CN105566312A - Triazacycle-containing benzoxazine and preparation method thereof - Google Patents
Triazacycle-containing benzoxazine and preparation method thereof Download PDFInfo
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- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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- C08G73/0655—Preparatory processes from polycyanurates
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Abstract
The invention discloses a triazacycle-containing benzoxazine and a preparation method thereof. The method is easy to implement and high in yield, and solves the problem of storage unstability of benzoxazine and cyanate ester; in addition, by using a hardening reaction of the benzoxazine compound having a triazacycle structure, a thermosetting polymer cured material with excellent properties can be obtained, and the dimensional stability and the thermal stability of the cured material are excellent.
Description
Technical field
The present invention relates to a kind of oxo nitrogen containing three nitrogen heterocyclics for benzocyclohexane and preparation method thereof, belong to technical field of compound preparation.
Background technology
Many documents show, after cyanate ester resin (cyanateester) is solidified into three nitrogen heterocyclic structures completely, due to the symmetry of three nitrogen heterocyclic structures, its cured article shows high glass transition temperature, high thermostability and low specific inductivity, so this resinoid is often used in electric equipment products, especially common in the printed circuit board (PCB) of high frequency communications.
Cyanate completely after solidification has splendid thermal properties, research shows, cyanate is directed into oxo nitrogen for being expected to improve the polyoxy that do not merge in benzocyclohexane (benzoxazine) for the character of nitrogen for benzocyclohexane, therefore, oxo nitrogen is studied by many team for the blending of benzocyclohexane and cyanate, as: Nair team (SanthoshKumar, K.S.; ReghunadhanNair, C.P.; Ninan, K.N.EuropeanPolymerJournal2009,45, (2), 494-502.), Kimura team (Kimura, H.; Ohtsuka, K.; Matsumoto, A.Expresspolymlett2011,5, (12), 1113-1122), Gu team (Li, X.; Gu, Y.PolymerChemistry2011,2, (12), 2778-2781.) and Lin team (Lin, C.H.; Huang, S.J.; Wang, P.J.; Lin, H.T.; Dai, S.A.Macromolecules2012,45, (18), 7461-7466.) all a lot of research is expanded to this field.What these researchs related to is different curing reactions, but identical phenomenon is all pointed in these different experiments: oxo nitrogen mixes for when benzocyclohexane and cyanate blending, and find that oxo nitrogen can catalysis cyanate ester three cyclisation (trimerization) for benzocyclohexane.
Recently, Lin team (Wang, M.W.; Jeng, R.J.; Lin, C.H.Macromolecules2015,48, (8), 2417-2421) also observe, in the methyl ethyl ketone solution including P-oda/BACY (1/1mol/mol) blending, (wherein P-oda represents 4,4 '-oxydianiline/phenol-basedbenzoxazine, BACY represents dicyanateesterofbisphenolA), the phenomenon of gelation can be there is after 30 DEG C, 24 hours.Therefore, Lin team proposes oxo nitrogen for lone-pair electron catalysis cyanate three cyclisation of the nitrogen-atoms on benzocyclohexane, forms the structure of three nitrogen heterocyclics.If synthesis has cyanate and the oxo nitrogen compound for benzocyclohexane structure simultaneously, will because oxo nitrogen to be for benzocyclohexane catalysis cyanate, this compound is existed and stores non-persistent risk, this is a large problem in the urgent need to address in field.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide a kind of oxo nitrogen containing three nitrogen heterocyclics for benzocyclohexane and preparation method thereof, synthesis step easily realizes, and solves and stores non-persistent problem.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
Containing the oxo nitrogen of three nitrogen heterocyclics for benzocyclohexane, its structural formula is:
Wherein, R
1for H or C1-C6 alkyl.
