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

A semi-aromatic hydrocarbon-based diamine and four-functionality technology, which is applied in organic chemistry and other fields, can solve the problems of unstable aliphatic aminooxazine ring, inability to obtain the target product, easy ring-opening reaction, etc., and achieve the total yield of the product Improvement, excellent thermal stability, low mechanical properties

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0029] 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

[0037] Except that the ethylamine in the synthesis step (3) was changed to n-butylamine, the solvent 40mL dioxane and 10mL chlorobenzene were changed to 40mL toluene and 10mL chlorobenzene, and the reaction time was changed from 24h to 12h, other conditions were the same as in Example 1 , other conditions are the same as in Example 1, and finally the N-semiaromatic hydrocarbon base diamine-bisphenol type tetrafunctional fluorenyl benzoxazine monomer derived from 4-methyl salicylaldehyde-butylamine is obtained, T m It was 108°C, and the yield was 62.7%.

[0038] 1 H NMR: 6.58~7.79 (m, 18H, Ar-H), 5.33 and 4.73 (d, 8H, O-CH 2 -N), (d,4H,O-CH 2 -N), 4.55 and 3.94 (d, 8H, Ar-CH 2 -N), 2.68(t,4H,N-CH 2 -), 2.30 (s, 6H, Ar-CH 3 ), 1.55 and 1.34 (m, 8H, -CH 2 -), 0.92 (t, 6H, -CH 3 ); FT-IR: 1495, 1384, 1366 and 1320, 1251 and 1223, 1155, 1076 and 1035, and 928-953.

[0039] Curing condition is the same as embodiment 1, the T of polybenzoxazine g : 318,T 5 :336,Y c : 39%. ...

Embodiment 3

[0041] Except that the 4-methyl-2-hydroxybenzaldehyde in the synthesis step (2) was changed to 2-hydroxybenzaldehyde, the heating and reflux time was changed from 6h to 8h, the ethylamine in the synthesis step (3) was changed to octylamine, and the solvent Change 40mL dioxane and 10mL chlorobenzene into 45mL chloroform and 5mL chlorobenzene, change the reaction temperature from 110°C to 62°C, change the reaction time from 24h to 48h, other conditions are the same as in Example 1, and finally obtain salicylaldehyde- Octylamine-derived N-semiaromatic diamine-bisphenol-type tetrafunctional fluorenylbenzoxazine, T m It was 66°C, and the yield was 72.3%.

[0042] 1 H NMR: 6.53~7.81 (m, 20H, Ar-H), 5.33 and 4.85 (d, 8H, O-CH 2 -N), 4.56 and 3.85 (d, 8H, Ar-CH 2 -N), 2.69 (t, 4H, N-CH-), 1.51 and 1.27 (m, 24H, -CH 2 -), 0.87(t,6H,-CH 3 ); FT-IR: 1497, 1379, 1368 and 1321, 1271 and 1225, 1155, 1076, 928-953 and 724 (long chain aliphatic hydrocarbon C-H rocking vibration).

[004...

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Abstract

The invention provides N-semi aromatic hydrocarbyl diamine-bisphenol 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-diamido-9, 9-bis-(4-hydroxy phenyl) fluorene, 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, and 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.

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-semiaromatic hydrocarbon-based diamine-bisphenol type 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(dihydrobenzoxazin...

Claims

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Application Information

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