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Bio-Based Mono-and Difunctional Phthalonitrile Resin Foams
Bunton, Caleb M ; Sitter, James D ; Richardson, Tyler J ; Dysart, Jennifer L ; Daniels, Grant C ; Atoyebi, Olufolasade F , et al.
Abstract: The development of two new bio-based phthalonitrile (PN) resin foams with intrinsic blowing agents is reported. The resins were characterized via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance (NMR), pycnometry, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), rheometry, and compression testing. The porosity of 3-[4-(3,4-Dicyanophenoxy)phenyl]-2-propenoic acid-phthalonitrile CAPN and 3-[3,4-di(3,4-Dicyanophenoxy)phenyl]-2-propenoic acid-phthalonitrile CFPN were calculated to be 0.610 and 0.437 respectively. Thermal and thermooxidative stability was determined for both resins under nitrogen and air environments. CAPN and CFPN displayed final char yields of 67% and 69% under nitrogen environments while the Td,5% under air environments were 200°C and 360°C respectively. Finally, compression analysis shows the CAPN to be a stiffer material than the larger CFPN foam resin.
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Keywords: biopolymers ; flame retardance ; renewable polymers ; thermosets
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Bio-Based Self-Curing Phthalonitrile Resins Derived from Cinnamaldehyde
Brown, Loren C ; Judge, Giuliana R ; Davis, Cole R ; Atoyebi, Olufolasade F ; Kerr, Andrew T ; Laskoski, Matthew
Abstract: A class of bio-based bifunctional phthalonitrile (PN) resins composed of cinnamaldehyde derivatives, aminophenol, and end-capped with a PN moiety is detailed. The cinnamic-imine PN (CIPN) resins were synthesized by utilizing environmentally friendly solvents methanol (MeOH) and acetone at ambient temperatures. Characterization of the resins was conducted via proton (1H) and carbon (13C) nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), infrared spectroscopy (IR), mechanical analysis, single crystal X-ray diffraction (XRD), and rheometry. The CIPN resins were self-curing due to the vinylic, imine, and PN moieties present and displayed a range of viscosities from 153−1546 cP at 225°C. The resulting CIPN polymers were prepared by post-curing up to 380°C and exhibited excellent thermal stability with Td5% above 510°C up to an 80% char yield. Moderate brittleness ranging from an initial storage modulus (G′ at 25°C) of 86−1295 MPa was observed among the CIPN resins. This combination of properties suggests that the bifunctional CIPN resins are excellent materials for high temperature thermosets in composite applications.
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Keywords: Phthalonitrile ; resin ; thermoset ; cinnamaldehyde ; self-curing ; imine
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Preparation and properties of bisphenol A polyetherketoneketone based phthalonitrile resins
Loren C. Brown ; Tyler J. Richardson ; Clair F. Lusk ; Nickolaus K. Weise ; Matthew Laskoski ;
Abstract: A promising high temperature phthalonitrile (PN) resin composed of a polyetherketoneketone (PEKK) core bridged by two bisphenol A linkers and end capped with PN groups is presented. This PEKK-PN resin was characterized via differential scanning calorimetry, thermogravimetric analysis, proton nuclear magnetic resonance spectroscopy, scanning electron microscopy, dynamic mechanical analysis, attenuated total reflection Fourier transform infrared, and rheometry. The PEKK-PN resin was evaluated with two different compositions containing 1) 70:30 PEKK-PN to bisphenol A PN (n = 0) and 2) pure PEKK-PN. The 70:30 PEKK-PN resin was mixed with bis[4-(3-aminophenoxy)phenyl]sulfone and exhibited a melt viscosity of 271 cP, much lower than the 657 cP viscosity of the pure PEKK-PN mixture. Void-free PEKK-PN polymers were easily prepared by degassing and curing up to 380°C, resulting in fully crosslinked networks exhibiting thermal stability above 500°C and a 75% char yield. Additionally, the cured PEKK-PN polymer samples displayed good mechanical integrity retaining 50% stiffness at 300°C. This combination of properties suggests these new PEKK-PN resins are excellent materials for high temperature thermosets in composite applications.
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Butler, Tristan ; Bunton, Caleb ; Ryou, Heonjune ; Dyatkin, Boris ; Weise, Nickolaus ; Laskoski, Matthew
Abstract: This effort assesses the correlation between chem. structures and performance-essential thermal, mech., and long-term stability properties of cross-linked thermosets. Resins of different mol. weights were prepared from the Bisphenol A based PEEK-like oligomeric phthalonitrile (BisA). Differential scanning calorimetry, which was used to investigate curing thermodn., indicated that BisA resins demonstrated pos. correlation between increasing oligomer mol. weight and both resulting m.ps. and cure initiation conditions. Characterization of thermal properties using thermogravimetric anal. (TGA) indicated a similar mol. weight trend, with char yields ranging between 57% and 73%. Rheol. studies of BisA of different mol. weights indicated significant viscosity increases in phthalonitriles that crosslinked from oligomers with higher mol. weights Moreover, the n = 1 chain length resin exhibited a gel point at 100°C lower than the n = 25 oligomer. Anal. of hardness of these cured polymers indicated that the resin crosslinked using the n = 1 oligomer was most brittle, while the thermoset derived from the n = 4 BisA demonstrated highest hardness. Aging of cured phthalonitriles indicated that the n = 10 remained most stable in long-duration high-temperature environments. This study suggests the use of preparing BisA thermosets from oligomers with different mol. weights as an effective strategy for improving toughness, albeit at the tradeoff of lower thermal stabilities.