The foregoing preparation method of oxo nitrogen for benzocyclohexane containing three nitrogen heterocyclics, reaction scheme is:
Concrete reactions steps is:
S1, three-step approach prepare P-ap: salicylic aldehyde, 4-amino-phenol and ethanol are added logical nitrogen and is provided with in the reactor of magnetic stirring apparatus, reaction mixture is at room temperature stirred 12 hours; Then, the sodium borohydride of the quality such as three parts was added in reactor every one hour, after adding for three times, reaction mixture is at room temperature stirred 12 hours further; Then, the mixture in reactor be poured into water and stir, filtering and obtain yellow mercury oxide, dry at 60 DEG C, obtain intermediate product 2-(((4-hydroxyphenyl) amino) methyl) phenol; Then, intermediate product, paraformaldehyde and Isosorbide-5-Nitrae-dioxan are inserted in the reactor being equipped with condenser and magnetic stirring apparatus, mixture is stirred 16 hours at 90 DEG C, finally, utilizes rotatory evaporator to remove 1,4-dioxan, obtains light red thick liquid and is P-ap;
S2, synthetic compound P-tta: P-ap, triethylamine and acetone are joined in the reactor being equipped with condenser and magnetic stirring apparatus, stir reaction solution 1 hour at 3-5 DEG C subsequently; Slowly drop in reactor after separately Cynuric Chloride being dissolved in acetone, and at room temperature stir 1 hour, and then react 1.5 hours under being warming up to reflux temperature (about 60 DEG C); Finally, by reaction solution impouring water, filter and obtain white depositions, with washing with acetone, and drying obtains product P-tta at 60 DEG C, and productive rate is up to 77%.
In addition, the invention also discloses a kind of preparation method of P-tta cured article: be placed in by P-tta on hot-plate and be heated to 150 DEG C, and ceaselessly stir, then pour sclerosis in aluminium dish into and obtain P-tta cured article, this cured article is a kind of thermoset macromolecule material of excellent performance.
Usefulness of the present invention is: the present invention proposes a kind of preparation method of oxo nitrogen for benzocyclohexane molecule with three nitrogen heterocyclic structures, the method easily realize and also productive rate high, solve the storage instability problem of oxo nitrogen for benzocyclohexane and cyanate; In addition, by the sclerous reaction of oxo nitrogen for benzocyclohexane compound that this has three nitrogen heterocyclic structures, the thermosetting polymer of excellent can be obtained, dimensional stability and thermostability good.
Accompanying drawing explanation
Fig. 1 is P-ap and the P-tta's that obtains of preparation method of the present invention
1h-NMR spectrogram;
Fig. 2 is P-ap and the P-tta's that obtains of preparation method of the present invention
13c-NMR spectrogram;
Fig. 3 is the DSC exotherm of P-oda and P-tta of the present invention;
Fig. 4 is that P-tta of the present invention is at every one-phase Wen Chiwen FTIR tracking map of 20 minutes;
Fig. 5 is the DMA graphic representation of P (the P-tta)-X of embodiment 2;
Fig. 6 is the TMA graphic representation of P (the P-tta)-X. of embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, concrete introduction is done to the present invention.
Raw material: the raw material in the present invention comprises: salicylic aldehyde (2-Hydroxybenzaldehyde), 4-amino-phenol (4-aminophenol) and sodium borohydride (sodiumborohydride), these three kinds of raw materials are all purchased from Alfa company; Paraformaldehyde (paraformaldehyde), Cynuric Chloride (2,4,6-trichloro-1,3,5-triazine) and triethylamine (triethylamine) all available from Acros; Other raw materials, without specified otherwise, are commercial.
Embodiment 1
First the present embodiment discloses a kind of oxo nitrogen containing three nitrogen heterocyclics for benzocyclohexane, and structural formula is as follows:
Wherein, R
1for H or C1-C6 alkyl.
