta-acyl chloride o-position), due to the strong electron-donating effect of the ortho-position hydroxyl group, the positive charge of the carbonyl carbonyl of the acyl chloride is greatly weakened, resulting in a reduction in the ability to react with the amino group or even difficulty

Method used

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  • Monomers and intermediates of AB type hydroxyl modified high polymer and preparation methods of monomers and intermediates
  • Monomers and intermediates of AB type hydroxyl modified high polymer and preparation methods of monomers and intermediates
  • Monomers and intermediates of AB type hydroxyl modified high polymer and preparation methods of monomers and intermediates

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0085] Example 1 Preparation of methyl 2-hydroxy-4-carboxybenzoate (α-MHT)

[0086] (1) Preparation of dimethyl hydroxy terephthalate (DMHT)

[0087] Add 15.00g HTA (0.082mol), 150mL methanol, 24.1mL SOCl to the reaction vessel 2 (0.330mol), heated, stirred and refluxed for 21 hours, then poured into a large amount of ice water, and a white precipitate was precipitated, adjusted to pH=8 with dilute ammonia water and filtered, and the filter cake was recrystallized with methanol to obtain 16.21g of white needle-shaped DMHT with a purity of 99.1%. Yield 94.16%.

[0088] (2) Preparation of α-MHT

[0089] Add 6.30g (0.030mol) DMHT and 5.00g NaOH (0.120mol) 200mL aqueous solution into the reaction vessel, stir in an ice-water bath, react at 0~5°C for 60min, pour into a beaker, adjust to pH = 8 with dilute hydrochloric acid, and filter out insoluble matter , add dilute hydrochloric acid to the filtrate to pH = 4.4, filter, dry the filter cake and recrystallize with methanol to ob...

Embodiment 2~7

[0090] The preparation of embodiment 2~7DMHT and α-MHT

[0091] (1) Preparation of dimethyl hydroxy terephthalate (DMHT)

[0092] Adopt the same operation of embodiment 1-(1) to synthesize DMHT, according to the parameter range described in table 1 (different amounts of SOCl 2 and different reaction times) to carry out experiments with different parameters, the results are shown in Table 1:

[0093] Table 1:

[0094] Example SOCl 2 equivalent Reflow time / h product purity / % Yield / % 2 2.99 7.5 DMHT 96.3 83.5 3 3.50 15 DMHT 98.6 89.4 Comparative example 1 1.5 0.5 β-Monoester 94.7 69.3

[0095] (2) Preparation of α-MHT

[0096] Using the same operation as in Example 1-(2) to synthesize α-MHT, experiment with different parameters according to the parameter range described in Table 2 (temperature, alkali dosage, reaction time, hydrolysis solvent), and the results are shown in Table 2:

[0097] Table 2:

[0098] ...

Embodiment 82

[0099] Example 82, Preparation of methyl 6-dihydroxy-4-carboxybenzoate (α-MDHT)

[0100] (1) Preparation of dimethyl 2,6-dihydroxyterephthalate (2,6-DMDHT)

[0101] Add 14.85g 2,6-DHTA (0.075mol), 150mL methanol, 22mL SOCl to the reaction vessel 2 (0.3mol), heated, stirred and refluxed for 21 hours, cooled and poured into a large amount of ice water, precipitated a white precipitate, adjusted to pH=8 with dilute ammonia water and filtered, and the filter cake was recrystallized with methanol to obtain 15.29g of 2,6-DMDHT, with a purity of 98.7% , yield 90.23%.

[0102] (2) Preparation of α-MDHT

[0103] Add 6.78g (0.030mol) 2,6-DMDHT and 5.00g NaOH (0.120mol) 200mL aqueous solution into the reaction vessel, stir in an ice-water bath, react at 2~5°C for 120min, then pour into a beaker, adjust the pH to 8 with dilute hydrochloric acid, Filter out insoluble matter, add dilute hydrochloric acid to the filtrate to pH = 4.4, filter, dry the filter cake and recrystallize with meth...

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Abstract

The invention discloses monomers and intermediates of an AB type hydroxyl modified high polymer, and preparation methods of the monomers and the intermediates. The intermediates include methyl o-hydroxyl p-carboxyl benzoate (I) and m-hydroxyl p-methoxycarbonyl benzoyl chloride (I'). The monomers of the AB type hydroxyl modified high polymer include a monomer (IV) of AB type hydroxyl modified PPTA (Poly-p-Phenylene Terephthamide) and a monomer (VIII) of AB type hydroxyl modified PBO (Poly-p-phenylenebenzobisthiazole), wherein R1 is H, R2 is OH, or R1 is OH and R2 is OH, and R is CH3 or C2H5. Due to introduction of hydroxyl in the AB type monomer, the light resistance, the composite cohesiveness and the axial pressure resistance of a high polymer prepared from the AB type hydroxyl modified high polymer can be improved, and moreover the preparation methods of the intermediate and the monomer have the characteristics of high yield, high selectivity and industrial production accordance.

Description

(1) Technical field [0001] This application relates to a type AB hydroxyl modified polymer monomer and its intermediates, including the key intermediate ortho-hydroxyl p-carboxybenzoic acid methyl ester, the intermediate meta-hydroxyl p-methoxycarbonyl benzoyl chloride and the AB type Monomers of hydroxyl-modified high polymers, and their preparation methods. (2) Background technology [0002] Terephthalic acid (TPA) is a dicarboxylic acid used to synthesize high-performance materials such as polyparaphenylene terephthalamide (PPTA), polyester (PET), and polyparaphenylenebenzobisoxazole (PBO). Similar to BB-type monomers, the introduction of hydroxyl groups into TPA can use the hydrogen bonds and surface polarity generated by it to improve the axial compression resistance and composite bonding properties of the material. In view of TPA after the introduction of hydroxyl groups: such as hydroxyterephthalic acid (HTA) or 2,6-dihydroxyterephthalic acid, since the hydroxyl grou...

Claims

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Application Information

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IPC IPC(8): C07C69/84C07C67/313C07C235/56C07C231/12C07D263/57C08G69/32D01F6/60C08G73/22D01F6/74
CPCC07C67/08C07C67/313C07C69/84C07C231/12C07C235/56C07D263/57C08G69/32C08G73/22D01F6/60D01F6/74
Inventor 金宁人赵德明张建庭郑志国张清义
Owner ZHEJIANG UNIV OF TECH
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