Abstract: The renewable and biosynthetic molecule, vanillin, were used in the preparation of new phthalonitrile (PN) and ethynylbenzene (EB) bifunctional resins without pre-modification of the vanillin structure. This PN resin was characterized by differential scanning calorimetry, thermogravimetric analysis, nuclear magnetic resonance spectroscopy, rheometry, and single crystal x-ray diffraction. The monomers exhibited excellent rheometric viscosities below 250 Cp at processing temperatures and a good pot life. After complete curing, the PN polymers exhibited thermal stability above 500℃, a glass transition temperature (Tg) above the final postcure temperature of 380℃, and exceptional retention of structural integrity over a large temperature range. These results suggest that vanillin derived EBPN based resins are excellent candidates for use in a variety of applications where high temperature and mechanical stability is critical.
Keywords:
biopolymers and renewable polymers ; resins ; thermosets
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1972, p. 3001 - 3006
3
[ 821-55-6 ]
[ 121-33-5 ]
[ 27113-22-0 ]
Reference：
[1] Journal of Medicinal Chemistry, 2017, vol. 60, # 23, p. 9821 - 9837
4
[ 121-33-5 ]
[ 73635-75-3 ]
Reference：
[1] Journal of Materials Chemistry A, 2018, vol. 6, # 15, p. 6667 - 6674
5
[ 121-33-5 ]
[ 79-07-2 ]
[ 186685-89-2 ]
Yield
Reaction Conditions
Operation in experiment
86%
With potassium carbonate In N,N-dimethyl-formamide; acetonitrileReflux
General procedure: A mixture of the corresponding halide (0.010 mol), hydroxybenzaldehyde (0.011 mol), and potassium carbonate (2.00 g, 0.0145 mol) in a mixture of acetonitrile-DMF (20 mL, 8 : 2, v/v) was refluxed for 5-7 h with stirring (TLC monitoring). After evaporation of the solvents, the residue was treated with water, a precipitate formed was filtered off, washed with 30percent aqueous methanol, and dried in air. Yields and physicochemical characteristics of aldehydes 9-12 are given in Table 4.
Reference：
[1] Russian Chemical Bulletin, 2015, vol. 64, # 2, p. 395 - 404[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 2, p. 395 - 404,10
[3] Russian Journal of General Chemistry, 2005, vol. 75, # 7, p. 1113 - 1124
[4] European Journal of Medicinal Chemistry, 2014, vol. 81, p. 1 - 14
General procedure: To a solution of the corresponding aromatic aldehyde (0.27 mmol) in EtOH (0.5 mL) was added urea (0.54 mmol) and CuSO4·5H2O (0.054 mmol). The mixture was stirred at 80 °C for 15 minutes before tetrahydrocurcumin or tetrahydrodemethoxycurcumin (0.27 mmol) was added. The reaction mixture was continued stirring for 24 hours and quenched with water (2 mL). The solution was washed with water (10 mL) and extracted with EtOAc (415 mL). The combined organic phases were washed with brine, dried over MgSO4 and concentrated under reduced pressure to afford crude product as a yellow brown oil. Purification was accomplished by column chromatography eluting with 60percent-75percent EtOAc/hexane to furnish compounds 8-17.
6-fluoro-2-(2-(4-hydroxy-3-methoxybenzylidene)hydrazino)benzothiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
With acetic acid; In ethanol; at 80℃; for 0.166667h;Microwave irradiation;
General procedure: A mixture of compound 2 (0.0549 g, 0.0003 mol), the appropriate aromatic aldehyde (0.00033 mol) and glacial acetic acid (0.1 mL) in ethanol (5 mL) was heated under microwave (20 W) at 80 °C for 10 min. On cooling, the precipitated solid was collected by filtration, washed with water, dried and crystallized to give compounds 3-29.
In ethanol; at 70 - 80℃; for 3h;
General procedure: The mixture of <strong>[78364-55-3]6-fluoro-2-hydrazinylbenzo[d]thiazole</strong> (2) (0.01 mol) and benzalde-hyde/substituted benzaldehyde (0.01 mol) was reuxed in ethanol (15 ml) at 70?80 °C for 3 h. The separated product obtained was ltered off, washed withdistilled water and recrystallized from methanol to give the correspondinghydrazone. The product obtained was further dissolved in acetic acid (20 ml) atroom temperature followed by the addition of sodium acetate (0.5 g). Bromine(2 mmol) in acetic acid (10 ml) was added dropwise to the reuxing reactionmixture. After 1 h, the mixture was poured onto crushed ice (100 g). The precipitateobtained was ltered off and crystallized from ethanol-dimethylformamide (1:1) togive crystals of (3a?3t).
3-methoxy-4-((1-methyl-1H-pyrazol-4-yl)methoxy)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 25℃; for 16h;Inert atmosphere;
o a solution of (l-methylpyrazol-4-yl) methanol (300 mg, 2.68 mmol, 1.00 equiv.), 4-hydroxy-3-methoxybenzaldehyde (448 mg, 2.95 mmol, 1.10 equiv.) and triphenylphosphine (773 mg, 2.95 mmol, 1.10 equiv.) in tetrahydrofuran (3 mL) was added diisopropylazodicarboxylate (573 uL, 2.95 mmol, 1.10 equiv.) drop-wise maintaining the temperature at 0°C under a nitrogen atmosphere and the reaction mixture was stirred at 25 °C for 16 hours. The reaction mixture was diluted with water (20 mL) and the aqueous layer extracted with ethyl acetate (20 mL x3). The combined organic layer was washed with brine (20 mL), dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by preparative HPLC to afford the desired product as a brown solid. MS (ESI+) m/z 247.0 (M+H)+.
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