For the reaction scheme of benzocyclohexane should be containing the oxo nitrogen of three nitrogen heterocyclics:
In order to more clearly understand this invention, set forth concrete reactions steps below in conjunction with reaction scheme:
S1, three-step approach prepare P-ap (4-(2H-benzo [e] [1,3] oxazin-3 (4H)-yl) phenol): salicylic aldehyde 5 grams (40.9 mmole), 4-amino-phenol 4.468 grams (40.9 mmole) and ethanol 50mL added logical nitrogen and be provided with in the 500mL glass round bottom reactor of magnetic stirring apparatus, reaction mixture is at room temperature stirred 12 hours; Then, the sodium borohydride of three parts 0.52 gram (13.7 mmole) was added in reactor every one hour, after adding for three times, reaction mixture is at room temperature stirred 12 hours further; Then, mixture in reactor to be poured in 500mL water and to stir, filtering and obtain yellow mercury oxide, dry at 60 DEG C, obtain intermediate product 2-(((4-hydroxyphenyl) amino) methyl) phenol, structural formula is:
this intermediate product
1h-NMR (DMSO-d6) analytical results is: δ=4.11 (s, 2H, ph-CH2-N), 5.33 (s, 1H ,-NH), 7.20-6.40 (m, 8H), 8.40 (s, 1H,-OH), 9.50 (s, 1H,-OH), this characterization result is consistent with the structure intending the intermediate product obtained;
Then, by intermediate product 1 gram (4.6 mmole), paraformaldehyde 0.1524 gram (5.1 mmole) and 1,4-dioxan 25mL inserts and is equipped with in the 100mL glass round bottom reactor of condenser and magnetic stirring apparatus, mixture is stirred 16 hours at 90 DEG C, finally, rotatory evaporator is utilized to remove 1,4-dioxan, obtain light red thick liquid and be P-ap (4-(2H-benzo [e] [1,3] oxazin-3 (4H)-yl) phenol).
S2, synthetic compound P-tta: the P-ap that this step is obtained by step S1 and Cynuric Chloride carry out nucleophilic substitution and be obtained by reacting target product P-tta.By P-ap1.0056 gram (4.6 mmole), triethylamine 0.4701 gram (4.6 mmole) and 20 milliliters, acetone join and are equipped with in the 100mL glass round bottom reactor of condenser and magnetic stirring apparatus, are stirred 1 hour by reaction solution subsequently at 3-5 DEG C; Slowly drop in reactor after separately Cynuric Chloride 0.2770 gram (1.5 mmole) being dissolved in 10 milliliters of acetone, and at room temperature stir 1 hour, and then react 1.5 hours under being warming up to reflux temperature; Finally, by reaction solution impouring water, filter and obtain white depositions, with washing with acetone, and drying obtains product P-tta at 60 DEG C, and productive rate is up to 77%.
Embodiment 2
Present embodiment discloses a kind of preparation method and excellent properties of P-tta cured article: be placed in by P-tta on hot-plate and be heated to 150 DEG C, and ceaselessly stir, then pour sclerosis in aluminium dish into and obtain P-tta cured article, this cured article is a kind of thermoset macromolecule material of excellent performance.
The aluminium dish size of preparation DMA sample is 5.0cm × 1.0cm × 0.3cm; The aluminium dish size of preparation TMA sample is 1.0cm × 1.0cm × 0.3cm.Curing condition is 180 DEG C (2h), 200 DEG C (2h), 220 DEG C (2h), 240 DEG C (2h), and some test piece can be hardened to 260 DEG C (2h).
It should be noted that, the code name of P-tta cured article is that P (P-tta)-X, X represent last stiffening temperature.Such as, the highest stiffening temperature is that the cured article of 240 DEG C (2h) is denoted as P (P-tta)-240.
Performance analysis instrument
(1), elementary errors scanning calorimeter (DifferentialScanningCalorimeter, DSC), model: Perkin-ElmerDSC7, nitrogen flow rate is 20mL/min.
(2), thermogravimetric weight loss analyser (ThermogravimetricAnalysis, TGA), model: ThermoCahnVersaTherm, nitrogen and air velocity are 20mL/min.
(3), Dynamic Mechanical Analyzer (DynamicMechanicalAnalyzer, DMA), model: Perkin-ElmerPyrisDiamond, the cured article obtained hardening makes the test piece of long 20mm, wide 10mm, thick 2mm, temperature rise rate is 5 DEG C/min, frequency is 1Hz, measures and stores modulus (StorageModulusE') and Tan δ curve.
(4), thermomechanical analyzer (ThermalMechanicalAnalysis, TMA), model: Perkin-ElmerPyrisDiamond, temperature rise rate is 5 DEG C/min.
