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N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof

A fully aromatic hydrocarbon-based bisphenol, four-functionality technology, applied in the direction of organic chemistry, can solve problems such as difficult to obtain target products, achieve the effect of expanding application fields, excellent thermal stability, and improving processing performance

Inactive Publication Date: 2014-07-23
HARBIN ENG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For 2,7-dihydroxy-9,9-bis-(4-aminophenyl)fluorene (abbreviated as bisphenol-bisamine fluorene), the molecule contains two phenolic hydroxyl groups and two amino groups at the same time. The Mannich condensation reaction is difficult to obtain the target product

Method used

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  • N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof
  • N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof
  • N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] (1) Synthesis of 2,7-dihydroxy-9,9-bis-(4-aminophenyl)fluorene

[0035] Add 0.05mol 2,7-dihydroxy-9-fluorenone, 0.40mol aniline and 0.015mol trifluoromethanesulfonic acid to a four-necked flask with a stirring rotor, a condenser tube, a thermometer and a gas inlet in sequence, and feed in nitrogen, React at 150°C for 10 h, then cool to room temperature, pour the product into 100 mL of 5 g / L sodium hydroxide ethanol solution, filter the precipitate, wash with ethanol, and dry in vacuum to obtain 2,7-dihydroxy-9,9 - Bis-(4-aminophenyl)fluorene (M-1), the yield is 92.3%.

[0036] (2) Synthesis of bis-trifluoroacetanilide-based bisphenol fluorene monomer

[0037] Add 100mL tetrahydrofuran and 0.05mol M-1 into a three-neck flask equipped with a stirring rotor and a condenser tube, stir in an ice-water bath for 15min, then slowly add 0.15mol trifluoroacetic anhydride dropwise, after the dropwise addition, continue the reaction at room temperature for 4h , remove tetrahydrof...

Embodiment 2

[0047] Except that 0.045mol potassium borohydride in the synthesis step (4) was changed to 0.018mol potassium carbonate, and the reaction time was changed from 7h to 16h, other conditions were the same as in Example 1, and finally BF-pa-1 was obtained, and the total yield of the product was 44.5% ( The calculation is based on the yield of synthesis steps 2 to 5, the same below).

Embodiment 3

[0049] Except that 0.045mol potassium borohydride in the synthesis step (4) was changed to 0.036mol ammonia water, the phenol in the synthesis step (5) was changed to cardanol, and the organic solvent was changed from 4mL chlorobenzene and 8mL xylene to 2mL chlorobenzene and 10mL dioxane ring, the reaction temperature was changed from 140°C to 110°C, and the reaction time was changed from 4h to 24h, other conditions were the same as in Example 1, and finally aniline-cardanol-derived N-fully aromatic hydrocarbon-based bisphenol-bisamine tetrafunctional Fluorenylbenzoxazine monomer (BF-pa-2), T m The temperature was 83°C, and the total yield of the product was 45.2%.

[0050] 1 H NMR: 6.58~7.43 (m, 28H, Ar-H), 5.74~5.83 and 4.96~5.04 (m, =CH- and -CH=CH 2 ), 5.41 and 5.34 (d, 8H, O-CH 2 -N), 4.71 and 4.55 (d, 8H, Ar-CH 2 -N), 2.73~2.77 (m, =CH-CH 2 -CH=), 2.41~2.47 (m, Ar-CH 2 -), 2.21~2.25 (m, =CH-CH 2 -), 1.25 ~ 1.97 (m, -CH 2 -), 0.82~0.85 (m, -CH 3 ) (Note: Except f...

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Abstract

The invention provides N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and a preparation method thereof. A new N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional benzoxazine monomer is obtained by the following steps: using trifluoroacetic anhydride to protect amino in 2, 7-dihydroxy-9, 9-bis-(4-amino phenyl) fluorene to produce 2, 7-dihydroxy-9, 9-bis-(4-trifluoroacetyl phenyl amino) fluorene, then performing Mannich condensation reaction of the 2, 7-dihydroxy-9, 9-bis-(4-trifluoroacetyl phenyl amino) fluorene and aliphatic amine and paraformaldehyde to produce a 9, 9-bis-(4-trifluoroacetyl phenyl amino) bisphenol fluorene-based benzoxazine monomer, then performing amino deprotection, and performing secondary Mannich condensation reaction with a phenolic compound and paraformaldehyde to finally obtain the new N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional benzoxazine monomer. The problems that fluorene-based benzoxazine with a structure with larger steric hindrance is small in molecular weight, low in crosslinking density, and poor in toughness and thermal performance reduction caused by the introduction of flexible groups can be solved, and the processing properties of polymers can be improved.

Description

technical field [0001] The present invention relates to an organic polymer material, and the present invention also relates to a preparation method of an organic polymer material, specifically a novel N-fully aromatic hydrocarbon-based bisphenol-bisamine tetrafunctional fluorenylbenzene Oxazines and methods for their preparation. Background technique [0002] 3,4-dihydro-1,3-benzoxazine (abbreviated as benzoxazine) is a kind of six-membered compound containing O and N atoms obtained by Mannich condensation reaction from amines, phenols and formaldehyde. Heterocyclic compounds. As early as the 1970s, Schreiber reported on benzoxazine oligomer modified epoxy resin in his patent (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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D498/04C08G73/06
CPCC07D498/04C08G73/06
Inventor 王军刘文彬潘兰王远亮李思琦
Owner HARBIN ENG UNIV
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