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Keywords: mechanical properties ; resins ; thermal properties ; thermosets
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CAS No. : | 31643-49-9 |
Formula : | C8H3N3O2 |
M.W : | 173.13 |
SMILES Code : | C1=C(C(=CC=C1[N+](=O)[O-])C#N)C#N |
MDL No. : | MFCD00040301 |
InChI Key : | NTZMSBAAHBICLE-UHFFFAOYSA-N |
Pubchem ID : | 97443 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319 |
Precautionary Statements: | P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | 1) A three-necked flask was charged with 103.9 g (600 mmo 1) of 4-nitro phthalonitrile, 800 mL of dimethyl sulfoxideAfter the powder was dissolved, 91.0 g (660 mmol) of potassium carbonate and 46.0 g (660 mmol) of sodium nitrite were added and heated at reflux to 160 C for 5 hours. After cooling to room temperature, the mixture was poured into a large amount of water, A yellow solid was precipitated and evacuated at 110 C and dried in vacuo to give 73.3 g of 4-hydroxy phthalonitrile in 85% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate; In dimethyl sulfoxide; | EXAMPLE 8 Preparation of 1,2-bis-(3,4-dicyanophenoxy)-3-fluorobenzene 3.60 g (0.02 moles plus 0.14 g excess) of 4-nitrophthalonitrile was dissolved in 50 ml anhydrous DMSO in a 100 ml three-necked flask fitted with a magnetic stirrer bar under nitrogen. 1.28 g (0.01 moles) of <strong>[363-52-0]3-fluorocatechol</strong> (Aldrich) was added to the mixture followed by 5 g of anhydrous potassium carbonate. The mixture was stirred at room temperature for 24 hours. The workup was as described in Example 5 and yielded 3.04 g of off-white crystals of the title compound (80percent theoretical yield). The product had the formula: STR15 The melting point was 198.5°-199.5° C. The elemental analysis for C22 H9 FN4 O2 was calc.: C, 69.47percent; H, 2.36percent; N, 14.73percent; found: C, 69.47percent; H, 2.34percent; N, 14.80percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE I; (p-Hydroxymethy-m-Methoxy Phenoxy)-4-Phthalonitrile Intermediate; To a 500 milliliter round bottom flask equipped with magnetic stir and nitrogen inlet was charged 42.1 grams of 4-hydroxy-3-methoxybenzyl alcohol (MW=154), 33.5 grams of potassium carbonate (MW=138), and 330 grams of ?dry? DMSO (in molecular sieve). The contents were heated in a 90 C. oil bath for about 1 hour. Thereafter, 41.9 grams of 4-nitrophthalonitrile (MW=173; obtained from TCI America, Portland, Oreg.) was added. The content were heated and stirred for 3 hours, after which a reverse phase TCL with methanol as the mobile phase was run which showed that no starting material remained in the reaction mixture (the Rfs were close). The contents were then poured into 1 liter of deionized water. The product precipitated out as a large chunk, which was filtered and collected. Infrared spectroscopy and TLC of the product indicated that none starting material, nitrophthalonitrile, remained. Then product was combined with methylene chloride and sonicated. Most of the solids dissolved. The mixture was then filtered and the filtrant was run through a silica plug. After the solvent was evaporated, about 59.3 grams of product was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃;Inert atmosphere; | To a 100 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added 1,3-dihydroxypyrimidine (5.00 g, 44.6 mmol), 4-nitrophthalonitrile (15.83 g, 91.4 mmol), powdered anhydrous K2CO3 (13.0 g, 94.2 mmol), and N,N-dimethylformamide (DMF) (100 mL). The resulting mixture was heated at 80 C. for 6-8 h. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the precipitation of a solid. The material was broken up and collected using a Buechner funnel. The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution, and finally with 200 mL of water until neutral. The solvent was removed in vacuo and the solid was vacuum dried to yield the heteroaromatic phthalonitrile (14.4 g, 90% yield). IR [cm-1]: delta 3058 (CCH), 2231 (C?N), 1610 (CN), 1589 (CC), 1491 (aromatic), 1281 (CH3), 1248 (C-O), 1173 (C-O), 970 (C-O), 834 (aromatic). