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

A semi-aromatic hydrocarbon-based bisphenol, tetrafunctional technology, applied in the direction of organic chemistry, etc., can solve the problems of unstable aliphatic amine-based oxazine ring, prone to ring-opening reaction, unable to obtain the target product, etc., and achieve the total product yield Improve, excellent thermal stability, the effect of expanding the application field

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

However, during the deprotection process of the amino group, the aliphatic aminooxazine ring is very unstable, and the ring-opening reaction is very easy to occur, resulting in the inability to obtain the target product

Method used

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] (1) Synthesis of 2,7-dihydroxy-9,9-bis-(4-aminophenyl)fluorene

[0029] 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%.

[0030] (2) Synthesis of substituted or unsubstituted o-hydroxybenzylamino bisphenol fluorene

[0031] Add 0.02mol M-1, 0.04mol 2-hydroxybenzaldehyde, 0.004mol sulfuric acid and 150mL ethanol into a three-necked flask equipped with a stirrer, a condenser, and a thermometer, heat and reflux for 8 hours, cool to room temperature after the reaction, and add 0.06 mol sodium borohydride, then continue to sti...

Embodiment 2

[0037] Except that the 2-hydroxybenzaldehyde in the synthesis step (2) was changed to 4-fluoro-2-hydroxybenzaldehyde, the reflux reaction time was changed from 8h to 6h, the butylamine in the synthesis step (3) was changed to octylamine, and the solvent was changed from 40mL dioxane and 10mL chlorobenzene are changed into 30mL toluene and 20mL chlorobenzene, and the reaction time is changed from 24h to 12h, other conditions are the same as in Example 1, and finally the N-semi Aromatic hydrocarbon-based bisphenol-diamine tetrafunctional fluorenyl benzoxazine monomer, T m The temperature is 68°C, and the yield is 69.3% (calculated based on the yields of synthesis steps 2 to 5, the same below).

[0038] 1 H NMR: 6.58~7.37 (m, 18H, Ar-H), 5.33 and 4.73 (d, 8H, O-CH on fluorene ring and benzene ring, respectively 2 -N), 4.55 and 3.94 (d, 8H, Ar-CH on the fluorene ring and benzene ring, respectively 2 -N), 2.68(t,4H,N-CH 2 -), 1.54 and 1.21 (m, 24H, -CH 2 -), 0.86(t,6H,-CH 3 )...

Embodiment 3

[0041] Except that the 2-hydroxybenzaldehyde in the synthesis step (2) is changed to 4-methoxy-2-hydroxybenzaldehyde, the butylamine in the synthesis step (3) is changed to cyclohexylamine, and the solvent consists of 40mL dioxane and 10mL of chlorobenzene was changed into 45mL of xylene and 5mL of chlorobenzene, the reaction temperature was changed from 110°C to 140°C, and the reaction time was changed from 24h to 12h, other conditions were the same as in Example 1, and finally 4-methoxy salicylaldehyde- N-semiaromatic hydrocarbon-based bisphenol-bisamine tetrafunctional fluorenyl benzoxazine monomer derived from cyclohexylamine, T m It was 112°C, and the yield was 77.8%.

[0042] 1 H NMR: 6.53~7.32 (m, 18H, Ar-H), 5.34 and 4.85 (d, 8H, O-CH on fluorene ring and benzene ring, respectively 2 -N), 4.56 and 4.05 (d, 8H, Ar-CH on the fluorene ring and benzene ring, respectively 2 -N), 3.45 (s, 6H, O-CH 3 ), 2.52 (m, 2H, N-CH-), 1.05~1.86 (m, 20H, -CH2 -); FT-IR: 1505, 1387, 1...

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Abstract

The invention provides N-semi aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and a preparation method thereof. A N-semi aromatic hydrocarbyl diamine-bisphenol tetrafunctional benzoxazine monomer is obtained by the following steps: reacting substituted or unsubstituted salicylaldehyde with 2, 7-dihydroxy-9, 9-bis-(4-amino phenyl) fluorene, then using sodium borohydride for reduction to obtain substituted or unsubstituted 2-hydroxy benzylamino bisphenol fluorene, and performing a one step Mannich condensation reaction of the substituted or unsubstituted 2-hydroxy benzylamino bisphenol fluorene and aliphatic amine and paraformaldehyde. The reaction process is simplified, the total product yield is increased; by adjusting of rigid and flexible groups in the aliphatic amine and the substituted or unsubstituted salicylaldehyde compound, the melting point of the benzoxazine monomer is improved, the crosslinking density and toughness of polybenzoxazine are improved, 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 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-semiaromatic hydrocarbon base bisphenol-bisamine 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 and...

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 王军刘文彬潘兰季显丰李思琦
Owner HARBIN ENG UNIV
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