Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof

A technology of benzoyloxyspirofluorenexanthene benzene and nitrobenzoyloxyspirofluorenexanthene, which is applied in the field of polymer materials and can solve the problems of increased polymer brittleness, high molecular chain rigidity, and toughness. Improve processing performance, improve flexibility, and lower melting point

Inactive Publication Date: 2013-09-18
HARBIN ENG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, spirofluorene xanthene also has a large molecular chain rigidity, increased brittleness and poor toughness of the polymer, which limits its application to a certain extent.

Method used

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  • Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof
  • Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Step 1: Add 5.0 g (13.7 mmol) of 3',6'-dihydroxy-spiro(fluorene-9,9'-xanthene) to a 250 mL three-necked flask equipped with a stirrer, dropping funnel and thermometer ), 50mL of anhydrous chloroform and 50mL of triethylamine, and then add dropwise 50mL of 4-nitrobenzoyl chloride (5.25g, 28.3mmol) chloroform solution at 2-4°C under stirring conditions. Continue to react under the conditions for 3 hours, raise the temperature, and react at reflux temperature for 16 hours. After the reaction, the solvent is evaporated under reduced pressure, and then washed with water, washed with ethanol, filtered, and dried in vacuum to obtain 7.04g of light yellow 3',6'- Bis(4-nitrobenzoyloxy)-spiro(fluorene-9,9'-xanthene) powder, yield 77.6%.

[0021] Step 2: Into a 150mL three-neck flask equipped with a stirrer, dropping funnel and thermometer, add 3',6'-bis(4-nitrobenzoyloxy)-spiro(fluorene-9 , 9'-oxanthene) 4.5g (6.8mmol), 0.4g palladium / carbon and 80mL of absolute ethanol, dropwis...

Embodiment 2

[0026] Except that the raw material phenol in the third step is replaced by m-cresol, and the dosage is 2.16g (20mmol), the others are the same as in Example 1, and finally 6.09g of light yellow benzoyloxy spirofluorenoxanthyl-m-cresol group is obtained. Benzoxazine monomer, yield 70.2%.

[0027] H NMR test results (500M, CDCl 3 , ppm): 6.66~8.08 (m, 28H, Ar-H), 5.39 (s, 4H, O-CH 2 -N), 4.67 (s, 4H, Ar-CH 2 -N), 2.31 (s, 6H, Ar-CH 3 ); infrared spectrum test results (KBr, cm -1 ): 1729 (stretching vibration of carbonyl group), 1383 (swing vibration of methylene on oxazine ring), 1260 and 1068 (C-O-C asymmetric and symmetric stretching vibration), 1181 (C-N-C asymmetric stretching vibration vibration), 958 (out-of-plane bending vibration of the C—H oxazine ring, which is also a characteristic peak of the oxazine ring). Combined with H NMR and IR spectra, it was confirmed that the obtained product was the target monomer.

[0028] The curing conditions are the same as in Ex...

Embodiment 3

[0030] Except that the raw material phenol in the third step is replaced by m-methoxyphenol, and the dosage is 2.48g (20mmol), the others are the same as in Example 1, and finally 6.41g of light yellow benzoyloxy-containing spirofluorenoxanthyl-m-methoxyphenol is obtained. Oxyphenoxybenzoxazine monomer, yield 71.3%.

[0031] H NMR test results (500M, CDCl 3 , ppm): 6.61~7.92 (m, 28H, Ar-H), 5.40 (s, 4H, O-CH 2 -N), 4.62 (s, 4H, Ar-CH 2 -N), 3.83 (s, 6H, Ar-OCH 3 ); infrared spectrum test results (KBr, cm -1 ): 1727 (stretching vibration of carbonyl group), 1385 (swing vibration of methylene on oxazine ring), 1269 and 1071 (asymmetric stretching vibration of C—O—C), 1181 (asymmetric stretching vibration of C—N—C vibration), 960 (out-of-plane bending vibration of the C—H oxazine ring, which is also a characteristic peak of the oxazine ring). Combined with H NMR and IR spectra, it was confirmed that the obtained product was the target monomer.

[0032] The curing conditions...

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Abstract

The invention provides spirofluorene xanthene benzoxazine containing a benzoyloxy group and a preparation method thereof. The method comprises the following steps: by taking spirofluorene xanthene bisphenol as a raw material, reacting spirofluorene xanthene bisphenol with 4-nitrobenzoyl chloride, carrying out a hydrazine hydrate-Pd / C catalytic reduction reaction, thereby obtaining 4-aminobenzoyl spirofluorene xanthene and obtaining a series of benzoxazine monomers through a Mannich condensation reaction. Due to the introduction of spirofluorene xanthene and benzoyloxy group, the polybenzoxazine resin has high glass transition temperature and excellent thermal stability; due to the introduction of alkyl or alkoxy, the thermal performance of the polybenzoxazine resin is reduced, the toughness and processing performance of the polymer are greatly improved, the comprehensive performance is greatly improved, and the polybenzoxazine resin can be widely applied to the fields of photoelectric materials, insulating materials, composite material matrix resins, ablation resistant resins and the like.

Description

technical field [0001] The invention relates to a polymer material, in particular to a benzoyloxy spirofluorenoxanthryl benzoxazine resin monomer. Background technique [0002] In the 1970s, Schreiber first reported the use of benzoxazine oligomers to modify epoxy resins in patents (German patent 2217099, "Phenolic resin as electric insulator"). In the 1980s, Higginbottom first discovered the crosslinking reaction of multifunctional benzoxazines in the research of coating materials (US Patent 4501864, "Polymerizable compositions comprising polyamines and poly(dihydrobenzoxazines)"). In 1994, Ishida and Ning first completed the performance research on polybenzoxazines (Ning hida H.X, IsPhenolic materials viaring-opening polymerization-synthesis and characterization of bisphenol-A based benzoxazines and their polymers.J Polym Sci A Polym Chem,1994 , 32:1121-1129p). Through a large number of studies, it has been found that benzoxazine resins have the same excellent properties...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D413/14C08G73/06
Inventor 王军任甜甜刘文彬余丽娇潘兰何轩宇
Owner HARBIN ENG UNIV
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