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N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof

A fully aromatic hydrocarbon-based diamine and four-functionality technology, which is applied in organic chemistry and other fields, can solve problems such as difficulty in obtaining target products, and achieve the effects of expanding application fields, excellent flame retardancy, and excellent thermal stability

Inactive Publication Date: 2014-07-02
HARBIN ENG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For 2,7-diamino-9,9-bis-(4-hydroxyphenyl)fluorene (abbreviated as bisamine-bisphenol 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 hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof
  • N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof
  • N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (1) Synthesis of 2,7-diamino-9,9-bis-(4-hydroxyphenyl)fluorene

[0034] Add 0.01mol 2,7-dinitro-9-fluorenone, 0.08mol phenol, 0.005mol trifluoromethanesulfonic acid and 0.001mol 3-mercaptopropionic acid to a three-necked flask with a stirring rotor, a condenser tube and a thermometer in sequence, Stirring was started, the reaction temperature was controlled at 55°C, and the reaction time was 3 hours. After the reaction, the product was washed with 20% ethanol solution for 3 to 5 times, and finally dried in vacuum to obtain 2,7-dinitro-9,9-bis -(4-hydroxyphenyl)fluorene, yield 86.8%; 0.05mol2,7-dinitro-9,9-bis-(4-hydroxyphenyl)fluorene, 100mL absolute ethanol and 2 grams of palladium carbon catalyst Add it into the above-mentioned three-necked flask, raise the reaction temperature to 85°C under stirring, then add dropwise 0.47mol80% hydrazine hydrate solution, finish the reaction after 36h, filter while it is hot, and remove most of the ethanol by distilling the filtrate...

Embodiment 2

[0046] Except that the aniline in the synthesis step (3) was changed to m-methoxyaniline, the organic solvent was changed from chlorobenzene (5mL) and toluene (10mL) to chlorobenzene (10mL) and dioxane (10mL), and the reaction temperature was changed from 120 ℃ was changed to 100 ℃, the reaction time was changed from 4h to 12h, 0.045mol sodium borohydride was changed to 0.060mol potassium borohydride in the synthesis step (4), and the reaction time was changed from 7h to 4h, other conditions were the same as in Example 1. Finally, a phenol-m-methoxyaniline-derived N-fully aromatic hydrocarbon-based bisamine-bisphenol-type tetrafunctional fluorenyl benzoxazine (BF-ap-2), T m The temperature is 143°C, and the total yield of the product is 51.5% (calculated based on the yield of synthesis steps 2 to 5, the same below).

[0047] 1 H NMR: 6.60~7.94 (m, 28H, Ar-H), 5.43 and 5.38 (d, 8H, O-CH on fluorene ring and benzene ring, respectively 2 -N), 4.81 and 4.66 (d, 8H, Ar-CH on the fl...

Embodiment 3

[0050] Except that the aniline in the synthesis step (3) was changed to m-toluidine, the organic solvent was changed from chlorobenzene (5mL) and toluene (10mL) to chlorobenzene (10mL) and xylene (5mL), and the reaction temperature was changed from 120°C to 140°C °C, the reaction time was changed from 4h to 12h, the phenol in the synthesis step (5) was changed to cardanol, the organic solvents chlorobenzene (2mL) and xylene (10mL) were changed to chlorobenzene (10mL) and toluene (6mL), and the reaction temperature Change from 140°C to 110°C, change the reaction time from 12h to 24h, other conditions are the same as in Example 1, and finally obtain N-fully aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl derived from cardanol-m-toluidine Benzoxazine Monomer (BF-ap-3), T m It is 79 ℃, and the total yield of product is 50.4%.

[0051] 1 H NMR: 6.58~7.93 (m, 26H, Ar-H), 5.74~5.82 and 4.95~5.04 (m, =CH- and -CH=CH 2 ), 5.38 and 5.31 (d, 8H, O-CH 2 -N), 4.70 and ...

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Abstract

The invention provides N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and a preparation method thereof. The method comprises the following steps: firstly, protecting amino in 2,7-diamino-9,9-bis-(4-hydroxyphenyl) fluorene by using trifluoroacetic anhydride to generate 2,7-bistrifluoroacetamido-9,9-bis(4-hydroxyphenyl) fluorene, and then carrying out Mannich condensation reaction with aromatic amine and paraformaldehyde to form a 2,7-bistrifluoroacetamido bisphenol fluorenyl benzoxazine monomer; carrying out amino deprotection, and then carrying out secondary Mannich condensation reaction with a phenolic compound and paraformaldehyde to finally obtain a novel N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine monomer. By adopting the N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and the preparation method thereof, the problems that the fluorenyl polybenzoxazine with a large steric hindrance structure is small in molecular weight, low in crosslinking density and poor in tenacity, and the thermal performance is reduced by introducing a flexible group are solved, the processing property of the polymer is improved, and controllable structure and performance of polybenzoxazine are achieved.

Description

technical field [0001] The invention relates to an organic polymer material, and also relates to a preparation method of the organic polymer material. Specifically, it is a novel N-fully aromatic hydrocarbon-based diamine-bisphenol type tetrafunctional fluorenyl benzoxazine and a preparation method thereof. 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)"). In 1994, Ishida a...

Claims

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Application Information

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IPC IPC(8): C07D265/16C08G73/06
CPCC07D265/16C08G73/06
Inventor 刘文彬何轩宇王军张彤杨铭
Owner HARBIN ENG UNIV
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