(5), superconduction nuclear magnetic resonance spectrometer (400MHzNuclearMagneticResonance, NMR), model: VarianUnityInova-400, DMSO-d
6chemical shift is δ=2.49ppm.
Performance characterization interpretation of result:
In embodiment 1, step S1 obtains product
1h-NMR (DMSO-d
6) analytical results is shown in Fig. 1: δ=4.50 (2H, H
4), 5.29 (2H, H
11), 6.64 (d, 2H, H
2), 6.70 (d, 1H, H
9), 6.84 (t, 1H, H
7), 6.93 (t, 2H, H
3), 7.06 (t, 1H, H
6), 7.07 (t, 1H, H
8), 8.96 (s, 1H, OH).
13c-NMR (DMSO-d
6) analytical results is shown in Fig. 2: δ=49.80 (C
4), 80.08 (C
11), 115.52 (C
2), 116.10 (C
9), 119.80 (C
3), 120.28 (C
7), 121.35 (C
5), 127.07 (C
6), 127.53 (C
8), 140.35 (C
12), 151.99 (C
10), 154.04 (C
1).From characterization result, the final product that this step obtains is P-ap:
In embodiment 1, step S2 obtains product
1h-NMR (DMSO-d
6) analytical results is shown in Fig. 1: δ=4.64 (s, 2H, H
13), 5.43 (s, 2H, H
6), 6.72 (d, 1H, H
8), 6.86 (t, 1H, H
10), 7.06 (t, 1H, H
9), 7.08 (d, 2H, H
4), 7.11 (d, 1H, H
11), 7.13 (d, 2H, H
3).
13c-NMR (DMSO-d
6) analytical results is shown in Fig. 2: δ=40.09 (C
13), 78.97 (C
6), 116.22 (C
8), 118.26 (C
3), 120.50 (C
10), 121.12 (C
12), 121.92 (C
4), 127.19 (C
11), 127.68 (C
9), 144.99 (C
5), 145.75 (C
7), 153.84 (C
2), 173.26 (C
1).From characterization result, the target product that this step obtains is P-tta:
Fig. 3 is the DSC scintigram of P-oda and P-tta, and from figure contrast, P-tta has lower exothermic peak temperature, and except three nitrogen heterocyclics, P-tta with P-oda has similar structure.Therefore, the exothermic peak temperature that P-tta is lower is inferred relevant with the existence of three nitrogen heterocyclics.
Fig. 4 is P-tta IR scintigram at different temperatures, as seen from the figure, is positioned at 1570cm
-1and 1371cm
-1the absorption peak of three nitrogen heterocyclics rises with temperature and reduces gradually, but at 1682cm
-1but the absorption peak of isocyanaurate isocyanic ester is had to generate.
Analyze in conjunction with DSC and IR, the sclerous reaction mechanism of P-tta may comprise two kinds:
The first is as shown in approach a equational below: the zwitterion (zwitter-ion) that oxo nitrogen is formed for benzocyclohexane open loop attacks three nitrogen heterocyclic structures, after resetting, form isocyanaurate (isocyanic ester) structure;
The second is as shown in equational approach b below, oxo nitrogen also can be cross-linked to form the oxo nitrogen of open loop for benzocyclohexane structure voluntarily for benzocyclohexane, therefore, have in cured article simultaneously three nitrogen heterocyclics, isocyanurate and open loop oxo nitrogen for benzocyclohexane structure.
Wherein, arylcyanurate (triazine) represents three nitrogen heterocyclics that aromatic base replaces; Alkylcyanurate represents three nitrogen heterocyclics that alkyl replaces;
A:insetion insertion reaction; B:ring-openingpolymerization ring-opening polymerization;
Alkylisocyanurate represents the isocyanic ester that alkyl replaces; Rearrangement represents rearrangement reaction;
Ring-openedbenzoxazine represents that the oxo nitrogen of open loop is for benzocyclohexane;
Carry out dynamic mechanical analysis (dynamicmechanicalanalysis, DMA) to the polymer oxo nitrogen hardened for benzocyclohexane cured article, as shown in Figure 5, the corresponding temperature of its tan δ crest is glass transition temperature (T to analytical results
g), as shown in Figure 5, when after 260 DEG C of sclerosis, the glass transition temperature of P-tta cured article is up to 279 DEG C.Meanwhile, thermal expansivity is measured by thermomechanical analyzer (TMA), as shown in Figure 6, when after 260 DEG C of sclerosis, the glass transition temperature of P-tta cured article is up to 265 DEG C, and thermal expansivity is 32ppm/ DEG C, illustrates that cured article has splendid dimensional stability.