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h;Inert atmosphere; | 3-methoxybenzoate (5.89 g, 0.03 mol) were dissolved inanhydrous DMF (60 mL) and anhydrous K2CO3 (13.82 g,0.1 mol) was added in portions during 30 min. The reactionmixture was stirred for 12 h at 80 C. After filtering the reactionmixture, the residue was extracted with CH2Cl2 andH2O and then was dried by rotary evaporation. After removalof the solvent, the crude product was purified by columnchromatography using silica gel and CHCl3:MeOH (15:1) aseluent to give 2, a white solid. Yield: 6.22 g (96 %). 1HNMR(500 MHz,DMSO-d6): d 8.07 (d, 1H, Ar-H), 7.75 (s, 1H, Ar-H), 7.69 (s, 1H, Ar-H), 7.67 (d, 1H, Ar-H), 7.35 (m, 2H, Ar-H), 4.37 (m, 2H, -CH2O-), 3.81 (s, 3H, Ar-OCH3), 1.35 (t,3H, -CH3). 13C NMR (126 MHz, DMSO-d6): d 164.42,159.98, 150.37, 144.59, 135.58, 128.18, 122.26, 121.77,120.96, 120.46, 116.03, 115.27, 114.75, 113.47, 107.66,60.45, 55.45, 13.30. HRMS (EI?): (m/z) = calcd for322.0953, found: 322.0955. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N,N-dimethyl-formamide; at 20 - 85℃; | The compound of the following formula (C) was synthesized in the following manner.42.6 g of 1,1-bis (4'-hydroxyphenyl) -cyclododecane and 150 mL of dimethylformamide were placed in a 500 mL flask (3 mL) Neck round bottom flask) and stirred at room temperature.After stirring, 41.9 g of 4-nitrophthalonitrile was further added, and 50 g of DMF was added and dissolved by stirring.50.2 g of potassium carbonate was added together with 50 g of DMF, and the temperature was raised to 85 DEG C with stirring.After cooling to room temperature, the cooled reaction solution was neutralized and precipitated by pouring into a 0.2N hydrochloric acid aqueous solution. The precipitate was filtered and washed with water.The filtered product was dried in a vacuum oven at 100 for one day to remove water and residual solvent to obtain the target product.NMR analysis of the target product was carried out using an apparatus (Agilent 500 MHz NMR device) (solvent: DMSO (d6)) and the result is shown in FIG. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; In N,N-dimethyl-formamide; at 85℃; for 5h; | Compound PN 1 of the following formula A was synthesized by a nitro displacement reaction. Specifically,4-hexylresorcinol (19.4 g) and 100 ml of DMF (dimethyl formamide) were placed in a 500 ml flask (3 neck round bottom flask) and stirred at room temperature. To the mixture, 34.6 g of 4-nitrophthalinitrile represented by the following formula (C) was added, and 50 g of DMF was further added, followed by stirring and dissolution. 41.5 g of potassium carbonate was added together with 50 g of DMF, and the temperature was raised to 85 while stirring.Reacted for about 5 hours,After cooling to room temperature, the cooled reaction solution was neutralized and precipitated by pouring into a 0.2 N aqueous hydrochloric acid solution. The precipitate was filtered and washed with water. The filtered product was dried in a vacuum oven at 100 for one day to remove water and residual solvent to obtain compound PN 1 of formula A in a yield of 85% by weight. The NMR analysis results for the compound of formula A are shown in Figure 1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.451 g; 0.098 g | With potassium carbonate; 3-Hydroxypropionitrile; In N,N-dimethyl-formamide; at 40℃; for 99h;Inert atmosphere; Molecular sieve; | 3-hydroxypropanenitrile (6.3 g, 88.63 mmol) was dissolved indry DMF (125 mL) under nitrogen and 4-nitrophthalonitrile(5.08 g, 29.36 mmol) and molecular sieve 4Å (10.80 g) wereadded. After stirring for 2 h, finely ground anhydrous potassiumcarbonate (13.50 g, 97.831 mmol) was added in portionsduring 3 h with efficient stirring. The reaction mixturewas stirred at 40 C under nitrogen for 96 h. The mixturewas then poured in to ice-water (300 g). The precipitate wasfiltered off, washed with water until neutral and dried. Thecrude product was extracted with chloroform (450 mL).The combined organic extracts were washed with water anddried with anhydrous Na2SO4 and evaporated to dryness.The resulting product was washed with water and thendried, yield 4,40-oxydiphthalonitrile (3) 0,098 g. The singlecrystals were obtained in DMF at room temperature viaslow evaporation. The other filtrate was acidified to pH 3with HCl and filtered off and washed with water until neutraland then dried, yield 4-hydroxyphthalonitrile (4)2.451 g. It was not necessary to purify the product more.The spectral specifications of 4,4’-oxydiphthalonitrile (3)and 4-hydroxyphthalonitrile (4) were consistent with literaturevalues.[27-32] |