In addition, carry out heat stable property analysis by thermogravimeter (thermalgravimetricanalysis, TGA), analytical results shows: in a nitrogen atmosphere, 5% weight loss temperature (T
d5) all can reach about 417 DEG C, and reach 68% respectively in the remaining rate of 800 DEG C of coke, this cured article presents good thermostability.
To sum up, the oxo nitrogen with three nitrogen heterocyclic structures of the present invention easily realize for the preparation method of benzocyclohexane molecule and also productive rate high, solve the storage instability problem of oxo nitrogen for benzocyclohexane and cyanate; In addition, by the sclerous reaction of oxo nitrogen for benzocyclohexane compound that this has three nitrogen heterocyclic structures, the thermosetting polymer of excellent can be obtained, dimensional stability and thermostability good.
More than show and describe ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (6)
1. contain the oxo nitrogen of three nitrogen heterocyclics for benzocyclohexane, it is characterized in that, its structural formula is:
Wherein, R
1for H or C1-C6 alkyl.
2. the oxo nitrogen containing three nitrogen heterocyclics as claimed in claim 1 is for the preparation method of benzocyclohexane, and it is characterized in that, reaction scheme is:
。
3. the oxo nitrogen containing three nitrogen heterocyclics as claimed in claim 1 is for the preparation method of benzocyclohexane, and it is characterized in that, reactions steps is:
S1, three-step approach prepare P-ap: salicylic aldehyde, 4-amino-phenol and ethanol are added and be provided with nitrogen inlet and be provided with in the reactor of magnetic stirring apparatus, reaction mixture is at room temperature stirred 12 hours; Then, the sodium borohydride of the quality such as three parts was added in reactor every one hour, after adding for three times, reaction mixture is at room temperature stirred 12 hours further; Then, the mixture in reactor be poured into water and stir, filtering and obtain yellow mercury oxide, dry at 60 DEG C, obtain intermediate product 2-(((4-hydroxyphenyl) amino) methyl) phenol; Then, intermediate product, paraformaldehyde and Isosorbide-5-Nitrae-dioxan are inserted in the reactor being equipped with condenser and magnetic stirring apparatus, mixture is stirred 16 hours at 90 DEG C, finally, utilizes rotatory evaporator to remove 1,4-dioxan, obtains light red thick liquid and is P-ap;
S2, synthetic compound P-tta: P-ap, triethylamine and acetone are joined in the reactor being equipped with condenser and magnetic stirring apparatus, stir reaction solution 1 hour at 3-5 DEG C subsequently; Slowly drop in reactor after separately Cynuric Chloride being dissolved in acetone, and at room temperature stir 1 hour, and then react 1.5 hours under being warming up to reflux temperature; Finally, by reaction solution impouring water, filter and obtain white depositions, with washing with acetone, and drying obtains product P-tta at 60 DEG C.
4. the oxo nitrogen containing three nitrogen heterocyclics according to claim 3 is for the preparation method of benzocyclohexane, and it is characterized in that, in described step S2, reflux temperature is 60 DEG C.
5. a preparation method for P-tta cured article, is characterized in that, is placed on hot-plate by the P-tta that claim 3 is obtained and is heated with stirring to 150 DEG C, then pours sclerosis in aluminium dish into and obtains P-tta cured article.
6. the cured article obtained by preparation method according to claim 5, is characterized in that, this cured article have simultaneously three nitrogen heterocyclics, isocyanic ester (isocyanurate) and open loop oxo nitrogen for benzocyclohexane structure, local structure are as follows:
Wherein, triazine represents three nitrogen heterocyclics, and alkylisocyanurate represents that the isocyanic ester that alkyl replaces, ring-openedbenzoxazine represent that the oxo nitrogen of open loop is for benzocyclohexane.
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